Maleic anhydride

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Maleic anhydride[1]
Maleic anhydride Maleic anhydride-3d.png
Sample of Maleic anhydride.jpg
Identifiers
CAS number 108-31-6 YesY
PubChem 7923
ChemSpider 7635 YesY
UNII V5877ZJZ25 YesY
EC-number 203-571-6
ChEBI CHEBI:474859 N
ChEMBL CHEMBL374159 YesY
RTECS number UE5950000
Jmol-3D images Image 1
Properties
Molecular formula C4H2O3
Molar mass 98.06 g/mol
Appearance White crystals
Density 1.48 g/cm3
Melting point 52.8 °C (127.0 °F; 325.9 K)
Boiling point 202 °C (396 °F; 475 K)
Solubility in water Reacts
Hazards
MSDS MSDS at J. T. Baker
EU classification Corrosive (C)
R-phrases R22, R34, R42/43
S-phrases (S2), S22, S26,
S36/37/39, S45
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calcium Special hazards (white): no codeNFPA 704 four-colored diamond
Flash point 102 °C (216 °F; 375 K)
Related compounds
Related acid anhydrides Succinic anhydride
Related compounds Maleic acid
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N (verify) (what is: YesY/N?)
Infobox references

Maleic anhydride is an organic compound with the formula C2H2(CO)2O. It is the acid anhydride of maleic acid. it is a colourless or white solid with an acrid odour. It is produced industrially on a large scale for applications in coatings and polymers.[2]

Production[edit]

Maleic anhydride was traditionally produced by the oxidation of benzene or other aromatic compounds. As of 2006, only a few smaller plants continue to use benzene. Instead, most maleic anhydride is produced by vapor-phase oxidation of n-butane. The overall process converts the methyl groups to carboxylate and dehydrogenates the backbone. The selectivity of the process reflects the robustness of maleic anhydride, with its conjugated double-bond system.

In both cases, benzene and butane are fed into a stream of hot air, and the mixture is passed through a catalyst bed at high temperature. The ratio of air to hydrocarbon is controlled to prevent the mixture from igniting. Vanadium pentoxide and molybdenum trioxide are the catalysts used for the benzene route, whereas vanadyl phosphate is used for the butane route.[2]

C4H10 + 3.5 O2 → C2H2C2O3 + 4 H2O ∆H = -1236 kJ/mol

The main competing process entails full combustion of the butane, a conversion that is twice as exothermic as the partial oxidation.

Industrial production of maleic anhydride is achieved by integration of following unit processes: catalyst packed bed reactor, adsorption tower, maleic acid reactor, distillation column. The reactant stream of n-butane and air mixture enters the packed bed reactor at a temperature of 120-150 ⁰C and a pressure of 2-3 atm. The product stream is then sent to a packed bed adsorption column, where the condensable maleic anhydride reacts with the water stream to give maleic acid and the non-condensable are sent for fuel gases treatment. The condensable stream from adsorption tower is sent to a maleic acid reactor, where maleic acid is again converted back to the anhydride. This product stream from reactor is sent to distillation column to obtain pure maleic anhydride as product.

Reactions[edit]

The chemistry of maleic anhydride is very rich, reflecting its ready availability and bifunctional reactivity. It hydrolyzes, producing maleic acid, cis-HOOC–CH=CH–COOH. With alcohols, the half-ester is generated, e.g., cis-HOOC–CH=CH–COOCH3.

Maleic anhydride is a classic substrate for Diels-Alder reactions.[3] It was used for work in 1928 on the reaction between maleic anhydride and 1,4-butadiene that Diels and Alder were awarded the Nobel prize in 1950. It is through this reaction that maleic anhydride converted to many pesticides and pharmaceuticals.

Maleic anhydride dimerizes in a photochemical reaction to form cyclobutane tetracarboxylic dianhydride (CBTA). This compound is used in the production of polyimides and as an alignment film for liquid crystal displays.[4]<

Maleic anhydride dimerization

It is also a ligand for low-valent metal complexes, examples being Pt(PPh3)2(MA) and Fe(CO)4(MA).

Uses[edit]

Around 50% of world maleic anhydride (MA) output is used in the manufacture of unsaturated polyester resins (UPR). Chopped glass fibres are added to UPR to produce fibreglass reinforced plastics which are used in a wide range of applications such as pleasure boats, bathroom fixtures, automobiles, tanks and pipes. However, the UPR market reflects general economic conditions as it is tied to the construction, automobile and marine industries.

The production of 1,4-butandiol (BDO) is also having an impact on the MA market. BDO is one of the world’s fastest growing chemicals used in the production of thermoplastic polyurethanes, elastane/Spandex fibres, polybutylene terephthalate (PBT) resins and many other products. However, BDO is made from a crude MA which is not traded and only used for this application.

Another market for MA is lubricating oil additives, which are used in gasoline and diesel engine crankcase oils as dispersants and corrosion inhibitors. Changes in lubricant specifications and more efficient engines have had a negative effect on the demand for lubricating oil additives, giving flat growth prospects for MA in this application.

There are a number of smaller applications for MA. The food industry uses MA in artificial sweeteners and flavour enhancements. Personal care products consuming MA include hair sprays, adhesives and floor polishes. MA is also used in water treatment chemicals, detergents, insecticides and fungicides, pharmaceuticals and copolymers.

Major producers[edit]

Company Location
Bartek Ingredients Inc. Canada
Sasol-Huntsman Germany
DSM NV The Netherlands
Flint Hills Resources LP USA
Huntsman Corporation USA
Huntsman Performance Products USA
Lanxess Corporation USA
Lonza Group AG Switzerland
Marathon Petroleum Company LLC USA
Mitsubishi Chemical Corporation Japan
Mitsui Chemicals, Inc Japan
Mitsui Chemicals Polyurethanes, Inc. Japan
Nippon Shokubai Co., Ltd Japan
NOF Corporation Japan
Polynt SpA Italy
Suzhou Synthetic Chemical Co, Ltd. China
Thirumalai Chemicals Ltd. India
TCL Industries Malaysia Sdn. Bhd. Malaysia

Source: Kirk & Othmer

World Maleic Anhydride Capacity By Region
Data in: kilo tonnes per annum

Region 2002 2012
North America 235 311
South & Central America 44 41
Western Europe 168 456
Central & Eastern Europe 64 58
Asia 315 483
Africa 10 10
Total 836 1359

Source: Kirk & Othmer

Worldwide demand[edit]

In 2007-2013, the average annual MAN market growth rate was 2.8% in the USA and 3.5% in Western Europe, while in Japan it dropped by 1.4%. Global MAN consumption grew by 6-7 % a year to 1.5 million tons in 2013. World MAN consumption is predicted by consultants to grow at around 3% per year up to 2016. Growth will be slower in Western Europe and the US, but higher in Central and Eastern Europe, Latin America and Asia, in particular China. According to CMR, demand in the US increased from 254,000 tons in 2009 to 281,000 tons in 2013. Growth in Central and South America is expected to be higher than North America at around 4% per year. In Western Europe, the MAN market is mature with growth predicted around 1.5-2 % per year, while in Central and Eastern Europe growth is much stronger at 4% per year. In Asia, China is the most important MAN market. According to China Chemical Reporter, China produced 236,000-tons in 2008, while it consumed 229,700-tons in the same year. Overall demand is expected to reach 394,000-tons by 2014. China produced around 800,000 tons of UPR during 2008, requiring around 160,000 tons of MAN. In 2014, China expects to produce 1.4 million tons of UPR with demand for MAN rising to about 280,000 tons in this application.

Packing and transport[edit]

Liquid maleic anhydride is available in road tankers and/or tank-containers which are made of stainless steel, which are insulated and provided with heating systems to maintain the temperature of 65-75°C. Tank cars must be approved for the transport of molten maleic anhydride.

Liquid/molten maleic anhydride is a dangerous material in accordance with RID/ADR.

Storage[edit]

  • Requirements for storage buildings
    • Local exhaust systems to take vapours away from the places of emission, and general ventilation in rooms.
    • Protection against static charges.
    • Impervious floor which makes it possible to collect the spilled material and which prevents its entry to the sewage system.
    • Storage rooms should be cool and dry.
  • Storage conditions
    • Keep ignition sources away - do not smoke. Product dust may form explosive air-dust mixtures.
    • Keep humidity away from storage rooms.
    • Keep containers tightly closed. Store them in cool, dry and well ventilated places.
    • Tanks / containers must be properly marked.
    • Hand-operated / portable fire-fighting equipment should be available in storage rooms.
    • Neutral gas blanketing is required inside storage tanks.

Effects on human health and the environment[edit]

This compound also poses relatively low-risk environmental hazards, an important feature for those applications. Exposure to maleic anhydride may cause respiratory tract, eye irritation, skin irritation and respiratory irritation. Maleic anhydride is a skin - and possibly respiratory – sensitizer.

Maleic anhydride is a low hazard profile chemical. Maleic anhydride rapidly hydrolyzes to form maleic acid in the presence of water and hence environmental exposures to maleic anhydride are not expected to occur. Maleic anhydride and maleic acid are biodegraded under aerobic conditions in sewage sludge and in soil and water as well.

Food starch for use in night markets sold from a supplier in Tainan city, Taiwan, were found to contain maleic anhydride in December 2013. The supplier was investigated regarding the 300 tons of tainted starch; an earlier inspection in November had found 32 tons.[5]

References[edit]

  1. ^ Merck Index, 11th Edition, 5586.
  2. ^ a b Kurt Lohbeck; Herbert Haferkorn; Werner Fuhrmann; Norbert Fedtke (2005), "Maleic and Fumaric Acids", Ullmann's Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, doi:10.1002/14356007.a16_053 
  3. ^ Samuel Danishefsky, Takeshi Kitahara, and Paul F. Schuda "Preparation and Diels-Alder Reaction of a Highly Nucleophilic Diene: trans-1-Methoxyl-3-Trimethylsiloxy-1,3-Butadiene and 5β-Methoxycyclohexan-1-one-3β,4β-Dicarboxylic acid Andhydride" Org. Synth. 1983, 61, 147
  4. ^ Horie, T.; Sumino, M.; Tanaka, T.; Matsushita, Y.; Ichimura, T.; Yoshida, J. I. (2010). "Photodimerization of Maleic Anhydride in a Microreactor Without Clogging". Organic Process Research & Development 14 (2): 100128104701019. doi:10.1021/op900306z.  edit
  5. ^ http://www.wantchinatimes.com/news-subclass-cnt.aspx?id=20131219000005&cid=1103

External links[edit]

Appendix[edit]

Physical Properties: Melting Point : 51-60 °C(lit.)

Boiling Point : 200 °C(lit.)

Density : 1.48

Vapor density : 3.4 (vs air)

Vapor pressure : 0.16 mm Hg ( 20 °C)

Freezing Point : 218 °F

Storage Temp. : Store at RT.

Form : powder

Water Solubility : 79 g/100 mL (25 °C)

Sensitive : Moisture Sensitive

Merck : 14,5704

BRN : 106909

Stability: Stable. Combustible. Incompatible with water, strong oxidizing agents, alkali metals, strong bases, amines, most common metals, polymerization catalysts and accelerators.