Acetic Acid production from Carbon Dioxide

Done by

Luluwa Al-Mutairi 203113380

Modhi Al-Nassar 203114383

Zainab Al-Fadhli 202113449

Overview:

• Introduction.• Properties of Carbon dioxide.• Sources of Carbon dioxide.• Capture and Regeneration of CO2.• Physical Utilization of CO2.• Chemical Utilization of CO2. • Acetic Acid.• Conventional method of Acetic Acid.• Production of acetic acid from Carbon dioxide. • Conclusion.

1. Introduction:

• CO2 is the major cause of global warming and it has a 64% of the greenhouse effect .

• The essential greenhouse gases are water vapor that result about 36-70% of the greenhouse influence, carbon dioxide (CO2) 9-26%, methane (CH4)4-9%, ozone 3-7%.

• Global warming : as the result of greenhouse effect that trap in the infrared rays of the sun.

Influences of Global warming are :

– Increase temperature of the earth. – Its responsibility of the appearance of new illnesses.

2. Properties of Carbon dioxide:

2.1Chemical Properties:

•Carbon dioxide dissolves very well in water.• Not chemically reactive• It is applied to extinguish fire hence it is not flammable gas.

2.2 Physical Properties:

• Colorless and odorless gas.• Becomes a solid at -78.5 ºC. • Slightly toxic.• Much denser than air.

3.Sources of Carbon Dioxide:3.1 Natural sources:

It is created naturally by human activities (respiration) and by thedecay of plants, also oceans is another large natural source of CO2.

3.2 Industrial sources:

-Types of industrial process CO2emissions:

1. Production and consumption of mineral products.2. Production of iron and steel. 3. Chemical production (ammonia and petrochemicals). 4. Consumption of petroleum products in feedstock and other end uses .

Fig.1: Pie chart shows how CO2 is produced .

3.3The Essential Sources of CO2 in the world

Fig .2: Shows the amount of CO2 emission per capita in the world

3.4 The Essential Sources of CO2 in Kuwait

Thermal Power Plants:

Fig.3. Thermal Power Plants in Kuwait.

Emission Carbon dioxide in power plant in Kuwait Emissions of CO2 from Natural gas (ton/yr) from

power plant in kuwait

8%

35%

14%12%

28%

3% Shawaikh

Shuiwba

Doha East

DohaWest

AlZour

Subia

Emissions of CO2 from Crude or heavy oil (ton/yr) from power plant in kuwait

13%

23%

39%

25%Doha East

Doha West

AlZour

Subia

Fig.5. Emissions of CO2 from Crude or heavy oil (ton/yr) from power plant in Kuwait.

Fig.4. Emissions of CO2 from natural gas (ton/yr) from power plant in Kuwait.

Refineries (Hydrogen plant):

Fig.6. the Refineries and Companies in Kuwait.

Refineries (Hydrogen plant):

Emissions of CO2 from Hydrogen plant (ton/day) from refineries in kuwait

37%

34%

29%

AL-Ahmadi

Mina Abdullah

Shuaiba

Fig.7. Emissions of CO2 from hydrogen plant (ton/yr) from refineries in Kuwait.

4. Capture and Regeneration of CO2

• The carbon dioxide capture is an important concept to reduce greenhouse gas emissions from sources such as fossil fuel power plants and refineries (mainly from hydrogen units).

Methods for CO2 capture:

Methods for CO2 Capture

Absorption AdsorptionMembrane Separation

Cryogenic

Physical ChemicalHybrid

Absorption Process

Organic Amine

Inorganic

MEA

NAK/ Carbonate/

ammonia

PSA TSA ESAGas Separation

MembraneGas Absorption

Membrane

Fig.8: The following separation methods are used to capture CO2 from fossil fuel.

4.1.Absorption• A specific gas can be separated from a mixture of gases by contacting the

mixture of gases with a solvent that will selectivity dissolve the specific gas.

Fig 9. Schematic of the absorption process.

4.1.1 Chemical Absorption

• chemical absorption can be used at low CO2 partial pressures ,since CO2 is an acid.

• The most common chemical absorption processes are organic solvent process (amine) , in organic solvent process and by caustic soda.

• The following Chemical solvents are used to remove CO2:

Organic solvent( amines).

• The major method used to remove CO2 and operation condition is depend on the type of amine( primary ,secondary and tertiary amines).

• The most common types of amine solvents are MEA, DEA, DIPA and MDE.

• Continue:

• The Most common amine is the monoethanol amine (MEA) from the primary amines.

• This type has many advantages such as low cost, works at low pressure and fast reaction kinetics.

Amine process:

Fig 10.Amine absorption unit for CO2 recovery from flue gas.

4.1.2 Physical Absorption

• It is as a good solution for capturing CO2 in hydrogen production unit, as well as in power plants.

• Physical absorption is more suitable for higher partial pressure .

• The removal efficiency of CO2 is around 90%.

• The most widely used process is flour process , purisol process, rectisol and sulfinol process.

• Flour process:

The flour solvent CO2 removal process is intended primarily for the purification of gases containing CO2 in high concentrations at high pressure.

• Purisol process:

This process uses n-methyl-2-pyrrolidone also known as NMP as a solvent. The solvent removes CO2 and hydrocarbons.

4.1.3Hybrid process:

• Hybrid solvents combine the of both the chemical and physical solvent and they are usually composed of a mixture of components.

4.2 Adsorption:• The intermolecular forces between gases such as CO2 and the surface of

certain solid materials permit separation by adsorption .

• The solid adsorbents, such as activated carbon and zeolits molecular sieves .

• Adsorption is widely used for the purification of hydrogen.

There are three types of adsorption such as :

1. Pressure swing adsorption PSA. 2. Temperature swing adsorption TSA. 3. Electric adsorption ESA.

4.3 Cryogenic:

• Cryogenic separation is widely used commercially for purification of CO2 from streams that already have high CO2 concentration .

• In a cryogenic separation system, CO2 is physically

separated from other gases by condensing it into a liquid form at an extremely low temperature

4.4Membranes:

• The selectivity of the membrane to different gases is intimately related to the nature of the material.

• The flow of the gas is usually driven by the pressure difference across the membrane.

• There are many types of membrane materials, such as polymers, metals and ceramics .

The following two types of membranes systems :

1.Gas separation membranes:

There differences in physical or chemical interactions between gases and a membrane ,causing one component to pass through the membrane faster than another .

2.Gas absorption membranes:

- Micro-porous solid membranes. - These membranes are used as contacting devices between gas flow

and liquid flow, through the membrane the carbon dioxide diffuses and is removed by the absorption liquid.

Principles of gas separation and gas absorption membranes

Fig.11. principles of gas separation and gas absorption membranes

5. Physical Utilization of CO2:

• In the food industry.

• For fire extinguish and artificial rain.

• In well re-injection.

• In nuclear fields: as in power plant cooling.

• Dry Ice

Dry Ice What is Dry Ice?

-Dry ice keeps items colder ,with temperature 109 degrees below zero (-78.5° C).

  How to Make Dry Ice?

-First Pressurizing (CO2)

- refrigerated to form liquid CO2; which is allowed to expand in an atmospheric chamber.

- CO2 converts from liquid CO2 to gas, -by an extreme drop in temperature some of the gas to freeze, yielding both

snow-like CO2 and vapor CO2

1) The “snow” is then hydraulically pressed into dry ice blocks and pellets.2)The CO2 vapor is captured and recycled using a recovery system to

maximize the yield of dry ice from each pound of liquid CO2.

Dry Ice Uses :

• To remove floor tiles , and skin imperfections. • In the poultry industry ,baking industry. • To lengthen the life of wet ice. • To shrink metal • To retard chemical catalysts. • To improve porosity in oil wells. • To pack ice cream on trips .• To purge fuel tanks .• By blood banks for shipping. • By the concrete industry to prevent heat buildup .• To freeze unstable ground .• To germinate food. • To freeze water lines without shutoff valves .

Fig 12. Shows carbon dioxide bubbles in a soft drink.

Fig 13. Shows small pellets of dry ice subliming in air.

6. Chemical Utilization of CO2

• In rubber and plastic industry

• In chemical industry: synthesis, polymers, inorganic carbonates.

• Caron dioxide can be used in some chemical processes as an inert gas, solvent and reagent.

• CO2 can be used to neutralize alkaline water.

• In methane reforming.

• Hydrogenation

• CO2+ 3 H2 CH3OH + H2O methanol• 2CO2+ 6H2 C2H5OH+ 3H2O ethanol• CO2+ H2 C H3-O-CH3 dimethyl ether

• Hydrocarbon Synthesis

• CO2+ 4 H2 CH4 + 2H2O methane • 2CO2+ 6 H2 C2H4 + 4H2O ethylene

Continue

• Carboxylic Acid Synthesis

• CO2+ H2 HC=O-OH formic acid

• CO2+ CH4 CH3-C=O-OH acetic acid

• Graphite synthesis

• CO2+ H2 C+ H2O

• CH4 C + H2

• CO2+ 4 H2 CH4 + 2H2O

• Amine Synthesis

• CO2+ 3 H2 +NH3 CH3 – NH2 + 2H2O methyl amine and higher amines.

Continue

• Hydrolysis and Photo catalyst Reduction

• CO2+ 2H2O CH3OH+ O2

• CO2+ H2O HC=O-OH+1/2 O2

• CO2+ 2H2O CH4+ 2O2

• Other Reaction

• CO2+ ethyl benzene styrene

• CO2+ C3H8 C3 H6 + H2 +CO

• Dehydrogenation of propane

•CO2+ CH4 2CO + H2 reforming

Continue

6.1 Acetic acid• Acetic acid is an important chemical and the most produced acid

in the world.

• It is known as ethanoic acid, and the structural formula is represented as CH3COOH.

• The major producers of synthetic acid are currently the United States, Western Europe, Japan, Canada, and Mexico .

• The total capacity in these countries is close to 4*10^6 t/a and production is 3*10^6 t/a.

• Physical properties: clear, colorless liquid with a pungent odor.

• Chemical properties: Although acetic acid is not unusually reaction, many useful and commercially valuable materials can be prepared from it.

• reacts with alcohols or olefins to form esters.

• Acetic acid also can be converted to acetyl chloride using chlorination agents (phosphorus trichloride or thionyl chloride).

• Acetic acid is a raw material for a number of commercial processes.

• Acetic acid also is used in the manufacture of acetic acid anhydride and chloroacetic acid.

6.1.1 Properties of Acetic Acid

6.2 Uses of Acetic Acid

in the production of vinyl acetate monomer, acetic anhydride and ester production .

in the manufacture of chloroacetic acid, plastics,photographic chemicals, food.

6.3 Production of Acetic Acid • Methanol carbonylation

In this process, methanol and carbon monoxide react to produce acetic acid according to the chemical equation:

CH3OH + CO → CH3COOH

• Acetaldehyde oxidation

This method remains the second most important manufacturing method

2 CH3CHO + O2 → 2 CH3COOH

6.4 .Comparison of Acetic acid process

• Conventional process:

- Methanol carbonylation: In Acetic acid production we find that Methanol carbonylation route is the conventional process and more than 60% of the world production is through this process.

Fig.14. flow sheet of acetic acid production by Methanol carbonylation.

6.6 Uses Carbon dioxide:

• Uses Carbon dioxide was new catalytic process that produces acetic acid which is one of potential chemical target.

• In principle, acetic acid can be produced by the direct reaction of methane and carbon dioxide:

CH4 + CO2 CH3OOH

Fig.15. flow diagram for acetic acid using CO2 as a raw material .

Process Methanol Carbonylation(conventional method)

Use Carbon dioxide .as a raw

materialRaw material Methanol, Carbon Monoxide Methane, Carbon Dioxide

Reaction CO+CH3OH CH3 COOH CH4+CO2 CH3COOH

Heat of reaction (DH) -135 kJ/mol 36 kJ/mol

Operating Conditions temperature

450 K 350 K

Operating Conditionspressure

30 bar 25 bar

Catalyst Use Hydrogen iodide catalyst Vanadium catalyst

Conversion 100% 97%

Equipment Reactor ,flash drum, four distillation columns

Reactor ,distillation column

6.7 Comparison of Acetic Acid Processes:

7.Conclusion:

• When we make comparing between to process we should study :

1. The cost of the equipments.2. The purity of the feed.3. The type of the reaction (what are they ?)4. The conversion of the reactor.

• When we make comparing between exothermic and endothermic reaction we see when use cooler for exothermic reaction is less cost and safety than use steam for endothermic reaction.

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