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 the decay 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 Fig.4. Emissions of CO2 from natural gas (ton/yr) from power plant in Kuwait. Fig.5. Emissions of CO2 from Crude or heavy oil (ton/yr) from power plant in Kuwait.

Refineries (Hydrogen plant): Fig.6. the Refineries and Companies in Kuwait.

Refineries (Hydrogen plant): 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: Fig.8: The following separation methods are used to capture CO2 from fossil fuel.

Fig 9. Schematic of the absorption process. 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.

Fig 10.Amine absorption unit for CO2 recovery from flue gas. 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: There are three types of adsorption such as : 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 13. Shows small pellets of dry ice subliming in air. 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.

Continue 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

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.

6.1.1 Properties of Acetic Acid 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.

6.2 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 .

6.7 Comparison of Acetic Acid Processes: Methanol Carbonylation (conventional method) Use Carbon dioxide .as a raw material Raw 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 Conditions pressure 30 bar 25 bar Catalyst Use Hydrogen iodide catalyst Vanadium catalyst Conversion 100% 97% Equipment Reactor ,flash drum, four distillation columns Reactor ,distillation column

7.Conclusion: When we make comparing between to process we should study : The cost of the equipments. The purity of the feed. The type of the reaction (what are they ?) 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.

Hopefully you enjoyed our presentation, Please feel free to ask any question =“) Kind Regards