2 Heuristics For Process Synthesis
2 Heuristics For Process Synthesis
Cheng-Liang Chen
LABORATORY
PSE
Chen CL
Design teams use heuristics when generating alternatives that make up a synthesis tree
Chen CL
Chen CL
Chen CL
Since both reactions are highly exothermic, they need to be controlled carefully. But a water spill into an ethylene-oxide storage tank could lead to an accident similar to the Bhopal incident. Often such processes are designed with two reaction steps, with storage of the intermediate, to enable continuous production, even when maintenance problems shut down the rst reaction operation.
Chen CL
Alternative 2: As ethylene-oxide is formed, react it with carbon dioxide to form ethylene-carbonate, a much less active intermediate that can be stored safely and hydrolyzed, to form the ethylene-glycol product, as needed:
Chen CL
Distribution of Chemicals
Heuristics 2 Use an excess of one chemical reactant in a reaction operation to completely consume a second valuable, toxic, or hazardous chemical reactant. Example: Using excess ethylene in dichloroethane ( vinyl chloride) production to consume completely the hazardous and toxic chlorine (Q: ethylene/chlorine ratio ?)
Chen CL
Distribution of Chemicals
Heuristics 3 Inert Species: When nearly pure products are required, eliminate inert species before the reaction operations, when the separations are easily accomplished, or when the catalyst is adversely aected by the inert. Do not do this when a large exothermic heat of reaction must be removed.
Chen CL
Distribution of Chemicals
Chen CL
Distribution of Chemicals
By positioning the distillation column rst, a nearly pure feed is sent to the reaction operation, providing a higher conversion to iso-butane.
Chen CL
10
Distribution of Chemicals
Heuristics 4 Purge Streams: Introduce liquid or vapor purge streams to provide exits for species that
enter the process as impurities in the feed produced by irreversible side-reactions
when these species are in trace quantities and/or are dicult to separate from the other chemicals. Lighter species leave in vapor purge streams, and heavier species exit in liquid purge streams. Example: NH3 Synthesis Loop.
Chen CL
11
Distribution of Chemicals
Heuristics 4
Example: Ammonia Process Purge The ammonia reactor loop is simulated to examine the eect of purge-to-recycle ratio on the compositions and ow rates of the purge and recycle streams. The following specications are made: Simulation Unit R1 F1 T (oF) 932 28 P (atm) 200 136.3
The combined feed stream, at 77oF and 200 atm, is comprised of lbmol/hr 24. 74.3 0.6 1.1 100.0 Mole Fraction 0.240 0.743 0.006 0.011 1.000
N2 H2 Ar CH4
Chen CL
12
Distribution of Chemicals
Heuristics 4
Example: Ammonia Process Purge Several variables are tabulated as a function of the purge/recycle ratio:
Purge/Recycle Ratio PROD Flow Rate (lbmole/hr) Recycle Flow Rate (lbmole/hr) Purge Flow Rate (lbmole/hr) Purge mole Fraction Purge Mole Fraction CH4
In all cases, the mole fraction of Ar and CH4 in the purge are signicantly greater than in the feed. As the purge/recycle ratio is decreased, the vapor euent from the ash vessel becomes richer in the inert species and less H2 and N2 are lost in the purge stream. However, this is accompanied by a signicant increase in the recycle rate and the cost of recirculation, as well as the reactor volume. The capital and operating costs should be estimated and a protability measure should be optimized as a function of the purge/recycle ratio.
Chen CL
13
Distribution of Chemicals
Heuristics 5 Do not purge valuable species or species that are toxic and hazardous, even in small concentrations.
Add separators to recover valuable species. Add reactors to eliminate toxic and hazardous species.
Chen CL
14
Distribution of Chemicals
Heuristics 6 Byproducts that are produced in reversible reactions, in small quantities, are usually not recovered in separators or purged. Instead, they are usually recycled to extinction.
Example: Reversible Production of Biphenyl in toluene hydrodealkylation process 2C6H6 C12H10 + H2
Chen CL
15
Distribution of Chemicals
Heuristics 7 For competing series or parallel reactions, adjust the temperature, pressure, and catalyst to obtain high yields of the desired products. In the initial distribution of chemicals, assume that these conditions can be satised - obtain kinetics data and check this assumption before developing a base-case design. Manufacture of allyl-chloride
Chen CL
16
Manufacture of allyl-chloride: Kinetic Data Reaction 1 2 3 HR Btu/lb-mole 4, 800 79, 200 91, 800 ko lb-mole/(hr ft3atm2) 206, 000 11.7 4.6 108 E/R o R 13, 600 3, 430 21, 300
Chen CL
17
Distribution of Chemicals
Heuristics 8 For reversible reactions, especially, consider conducting them in a separation device capable of removing the products, and hence, driving the reactions to the right. Such reaction-separation operations lead to very dierent distributions of chemicals. Example: Manufacture of Ethyl-acetate using reactive distillation.
Conventionally, this would call for reaction: M eOH + HOAc M eOAc + H2O
Chen CL
18
Separations
Heuristics 9 Separate liquid mixtures using distillation and stripping towers, and liquid-liquid extractors, among similar operations, and so on, with the unreacted chemicals recovered in a liquid phase and recycled to the reaction operation. Heuristics 10 Attempt to (partially) condense vapor mixtures with cooling water (typically to 35oC) or a refrigerant. Then, use Heuristic 9. Vapor/liquid purges are added when necessary to remove inerts that concentrate in the vapor/liquid and are not readily separated. Heuristics 11 Separate vapor mixtures using partial condensers, cryogenic distillation, absorption towers, adsorbers, membrane devices.
Chen CL
19
Separations
Heuristics 9-11 Flowsheet to separate liquid reactor euents
Chen CL
20
Separations
Heuristics 9-11 Flowsheet to separate vapor reactor euents
Chen CL
21
Separations
Heuristics 9-11 Flowsheet to separate vapor/liquid reactor euents
Chen CL
22
Separation Operations
involving solid particles
Crystallization occurs in three dierent modes:
Solution Crystallization applies mainly to inorganic chemicals, which are crystallized from a solvent (often water) with an operating temperature far below the melting point of the crystals. Precipitation is fast solution crystallization that produces large numbers of very small crystals. It usually refers refers to the case where one product of two reacting solutions is a solid of low solubility (e.g., precipitation of insoluble silver chloride when aqueous solutions of silver nitrate and sodium chloride are mixed together). In Melt Crystallization, two or more chemicals of comparable melting points are separated at an operating temperature in the ranges of melting temperatures (e.g., production of pure silicon wafers from a melt consisting of SiO2).
Crystallization is capable of producing very pure chemicals when conducted according to the following heuristics:
Chen CL
23
Separation Operations
involving solid particles
Heuristics 12 Crystallize inorganic chemicals from a concentrated aqueous solution by chilling when solubility decreases signicantly with decreasing temperature. Keep the solution at most 1 to 2oF below the saturation temperature at the prevailing concentration. Use crystallization by evaporation, rather than chilling, when solubility does not change signicantly with temperature.
Chen CL
24
Separation Operations
involving solid particles
Heuristics 13 Crystal growth rates are approximately the same in all directions, but crystals are never spheres. Crystal growth rates and sizes are controlled by limitlllg the extent of supersaturation. S = C/Csaturation, where C is concentration, usually in the range 1.02 < S < 1.05. Growth rates are inuenced greatly by the presence of impurities and of certain specic additives that vary from case to case.
Chen CL
25
Separation Operations
involving solid particles
Heuristics 14 Separate organic chemicals by melt crystallization with cooling, using suspension crystallization, followed by removal of crystals by settling, ltration, or centrifugation. Alternatively, use layer crystallization on a cooled surface, with scraping or melting to remove the crystals. If the melt forms a solid solution instead of a eutectic, use repeated melting and freezing steps, called fractional melt crystallization, or zone melting to obtain nearly pure crystalline products.
Chen CL
26
Separation Operations
involving solid particles
Prior to crystallization, it is common to employ evaporation to concentrate a solution, particularly an aqueous solution of inorganic chemicals. Because of the relatively high cost of evaporating water with its very large heat of evaporation, the following heuristics are useful for minimizing the cost.
Chen CL
27
Separation Operations
involving solid particles
Heuristics 15 Using multiple evaporators (called eects) in series, the latent heat of evaporation of water is recovered and reused. With a single evaporator, the ratio of the amount of water evaporated to the amount of external steam supplied to cause the evaporation is typically 0.8. For two eects, the ratio becomes 1.6; for three eects 2.4, and so forth. The magnitude of the boiling point elevation caused by the dissolved inorganic compounds is a controlling factor in selecting the optimal number of eects. The elevation is often in the range of 3 to 10oF between solution and pure water boiling points. When the boiling point rise is small, minimum evaporation cost is obtained with 8 to 10 eects. When the boiling-point rise is appreciable, the optimal number of eects is small, 6 or less. If necessary, boost interstage steam pressures with steam-jet or mechanical compressors.
Chen CL
28
Separation Operations
involving solid particles
Heuristics 16 When employing multiple eects, the liquid and vapor ows may be in the same or dierent directions. Use forward feed, where both liquid and vapor ow in the same direction, for a small number of eects, particularly when the liquid feed is hot. Use backward feed, where liquid ows in a direction opposite to vapor ows, for cold feeds and/or a large number of eects. With forward feed, intermediate liquid pumps are not necessary, whereas they are for backward feed.
Chen CL
29
Separation Operations
involving solid particles
Solution Crystallization produces a slurry of crystals and mother liquor, which is partially separated by ltration or centrifugation into a wet cake and a mother liquor.
Filtration through a lter medium of porous cloth or metal may be carried out under gravity, vacuum, or pressure. Centrifugation may utilize a solid bowl or a porous bowl with a lter medium.
Filtration rate is best determined by measuring the rate of cake thickness buildup using a small-scale laboratory vacuum leaf lter test with the following criteria:
Rapid, 0.1 to 10 cm/s; Medium, 0.1 to 10 cm/min; Slow, 0.1 to 10 cm/hr.
Chen CL
30
Separation Operations
involving solid particles
Heuristics 17 When crystals are fragile, eective washing is required, and clear mother liquor is desired, use gravity, top-feed horizontal pan ltration for slurries that lter at a rapid rate; vacuum rotary drum ltration for slurries that lter at a moderate rate; and pressure ltration for slurries that lter at a slow rate. Heuristics 18 When cakes of low moisture content are required, use solid-bowl centifugation if solids are permitted in the mother liquor, centrifugal ltration if eective washing is required.
Chen CL
31
Separation Operations
involving solid particles
Wet cakes from ltration or centrifugation operations are sent to dryers for removal of remaining moisture. A large number of dierent types of commercial dryers have been developed to handle the many dierent types of feeds, which include not only wet cakes, but also pastes, slabs, lms, slurries, and liquids. The heat for drying may be supplied from a hot gas in direct contact with the wet feed or it may be supplied indirectly through a wall. Depending on the thickness of the feed and the degree of agitation, drying times can range from seconds to hours. The following heuristics are useful in making a preliminary selection of drying equipment.
Chen CL
32
Separation Operations
involving solid particles
Heuristics 19 For granular material, free owing or not, of particle sizes from 3 to 15 mm, use continuous tray and bell dryers with direct heat. For free-owing granular solids that are not heat sensitive, use an inclined rotary cylindrical dryer, where the heat may be supplied directly from a hot gas or indirectly from tubes, carrying steam, that run the length of the dryer and are located in one or two rings concentric to and located just inside the dryer rotating shell. For small, free-owing particles of 1 to 3 mm in diameter, when rapid drying is possible, use a pneumatic conveying dryer with direct heat. For very small free-owing particles of less than 1 mm in diameter, use a uidized-bed dryer with direct heat.
Chen CL
33
Separation Operations
involving solid particles
Heuristics 20 For pastes and slurries of ne solids, use a drum dryer with indirect heat. For a liquid or pumpable slurry, use a spray dryer with direct heat.
Chen CL
34
Chen CL
35
Chen CL
36
Chen CL
37
Chen CL
38
Chen CL
39
Chen CL
40
Chen CL
41
Chen CL
42
Chen CL
43
Chen CL
44
Chen CL
45
Chen CL
46
Chen CL
47
Chen CL
48
Chen CL
49
Chen CL
50
Chen CL
51
Chen CL
52
Chen CL
53
Chen CL
54
Chen CL
55
Chen CL
56
Chen CL
57
(THp)
for
P2 P1
where SCFM = standard cubic feet of gas per minute at 60oF and 1 atm (379 SCF/lbrmol), T1 = gas inlet temperature in oR, inlet and outlet pressures, P1 and P2, are absolute pressures, and a = (k 1)/k , with k = the gas specic heat ratio, Cp/Cv . Estimate the theoretical exit temperature, T2 for a gas compressor from: a P2 T2 = T1 P1
Chen CL
58
Chen CL
59
Optimal interstage pressures correspond to equal Hp for each compressor. Therefore, based on the above equation for theoretical compressor Hp, estimate interstage pressures by using approximately the same compression ratio for each stage with an intercooler pressure drop of 2 psi or 15 kPa.
Chen CL
60
Chen CL
61
Chen CL
62
Chen CL
63
Chen CL
64
W =
V1
V dP
It
follows that it is more ecient to pump a liquid than to compress a gas. Thus, it is almost always preferable to condense a vapor, pump it, and vaporize it, rather than compress it.
Chen CL
65
Alternative 2: Vaporize the liquid rst. 4.21 107 Btu/hr to vaporize, 1897 brake Hp to compress
Chen CL
66
Vacuum
When process pressures less than the ambient pressure are required (common in crystallization, distillation, drying, evaporation, pervaporation), vacuum devices are needed. A vacuum system is used to remove the air together with any associated vapor in the process stream that pass through the equipment. A vacuum inside equipment causes inleakage of ambient-pressure air For continuous operation, vacuums are predominantly in the range of 1 to 760 torr (0.13 to 101.3 kPa). It is common to use a vacuum pump, which compresses the gas from vacuum (suction pressure) to ambient pressure; or a jet-ejector system, which uses a ow of pressurized water or steam to mix with and remove the gas to create the vacuum. To design the vacuum system, it is necessary to estimate the inleakage of air, determine the total amount of gas (inleakage plus associated vapor) to be removed, and select an appropriate system for the vacuum level required.
Chen CL
67
Vacuum
Heuristics 44 Estimate inleakage of air by: w = kV 0.667 where w = lb/hr of air inleakage, V = ft3 of volume of the equipment under vacuum, and k = 0.20 for pressures greater than 90 torr, k = 0.15 for pressures between 21 and 89 torr, k = 0.10 for pressures between 3 and 20 torr, and k = .051 for pressures between 1 and 3 torr.
Chen CL
68
Vacuum
Heuristics 45 To reduce the amount of gas sent to the vacuum system if its temperature is greater than 100oF, add a condenser using cooling water before the vacuum system. The gas leaving the condenser will be at a dew-point temperature of 100oF at the vacuum pressure. Heuristics 46 For pressures down to 10 torr and gas ow rates up to 10, 000 ft3/min at the inlet to the vacuum system, use a liquid-ring vacuum pump. For pressures down to 2 torr and gas ow rates up to 1, 000, 000 ft3/min at the inlet to the vacuum system, use a steam-jet ejeclor system (one-stage for 100 to 760 torr, two-stage for 15 to 100 torr, and three-stage for 2 to 15 torr). Include a direct-contact condenser between stages.
Chen CL
69
Vacuum
Heuristics 47 For a three-stage steam-jet ejector system used to achieve a vacuum of 2 torr, 100 pounds of 100 psig steam per pound of gas are required. Heuristics 48 If the solid particles are small in size, low in particle density, and are not sticky or abrasive, use pneumatic conveying with air at 1 to 7 ft3/ft3 of solids and 35 to 120 ft/s air velocity for distances up to 400 ft. Otherwise, for sticky and/or abrasive solids of any size and density, use a screw conveyer and/or bucket elevator for distances up to 150 ft. For solid particles of any size and shape, and not sticky, use a belt conveyor, with inclination up to 30o if necessary, for long distances up to a mile or more.
Chen CL
70
Chen CL
71
Materials with a Mohs scale from 1 to 3 are considered soft and include graphite, many plastics, asphalt, sulfur, many inorganic salts, marble, and anthracite coal. Intermediate hardness extends from Mohs scale of 4 to 6 and includes limestone, asbestos, and glass. Hard materials are characterized by a Mohs scale of 7 to 10 and include sand, granite, and emery.
Chen CL
72
Chen CL
73
Chen CL
74
Chen CL
75
Chen CL
76
Chen CL
77
Chen CL
78
Chen CL
79