A Seminar report

Acrolien

Index

SR. NO.
1 2 3 4 6 7 8 9 10 11 HISTORY INTRODUCTION PROPERTIES

CONTENTS

PAGE NO.
3 4 6 7 8 9 10 11 12 19

APPLICATION AND USES MANUFACTURING PROCESS PROCESS SELECTION PROCESS DESCRIPTION OF METHACRYLIC ACID FLOWSHEET FORMANUFACTURING METHACRYLIC ACID MATERIAL SAFETY DATA SHEET REFERENCES

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Acrolien

HISTORY Acrolien was discovered in 1843 by Redtenbacher.It was remained as laboratory chemicals with Acrylonitrile until the devlopment of some large scale polymerisatin processes. Preperative methods were replaced by commercial catalytic processes and expensive chemicals by cheaper raw matarials to obtain these important unsaturated intermediates in chemical industry. Acrolein is primarily used as an intermediate in the synthesis of acrylic acid and as abiocide. It may be formed from the breakdown of certain pollutants in outdoor air or from the burning of organic matter including tobacco, or fuels such as gasoline or oil. It is toxic to humans following inhalation, oral or dermal exposures. Acrolein has been used to make modified food starch, synthetic glycerine, acrolein polymers, polyurethane, and polyester resins. It has also been used in military poison gas mixtures. Acrolein has been produced commercially since 1938.

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Acrolien INTRODUCTION

Acrolein is a clear, colorless, or yellow liquid with a pungent, suffocating odor. It is very flammable and may polymerize violently. Acrolein should be stored in a cool, dry, wellventilated area intightly sealed containers separated from alkaline materials such as caustics, ammonia, organic amines, or mineral acids, strong oxidizers, and oxygen. Acrolein is soluble in water, alcohol, ether and acetone. Acrolein is primarily used as an intermediate in the synthesis of acrylic acid and as abiocide. It may be formed from the breakdown of certain pollutants in outdoor air or from the burning of organic matter including tobacco, or fuels such as gasoline or oil. It is toxic to humans following inhalation, oral or dermal exposures. Acrolein is a highly toxic, flammable material with extreme lacrimatory properties. It is a widely used intermediate in the production of building materials, herbicides andalgaecides, water treatment chemicals, and essential amino acids like methionine. Acute (short-term) inhalation exposure may result in upper respiratory tract irritation and congestion.. The largest single use for Acrolein is as an unisolated intermediate in the manufacture of acrylic acid, most of which is converted to its lower alkyl esters. Acrolein is also used as aherbicide and algicide in irrigation waters and drainage ditches; as a biocide in the control of algae, weeds, as a slimicide in the paperindustry; as a biocide in oil wells and liquid petrochemical fuels; in the cross-linking of protein collagen in leather tanning; as a tissue fixative in histological samples; as a warning agent in methyl chloride refrigerant; and as an intermediate in the manufacture of methionine and itshydroxyl analogue, glutaraldehyde, ally1 alcohol, pyridine. Acrolein has been used to make modified food starch, synthetic glycerine, acrolein polymers, polyurethane, and polyester resins. It has also been used in military poison gas mixtures.Partial oxidation of Acrolein is a commercially important reaction, its product acrylic acid being widely used industrially for producing resins, dyes, glues, non woven fabrics, etc. Partial oxidation of Acrolein is also a convenient model reaction because, the number of reaction products is moderate (CO, CO2).

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Acrolien

STRUCTURE : 2D structure

3D structure

It is also known as 2-propen-1-one, prop-2-en-1-al, acraldehyde, acrylaldehyde, acrylicaldehyde, allyl aldehyde, ethylene aldehyde, aqualine

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Acrolien PHYSICAL & CHEMICAL PROPERTIES

CHEMICAL NAMES AND FORMULAS Name IUPAC Name Formula Compound formula Acrolien 2-propenal CH2=CH-CHO C3H4O

PHYSICAL & CHEMICAL PROPERTIES Molar mass Appearance Boiling point Melting point Density Polymerisation Reactivity with water 56.06 g/mol Colorless to yellow liquid 530C -880C 0.839 g/cm2 Undergoes uncatalysed autopolymerisation at No reaction

THERMODYNAMIC PROPERTIES Auto ignition point Latent heat of vaporisation Heat of combustion Critical pressure Critical temperature Flash point 4530F 5.023*103 J/KG -290*105 J/kg 50.0atm 2540C -17.8

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Acrolien APPLICATION & USES :

Acrolein is a highly toxic, flammable material with extreme lacrimatory properties. It is a widely used intermediate in the production of building materials, herbicides and algaecides, water treatment chemicals, and essential amino acids like methionine. Acrolein is primarily used as an intermediate in the synthesis of acrylic acid and as a biocide. The largest single use for Acrolein is as an unisolated intermediate in the manufactureof acrylic acid, most of which is converted to its lower alkyl esters. Acrolein has been used to make modified food starch, synthetic glycerine, acrolein polymers, polyurethane Acrolein test. Acrolein test is a test for the presence of glycerin or fats. A sample is heated with potassium bisulfate, and acrolein is released if the test is positive.[8] When a fat is heated strongly in the presence of a dehydrating agent such as potassium bisulfate (KHSO4), the glycerol portion of the molecule is dehydrated to form the unsaturated aldehyde, acrolein (CH2=CHCHO), which has the peculiar odor of burnt grease.

Acrolein is also used as aherbicide and algicide in irrigation waters and drainage ditches; as a biocide in the control of algae, weeds, as a slimicide in the paperindustry; as a biocide in oil wells and liquid petrochemical fuels; in the cross-linking of protein collagen in leather tanning; as a tissue fixative in histological samples; as a warning agent in methyl chloride refrigerant; and as an intermediate in the manufacture of methionine and its hydroxyl analogue, glutaraldehyde, ally1 alcohol, pyridine.

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Acrolien

MANUFACTURING PROCESS For the production of Acrolein there are two processes mainly considered in industry

1. PRODUCTION WITH GLYCERIN

Namely production by glycerin can be considered as an economic alternative since glycerin can be obtained from soap production. In addition glycerin is a side product of the transesterification of vegetable oils to manufacture biodiesel. This means as the biodiesel production increases it would be easy to find great amount of glycerin at lower costs. From the environmental perspective glycerin process would be more environments friendly since there is no any oxidation reactions, no carbon dioxide emissions.

2.PARTIAL OXIDATION OF PROPYLENE

In this process Propylene which is obtained from crude-oil resources is use as raw material.This process is not considered to be feasible in long term because of increasing crude oil prices and the depletion of crude oil resources.propylene is heated with the water and then oxidized to acroline by burning with oxygen.

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Acrolien

PROCESS SELECTION
Though the production of acrolein from glycerin is environmentally safe, we select the production of acrolein from partial oxidation of propylene due to the following reasons: Simplicity of the process.

Widely accepted in industries.

Overall yield of the process.

Low maintainance cost of process & economic feasiability of process.

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Acrolien

PROCESS DESCRIPTION FOR MANUFACTURING OF ACROLIEN

The current industry standard for production of Acrolein is via the catalytic partial oxidation of Propylene. . PROCESS DESCRIPTION A base case PFD is shown in Figure . Propylene (Stream 2), steam (Stream 4), and compressed air (Stream 6) are mixed and heated to 250C. The resultant stream(Stream 8) is sent to a catalytic packed bed reactor where propylene and oxygen react to form acrolein. The reactor effluent is quickly quenched to 50C with deionized water(Stream 13) to avoid further homogeneous oxidation reactions. Stream 14 is then sent to an absorber, T-101, where it is scrubbed with water and acrolein is recovered in the bottoms (Stream 17). The off gas, Stream 16, is sent to an incinerator for combustion Stream 17 is then distilled in T-102 to separate acrolein and propylene from water and2acrylic acid. The bottoms (Stream18) consisting of wastewater and acrylic acid are sent to waste treatment. The distillate (Stream 19) is sent to T-103 where propylene is separated from acrolein and the remaining water in the system. The distillate from T-103, contains 98.4% propylene. The possibility of recycling this stream can beinvestigated. The bottoms (Stream 21) is then sent to T-104 where acrolein is separatedfrom water. Stream 23 is sent to waste treatment, and the distillate (Stream 22) consistsof 98% pure acrolein.

Equipment Description C-101 Feed Air Compressor;E-101 Reactor ;PreheaterE-102; CondenserE-103 ;Reboiler4; E-104 Condenser;E-105 Reboiler;E-106 Condenser;E-107 Reboiler;P-101A/B ;Water PumpP-

102A;B;Reflux PumpP-103A/B; Reflux Pump;P-104A/B; Reflux PumpR-101 ; Packed Bed Reactor;T-101 Acrolein Absorber;T-102 Water Distillation Tower;T-103 Propylene Distillation Tower;T-104 Acrolein Distillation Tower;V-101 Reflux Vesse;lV-102 Reflux Vessel;V-103 Reflux Vessel.

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Acrolien

FLOW SHEET FOR MANUFACTURE OF ACROLEIN

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MATERIAL SAFETY DATA SHEET

Section 1: Chemical Product Product Name: Acrolien Chemical Formula: C3H4O CAS: 107-02-8

Section 2: Composition and Information on Ingredients Toxicological Data on Ingredients: Acrolein: ORAL (LD50): Acute: 26 mg/kg [Rat]. 13.9 mg/kg [Mouse]. 7 mg/kg [Rabbit]. DERMAL (LD50): Acute: 200 mg/kg [Rabbit]. VAPOR (LC50): Acute: 18 mg/m 4 hours [Rat]. 66 ppm 6 hours [Mouse]. Section 3: hazards identification Potential acute health effects: very hazardous in case of skin contact (irritant), of eye contact (irritant), of ingestion, of inhalation. hazardous in case of skincontact (permeator). slightly hazardous in case of skin contact (corrosive), of eye contact (corrosive). liquid or spray mist mayproduce tissue damage particularly on mucous membranes of eyes, mouth and respiratory tract. skin contact may produce. Potential chronic health effects: carcinogenic effects: not classifiable for human. mutagenic effects: mutagenic for mammalian somatic cells. mutagenic for bacteria and/or yeast. teratogenic effects: not available. Developmental toxicity: not available. The substance is toxic to lungs, upper respiratory tract. The substance may be toxic to skin, eyes. Repeated or prolonged exposure to the substance can produce target organs damage. repeated or prolonged contact with spray mist May produce chronic eye irritation and severe skin irritation. repeated or prolonged exposure to spray mist may produce.
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Section 4: first aid measures Eye Contact: Check for and remove any contact lenses. Immediately flush eyes with running water for at least 15 minutes, keeping eyelidsopen. Cold water may be used. Get medical attention immediately. Skin Contact: In case of contact, immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Cover the irritated skin with an emollient. Cold water may be used. Wash clothing before reuse. Thoroughly clean shoes before reuse. Get medical attention immediately. Serious Skin Contact: Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream. Seek immediate medical attention. Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical attention immediately. WARNING: It may be hazardous to the person providing aid to give mouth-to-mouth resuscitation when the inhaled material is toxic, infectious or corrosive. Seek immediate medical attention. Ingestion: If swallowed, do not induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Loosen tight clothing such as a collar, tie, belt or waistband. Get medical attention immediately. Serious Ingestion: Not available

Section 5: Fire and Explosion Data Flammability of the Product: Flammable. Auto-Ignition Temperature: 220C (428F) Flash Points: CLOSED CUP: -26C (-14.8F). OPEN CUP: -18C (-0.4F) (Cleveland).
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Flammable Limits: LOWER: 2.8% UPPER: 31% Products of Combustion: These products are carbon oxides (CO, CO2). Fire Hazards in Presence of Various Substances: Highly flammable in presence of open flames and sparks, of heat. Flammable in presence of oxidizing materials. Explosion Hazards in Presence of Various Substances: Risks of explosion of the product in presence of mechanical impact: Not available. Risks of explosion of the product in Presence of static discharge: Not available. Slightly explosive in presence of heat. Fire Fighting Media and Instructions: Flammable liquid, soluble or dispersed in water. SMALL FIRE: Use DRY chemical powder. LARGE FIRE: Use alcohol foam, Water spray or fog. Special Remarks on Fire Hazards: Vapors may form explosive mixtures with air. Vapor may travel considerable distance to source of ignition and flash back. When heated to decomposition it emits toxic fumes of carbon monoxide, peroxide sp. 3 Special Remarks on Explosion Hazards: Vapors may form explosive mixtures with air. Section 6: Accidental Release Measures Small Spill: Dilute with water and mop up, or absorb with an inert dry material and place in an appropriate waste disposal container. Large Spill: Flammable liquid. Corrosive liquid. Poisonous liquid. Keep away from heat. Keep away from sources of ignition. Stop leak if without risk. Absorb with DRY earth, sand or other non-combustible material. Do not get water inside container. Do not touch

Spilled material. Use water spray curtain to divert vapor drift. Use water spray to reduce vapors. Prevent entry into sewers, Basements or confined areas; dike if needed. Call for assistance on disposal. Be careful that the product is not present at a concentration level above TLV. Check TLV on the MSDS and with local authorities.

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Section 7: Handling and Storage Precautions: Keep away from heat. Keep away from sources of ignition. Ground all equipment containing material. Do not ingest. Do not breathe gas/fumes/ vapor/spray. Never add water to this product. In case of insufficient ventilation, wear suitable respiratory equipment. If ingested, seek medical advice immediately and show the container or the label. Avoid contact with skin and eyes. Keep away from incompatibles such as oxidizing agents, acids, alkalis. Storage: Store in a segregated and approved area. Keep container in a cool, wellventilated area. Keep container tightly closed and sealed until ready for use. Avoid all possible sources of ignition (spark or flame). Do not store above 8C (46.4F). Refrigerate. Sensitive to light.

Section 8: Exposure Controls/Personal Protection Engineering Controls: Provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapors below their respective ethers hold limit value. Ensure that eyewash stations and safety showers are proximal to the work-station location. Personal Protection: Face shield. Full suit. Vapor respirator. Be sure to use an approved/certified respirator or equivalent. Gloves. Boots. Personal Protection in Case of a Large Spill: Splash goggles. Full suit. Vapor respirator. Boots. Gloves. A self contained breathing apparatus should be used to avoid inhalation of the product. Suggested protective clothing might not be sufficient; consult a specialist BEFORE handling this product. Exposure Limits: TWA: 0.1 STEL: 0.3 from ACGIH (TLV) [United States] TWA: 0.23 STEL: 0.69 from ACGIH (TLV) [United States] Consult local authorities for acceptable exposure limits.

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Acrolien

Section 9: Physical and Chemical Properties Physical state and appearance: Liquid. (Liquid.) Odor: Disagreeable and choking. Piercing. Extremely sharp. Extremely acrid Taste: Not available. Molecular Weight: 56.06 g/mole Color: Colorless to light yellow. p. 4 pH (1% solution/water): 7 [Neutral.] Boiling Point: 52.5C (126.5F) Melting Point: -88C (-126.4F) Critical Temperature: 254C (489.2F) Specific Gravity: 0.8389 (Water = 1) Vapor Pressure: 28 kPa (@ 20C) Vapor Density: 1.94 (Air = 1) Volatility: Not available. Odor Threshold: 0.21 ppm Water/Oil Dist. Coeff.: The product is equally soluble in oil and water; log(oil/water) = 0 Ionicity (in Water: Not available. Dispersion Properties: See solubility in water, diethyl ether. Solubility: Soluble in cold water, hot water, diethyl ether. Soluble in petroleum ether, alcohol, oxygenated solvents. Miscible with lower alcohols, ketones, benzene. Solubility in water: 208 g/kg @ 20 deg. C; 212,000 mg/l @ 25 deg.C Section 10: Stability and Reactivity Data Stability: The product is stabilized with Hydroquinone. However, it may form unstable peroxides over time. Instability Temperature: Not available. Conditions of Instability: Heat, ignition sources, incompatible materials, light. Incompatibility with various substances: Reactive with oxidizing agents, acids, alkalis.
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Corrosivity: Non-corrosive in presence of glass. Special Remarks on Reactivity: Incompatible with amines. Incompatible with oxygen and peroxides. May polymerize on exposure to light, or in presence of alkali or strong acid forming disacryl. Incompatible with oleum, ethyleneimine, chlorosulfonic acid, ammonium hydroxide, 2-aminoethanol, alkalis, strong acids, mineral acids, oxidizers, ammonia may form shock sensitive peroxides overtime.

Polymerizes readily unless inhibited (stabilized) Special Remarks on Corrosivity: Non-corrosive to iron and steel at room temperature Polymerization: Will not occur with the product as is. This product is stabilized with Hydroquinone. However, it will polymerize of not stabilized or in contact with acids (including sulfur dioxide), alkalis, volatile amines, salts, thiourea, oxidants (air), and on exposure to light and heat.

Section 11: Toxicological Information Routes of Entry: Absorbed through skin. Dermal contact. Eye contact. Inhalation. Ingestion. Toxicity to Animals: WARNING: THE LC50 VALUES HEREUNDER ARE ESTIMATED ON THE BASIS OF A 4-HOUR EXPOSURE. Acute oral toxicity (LD50): 7 mg/kg [Rabbit]. Acute dermal toxicity (LD50): 200 mg/kg [Rabbit]. Acute toxicity of the vapor (LC50): 18 mg/m3 4 hours [Rat]. Chronic Effects on Humans: CARCINOGENIC EFFECTS: 3 (Not classifiable for human.) by IARC. MUTAGENIC EFFECTS: Mutagenic for mammalian somatic cells. Mutagenic for bacteria and/or yeast. Causes damage to the following organs: lungs, upper respiratory tract. May cause damage to the following organs: skin, eyes. Other Toxic Effects on Humans: Very hazardous in case of skin contact (irritant), of ingestion, Hazardous in case of skin contact (permeator), of inhalation (lung corrosive). Slightly hazardous in case of skin contact (corrosive), of eye contact (corrosive).
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Special Remarks on Toxicity to Animals: Not available. Special Remarks on Chronic Effects on Humans: May cause adverse reproductive effects. May affect genetic material (mutagenic) Special Remarks on other Toxic Effects on Humans: Acute Potential Health Effects: Skin: Causes severe irritation. May cause skin burns. May be fatal if absorbed through skin.

Eyes: Causes severe irritation. May cause corneal burns. It is a lacrimating agent. Inhalation: May be fatal if inhaled. It causes respiratory tract irritation. It is a severe pulmonary irritatant. Syptoms may include difficulty breathing (dyspnea), chest congestion, bronchospasm. Delayed of acute lung injury (acute pulmonary edema, emphysema), permanent lung damage may also occur. Nausea, vomiting, and CNS can also occur. Death may result from acute lung injury and/or respiratory failure.

Ingestion: May be fatal if swallowed. May produce severe irritation of the mouth, and gastrointestinal tract. It may also affect behavior/central nervous system (general anesthetic, somnolence).

Section 12: Ecological Information Ecotoxicity: Not available. BOD5 and COD: Not available. Products of Biodegradation: Possibly hazardous short term degradation products are not likely. However, long term degradation products may arise. Toxicity of the Products of Biodegradation: The products of degradation are less toxic than the product itself. Special Remarks on the Products of Biodegradation: Not available

Section 13: Disposal Consideration Waste Disposal: Waste must be disposed of in accordance with federal, state and local environmental control regulations.

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REFERENCES Handbook Of Polymer Data, Thomas.O.Brien Kirk, Othmer: Encyclopedia of Chemical Technology- Vol. 17,18. Perrys Chemical Engineers Handbook, Robert H. Perry, Don W. Green 7th Edition. Wikipedia (www.wikipedia.org) Chemweb (www.chemweb.com) Chemical weekly (www.chemicalweekly.com)

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