Abo, Lynette Mae G.

Dorol, Eralyn Mae A.

Garcia, Mary Grace N.
 Figure 1. Block Flow Diagram of Production of Acetaldehyde from Oxidation of Ethylene.

The first process is the oxidation of ethylene to acetaldehyde using an aqueous solution of palladium chloride and copper chloride. In the reactor,

ethylene and oxygen are fed with a temperature of 125 °C and a pressure of 3 atm. The main reaction is C2H4 + 0.5 O2  CH3CHO.

First, the reaction in the reactor is C2H4 + PdCl2 + H2O  CH3CHO + Pd + 2HCl. During the reaction, PdCl2 is reduced to metal palladium and

HCL, together with acetaldehyde. The metal palladium is then re-oxidized to PdCl2 with CuCl2: Pd + 2CuCl2  PdCl2 + 2CuCl.

During the catalyst regeneration, CuCl2 formed is re-oxidized with oxygen or air: 2CuCl + 0.5 O2 + 2HCl  2CuCl2 + H2O. The net result is

C2H4 + 0.5 O2 CH3CHO. Second, the outlet from the reactor is fed to a catalyst separator/gas liquid separator to recover the catalyst. The activated

catalyst is now recycled to the reactor while the deactivated catalyst (spent catalyst) is regenerated to the catalyst regenerator at 175 °C and then

recycled it back to the reactor. The vapor from the separator includes steam, C2H4, CH3CHO, CO2, and O2. It is then passed to partial condenser with
a temperature of about 30-80 °C. Next, the acetaldehyde is being washed out from the gas scrubber. The scrubbing liquid which is the water is

sprinkled by specialize nozzles into the scrubber. CH3CHO and impurities are absorbed in scrubbing liquid while the rest is being sent to wet-seal

compressor and from there, the scrub gas recycle (C2H4, CO2, O2) is sent to the reactor. Water, acetaldehyde, and impurities is sent to boiler at a

temperature of 130 °C, and then the acetaldehyde will now be sent to distillation column 1 to separate CH3CHO from impurities and then, distillation

2 for purification.
 2.) Production from oxidation of ethanol

Ethyl alcohol or ethanol is able to produce acetaldehyde with the use of the oxidation mechanism. Water molecule from ethanol is removed in

a catalyst like silver and generates a single acetaldehyde molecule. This process is very similar to the production process of formaldehyde, huge

difference is this process requires two distillation columns.

Figure 2. Block Flow Diagram of Production of Acetaldehyde from Oxidation of Ethanol.

 Pre-heated Ethanol at 280°C to 300°C is charged into the saturator where it is heated together with compressed air, and is overheated up to

400°C before entering the reactor in order for it to react later. The saturated ethanol and air that was overheated enters the reactor where silver

catalyst is present, and is operating at 500°C to 650°C and 2 to 5 atm. The operating pressure are these low because acetaldehyde formation does

not favor high pressure.

The main reactions that take place are:

C2H5OH + ½ O2 → CH3CHO + H2O

C2H5OH → CH3CHO + H2

And the by-products that formed are:

C2H5OH + O2 → CH3COOH + H2O

C2H5OH + ½ O2 → CH4 + CO + H2O

C2H5OH + 2 O2 → 2 CO2 + 3 H2O

The stream is then instantly cooled before being sent to an absorption column where the column uses water to absorb acetaldehyde and

unconverted ethanol. The absorber is maintained at 2°C and 2 bar a. The next stage would be a two-stage distillation column. In the first column,

pure acetaldehyde can be retrieved in the distillate while the bottoms would contain water, ethanol, and a small portion of acetic acid. This column

is preferably operated at 3 bar a. The bottoms would be divided, and one part would be distributed to the mixing condenser, while the other would

be sent to the ethanol column to recover the unconverted ethanol and sent back to the process.
 3.) Production Acetaldehyde from dehydrogenation of ethanol

Figure 3. Block Flow Diagram of Production of Acetaldehyde from Dehydrogenation of Ethanol.

 Figure 4. Block Flow Diagram for UNIT 1

Process description for unit 1

A PFD of Unit 1 is shown in Figure.2 Ethanol, an 85-wt.% solution in water, Stream 1, is combined with 85-wt.% ethanol recycle stream,

Stream 23, from Unit 2. The resultant stream, Stream 2, is then pumped to 100 psia and heated to 626°F in 2 heaters before being fed to

Reactor, an isothermal, catalytic, packed-bed reactor, where the ethanol is dehydrogenated to form acetaldehyde. The reactor effluent is then
 cooled in 2 coolers. The resultant two-phase stream, Stream 8, is then separated in the flash tank vessel separator. The vapor, Stream 9, is

sent to absorber where it is contacted with water, which absorbs the acetaldehyde and ethanol from the vapor stream. The resulting vapor

effluent, Stream 11, is then sent for further processing and recovery of valuable hydrogen. Alternatively, this stream could be used as fuel.

Stream 12, the liquid, is combined with Stream 14, the liquid effluent from flash tank, and sent to Unit 2.

Figure 5. Block Flow Diagram for UNIT 2

Process description for unit 2

A PFD for Unit 2 is shown in Figure.3. Stream 15 enters distillation1 where the crude acetaldehyde, Stream 16, exits as the distillate.

This crude acetaldehyde is then sent to distillation2 where the acetaldehyde is purified to 99.9-wt.%, Stream 17. The bottom, Stream 18, is
 sent to waste treatment. The bottom from distillation1, Stream 19, is sent to distillation3 to begin the purification process of ethanol. In

distillation3, ethyl acetate and some water is removed from Stream 19 and exits as the distillate, Stream 20, which is then sent to waste

treatment. The bottom, Stream 21, is sent to component splitter where ethanol is separated from butanol, ethyl acetate, and most of the water.

These impurities exit in Stream 22 and are sent to waste treatment. The distillate consists of an 85-wt% solution of ethanol, which is then

recycled back to Unit 1 to be used in the feed. Waste streams, Streams 18, 20, and 22, all contain small quantities of valuable chemicals.

Detailed description:
Equipment description:

Mixer To mix stream 1 with the recycle

Pump Increase feed pressure

Heater Evaporates the feed

heater Heats the vapor feed

Packed-bed reactor Dehydrogenation reaction takes place

cooler Cools reactor effluent

Cooler Cools reactor effluent

Flash vessel separator Separate gases from liquid fraction

absorber Separate hydrogen has from flash vapor

effluent

heater Heats flash liquid effluent

mixer To mix 2 streams

distillation Separates acetaldehyde

 distillation Separates ethanol solution

distillation Reduce water content in ethanol solution

Component splitter Remove acetaldehyde and ethyl acetate

traces

Reactions:
CATALYST : Ni/SnO2

TEMP (°C) Conversion % Acetaldehyde Selectivity

200 1.24 100

250 9.23 98.87

300 41.48 83.73

350 33.11 84.07

The figure shows that Ni/SnO2 was more active and stable for the production of acetaldehyde from ethanol at 300 °C.

• Ni/SnO2 catalysts exhibited better catalytic ethanol dehydrogenation

• Using Ni/SnO2 with 10 wt% of Ni content and reaction temperature at 300 °C for production of acetaldehyde in order to achieve high

activity and good selectivity

Alternative No. of Catalyst Raw Availability Unusual condition
main material raw material
equipment

A 9 Palladium Ethylene Available The oxygen content of the recycle gas is limited to maximum
locally
9 % mol to stay safely below flammable range

B 15 Silver Ethanol It should be The temperature in the absorber is 2 C . Low temperature is need
imported
C 15 Ni- based Ethanol It should be High pressure in most equipment
imported

Comparison between alternatives:

4. )Production of Acetic Acid from Acetaldehyde

Off gas

CH3CHO Acetic acid

MAIN Distillation 1 Distillation 2
Reactor 2
REACTOR
O2

Manganese acetate
 In this process, acetaldehyde is converted to acetic acid by oxidation of acetaldehyde in the presence of manganese acetate. In the reactor, the

main reaction is CH3CHO + O2  CH3COOH. The first step of the process is that acetaldehyde and oxygen is being fed in the reactor. The oxygen

is being pumped at normall conditions of pressure of 760 mmhg and 0 C. The catalyst is also fed in the reactor. When the oxygen is used, the

temperature will change from 70 C to 80 C at a pressure that is sufficient to keep the phase of the acetaldehyde to be liquid. The reaction mixture

is then drawn off the top of the tower and is diluted continuously in numerous distillation column. Crude acetic acid will be recovered on the top of

the distillation column while the residue containing the catalyst will be at the bottom.
 REFERENCES:
Alsaleh, A., Alshemali, A., Almtairi, A., Alazmi, H., & Elbadawi, I. (n.d.) Production of Acetaldehyde. Department of Chemical Engineering,
Kuwait University.
Sushmita, S., & Vinay, J. (2012). Production of Acetaldehyde. JAYPEE UNIVERSITY OF ENGINEERING AND TECHNOLOGY.
Eliasson, J. (2010). Design of a Plant for Manufacturing of Acetaldehyde. Department of Chemical Engineering, Lund University.
Retrieved from: http://www.chemeng.lth.se/exjobb/E572.pdf
Retrieved from: http://www.inclusive-science-engineering.com/ethyl-alcohol-oxidation-process-flow-diagram-produce-acetaldehyde/
Retrieved from: http://www.inclusive-science-engineering.com/processes-for-manufacturing-acetic-acid/
Retrieved from:
https://www.researchgate.net/profile/Prudhvi_Raj18/publication/296525796_Manufacture_of_Acetic_acid_through_the_methanol_carbonylation_
route/links/56d66a7d08aebe4638ac73b7/Manufacture-of-Acetic-acid-through-the-methanol-carbonylation-route.pdf
Retrieved from: https://www.google.ch/patents/US4094901