Chemical Process Industrie

University of Diyala Chemical

Engineering Department

Lecture(3)

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INTERMEDIATES AND DERIVATIVES:
Methanol CH3OH
Feed: NG or associated gas
CO+ 2H2 ↔ CH3OH

Description: (1) Gas feedstock is compressed (if required), desulfurized (2) the optional
saturator ,where some process steam is generated. The saturator is used where
maximum water recovery is important. Further process steam is added, and the mixture
is preheated and sent to the pre-reformer (3), using the Catalytic- Rich-Gas process.
Steam raised in the methanol converter is added, along with available CO 2 , and the
partially reformed mixture is preheated and sent to the reformer (4). High-grade heat in
the reformed gas is recovered as high-pressure steam (5), boiler feed water preheat, and
for reboil heat in the distillation system (6). The high-pressure steam is used to drive the
main compressors in the plant. After final cooling, the synthesis gas is compressed (7)

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and sent to the synthesis loop. The loop can operate at pressures between 70 to 100 bar.
The converter design does impact the loop pressure, with radial-flow designs enabling
low loop pressure even at the largest plant size. Low loop pressure reduces the total
energy requirements for the process.
The synthesis loop comprises a circulator (8) and the converter operates around 200°C
to 270°C, depending on the converter type. Reaction heat from the loop is recovered as
steam, and is used directly as process steam for the reformer.
A purge is taken from the synthesis loop to remove inerts (nitrogen, methane), as well
as surplus hydrogen associated with non-stoichiometric operation. The purge is used as
fuel for the reformer. Crude methanol from the separator contains water, as well as
traces of ethanol and other compounds. These impurities are removed in a two-column
distillation system (6). The first column removes the light ends such as ethers, esters,
acetone and dissolved non condensable gases. The second column removes water,
higher alcohols and similar organic heavy ends.
Acetic acid CH3COOH
CH3OH + CO →CH3COOH
Feed:. Methanol and carbon monoxide (CO) are reacted with the carbonylation
reaction using a heterogeneous Rh catalyst.

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Description: Fresh methanol from absorber(7) & (8)., mixed with the recycle liquid
from the recycle surge drum (6). This stream is charged to a unique bubble column
reactor (1).
Carbon monoxide is compressed and sparged into the reactor riser. Catalyst is an
immobilized Rh complex catalyst on solid support, which offers higher activity and
operates under less water conditions in the system due to heterogeneous system, and
therefore, the system has much less corrosivity. Reactor effluent liquid is withdrawn and
flash-vaporized in the Flasher (2).
The vaporized crude acetic acid is sent to the dehydration column (3) to remove water
and any light gases. Dried acetic acid is routed to the finishing column (4).

Ethylene Derivatives:
Ethylene oxide
CH2=CH2+0.5 O2 CH2-----CH2
O

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Application: To produce ethylene oxide (EO) from the direct oxidation of ethylene
using the Dow Meteor process.
Description: The Meteor Process, a technology first commercialized in1994
1- is a simpler 2- safer process for the production of EO 3- having lower capital
investment requirements and 4- lower operating costs. Meteor Process
A-ethylene and oxygen are mixed and passed through a single-train, multi tubular
catalytic reactor (1) to selectively process is a simpler, safer technology with lower
facility investment costs. B- Heat is recovered from the reactor outlet gas before it
enters the EO absorber (2) where EO is scrubbed from the gas by water. The EO-
containing water from the EO absorber is concentrated by stripping (3). the EO reactor,
is removed via activated, hot The cycle gas exiting the absorber is fed to the CO2
removal section (4,5) where CO2, which is co-produced in potassium carbonate
treatment. The CO2 lean cycle gas is recycled by compression back to the EO reactor.
Advantages:
Plant with one reactor work with high selectivity with low conversion for each
cycle. Reactants used with high concentration which reduced the capital cost.
Disadvantages:
1- The demand for additional units e.g. oxygen separation unit (high purity).
2- The need of CO2removal from recycle gas.
3- N2 must be removed from recycle gas; additional units.
However oxidation by O2 is more economic when high capacity production
is used.
EO Uses:
1-In production of ethylene glycol(anti freeze agent).
2-Used as surfactant. 3-In production of polyester.
4-In manufacture of Hydraulic fluid.

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Other old method utilized air for oxidation:
Two reactors and two absorber to complete oxidation of E to produce EO.
T=260-290OC, P=10-13 atm.
Cata: Ag/Al2O3 + Promotor: Ba, K + Inhibitor AgCl ,NaI ,used as
sphere to reduce pressure drop.
Ethylene glycol :

Application: To produce ethylene glycols (MEG, DEG, TEG) from ethylene oxide
(EO) using Dow’s Meteor process.
Description: In the Meteor Process, an EO/water mixture is preheated and fed
directly to an adiabatic reactor (1), which can operate with or without a catalyst. An
excess of water is provided to achieve high selectivities to monoethylene glycol (MEG).

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Diethylene (DEG) and triethylene (TEG) glycols are produced as co products. In a
catalyzed mode, higher selectivities to MEG can be obtained, thereby reducing DEG
production to one-half that produced in the uncatalyzed mode. Excess water from the
reactor effluent is efficiently removed in a multi effect evaporation system (2). The
concentrated water/glycols stream from the evaporation system is fed to the water
column (3) where the remaining water and light ends are stripped from the crude
glycols. The water-free crude
glycol stream is fed to the MEG refining column (3) where polyester-grade MEG,
suitable for polyester fiber and PET production, is recovered. DEG and TEG exiting the
base of the MEG refining column can be recovered as high-purity products by
subsequent fractionation.
Uses:
1-Polyester(fibers and films). 2- PET .3-Anti freeze agent. 4-Gas drying

Vinyl chloride:
Vinylchloride monomer VCM CH(Cl)=CH2 :

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Description: PVC slurry discharged from reactors contains significant amounts of
VCM ( >30,000 ppm) even after initial flashing. This process effectively removes the
remaining VCM so that the monomer is recovered and reused.
-The PVC slurry, containing VCM, is continuously fed to the stripping column (1). The
slurry passes counter-currently to steam, which is fed into the base of the column. All
process operations, including grade change, are automatically done in a completely
closed system.

Ethanolamines, MEA,DEA &TEA:

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Description: Ammonia (2) and water are separated and recycled to the reaction system.
Vacuum distillation (4,5,6,7) is used to produce pure MEA, DEA and TEA. A saleable
heavies tar byproduct is also produced. solution, recycled amines and ethylene oxide are
fed continuously to a reaction system (1) that operates under mild conditions and
simultaneously produces MEA, DEA and TEA. The reactor products are sent to a
separation system where ammonia Technical grade TEA (85wt%) can also be produced
if required.
Uses:
1-Gases softening. 2-Detergent production. 3-Corrosin stabilizers
4-Chlorinated HCs stabilizers :decrease its decomposition.
Propylene derivatives:
Acrylonitrile CH2=CHCN:

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Application: A process to produce high-purity acrylonitrile and high-purity hydrogen
cyanide from propylene, ammonia and air. Recovery of byproduct acetonitrile is
optional.
Description: Propylene, ammonia, and air are fed to a fluidized bed reactor to produce
acrylonitrile (ACRN) using DuPont’s proprietary catalyst system. Other useful products
from the reaction are hydrogen cyanide (HCN) and acetonitrile (ACE). The reaction is
highly exothermic and heat is recovered from the reactor by producing high-pressure
steam. The reactor effluent is quenched and neutralized with a sulfuric solution to
remove the excess ammonia.
The product gas from the quench is absorbed with water to recover the ACRN, HCN,
and ACE. The aqueous solution of ACRN, HCN, and ACE is then fractionated and
purified into high-quality products. The products’ recovery and purification is a highly
efficient and low-energy consumption process.
Uses: For production of Acrylic fibers ,flexible plastic ,Rubber and resins.

Derivatives of C4 hydrocarbons:
Methyl-Tetra-Butyl-Ether (MTBE) (CH3)3COCH3

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Feed: methanol and isobutene to produce the high-octane oxygenate—methyl tertiary
butyl ether (MTBE).
Feeds: C4-cuts from steam cracker and FCC units with isobutene contents range from
12% to 30%.
Uses: MTBE and other tertiary alkyl ethers are primarily used in gasoline blending as
an octane enhancer to improve hydrocarbon combustion efficiency.
Description: The technology features a two-stage reactor system of which the
first reactor is operated in the recycle mode. With this method, a slight expansion
of the catalyst bed is achieved which ensures very uniform concentration profiles
within the reactor and, most important, avoids hot spot formation. Undesired side
reactions, such as the formation of dimethyl ether (DME), are minimized.The
reactor inlet temperature ranges from 45°C at start-of-run to about 60°C at end-
of-run conditions. One important factor of the two stage system is that the
catalyst may be replaced in each reactor separately, without shutting down the
MTBE unit.
The catalyst used in this process is a cation-exchange resin and is available from several
catalyst manufacturers. Isobutene conversions of 97% are typical for FCC feedstocks.
Higher conversions are attainable when processing steam-cracker C4 cuts that contain
isobutene concentrations of 25%.
MTBE is recovered as the bottoms product of the distillation unit. The methanol-rich C4
distillate is sent to the methanol-recovery section. Water is used to extract excess
methanol and recycle it back to process. The isobutene-depleted C4 stream may be sent
to a raffinate stripper or to a molsieve-based unit to remove other oxygenates such as
DME, MTBE, methanol and tert-butanol.
Very high isobutene conversion, in excess of 99%, can be achieved through a
debutanizer column with structured packings containing additional catalyst. This
reactive distillation technique is particularly suited when the raffinate-stream from the
MTBE unit will be used to produce a high-purity butene-1 product.
Uses: Octane booster.

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Benzene derivative:
Ethylbenzene C6H5CH2CH3:
AlCl3
CH2=CH2+C6H6 C6H5CH2CH3
BF3

Application: Advanced technology to produce high-purity ethylbenzene (EB)

alkylating benzene with ethylene using patented catalytic distillation (CD) technology.
The CDTECH EB process uses a specially formulated zeolite alkylation catalyst
packaged in a proprietary CD structure. The process is able to handle a wide range in
ethylene feed composition— from 10% to 100% ethylene.
Description: The CD alkylator stripper (1) operates as a distillation column.
Alkylation and distillation occur in the alkylator in the presence of a zeolite catalyst
packaged in patented structured packing. Unreacted ethylene and benzene vapor from
the alkylator top are condensed and fed to the finishing reactor (2) where the remaining
ethylene reacts over zeolite catlayst pellets. The alkylator stripper bottoms is
fractionated (4, 5) into EB product, polyethylbenzenes and flux oil. The

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polyethylbenzenes are transalkylated with benzene over zeolite catalyst pellets in the
transalkylator (3) to produce additional EB. The ethylene can be polymer grade or, with
only minor differences in the process scheme, dilute ethylene containing as little as 10
mol% ethylene as in FCC offgas. Reactors are designed for 3 to 6 years of uninterrupted
runlength. The process does not produce any hazardous effluent. Low operating
temperatures allow using carbon steel for all equipment.
Uses: 0.5 consumption of B:in EB production: which is used in production of styrene.

Styrene C6H5CH=CH2:

Application: To produce polymer-grade styrene monomer (SM) by dehydrogenating

ethylbenzene (EB) to form styrene using the Lummus/UOP “Classic” styrene process
for new plants and the Lummus/UOP SMART process for revamps involving plant
capacity expansion.
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Description: In the Classic SM process, EB is catalytically dehydrogenated to styrene
in the presence of steam. The vapor phase reaction is carried out at high temperature
under vacuum. The EB (fresh and recycle) is combined with superheated steam, and the
mixture is dehydrogenated in a multistage reactor system (1). A heater reheats the
process gas between stages. Reactor effluents are cooled to recover waste heat and
condense the hydrocarbons and steam.
Uncondensed offgas— containing mostly hydrogen— is compressed and is used as
fuel. Condensed hydrocarbons from an oil/water separator (2) are sent to the distillation
section. Process condensate is stripped to remove dissolved aromatics.
A fractionation train (3,4) separates high-purity styrene product, unconverted EB, which
is recycled, and the relatively minor byproduct tar, which is used as fuel. Toluene is
produced (5,6) as a minor byproduct and benzene (6) is normally recycled to the
upstream EB process.
Typical SM product purity ranges normally recycled to the upstream EB process.
Typical SM product purity ranges from 99.85% to 99.95%. The process provides high-
product yield due to a unique combination of catalyst and operating conditions used in
the reactors and the use of a highly effective polymerization inhibitor in the
fractionation columns.

Cumene:

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Description: Benzene is alkylated to cumene over a zeolite catalyst in a fixed-bed,
liquid-phase reactor. Fresh benzene is combined with recycle benzene and fed to the
alkylation reactor (1). The benzene feed flows in series through the beds, while fresh
propylene feed is distributed equally between the beds. This reaction is highly
exothermic, and heat is removed by recycling a portion of reactor effluent to the reactor
inlet and injecting cooled reactor effluent between the beds. In the fractionation section,
propane that accompanies the propylene feedstock is recovered as LPG product from
the overhead of the depropanizer column (2), unreacted benzene is recovered from the
overhead of the benzene column (4) and cumene product is taken as overhead from the
cumene column (5). Diisopropylbenzene (DIPB) is recovered in the overhead of the
DIPB column (6) and recycled to the transalkylation reactor (3) where it is
transalkylated with benzene over a second zeolite catalyst to produce additional
cumene. A small quantity of heavy byproduct is recovered from the bottom of the DIPB
column(6) and is typically blended to fuel oil. The cumene product has a high purity
(99.96 – 99.97 wt%), and cumene yields of 99.7 wt% and higher are achieved. The
zeolite catalyst is noncorrosive and operates at mild conditions; thus, on-steel
construction is possible. Catalyst cycle lengths are two years and longer. The catalyst is

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fully regenerable for an ultimate catalyst life of six years and longer. Existing plants that
use SPA or AlCl3 catalyst can be revamped to gain the advantages of Q-Max cumene
technology while increasing plant capacity.

Phenol:

Application: The Sunoco/UOP phenol process produces high-quality phenol and

acetone by liquid-phase peroxidation of cumene.

Description: Key process steps:

Oxidation and concentration (1): Cumene is oxidized to cumene hydroperoxide (CHP
selectivity of CHP. CHP is then concentrated and unreacted cumene is recycled back to
the oxidation section.

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Decomposition and neutralization (2): CHP is decomposed to phenol and acetone.
This unique design achieves a very high selectivity to phenol, acetone.The high total
yields from oxidation and decomposition combine to achieve 1.31wt cumene/wt phenol
without tar cracking.
Phenol and acetone purification (3): Phenol and acetone areseparated and purified. A
small amount of byproduct is rejected as heavy residue.
AMS hydrogenation or AMS refining (4): AMS is hydrogenated back to cumene and
recycled to oxidation, or AMS is refined for sale.
Uses: Raw materials or intermediate for production of:
1- Phenol-formaldehyde resins 2- Bisphenol(for production of epoxy)
3-Caprolactum(for production of Nylon6 monomer) 4-Adipic acid(for production of
Nylon 66 monomer) 5- Salicylic acid(Aspirin production)
6-Phenol alkyl (Rubber chemical) or(production of Detergent).

Adipic acid :
COOH(CH2)4COOH
Raw materials: Butadiene, CO &H2O.
CH2=CH-CH=CH2 +2CO + 2H2O→HOOC(CH2)4COOH.
Buadiene Adipic acid
T=220OC P=75 atm. Cata: RdCl2/CH3I Yield" 49%
Uses: For production of Nylon66 directly or through Hexamethyldiamine HMDA

Cyclohexane:

Application: Produce high-purity cyclohexane by liquid-phase catalytic hydrogenation

of benzene.

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Description: The main reactor (1) converts essentially all the feed isothermally in the
liquid phase at a thermodynamically-favorable low temperature using a continuously-
injected soluble catalyst. The catalyst’s high activity allows use of low hydrogen partial
pressure, which results in fewer side reactions, e.g., isomerization or hydrocracking.
The heat of reaction vaporizes cyclohexane product and, using pump around circulation
through an exchanger, also generates steam (2). With the heat of reaction being
immediately removed by vaporization, accurate temperature control is assured. A vapor-
phase fixed-bed finishing reactor (3) completes the catalytic hydrogenation of any
residual benzene. This step reduces residual benzene in the cyclohexane product to very
low levels. Depending on the purity of the hydrogen make-up gas, the stabilization
section includes either an LP separator (4) or a small stabilizer to remove the light ends.

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Toluene derivatives:
Benzoic acid C6H5COOH:
Raw materials: Toluene ,oxygen
[O]
C6H5CH3 C6H5COOH.
Toluene Benzoic acid
Oxidation of toluene in liquid phase
Cata.: Cobalt salt at T=165OC. or
Cobalt bromide at T=140-165 OC
P=27 atm

Xylene derivatives:
Terephthalic acid (EPTA) COOH(C6H5)COOH

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Uses; terephthalic acid is an excellent raw material for engineering plastics and
packaging materials, bottles, other food containers including hot fill, as well as films.
The process is proven to be suitable for the production of all kinds of polyester fibers
and containers without limitation, at international first-grade quality.
Description: Crude terephthalic acid (1,2,3): CTA is produced by the catalytic
oxidation of p-xylene with air in the liquid phase using acetic acid as a solvent (1).
The feed mix— p-xylene, solvent and catalyst— together with compressed air is
continuously fed to the reactor, which is a bubble-column oxidizer. It operates at
moderate temperature and offers an extremely high yield. The oxidizer product is
known as crude terephthalic acid (CTA) due to the high level of impurities contained.
Many impurities are fairly soluble in the solvent. In the CTA separation step (2),
impurities can be effectively removed from the product by exchanging the reaction
liquor with lean solvent from the solvent recovery system. The reactor overhead vapor,
mainly reaction water, acetic acid and nitrogen is sent to the solvent-recovery system
(3), where water is separated from the solvent by distillation. After recovering its
energy, the offgas is sent to a regenerative thermal oxidation unit for further cleaning.
Polymer-grade terephthalic acid (5,6): The crude acid is purified to obtain EPTA in a
post-oxidation step, at elevated temperature conditions.
Catalyst recovery (4): After exchanging the liquor in the CTA separation, the
suspended solids are separated and removed as CTA residue, which can be burned in a
fluidized-bed incinerator or, if desirable, used as land fill. The soluble impurities are
removed from the filtrate within the filtrate treatment section, and the dissolved catalyst
is recycled.

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