CHAPTER 4

PLANT CAPACITY, LOCATION

AND ENVIRONMENTAL

CONSIDERATIONS

157
I. INTRODUCTION

The proposed plant produces vanillin from nephelium lappaceum (rambutan peel)

via nitrobenzene oxidation method. Vanillin (4-hysroxy-3-methoxybenzaldehyde) is the

substantial component of vanilla, which is considered to be an important material to be

widely used in flavoring worldwide. This will be the first plant to be estalblished in the

Philippines.

This product is produced industrially as a fine powder that consists of pure and rich

creamy charateristics of vanilla consumed for its aromatic component and properties of a

flavoring agent. Thus, it will be offered in food industries or any industries that

manufacture products that are non-toxic and safe for consumption. The said product will

have a purity of greater than or equal to 98% and yields above 83% in purifcation process

that employs crystallization.

Applications of Vanillin are mainly used in fragrance, food, pharmaceutical

products, fine chemicals, personal care, cosmetics, and animal fats. Moreover, vanillin

that were used in the animal feed to mask the flavor and as a nutritional ingredient. Aside

from its ability to mask flavors, its effect on taste and its odor is applied in perfumes or

aerosols for its masking ability to deodorize. Innovations and continous discoveries in the

field of chemical process industries arises in search of a new product that will fit in the

market. In line with this, vanillin would make a milestone as the demand will rise from

different market whether improving its sale or aiming to develop a new product that will

bloom in the business.

158
 The product vanillin, when stored in a sealed container at a cool and dry place

away from moisture, alkaline atmosphere, and oxidizing agents, has shelf life that can last

up to two (2) years from the date of manufacture. It is not produced by any processing aids

that was derived by genetic modifications thereby conforms with the specifications of EU,

FCC, and JECFA. Applications in food and beverages has been certified by Halal and

under ISO 9001:2008 and ISO 22000:2005 certifications.

The market for vanillin is highly concentrated in nature and most of the

manufacturers have their facilities acroos the globe. However, vanillin is for most

imported by different countries other than Philippines in Southeast Asia. For this plant

design, the importation data will be used in the analysis of supply and demand. Also, the

availability of the raw material used was analyzed based on the consumption and

production of rambutan in the Philippines.

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II. PLANT CAPACITY DETERMINATION

A. SUPPLY ANALYSIS OF VANILLIN

According to the Department of Trade Industry, there are no local suppliers or

manufacturers of the vanillin product with the commodity description of 4-hydroxy-3-

methoxybenzaldehyde. The supply of vanillin was mainly imported and the historical

annual importation data acquired from Department of Trade and Industry-Bureau of

Import Services- Import Policy and Monitoring Division (BIS-IPMD) with the HS Code

29124100 are shown below.

Table 4.1. Annual Importation Data of Vanillin in the Philippines

NET MASS (MT)

Origin 2015 2016 2017 AVERAGE PERCENTAGE
China 61.85 67.13 96.76 75.25 38.08%
France 24.64 35.3 28.27 29.40 14.88%
Indonesia 0 2.7 0 0.90 0.46%
Netherlands 0.68 1.96 4.16 2.27 1.15%
Norway 0.39 6.06 2.54 3.00 1.52%
Singapore 10.5 23.72 34.84 23.02 11.65%
United States of America 85.19 64.32 41.86 63.79 32.28%
TOTAL 183 201 208 198 100.00%

Source: Bureau of Import Services – Import Policy and Monitoring Division

(BIS-IPMD) of the Department of Trade and Industry (DTI)

According to the table above, China has the highest amount of importation of

vanillin since 2015 until 2017 with an average of 75.25 MT. This indicates that China is

the main supplier of vanillin providing 38.08% of the supply to the Philippines within the

past three (3) consecutive years followed by the provision of United States of America at

32.28% of the total supply in the Philippines. China and United States of America are the

chief importers and suppliers of the said material. The amount in year 2015 that was

160
produced by USA was more than what was provided until the Philippines greatly depended

on China in the upcoming years.

On the other hand, Indonesia was only able to provide 0.46% of the total average

of vanillin having the least import in year 2016 which have been reported to have supplied

once. Slight imports were made from the countries Indonesia, Netherlands, and Norway

wherein the average amount imported from the last three years are 0.90, 2.27, and 3.00 in

MT respectively. As such imports were only able to contribute up to 3.12% of the total

average supply.

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 B. DEMAND ANALYSIS OF VANILLIN

In accordance with the previous reports regarding the annual importation of

vanillin in the Philippines, the demand increases in amount that is supplied by the

Philippine business importers. Moreover, the amount needed for vanillin is expected to

rise as business franchise and other food related industries has been a prospect among

aspiring entrepreneurs especially in the Philippines. An overall data provided by Bureau

of Import Services – Import Policy and Monitoring Division (BIS-IPMD) from the office

of Department of Trade and Industry (DTI) shows that vanillin has mostly intervened in

the food and beverage industries for 45.39% of the stock which is almost half of being

consumed compared with the other industries.

Figure 4.1. Industries that Use Vanillin and their Average Annual Consumption

23.13%
Food and Beverage
45.39%
Pharmaceuticals
Others
31.48%

Figure 4.1 depicts the average annual consumption of vanillin by different

industries in the Philippines from year 2015 until 2017. It has been noted by the Trade

Statistics Division under Philippine Statistics Authority (PSA) that there were no exporters

nor local manufacturers of vanillin in the Philippines, thereby; the demand relies on the

import that is equal to the quantity supplied. Major consumers of vanillin has been

162
generalized into three industrial categories and ranked accordingly to its purpose and

consumption namely food and beverage, pharmaceuticals, and other industries with the

least usage or minor purposes that utilize vanillin.

Table 4.2. Industries that Use Vanillin and their Average Annual Consumption

AVERAGE ANNUAL CONSUMPTION

OF VANILLIN FROM 2015 TO 2017
INDUSTRY (MT) PERCENTAGE
Food and Beverage 83.97 45.39%
Pharmaceuticals 58.25 31.48%
Others 42.79 23.13%
TOTAL 185 100.00%

Source: Bureau of Import Services – Import Policy and Monitoring Division

(BIS-IPMD) of the Department of Trade and Industry (DTI)

As shown in Table 4.2, the total average annual consumption of vanillin by

different industries in the Philippines is 185 MT. Food and beverage industries, being the

top consumer of vanillin with an average amount of 83.97 MT, have widely used it as a

substitute for vanilla. Extensive applications of vanilla in food, beverages, pharmaceutical

industries, and perfumeries increases the demand but with limited supply. Hence, vanillin

required more resources for its production as it can also be used in the pharmaceutical

industry including the Philippines. Pharmaceutical industries, as the second top consumer,

have been promoting the interest in healthy food and preservatives for their products using

vanillin amounting to 58.25 MT. Lastly, other industries that are manufacturing products

intended for external use or application amounts to an average of 42.79 MT.

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 Table 4.3. Average Vanillin Consumption of Some Companies in Different

Industries

FOOD AND BEVERAGE

AVERAGE ANNUAL
CONSUMPTION OF
VANILLIN FROM 2015 TO
COMPANY 2017 (MT) PERCENTAGE
Non-Alcoholic Beverages 51.37 61.18%
Flavor, Seasonings and Spices 15.59 18.57%
Flour and Flour-based Products 11.26 13.41%
Miscellaneous 5.75 6.85%
TOTAL 83.97 100%
PHARMACEUTICAL INDUSTRY
AVERAGE ANNUAL
CONSUMPTION OF
VANILLIN FROM 2015 TO
COMPANY 2017 (MT) PERCENTAGE
Healthcare Products 31.52 54.11%
Cosmetics 10.36 17.79%
Medicine 9.13 15.67%
Miscellaneous 7.24 12.43%
TOTAL 58.25 100%

Source: Bureau of Import Services – Import Policy and Monitoring Division

(BIS-IPMD) of the Department of Trade and Industry (DTI)

Table 4.3 specifies the companies that consume vanillin in the food and beverage

and pharmaceutical industries. Non-Alcoholic Beverages consumed most of the vanillin

in the food and beverage at 51.37 MT. Some of the remarkable companies of Non-

Alcoholic Beverages such as Pepsi-Cola Products were reported to consume most of

vanillin in its category, giving their drinks an enhancement to its flavor. Meanwhile,

Healthcare Products are the top consumer under the pharmaceutical industries with an

average amount of 31.52 MT within 2015 to 2017. Healthcare products are provided for

improvement of health or maintenance as supplements in many forms, including tea,

164
liquids, powders, etc. As reported within the past three years, Johnson & Johnson

Philippines, Inc. has been the top consumer of vanillin under the Healthcare Products.

With the amount of 15.59 MT and 10.36 MT, uses of vanillin in companies

manufacturing Flavor, Seasonings, and Spices and Cosmetics were the next top consumer

in the food and beverage and pharmaceutical industries respectively. Knowing that these

industries are one of the biggest companies that gave an impact in the Philippine market,

the following companies will also be utilizing vanillin as part of a vital role in

manufacturing. In the same manner, RFM Corporation and Abbott Philippines were

known to be the next top consumer of vanillin under Food and Beverage, and

Pharmaceutical Industries respectively. Small enterprises or minor vanillin utilization of

food and beverage garnered 5.75 MT along with the other companies under the

pharmaceutical industries at 7.24 MT. Combining all of the consumed vanillin from both

food and beverage and pharmaceutical industries, the quantity would amount to 142.22

MT.

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 Figure 4.2. Average Vanillin Consumption in Food and Beverage

6.85%
Non-Alcoholic
13.41% Beverages
Flavor, Seasonings and
Spices

18.57% Flour and Flour-based

61.18% Products
Miscellaneous

Figure 4.2 illustrates the average vanillin consumption of companies in Food and

Beverage Industries. Most of the vanillin consumed were accounted for the companies

manufacturing Non-Alcoholic Beverages at 61.18% of the total consumption. Also,

vanillin is considered to be the main constituent of the products made such as juice, milk,

coffee, carbonated drinks, etc. Because of that, the claim is said to be true when it comes

to the highest industrial consumption of vanillin made by Non-Alcoholic Beverages.

Flavor, Seasonings, and Spices were the next top consumer of vanillin in the

market at 18.57% of the total consumption because of its fragrant aroma and rich flavor.

Moreover, vanillin is widely used in catering services, brewery, bakery, or any other food

and meal preparation since it is preferred to be supplied in powdered form for cooking.

Thereby, covering 13.41% of the industrial utilization of vanillin made by Flour and Flour-

based Products. Altogether, these products may be baking goods, chocolates, pastries,

condiments, etc.

166
 The smallest portion for the vanillin consumption in food and beverage falls under

Miscellaneous at 6.85%. Products made are not suitable for human consumption such as

animal feeds, food and drug laboratory testing, replication of food for commercial

advertisement, etc.

Figure 4.3. Average Vanillin Consumption in Pharmaceutical Industry

12.43%

Healthcare Products
15.67% Cosmetics
54.11% Medicine
Miscellaneous
17.79%

Figure 4.3 shows the percentage of consumption of vanillin in the pharmaceutical

industry. Healthcare products such as herbal tea, vitamins and supplements, oral hygiene,

etc. consumed most of the vanillin among all companies with the percentage share of

54.11%.

Cosmetics are categorized under the pharmaceutical industry that accounts for

17.79% of the total vanillin consumption. Being the second heavy consumer in the

pharmaceutical industry, vanillin is widely used in perfumery, makeup, skin care, etc. On

the other hand, medicinal use of vanillin is the third largest consumer in the pharmaceutical

167
industry wherein 15.67% of the total demand for vanillin in the market supply. In addition

to that, the application of vanillin in the medical field is to encourage children and

eliminate the fear in consuming vitamins or medicine by its enhanced flavor and good

aroma.

Other companies and usage of vanillin in the pharmaceutical industry accounts for

12.43% of the total vanillin consumption. In other studies, vanillin can also be used in

prolonging the shelf life of products sold in the pharmaceutical market to increase its

availability for its necessity. Moreover, other uses of vanillin in the pharmaceutical

industries were labeled as miscellaneous to represent the non-human consumption such as

veterinarian medicine and healthcare, household cleaning products for kitchenware, etc.

168
 C. AVAILABILITY OF RAMBUTAN (Nephelium lappaceum) PEELS

Rambutan (Nephelium lappaceum) is a fruit that is less known yet popular for its

exotic appearance and attractive color along with its exquisite taste. The demand for

rambutan rises in the season of its fruitage and its region of harvest in some tropical

countries of Asia including Philippines. Its cultivation can exist among plantations for

mass production or simply grown at home in some areas for local consumption.

Rambutan is widely produced in Thailand which has been considered to be the leading

producer of the fruit and mostly cultivated along with Malaysia.

Table 4.4. Seasonal Production of Rambutan in the Philippines

First Second Third Fourth

Year Quarter Quarter Quarter Quarter Annual
2015 14605.17 11277.41 108152.19 50840.77 184876
2016 9984.02 10950.22 106925.66 33172.72 161033
2017 7386.63 7896.06 75267.25 36805.81 127356

Source: National Seed Industry Council (NSIC) formerly known as Philippine Seed
Board (PSB)

Outstanding selections of rambutan varietiers are found thorughout the country

and registrered in the Philippine Seed Board (PSB) which is now known as National Seed

Industry Council (NSIC) where the database of Crop Statistics of the Philippines under

the Philippine Statistics Authority (PSA) gathers the raw data and percentage of crop

volume production. In table 4.4, rambutan was found to be grown seasonal whereas the

bearing of the fruit takes place in the thrid quarter of the year. Morevover, the third

quarter of the year ranges from July to September that yields an average of 61.33% of

the annual harvest. On the other hand, rambutan production is at scarcity in the first half

169
of the year having an average of 6.63% and 6.37% in the first and second quarter

respectively. This is an important factor in planning the schedule for the plant to operate

continuously or seasonally depending on what factors or conditions may intervene.

According to the Crops Statistics of the Philippines, rambutan falls under the

catergory of fruit crops when grouped in accordance to its commodity. The fruit is

commonly eaten after tearing the rind (peel) and pulling out the edible part in the middle.

The consumption of rambutan is proportionate in generating waste materials (e.g.

rambutan peels). The anatomy of a rambutan fruit contains 45.9% of its weight to be the

peel and 7.0% of its seed. Hence, it can generate large amount of waste and an attention

should be addressed to utilize its potential, Upon exploring its capabilities, it can

contribute to the sustainability of the environment and the economy if the waste material

will be utilized into another product to meet an industrial demand.

Knowing that the rambutan peel is an agricultural waste, the material inclined to

the fruit is abundant in crop industries and market. Rambutan peel may be referred to as

pericarp in some journals which weighs from 10.5 to 17.3 grams. The whole fruit

typically weighs around 22.9 to 34.7 grams thereby consisting 45.9 to 49.9% of its weight

as its peel. Consisting high percentage of unconsumed material lessens the value of the

fruit and hence making its purpose secondary. The primary purpose of rambutan is

converting the raw waste into a useful product namely vanillin.

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 Table 4.5. Annual Production of Rambutan in the Philippines

NET MASS (MT)

REGION 2015 2016 2017 AVERAGE PERCENTAGE
Luzon 58697.66 59331.09 66629.85 61552.87 39.02%
Visayas 5591.67 2551.08 4110.96 4084.57 2.59%
Mindanao 120586.2 99150.45 56614.95 92117.20 58.39%
TOTAL 184876 161033 127356 157755 100.00%

Source: Philippine Statistics Authority (PSA)

Figure 4.4. Annual Production of Rambutan in the Philippines

39.02% Luzon
Visayas
58.39% Mindanao

2.59%

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 Table 4.5 shows the annual production of rambutan (Nephelium lappaceum) in the

Philippines categorized into three island divisions namely Luzon, Visayas, and Mindanao

for the past three years starting at 2017. An average annual production of each island

divisions yielded 61,552.87 MT, 4,084.57 MT, and 92,117.20 MT respectively wherein

the most harvested rambutan was achieved in Mindanao. More than half of the total supply

of rambutan in the Philippines collected at 58.60% from Mindanao will be a viable source

for the raw materials.

Considering the location for the main supply of the raw materials is a determining

factor to setup an industrial plant. Moreover, its aim is to minimize the possible costs (e.g.

transportation, storage for handling, manpower, etc.) and maximize the time that was

supposed to be delivered at fresh quality. Prolonging the time after harvest and

consumption may lead to losses such as spoilage and decrease in attainable maximum

capacity thereby making Mindanao as an ideal location.

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 Table 4.6. Annual Production of Rambutan in Mindanao

NET MASS (MT)

REGION 2015 2016 2017 AVE PERCENTAGE
ZAMBOANGA
PENINSULA 40063.8 35234.22 14399.91 29899.31 32.46%
NORTHERN
MINDANAO 9313.5 9692.76 9223.83 9410.03 10.22%
DAVAO REGION 22731.24 21362.67 16410.45 20168.12 21.89%
SOCCSKSARGEN 32160.24 19955.04 7632.03 19915.77 21.62%
CARAGA 15760.92 9691.5 8578.29 11343.57 12.31%
ARMM 556.5 533.4 370.44 486.78 0.53%
NEGROS ISLAND
REGION 0 2680.86 0 893.62 0.97%
TOTAL 120586 99150 56615 92117 100.00%

Source: Philippine Statistics Authority (PSA)

Figure 4.5. Annual Production of Rambutan in Mindanao

0.53% 0.97%
ZAMBOANGA
PENINSULA
12.31%
NORTHERN
MINDANAO
32.46%
DAVAO REGION
21.62%
SOCCSKSARGEN

10.22% CARAGA

21.89% ARMM

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 Table 4.6 shows the annual production of rambutan in the regions of Mindanao

that was reported within the past three years. Most of the rambutan supply was

produced in the Zamboanga peninsula, the second largest island in the Philippines,

providing 32.46% of the total production in Mindanao. With an average amount of

29,899.31 MT from year 2015 until 2017, the island region is capable of supplying

more than all of the regions in Visayas and can meet nearly half of the production in

Luzon.

Being the most abundant producer of rambutan in Mindanao, the desired plant

can be situated in some of the cities or provinces in the Zamboanga peninsula that will

be fairly advantageous especially in some local areas consuming the fruit immediately

after harvest. Local administration can cooperate to the consumers that utilizes more

on the fruit that disposes its peel for mass collection. The local consumers can also be

food manufacturers or other industries utilizing solely on the fruit which are susceptible

to raw waste generation from peel.

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 Table 4.7. Annual Production of Rambutan and Rambutan Peel Recovery in
Zamboanga Peninsula

Annual Production of Rambutan in Zamboanga Peninsula (Altered)

NET MASS (MT) AVE %
PROVINCE/CITY 2015 2016 2017 AVE (Peel) (Peel)
Zamboanga del Norte 33,631.50 30,632.91 10149.72 24804.71 11971.72 82.96%
Zamboanga del Sur 3,723.09 2,057.58 1754.76 2,511.81 1,212.30 8.40%
Zamboanga Sibugay 2,662.80 2,497.11 2450.49 2,536.80 1,224.36 8.48%
Zamboanga City 46.41 46.62 44.94 45.99 22.20 0.15%
TOTAL 40064 35234 14400 29899 14430.57 100.00%

Source: Philippine Statistics Authority (PSA)

Figure 4.6. Annual Production of Rambutan and Rambutan Peel Recovery in

Zamboanga Peninsula

0.15%

8.48%
8.40%
Zamboanga del Norte
Zamboanga del Sur
Zamboanga Sibugay
Zamboanga City
82.96%

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 Table 4.7 presents the annual production of rambutan in the provinces and cities

of Zamboanga for the past three years. Zamboanga del Norte produced almost all of

the rambutan in the Zamboanga Peninsula from 2015 to 2017 with an average of

24,804.71 MT. With an average annual production of 82.96% of the total annual

production in the region, Zamboanga del Norte is suitable of producing rambutan on

its own and capable in providing rambutan peels as its by-product.

Table 4.7 also shows the possible amount of rambutan peel that can be recovered

from the produced rambutan, being 48.3% of the whole mass, in the regions of Mindanao

from 2015 to 2017. Since Zamboanga Peninsula produces the most rambutan among all

of the regions in Mindanao, 32.46% of the entire rambutan peels that were generated

corresponds to an average amount of 14,430.57 MT. Two of the regions in Mindanao that

can almost meet half of the whole production and/or recovery were the regions of Davao

and Soccsksargen with 21.62% and 21.89% respectively. Regardless, Zamboanga

Peninsula was slightly on par with the two regions mentioned.

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Table 4.8. Distribution of Rambutan in Zamboanga del Norte

Annual Rambutan Harvest from Zamboanga del Norte (MT) 24805

AVERAGE
RAMBUTAN
FRUIT PROCESSING PERCENTAGE PEEL
CONSUMPTION
COMPANIES UTILIZATION RECOVERED
(MT)
(MT)
Polyfruits Farm 16381.03 66.04% 7912.04
Southern Philippine
4221.76 17.02% 2039.11
Fresh Fruits Corporation
Lapanday Foods 2100.96 8.47% 1014.76
RJ-Sun Tropical Herbs
1113.73 4.49% 537.93
and Fruits
Martsons Food
987.23 3.98% 476.83
Corporation
TOTAL 24805 100.00% 11980.67

Source: Department of Agriculture

Table 4.8 above shows the distribution of rambutan and its utilization while

generating waste rambutan peels to be recovered. To properly estimate the available

amount of material to be consumed, each fruit processing companies should be considered.

Based on the data above, the highest percentage of rambutan that has been utilized was

Polyfruits Farm at 66.04% utilization. From the total 24,805 MT of rambutan that can be

consumed, 11,980.67 MT of rambutan peels can be recovered. Since Polyfruits Farm

consumed 16,381.03 MT of rambutan, 7,912.04 MT of rambutan peel was generated as

waste.

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 Table 4.9. Estimation of the Availability of Rambutan Peels

Estimation of the Availability of Rambutan Peels

AVERAGE RAMBUTAN
Estimated Available Rambutan Peels
PEELS AVAILABLE (MT)

Rambutan Peels from Polyfruits Farm 7912.04

Available Peels for Vanillin Production
1582.41
(20% of Peels from Polyfruits Farm)

Table 4.9 shows the estimation of the availability of rambutan peels for the

production of vanillin. As mentioned earlier, 66.04% of the total amount of rambutan

utilized in Zamboanga del Norte province were used by Polyfruits Farm at an average

amount of 7,912.04 MT. Since rambutan peels are generated waste and does not have any

use other than being disposed, about 20% of the rambutan peels can be allocated for the

proposed industrial plant. Hence, the available rambutan peels would amount to 1,582.41

MT.

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 D. ANALYSIS OF VANILLIN (SUPPLY AND DEMAND) AND

RAMBUTAN PEEL

The primary objective of the manufacturing plant is to minimize the importation

of vanillin from other countries which will lessen expenditures such as transportation and

storage costs of local consumers. Since there are no local manufacturers of vanillin in the

Philippines, the average annual importation supply will be purely based on the average

annual vanillin demand.

Table 4.10 presents the annual average supply and demand, and the average

amount rambutan peels available for the production of vanillin. Closer observation on the

table shows that the average annual supply of vanillin is 185 MT. Moreover, 70% was

assumed for the supply of vanillin to be consumed by the industries which is 130 MT.

Table 4.10. Annual Average Supply and Demand, and the Average Amount

Rambutan Peels Available for the Production of Vanillin

Category Rambutan Peels (MT) Vanillin (MT)

Average Annual Demand 185
(70% of Annual Demand) 130
Average Annual Rambutan Peels Available 1,582.41 200

The proposed plant is aimed to produce a food-grade type of vanillin having the

quality used in food, beverages, pharmaceuticals, and all other consumable goods that are

considered edible or for internal usage. The average amount of vanillin is 200 MT that can

be produced from the 20% available rambutan peels amounting to 1,582.41 MT from

Polyfruits Farm in Zamboanga del Norte. It will create an excess vanillin supply that is

179
susceptible to wastage. Therefore, the plant capacity was set to provide 70% of the average

annual demand. Numerically, around 130 MT vanillin per year will be produced against

the demand of 185 MT per year. With the abundance of rambutan generating rambutan

peels, vanillin can be produced sufficiently to meet the demands of the industries in the

Philippines. Thus, eliminating the need of import for most of the industries if they would

rather choose a domestic supply. However, the proposed plant should not necessarily

eliminate the whole demand for vanillin in the Philippines and should be limited to food

and beverage industries. This is to maintain the trade relationship between countries and

possible export of vanillin.

Backward Computation

130 MT vanillin 1000 kg 1 year

x ( )x( ) = 433.33 ≈ 500 kg vanillin/day
year 1 MT 300 days

C91 H94O36 → 4C8 H8 O3 + 5 C9 H10O4 + 2 C7 H6 O2

1 kmol Vanillin 1
500 kg Vanillin Product x (0.98) x ( ) 𝑥( )
152.15 kg Vanillin 0.95

1 kmol Lignin 1,763.85 kg Lignin 1 kg Rambutan Peel

( )x( )x ( )
4 kmol Vanillin 1 kmol Lignin 0.3779 kg Lignin

= 3,955.72 ≈ 4,000 kg Rambutan Peel

4,000 kg Rambutan Peel 1 MT

x ( )x
day 1000 kg

300 days
( ) = 1,200 MT Rambutan Peel/year
1 year

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 The 130 MT annual demand of vanillin can be produced by 1,200 MT of Rambutan

peel annually, which is possible because of the 1,582.41 MT of rambutan peels that can

be recovered annually from Polyfruits Farm. Due to mechanical losses of some equipment

in the production process, 4,800 kg/day or 1440 MT/year of rambutan peel will be used to

have a 500 kg/day of vanillin product.

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 E. CONCLUSION AND PLANT CAPACITY RECOMMENDATION

The demand of vanillin in the local industries in the Philippines will be

accommodated by the proposed plant that will be established in the province of

Zamboanga del Norte. Polyfruits Farm will be the primary source of the raw materials

since they are the highest consumer of rambutan in the region. While other fruit processing

companies can supply or provide additional raw materials in manufacturing vanillin, the

design for plant capacity was limited to Polyfruits Farms for conservational purposes and

safety allowance if shortage will occur. Since 1,582.41 MT produced annually will yield

200 MT of vanillin, it will be more than the annual average vanillin demand of 185 MT.

Based on the supply and demand data analysis of vanillin and rambutan peels, building a

manufacturing plant that utilizes only 1,440 MT of rambutan peels annually will be

distributed into daily consumption of raw materials that is constant throughout the year.

The resulting capacity will be able to achieve 130 MT per year. With 300 working days in

a year, the daily consumption of rambutan peels would be 4,800 kg per day. The

production capacity of vanillin would be 500 kg per day based on the assumption of the

plant operating on 300 working days.

Production capacity was determined primarily from the following:

1. There is an abundance of rambutan produced in Zamboanga del Norte that are

being consumed by Polyfruits Farm. Upon consuming the rambutan fruits, Polyfruits Farm

generates the raw material that will support the need of our plant of 1,582.41 MT rambutan

peels annually. This uses 59.48% of the total available rambutan peels recovered in

Zamboange del Norte that is being generated by Polyfruits Farm.

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 2. Annual local demand of vanillin is 185 MT of which all industries utilizing vanillin

relies on the product being imported from other countries. With the capability of producing

130 MT per year (500 kg per day), the production capacity should not create an excess

supply that is higher than 185 MT per year nor produce significantly lower than the plant

capacity. It should be kept in mind that going higher or lower than the intended plant

capacity will not make a profitable business.

3. Quality and purity of product is essential in any manufacturing process. Vanillin

produced by the proposed plant has high purity and the same quality with imported

vanillin. On the other hand, the product can be sold at a lower price because rambutan peel

is used as a raw material in the production of vanillin, thus, reducing the need to import

the said product.

Table 4.11. Plant Capacity and Plant Operation Summary

VANILLIN PLANT CAPACITY

Plant Capacity 130 MT/yr
Daily Capacity 500 kg/day
Rambutan Peels Required 1,440 MT/yr
No. of Working Days 300 days/yr

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III. PLANT LOCATION

Candidate Sites

Figure 4.7: Candidate Site A (Zamboanga del Norte)

Source: Google Maps

Figure 4.8: Candidate Site B (Davao del Sur)

Source: Google Maps

157
 Shown in the figures above are the two possible sites for this vanillin production

plant. One in Zamboanga del Norte and the other would be in Davao del Sur. The two

were selected based on the following criteria: raw material availability, proximity of

markets, energy availability, climate behavior, transportation facilities, water supply,

waste disposal, labor supply, taxation and legal restrictions, site characteristics, flood and

fire protection, and other community factors. The two locations are going to be evaluated

from a scale of 1 to 10 in each criteria.

A. Raw Material Availability

Rambutan peels are not the only raw materials needed in the production of vanillin

since it also needs water supply and other resources to make an excellent quality product.

Being the deciding factor in locating the construction of the manufacturing plant, it has

been studied based on numerous reasons found in this chapter. Suppliers and buyers can

barter at their own convenience and boost the economy of the region while minimizing the

waste generated by the fruit.

From the previous figures shown regarding the demand and supply of rambutan in

the Philippines, it was suggested that the two aforementioned locations be chosed due to

their proximity to the potential source of rambutan peels. Polyfruits farm, which is the

company that consumes the most rambutan in the Philippines, is located in Zamboanga

del Norte and Southern Philippine Fruits Corporation, second largest consumer of

rambutan in the Philippines, is located in Davao del Sur. With this, a rating of 5 and 4 are

given to the Zamboanga del Norte and Davao del Sur Site respectively for raw materials

availability.

158
B. Market

In the development of the plant, product specialists would be trained for necessary

evaluation of marketability whenever the product seeks improvement. Sales and marketing

will be the extending hand in the industry to support the economic speculation. Since

profitability is a primary goal of the business, technical abilities and sale expertise build

the marketing relationship of the community around the manufacturing vicinage.

For the Zamboanga site, the public market, which is the potential intermediate

distributor, is nearer compared to the public market in the Davao Site and is less congested

compared to that of Davao del Sur. However, despite having a farther distance to the

intermediate distributors and being more congested, the Davao Site has easy access to

ports which can ease the distribution of the product to clients outside of the region. More

so, the national highway in Davao del Sur has access to ports. The down side is the

congestion of traffic within the vicinity. With this, the Davao del Sur site earns a rating of

5 and the Zamboanga del Norte site gets 4.

159
C. Energy Availability

Control of energy and its direction are scrutinized by engineers and other technical

personnel. It may involve the expenses in raw material transportation, consumption of

electricity, and heat activities among cooling processes or chemical reactions that are

affected by the weather conditions. Although, energy costs are constantly changing which

renders long-termed plans more difficult to establish.

Being a major cost in the industry, it is still possible to minimize the energy

consumption by modifying operating procedures based on the advancement in alternative

energy resources. The two sites could come close to each other when it comes to energy

availability since both sides technically has the same type of source of electricity. The two

sites both get a rating of 4 in terms of energy availability.

160
D. Climate

Other than affecting the transportation facilities such as rain increasing the risk of

road accidents due to wet slippery roads or flooding, climate change is capable of

compromising the product manufacturing inside the plant and its quality outside on the

road. Not only it can delay the transportation services, it can also affect the employees in

terms of their productivity under the weather conditions. While climate change is an

emerging environmental concern, the production facility is responsible for reducing waste

generation that could be a contributor in altering nearby weather conditions (i.e. excessive

water consumption could lead to exhausting the water reservoir and an arid land).

The Davao del Sur site is situated closer to a coastline. This may be an issue when

the rainy season approach. Although both provinces are situated on a coastline. With this,

the Zamboanga del Norte location has a slight advantage, gaining a rating of 4 while the

Davao del Sur location gets 3.

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E. Transportation Facilities

One of the fixed capital cost investment is the transport facilities which includes

basic construction materials such as roads, yards, railroad sidings, fences, docks, etc.

which depends on the location of the plant. It is important to run a production schedule

since businesses are affected by time requiring forecasting in long delivery orders.

Because time is relevant to money, travel time and distance should be kept short as

possible in order for the supply of raw materials and distribution of the product will not be

costly.

Davao del Sur is much more congested compared to Zamboanga del Norte. Rush

hour traffic may cause some inconveniences and delays in terms of delivery of supplies.

Although both locations have access to major roads and highways, the rurality of

Zamboanga del Norte gains advantage for this criteria and gets a rating of 4. Davao del

Sur location gets 3.

F. Water Supply

There are three major facilities inside the plant complex that will require water

supply according to its purpose namely (1) industrial, (2) utilities, and (3) domestic. Being

the largest consumer of the water supply, the industrial facilities involve the manufacturing

process that requires completely treated water in converting the raw materials into a

desired product. This is followed by the utilities since certain unit operations require steam

or cooling waters. In spite of recirculating waters, utility water should not last that long as

periodic maintenance requires drainage and blowdown to prevent corrosion, fouling, or

162
scale buildups. Lastly, domestic water is used for kitchen and bathroom purposes. Overall,

water is a valuable resource used widely in many applications.

All pipes completely installed in the process include supports, fittings, valves, installation

labor, miscellaneous items, and its cost depends on its availability and the available water

reservoir. For water supply, both sites heavily really on the 3 major reservoirs of the

region, namely Northern Mindanao, Southeastern Mindanao and Southern Mindanao.

However, the Zamboanga Site may be advantageous in this case because it is situated near

the Dipolog River. The two sites are tied in this category with a rating of 4.

G. Waste Disposal

Wastes from industrial operations must be disposed environmentally safe and

acceptable manner. While it is possible to hire a third party in handling wastes, the

manufacturing plant can have its own waste management facility. There will always be an

expense in disposal of wastes as a bearing of the manufacturing department and it is a

responsibility in the maintenance to seek caution in the surrounding district.

In terms of waste disposal, being more urbanized compared to its opposing site,

the Davao Site would have an advantage in this category since it would be relatively easier

to have access to waste disposal facilities. The expenditures are treated separately because

of the complexity and variety of the process requirements making the cost estimation

difficult. Thus, the higher rating of 4 goes to the Davao del Sur site while the Zamboanga

del Norte site gets 3.

163
H. Labor Supply

Technical operators provide the support in the success of the industry on par with

the proficiency in design. Without their involvement, the production will not prosper and

there will be no livelihood opportunities in return. Some jobs may require higher

qualifications for an individual to work but barely earns a living. While other chemical

processing industries remove job opportunities for the less fortunate nontechnical

personnel by embracing automation of the operation, machines cannot replace the entirety

of an individual because they provide the morale in workspace regardless of their

capabilities.

As per the Philippine Statistics Authority, from the ages of 15 and above, the

unemployment and underemployment rate of Zamboanga Peninsula are 4.3% and 12.2%

respectively as of 3.1% and 8.2% in the same manner for Davao Region. From this data,

both sites are shown to have no problem in potentially supplying workforce for the

proposed plant. Both sites are rated 5 for labor availability.

I. Taxation and Legal Restrictions

All types or real properties such as buildings, lands, equipment, and developments

contributes to the revenue under the real property tax of the local government units.

With regards to taxation and legal restrictions, since the candidate sites are in

situated in neighboring regions, the two sites are observed to almost have the same

ordinances when it comes to the operation of production plants so both sites are rated 3.

164
J. Site Characteristics

Engineering firms that specializes in construction are available in industries

looking for design may either offer partnership in their project participation or as an

independent organization. Since this industry would start from the beginning, it will be

considered as a small company and at the same time would be too early to have its own

construction department in erecting more facilities. It has to gain years of experience until

the industry will be able to make development within the company and the outside

community based on the records made.

Being a rural area, the Zamboanga Site is less likely to have a better quality of land

compared to that of the urbanized Davao area. The pricing of the land areas also play a

significant role in the determination of the plant site since Davao del Sur is highly

urbanized compared to Zamboanga del Sur, land prices between the two regions would

have large differences with the Davao Region having higher land prices compared to that

of the Zamboanga Peninsula which would make the Zamboanga del Norte site more

favorable at a rating of 5 for site characteristics and Davao del Sur falls behind at 3.

K. Flood and Fire Protection

Precautionary measures are needed to prevent fire as nothing else could be more

destructive than it while fighting fire must be strategically considered ahead prior to its

design. All personnel must be kept safe from disasters whether in reality or a bothersome

though whenever a scenario comes to their mind. It is important that the employees are

165
made aware of any work hazard and standard safety protocols are both properly oriented

and practiced

The urbanization of the Davao Region would be an advantage in terms of fire protection.

The possible disadvantage of the Davao site would be its closeness to the sea, which could

cause flooding in cases of super typhoons. Both of the candidate sites are situated in

tropical to mild climates, which makes weather factors not a problem for the operation of

the plant. With the pros and cons, fire protection for both sites are rated at 4.

L. Community Factors

The reputation of the company and its impression highly affects both the

community and the industry itself. Publicity and physical aspects of the plant can either

disturb the neighboring community or make it prosper and vice versa once the plant has

been built.

The abundance of establishment in the urbanized site in the Davao Region could

be the downside in this category. The community may argue that the construction of

another production plant may contribute to the congestion in the area. The vastness of

undeveloped landmass in the Zamboanga Peninsula, therefore, is a plus for this category.

Despite having a large area of undeveloped landmass, the Zamboanga Peninsula still has

access to a good number of basic facilities. With this, community factors for the

Zamboanga del Norte site is rated at 5 and the Davao del Sur site, again, falls behind at 3.

166
 Table 4.12. Plant Location Ratings

(1) – Very Poor (2) – Poor (3) – Adequate (4) – Good (5)–Very Good

Zamboanga del Norte

Factors Davao del Sur Site
Site
1. Raw materials
5 4
availability
2. Markets 4 5
3. Energy availability 4 4
4. Climate 4 3
5. Transportation facilities 4 3
6. Water supply 4 4
7. Waste disposal 3 4
8. Labor supply 5 5
9. Taxation and legal
3 3
restrictions
10. Site characteristics 5 3
11. Flood and fire
4 4
protection
12. Community Factors 5 3

TOTAL
50 45

Conclusion

Economics and an absolute location for the production plant is significantly

influenced by the raw material availability, markets, energy, and transportation facilities.

Additional considerations are involved that affects locating the plant such as waste

disposal, water supply, labor supply, site characteristics, taxation and legal restrictions,

community factors, and risk management. Because of the chemical concerns, the

likelihood of being situated out of the city congestions impends to a smaller community

where the business manufacture can focus on their resources without any obtrusion.

167
 Process material balance enabled to estimate the amount needed for the raw

materials to be consumed by the manufacturing plant. Manufacturing site would be placed

on the area with the most available raw materials since the production will not exist in the

absence of rambutan peels. It should be noted that raw material is the highest expense in

the production due to its demand in manufacturing vanillin. Even if the prices are generally

higher than what was expected, the proximity of the plant will minimize the cost in terms

of transportation while negotiations can be made with ease from the suppliers because of

the convenience within the vicinity.

The physical condition of the vanillin product involving the particle shape and size,

color, and crystal structure has a great influence on marketability. Therefore, the quality

of the product is best when preserved, stored, and handled properly over time. While

storage and packaging are an additional expense and costs expensively, it is important to

have the product reach the market immediately after being manufactured. Hence, direct

buyers are the key solution that will take responsibility in this burden.

After the overall evaluation of the two sites, it turns out that both are suitable sites

for a vanillin production plant, especially in terms of energy availability, water and labor

supply and flood and fire protection, but the best fitted site for this proposed vanillin plant,

especially in terms of raw materials availability, climate, transportation facilities, site

characteristics, and community factors, would be in close proximity prior to Polyfruits

farm in Zamboanga del Norte.

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IV. ENVIRONMENTAL AUDITING

I. INTRODUCTION

In the production of vanillin from rambutan peels, there are materials that are

considered wastes as the plant operates. Solid and liquid wastes such as cellulose and

hemicellulose pulps, sodium hydroxide, sulfuric acid, sodium sulfate, by-products

syringaldehyde and p-hydroxybenzaldehyde, solvent diethyl-ether and other organic

materials will undergo treatment and recycling processes. There are limitations set by the

Department of Environment and Natural Resources (DENR) for hazardous chemical

wastes for air, water, and land. RA 9003 and DAO 2016-08 comprise the guidelines and

the standards for the solid management systems, water quality and general effluent

systems. The effluent released from the plant is classified as Class C.

In the classifications of hazardous wastes made by the DENR, sulfuric acid is

considered as waste only if it has a pH value that is equal or less than 6.5. On the other

hand, alkali wastes such as potash, caustic soda, lime slurries, ammonium hydroxide and

others will only be considered if their pH is equal or greater than 9.0. Water pollution is a

major problem in the industrial operation and might impose detrimental effect in its

environment. Any changes of physical, chemical, or biological properties of a body of

water may result in the hazardous alterations in its quality.

The Philippine Clean Water Act of 2004. Republic Act (RA) No. 9275 titled “An

Act Providing for a Comprehensive Water Quality Management and for Other Purposes”,

also known as the Philippine Clean Water Act of 2004 is the law that demands the

management of water quality in all bodies of water. This law assigns the moderation and

169
control of pollution from land-based sources. It aims the planning and regulations of the

facilities to be managed by the proposed plant.

According to the material balances, the wastes that are being produced such as

sulfuric acid and sodium hydroxide didn’t meet the pH limitations set by the DENR. While

the solvents or other chemicals introduced in the process are capable of being regenerated

for a lower plant operation cost, the environmental design was considered to have no

regeneration as a basis whenever the operation fails to recover the materials. The

manufacturing plant is in observation of a conservative practice for safety purposes (i.e. if

the plant is incapable of recovering sulfuric acid, what would be the action needed for the

disposal). With the assumption of an incapacitated regeneration and materials recovery,

discussions were made in this section.

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II. POSSIBLE EMISSIONS

In designing the waste management and pollution control for the proposed plant,

the possible emissions were classified in the form of liquid, solid, and gas. The physical,

chemical, and biological properties of the environment will be altered if these emissions

were not controlled. Hence, an adverse effect is imminent towards the beneficial use and

the aesthetic quality of the environment. By identifying the different forms of emissions,

the emerging pollutants can now be categorized accordingly to its type. The level of its

effect has been assessed whether it is in significant or insignificant.

A. LIQUID

The primary aim of the environmental audit is to minimize the waste generation

and its operating cost. Certain parameters will affect the technology needed for the

treatment of liquid disposal. Water classification is needed to establish the appropriate

method and technique to suffice the regulatory requirements. Since the materials are

deemed as waste, the manufacturing plant will not expend further on treating the effluents

into streams classified with higher beneficial use other than class C (Recreational Water

Class II for water activities such as boating). As shown below, pollutants were identified

according to its type.

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 Table 4.13.a. Possible Emissions in Liquid Form

Pollutant Type Level

Organic Compounds Organics Significant
Sodium Hydroxide Basic Solution Significant
Sulfuric Acid Acid Solution Significant
Sodium sulfate Water-insoluble Significant
Syringaldehyde Organics Significant
P-hydroxybenzaldehyde Organics Significant
Nitrobenzene Water-insoluble Significant

Because of the several types of pollutants that can be found in liquid form, it is

practical to group these substances together as a homogenized wastewater. Moreover,

these substances share the same pollution effects to the surrounding environment and will

not be treated on a substance-by-substance basis. In that manner, the treatment facility will

not require any additional processes and further operational cost. While some pollutants

remain because of it insolubility in the water, these substances are considered as priority

pollutants (Eckenfelder, 1989). For regulatory purposes, these substances are to be treated

as an individual before being grouped with the other water-soluble pollutants in the

wastewater.

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B. SOLID

Aside from the organic substances found in the wastewater emitted by the process

operation, other organic materials are found in solid form. These solid wastes are insoluble

in water and can be subjected to bacterial decomposition. Even if there is no bacterial

intervention, the end product will always be achieved but at a slower rate. It is advisable

to utilize a biological activity to increase the rate of decomposition while lowering its

hazardous environmental exposure. The end product is called humus or compost, wherein

the process is called composting wherein biodegradable organic solids undergo

decomposition by means of bacterial conversion (Green & Perry, 2008). Some of the

concerning solid waste are listed below.

Table 4.13.b. Possible Emissions in Solid Form

Pollutant Type Level

Ash Water-insoluble Insignificant
Cellulosic biomass Water-insoluble Significant

While there are alternative methods in solid waste management such as thermal

processes (thermal conversion, incineration, combustion, gasification, pyrolysis, etc.),

biological processes (composting, anaerobic digestion, fermentation, etc.) are more

suitable in terms of energy consumption, operational cost, profit or losses, and efficiency.

The primary goal of observing the possible solid waste generation is to simply reduce and

eliminate the detrimental effect of waste materials on human health and the environment.

Upon executing the solid waste management, it promotes economic growth and supports

superior quality of life (Leblanc, 2019).

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C. GAS

The pollutants found in the atmosphere are classified into two wide categories

namely naturally-made and human-made. While pollutants that are naturally occurring

(dust, volcanic emissions, ozone produced by lightning and from the ozone layer, pollens,

biological activities that form gaseous odors, etc.), human-made air pollution is given

more attention since it is controllable and it poses significant impact to the environment

than the ones occurring naturally (Green & Perry, 2008). With that, the environmental

design of this proposed plant is aimed to control the gaseous emissions of the operation

since it may bring harm on the surrounding environment. To assess the environment

consideration needed for controlling air pollution, the table below shows the identified

pollutant found in gaseous stream.

Table 4.13.c. Possible Emissions in Gaseous Form

Pollutant Type Level

Diethyl ether VOC Significant

The air pollutant found within the manufacturing plant is considered as a primary

pollutant since it is emitted within the range of the identifiable source. Being one of the

major air pollutants, the emitted gas is classified as a volatile organic compound (VOC).

Moreover, the pollutant is capable of inducing health-related risks since it can accumulate

within the tropospheric ozone. Along with nitrogen oxides, it is considered as ozone

precursors and one of the major constituent of photochemical smog (Olaño, 2012). There

is a wide selection for air pollution control equipment that can deal with the pollutant

mentioned above which will be discussed later on.

174
III. ABATEMENT PROGRAM

The industrial operation will produce some wastewaters that must be discharged

and returned to the environment. Such processes involved within the manufacturing plant

were classified as (1) process wastewaters, (2) cooling wastewaters, and (3) domestic

wastewaters. Process wastewaters are comprised of washing of materials and products,

spillage, non-cooling processes, and leakages. Cooling wastewaters result from several

cooling processes that will be disposed after reaching certain amount of cycles within the

cooling system. Lastly, domestic wastewaters are produced by washing facilities, plant

workers, and cafeterias.

For health related concerns and safe practical application for environmental

hazards, domestic wastewaters will be handled by typical sanitary-sewage system. In this

manner, pathogenic microorganisms that are capable of spreading diseases are controlled.

On the other hand, process wastewaters does not pose the threat that the pathogenic

microorganisms possess. However, process wastewaters are capable of damaging the

environment just as compromising the integrity of the processes and equipment. Thereby,

an appropriate treatment is needed to maintain the quality that is mutually needed by the

manufacturing plant and its environment. The least dangerous among the classified

wastewater are from the cooling systems. In spite of being the least, it should not be

overlooked as cooling wastewaters may contain process wastewaters that have leaked

during the operation.

The proposed plant will focus on the proper disposal of process wastewater and air

pollutants. By identifying the major pollution contributors found inside the manufacturing

175
plant, the table shown below summarizes the type of pollution and its threshold limit on a

daily basis along with its recommended abatement program respectively.

176
 Table 4.14. Abatement Programs

Type Source Level Threshold / Abatement

Allowable Program
Limit
Organic K-2, K- BOD > 50 BOD ≤ 50 Chemical Precipitation,
Compounds 3, K-4, mg/L, COD mg/L, COD ≤ Activated Sludge
F-4 > 100 mg/L 100 mg/L Process
Basic Solution K-2, F-4, pH > 10 pH ≤ 9.5 Neutralization
K-4
Acidic K-3 pH < 3 pH ≥ 6.0 Neutralization
Solution
Sodium K-3, F-4, > 45,000 500 mg/L Chemical Precipitation
Sulfate K-4 mg/L
Nitrobenzene F-4, K-4 > 130,000 0.5 mg/L Activated Sludge
mg/L Process
Cellulosic K-2, K- BOD > 50 BOD ≤ 50 Composting, Activated
Biomass 3, F-4 mg/L, TSS > mg/L, TSS ≤ Sludge Process
100 mg/L 100 mg/L
VOC D-3 > 10 mg/m3 ≤ 10 mg/m3 Carbon Filter
Adsorption, Chemical
Precipitation, Activated
Sludge Process

Source: Department of Environment and Natural Resources (DENR) – DENR

Administrative Order (DAO) No. 2016-08 (DENR, 2016)

The abatement program for the following pollutants mentioned above will undergo

as an influent wastewater wherein every substances will enter the treatment facility as one.

The environmental design for this plant aimed to eliminate complex treatment processes

(substance-by-substance) wherein individual treatment for each pollutant is no longer

necessary. The treatment method will include separation of solid and liquid impurities in

the carrier water whether it is dissolved or suspended in the body. A conventional activated

sludge process will be the most applicable treatment method in improving the quality of

the wastewater.

177
 Gaseous emissions are controlled by fundamentally developed unit operations of

chemical engineering. Among the methods used in treating air pollution that has to deal

with volatile organic compounds (VOCs) are adsorption equipment. In the design of the

equipment for gas-adsorption is almost similar in designing the equipment for gas-

absorption by interchanging the liquid solvent with a solid adsorbent. While air pollutants

are not given much attention, VOCs pose harm in the atmosphere. Generally, these

carbonaceous emissions are considered greenhouse gases and were known as ozone

precursors in its technical term. Further review of the situation reveals that a secondary

ozone are formed closer to the earth’s surface when the emission of VOCs are not

controlled. With that, heat emissions are entrapped inside the surface of the earth known

as the greenhouse effect that causes global warming. Also, the USDA imposes the greater

threat of VOCs in the ecosystem as it is capable of causing respiratory issues, necrosis and

chlorosis in plants, and other health-induced irritations (USDA NRCS, 2012).

Adsorption is an effective as an abatement method for gaseous streams. It involves

it involves the introduction of a particle to a gaseous stream in which the gas molecules

would adhere to the surface of the particle. Hence, removing the unwanted molecule from

the stream. Volatile organic compounds (VOC) can be easily adsorbed using naturally

occurring zeolites to reduce its emission in the atmosphere.

178
A. Pre-treatment

All solid and liquid emissions from the unit operations would yield several stream

that would be combined with ease except gaseous emissions specifically diethyl ether. In

order to include diethyl ether in the wastewater treatment, the equipment emitting the VOC

would let the vapor pass through an equipment with a bed of activated carbon filters. The

working principle of activated carbon filters is a regenerative activated carbon adsorption

wherein the coal bed (adsorbent) can be regenerated through desorption or by replacement.

While inert air can be used to regenerate the filter bed, it is more preferable to use steam

instead since the goal is to remove the VOC from air and merge it with the liquid waste

stream. The diagram below would be the result of the pre-treatment process.

Figure 4.9. Schematic Diagram of Wastewater Pre-treatment Process

Organic
Compounds

Basic
Solution

Acidic
Solution

Sodium Primary
Influent Wastewater
Sulfate Treatment

Nitrobenzen
e

Cellulosic
Biomass

Regenerative Activated
VOC
Carbon Adsorption

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1. Equalization

This is the initial step prior to further wastewater treatment since it is considered

as the most important device in pretreatment. Equalization is highly favored for batch

discharge of concentrated wastes in order to homogenize the bulk. Without this method,

the streams at varying concentration and different flow rates could overload the treatment

facility. Hence, an equalization basin is provided with mechanical mixing to suppress the

chemical and physical activity of the influent. Additionally, aeration is promoted on the

surface to induce biodegradable activity in the wastewater. This operation could last up to

two (2) days to achieve an optimal working conditions.

Being a mixing tank that homogenizes all wastewater incoming from various

sources, the equalization process eliminates the need for multiple wastewater treatment

plant by blending all wastewater influent into one instead of requiring one for each

incoming stream. There were reports made that the residence time for a process can take

up to 5 to 6 hours when additional floating mixer was added. An equalization tank can

also be a neutralization tank which will be discussed on the next process.

180
2. Neutralization

The injection of neutralizing-chemicals were previously applied or only used when

necessary since the operation will be slightly more costly. Modifications can be made such

as providing a floating agitator above the surface where common chemicals such as lime

powder, Ca(OH)2, or hydrochloric acid, HCl, are used to treat the wastewater if the pH is

beyond its acceptable range of limit. In some cases, neutralization tank that were built

separately from the equalization tank has been used as Biological Conditioning and

Control Reactor (BCCR). This is usually applied in systems that utilizes an Upflow

Anaerobic Sludge Blanket Reactor (UASB) for nearly removing the entire chemical

oxygen demand (COD) in the wastewater. However, this plant design will not dwell

further to that kind of technology since it will require flares in destroying the methane

produced by the biological conversion of the waste materials.

Although this operation is optional, acidified or alkaline wastewaters must be

neutralized prior to discharge. However, neutralization is often utilized because of the

previous step tends to nearly achieve a neutral pH. The basin used for equalization could

be the same basin used for neutralization if adjustment of pH is necessary. Common

chemical neutralizers used are sodium hydroxide and sulfuric acid to neutralize a low-pH

or high-pH respectively. With the absence or restriction of the two easiest chemical to

handle, another alternatives such as lime and hydrochloric acid can be used. In this part of

the process, all the concern for the basic and acidic solution from the unit operations would

have been solved.

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B. Primary Treatment

Primary treatment aims to remove pollutants directly by physical methods that

would greatly reduce the amount of solids present with minimum effort. Usually, solid

materials tend to be separated through gravitational means either by settling on the bottom

of the basin or floating on the surface of the wastewater. Additional devices are provided

to aid in the removal of the solid particles while some may require chemical modification

to cause changes in the physical properties of the solids. A schematic diagram below

provides an illustration of the primary treatment after the pre-treatment process.

Figure 4.10. Schematic Diagram of Wastewater Primary Treatment Process

Influent
Wastewater

Land
Screening
Application

Grit Chemical Secondary

Sedimentation Sedimentation
Chamber Precipitation Treatment

Sludge

182
A. Screening

The primary wastewater treatment begins with a thorough fine screening of

suspended solids in the wastewater influent. The removal of the coarse materials could

prevent the damage in the pump, piping impellers, and other equipment. Also, this can

greatly reduce the overall treatment requirements while condition the wastewater feed in

the next treatment process.

Coarse and settleable solids are removed by interception on racks, bar, or fine

screens which maybe manually cleaned. The materials for the screens can be made of

parallel bars, rods, wires, cloth mesh, or perforated plates depending on its availability in

the market. Since wastewater treatment is aimed in removing pollutants with minimal

effort, these simple but durable materials has proven effective in physically removing

solids such as rocks, plastics, or any non-biodegradable materials that cannot be treated by

the preceding processes. With screening, solid materials are removed to reduce the damage

it can make on the equipment, prevent interferences in the operation of the process, recover

possible valuable materials, and remove the possibilities of entrapment or clogging in

pumps or pipelines.

183
B. Grit Chambers

Inert particles that are hard or solid wastes that are washed up along the flow path

are normally encountered and it is expected to occur in this situation. Thereby, grit

chambers are introduced in this step in which grit that has settled on the bottom of the

chamber can be collected along with the solid waste materials recovered later in the

process to be properly disposed. Not all solids will settle as some will float and cause

complications if not removed immediately.

Any washed up sand, gravel, inert particles, or any sediments are removed through

grit chambers through controlled flow rates of wastewater or by centrifugal action of

aerated chambers. In many cases, air is diffused inside the chamber to create a mixing

pattern with centrifugal forces acting on the large and heavy solid particulates to friction

against the walls. The operation could last up to three (3) minutes for the retention of the

solid materials for rapid separation from the wastewater.

184
C. Sedimentation

Remaining particles carried by the effluent from the grit chambers are removed by

gravity inside the sedimentation tanks. Tanks are either rectangular or cylindrical and are

designed based on the depth that the particles can slowly settle, the overflow rate above

the surface where the previous effluent is being discharged, and its retention time. The

incoming flowrate is observed so that it does not interfere with the sedimentation of the

particles achieving its maximum settling velocity. After the solids have settled on the floor,

they can be removed by mechanically scraping and washed by the hydraulic flow. Sludge

collectors are installed at the bottom to collect flocculated solids efficiently without large

fraction of wastewater.

Since not all solids are suspended, some solids are dissolved and may require

additional process after going through the sedimentation tank. Hence, another tank is

required after the process wherein the dissolved solids were successfully collected. In

many industrial applications, the operation time takes around two (2) hours of retention.

Once the operation time has been designed or established, it should be properly executed

as premature operations could lead to excessive removal of wastewater with the sludge or

prolonged operation could cause the sludge to densely compact. Design criteria is provided

below for sedimentation tanks.

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 Table 4.15. Design Criteria for Primary Sedimentation Tanks

Gravity Sedimentation Tank

Operation Time 2 hours
Organic Solids Limit 5 – 10 %
Inorganic Solids Limit 20 – 30%
Centrifugal Sludge Pump 5 – 6% Solids
Pumps Positive-Displacement
10%
Sludge Pump
40.74 m3/(m2 • day)
Surface Overflow Rate (SOR)
1000 gal/(ft2 • day)
3.0 m
Minimum Depth
10 ft
6.0 m
Circular Sedimentation Tank Minimum Diameter
20 ft
Rectangular Tank Length-to-Width Ratio 5:1
186 m3/(m • day)
Hydraulic Overflow Rate Limit
15,000 gal/(ft • day)
Source: Waste Management: Industrial Wastewater Management – Gravity
Sedimentation (Theodore, et al., 2007)

Different types of solids inside the sedimentation tank should not exceed the range

as mentioned above in order for the equipment to run smoothly. The limit for a centrifugal

sludge pump that can handle the total solids is between 5 – 6% and could be upgraded to

10% using positive-displacement sludge pump. Solid concentration of more than 10%

loses its fluid-like properties which will require more devices to handle it as a semi-solid

rather than a fluidized flow. The rate of discharge or effluent flow rate of the tank is

described by the surface overflow rate (SOR) wherein the optimal flow is prescribed as

40.74 m3/(m2 • day). It does not necessarily mean that lowering SOR would enhance the

quality of the effluent in removing solids just as increasing it will not make it improve.

Surface area is more prioritized than the depth of the tank since the source of the overflow

is on the surface based on the minimum depth and minimum diameter of a cylindrical tank.

Moreover, tanks that are wider but shallow in depth allows the solids to settle completely

186
and also encourage photocatalytic activities of nanomaterials in improving wastewater

treatment. The wastewater feed is limited by the effluent weirs having a maximum

hydraulic overflow rate of 186 m3/(m • day) so that it will not overwhelm the sedimentation

tank. While it is possible, it is necessary for the feed rate to be less than its limit for safety

allowance and conservational practices. While insoluble materials and suspended solids

are being removed in this process, some of the organic pollutants are treated as well since

there will be an intervention of activated sludge which will be discussed later.

187
D. Chemical Precipitation

Addition of chemicals for the purpose of precipitating, coagulating, and

flocculation are involved in this method to remove any dissolved solids in the wastewater.

With chemical precipitation, small particles and remainders of the pervious process

agglomerates into larger particles. There is a wide selection of chemicals that can be used

to precipitate and coagulate the waste materials inside a chemical precipitation system. A

list of common precipitants and coagulants is provided below.

Table 4.16. Chemicals Used for Wastewater Treatment Chemical Precipitation

Chemical Additives / Modifiers

Lime – Ca(OH)2
Ferric Chloride – FeCl3
Soda Ash – Na2CO3
Common Precipitants
Ferric Sulfate – Fe2(SO4)3
Alum – Al2(SO4)3•14H2O
H2SO4 and SO2
Alum – Al2(SO4)3•14H2O
Common Coagulants
Copperas – FeSO4•7H2O
Source: Waste Management: Industrial Wastewater Management – Chemical
Precipitation (Theodore, et al., 2007)

The chemical precipitation system is in between the two sedimentation tank with

a flocculation system before the second sedimentation tank. It requires rapid mixing

wherein its mixer is either located inside a circular sedimentation tank or before a

rectangular sedimentation tank. Turbulence in system is allowed for thorough mixing and

will allow the particles to collide and agglomerate into larger sizes. Rapid mixing can take

up to 30 seconds of retention and each flocculating units can last up to 20 minutes of

retention time. Chemical precipitation is capable of removing 50% of the soluble organics,

95% of the suspended solids, and some heavy metals present in the wastewater.

188
C. Secondary Treatment

This technology use microorganisms, primarily bacteria, to reduce any

biodegradable organic content in the wastewater stabilize waste components.

Microorganisms consume organic matter from the wastewater and oxygen for respiration

wherein millions of aerobic and facultative microorganisms remove pollutants through

living and growing process. The principle of secondary treatment focuses on the activated

sludge system. Wastewater is aerated in a tank in the beginning of the process to provide

the bacteria with adequate oxygen. In here, the bacteria is encouraged to grow by feeding

on the food (BOD) at a suitable temperature and time. As the bacteria consume

biochemical oxygen demand (BOD), they grow and multiply. Thereafter, the treated

wastewater flows into a secondary clarifier wherein its sludge is less dense than primary

clarifiers (previous sedimentation tanks). Bacterial cells settle and can be removed from

the clarifier as sludge. Part of the sludge is recycled back to the activated sludge tank to

maintain the bacterial population while the rest is collected for disposal or could be used

for land applications such as composting. The secondary treatment process is illustrated

in the schematic diagram below.

Figure 4.11. Schematic Diagram of Wastewater Secondary Treatment Process

Secondary
Primary
Aeration Sedimentation Treated
Effluent
Effluent

Land
Sludge
Application

189
2. Aeration

The primary influent of the sedimentation tank from the previous process flows

down into an aeration lagoon. Biological treatment begins here as two different sludge is

present where anaerobic sludge settles at the bottom and undergoes anaerobic digestion

while aerobic sludge remains on the surface which prevents odors. Afterwards, the

wastewater flows down in an extended aeration tank to be aerated inside with the activated

sludge. In here, there is control in the environment of the system because it utilizes aeration

equipment that are either diffused or mechanical. Diffused aeration systems can provide

high oxygen transfer efficiencies and allow easy configuration while mechanical aeration

systems are cheaper. In here, BOD is removed by heterotrophic bacteria that hydrolyzes

the organic materials containing nitrogen into an ammonium-N. Heterotrophic aerobic

bacteria utilize oxygen, organic material, ammonium-N, and ortho-P to produce carbon

dioxide, water, and more bacterial cells. The chemical reaction would be (Abulencia,

2019):

Oxidation and Synthesis:

COHNS (organic) + O2 + Nutrients + Bacteria → CO2 + NH3 + C5H7NO2 (new bacterial

cell)

Endogenous Respiration:

C5H7NO2 + 5O2 → 5CO2 + NH3 + 2H2O

190
 Sufficient oxygen must be provided by the aeration equipment to achieve the

highest oxygen demand; otherwise, the system will not be able to meet the proper

treatment. Regardless of the aeration equipment used, the oxygen-transfer rates should be

stable at 0.6 to 1.4 kg O2/kg BOD5 or lb O2/lb BOD5 in the aeration tanks. More sludge

removal is required when oxygen-transfer rates are low since sludge handling should be

balanced against the demand of oxygen transfer. Stabilized organics are converted into

suspended solids and can be further destroyed since most of the solids are biodegradable.

191
3. Sedimentation

The activated sludge is recycled to control the population of the microorganism in

extended aeration tanks while aeration lagoon has limited use in the digestion and disposal

of sludge. Nevertheless, the biochemical oxygen demand is affected without the sludge

recirculation. This step is also known as the secondary sedimentation where high-quality

effluent is produced by separating suspended solids from the treated liquid. Moreover,

excess biological solids are eliminated from the secondary treatment system to control the

cell residence time of the biomass. In the actual operations, reports based on the design

criteria for most sedimentation tanks is shown below.

Table 4.17. Design Criteria for Secondary Sedimentation Tanks

Secondary Clarifiers
Retention / Operation Time 2 hours
33 m3/(m2 • day)
Optimal
800 gal/(ft2 • day)
Surface Overflow
24 m3/(m2 • day)
Rates
Previous Designs 16 m3/(m2 • day)
12 m3/(m2 • day)
186 m3/(m • day)
Maximum
Hydraulic Overflow 15,000 gal/(ft • day)
Rate Limit 124 m3/(m • day)
Minimum
10,000 gal/(ft • day)
3.0 m
10 ft
4.5 m
Minimum Depth Mixed Liquor 3000 mg/L
15 ft
Suspended Solids
6.0 m
(MLSS) > 4000 mg/L
20 ft
Source: Waste Management: Industrial Wastewater Management – Sedimentation Tanks

(Theodore, et al., 2007)

192
 One of the important factor in the design of secondary sedimentation tanks is its

retention time averaging at 2 hours of raw wastewater flows. Prolonging the operation

time would cause rising sludge problems while short retention yields poor separation of

solids with excess sludge recycling. Surface overflow rates were originally designed at 33

m3/(m2 • day) but other emerging industries developed reduced average flowrates in search

of an improved quality of the effluent. However, the results of those previous design did

not manifest and the optimal design would still be 33 m 3/(m2 • day). Effluent weirs are the

rotating hydraulic arms in the sedimentation tank were the wastewater feed enters and falls

on the surface. Effluent-overflows or simply hydraulic overflow rates are limited to a

maximum of 186 m3/(m • day) just like the design for a primary sedimentation tanks with

the exception of having a minimum overflow rate of 124 m 3/(m • day). The reduction of

hydraulic overflow rates is greatly achieved by dual-side effluent weirs which are attached

on the opposite of each other. While it improves the reduction of overflow rates, it poses

hydraulic problems and more maintenance in cleaning however. Therefore, it is practical

to design only one effluent weir with proper adjustment in the flow rate of the feed to

maintain the volume of the wastewater inside the clarifier.

The depth of the secondary sedimentation tanks is based on the biological solids

known as Mixed Liquor Suspended Solids (MLSS) that has settled on the bottom and to

be continuously returned to the aeration system. In this manner, sludge blanket is

controlled in the clarifier to maintain a sufficient amount of active organisms in service.

The design in the depth of the secondary sedimentation tanks does not necessarily mean

to control MLSS but to control the depth of the solids inside the tank. The default for the

depth is 3.0 m but it can be built deeper depending on the MLSS concentration as shown

193
on the table above. The recycling rate of the activated sludge contains 25 to 50% of MLSS

that is around 3300 mg/L.

Finally, the treated wastewater that has entered from the clarifier is discharged to

any nearest body of water while the sludge settles in the clarifier. Some of the excess

sludge is removed by the clarifier surface scraper and dried in the sludge drying bed which

can be used as compost or any other agricultural/land applications for an added purpose

and value.

194
4. Composting

The last and the least concern of the waste management of the production plant

after the tedious process are the solid waste materials recovered from treatment operation.

In order to abide on the solid waste management, the production plant will adhere to the

Integrated Solid Waste Management (ISWM) which provides the application and selection

of suitable technologies, techniques, and management programs to achieve waste

management objectives specifically. Moreover, the factors will include the types of waste

collected, frequency of collection, its acceptability of the disposal system in the

environment, customer satisfaction, and the location of the disposal site. A simple diagram

is illustrated below for the hierarchy of ISWM.

Figure 4.12. Hierarchy of Integrated Solid Waste Management

Waste Prevention and Minimization

Recycling and Reuse

Transformation

Landfill

Source: Integrated Solid Waste Management for Local Governments – A Practical

Guide (Susantono & Locsin, 2017)

195
 The hierarchy represents the process of solid waste management where the trend

starts from the top and the volume of waste generated is represented as an inverted

pyramid. With the apex of the pyramid being at the bottom, that is the ultimate solution

for most solid waste management at a minimum environmental pollution. The plant

appreciably follows this program as the recovered solid wastes from the production and

previous treatment are subjected to undergo this process until the bottom end. Waste

activated sludge, collected biomass, and biodegradable solid organic matters will be

considered as mulch or compost materials in simplest form. In spite of being categorized

under landfills, it does not necessarily mean that there will be no other purposes involved

other than the name itself. Nearby agricultural lands can find it useful in fertilizing their

croplands such as Rambutan farms to establish a mutual business relationship between the

production facility and the suppliers (farmers). Further detailed process is provided below

which involves an anaerobic composting processes.

196
Table 4.18. Important Design Considerations for Anaerobic Composting Processes

Item Comment
For optimum results the size of solid waste should be between 25
Particle Size
and 75 mm (1 and 3 in).
Composting time can be reduced by seeding with partially
decomposed solid wastes to the extent of about 1 to 5 percent by
Seeding and
weight. Sewage sludge can also be added to prepared solid wastes.
Mixing
When sludge is added, the final moisture content is the controlling
variable
To prevent drying, caking, and air channeling, material in the
Mixing or process of being composted should be mixed or turned on a regular
Turning schedule or as required. Frequency of mixing or turning will
depend on the type of composting operation.
Air with at least 50 percent of the initial oxygen concentration
Air
remaining should reach all part of the composting material for
Requirements
optimum results, especially in mechanical systems.
Total Oxygen
The theoretical quantity of oxygen required can be estimated.
Requirements
Moisture content should be in the range between 50 and 60 percent
Moisture
during the composting process. The optimum value appears to be
Content
about 55 percent.
For best results, the temperature should be maintained between 322
and 327 K (130 and 140°F) for the first few days and between 327
Temperature and 333 K (130 and 140°F) for the remainder of the active
composting period. If the temperature goes beyond 339 K (150°F),
biological activity is reduced significantly.
Initial carbon-nitrogen ratios (by mass) between 35 and 50 are
Carbon-nitrogen optimum for aerobic composting. At lower ratios ammonia is given
Ratio off. Biological activity is also impeded at lower ratios. At higher
ratios nitrogen may be a limiting nutrient.
To minimize the loss of nitrogen in the form of ammonia gas, pH
pH
should not rise above about 8.5.
If the process is properly conducted, it is possible to kill all the
Control of pathogens, weeds, and seeds during the composting process. To do
Pathogens this, the temperature must be maintained between 333 and 334 K
(140 and 160°F) for 24 hours.
Source: Solid Wastes: Engineering Principles and Management Issues (Tchobanoglous,

Theisen, & Eliassen, 1977)

197
 Prior to the biological composting process, the conversion of the waste product is

humus-like material that requires preprocessing such as shredding and air separation. To

simplify the whole process, it is summarized into three basic steps namely (1) preparation

of solid wastes, (2) decomposition of the solid wastes, and (3) size reduction. Nutrient and

moisture addition are involved in the preparation step. There are several methods and

techniques developed in the decomposition step. After being successfully converted into

humus, the third step is aimed as a product and marketing opportunity which depends on

the characteristics of the size requiring size reduction. The final step may be optional but

the processes involved are fine grinding, blending with various additives, granulation,

bagging, storage, shipping, or probably directly sold in the market.

It is expected for the local government to prosper in implementing regulations in

various disposal of both nonhazardous and hazardous wastes, it is judicious to establish a

planned development for the programs that are both short-termed and long-termed in

preserving the environment while dealing with waste management in all aspect. This

manufacturing plant is on par with the environmental engineering design and striving with

compliance in regulation of the local government units.

198
 LIST OF REFERENCE

Abulencia, A. (2019). Biological Nutrient Removal - Ultimate Solution to Comply with

DAO 2016-08. Biological Nutrient Removal - Ultimate Solution to Comply with

DAO 2016-08. Las Piñas: Mach Union Training Center.

DENR. (2016, May 24). Water Quality Guidelines and General Effluent Standards of

2016. Retrieved from Department of Environment and Natural Resources:

https://server2.denr.gov.ph/uploads/rmdd/dao-2016-08.pdf

Eckenfelder, W. W. (1989). Industrial Water Pollution Control. New York: McGraw-

Hill.

Green, D., & Perry, R. (2008). Perry's Chemical Engineer's Handbook. New York:

McGraw-Hill.

Leblanc, R. (2019, October 11). An Introduction to Solid Waste Management. Retrieved

from The Balance Small Business: https://www.thebalancesmb.com/an-

introduction-to-solid-waste-management-2878102

Olaño, S. S. (2012). Reviewer for Chemical Engineering Licensure Examination.

Manila: Manila Review institute, inc.

Susantono, B., & Locsin, M. C. (2017). Integrated Solid Waste Management for Local

Governments - A Pratical Guide. Mandaluyong: Asian Devlopment Bank.

Tchobanoglous, G., Theisen, H., & Eliassen, R. (1977). Solid Wastes: Engineering

Principles and Management Issues. New York: McGraw-Hill.

Theodore, L., Weiss, K. N., McKenna, J. D., Smith, F. L., Sharp, R. R., Santoleri, J. J.,

& McGowan, T. F. (2007). Waste Management. In D. W. Green, & R. H. Perry,

Perry's Chemical Engineers' Handbook (pp. 4-106). New York: McGraw-Hill.

199
USDA NRCS. (2012, March). Air Ozone Precursors. Retrieved from United States

Department of Agriculture Natural Resources Conservation Service Resource

Concerns:

https://www.climatesignals.org/sites/default/files/resources/ozone%20precursors.

pdf

200
 CHAPTER 5

MASS AND ENERGY

BALANCE

201
 Chapter 5

Mass and Energy Balance

I. Introduction

The most vital part in an industrial production that involves manufacturing processes

is the material and energy balance. This is achieved once the literature survey is finished,

the specific objectives and the plant size has been determined from its demand study. This

is a crucial step as it affects the sizing and thereby influences the economics of the plant.

The study on market demand and raw material availability has provided the basis needed

for assessing the proper size of the manufacturing plant. The size of the plant should be

inclined to the raw material availability and the market demand. Based on this, material

and energy balances are done.

Material balance is considered as the heart of all mass-related computations in the

overall production. It holds the essential part of controlling the processes, specifically the

yields of products. It establishes the tentative stages in innovating processes. It is important

in the progression of the plant design from the pioneer trial of a plant process until the

plant is steadily and continuously operating. Material balance follows the principle of

conservation of mass which states that matter cannot be created nor destroyed. It accounts

for the entering and leaving materials and identifies which of those have been consumed

or converted over the entire process. It is also applied to the rest of the equipment where

inflows of any matter should be balanced with the outflow streams.

Energy can exist in several forms – chemical energy, heat, mechanical energy, and

electrical energy. The total energy is conserved, but energy can be transformed from one

202
kind into another. In process design, energy balances are made to determine the energy

requirements of the process: heating, cooling, and power required. From the raw feed unto

the final product, energy balances are used in the inspection and maintenance of each stage

or process. In plant operation, an energy balance audit on the plant will show the pattern

of energy use and suggest areas for conservation and savings. Even in extending the overall

total production system, energy balances are used.

Material and energy balances can be uncomplicated, but at some circumstances it

can be very difficult to comprehend. However, once understood properly, it will give a

huge impact on the design of the processes. Studies on material and energy balances is a

way of improving processes in cheapest way possible.

203
II. Summary of Assumptions and Equations for Mass Balance

A. Summary of Assumptions

EQUIPMENT ASSUMPTIONS
Storage Tank  Rambutan peels are stored at storage tank.
(F-1)  No losses in composition upon storing.

Washer  All impurities will be removed from the rambutan peels

(W-1)  The washed rambutan peels will contain 3.0% of water
entered.
 1:1.5 mass to volume ratio of rambutan peels to water

Hammer Mil  According to Coulson and Richardson: “0.05% mass loss

(K-1) due to adhesion in the equipment”

Mixing Tank  For every 2 kg Rambutan peel fiber, 1 L NaOH solution

(F-2) (4% w/w) is added.
 100% of cellulose, hemicellulose, and extractives will
dissolve using NaOH solution.
 Water content of rambutan peels is added to total H2O
content.

Cooler  No losses upon cooling.

(D-1)

Thickener  90% of the cellulose, hemicellulose, extractives, ash, water

(K-2) and NaOH are collected in the thickener overflow.
 According to Coulson and Richardson: “0.05% mass loss
due to adhesion in the equipment”
Acidification  0.85 kg of 72% (w/w) H2SO4 solution per 100 kg lignin is
Tank added.
(F-3)  10% of Lignin was soluble in H2SO4 solution.

Leaf Filter 1. 2% of H2SO4, Na2SO4, Cellulose, Hemicellulose, extractives,

(K-3) and Ash will go to the Lignin stream
2. 80% of water is collected in the Filtrate.
3. According to Coulson and Richardson: “0.05% mass loss
due to adhesion in the equipment”

Autoclave  50% (w/w) NaOH solution. Ratio of 5 kg lignin / 1 kg NaOH

Reactor solution
(J-1)  0.4:1 volume to mass ratio of 99% nitrobenzene to lignin
 The over-all conversion of lignin is 95%.

204
 Cooler  No losses upon cooling.
(D-2)

Extraction Tank1. The distribution ratio of diethyl ether with vanillin is 23.44.
(F-4) 2. 96% yield of extraction of vanillin. 10:1 mass to volume ratio
of solubility of vanillin to water.
 1% of Syringaldehyde, P-hydrobenzaldehyde, Nitrobenzene,
NaOH and other cellulosic material will go to the extract
Vacuum  The boiling of diethyl ether, water and vanillin are 34.6℃,
Evaporator 100℃, and 285℃ respectively
(D-3)  99% of the diethyl ether is evaporated.

Cooling  2.5:100 mass to mass solubility ratio of vanillin to solution.

Crystallizer
(J-2)

Centrifugal  35% of mother liquor will adhere to the crystals.

Filter  According to Coulson and Richardson: “0.05% mass loss
(K-4) due to adhesion in the equipment”

Rotary dryer  98% of Vanillin Produced

(D-4)

Cooler  No losses during cooling

(D-5)

 All products has an average size of Mesh 4 or 5 mm

Ball mill (K-5) &
Screener  The recycle stream is 10% of the feed to the screener
(K-6)  According to Coulson and Richardson: “0.05% mass loss
due to adhesion in the equipment

Storage Tank  Vanillin is stored at the storage tank. There are no losses in
(F-5) composition upon storing.

205
B. Summary of Equations

EQUIPMENT EQUATIONS

Storage Tank (F-1)

Washer (W-1)

Hammer Mill (K-

1)

Cooler (D-1)

Mixing Tank (F-2)

∑ Mass In = ∑ Mass Out
Thickener (K-2)

Acidification Tank
(F-3)

Leaf Filter (K-3)

Cooler (D-2)

Extraction Tank
(F-4)

Vacuum
Evaporator (D-3)

Cooling
Crystallizer (J-2)

Centrifugal Filter
(K-4)

Rotary dryer (D-4)

Cooler (D-5)

Ball mill (K-5)

Screener (K-6)

Storage Tank (F-5)

206
 ∑ Mass In = ∑ Mass Out
Acidification Tank
(F-3)
Reaction:

2 𝑁𝑎𝑂𝐻 + 𝐻2𝑆𝑂4 → 𝑁𝑎2𝑆𝑂4 + 2 𝐻2𝑂

Autoclave Reactor ∑ Mass In = ∑ Mass Out

(J-1)

Reaction:

Conversion: 95% of lignin was converted to vanillin.

Constants:
𝑀𝑊𝑙𝑖𝑔𝑛𝑖𝑛 = 1,763.85 𝑔/𝑚𝑜𝑙
𝑀𝑊𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 = 152 𝑔/𝑚𝑜𝑙
𝑀𝑊𝑠𝑦𝑟𝑖𝑛𝑔𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 = 182 𝑔/𝑚𝑜𝑙
𝑀𝑊𝑃−ℎ𝑦𝑑𝑟𝑜𝑥𝑦𝑏𝑒𝑛𝑥𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 = 122 𝑔/𝑚𝑜𝑙

207
III. Summary of Assumptions and Equations For Energy Balance

A. Summary of Assumptions

EQUIPMENT ASSUMPTIONS
Mixing Tank  Feed enters at 25°C.
(F-2)  NaOH solution enters at 25°C.
 Entering Steam is saturated (180 kPa and 116.9 °C) and the
condensate is a saturated liquid.
Cooler  The feed enters at 75°C.
(D-1)  The temperature at Heat Exchanger is maintained at 25°C.
 Cooling Water enters at 20°C and leaves at 50°C.
Autoclave  The feed enters at 25°C.
Reactor  NaOH solution enters at 25°C.
(J-1)  Nitrobenzene enters at 25°C.
 The temperature inside the Autoclave Reactor is maintained at
170°C.
 Entering Steam is saturated (1,170 kPa and 460K) and the
condensate is a saturated liquid.
Cooler  The feed enters at 170°C.
(D-2)  The temperature at Heat Exchanger is maintained at 25°C.
 Cooling Water enters at 20°C and leaves at 50°C.
Vacuum  Feed enters at 25°C.
Evaporator  Entering Steam is saturated (10.546 kPa and 46.85 °C) and the
(D-3) condensate is a saturated liquid.

Cooling  The Feed enters at 65°C.

Crystallizer  The crystallization will commence at 10°C.
(J-2)  The cooling water will enters at 5°C and leaves at 30°C.
Rotary Dryer  The crystals will enter at 30°C.
(D-4)  The dried vanillin will leave at 60°C.
 Relative humidity of air is 78%.
 Preheated air will enter at 80°C and leave at 70°C.
Cooler  The feed enters at 60°C.
(D-2)  The temperature at Heat Exchanger is maintained at 25°C.
 Cooling Water enters at 20°C and leaves at 50°C.

208
B. Summary of Equations

EQUIPMENT EQUATIONS
Mixing Tank
(F-2) 𝑄𝑡𝑜𝑡𝑎𝑙 = ∆𝐻𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑝𝑒𝑒𝑙 𝑓𝑖𝑏𝑒𝑟 𝑠𝑜𝑙𝑛(25−75)℃
+ ∆𝐻𝑑𝑖𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑁𝑎𝑂𝐻 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑄𝑠𝑡𝑒𝑎𝑚

Steam Requirement:

𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑚𝑠𝑡𝑒𝑎𝑚 𝜆𝑠𝑡𝑒𝑎𝑚

Cooler
(D-1) 𝑄𝑡𝑜𝑡𝑎𝑙 = ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡(75−25)℃

𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑃𝑒𝑒𝑙 𝐹𝑖𝑏𝑒𝑟 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

(𝑚𝐶𝑝𝑑𝑇)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −(𝑚𝐶𝑝𝑑𝑇)𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑃𝑒𝑒𝑙 𝐹𝑖𝑏𝑒𝑟 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Coolant Requirement:
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑚𝐶𝑝𝑑𝑇

Acidification
Tank 𝑄𝑡𝑜𝑡𝑎𝑙 = ∆𝐻𝑎𝑐𝑖𝑑𝑖𝑓𝑖𝑒𝑑 𝑙𝑖𝑔𝑛𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(25−30)℃ + ∆𝐻𝑟𝑥𝑛@25℃
(F-3) + ∆𝐻𝑑𝑖𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑄𝑡𝑜𝑡𝑎𝑙 = −𝑄𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟

Coolant Requirement:
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑚𝐶𝑝𝑑𝑇

Autoclave
Reactor 𝑄𝑡𝑜𝑡𝑎𝑙 = ∆𝐻𝑐𝑟𝑢𝑑𝑒 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(25−170)℃ + ∆𝐻𝑚𝑎𝑖𝑛 𝑟𝑥𝑛@25℃
(J-1) + ∆𝐻𝑠𝑖𝑑𝑒 𝑟𝑥𝑛@25℃

Steam Requirement:
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑚𝑠𝑡𝑒𝑎𝑚 𝜆𝑠𝑡𝑒𝑎𝑚

209
 Cooler
(D-2) 𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑐𝑟𝑢𝑑𝑒 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

(𝑚𝐶𝑝𝑑𝑇)𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −(𝑚𝐶𝑝𝑑𝑇)𝑐𝑟𝑢𝑑𝑒 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Coolant Requirement:
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑚𝐶𝑝𝑑𝑇

Vacuum 𝑄𝑓𝑒𝑒𝑑 = ∑ 𝑚𝐶𝑝𝑑𝑇

Evaporator
(D-3)
𝐻𝑣𝑎𝑝 = (𝑚𝑖 𝐻𝑣 𝑖 )
𝑉𝑎𝑝𝑜𝑟 𝑠𝑡𝑟𝑒𝑎𝑚

𝑄𝑇𝑜𝑡𝑎𝑙 = 𝑄𝑓𝑒𝑒𝑑 + 𝐻𝑣𝑎𝑝

Heating Water Requirement:

𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑚𝑠𝑡𝑒𝑎𝑚 𝜆𝑠𝑡𝑒𝑎𝑚

Cooling
Crystallizer 𝑄𝑡𝑜𝑡𝑎𝑙 = (𝑚𝐶𝑝𝑑𝑇)𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑒𝑑 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛
(J-2)

Coolant Requirement:

𝑄𝑡𝑜𝑡𝑎𝑙 = −(𝑚𝐶𝑝∆𝑑)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟

Rotary Dryer
(D-4) 𝑄𝑡𝑜𝑡𝑎𝑙 = (𝑚𝐶𝑝𝑑𝑇)𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑐𝑟𝑦𝑠𝑡𝑎𝑙 + (𝑚∆𝐻)𝑣𝑎𝑝
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑄𝑎𝑖𝑟
𝑄𝑎𝑖𝑟 = ѡ𝐶𝑠 ∆𝑇
𝐶𝑠 = 1.005 + 1.88𝜘

Cooler
(D-5)
𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠

(𝑚𝐶𝑝𝑑𝑇)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 = −(𝑚𝐶𝑝𝑑𝑇)𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠

Coolant Requirement:
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑚𝐶𝑝𝑇

210
C. Summary of Constants

SUBSTANCE PRESSURE TEMP. ENTHALPHY SPECIFIC REF.

HEAT
Steam 10.546 kPa 46.85°C 2,587.89 kJ/kg - Perry’s
Handbook
180 kPa 116.9°C 2708.05 kJ/kg - Perry’s
Handbook
1,170 kPa 186.85° 2785.22 𝑘𝐽/𝑘𝑔 - Perry’s
C Handbook
Using
Cellulose - - - 1.549 Modified
kJ/kg·K Kopp's
Rule ChE
Handbook
8th ed. p.
2-497
Using
Hemicellulose - - - 1.3143 Modified
kJ/kg·K Kopp's
Rule ChE
Handbook
8th ed. p.
2-497
Using
Lignin - - - 1.2315 Modified
kJ/kg·K Kopp's
Rule ChE
Handbook
8th ed. p.
2-497
Using
Ash - - - 0.84 Modified
kJ/kg·K Kopp's
Rule ChE
Handbook

211
 8th ed. p.
2-497
Using
Extractives - - - 1.0812 Modified
kJ/kg·K Kopp's
Rule ChE
Handbook
8th ed. p.
2-497
Water - - - 4.184 Perry’s
kJ/kg·K Handbook
http://ww
NaOH - - - 3.930 w.endme
kJ/kg·K mo.com/c
hem/speci
ficheatsea
rch.php?q
=Sulfuric
%20Acid
http://ww
H2SO4 - - - 1.340 w.endme
kJ/kg·K mo.com/c
hem/speci
ficheatsea
rch.php?q
=Sulfuric
%20Acid
Dry air - - - 1.006 https://ww
kJ/kg·K w.enginee
ringtoolbo
x.com/air-
specific-
heat-
capacity-
d_705.htm
l

212
Heat of Formations:
SUBSTANCE Hf (kJ/kg) REFERENCE
Lignin -3667.42 Voitkevich, O. V., 2012
Vanillin -3,050 webbook.nist.gov
Syringaldehyde -1,953.46 https://www.sigmaaldrich.com/catalog/product/aldrich/s
7602?lang=en&region=PH
p- -1753.77 webbook.nist.gov
Hydroxybenzald
ehyde
NaOH -11728.75 Green, D.W., ed. (2007). Perry's Chemical Engineers'
Handbook (8th ed.). Mcgraw-Hill. p. 2–
191. ISBN 9780071422949
H2SO4 -8306.12 Green, D.W., ed. (2007). Perry's Chemical Engineers'
Handbook (8th ed.). Mcgraw-Hill. p. 2–
191. ISBN 9780071422949
Na2SO4 -9750.00 http://www.wiredchemist.com/chemistry/data/entropi
es-inorganic
Nitrobenzene −449.39 https://pubchem.ncbi.nlm.nih.gov/compound/Nitrobe
nzene
Nitrosobenzene −1851.21 https://pubchem.ncbi.nlm.nih.gov/compound/nitrosob
enzene

Heat of Vaporization:
SUBSTANCE Hv(kJ/kg) REFERENCE
H2O 2,260 -
Diethyl ether 353.65 https://webbook.nist.gov/cgi/cbook.cgi?ID=C60297&
Mask=4

213
IV. MASS BALANCE COMPUTATION

Raw Material Plant Capacity

Rambutan Peel 𝑘𝑔 𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛
500
𝑑𝑎𝑦

Overall Chemical Reaction:

Formula Statement:
Rambutan Peel Requirement = (Plant Capacity)(Product Purity)(Mass to Mole
Conversion of Vanillin)(Stoichiometric Ratio between Lignin and Vanillin from
Nitrobenzene Oxidation Reaction)(Percent Conversion of Vanillin from Lignin)(Mole to
Mass Conversion of Lignin)(Percent weight of Lignin in Rambutan Peel)

Numerical Calculation:
500 𝑘𝑔 𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑃𝑟𝑜𝑑𝑢𝑐𝑡 1 𝑘𝑚𝑜𝑙𝑒 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛
= ( ) (0.98) ( )( )
𝑑𝑎𝑦 152.15 𝑘𝑔 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 4 𝑘𝑚𝑜𝑙 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛
1 1763.85 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 1 kg Rambutan Peel
( )( )( )
0.95 1 𝑘𝑚𝑜𝑙𝑒 𝑙𝑖𝑔𝑛𝑖𝑛 0.3779 kg Lignin

3955.72𝑘𝑔 𝑟𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑝𝑒𝑒𝑙

𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑃𝑒𝑒𝑙 𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑚𝑒𝑛𝑡 =
𝑑𝑎𝑦
𝟒𝟎𝟎𝟎 𝒌𝒈 𝒓𝒂𝒎𝒃𝒖𝒕𝒂𝒏 𝒑𝒆𝒆𝒍
≈
𝒅𝒂𝒚

Due to mechanical losses of some equipment in the production process, 4,800

kg/day or 1440 MT/year of rambutan peel will be used to have a 500 kg/day of vanillin

product.

214
V. DETAILED MASS BALANCE

Equipment Name: Rambutan Peel Storage Tank

Equipment Code: F-1

TO W-1
RAMBUTAN PEELS
Average size: 20-30 mm

RAMBUTAN PEELS

F-1

MASS IN MASS OUT

RAMBUTAN PEELS RAMBUTAN PEELS (To W-1)

Cellulose 1,165.44 kg Cellulose 1,165.44 kg
Hemicellulose 557.76 kg Hemicellulose 557.76 kg
Lignin 1,794.72 kg Lignin 1,794.72 kg
Extractives 475.20 kg Extractives 475.20 kg
Ash 236.64 kg Ash 236.64 kg
Impurities 48.00 kg Impurities 48.00 kg
Water 522.24 kg Water 522.24 kg
TOTAL MASS IN kg TOTAL kg
4,800.00 MASS OUT 4,800.00

Rambutan Peels 4,800.00 kg Rambutan Peels(To W- 4,800.00 kg

1)
TOTAL MASS 4,800.00 kg TOTAL MASS OUT 4,800.00 kg
IN

215
Basis:

1. 4,800 kg/day enters the rambutan peel storage tank and operation is 1 day.

2. The rambutan peel feed to the tank is composed of 24.28% cellulose, 11.62%
Hemicellulose, 37.39% lignin, 9.90% extractives, 4.93% ash, 1% impurities, and
10.88% Water. (Ref: Oliveira, E. S., Santos, J. B., Goncalves, A. B., Mattedi, S., &
Jose, N. M. (2016). Characterization of the Rambutan Peel Fiber (Nephelium
lappaceum) as a Lignocellulosic Material for Technological Application. Chemical
Engineering Transaction.)

Computations:

Basis: 4,800 kg of Rambutan Peels Feed

Cellulose = 0.2428 (4,800 kg) = 1165.44 kg

Hemicellulose = 0.1162 (4,800 kg) = 557.76 kg

Lignin = 0.3739 (4,800 kg) = 1794.72 kg

Extractives = 0.0990 (4,800 kg) = 475.20 kg

Ash = 0.0493 (4,800 kg) = 236.64 kg

Impurities = 0.01 (4,800 kg) = 48.00 kg

Water = 0.1088 (4,800 kg) = 522.24 kg

Cellulose Balance:

Cellulose In = Cellulose Out = 1165.44 kg

Hemicellulose Balance:

Hemicellulose In = Hemicellulose Out = 557.76 kg

Lignin Balance:

Lignin In = Lignin Out = 1,794.72 kg

216
Extractives Balance:

Extractives In = Extractives Out = 475.20 kg

Ash Balance:

Ash In = Ash Out = 236.64 kg

Impurities Balance:

Impurities In = Impurities Out = 48.00 kg

Water Balance:

Water In = Water Out = 522.24 kg

Total Mass Output:

Total Mass Output = Cellulose Out + Hemicellulose Out + Lignin Out + Extractives Out

+ Ash Out + Impurities Out + Water Out

Total Mass Output = 1165.44 + 557.76 + 1794.72 + 475.20 + 236.64 + 48.00 + 522.24

Total Mass Output = 4,800.00 kg

Mass Output Composition:

Component Amount Percentage

Cellulose 1165.44 kg 24.28 %

Hemicellulose 557.76 kg 11.62 %

Lignin 1,794.72 kg 37.39 %

Extractives 475.20 kg 9.90 %

Ash 236.64 kg 4.93 %

Impurities 48.00 kg 1.00 %

Water 522.24 kg 10.88 %

TOTAL 4,800.00 kg 100.00%

217
Equipment Name: Washer

Equipment Code: W-1

Wash Water

(1.5 L H2O per

1 kg Impurities)

FROM F-1 TO K-1

W-1
RAMBUTAN PEELS WASHED RAMBUTAN PEELS

IMPURITIES AND WATER

To Wastewater Treatment System

MASS IN MASS OUT

RAMBUTAN PEELS (From F-1) WASHED RAMBUTAN PEELS (To

K-1)
Cellulose 1165.44 kg Cellulose 1165.44 kg
Hemicellulose 557.76 kg Hemicellulose 557.76 kg
Lignin 1794.72 kg Lignin 1794.72 kg
Extractives 475.20 kg Extractives 475.20 Kg
Ash 236.64 kg Ash 236.64 Kg
Impurities 48.00 kg Water 17.82 Kg
Water 522.24 kg TOTAL 4,247.58 Kg
TOTAL 4,800.00 kg
IMPURITIES
WATER Water 576.20 kg
Water 71.78 kg Impurities 48.00 kg
TOTAL 624.20 kg

TOTAL MASS IN 4,871.78 kg TOTAL 4,871.78 kg

MASS OUT

Rambutan Peels 4,800.00 kg Rambutan Peels 4,247.58 kg

(from F-1) (To K-1)
Water 71.78 kg Impurities 624.20 kg
TOTAL MASS IN 4,871.78 kg TOTAL MASS OUT 4,871.78 kg

218
 Assumptions:

1. All impurities will be removed from the rambutan peels

2. The washed rambutan peels will contain 3.0% of water entered.

3. 1:1.5 mass to volume ratio of rambutan peels to water

Computations:

Basis: 4,800.00 kg of Rambutan Peel from F-1

Rambutan Peel In:

 Cellulose = 1,165.44 kg

 Hemicellulose = 557.76 kg

 Lignin = 1,794.72 kg

 Extractives = 475.20 kg

 Ash = 236.64 kg

 Impurities = 48.00 kg

 Water = 522.24 kg

Total Rambutan Peel = 4,800.00 kg

Water Balance:

1.5 L H2O 0.997 𝑘𝑔 𝐻2 𝑂

Water for washing: = x 48 kg Impurities x
1 kg Impurities 𝐿 𝐻2 𝑂

𝐖𝐚𝐭𝐞𝐫 𝐟𝐨𝐫 𝐰𝐚𝐬𝐡𝐢𝐧𝐠 = 𝟕𝟏. 𝟕𝟖 𝐤𝐠 𝑯𝟐 𝑶

Total Water In = Water Rambutan Peel + Water washing

Total Water In = 522.24 + 71.78 = 594.02 kg

219
Washed Rambutan Peel Stream:

Cellulose Balance:

Cellulose In = Cellulose Out = 1165.44 kg

Hemicellulose Balance:

Hemicellulose In = Hemicellulose Out = 557.76 kg

Lignin Balance:

Lignin In = Lignin Out = 1,794.72 kg

Extractives Balance:

Extractives In = Extractives Out = 475.20 kg

Ash Balance:

Ash In = Ash Out = 236.64 kg

Water Balance

Water Out = 3% (Total Water

In)

Water Out = 0.03 (594.02 kg) =17.82 kg

Washed Rambutan Peel Output Composition:

Component Amount Percentage

Cellulose 1,165.44 kg 27.44 %
Hemicellulose 557.76 kg 13.13 %
Lignin 1,794.72 kg 42.25 %
Extractives 475.20 kg 11.19 %
Ash 236.64 kg 5.57 %
Water 17.82 kg 0.42 %
TOTAL 4,247.58 kg 100.00%

220
Impurities Stream:

Impurities:

Impurities Out = Impurities In

Impurities Out = 48.00 kg

Water Balance

Water Rambutan Peel + Water washing = Water washed rambutan + Water impurities

Water impurities= 522.24 + 71.78 – 17.82 = 624.20 kg

Impurities Output Composition:

Component Amount Percentage

Impurities 48.00 kg 7.69 %

Water 576.20 kg 92.31 %

TOTAL 624.20 kg 100.00%

221
Equipment Name: Hammer Mill

Equipment Code: K-1

TO F-2
FROM W-1 Average size: 1000 microns
K-1
WASHED RAMBUTAN PEELS MILLED RAMBUTAN
PEEL FIBER

MASS IN MASS OUT

WASHED RAMBUTAN PEELS (From W-1) MILLED RAMBUTAN PEEL (To

F-2)
Cellulose 1,165.44 kg Cellulose 1,164.86 kg
Hemicellulose 557.76 kg Hemicellulose 557.48 kg
Lignin 1,794.72 kg Lignin 1,793.82 kg
Extractives 475.20 kg Extractives 474.96 kg
Ash 236.64 kg Ash 236.52 kg
Water 17.82 kg Water 17.81 kg
TOTAL 4,247.58 kg TOTAL 4,245.46 kg

LOSSES 2.12 kg

TOTAL MASS IN 4,247.58 kg TOTAL 4,247.58 kg

MASS OUT

Washed Rambutan Peel 4,247.58 kg Milled Rambutan 4,245.46 kg

(From W-1) Peel (To F-2)
Losses 1.77 kg
TOTAL MASS IN 4,247.58 kg TOTAL MASS OUT 4,247.58 kg

222
Assumptions:

1. According to Coulson and Richardson: “0.05% mass loss due to adhesion in the
equipment”

Computations:

Basis: 4,247.58 kg of Washed Rambutan Peel Feed from W-1

Mass Input Composition:

Washed Rambutan Peel In:

 Cellulose = 1165.44 kg
 Hemicellulose = 557.76 kg
 Lignin = 1794.72 kg
 Extractives = 475.20 kg
 Ash = 236.64 kg
 Water = 17.82 kg
Total Washed Rambutan Peel = 4,247.58 kg

Milled Rambutan Stream:

Cellulose Balance:

Cellulose Out = 0.9995 (Cellulose In) = 1164.86 kg

Hemicellulose Balance:

Hemicellulose Out = 0.9995 (Hemicellulose In) = 557.48 kg

Lignin Balance:
Lignin Out = 0.9995 (Lignin In) = 1793.82 kg

Extractives Balance:

Extractives Out = 0.9995 (Extractives In) = 474.96 kg

223
 Ash Balance:

Ash Out = 0.9995 (Ash In) = 236.52 kg

Water Balance:

Water Out = 0.9995 (Water In)

Water Out = 17.81 kg

Milled Rambutan Peel Output Composition:

Component Amount Percentage

Cellulose 1,164.86 kg 27.44 %

Hemicellulose 557.48 kg 13.13 %

Lignin 1,793.82 kg 42.25 %

Extractives 474.96 kg 11.19 %

Ash 236.52 kg 5.57 %

Water 17.81 kg 0.42 %

TOTAL 4,245.46 kg 100.00 %

Losses Stream:

0.0005
𝐿𝑜𝑠𝑠𝑒𝑠 = 𝑀𝑖𝑙𝑙𝑒𝑑 𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑃𝑒𝑒𝑙 ×
0.9995

𝟎. 𝟎𝟎𝟎𝟓
𝑳𝒐𝒔𝒔𝒆𝒔 = 𝟒, 𝟐𝟒𝟕. 𝟓𝟖 × = 𝟐. 𝟏𝟐 𝒌𝒈
𝟎. 𝟗𝟗𝟗𝟓

224
Equipment Name: Mixing Tank

Equipment Code: F-2

4% (w/w) NaOH

(1 L NaOH solution per

2 kg Rambutan Peel)

FROM K-1 TO D-1

Average size: 1000 microns pH = >10.5

MILLED RAMBUTAN F-2 RAMBUTAN PEEL FIBER

PEEL FIBER SOLUTION

SAT. STEAM CONDENSATE

MASS IN MASS OUT

MILLED RAMBUTAN PEEL FIBER RAMBUTAN PEEL FIBER

(From K-1) SOLUTION
(To D-1)
Cellulose 1,164.86 kg Cellulose 1,164.86 kg
Hemicellulose 557.48 kg Hemicellulose 557.48 kg
Lignin 1,793.82 kg Lignin 1,793.82 kg
Extractives 474.96 kg Extractives 474.96 kg
Ash 236.52 kg Ash 236.52 kg
Water 17.81 kg Water 2,169.32 kg
TOTAL 4,245.46 kg NaOH 16.80 kg

NaOH SOLUTION TOTAL MASS 6,453.09 kg

OUT
NaOH 88.31 kg
Water 2119.33 kg
TOTAL 2207.64 kg

TOTAL MASS IN 6,453.09 kg

Milled Rambutan Peel 4,245.46 kg Rambutan Peel Fiber 6,453.09 kg

Fiber (From K-1) Solution (To D-1)
NaOH Solution 2,207.64 kg
TOTAL MASS IN 6,453.09 kg TOTAL MASS OUT 6,453.09 kg

225
 Assumptions:

1. For every 2 kg Rambutan peel fiber, 1 L NaOH solution (4% w/w) is added.

2. 100% of cellulose, hemicellulose, and extractives will dissolve using NaOH solution.

3. Water content of rambutan peels is added to total H2O content.

Computations:

Basis: 4,245.46 kg of Milled Rambutan Peels to F-2

Milled Rambutan Peel In:

 Cellulose = 1,164.86 kg

 Hemicellulose = 557.48 kg

 Lignin = 1,793.82 kg

 Extractives = 474.96 kg

 Ash = 236.52 kg

 Water = 17.81 kg

Total Milled Rambutan Peel = 4,245.46 kg

Hemicellulose dissolved to NaOH solution = 1.0 (557.48 kg) = 557.48 kg

1 𝑘𝑔 𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑥 557.48 𝑘𝑔 ℎ𝑒𝑚𝑖𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 = 557.48 𝑘𝑔 𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
1 𝑘𝑔 ℎ𝑒𝑚𝑖𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒

Cellulose dissolved to NaOH solution = 1.0 (1,164.86 kg) = 1,164.86 kg

1 𝑘𝑔 𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑥 1,164.86 𝑘𝑔 𝐶𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 = 1,164.86 𝑘𝑔 𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
1 𝑘𝑔 𝐶𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒

Extractives dissolved to NaOH solution = 1.0 (474.96 kg) = 474.96 kg

1 𝑘𝑔 𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑥 474.96 𝑘𝑔 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑣𝑒𝑠 = 474.96 𝑘𝑔 𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
1 𝑘𝑔 𝐸𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑣𝑒𝑠

226
Cellulose + NaOH  Cellulose, Na+ + H2O

1 𝑘𝑚𝑜𝑙 𝐶𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 1 𝑘𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 40 𝑘𝑔 𝑁𝑎𝑂𝐻

NaOH used = 1,164.86 kg cellulose x 𝑥 1 𝑘𝑚𝑜𝑙 𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 𝑥 1 𝑘𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 =
651.60 𝑘𝑔

71.51 𝑘𝑔

1 𝑘𝑚𝑜𝑙 𝐶𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 1 𝑘𝑚𝑜𝑙 𝐻2𝑂 18.0 𝑊𝑎𝑡𝑒𝑟

Water formed = 1,164.86 kg cellulose x 𝑥 1 𝑘𝑚𝑜𝑙 𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 𝑥 1 𝑘𝑚𝑜𝑙 𝑤𝑎𝑡𝑒𝑟 =
651.60 𝑘𝑔

32.18

Rambutan Peel Fiber Solution Stream:

NaOH Balance:

𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐼𝑛

1 𝐿 𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1.04 𝑘𝑔

= × 4,245.46 𝑘𝑔 𝑟𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑝𝑒𝑒𝑙𝑠 ×
2 𝑘𝑔 𝑟𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑝𝑒𝑒𝑙𝑠 𝐿 𝑁𝑎𝑂𝐻

𝑁𝑎𝑂𝐻 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐼𝑛 = 2,207.64 𝑘𝑔

NaOH in = 0.04 (2,207.64 kg) = 88.31 kg

Theoretical NaOH Solution = NaOHcellulose + NaOHHemicellulose + NaOHExtractives

Theoretical NaOH Solution = 1,164.86 + 557.48 + 474.96 kg = 2,197.30 kg

Excess NaOH Solution = 2,207.64 – 2,197.30= 10.34 kg

NaOH Out = 88.31kg -71.51 = 16.80 kg

Water Balance:

Water In = Water Milled Rambutan Peel + Water NaOH solution+WaterReaction

Water In = 17.81 + 0.96 (2,207.64) = 2,137.14 kg +32.18 =2169.32

Cellulose Balance:

Cellulose Out = 0.9995 (Cellulose In) = 1,164.86 kg

227
Hemicellulose Balance:

Hemicellulose Out = 0.9995 (Hemicellulose In) = 557.48 kg

Lignin Balance:

Lignin Out = 0.9995 (Lignin In) =1,793.82 kg

Extractives Balance:

Extractives Out = 0.9995 (Extractives In) = 1,793.82 kg

Ash Balance:

Ash Out = 0.9995 (Ash In) = 236.52 kg

Rambutan Peel Fiber Solution Output Composition:

Component Amount Percentage

Cellulose 1,164.86 kg 18.66 %

Hemicellulose 557.48 kg 8.64 %

Lignin 1,793.82 kg 27.80 %

Extractives 474.96 kg 7.36 %

Ash 236.52 kg 3.67 %

NaOH 16.80 kg 0.26 %

Water 2,169.32 kg 33.62 %

TOTAL 6,453.09 kg 100.00%

228
Equipment Name: Cooler

Equipment Code: D-1

Water

FROM F-2 TO K-2

pH = >10.5 pH = >10.5
RAMBUTAN PEEL FIBER D-1 COOLED RAMBUTAN
SOLUTION PEEL FIBER
SOLUTION

Water

MASS IN MASS OUT

RAMBUTAN PEEL FIBER COOLED RAMBUTAN PEEL

SOLUTION (from F-2) FIBER SOLUTION (to K-2)
Cellulose 1,164.86 kg Cellulose 1,164.86 kg
Hemicellulose 557.48 kg Hemicellulose 557.48 kg
Lignin 1,793.82 kg Lignin 1,793.82 kg
Extractives 474.96 kg Extractives 474.96 kg
Ash 236.52 kg Ash 236.52 kg
Water 2,169.32 kg Water 2,169.32 kg
NaOH 16.80 kg NaOH 16.80 kg

TOTAL MASS IN 6,453.09 kg TOTAL MASS 6,453.09 k

OUT g

Rambutan Peel 6,453.09 kg Cooled Rambutan Peel 6,453.09 kg

Fiber Solution Fiber Solution (To K-2)
(From F-2)
TOTAL MASS IN 6,453.09 kg TOTAL MASS OUT 6,453.09 kg

229
 Assumptions:

1. No change in mass upon cooling.

Computations:

Basis: 6,453.09 kg of rambutan peel fiber solution to D-1.

Rambutan Peel Fiber Solution In:

 Cellulose = 1,164.86 kg

 Hemicellulose = 557.48 kg

 Lignin = 1,793.82 kg

 Extractives = 474.96 kg

 Ash = 236.52 kg

 NaOH = 16.81 kg

 Water = 2,169.32 kg

Total Rambutan Peel Fiber Solution = 6,453.09 kg

Cellulose Balance:

Cellulose In = Cellulose Out = 1,164.86 kg

Hemicellulose Balance:

Hemicellulose In = Hemicellulose Out = 557.48 kg

Lignin Balance:
Lignin In = Lignin Out = 1,793.82 kg

230
Extractives In = Extractives Out = 474.96 kg

Extractives Balance:

Ash Balance:
Ash In = Ash Out = 236.52 kg

NaOH Balance:

NaOH In = NaOH Out = 16.81 kg

Water Balance:

Water In = Water Out = 2,169.32 kg

Cooled Rambutan Peel Fiber Solution Output Composition:

Component Amount Percentage

Cellulose 1,164.86 kg 18.66 %

Hemicellulose 557.48 kg 8.64 %

Lignin 1,793.82 kg 27.80 %

Extractives 474.96 kg 7.36 %

Ash 236.52 kg 3.67 %

NaOH 16.81 kg 0.26 %

Water 2,169.32 kg 33.62 %

TOTAL 6,453.09 kg 100.00%

231
Equipment Name: Thickener

Equipment Code: K-2

THICKENER OVERFLOW
To Wastewater Treatment
System

FROM D-1
pH = >10.5
COOLED RAMBUTAN
PEEL FIBER K-2
SOLUTION
TO F-3
WET SLUDGE FIBER

MASS IN MASS OUT

COOLED RAMBUTAN PEEL FIBER WET SLUDGE FIBER (To F-3)

SOLUTION (From D-1)
Cellulose 1,204.19 kg Lignin 1,792.93 kg
Hemicellulose 557.48 kg NaOH 1.67 kg
Lignin 1,793.82 kg Water 215.85 kg
Extractives 474.96 kg Cellulose 119.82 kg
Ash 236.52 kg Hemicellulose 55.47 kg
Water 2,169.32 kg Extractives 47.26 kg
NaOH 16.81 kg Ash 23.53 kg
TOTAL MASS IN 6,453.09 kg TOTAL 2,256.52 kg
THICKENER OVERFLOW
NaOH 15.12 kg
Water 1,952.39 kg
Cellulose 1,083.77 kg
Hemicellulose 501.73 kg
Extractives 427.47 kg
Ash 212.87 kg
TOTAL 4,193.34 kg
LOSSES 3.23 kg
TOTAL MASS OUT 6,453.09 kg

Cooled Rambutan Peel Fiber 6,453.09 kg Wet Sludge Fiber (To F-3) 2,256.52 kg
Solution (From D-1) Thickener Overflow 4,193.34 kg
Losses 3.23 kg
TOTAL MASS IN 6,453.09 kg TOTAL MASS OUT 6,453.09 kg

232
 Assumptions:

1. 90% of the cellulose, hemicellulose, extractives, ash, water and NaOH are collected in

the thickener overflow.

2. According to Coulson and Richardson: “0.05% mass loss due to adhesion in the
equipment”

Computations:

Basis: 6,453.09 of Cooled Rambutan Peel Fiber Solution to K-2

Cooled Rambutan Peel Fiber In:

 Cellulose = 1,204.19 kg

 Hemicellulose = 557.48 kg

 Lignin = 1,793.82 kg

 Extractives = 474.96 kg

 Ash = 236.52 kg

 NaOH = 16.80 kg

 Water = 2,169.32 kg

Total Cooled Rambutan Peel Fiber Solution = 6,453.09 kg

Wet Sludge Fiber Stream:

Lignin Balance:
Lignin Out = 0.9995 (Lignin In) =1,792.03 kg
NaOH Balance:
NaOH Out = 0.0995 (NaOH In) = 1.67 kg
Water Balance:
Water Out = 0.0995 (Water In) = 215.85 kg

233
 Cellulose Balance:
Cellulose Out = 0.0995 (Cellulose In) = 119.82 kg
Hemicellulose Balance:
Hemicellulose = 0.05 (Hemicellulose = 55.47 kg
Out In)
Extractives Balance:
Extractives Out = 0.05 (Extractives In) = 47.26 kg
Ash Balance:
Ash Out = 0.05 (Ash In) = 23.53 kg

Wet Sludge Fiber Output Composition:

Component Amount Percentage

Lignin 1,792.93 kg 79.46 %

NaOH 1.67 kg 0.07 %

Water 215.85 kg 9.57 %

Cellulose 119.82 kg 5.31 %

Hemicellulose 55.47 kg 2.46 %

Extractives 47.26 kg 2.09 %

Ash 23.53 kg 1.04 %

TOTAL 2,255.62 kg 100.00%

Losses Stream:

𝟎. 𝟎𝟎𝟎𝟓
𝑳𝒐𝒔𝒔𝒆𝒔 = 𝑾𝒆𝒕 𝑺𝒍𝒖𝒅𝒈𝒆 𝑭𝒊𝒃𝒆𝒓 ×
𝟎. 𝟗𝟗𝟗𝟓

𝟎. 𝟎𝟎𝟎𝟓
𝑳𝒐𝒔𝒔𝒆𝒔 = 𝟔, 𝟒𝟓𝟑. 𝟎𝟗 × = 𝟑. 𝟐𝟑 𝒌𝒈
𝟎. 𝟗𝟗𝟗𝟓

234
Thickener Overflow Stream:

NaOH Balance:
NaOH Out = 0.90 (NaOH In) = 15.12 kg
Water Balance:
Water Out = 0.90 (Water In) = 1,952.39 kg
Cellulose Balance:
Cellulose Out = 0.90 (Cellulose In) = 1,083.77 kg
Hemicellulose Balance:
Hemicellulose Out = 0.90 (Hemicellulose = 501.73 kg
In)
Extractives Balance:
Extractives Out = 0.90 (Extractives = 427.47 kg
In)
Ash Balance:
Ash Out = 0.90 (Ash In) = 212.87 kg

Thickener Overflow Output Composition:

Component Amount Percentage

NaOH 8.02 kg 0.36 %

Water 1,956.67 kg 45.56 %

Cellulose 1,048.37 kg 25.00 %

Hemicellulose 501.73 kg 11.96 %

Extractives 427.47 kg 10.19 %

Ash 212.87 kg 5.08 %

TOTAL 4,193.34 kg 100.00%

235
Equipment Name: Acidification Tank

Equipment Code: F-3

72% (w/w) H2SO4

(0.85 kg H2SO4 solution per

100 kg lignin)

FROM K-2 TO K-3

pH = >10.5 pH = 2 – 3
WET SLUDGE FIBER F-3 ACIDIFIED LIGNIN
SOLUTION

Water
Cooling Water
Cooling Water

MASS IN MASS OUT

WET SLUDGE FIBER (From K-2) ACIDIFIED LIGNIN SOLUTION (To K-3)
Lignin 1,792.93 kg Insoluble Lignin 1,613.63 kg
NaOH 1.67 kg Water 220.87 kg
Water 215.85 kg H2SO4 8.93 kg
Cellulose 119.82 kg Na2SO4 2.97 kg
Hemicellulose 55.47 kg Cellulose 119.82 kg
Extractives 47.26 kg Hemicellulose 55.47 kg
Ash 23.53 kg Ash 23.53 kg
TOTAL 2,256.52 kg Extractives 47.26 kg
Soluble Lignin 179.29 kg
H2SO4 SOLUTION TOTAL MASS OUT 2,271.76 Kg
Water 4.27 kg
H2SO4 10.97 kg
TOTAL 15.24 kg
TOTAL MASS IN 2,271.76 kg

Wet Sludge Fiber 2,256.52 kg Acidified Lignin Solution 2,271.76 kg

(From K-2) (To K-3)
H2SO4 Solution 15.24 kg
TOTAL MASS IN 2,271.76 kg TOTAL MASS OUT 2,271.76 kg

236
 Basis:

1. 0.85 kg of 72% (w/w) H2SO4 solution per 100 kg lignin is added. (Ref: Jablonsky, M.,

Haz, A., Skulcova, A., & Dubinyova, L. (2015). Products of Nitrobenzene oxidation

from non wood lignin isolated by sulphuric acid.)

Assumption:

1. 10% of Lignin was soluble in H2SO4 solution.

Computations:

2,256.52 kg of wet sludge fiber from K-2

Wet Sludge In:

 Lignin = 1,792.93 kg

 NaOH = 1.67 kg

 Water = 215.85 kg

 Cellulose = 119.82 kg

 Hemicellulose = 55.47 kg

 Ash = 47.26 kg

 Extractives = 23.53 kg

Total = 2,256.52 kg

237
Acidified Lignin Stream:

Side reaction:

2 NaOH + H2SO4  Na2SO4 + 2 H2O

H2SO4 Balance:

0.85 𝑘𝑔 𝐻2 𝑆𝑂4 solution

𝐻2 𝑆𝑂4 solution in = (1,792.93 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛)
100 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛

𝐻2 𝑆𝑂4 solution in = 15.24 𝑘𝑔

Mass 𝐻2 𝑆𝑂4 In = 0.72(15.24 𝑘𝑔) = 𝟏𝟎. 𝟗𝟕 𝒌𝒈

𝐻2 𝑆𝑂4 𝑆𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

1 kmol NaOH 1 kmol H2SO4 98.07 kg H2SO4

= 1.67 kg NaOH ( )( )( )
40 kg NaOH 2 kmol NaOH 1 kmol H2SO4

𝐻2 𝑆𝑂4 𝑆𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 2.05 𝑘𝑔

H2SO4 out = H2SO4 H2SO4 soln - H2SO4 side reaction

𝐻2 𝑆𝑂4 Out = 10.97 − 2.05 = 𝟖. 𝟗𝟑 𝐤𝐠

Na2SO4 Balance:

Na2SO4 Out = Na2SO4 formed

1 𝑘𝑚𝑜𝑙 1 𝑘𝑚𝑜𝑙 Na2 SO4 142.07 𝑘𝑔 Na2 SO4

Na2 SO4 out = 1.67 kg NaOH × 40 𝑘𝑔 𝑁𝑎𝑂𝐻 × ×
2 𝑘𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 1 𝑘𝑚𝑜𝑙 Na2 SO4

𝐍𝐚𝟐 𝐒𝐎𝟒 𝐨𝐮𝐭 = 𝟐. 𝟗𝟕 𝐤𝐠

Water Balance:

Mass H2 O H2 SO4soln = 0.28(15.24 𝑘𝑔) = 𝟒. 𝟐𝟕 𝒌𝒈

1 kmol NaOG 2 kmol H2O 18 kg H2O

𝐻2 O formed = 1.67 kg NaOH ( )( )( )
40 kg NaOH 2 kmol NaOH 1 kmol H2O

238
 𝐻2 O formed = 0.75 kg

Total Water out = Waterwet sludge + WaterH2SO4 soln + Water side reaction

Total Water out =212.65 kg + 4.27 kg + 0.75 kg = 220.87 kg

Insoluble Lignin Balance:

Insoluble Lignin Out = 0.90 (Lignin In) = 1,613.63 kg
Soluble Lignin Balance:
Soluble Lignin Out = 0.10 (Lignin In) = 179.29 kg
Cellulose Balance:
Cellulose Out = Cellulose In = 119.82 kg
Hemicellulose Balance:
Hemicellulose Out = Hemicellulose In = 55.47 kg
Extractives Balance:
Extractives Out = Extractives In = 47.26 kg
Ash Balance:
Ash Out = Ash In = 23.53 kg

Acidified Lignin Solution Mass Output Composition:

Component Amount Percentage

Insoluble Lignin 1,613.63 kg 71.03 %
Water 220.87 kg 9.72 %
H2SO4 8.93 kg 0.39 %
Na2SO4 2.97 kg 0.13 %
Cellulose 115.90 kg 5.27 %
Hemicellulose 55.47 kg 2.44 %
Ash 23.53 kg 1.04 %
Extractives 47.26 kg 2.08 %
Soluble Lignin 179.29 kg 7.89 %
TOTAL 2,271.77 kg 100.00%

239
pH Validation:
𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻
Wet sludge in: 𝑝𝑂𝐻 = − log ( )
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑚𝑜𝑙𝑒𝑠 𝐻2𝑆𝑂4
Lignin = 1,792.93 kg 𝑝𝐻 = − log ( )
NaOH = 8.79 kg 𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Water = 212.65 kg 𝑝𝐻 = 14 − 𝑝𝑂𝐻
Cellulose = 115.90 kg
Hemicellulose = 55.47 kg
Extractives = 47.29 kg
Ash = 23.53 kg

1 𝑘𝑚𝑜𝑙𝑒 𝑁𝑎𝑂𝐻 1000 𝑚𝑜𝑙𝑒

𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻 = 8.79 𝑘𝑔 𝑥 𝑥 = 219.75 moles NaOH
40 𝑘𝑔 𝑁𝑎𝑂𝐻 1 𝑘𝑚𝑜𝑙𝑒 𝑁𝑎𝑂𝐻

219.75 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻

𝑝𝑂𝐻 = − log ( ) = −0.01
1𝐿
212.65 𝑘𝑔 𝐻2 𝑂 𝑥 1 𝑘𝑔 𝐻 𝑂
2

𝑝𝐻 = 14 − (−0.01) = 14.01

Acidified Lignin Solution:

Insoluble Lignin = 1,613.63 kg

Soluble Lignin = 179.29 kg
Water = 220.8 kg
H2SO4 = 0.21 kg
Na2SO4 = 15.60 kg
Cellulose = 115.90 kg
Hemicellulose = 55.47 kg
Extractives = 47.26 kg
Ash = 23.53 kg

1 𝑘𝑚𝑜𝑙𝑒 𝐻2 𝑆𝑂4 1000 𝑚𝑜𝑙𝑒

𝑚𝑜𝑙𝑒𝑠 𝐻2 𝑆𝑂4 = 2.05 𝑘𝑔 𝑥 𝑥 = 2.14 moles 𝐻2 𝑆𝑂4
98 𝑘𝑔𝐻2 𝑆𝑂4 1 𝑘𝑚𝑜𝑙𝑒 𝐻2 𝑆𝑂4

1.78 𝑚𝑜𝑙𝑒𝑠 𝐻2 𝑆𝑂4

𝑝𝐻 = − log ( 1𝐿 ) = 2.01
220.87 𝑘𝑔 𝐻2 𝑂 𝑥
1 𝑘𝑔 𝐻2 𝑂

240
Equipment Name: Leaf Filter

Equipment Code: K-3

ACIDIFIED LIGNIN
SOLUTION (FILTRATE)
To Wastewater Treatment
System

FROM F-3
pH = 2 – 3
K-3
ACIDIFIED LIGNIN
SOLUTION

TO J-1
LIGNIN

MASS IN MASS OUT

ACIDIFIED LIGNIN SOLUTION LIGNIN (To J-1)

(From F-3) Insoluble Lignin 1,613.83 kg
Insoluble Lignin 1,613.63 kg Water 44.06 kg
Water 220.87 kg Na2SO4 0.06 kg
H2SO4 8.93 kg Cellulose 2.34 kg
Na2SO4 2.97 kg Hemicellulose 1.08 kg
Cellulose 119.82 kg Ash 0.46 kg
Hemicellulose 55.47 kg Extractives 0.92 kg
Ash 23.53 kg Soluble Lignin 3.50 kg
Extractives 47.26 kg TOTAL 1,665.42 kg
Soluble Lignin 179.29 kg
TOTAL MASS IN 2,271.76 kg ACIDIFIED LIGNIN SOLUTION (FILTRATE)
Water 176.69 kg
H2SO4 8.75 kg
Na2SO4 2.91 kg
Cellulose 117.42 kg
Hemicellulose 54.36 kg
Ash 23.06 kg
Extractives 46.31 kg
Soluble Lignin 175.71 kg
TOTAL 605.22 kg

LOSSES 1.14 kg
TOTAL MASS OUT 2,271.76 kg

Acidified Lignin 2,271.76 kg Lignin (To J-1) 1,665.42 kg

Solution (From F-3) Acidified Lignin Solution 605.22 kg
(Filtrate)
Losses 1.14 kg
TOTAL MASS IN 2,271.76 kg TOTAL MASS OUT 2,271.76 kg

241
 Assumptions:

1. 2% of H2SO4, Na2SO4, Cellulose, Hemicellulose, extractives, and Ash are adhered in

the Lignin stream

2. 80% of water is collected in the Filtrate.

3. According to Coulson and Richardson: “0.05% mass loss due to adhesion in the
equipment”
Computations:

Basis: 2,271.76 kg of Acidified Lignin Solution to K-3

Acidified Lignin Solution In:

 Insoluble Lignin = 1,613.63 kg

 Water = 220.87 kg

 H2SO4 = 8.93 kg

 Na2SO4 = 2.97 kg

 Cellulose = 119.82 kg

 Hemicellulose = 55.47 kg

 Extractives = 23.53 kg

 Ash = 47.26 kg

 Soluble Lignin = 179.29 kg

TOTAL = 2,271.76 kg

242
Filtrate Stream

Soluble Lignin Balance:

Soluble Lignin Out = 0.98 (Soluble Lignin = 175.71 kg
In)
Water Balance:
Water Out = 0.80 (Water In) =176.69 kg

H2SO4 Balance:
H2SO4 Out = 0.98 (H2SO4 In) = 8.75 kg
Na2SO4 Balance:
Na2SO4 Out = 0.98 (Na2SO4 In) = 2.91 kg
Cellulose Balance:
Cellulose Out = 0.98 (Cellulose In) = 117.42 kg
Hemicellulose Balance:
Hemicellulose Out = 0.98 (Hemicellulose = 54.36 kg
In)
Extractives Balance:
Extractives Out = 0.98 (Extractives In) = 46.31 kg
Ash Balance:
Ash Out = 0.98 (Ash In) = 23.06 kg

Acidified Lignin Solution (Filtrate) Output Composition:

Component Amount Percentage

Water 176.69 kg 29.20 %
H2SO4 8.75 kg 1.45 %
Na2SO4 2.91 kg 0.48 %
Cellulose 117.42 kg 19.40 %
Hemicellulose 54.36 kg 8.98 %
Ash 23.06 kg 3.81 %
Extractives 46.31 kg 7.65 %
Soluble Lignin 175.71 kg 29.03 %
TOTAL 605.21 kg 100.00%

243
Lignin Stream:
Insoluble Lignin Balance:
Insoluble Lignin Out = 0.9995 (Insoluble Lignin In) = 1,612.83 kg
Soluble Lignin Balance:
Soluble Lignin Out = 0.02 (Soluble Lignin In) = 3.50 kg
Water Balance:
Water Out = 0.20 (Water In) = 44.06 kg
Na2SO4 Balance:
Na2SO4 Out = 0.02 (Na2SO4 In) = 0.06 kg
Cellulose Balance:
Cellulose Out = 0.02 (Cellulose In) = 2.34 kg
Hemicellulose Balance:
Hemicellulose Out = 0.02 (Hemicellulose In) = 1.08 kg
Extractives Balance:
Extractives Out = 0.02 (Extractives In) = 0.92 kg
Ash Balance:
Ash Out = 0.02 (Ash In) = 0.46 kg

Lignin Streams Mass Output Composition:

Component Amount Percentage

Insoluble Lignin 1,612.83 kg 96.84 %
Water 44.06 kg 2.65 %
Na2SO4 0.06 kg 0.02 %
Cellulose 2.26 kg 0.14 %
Hemicellulose 1.08 kg 0.06 %
Ash 0.46 kg 0.03 %
Extractives 0.92 kg 0.06 %
Soluble Lignin 3.50 kg 0.21 %
TOTAL 1,665.42 kg 100.00%
Losses Stream:

0.0005
𝐿𝑜𝑠𝑠𝑒𝑠 = 𝐿𝑖𝑔𝑛𝑖𝑛 ×
0.9995

0.0005
𝑳𝒐𝒔𝒔𝒆𝒔 = 1,665.42 × = 𝟏. 𝟏𝟒 𝒌𝒈
0.9995

244
Equipment Name: Autoclave Reactor

Equipment Code: J-1

Nitrobenzene
(C6H5NO2)
0.5 M NaOH
Solution
(0.4 L nitrobenzene
(5 kg Lignin per 1 kg
per 1 kg Lignin)
NaOH solution)

FROM K-3 TO D-2

LIGNIN CRUDE VANILLIN SOLUTION

J-1

SAT. STEAM CONDENSATE

MASS IN MASS OUT

LIGNIN (From K-3) CRUDE VANILLIN SOLUTION (To D-2)

Insoluble Lignin 1,612.83 kg Vanillin 534.14 kg
Water 44.06 kg Syringaldehyde 799.40 kg
Na2SO4 0.06 kg p-Hydroxybenzaldehyde 214.31 kg
Cellulose 2.34 kg Nitrobenzene 658.48 kg
Hemicellulose 1.08 kg NaOH 161.28 kg
Ash 0.46 kg Water 213.09 kg
Extractives 0.92 kg Na2SO4 0.06 kg
Soluble Lignin 3.50 kg Cellulose 2.34 kg
TOTAL 1,665.42 kg Hemicellulose 1.08 kg
Extractives 0.92 kg
NaOH 161.28 kg Soluble Lignin 3.50 kg
Insoluble Lignin 80.64 kg
NITROBENZENE SOLN Ash 0.46 kg
Nitrobenzene 774.16 kg Nitrosobenzene 100.18 kg
Water 7.74 kg TOTAL MASS OUT 2,769.88 kg
TOTAL 781.90 kg

TOTAL MASS IN 2,769.88 kg

Lignin (from K-3) 1,665.42 kg

NaOH 322.56 kg Crude Vanillin Solution 2,769.88 kg
Nitrobenzene 774.16 kg (To D-2)
TOTAL MASS IN 2,769.88 kg TOTAL MASS OUT 2,769.88 kg

245
 Basis:

1. 1:5 mass to mass ratio of 50% w/w NaOH solution to lignin

2. 0.4:1 volume to mass ratio of 99% nitrobenzene to lignin (Ref: Products of
Nitrobenzene oxidation from non wood lignin isolated by sulphuric acid by Jablonsky,
M., Haz, A., Skulcova, A., & Dubinyova, L. (2015).)
3. The over-all conversion of lignin is 95%. (Ref: Catalytic Wet-Air Oxidation of Lignin
in a Three-Phase Reactor with Aromatic Aldehyde Production by Sales et., al)

Computations:

Overall Chemical Reaction:

C91H94O36 + C6H5NO2  4C8H8O3 + 5C9H10O4 + 2C7H6O2+ C6H5NO

1,665.42 kg of Lignin fed to J-1

Lignin in:

 Insoluble Lignin = 1,612.83 kg

 Water = 44.06 kg

 Na2SO4 = 0.06 kg

 Cellulose = 2.34 kg

 Hemicellulose = 1.08 kg

 Extractives = 0.92 kg

 Ash = 0.92 kg

 Soluble Lignin = 3.50 kg

TOTAL = 1,665.42 kg

Crude Vanillin Solution Stream:

Insoluble Lignin Balance:

𝐼𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝐿𝑖𝑔𝑛𝑖𝑛 𝐼𝑛 = 𝑅𝑒𝑎𝑐𝑡𝑒𝑑 𝑖𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝑙𝑖𝑔𝑛𝑖𝑛 + 𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑖𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝑙𝑖𝑔𝑛𝑖𝑛

246
𝑅𝑒𝑎𝑐𝑡𝑒𝑑 𝐼𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝐿𝑖𝑔𝑛𝑖𝑛 = 0.95 (1,612.83 𝑘𝑔) = 𝟏, 𝟓𝟑𝟐. 𝟏𝟗 𝒌𝒈

𝐼𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝐿𝑖𝑔𝑛𝑖𝑛 𝑂𝑢𝑡 = 𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝐼𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝐿𝑖𝑔𝑛𝑖𝑛 = 1,612.83 − 1,532.19

= 𝟖𝟎. 𝟔𝟒 𝒌𝒈

NaOH Solution Balance:

1𝑘𝑔 𝑁𝑎𝑂𝐻 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑁𝑎𝑂𝐻 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑛𝑒𝑒𝑑𝑒𝑑 = × 1,612.83 𝑘𝑔 = 𝟑𝟐𝟐. 𝟓𝟕 𝒌𝒈
5 𝑘𝑔 𝐼𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝐿𝑖𝑔𝑛𝑖𝑛

𝑁𝑎𝑂𝐻 𝐼𝑛 = 0.50 (322.57 𝑘𝑔) = 161.28 𝑘𝑔

𝑁𝑎𝑂𝐻 𝑂𝑢𝑡 = 𝑁𝑎𝑂𝐻 𝐼𝑛 = 𝟏𝟔𝟏. 𝟐𝟖 𝒌𝒈

𝑁𝒊𝒕𝒓𝒐𝒔𝒐𝒃𝒆𝒏𝒆𝒏𝒆 𝒃𝒂𝒍𝒂𝒏𝒄𝒆:

𝑁𝑖𝑡𝑟𝑜𝑠𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 𝑓𝑜𝑟𝑚𝑒𝑑

1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛
= 1,612.83 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 ×
1,763.85 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛

1 𝑘𝑚𝑜𝑙 𝑁𝑖𝑡𝑟𝑜𝑠𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 107.11 𝑁𝑖𝑡𝑟𝑜𝑠𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒𝑒

× × = 𝟏𝟎𝟎. 𝟏𝟖 𝒌𝒈
1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝑁𝑖𝑡𝑟𝑜𝑠𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒

Nitrobenzene Balance:

𝑁𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 𝑂𝑢𝑡 = 𝑁𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 𝐼𝑛

0.4 𝐿 𝑛𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 1.2 𝑘𝑔

𝑁𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 𝐼𝑛 = × 𝑛𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 × 1,612.83 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 ×
1 𝑘𝑔 𝐿𝑖𝑔𝑛𝑖𝑛 1𝐿

99% 𝑝𝑢𝑟𝑖𝑡𝑦=774.16

𝑁𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 𝑂𝑢𝑡 =

1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝑁𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒

= 1,612.83 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 × ×
1,763.85 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛

123. 11 𝑁𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒
×
1 𝑘𝑚𝑜𝑙 𝑁𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒

Nitrobenzene out = 774.16 − 123.11 = 658.48 kg

247
Water Balance:

𝑊𝑎𝑡𝑒𝑟 𝑂𝑢𝑡 = 𝑊𝑎𝑡𝑒𝑟 (𝑙𝑖𝑔𝑛𝑖𝑛 𝑠𝑡𝑟𝑒𝑎𝑚) + 𝑊𝑎𝑡𝑒𝑟 (𝑛𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒)

0.01
𝑊𝑎𝑡𝑒𝑟 𝑂𝑢𝑡 = 44.06 + 774.15 𝑘𝑔 × = 𝟓𝟏. 𝟖𝟖 𝒌𝒈
0.99
Vanillin Balance:
𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑂𝑢𝑡 = 𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑃𝑟𝑜𝑑𝑢𝑒𝑑
1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛 4 𝑘𝑚𝑜𝑙 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛
𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑂𝑢𝑡 = 1,612.83 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 × ×
1,763.85 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛
152.17 𝑘𝑔 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛
× = 𝟓𝟑𝟒. 𝟏𝟒 𝒌𝒈
1 𝑘𝑚𝑜𝑙 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛

Syringaldehyde Balance:
𝑆𝑦𝑟𝑖𝑛𝑔𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑂𝑢𝑡 = 𝑆𝑦𝑟𝑖𝑛𝑔𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑
𝑆𝑦𝑟𝑖𝑛𝑔𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑂𝑢𝑡
1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛
= 1,612.83 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 ×
1,763.85 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛
5 𝑘𝑚𝑜𝑙 𝑠𝑦𝑟𝑖𝑛𝑔𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 182.19 𝑘𝑔 𝑠𝑦𝑟𝑖𝑛𝑔𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
× ×
1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝑠𝑦𝑟𝑖𝑛𝑔𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
= 𝟕𝟗𝟗. 𝟒𝟎 𝒌𝒈
p-Hydroxybenzaldehyde Balance:
𝑃 − ℎ𝑦𝑑𝑟𝑜𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑂𝑢𝑡 = 𝑃 − ℎ𝑦𝑑𝑟𝑜𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑
𝑃 − ℎ𝑦𝑑𝑟𝑜𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛
= 1,612.83 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 ×
1,763.85 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛
2 𝑘𝑚𝑜𝑙 𝑃 − ℎ𝑦𝑑𝑟𝑜𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
×
1 𝑘𝑚𝑜𝑙 𝑙𝑖𝑔𝑛𝑖𝑛
122.11 𝑘𝑔 𝑃 − ℎ𝑦𝑑𝑟𝑜𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
× = 𝟐𝟏𝟒. 𝟑𝟏 𝒌𝒈
1 𝑘𝑚𝑜𝑙 𝑃 − ℎ𝑦𝑑𝑟𝑜𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
Na2SO4 Balance:
Na2SO4 Out = Na2SO4 In = 0.06 kg
Cellulose Balance:
Cellulose Out = Cellulose In = 2.34 kg
Hemicellulose Balance:
Hemicellulose Out = Hemicellulose In = 1.08 kg
Extractives Balance:
Extractives Out = Extractives In = 0.92 kg
Ash Balance:
Ash Out = Ash In = 0.46 kg
Soluble Lignin Balance:

248
 Soluble Lignin Out = Soluble lignin In = 3.50 kg
Crude Vanillin Solution Output Composition:

Component Amount Percentage

Vanillin 534.13 kg 19.28 %

Syringaldehyde 799.40 kg 28.86 %

p-Hydroxybenzaldehyde 214.31 kg 7.74 %

Nitrobenzene 658.48 kg 27.77 %

NaOH 161.28 kg 5.82 %

Water 213.09 kg 7.69 %

Na2SO4 0.06 kg 0.01 %

Cellulose 2.34 kg 0.08 %

Hemicellulose 1.08 kg 0.04 %

Extractives 0.92 kg 0.03 %

Ash 0.46 kg 0.02 %

Insoluble Lignin 80.64 kg 2.91 %

Soluble Lignin 3.50 kg 0.13%

Nitrosobenzene 100.18 kg 3.62 %

TOTAL 2,769.88 kg 100.00%

249
Equipment Name: Cooler

Equipment Code: D-2

Water

FROM J-1 TO F-4

D-2 COOLED CRUDE
CRUDE VANILLIN SOLUTION
VANILLIN SOLUTION

Water

MASS IN MASS OUT

CRUDE VANILLIN SOLUTION COOLED CRUDE VANILLIN

(From J-1) SOLUTION (To F-4)
Vanillin 534.14 kg Vanillin 534.14 kg
Syringaldehyde 799.40 kg Syringaldehyde 799.40 kg
p- 214.31 kg p- 214.31 kg
Hydroxybenzaldeh Hydroxybenzald
yde ehyde
Nitrobenzene 658.48 kg Nitrobenzene 658.48 kg
NaOH 161.28 kg NaOH 161.28 kg
Water 213.09 kg Water 213.09 kg
Na2SO4 0.06 kg Na2SO4 0.06 kg
Cellulose 2.34 kg Cellulose 2.34 kg
Hemicellulose 1.08 kg Hemicellulose 1.08 kg
Extractives 0.92 kg Extractives 0.92 kg
Soluble Lignin 3.50 kg Soluble Lignin 3.50 kg
Insoluble Lignin 80.64 kg Insoluble Lignin 80.64 kg
Ash 0.46 kg Ash 0.46 kg
Nitrobenzene 226.18 kg Nitrobenzene 226.18 kg
TOTAL MASS 2,769.88 kg TOTAL MASS 2,769.88 kg
IN OUT

Crude Vanillin Solution 2,769.88 kg Cooled Crude Vanillin 2,769.88 kg

(From J-1) Solution (To F-4)
TOTAL MASS IN 2,769.88 kg TOTAL MASS OUT 2,769.88 kg

250
 Assumptions:

1. No change in mass upon cooling.

Computations:

Basis: 2,769.88 kg of Crude Vanillin Solution fed to D-2

Crude vanillin solution In:

 Vanillin = 534.14 kg

 Syringaldehyde = 799.40 kg

 p-Hydroxybenzaldehyde = 214.31 kg

 Nitrobenzene = 651.05 kg

 NaOH = 161.28 kg

 Water = 213.09 kg

 Na2SO4 = 0.06 kg

 Cellulose = 2.34 kg

 Hemicellulose = 1.08 kg

 Extractives = 0.92 kg

 Ash = 0.46 kg

 Insoluble Lignin = 80.64 kg

 Soluble Lignin = 3.50 kg

 Nitrosobenzene = 226.23 kg

TOTAL = 2,769.88 kg

251
Cooled Crude Vanillin Solution Stream:
Vanillin Balance:
Vanillin Out = Vanillin In = 534.14 kg
Syringaldehyde Balance:
Syringaldehyde Out = Syringaldehyde In = 799.40 kg
P-hydrobenzaldehyde Balance:
P-hydrobenzaldehyde Out = P-hydrobenzaldehyde In = 214.31 kg
Nitrobenzene Balance:
Nitrobenzene Out = Nitrobenzene In = 658.48 kg
NaOH Balance:
NaOH Out = NaOH In = 161.28 kg
Water Balance:
Water Out = Water In = 213.09 kg
Na2SO4 Balance:
Na2SO4 Out = Na2SO4 In = 0.06 kg
Cellulose Balance:
Cellulose Out = Cellulose In = 2.34 kg
Hemicellulose Balance:
Hemicellulose Out = Hemicellulose In = 1.08 kg
Extractives Balance:
Extractives Out = Extractives In = 0.92 kg
Ash Balance:
Ash Out = Ash In = 0.46 kg
Soluble Lignin Balance:
Soluble Lignin Out = Soluble lignin In = 3.50 kg
Insoluble Lignin Balance:
Insoluble Lignin Out = Insoluble lignin In = 80.64 kg
Nitrosobenzene Balance:
Nitrosobenzene Out = Nitrobenzene In = 100.18 kg

252
Cooled Crude Vanillin Solution Output Composition:

Component Amount Percentage

Vanillin 534.14 kg 19.09 %

Syringaldehyde 799.40 kg 28.57 %

p-Hydroxybenzaldehyde 214.31 kg 7.66 %

Nitrobenzene 658.48 kg 27.95 %

NaOH 161.28 kg 5.82 %

Water 213.09 kg 7.69 %

Na2SO4 0.06 kg 0.01 %

Cellulose 2.34 kg 0.08 %

Hemicellulose 1.08 kg 0.04 %

Extractives 0.92 kg 0.03 %

Ash 0.46 kg 0.02 %

Insoluble Lignin 80.64 kg 2.91 %

Soluble Lignin 3.50 kg 0.13%

Nitrosobenzene 100.18 kg 6.76%

TOTAL 2,769.88 kg 100.00%

253
Equipment Name: Liquid-Liquid Extractor
Equipment Code: F-4
C4H10O
(diethyl ether)
(4.5 kg diethyl ether per
1 kg Vanillin)

FROM D-2 TO D-3

F-4
COOLED CRUDE VANILLIN – RICH LAYER
VANILLIN SOLUTION

SYRINGALDEHYDE – RICH LAYER

To Wastewater Treatment System
Recovery System for NaOH, C6H5NO2,
C9H10O4 & C7H6O2

MASS IN MASS OUT

COOLED CRUDE VANILLIN VANILLIN-RICH LAYER (To D-3)
SOLUTION(From D-2)
Vanillin 534.14 kg Vanillin 512.78 kg
Syringaldehyde 799.40 kg Syringaldehyde 7.99 kg
p-Hydroxybenzaldehyde 214.31 kg p-Hydroxybenzaldehyde 2.14 kg
Nitrobenzene 658.48 kg Nitrobenzene 6.58 kg
NaOH 161.28 kg NaOH 1.61 kg
Water 213.09 kg Water 210.96 kg
Na2SO4 0.06 kg Insoluble Lignin 0.81 kg
Cellulose 2.34 kg Diethyl ether 2,050.26 kg
Hemicellulose 1.08 kg Nitrosobenzene 2.27 kg
Extractives 0.92 kg TOTAL 2 794.13 kg
Soluble Lignin 3.50 kg SYRINGALDEHYDE-RICH LAYER
Insoluble Lignin 80.64 kg Vanillin 21.37 kg
Ash 0.46 kg Syringaldehyde 791.40 kg
Nitrobenzene 226.18 kg p-Hydroxybenzaldehyde 212.17 kg
TOTAL 2,769.88 kg Nitrobenzene 651.89 kg
NaOH 159.67 kg
Na2SO4 0.06 kg
PURE DIETHYL ETHER Cellulose 2.34 kg
Diethyl ether 2,070.96 kg Hemicellulose 1.08 kg
TOTAL 2,070.96 kg Extractives 0.92 kg
Ash 0.46 kg
TOTAL MASS IN 4,840.84 kg Insoluble Lignin 79.83 kg
Soluble Lignin 3.50 kg
Water 2.13 kg
Nitrosobenzene 99.18 kg
TOTAL 2,046.71 kg
TOTAL MASS OUT 4,840.84 kg

Cooled Crude Vanillin 2,769.88 kg Vanillin-Rich 2,794.13 kg

Solution(From D-2) Layer(To D-3)
Pure diethyl ether 2,070.96 kg Syringaldehyde-Rich 2,046.71 kg
Layer
TOTAL MASS IN 4,840.84 kg TOTAL MASS 4,840.84 kg
OUT

254
 Basis:

1. The distribution ratio of diethyl ether with vanillin is 23.44.

2. 96% yield of extraction of vanillin. (Ref: Recovery of vanillin and syringaldehyde from

lignin oxidation: A review of separation and purification processes by Mota, et al.)

Assumption:

1. 10:1 mass to volume ratio of solubility of vanillin to water.

2. 1% of Syringaldehyde, P-hydrobenzaldehyde, Nitrobenzene, NaOH and other

cellulosic material are adhered to extract.

Computations:

2,769.88 kg of Cooled Crude Vanillin Solution mixture to F-4

Cooled Crude Vanillin Solution In:

 Vanillin = 534.14 kg
 Syringaldehyde = 799.40 kg
 p-Hydroxybenzaldehyde = 214.31 kg
 Nitrobenzene = 658.48 kg
 NaOH = 161.28 kg
 Water = 213.09 kg
 Na2SO4 = 0.06 kg
 Cellulose = 2.34 kg
 Hemicellulose = 1.08 kg
 Extractives = 0.92 kg
 Ash = 0.46 kg
 Insoluble Lignin = 80.64 kg
 Soluble Lignin = 3.50 kg
 Nitrosobenzene = 100.18 kg
TOTAL = 2,769.88 kg

255
 𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑒𝑥𝑡𝑟𝑎𝑐𝑡
𝐷𝑖𝑠𝑡𝑟𝑖𝑏𝑢𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑖𝑜 = = 23.44
𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑟𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒

0.96(534.14) 𝑘𝑔 𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 (𝐸𝑥𝑡𝑟𝑎𝑐𝑡)

𝐷𝑖𝑒𝑡ℎ𝑦𝑙 𝑒𝑡ℎ𝑒𝑟 𝑛𝑒𝑒𝑑𝑒𝑑
=
0.04 534.14)𝑘𝑔 𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 (𝑅𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒)
(
791.31 𝑘𝑔 𝑠𝑦𝑟𝑖𝑛𝑔𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒

Diethyl ether needed = 2,070.96 kg

Vanillin-Rich Layer Stream:

Vanillin Balance:
Vanillin Out = 0.96 (Vanillin In) = 512.78 kg
Syringaldehyde Balance:
Syringaldehyde Out = 0.01 (Syringaldehyde In) = 7.99 kg
P-hydrobenzaldehyde Balance:
P-hydrobenzaldehyde Out = 0.01 (P-hydrobenzaldehyde In) = 2.14 kg
Nitrobenzene Balance:
Nitrobenzene Out = 0.01 (Nitrobenzene In) = 6.58 kg
NaOH Balance:
NaOH Out = 0.01 (NaOH In) = 1.61 kg
Insoluble Lignin Balance:
Insoluble Lignin Out = 0.01 (Insoluble lignin In) = 0.81 kg
Diethyl ether Balance:
Diethyl ether Out = Diethyl ether In = 2,070.96 kg
Water Balance
Water Out = 0.98 (Water In) = 210.96 kg
Nitrosobenzene Balance:
Nitrosobenzene Out = 0.01 (Nitros0benzene In) = 1.00 kg

256
Vanillin-Rich Layer Output Composition:

Component Amount Percentage

Vanillin 512.78 kg 18.35 %
Syringaldehyde 7.99 kg 0.29 %
p-Hydroxybenzaldehyde 2.14 kg 0.08 %
Nitrobenzene 6.58 kg 0.24 %
NaOH 1.61 kg 0.06 %
Water 210.96 kg 7.55 %
Insoluble Lignin 0.81 kg 0.03 %
Diethyl Ether 2 050.26 kg 73.38 %
Nitrosobenzene 1.00 kg 0.04 %
TOTAL 2,794.13 kg 100.00%

Syringaldehyde-Rich Layer Composition:

Vanillin Balance:
Vanillin Out = 0.04 (Vanillin In) = 21.37 kg
Syringaldehyde Balance:
Syringaldehyde Out = 0.99 (Syringaldehyde In) = 791.40 kg
P-hydrobenzaldehyde Balance:
P-hydrobenzaldehyde = 0.99 (P-hydrobenzaldehyde = 212.17
Out In) kg
Nitrobenzene Balance:
Nitrobenzene Out = 0.99 (Nitrobenzene In) = 651.89 kg
NaOH Balance:
NaOH Out = 0.99 (NaOH In) = 159.67 kg
Na2SO4 Balance:
Na2SO4 Out = 0.99 (Na2SO4 In) = 0.06 kg
Cellulose Balance:
Cellulose Out = Cellulose In = 2.34 kg
Hemicellulose Balance:
Hemicellulose Out = Hemicellulose In = 1.08 kg
Extractives Balance:
Extractives Out = Extractives In = 0.92 kg
Ash Balance:

257
 Ash Out = Ash In = 0.46 kg
Soluble Lignin Balance:
Soluble Lignin Out = Soluble lignin In = 3.50 kg
Insoluble Lignin Balance:
Insoluble Lignin Out = 0.99 (Insoluble = 79.83
lignin In) kg
Water Balance
Water Out = 0.02 (Water In) = 2.13 kg

Nitrosobenzene Balance:
Nitrosobenzene Out = 0.99 (Nitrosobenzene In) = 223.92 kg

Syringaldehyde-Rich Layer Output Composition:

Component Amount Percentage
Vanillin 21.37 kg 1.04 %
Syringaldehyde 791.40 kg 38.67 %
p-Hydroxybenzaldehyde 212.17 kg 10.37 %
Nitrobenzene 651.89 kg 31.85 %
NaOH 159.67 kg 7.80 %
Na2SO4 0.06 kg 0.01 %
Cellulose 2.34 kg 0.11 %
Hemicellulose 1.08 kg 0.05 %
Extractives 0.92 kg 0.05 %
Ash 0.46 kg 0.02 %
Insoluble Lignin 79.83 kg 3.90 %
Soluble Lignin 3.50 kg 0.17 %
Water 2.13 kg 0.10 %
Nitrosobenzene 99.18 kg 4.85 %
TOTAL 2,046.71 kg 100.00%

258
Equipment Name: Vacuum Evaporator

Equipment Code: D-3

Vapor
Recovery System for
C4H10O (diethyl ether)

FROM F-4 TO J-2

D-3
VANILLIN – RICH LAYER CONCENTRATED
VANILLIN SOLUTION

SAT. STEAM CONDENSATE

MASS IN MASS OUT

VANILLIN-RICH LAYER CONCENTRATED VANILLIN

(From F-4) SOLUTION (To J-2)
Vanillin 512.78 kg Vanillin 512.78 kg
Syringaldehyde 7.99 kg Syringaldehyde 7.99 kg
p-Hydroxybenzaldehyde 2.14 kg p-Hydroxybenzaldehyde 2.14 kg
Nitrobenzene 6.58 kg Nitrobenzene 6.58 kg
NaOH 1.61 kg NaOH 1.61 kg
Water 210.96 kg Water 210.96 kg
Insoluble Lignin 0.81 kg Insoluble Lignin 0.81 kg
Diethyl ether 2,050.26 kg Diethyl ether 20.50 kg
Nitrosobenzene 1.00 kg Nitrosobenzene 1.00 kg
TOTAL MASS IN 2,794.13 kg Total 764.38 kg

VAPOR
Diethyl Ether 2,029.75 kg
Total 2,029.75 kg
TOTAL MASS OUT 2,029.75 kg

Vanillin-Rich Layer 2,794.13 kg Concentrated Vanillin 764.38 kg

(From F-4) Solution (To J-2)
Vapor 2,029.75 kg
TOTAL MASS IN 2,794.13 kg TOTAL MASS OUT 2,794.13 kg
Basis:

259
 Assumptions:

1. 96% of Vanillin produced.

2. 35% of water remained in Vanillin

Computations:

2,794.13 kg of Vanillin-Rich Layer to D-3

Vanillin-Rich Layer In:

 Vanillin 512.78 kg

 Syringaldehyde 7.99 kg

 p-Hydroxybenzaldehyde 2.14 kg

 Nitrobenzene 6.58 kg

 NaOH 1.61 kg

 Water 210.96 kg

 Insoluble Lignin 0.81 kg

 Diethyl Ether 2,050.26 kg

 Nitrosobenzene 1.00 kg

TOTAL 2,794.13 kg

Concentrated Vanillin Solution Stream:

Vanillin Balance:
Vanillin Out = Vanillin In = 512.78 kg
Syringaldehyde Balance:
Syringaldehyde Out = Syringaldehyde In = 7.99 kg

P-hydrobenzaldehyde Balance:
P-hydrobenzaldehyde Out = P-hydrobenzaldehyde In = 2.14 kg
Nitrobenzene Balance:
Nitrobenzene Out = Nitrobenzene In = 6.58 kg

260
 NaOH Balance:
NaOH Out = NaOH In = 1.61 kg
Insoluble Lignin Balance:
Insoluble Lignin Out = Insoluble lignin In = 0.81 kg
Water Balance:
Water Out = Water In = 210.96 kg
Diethyl ether Balance:
Diethyl ether Out = 0.01 (Diethyl ether In) = 20.50 kg

Nitrosobenzene Balance:
Nitrosobenzene Out = Nitrosobenzene In = 1.00 kg

Concentrated Vanillin Solution Mass Output Composition:

Component Amount Percentage

Vanillin 512.78 kg 67.08 %

Syringaldehyde 7.99 kg 1.05 %

P-hydrobenzaldehyde 2.14 kg 0.28 %

Nitrobenzene 6.58 kg 0.86 %

NaOH 1.61 kg 0.21 %

Water 210.96 kg 27.60 %

Insoluble Lignin 0.81 kg 0.11 %

Diethyl Ether 20.50 kg 2.68 %

Nitrosobenzene 1.00 kg 0.13 %

TOTAL 764.38 kg 100.00%

261
Vapor Composition:

Diethyl ether Balance:

Diethyl Ether In = Diethyl Ether (Vapor) + Diethyl Ether (Concentrated)

Diethyl Ether Out (Vapor) = 2,050.26 – 20.50 = 2,029.75 kg

Vapor Mass Output Composition:

Component Amount Percentage

Diethyl ether 2 029.75 kg 100.00 %

TOTAL 2 029.75 kg 100.00 %

262
Equipment Name: Cooling Crystallizer

Equipment Code: J-2

FROM D-3 TO K-4

CONCENTRATED VANILLIN VANILLIN MAGMA
SOLUTION J-2

Cooling Water

Water Cooling Water

MASS IN MASS OUT

CONCENTRATED VANILLIN VANILLIN MAGMA (To K-4)

SOLUTION (From D-3)
Vanillin 512.78 kg CRYSTAL
Syringaldehyde 7.99 kg Vanillin 510.78 kg
P-hydrobenzaldehyde 2.14 kg
Nitrobenzene 6.58 kg MOTHER LIQUOR
NaOH 1.61 kg Vanillin 2.00 kg
Water 210.96 kg Syringaldehyde 7.99 kg
Insoluble Lignin 0.81 kg P-hydrobenzaldehyde 2.14 kg
Diethyl Ether 20.50 kg Nitrobenzene 6.58 kg
Nitrosobenzene 1.00 kg NaOH 1.61 kg
Total 764.38 kg Water 210.96 kg
Insoluble Lignin 0.81 kg
TOTAL MASS IN 764.38 kg Diethyl Ether 20.50 kg
Nitrobenzene 1.00 kg
Total 253.60 kg
TOTAL MASS OUT 764.38 kg

Concentrated Vanillin 764.38 kg Vanillin Magma 764.38 kg

Solution (From D-3) (To K-4)
TOTAL MASS IN 764.38 kg TOTAL MASS OUT 764.38 kg

263
 Assumptions:

1. 2.5:100 mass to mass solubility ratio of vanillin to water.

Computations:

764.38 kg of Concentrated Vanillin Solution fed to J-2.

Liquid Mixture In:

 Vanillin = 512.78 kg

 Syringaldehyde = 7.99 kg

 P-hydrobenzaldehyde = 2.14 kg

 Nitrobenzene = 6.58 kg

 NaOH = 1.61 kg

 Water = 210.96 kg

 Insoluble Lignin = 0.81 kg

 Diethyl Ether = 20.50 kg

 Nitrosobenene = 1.00 kg

TOTAL = 764.38 kg

Overall Mass Balance:

720.68 = 𝐶 + 𝑀𝐿

Overall Solute Mass Balance:

𝟐. 𝟓
𝟓𝟏𝟐. 𝟕𝟖 = 𝑪 (𝟏) + 𝑴𝑳 ( )
𝟏𝟎𝟐. 𝟓

Vanillin Crystals = 510.78 kg

Mother Liquor = 253.60 kg

264
Total Mother Liquor = 220.96+7.99+2.14+6.58+1.61+0.81+20.50 = 253.60

Vanillin Magma Stream:

Vanillin Crystals = 510.78 kg

Mother Liquor:

Water Balance:
Water Out = Water In = 210.96 kg
Vanillin Balance:
Vanillin Out = Vanillin In – Vanillin crystals
Vanillin Out = 512.78 – 510.78 = 2.00 kg
Syringaldehyde Balance:
Syringaldehyde Out = Syringaldehyde In = 7.99 kg
P-hydrobenzaldehyde Balance:
P-hydrobenzaldehyde Out = P-hydrobenzaldehyde In = 2.14 kg
Nitrobenzene Balance:
Nitrobenzene Out = Nitrobenzene In = 6.58 kg
NaOH Balance:
NaOH Out = NaOH In = 1.61 kg
Insoluble Lignin Balance:
Insoluble Lignin Out = Insoluble lignin In = 0.81 kg
Diethyl ether Balance:
Diethyl ether Out = Diethyl ether In = 20.50 kg
Nitrosobenzene Balance:
Nitrosobenzene Out = Nitrosobenzene In = 1.00 kg

265
Vanillin Magma Output Composition:

Component Amount Percentage

Crystals

Vanillin 510.78 kg 100 %

Mother Liquor

Vanillin 2.78 kg 0.79 %

Syringaldehyde 7.99 kg 3.15 %

P-hydrobenzaldehyde 2.14 kg 0.85 %

Nitrobenzene 6.58 kg 2.60 %

NaOH 1.61 kg 0.64 %

Water 210.96 kg 83.19 %

Insoluble Lignin 0.81 kg 0.32 %

Diethyl Ether 20.50 kg 8.08 %

Nitrosobenzene 1.00 0.40 %

TOTAL 764.38 kg 100.00%

266
 Equipment Name: Centrifugal Filter

Equipment Code: K-4

FROM J-2
MOTHER LIQUOR
VANILLIN MAGMA To Wastewater Treatment System

K–4

TO D-4
WET VANILLIN CRYSTALS

VANILLIN MAGMA (From J-2) WET VANILLIN

CRYSTAL CRYSTAL (To D-
4)
Vanillin 510.78 kg Vanillin 510.52 kg
Mother Liquor 50.59 kg
MOTHER LIQUOR TOTAL 561.12 kg
Vanillin 2.00 kg
Syringaldehyde 7.90 kg MOTHER LIQOUR
P-hydrobenzaldehyde 2.14 kg Vanillin 1.60 kg
Nitrobenzene 6.58 kg Syringaldehyde 6.40 kg
NaOH 1.61 kg P- kg
hydrobenzaldehyde 1.71
Water 210.96 kg Nitrobenzene 5.27 kg
Insoluble Lignin 0.81 kg NaOH 1.29 kg
Diethyl Ether 20.50 kg Water 168.77 kg
Nitrosobenzene 1.00 kg Nitrosobenzene 0.80 kg
Total 253.60 kg Insoluble Lignin 0.65 kg
TOTAL MASS IN 764.38 kg Diethyl Ether 16.40 kg
TOTAL 202.88 kg
LOSSES 0.38 kg
TOTAL MASS 764.38 kg
OUT

Wet Vanillin Crystals (To D-4) 561.12 kg

Vanillin Magma 764.38 kg Mother Liquor 202.88 kg
Losses 0.38 kg
TOTAL MASS IN 764.38 kg TOTAL MASS OUT 764.38 kg

267
 Assumptions:

1. 15% of mother liquor will remain in the crystals.

2. According to Coulson and Richardson: “0.05% mass loss due to adhesion in the
equipment”

Computations:

Basis: 764.38 kg of Vanillin Magma fed to K-4

Magma In:

Crystals

 Vanillin = 510.78 kg

Mother Liquor =

 Vanillin = 2.00 kg

 Syringaldehyde = 7.99 kg

 P-hydrobenzaldehyde = 2.14 kg

 Nitrobenzene = 6.58 kg

 NaOH = 1.61 kg

 Water = 210.96 kg

 Insoluble Lignin = 0.81 kg

 Diethyl Ether = 20.50 kg

 Nitrosobenzene = 1.00 kg

TOTAL = 764.38 kg

268
Mother Liquor Stream:

Water Balance:
Water Out = 0.85 (Water In) = 168.77 kg
Vanillin Balance:
Vanillin Out = 0.85 (Vanillin In – Vanillin crystals)
Vanillin Out = 0.85 (507.59– 502.02) =1.60 kg
Syringaldehyde Balance:
Syringaldehyde Out = 0.85(Syringaldehyde In) = 6.40 kg
P-hydrobenzaldehyde Balance:
P-hydrobenzaldehyde Out = 0.85(P-hydrobenzaldehyde In) = 1.71 kg
Nitrobenzene Balance:
Nitrobenzene Out = 0.85 (Nitrobenzene In) = 5.27 kg
NaOH Balance:
NaOH Out = 0.85(NaOH In) = 1.29 kg
Insoluble Lignin Balance:
Insoluble Lignin Out = 0.85(Insoluble lignin In) = 0.65 kg
Diethyl ether Balance:
Diethyl ether Out = 0.85(Diethyl ether In) = 16.40 kg
Nitrosobenzene Balance:
Nitrosobenzene Out = 0.85 (Nitrosobenzene In) = 0.80 kg

Total Mother Liquor = 202.88 kg

Mother Liquor Output Composition:

Component Amount Percentage

Vanillin 1.60 kg 0.79 %
Syringaldehyde 6.40 kg 3.15 %
P-hydrobenzaldehyde 1.71 kg 0.85 %
Nitrobenzene 5.27 kg 2.60 %
NaOH 1.29 kg 0.64 %
Water 168.77 kg 83.19 %
Insoluble Lignin 0.65 kg 0.32 %
Diethyl Ether 16.40 kg 8.08 %
Nitrosobenzene 0.80 kg 0.40 %
TOTAL 202.88 kg 100.00%

269
Wet Vanillin Crystals Composition:

Vanillin Balance:
Vanillin Out = 0.9995 (Vanillin In) = 510.52 kg
Mother Liquor Balance:
𝟎. 𝟏𝟒𝟗𝟓
𝑴𝒐𝒕𝒉𝒆𝒓 𝑳𝒊𝒒𝒖𝒐𝒓 𝑶𝒖𝒕 = 𝟐𝟓𝟑. 𝟔𝟎 × = 𝟓𝟎. 𝟓𝟗 𝒌𝒈
𝟎. 𝟖𝟓

Wet Vanillin Crystals Output Composition:

Component Amount Percentage

Vanillin 510.52 kg 90.98 %

Mother Liquor 50.59 kg 9.02 %

TOTAL 561.12 kg 100.00%

Losses Stream:

0.0005
𝐿𝑜𝑠𝑠𝑒𝑠 = 𝑊𝑒𝑡 𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝐶𝑟𝑦𝑠𝑡𝑎𝑙𝑠 ×
0.9995

0.0005
𝑳𝒐𝒔𝒔𝒆𝒔 = 579.67 × = 𝟎. 𝟑𝟖 𝒌𝒈
0.9995

270
Equipment Name: Rotary Dryer

Equipment Code: D-4

Vapor Out
H2O with impurities, Air
To recovery system

Hot Air
FROM K-4 Air
D-4 RH (78%)
WET VANILLIN
CRYSTALS
TO D-5
DRIED VANILLIN
CRYSTALS

MASS IN MASS OUT

WET VANILLIN CRYSTALS DRIED VANILLIN CRYSTALS

(From K-4) (To D-5)
Vanillin 510.52 kg Vanillin 510.52 kg
Impurities 50.59 kg Impurities 10.42 kg
(Mother Liquor)
Total 561.12 kg Total 520.94 kg

TOTAL MASS IN 561.12 kg VAPOR OUT

H2O 40.17 kg
Total 40.17 kg

TOTAL MASS OUT 561.12 kg

Wet Vanillin Crystal 561.12 kg Dried Vanillin Crystals 520.94 kg

(From K-4) (To D-5)
Vapor Out 40.17 kg
TOTAL MASS IN 561.12 kg TOTAL MASS OUT 561.12 kg

271
 Assumptions:

1. 98% of Vanillin Produced

Computations:

Basis: 561.12 kg wet vanillin crystals fed to D-4

Crystal In:

 Vanillin = 510.52 kg

 Impurities = 50.59 kg

TOTAL = 561.12 kg

Dried Vanillin Crystals Stream:

Vanillin Balance:
502.02 (0.8753) = Dried Vanillin Crystals (0.98)
Dried Vanillin Crystals= 561.12 kg
Vanillin Out = Vanillin In = 510.52

Dried Vanillin Crystal Stream Balance:

Impurities = Dried Vanillin Crystals – Vanillin Crystals

Impurities = 561.12 – 510.52 = 50.59 kg

Dried Vanillin Crystals Mass Output Composition:

Component Amount Percentage

Vanillin 510.52 kg 98.00 %

Impurities 10.42 kg 2.00 %

TOTAL 520.94 kg 100.00%

272
Vapor Composition:

Impurities Balance:
Impurities In = Impurities (Dried Vanillin Crystals) + Impurities Out

Impurities In = 50.59 – 10.42 = 40.17 kg

Vapor Output Composition:

Component Amount Percentage

Impurities 40.17 kg 100.00 %

TOTAL 40.17 kg 100.00%

273
Equipment Name: Cooler

Equipment Code: D-5

Water

FROM D-4 TO K-5

DRIED VANILLIN D-5 COOLED VANILLIN
CRYSTALS CRYSTALS

Water

MASS IN MASS OUT

DRIED VANILLIN CRYSTALS COOLED VANILLIN CRYSTALS

(From D-4) (TO K-5)
Vanillin 510.52 kg Vanillin 510.52 kg
Impurities 10.42 kg Impurities 10.42 kg
Total 512.27 kg Total 512.27 kg

TOTAL MASS IN 520.94 kg TOTAL MASS OUT 520.94 kg

Dried Vanillin Crystals 520.94 kg Cooled Vanillin Crystals 520.94 kg

(From D-4) (To K-5)
TOTAL MASS IN 520.94 kg TOTAL MASS OUT 520.94 kg

274
 Assumptions:

1. No losses during cooling

Basis: 520.94 kg Dried vanillin crystals fed to D-5

Computations:

Dried Vanillin Crystals In:

 Vanillin = 510.52 kg

 Impurities = 10.42 kg

TOTAL = 520.94 kg

Cooled Vanillin Crystals Composition:

Impurities Balance:
Impurities Out = Impurities In = 10.42 kg
Vanillin Balance:
Vanillin Out = Vanillin In = 510.52 kg

Cooled Vanillin Crystals Output Composition:

Component Amount Percentage

Vanillin 510.52 kg 98.00 %

Impurities 10.42 kg 2.00 %

TOTAL 520.94 kg 100.00%

275
Equipment Name: Ball mill and Screener

Equipment Code: K-5 & K-6

RECYCLED VANILLIN
CRYSTALS
Average size: > 53 microns

FROM D-5 TO K-6 TO F-6

COOLED VANILLIN K-5 K-6
MILLED VANILLIN VANILLIN CRYSTALS
CRYSTALS CRYSTALS Average size: 53 microns

Average size: 53 microns

MASS IN MASS OUT

COOLED VANILLIN CRYSTALS VANILLIN CRYSTALS (To F-5)

(From D-5)
Vanillin 510.52 kg Vanillin 510.52 kg
Impurities 10.42 kg Impurities 10.42 kg
Total 520.94 kg Total 520.94 kg

TOTAL MASS IN 520.94 kg TOTAL MASS OUT 520.94 kg

Cooled Vanillin Crystals 520.94 kg Vanillin Crystals(To F-6) 510.27 kg

(From D-5)
Losses 0.26 kg
TOTAL MASS IN 520.94 kg TOTAL MASS OUT 520.94 kg

276
 Assumptions:

1. All products has an average size of Mesh 4 or 5 mm

2. The recycle stream is 10% of the feed to the screener

Basis:
520.94 kg Cooled vanillin crystals fed to K-5

Computations:

Cooled Vanillin Crystals In:

 Vanillin = 510.27 kg

 Water = 10.41 kg

TOTAL = 510.27 kg

Vanillin Crystals Composition:

Impurities Balance:
Impurities Out = 0.9995(Impurities In) = 10.41 kg
Vanillin Balance
Vanillin Out = 0.9995 (Vanillin In) = 510.27 kg

Vanillin Crystals Output Composition:

Component Amount Percentage

Vanillin 510.27 kg 98.00 %

Impurities 10.41 kg 2.00 %

TOTAL 512.01 kg 100.00%

277
Screened and Ground Vanillin = 510.27 kg
Recycle Stream = 10.00% of Screened and Ground Vanillin
Recycle Stream = 0.10(510.27 kg) = 51.027 kg
Screened and Ground Vanillin = Ground Vanillin − Recycle
Screened and Ground Vanillin = 510.27 kg − 51.027 kg = 459.243 kg
After the Iteration
GRINDER SCREENER
Vanillin Recycle Feed K-5 Output Ground Screened
RUN Feed (kg) (kg) (kg) K-5 (kg) Vanillin and
(kg) Ground
Vanillin
(kg)
1 510.27 0 510.27 510.27 510.27 459.243
2 510.27 51.027 561.297 561.297 561.297 505.167
3 510.27 56.130 566.400 566.400 566.400 509.760
4 510.27 56.640 566.910 566.910 566.910 510.270
5 𝟓𝟏𝟎. 𝟐𝟕 56.640 566.910 566.910 566.910 510.270
6 510.27 56.640 566.910 566.910 566.910 510.270
7 510.27 56.640 566.910 566.910 566.910 510.270
8 510.27 56.640 566.910 566.910 566.910 510.270
9 510.27 56.640 566.910 566.910 566.910 510.270

𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑅𝑒𝑐𝑦𝑐𝑙𝑒 𝑓𝑟𝑜𝑚 𝑆𝑐𝑟𝑒𝑒𝑛𝑒𝑟 = 56.07 𝑘𝑔

Losses Stream:

0.0005
𝐿𝑜𝑠𝑠𝑒𝑠 = 𝐷𝑟𝑖𝑒𝑑 𝑉𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝐶𝑟𝑦𝑠𝑡𝑎𝑙𝑠 ×
0.9995

0.0005
𝑳𝒐𝒔𝒔𝒆𝒔 = 512.01 × = 𝟎. 𝟐𝟔 𝒌𝒈
0.9995

278
Equipment Name: Storage Tank

Equipment Code: F-5

FROM K-6
Average size: 53 microns VANILLIN
STORAGE TANK
VANILLIN CRYSTALS
F-6

MASS IN

VANILLIN CRYSTALS (From K-6)

Vanillin 510.27 kg
Impurities 10.41 kg
TOTAL 520.68 kg

Vanillin Crystals 520.68 kg

TOTAL MASS IN 520.68 kg

279
 Assumptions:

1. No change in feed composition upon storage.

Computations:

Basis: 520.68 kg of Vanillin Crystals fed to F-5.

Vanillin Crystals In:

 Vanillin = 510.27 kg

 Water = 10.41 kg

TOTAL = 520.68 kg

Vanillin Crystals Composition:

Impurities Balance:
Impurities Out = Impurities In
Impurities Out = 10.41 kg
Vanillin Balance:
Vanillin Out = Vanillin In
Vanillin Out = 510.27 kg

Final Vanillin Crystals Composition:

Component Amount Percentage

Vanillin 510.27 kg 98.00 %

Impurities 10.41 kg 2.00 %

TOTAL 520.68 kg 100.00%

280
VI. DETAILED ENERGY BALANCE

Equipment Name: Mixing Tank

Equipment Code: F – 2

NaOH Solution
T = 25°C
Total Mass = 2,207.64 kg

FROM K-1 TO D-1

Milled Rambutan Peel Rambutan Peel Fiber
Fiber F–2 Solution
T = 25°C T = 75°C
Total Mass = 4,245.46 kg Q = 1,419,191.22 KJ Total Mass = 6,453.09 kg

STEAM IN = 524.06 kg STEAM OUT = 524.06 kg

T = 116.9°C; P = 180 kPa T = 116.9°C; P = 180 kPa

Milled Rambutan Peel 4,245.46 kg Rambutan Peel Fiber 6,453.09 kg

Fiber (From K-1) Solution (To D-1)
NaOH Solution 2,207.64 kg
TOTAL MASS IN 6,453.09 kg TOTAL MASS OUT 6,453.09 kg

281
Assumptions:

1. The milled Rambutan peels and supplied NaOH Solution enters the tank at a
temperature of 25°C.
2. The extracted Rambutan peels leave at 75°C.
3. Steam at 180 kPa is used to maintain the temperature of the tank at 75°C.
4. Steam enters as saturated vapor and condensate leaves as saturated liquid.
Detailed Computations:

Equations:

𝑄𝑡𝑜𝑡𝑎𝑙 = ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡(25−75)℃ + ∆𝐻𝑑𝑖𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑁𝑎𝑂𝐻 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟 + ∆𝐻𝑟𝑥𝑛@25

𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑄𝑠𝑡𝑒𝑎𝑚
𝑄𝑠𝑡𝑒𝑎𝑚 = 𝑚𝑠𝑡𝑒𝑎𝑚 𝜆𝑠𝑡𝑒𝑎𝑚

Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [1793.82 kg lignin (1.23 ) (75 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1164.86 kg cellulose (1.55 ) (75 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [557.48 kg hemicellulose (1.31 ) (75 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [474.96 kg extractives (1.08 ) (75 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [236.52 kg ash (0.84 ) (75 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [17.81 kg moisture (4.18 ) (75 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [88.31 kg NaOH (3.93 ) (75 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [2119.33 kg water (4.18 ) (75 − 25)℃]
𝑘𝑔 − ℃
= 736,798.6 kJ

282
Heat of dissolution of NaOH in water:
𝑘𝐽 𝑘𝑚𝑜𝑙 1000𝑚𝑜𝑙
∆𝐻𝑑𝑖𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = (88.31 kg NaOH) (−44.51 )( )( )
𝑚𝑜𝑙 40 𝑘𝑔 𝑘𝑚𝑜𝑙
∆𝑯𝒅𝒊𝒔𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 = 𝟒𝟔𝟎 𝟐𝟗𝟐. 𝟒𝟒 𝒌𝑱

Heat of reaction:

∆𝐻𝑟𝑥𝑛@25℃ = 𝑚∆𝐻𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑚∆𝐻𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

𝑘𝐽
∆𝐻𝑟𝑥𝑛@25℃ = 33.18 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 (−15,877.78 )
𝑘𝑔
𝑘𝐽
+ 1,256.86 𝑘𝑔 alkali cellulose (−998.5 )
𝑘𝑔
𝑘𝐽
− [8.79 𝑘𝑔 𝑁𝑎𝑂𝐻 (−11,728.75 )
𝑘𝑔
𝑘𝐽
+ 1,164.86 𝑘𝑔 cellulose (−1421.0 )]
𝑘𝑔
∆𝑯𝒓𝒙𝒏@𝟐𝟓℃ = 𝟕𝟖𝟎, 𝟔𝟓𝟒. 𝟓𝟑 𝒌𝑱

𝑄𝑡𝑜𝑡𝑎𝑙 = 736,798.65 kJ + 460 292.44 kJ + 780 654.53 kJ

𝑸𝒕𝒐𝒕𝒂𝒍 = 𝟏, 𝟒𝟏𝟗, 𝟏𝟗𝟏. 𝟐𝟐 𝒌𝑱

Solving for steam requirement:

𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑄𝑠𝑡𝑒𝑎𝑚
𝑄𝑠𝑡𝑒𝑎𝑚 = 𝑚𝑠𝑡𝑒𝑎𝑚 𝜆𝑠𝑡𝑒𝑎𝑚
𝜆𝑠𝑡𝑒𝑎𝑚 @180𝑘𝑃𝑎 = 2708.05 𝑘𝐽/𝑘𝑔
1 419 191.22 𝐾𝐽
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚 =
2708.05 𝑘𝐽/𝑘𝑔

Mass of steam = 524.06 kg

283
Equipment Name: Cooler

Equipment Code: D – 1

FROM F-2 TO K-2

Rambutan Peel Fiber Cooled Rambutan Peel
Solution D–1 Fiber Solution
T = 75°C T = 25°C
Total Mass = 6,453.09 kg Q = -732,518.74 KJ Total Mass = 6,453.09 kg

WATER COOLING WATER COOLING

OUT = 5,841.46 kg IN = 5,841.46 kg
T = 50°C T = 20°C

Rambutan Peel 6,453.09 kg Cooled Rambutan Peel 6,453.09 kg

Fiber Solution Fiber Solution (To K-2)
(From F-2)
TOTAL MASS IN 6,453.09 kg TOTAL MASS OUT 6,453.09 kg

284
Assumptions:

1. The rambutan peel fiber solution enters the cooler at a temperature of 75°C.

2. The cooled mixture leaves at 25°C.

3. Cooling water at 20°C is used to cool the mixture.

4. The cooling water leaves at 50°C.

Detailed Computations:

Equations:

𝑄𝑡𝑜𝑡𝑎𝑙 = ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡(75−25)℃

𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑃𝑒𝑒𝑙 𝐹𝑖𝑏𝑒𝑟 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

(𝑚𝐶𝑝𝑑𝑇)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 = −(𝑚𝐶𝑝𝑑𝑇)𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑃𝑒𝑒𝑙 𝐹𝑖𝑏𝑒𝑟 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [1793.82 kg lignin (1.23 ) (25 − 75)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1164.86 kg cellulose (1.55 ) (25 − 75)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [557.48 kg hemicellulose (1.31 ) (25 − 75)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [474.96 kg extractives (1.08 ) (25 − 75)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [236.52 kg ash (0.84 ) (25 − 75)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [17.81 kg moisture (4.18 ) (25 − 75)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [88.31 kg NaOH (3.93 ) (25 − 75)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [2119.33 kg water (4.18 ) (25 − 75)℃]
𝑘𝑔 − ℃
= -732,518.74 kJ

285
Solving for cooling water requirement:
𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑃𝑒𝑒𝑙 𝐹𝑖𝑏𝑒𝑟 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝐾𝐽
−(−736,798.6 7 )𝐾𝐽 = 𝑚 (4.18 ) (50 − 20)℃
𝐾𝑔 − ℃

732,518.74 𝑘𝐽
𝑚=
𝐾𝐽
(4.18 )
𝐾𝑔 − ℃ (50 − 20)℃

Mass of cooling water = 5,841.46 kg

286
Equipment Name: Acidification Tank

Equipment Code: F – 3

H2SO4 Solution
T = 25°C
Total Mass = 15.24 kg

TO K-3
FROM K-2 Acidified Lignin
Wet Sludge Fiber F–3 Solution
T = 25°C T = 30°C
Total Mass = 2,256.52 kg Q = -4,939.22 kJ Total Mass = 2,271.77 kg

WATER COOLING WATER COOLING

IN = 118.16 kg OUT = 118.16 kg
T = 20°C T = 50°C

Wet Sludge Fiber 2,256.52 kg Acidified Lignin Solution 2,271.7\ kg

(From K-2) (To K-3)
H2SO4 Solution 15.24 kg
TOTAL MASS IN 2,271.77 kg TOTAL MASS OUT 2,271.77 kg

287
Assumptions:

1. Cooling water will enter at 20°C and leave at 30°C.

2. The acidified lignin solution will be maintained at 30°C.

Detailed Computations:

Equations:

𝑄𝑡𝑜𝑡𝑎𝑙 = ∆𝐻𝑎𝑐𝑖𝑑𝑖𝑓𝑖𝑒𝑑 𝑙𝑖𝑔𝑛𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(25−30)℃ + ∆𝐻𝑟𝑥𝑛@25℃ + ∆𝐻𝑑𝑖𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑄𝑡𝑜𝑡𝑎𝑙 = −𝑄𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟

𝑄𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = (𝑚𝐶𝑝𝑑𝑇)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟

Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [1613.63 kg insoluble lignin (1.23 ) (30 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [119.82 kg cellulose (1.55 ) (30 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [55.47 kg hemicellulose (1.31 ) (30 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [47.26 kg extractives (1.08 ) (30 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [23.53 kg ash (0.84 ) (30 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [220.87 kg water (4.18 ) (30 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [8.93 kg 𝐻2 𝑆𝑂4 (1.34 ) (30 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [2.97 kg 𝑁𝑎2 𝑆𝑂4 (0.90 ) (30 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [179.29 kg soluble lignin (1.10 ) (30 − 25)℃]
𝑘𝑔 − ℃
= 𝟏𝟕, 𝟐𝟒𝟔. 𝟎𝟗 𝐤𝐉

288
Heat of reaction:

∆𝐻𝑟𝑥𝑛@25℃ = 𝑚∆𝐻𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑚∆𝐻𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

𝑘𝐽 𝑘𝐽
∆𝐻𝑟𝑥𝑛@25℃ = 0.75 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 (−15,877.78 ) + 2.97 𝑘𝑔 𝑁𝑎2 𝑆𝑂4 (−9,750 )
𝑘𝑔 𝑘𝑔
𝑘𝐽
− [1.67 𝑘𝑔 𝑁𝑎𝑂𝐻 (−11,728.75 )
𝑘𝑔
𝑘𝐽
+ 2.05 𝑘𝑔 𝐻2 𝑆𝑂4 (−8,306.12 )]
𝑘𝑔
∆𝑯𝒓𝒙𝒏@𝟐𝟓℃ = −𝟒 𝟐𝟕𝟐. 𝟏𝟔 𝒌𝑱

Heat of dissolution of H2SO4 in water:

𝑘𝐽 𝑘𝑚𝑜𝑙 1000𝑚𝑜𝑙
∆𝐻𝑑𝑖𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = (10.97 kg 𝐻2 𝑆𝑂4) (−71.76 )( )( )
𝑚𝑜𝑙 98 𝑘𝑔 𝑘𝑚𝑜𝑙
∆𝑯𝒅𝒊𝒔𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 = −𝟖 𝟎𝟑𝟒. 𝟕𝟏 𝒌𝑱

𝑄𝑡𝑜𝑡𝑎𝑙 = 17,246.09 kJ + (−4 272.16 𝑘𝐽) + (−8 034.71 𝑘𝐽)

𝑸𝒕𝒐𝒕𝒂𝒍 = −𝟒, 𝟗𝟑𝟗. 𝟐𝟐 𝒌𝑱

Cooling water requirement:

𝑄𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −(−11,936.64 𝑘𝐽)
4 939.22 𝑘𝐽
𝑚𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 =
𝐾𝐽
4.18 𝑘𝑔 − 𝐾 (30 − 20)𝐾

𝒎𝒄𝒐𝒐𝒍𝒊𝒏𝒈 𝒘𝒂𝒕𝒆𝒓 = 𝟏𝟏𝟖. 𝟏𝟔𝒌𝒈

289
Equipment Name: Autoclave Reactor

Equipment Code: J – 1

NaOH Solution Nitrobenzene Solution

T = 25°C T = 25°C
Total Mass = 322.56 kg Total Mass = 781.90 kg

FROM K-3 TO D-2

Lignin J–1 Crude Vanillin Solution
T = 25°C T = 170°C
Total Mass = 1,665.42 kg Q = 2,719,995.26 KJ Total Mass = 2,769.88 kg

STEAM IN = 976.58 kg STEAM IN = 976.58 kg

T = 186.85°C; P = 1,170 kPa T = 186.85°C; P = 1,170 kPa

Lignin (from K-3) 1,665.42 kg

NaOH 322.57 kg Crude Vanillin Solution 2,769.88 kg
Nitrobenzene 781.90 kg (To D-2)
TOTAL MASS IN 2,769.88 kg TOTAL MASS OUT 2,769.88 kg

290
Assumptions:

1. The lignin stream enters the tank at a temperature of 25°C.

2. The supplied NaOH solution and Nitrobenzene enters the tank at 25°C.

3. The reaction temperature is at 170°C.

4. Steam at 1,170 kPa and 460K is used to maintain the temperature of the tank at

170°C.

5. Steam enters as saturated vapor and leaves as saturated liquid.

Detailed Computations:

Equations:

𝑄𝑡𝑜𝑡𝑎𝑙 = ∆𝐻𝑐𝑟𝑢𝑑𝑒 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(25−170)℃ + ∆𝐻𝑚𝑎𝑖𝑛 𝑟𝑥𝑛@25℃ + ∆𝐻𝑠𝑖𝑑𝑒 𝑟𝑥𝑛@25℃

Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [5344 kg vanillin (1.24 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [799.40 kg syringaldehyde (1.25 ) (170 − 25)℃]
𝑘𝑔 − ℃
+ [214.31 kg p
𝑘𝐽
− hydroxybenzaldehyde (1.22 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [658.48 kg nitrobenzene (1.19 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [100.18 kg nitrosobenzene (1.09 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [161.28 kg NaOH (3.93 ) (170 − 25)℃]
𝑘𝑔 − ℃

291
 𝑘𝐽
+ [213.09 kg water (4.18 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [2.26 kg cellulose (1.55 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.08 kg hemicellulose (1.31 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.92 kg extractives (1.08 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.46 kg ash (0.84 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.30 kg 𝑁𝑎2 𝑆𝑂4 (0.90 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [3.50 kg soluble lignin (1.10 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [80.64 kg insoluble lignin (1.23 ) (170 − 25)℃]
𝑘𝑔 − ℃
= 𝟔𝟑𝟏, 𝟑𝟎𝟖. 𝟏𝟕 𝐤𝐉
Heat of reaction at 25℃:
∆𝐻𝑟𝑥𝑛@25℃ = 𝑚∆𝐻𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑚∆𝐻𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
𝑘𝐽
∆𝐻𝑟𝑥𝑛@25℃ = [534.14 𝑘𝑔 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 (−3050.00 )
𝑘𝑔
𝑘𝐽
+ 799.40 𝑘𝑔 syringaldehyde (−1953.46 )
𝑘𝑔
𝑘𝐽
+ 214.31 𝑘𝑔 𝑝ℎ𝑦𝑑𝑟𝑜𝑥𝑦𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 (−1753.77 )
𝑘𝑔
𝑘𝐽
+ 100.18 𝑘𝑔 𝑛𝑖𝑡𝑟𝑜𝑠𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 (−1851.21 )]
𝑘𝑔
𝑘𝐽
− 1532.19 𝑘𝑔 𝑙𝑖𝑔𝑛𝑖𝑛 (−3667.42 )
𝑘𝑔
𝑘𝐽
− 123.11 𝑘𝑔 𝑛𝑖𝑡𝑟𝑜𝑏𝑒𝑛𝑧𝑒𝑛𝑒 (−449.39 )
𝑘𝑔

∆𝑯𝒓𝒙𝒏@𝟐𝟓℃ = 𝟐, 𝟎𝟖𝟖, 𝟔𝟖𝟕. 𝟎𝟗 𝒌𝑱

292
 𝑄𝑡𝑜𝑡𝑎𝑙 = ( 646,552.16 kJ) + (1,651,256.42 𝑘𝐽)
𝑸𝒕𝒐𝒕𝒂𝒍 = 𝟐, 𝟕𝟏𝟗, 𝟗𝟗𝟓. 𝟐𝟔 𝒌𝑱
*System is endothermic

Solving for steam requirement:

𝑄𝑠𝑡𝑒𝑎𝑚 = 𝑚𝑠𝑡𝑒𝑎𝑚 𝜆𝑠𝑡𝑒𝑎𝑚
𝜆𝑠𝑡𝑒𝑎𝑚 @932𝑘𝑃𝑎 = 2782.73 𝑘𝐽/𝑘𝑔ca
2 719 995.26 𝒌𝐽
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚 =
2785.22 𝑘𝐽/𝑘𝑔
Mass of steam = 976.58 kg

293
Equipment Name: Cooler

Equipment Code: D – 2

TO F-4
FROM J-1
Cooled Crude Vanillin
Crude Vanillin Solution
D–2 Solution
T = 170°C
T = 25°C
Total Mass = 2,769.88 kg
Q = -630,044.81 KJ Total Mass = 2,769.88 kg

WATER COOLING WATER COOLING

OUT = 5,024.28 kg IN = 5,024.28 kg
T = 50°C T = 20°C

Crude Vanillin Solution 2,769.88 kg Cooled Crude 2,769.88 kg

(From J-1) Vanillin Solution
(To F-4)
TOTAL MASS IN 2,769.88 kg TOTAL MASS 2,769.88 kg
OUT

294
Assumptions:

1. The crude vanillin solution enters the cooler at a temperature of 170°C.

2. The cooled mixture leaves at 25°C.

3. Cooling water at 20°C is used to cool the mixture.

4. The cooling water leaves at 50°C.

Equations:

𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑐𝑟𝑢𝑑𝑒 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑆𝑜𝑙𝑢𝑡𝑖𝑛

(𝑚𝐶𝑝𝑑𝑇)𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −(𝑚𝐶𝑝𝑑𝑇)𝑐𝑟𝑢𝑑𝑒 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [534.14 kg vanillin (1.24 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [799.40 kg syringaldehyde (1.25 ) (25 − 170)℃]
𝑘𝑔 − ℃
+ [214.31 kg p
𝑘𝐽
− hydroxybenzaldehyde (1.22 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [658.48 kg nitrobenzene (1.19 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [100.18 kg nitrosobenzene (1.09 ) (170 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [161.28 kg NaOH (3.93 ) (25 − 170)℃]
𝑘𝑔 − ℃

295
 𝑘𝐽
+ [213.09 kg water (4.18 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [2.26 kg cellulose (1.55 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.08 kg hemicellulose (1.31 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.92 kg extractives (1.08 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.46 kg ash (0.84 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.30 kg 𝑁𝑎2 𝑆𝑂4 (0.90 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [3.50 kg soluble lignin (1.10 ) (25 − 170)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [80.64 kg insoluble lignin (1.23 ) (25 − 170)℃]
𝑘𝑔 − ℃
= −𝟔𝟑𝟎, 𝟎𝟒𝟒. 𝟖𝟏 𝐉

Solving for cooling water requirement:

𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑅𝑎𝑚𝑏𝑢𝑡𝑎𝑛 𝑃𝑒𝑒𝑙 𝐹𝑖𝑏𝑒𝑟 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝐾𝐽
−(− 646,552.16 )𝐾𝐽 = 𝑚 (4.18 ) (50 − 20)℃
𝐾𝑔 − ℃

661,152.76 𝑘𝐽
𝑚=
𝐾𝐽
(4.18 )
𝐾𝑔 − ℃ (50 − 20)℃

Mass of cooling water = 5,024.28 kg

296
Equipment Name: Vacuum Evaporator

Equipment Code: D – 3

Vapor
(T = 28.47°C)
Total Mass = 2,029.75 kg

FROM F-4 TO J-2

D–3 Concentrated Vanillin
Vanillin Rich Layer
Solution
T = 25°C
Q = 768,741.35 KJ T = 28.93°C
Total Mass = 2,794.13 kg
Total Mass = 764.38 kg
P = 0.8 atm

STEAM IN = 297.05 kg STEAM OUT = 297.05 kg

T = 46.85°C; P = 10.55 kPa T = 46.85°C; P = 10.55 kPa

Vanillin-Rich Layer 2,794.13 kg Concentrated Vanillin 764.38 Kg

(From F-4) Solution (To J-2)
Vapor 2,029.75 Kg
TOTAL MASS IN 2,794.13 kg TOTAL MASS OUT 2,794.13 Kg

297
Assumptions:

1. The vanillin-rich extract enters the tank at a temperature of 25°C.

2. The vanillin-rich liquid leaves at 60°C.

3. Steam at 10.55 kPa is used.

4. Steam enters as saturated vapor and leaves as saturated liquid.

Detailed Computations:

Operating conditions:

For diethyl ether:

760 𝑚𝑚𝐻𝑔
𝑃 = 0.8𝑎𝑡𝑚 𝑥 = 608 𝑚𝑚𝐻𝑔
1 𝑎𝑡𝑚
1071.54
𝑙𝑜𝑔 (𝑃) = 6.96559 −
227.774 + 𝑇
1071.54
𝑙𝑜𝑔 (608) = 6.96559 −
227.774 + 𝑇
𝑻 = 𝟐𝟖. 𝟒𝟕𝒐 𝑪

Boiling point elevation:

∆𝑇𝑏 = 𝐾𝑏 𝑚 ;

𝐾𝑏 = 𝑒𝑏𝑢𝑙𝑙𝑖𝑜𝑠𝑐𝑜𝑝𝑖𝑐 (𝑏𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 𝑒𝑙𝑒𝑣𝑎𝑡𝑖𝑜𝑛) 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑜𝑓𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛

𝑚 = 𝑚𝑜𝑙𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

0.304 𝑘𝑔 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 ℃ 507.59 𝑘𝑔 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 1 𝑚𝑜𝑙

∆𝑇𝑏 = ( )( ) (1000 )
𝑚𝑜𝑙 𝑘𝑔 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 2212.11 𝑘𝑔 𝑑𝑖𝑒𝑡ℎ𝑦𝑙 𝑒𝑡ℎ𝑒𝑟 𝑘𝑔𝑚𝑜𝑙
152.17 𝑘𝑔𝑚𝑜𝑙 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛

∆𝑇𝑏 = 0.46 ℃

𝑇𝑠𝑜𝑙𝑛 = 28.47℃ + 0.46℃

𝑻𝒔𝒐𝒍𝒏 = 𝟐𝟖. 𝟗𝟑℃

298
Equations:

(∆𝐻)𝑒𝑥𝑡𝑟𝑎𝑐𝑡 + 𝑚𝑣 𝐻𝑣 = 𝑄𝑇𝑜𝑡𝑎𝑙

𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑚𝑠𝑡𝑒𝑎𝑚 𝜆𝑠𝑡𝑒𝑎𝑚

Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [512.78 kg vanillin (1.24 ) (28.93 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [7.99 kg syringaldehyde (1.25 ) (28.93 − 25)℃]
𝑘𝑔 − ℃
+ [2.14 kg p
𝑘𝐽
− hydroxybenzaldehyde (1.22 ) (28.93 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [6.58 kg nitrobenzene (1.19 ) (28.93 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.00 kg nitrosobenzene (1.09 ) (28.93 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.61 kg NaOH (3.93 ) (28.93 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [210.96 kg water (4.18 ) (28.93 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.81 kg insoluble lignin (1.23 ) (28.93 − 25)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [2 050.26 kg diethyl ether (5.50 ) (28.93 − 25)℃]
𝑘𝑔 − ℃

= 𝟓𝟎, 𝟗𝟏𝟗. 𝟑𝟖 𝒌𝑱

Heat of Vaporization:

∆𝐻𝑣𝑎𝑝 = 𝑚𝑣 𝐻𝑣
𝑘𝐽
∆𝐻𝑣𝑎𝑝 = [(2 029.75 𝑘𝑔 𝑑𝑖𝑒𝑡ℎ𝑦𝑙 𝑒𝑡ℎ𝑒𝑟) (353.65 )]
𝑘𝑔

∆𝑯𝒗𝒂𝒑 = 𝟕𝟏𝟕 𝟖𝟐𝟏. 𝟗𝟕 𝒌𝑱

299
 𝑄𝑡𝑜𝑡𝑎𝑙 = (∑ 𝑚𝐶𝑝𝑑𝑇)𝑒𝑥𝑡𝑟𝑎𝑐𝑡 + 𝑚𝑣𝑎𝑝𝑜𝑟 𝜆𝑣𝑎𝑝𝑜𝑟
𝑄𝑡𝑜𝑡𝑎𝑙 = 53,904.31 kJ + 774,491.15 kJ
𝑸𝒕𝒐𝒕𝒂𝒍 = 𝟕𝟔𝟖, 𝟕𝟒𝟏. 𝟑𝟓 𝑱

Solving for steam requirement:

𝑄𝑠𝑡𝑒𝑎𝑚 = 𝑚𝑠𝑡𝑒𝑎𝑚 𝜆𝑠𝑡𝑒𝑎𝑚
𝜆𝑠𝑡𝑒𝑎𝑚 @180 𝑘𝑃𝑎 = 2708.05 𝑘𝐽/𝑘𝑔
768 741.35 𝑘𝐽
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚 =
2,587.89 𝑘𝐽/𝑘𝑔
Mass of steam = 297.05 kg

300
Equipment Name: Cooling Crystallizer

Equipment Code: J – 2

FROM D-3 TO K-4

Concentrated Vanillin
Vanillin Magma
Solution J–2
T = 30°C
T = 28.93°C
Total Mass = 764.38 kg
Total Mass = 764.38 kg Q = -91,159.79 KJ

WATER COOLING WATER COOLING

IN = 872.34 kg OUT = 872.34 kg
T = 5°C T = 15°C

Concentrated Vanillin 764.38 kg Vanillin Magma 764.38 kg

Solution (From D-3) (To K-4)
TOTAL MASS IN 764.38 kg TOTAL MASS OUT 764.38 kg

301
Assumptions:

1. The dissolved vanillin mixture enters the crystallizer at 65°C.

2. The magma leaves at 10°C.

3. Cooling water at 5°C will be used.

4. The cooling water will leave at 30°C.

Detailed Computations:

Equations:

𝑄𝑡𝑜𝑡𝑎𝑙 = (𝑚𝐶𝑝∆𝑇)𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑒𝑑 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛

𝑄𝑡𝑜𝑡𝑎𝑙 = −(𝑚𝐶𝑝∆𝑇)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟

Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [512.78 kg vanillin (1.24 ) (10 − 65)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [7.99 kg syringaldehyde (1.25 ) (10 − 65)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [2.14 kg p − hydroxybenzaldehyde (1.22 ) (10 − 65)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [6.58 kg nitrobenzene (1.19 ) (10 − 65)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.61 kg NaOH (3.93 ) (10 − 65)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [210.96 kg water (4.18 ) (10 − 65)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.81 kg insoluble lignin (1.23 ) (10 − 65)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [20.50 kg diethyl ether (5.50 ) (10 − 65)℃]
𝑘𝑔 − ℃

𝑸𝒕𝒐𝒕𝒂𝒍 = −𝟗𝟏 𝟏𝟓𝟗. 𝟕𝟗 𝒌𝑱

302
Solving for cooling water requirement:

𝑄𝑡𝑜𝑡𝑎𝑙 = −(𝑚𝐶𝑝∆𝑇)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟

−91 159.79 𝑘𝐽
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −
𝐾𝐽
4.18 𝐾𝑔 − 𝐾 × (30 − 5)°∁

Mass of cooling water = 872.34 kg

303
Equipment Name: Rotary Dryer

Equipment Code: D – 4

Vapor
Total Mass = 40.17 kg

FROM K-4 TO D-5

Wet Vanillin Crystals Dried Vanillin Crystals
D–4
T = 30°C T = 60°C
Total Mass = 561.12 kg Total Mass = 520.94 kg
Q = 109,234.98 KJ

HOT AIR = 10,457.94 kg

T = 80°C HOT HUMID AIR = 10,457.94 kg
%RH = 78% T = 70°C

Wet Vanillin Crystal 561.12 kg Dried Vanillin Crystals 520.94 kg

(From K-4) (To D-5)
Vapor Out 40.17 kg
TOTAL MASS IN 561.12 kg TOTAL MASS OUT 561.12 kg

304
Assumptions:
1. The crystals will enter at 30°C.
2. The dried vanillin will leave at 60°C.
3. Relative humidity of air is 78%.
4. Preheated air will enter at 80°C and leave at 70°C.

Detailed Computations:
Equations:
𝑄𝑡𝑜𝑡𝑎𝑙 = (∆𝐻)𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑐𝑟𝑦𝑠𝑡𝑎𝑙 + (𝑚∆𝐻)𝑣𝑎𝑝

𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑄𝑎𝑖𝑟
𝑄𝑎𝑖𝑟 = ѡ𝐶𝑠 ∆𝑇
𝐶𝑠 = 1.005 + 1.88𝜘
Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [510.52 kg vanillin (1.24 ) (60 − 30)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.59 kg syringaldehyde (1.25 ) (60 − 30)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.43 kg p − hydroxybenzaldehyde (1.22 ) (60 − 30)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.31 kg nitrobenzene (1.19 ) (60 − 30)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.32 kg NaOH (3.93 ) (60 − 30)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [42.09 kg water (4.18 ) (60 − 30)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.16 kg insoluble lignin (1.23 ) (60 − 30)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [4.09 kg diethyl ether (5.50 ) (60 − 30)℃]
𝑘𝑔 − ℃

= 𝟐𝟓, 𝟎𝟕𝟎. 𝟏𝟏 𝒌𝑱

305
Heat of Vaporization:

∆𝐻𝑣𝑎𝑝 = ∑ 𝑚𝑣 𝐻𝑣
𝑘𝐽 𝑘𝐽
∆𝐻𝑣𝑎𝑝 = [(42.09 𝑘𝑔 ) (2260.00 )] + [(4.09 𝑘𝑔 ) (353.65 )]
𝑘𝑔 𝑘𝑔

∆𝑯𝒗𝒂𝒑 = 𝟖𝟒, 𝟏𝟔𝟒. 𝟖𝟕 𝒌𝑱

𝑄𝑡𝑜𝑡𝑎𝑙 = 27,477.28 kJ + 127,906.96 kJ

𝑸𝒕𝒐𝒕𝒂𝒍 = 𝟏𝟎𝟗, 𝟐𝟑𝟒. 𝟗𝟖 𝒌𝑱

Solving for mair:

𝑄𝑎𝑖𝑟 = ѡ𝐶 ∆𝑇
𝐶𝑠 = 1.005 + 1.88𝜘

Using psychometric chart from Perry’s Handbook, absolute humidity (ϰ) at 30℃ dry bulb
temperature and 78% relative humidity is 0.02102 kg H2O per kg dry air.

𝐶𝑠 = 1.005 + 1.88(0.02102)
𝐾𝐽
𝐶𝑠 = 1.0445
𝑘𝑔 𝑑𝑟𝑦 𝑎𝑖𝑟 − 𝐾
109 234.98 𝑘𝐽
𝑚𝑎𝑖𝑟 = ѡ =
𝐾𝐽
1.0445 𝑘𝑔 𝑑𝑟𝑦 𝑎𝑖𝑟 − 𝐾 × (80 − 70)𝐾

𝒎𝒂𝒊𝒓 = 𝟏𝟎, 𝟒𝟓𝟕. 𝟗𝟒 𝒌𝒈

306
Equipment Name: Cooler

Equipment Code: D – 5

FROM D-4 TO K-5

Cooled Vanillin
Dried Vanillin Crystals
D–5 Crystals
T = 60°C
T = 25°C
Total Mass = 520.94 kg
Q = -29,248.51 KJ Total Mass = 520.94 kg

WATER COOLING WATER COOLING

OUT = 233.24 kg IN = 233.24 kg
T = 50°C T = 20°C

Dried Vanillin Crystals 520.94 kg Cooled Vanillin Crystals 520.94 kg

(From D-4) (To K-5)
TOTAL MASS IN 520.94 kg TOTAL MASS OUT 520.94 kg

307
Assumptions:

1. The feed enters at 60°C.

2. The temperature is maintained at 25°C.
3. Cooling Water enters at 20°C and leaves at 50°C.

Detailed Computations:

Equations:

𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠

(𝑚𝐶𝑝𝑑𝑇)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 = −(𝑚𝐶𝑝𝑑𝑇)𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠

Solving for QT:

∑ 𝑚𝐶𝑝(𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )

𝑘𝐽
= [510.52 kg vanillin (1.24 ) (25 − 60)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.59 kg syringaldehyde (1.25 ) (25 − 60)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.43 kg p − hydroxybenzaldehyde (1.22 ) (25 − 60)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [1.31 kg nitrobenzene (1.19 ) (25 − 60)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.32 kg NaOH (3.93 ) (25 − 60)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [42.09 kg water (4.18 ) (25 − 60)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [0.16 kg insoluble lignin (1.23 ) (25 − 60)℃]
𝑘𝑔 − ℃
𝑘𝐽
+ [4.09 kg diethyl ether (5.50 ) (25 − 60)℃]
𝑘𝑔 − ℃

𝑸𝒕𝒐𝒕𝒂𝒍 = −𝟐𝟗, 𝟐𝟒𝟖. 𝟓𝟏 𝒌𝑱

308
Solving for cooling water requirement:
𝑄𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝑤𝑎𝑡𝑒𝑟 = −𝑄𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠
(𝑚𝐶𝑝∆𝑇)𝑐𝑜𝑜𝑙𝑖𝑛𝑔 = −(𝑚𝐶𝑝∆𝑇)𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠
𝐾𝐽
−(−29 248.51 )𝐾𝐽 = 𝑚 × 4.18 × (50 − 20)℃
𝐾𝑔 − ℃
Mass of cooling water = 233.24 kg

309