Project Report FINAL

PRODUCTION AND PLANT DESIGNFOR MANUFACTURE OF METHOXYACETONE

INDEX

Chapter Description Page no.

Chapter 1 Abstract 3-4

Chapter 2 Introduction 5 - 7

1.1 Introduction 6

1.2 Applications of methoxyacetone 7

Chapter 2 Literature Survey 8-9

Chapter 3 Properties of Chemicals and Catalyst 10-14

3.1 Properties of methoxy-2 -propanol 11

3.2 Properties of methoxyacetone 12

3.3 Properties of CATALYST copper chromite 13

3.4 Properties of hydrogen 14

Chapter 4 Health & Safety Aspects 15-19

Chapter 5 Methods of Production 20-21

Chapter 6 Selection and Justification of the Process 22-23

B.V.C.O.E Navi-Mumbai (2012-13) Page 1


Chapter 7 Detail study of Selected Process 24-27

7.1 Flow sheet for production of methoxyacetone 25

7.2 Process description 27

Chapter 8 Thermodynamics Feasibility 28-34

8.1 Gibbs free energy calculations 29

8.2 Heat of reaction calculations 34

Chapter 9 Conclusion & scope for future work 35-36

Chapter 10 References 37- 38



Chapter 1

ABSTRACT



PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

The study involves the synthetic methods of catalytic dehydrogenation of alkylene glycol ether to ether ketone or aldehyde is disclosed. The dehydrogenation is performed with copper chromite catalyst and at least 5 wt % of water based on alkylene glycol ether. It has been found that the selectivity to formation of ether ketone or aldehyde increases with increasing the amount of water in the alkylene glycol ether.

Methoxyacetone is a prime product with many useful intermediate. It is used as a polar organic solvent ,a chemical intermediate , a Schiff base reagent ,as an additive for cement construction and in cryogenic preservation of organs.

It has the IUPAC name - Methoxyacetone . It has the following synonyms, Methoxy-2-propanone, 1 –Methoxypropan-2-one.



Chapter 2

INTRODUCTION



The project involves designing and production of alkoxyacetone. In particular it involves

vapor phase oxidation of 1-alkoxy-2-propanol to alkoxyacetone using copper chromite catalyst.

It involves catalytic dehydrogenation of alkylene glycol ether to ether ketone or aldehyde. The

dehydrogenation is performed with copper chromite catalyst and water based on alkylene glycol

ether. It has been found that the selectivity to formation of ether ketone or aldehyde increases with

increasing the amount of water in the alkylene glycol ether.

In this vapor phase oxidation is carried out to avoid the use of hazardous hydrogen peroxide which

may be harmful if not handled with care. Thus oxidation or dehydrogenation along with multiple

distillation operation yields methoxyacetone.



Applications

IUPAC name: Methoxyacetone.

It has the following synonyms: Methoxy-2-propanone,

Methoxypropan-2-one

Methoxyacetone (1-methoxy-2-propanone) provides a key to structural piece in the synthetic route to metolachlor and other herbicidal compositions (see, e.g., U.S. Pat. Nos. 4,666,502 and 5,576,188).

E.g. (U.S. Pat. No. 4,666,502)

Synthesis of heteroaromatic compounds bearing at one ring C-atom a N-substituted chloroacetylamino group, their use as herbicides, agricultural compositions. These compounds are particularly effective herbicides having an appropriate soil persis tence.

E.g. (U.S. Pat. No. 5,576,188)

Synthesis of hybridoma cell lines which produce said monoclonal antibodies and to immunological methods for detecting metolachlor in samples of soil, water or air using said monoclonal antibodies and to the test kits which can be used within the scope of these detection methods.

In addition, methoxyacetone has been used as a polar organic solvent, a chemical intermediate, a Schiff base reagent, an additive for cement 15 compositions, and as an aid in the cryogenic preservation of organs.



Chapter 3

LITERATURE SURVEY



The literature survey has been done on the basis of U.S patents. Development of entire

manufacturing and designing of plant process is based on these patents.

U.S patent – 3625836

Patent - Dec7, 1971

A method for recovering alkoxyacetones from mixtures of alkoxyacetone and the corresponding

1-alkoxy-2-propanol by adding water to the mixture and distilling to form a lower boiling

alkoxyacetone-water azeotrope.

U.S patent – 6376718

Patent – Nov 17, 2000

A catalytic dehydrogenation of alklyene glycol ether to ether ketone or aldehyde is disclosed.

The dehydrogenation is performed with copper chromite catalyst and at least 5 wt. % of water

based on alklyene glycol ether. It has been found that the selectivity to formation of ether ketone

or aldehyde increases with increasing the amount of water in the alkylene glycol ether.



Chapter 4

PROPERTIES OF CHEMICALS AND CATALYST



PROPERTIES OF METHOXY-2-PROPANOL:

Physical State: Liquid

Appearance: Colorless liquid

Molecular Formula: C4H10O2

Molecular Weight: 90.12

Boiling Point: 120° C at 760 mm Hg

Melting Point: -95 ° C

Flash Point: 36.11 ° C

Vapor Pressure: 11.8 mm Hg at 25 °C

Vapor Density (Relative to Air): 3.11

Specific Gravity: 0.924 at 20°C

Water Solubility: greater than or equal to 100 mg/ml at18.89 ° C



PROPERTIES FOR METHOXYACETONE:

Physical State: Liquid

Appearance: clear yellow

Molecular Formula: C4H8O2


Boiling Point: 118 0C ( 760.00 mmHg )

Melting Point: -660C

Vapor Pressure: 16 (250C)

Vapor Density: 3.04

Specific Gravity/Density: 0.9570 g/cm3

Water Solubility: Miscible.



PROPERTIES OF COPPER CHROMITE:

Physical state: Solid

Appearance: gray-black tetragonal crystals

Molecular formula: Cr2CuO4


Density: 4.5 g/cm3

Water Solubility: insoluble

Stability: air and moisture stable



PROPERTIES OF HYDROGEN:

Physical state: Gas

Appearance: Colorless gas

Molecular formula: H2

Molecular Weight: 2

Boiling point: - 252.8 °C

Melting point: - 259.2 °C

Density: 0.0899x10 -3 g.cm -3 at 20 °C

Solubility: Negligible

Stability: Highly flammable

(The gas mixes well with air, explosive mixtures are easily formed)



Chapter 5

HEALTH & SAFETY ASPECTS



Methoxyacetone:

Potential Health Effects

Eye: Causes eye irritation.

Skin: Causes skin irritation. May cause cyanosis of the extremities.

Ingestion: May cause gastrointestinal irritation with nausea, vomiting and diarrhea. Ingestion of

large amounts may cause CNS depression.

Inhalation: Causes respiratory tract irritation. Vapors may cause dizziness or suffocation.

Chronic: Prolonged or repeated skin contact may cause dermatitis. Effects may be delayed.

Safety Measures:

Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting

the upper and lower eyelids. Get medical aid.

Skin: Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing

contaminated clothing and shoes. Wash clothing before reuse.

Ingestion: Do not induce vomiting. If victim is conscious and alert, give 2-4 cupful’s of milk or

water.



METHOXY-2-PROPANOL


Vapor: Irritating to eyes, nose, and throat.

Liquid: Irritating to skin and eyes.

Health Hazard: Flammable and/or toxic gases are generated by the combination of alcohols

with alkali metals, nitrides, and strong reducing agents.

Safety Measures:

Eyes: Wear appropriate eye protection to prevent eye contact

Working Cloths: Work clothing that becomes wet should be immediately removed due to its

flammability hazard (i.e. for liquids with flash point < 100°F)

First Aid:

EYES: First check the victim for contact lenses and remove if present. Flush victim's eyes with water or

normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison

control center. Do not put any ointments, oils, or medication in the victim's eyes without specific

instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a

hospital even if no symptoms (such as redness or irritation) develop.

SKIN: IMMEDIATELY flood affected skin with water while removing and isolating all

contaminated clothing. Gently wash all affected skin areas thoroughly with soap and water. If

symptoms such as redness or irritation develop, IMMEDIATELY call a physician and be

prepared to transport the victim to a hospital for treatment.



INHALATION: IMMEDIATELY leave the contaminated area; take deep breaths of fresh air. If

symptoms (such as wheezing, coughing, shortness of breath, or burning in the mouth, throat, or

chest) develop, call a physician and be prepared to transport the victim to a hospital. Provide

proper respiratory protection to rescuers entering an unknown atmosphere. Whenever possible,

Self-Contained Breathing Apparatus (SCBA) should be used; if not available, use a level of

protection greater than or equal to that advised under Protective Clothing.

INGESTION: DO NOT INDUCE VOMITING. If the victim is conscious and not convulsing,

give 1 or 2 glasses of water to dilute the chemical and IMMEDIATELY call a hospital or poison

control center. Be prepared to transport the victim to a hospital if advised by a physician. If the

victim is convulsing or unconscious, do not give anything by mouth, ensure that the victim's

airway is open and lay the victim on his/her side with the head lower than the body. DO NOT

INDUCE VOMITING. IMMEDIATELY transport the victim to a hospital.

Fire Hazard

Air & Water Reactions: Highly flammable. Soluble in water. Oxidizes readily in air to form

unstable peroxides that may explode spontaneously.

Fire Hazard: FLAMMABLE. Flashback along vapor trail may occur. Vapor may explode if

ignited in an enclosed area.



HYDROGEN


Eyes: Contact with rapidly expanding gas may cause burns or frostbite. Contact with cryogenic

Liquid can cause frostbite and cryogenic burns.

Skin: Contact with rapidly expanding gas may cause burns or frostbite. Contact with cryogenic

Liquid can cause frostbite and cryogenic burns.

Accidental release measures

Personal precaution: Immediately contact emergency personnel. Keep unnecessary personnel

away. Use suitable protective equipment. Shut off gas supply if this can be done safely. Isolate

area until gas has dispersed.

Environmental precautions: Avoid dispersal of spilled material and runoff and contact with

soil, waterways, drains and sewers.

Methods for cleaning up: Immediately contact emergency personnel. Stop leak if without risk.



Chapter 6

METHOD OF PRODUCTION



Methoxyacetone is mainly formed by catalytic dehydrogenation process. It is carried in

following ways:

1. By dehydrogenation of 1-methoxy-2-propanol in presences of hydrogen peroxide

in liquid phase.

2. By dehydrogenation of 1-methoxy-2-propanol in presence of copper chromite in

vapor phase.



Chapter 7

SELECTION AND JUSTIFICATION OF PROCESS



The dehydrogenation of 1-methoxy-2-propanol in presence of copper chromite in vapour

phase is carried out. This is because of following reasons:

1. Copper chromite catalyst can be easily prepared.

2. Risk of handling hazardous hydrogen peroxide is avoided.

3. Easy separation of mixture product.

4. Toluene used as n entrainer can be easily recovered

5. Hydrogen gas separated is flared

6. Mild conditions ,simple equipment design and reagents are readily available



Chapter 8

Detail study of Selected Process





PROCESS DISCRIPTION

1. The process involves catalytic dehydrogenation 1-methoxy-2-propanol to methoxy

acetone. This is generally a vapor-phase oxidation using copper chromite as a catalyst.

2. At start 1-methoxy-2-propanol and water in proportions are mixed and mixture is send to

thin film evaporator. The heat exchanger is used to increase the temperature above the

desired range. In evaporator steam is used as a heating medium. The temperature of about

140 °C is reached. The vapors formed are reheated in heat exchanger to about 290°C

using dowtherm oil.

3. The vapors are sent to catalytic dehydrogenation unit. The unit is a fixed bed reactor

using copper chromite as a catalyst .Reactor is provided with jacket. Heating oil mainly

dowtherm oil is used. The temperature of the oil is about 280°C. Dehydrogenation is

carried out and crude product is obtained from the bottom.

4. The crude product from reactor contains mixture of water, methoxyacetone, hydrogen

gas, methoxy-2-propanol. The product stream is passed through the condenser. Cooling

water is used as the medium. Two condensers are used for effective temperature

difference.

5. The condensate contains liquid-gas mixture, thus they are sent to gas-liquid separator.

Here gas liquid separation results, and released hydrogen gas is flared.

6. The condensate liquid obtained contains mixture of water, methoxyacetone and some

amount of unreacted 1-methoxy-2-propanol. The mixture is subjected to distillation for

separation.



7. Distillation of feed mixture to distillation unit is carried out .various cuts are obtained

from the separation unit. They are as follows

Low boiling impurities Methoxyacetone + water azeotrope Methoxy-2-propanol + water Methoxyacetone + water + methoxy-2-propanol

8. Methoxy-2-propanol + water is recycled back and sent to heat exchanger. Methoxyacetone + water forms a binary azeotrope which is subjected to further azeotropic distillation.

9. In order to alter the volatility toluene or benzene are used as an entrainer

10. Here toluene is used has an entrainer as benzene is carcinogenic. Toluene alters the

volatility and forms a lower boiling azeotrope with water and methoxyacetone is

separated out.

11. The mixture is condensed and separated out and methoxyacetone is recovered.

12. Toluene + water are then subjected to further separation from which toluene is recovered

and water is send to ETP plant.



Chapter 9

THERMODYNAMICS FEASIBILITY



REACTION OF METHOXY-ACETONE

CH3-CH (OH)-CH2-O-CH3 CH3-CO-CH2-O-CH3 + H2

(METHOXY-2-PROPANOL) (METHOXY-ACETONE)

CONVERSION = 70% / PASS

SELECTIVITY = 97.5%

AS,

YIELD = CONVERSION x SELECTIVITY

= 0.7 x 0.975

= 0.68



RAW MATERIAL:

METHOXY 2-PROPANOL

MOLECULAR WEIGHT: 90

MOLECULAR FORMULA: CH3-CH(OH)-CH2-O-CH3

Domalsk-Hearing group contribution values for std. state thermal properties

Perry's Chemical Engineers Handbook-8th Edition

GROUP n∆H

Of

(KJ/mole)

∆SO

(J/mol. K)

∆Hsf

(KJ/mole)

S(J/mol. K)

C-(3H)(C) 1 -42.26 127.32 -47.61 80.30

C-(2C)(H)(O) 1 -26.1 -43.05 -27.6 -29.83

C-(2H)(C)(O) 1 -32.9 43.43 -35.8 32.89

C-(3H)(O) 1 -42.26 127.32 -47.61 83.3

O-(C)(H) 1 -159.33 121.5 -191.5 43.89

TOTAL-302.85 376.52 -350.12 213.25



PRODUCT:

METHOXY ACETONE

MOLECULAR WEIGHT: 88

CHEMICAL FORMULA: C4H8O2

Domalsk-Hearing group contribution values for std. state thermal properties

Perry's Chemical Engineers Handbook-8th Edition

GROUP n∆H

Of

(KJ/mole)

∆SO

(J/mol. K)

∆HS

f

(KJ/mole)

S(J/mol. K)

C-(3H)(C) 1 -42.26 127.32 -47.61 83.3

CO-(2C) 1 -132.67 64.31 -152.76 33.81

C-(2H)(C)(O) 1 -32.9 43.43 -35.8 32.5

C-(3H)(O) 1 -42.26 127.32 -47.61 83.

TOTAL-250.01 302.38 -283.78 233



STANDARD HEAT OF FORMATION AT 298.15 K:

∆HSf = [-283.78] – [- 350.12]

= 66.34 Kj/mol

GIBBS FREE ENERGY:

∆GSf = ∆HS

f- T∆SS

= 66.34 – 298.15 X [233 – 213.25]

= -5822.12 Kj/mol

HEAT CAPACITY OF LIQUID AND VAPOR MIXTURES CAN BE ESTIMATED AS MOLE FRACTION OF THE PURE COMPOUND VALUES



c

Cpm = ∑ Xi Cpi

i=1

IDEAL HEAT CAPACITY AT REACTION TEMPERATURE: 2800C (553 K)

A. METHOXY-2-PROPANOL(MEPA)

Benson* and CHETAH Group Contributions for Ideal Gas Heat Capacity. Perry's Chemical Engineers Handbook-8th Edition

GROUP n Cp 553 K (J/mol k) C-(3H)(C) 1 42.26 C-(2C)(H)(O) 1 35.52 C-(2H)(C)(O) 1 37.105 C-(3H)(O) 1 42.26 O-(C)(H) 1 21.035 TOTAL 178.38

B. METHOXY ACETONE (MEA)

Benson* and CHETAH† Group Contributions for Ideal Gas Heat Capacity. Perry's Chemical Engineers Handbook-8th Edition

GROUP n Cp 553 K (J/mol k) C-(3H)(C) 1 42.56 CO-(2C) 1 21.455 C-(2H)(C)(O) 1 37.105 C-(3H)(O) 1 42.26 O=C 1 15.07 TOTAL 158.145

• CpMEPAAT 553 K = 0.178 KJ/ mol. K

• CpMEAAT 553 K = 0.158 KJ/ mol. K



∆HOMEPA AT 553 K = Hf298.15 + Cp ∆ T

= -350.12 + 0.178(553 -298.15)

= -304.76 KJ/mol

∆HOMEA AT 553 K = Hf298.15 + Cp ∆ T

= -283.78 + 0.158(553 -298.15)

= -243.5 KJ/mol

∆H 353K = ∆Hfproduct – ∆Hfreactant

= [-243.5] – [- 304.76]

= 61.25 KJ/mol (i.e. endothermic)

∆H 353K = 61.23 X 103 J/mol

= 61.23/ (4.187 X 10-3 X 88)

= 166.23 Kcal/kg



Chapter 10

CONCLUSION AND FUTURE WORK



Thus vapor phase oxidation of 1-methoxy-2-propanol to methoxyacetone

using catalyst is studied. Higher conversion of alcohol to ketone and good

selectivity is obtained.

The Process is thermodynamically feasible and thus future work of the process is

feasible. Future work includes design and costing of entire manufacturing process

of methoxyacetone. Thus detailed study of development of entire process is

necessary for future scope.



Chapter 11

REFERENCES



* Perry's Chemical Engineers Handbook-8th Edition

* Coulson & Richardson's Chemical Engineering. Vol. 6

* http://www.chemspider.com

* http://www.freepatents.com

* http://www.wikipedia.com

* US Balan’s Patent (Patent No.6376718)

*US Patent (Patent No. 3625836)


http://www.wikipedia.com/

http://www.freepatents.com/

http://www.chemspider.com/

Project Report FINAL

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