PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

INDEX
Chapter Chapter 1 Chapter 2 1.1 1.2 Description Abstract Introduction Introduction Applications of methoxyacetone Page no. 3-4 5-7 6 7

Chapter 2 Chapter 3 3.1 3.2 3.3 3.4 Chapter 4

Literature Survey Properties of Chemicals and Catalyst Properties of methoxy-2 -propanol Properties of methoxyacetone Properties of CATALYST copper chromite Properties of hydrogen Health & Safety Aspects

8-9 10-14 11 12 13 14 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

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 7 7.1 7.2

Detail study of Selected Process Flow sheet for production of methoxyacetone Process description

24-27 25 27

Chapter 8 8.1 8.2

Thermodynamics Feasibility Gibbs free energy calculations Heat of reaction calculations

28-34 29 34

Chapter 9

Conclusion & scope for future work

35-36

Chapter 10

References

37- 38

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

Page 2

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 1 ABSTRACT

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

Page 3

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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-2propanone, 1 Methoxypropan-2-one.

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

Page 4

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 2 INTRODUCTION

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

Page 5

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE 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.

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

Page 6

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF 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 persistence. 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.

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

Page 7

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 3 LITERATURE SURVEY

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

Page 8

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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.

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

Page 9

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 4 PROPERTIES OF CHEMICALS AND CATALYST

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

Page 10

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

PROPERTIES OF METHOXY-2-PROPANOL:

Physical State: Appearance:

Liquid Colorless liquid

Molecular Formula:

C4H10O2 90.12

Molecular Weight:

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 20C

Water Solubility:

greater than or equal to 100 mg/ml at18.89 C

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

Page 11

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

PROPERTIES FOR METHOXYACETONE:

Physical State:

Liquid

Appearance:

clear yellow

Molecular Formula:

C4H8O2

Molecular Weight:

88.11

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.

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

Page 12

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

PROPERTIES OF COPPER CHROMITE:

Physical state:

Solid

Appearance:

gray-black tetragonal crystals

Molecular formula:

Cr2CuO4 311.08

Molecular Weight:

Density:

4.5 g/cm3

Water Solubility:

insoluble

Stability:

air and moisture stable

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

Page 13

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

PROPERTIES OF HYDROGEN:

Physical state:

Gas

Appearance:

Colorless gas

Molecular formula:

H2

Molecular Weight:

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)

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

Page 14

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 5 HEALTH & SAFETY ASPECTS

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

Page 15

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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 cupfuls of milk or water.

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

Page 16

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

METHOXY-2-PROPANOL Potential Health Effects

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 < 100F)

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.

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

Page 17

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE 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.

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

Page 18

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

HYDROGEN Potential Health Effects

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.

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

Page 19

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 6 METHOD OF PRODUCTION

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

Page 20

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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.

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

Page 21

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 7 SELECTION AND JUSTIFICATION OF PROCESS

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

Page 22

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE 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

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

Page 23

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 8 Detail study of Selected Process

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

Page 24

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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

Page 25

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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 290C 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 280C. 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.

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

Page 26

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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.

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

Page 27

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 9 THERMODYNAMICS FEASIBILITY

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

Page 28

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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

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

Page 29

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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
O f

(KJ/mole)

S (J/mol. K)

s f

S (J/mol. K)

(KJ/mole)

C-(3H)(C)

-42.26

127.32

-47.61

80.30

C-(2C)(H)(O)

-26.1

-43.05

-27.6

-29.83

C-(2H)(C)(O)

-32.9

43.43

-35.8

32.89

C-(3H)(O)

-42.26

127.32

-47.61

83.3

O-(C)(H)

-159.33

121.5

-191.5

43.89

-302.85 TOTAL

376.52

-350.12

213.25

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

Page 30

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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

O f

(KJ/mole)

S (J/mol. K)

S f

S (J/mol. K)

(KJ/mole)

C-(3H)(C)

-42.26

127.32

-47.61

83.3

CO-(2C)

-132.67

64.31

-152.76

33.81

C-(2H)(C)(O) 1

-32.9

43.43

-35.8

32.5

C-(3H)(O)

-42.26

127.32

-47.61

83.

-250.01 TOTAL

302.38

-283.78

233

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

Page 31

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

STANDARD HEAT OF FORMATION AT 298.15 K:

HSf = [-283.78] [- 350.12] = 66.34 Kj/mol

GIBBS FREE ENERGY:

GSf = HSf- TSS = 66.34 298.15 X [233 213.25] = -5822.12 Kj/mol

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

Page 32

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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 C-(3H)(C) C-(2C)(H)(O) C-(2H)(C)(O) C-(3H)(O) O-(C)(H) TOTAL B. METHOXY ACETONE (MEA) n 1 1 1 1 1 Cp 553 K (J/mol k) 42.26 35.52 37.105 42.26 21.035 178.38

Benson* and CHETAH Group Contributions for Ideal Gas Heat Capacity. Perry's Chemical Engineers Handbook-8th Edition
GROUP C-(3H)(C) CO-(2C) C-(2H)(C)(O) C-(3H)(O) O=C TOTAL n 1 1 1 1 1 Cp 553 K (J/mol k) 42.56 21.455 37.105 42.26 15.07 158.145

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

Page 33

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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

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

Page 34

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 10 CONCLUSION AND FUTURE WORK

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

Page 35

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

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.

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

Page 36

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

Chapter 11 REFERENCES

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

Page 37

PRODUCTION AND PLANT DESIGN FOR MANUFACTURE OF METHOXYACETONE

* 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 Balans Patent (Patent No.6376718) *US Patent (Patent No. 3625836)

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

Page 38