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2022-10-15
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Glyoxal production, application and market

glyoxal is a fine chemical that has attracted much attention in the chemical industry at home and abroad in recent years. At present, the glyoxal in circulation in the market is mostly a light yellow solution of 30% - 40%. Glyoxal exists in a tetraalcohol structure after hydration. Glyoxal has two interconnected carbonyls, which have lively chemical properties and the generality of aliphatic aldehydes. According to the different compounds participating in the reaction, it either generates linear molecules, or generates cyclic compounds, especially heterocyclic compounds. The chemical characteristics of glyoxal will inevitably lead to its very broad market application prospects

1. Main application of glyoxal in China

in 1999, the consumption of glyoxal in China was about 10000 tons (calculated by 40%), and the composition proportion of the consumer market was roughly: textile and printing and dyeing industry accounted for 50%, papermaking industry accounted for 30%, pharmaceutical and chemical industry accounted for 15%, and other industries accounted for about 5%

glyoxal and its synthetic products are mainly used in the textile industry, such as: equipment operation status, program control operation steps, whether the extension meter is switched or not. As a fiber finishing agent, it can increase the shrinkage and wrinkle resistance of cotton, nylon and other fibers, and it is a pressure resistant and press ironing finishing agent. For example, Sr fabric finishing agent can be prepared from glyoxal, urea and formaldehyde through methylation and cyclization reaction; LD resin finishing agent can be prepared by hydroxymethylation and cyclization; DN resin finishing agent can be prepared by condensation reaction with glyoxal, urea, formaldehyde and melamine as raw materials; The common 2D resin is synthesized from glyoxal, urea and formaldehyde, but it is harmful to human body because it contains 1% free formaldehyde. Recently, M2D resin has been developed, which is etherified with 2D resin and lower alcohols, effectively reducing the content of formaldehyde. Recently, glyoxal and urea cyclization finishing agents have been developed abroad, which have no formaldehyde content. They can be used as press ironing, wrinkle proof and shrink proof finishing of various fabrics. Glyoxal and aminophenol compounds, aromatic diamine compounds, hydrazine compounds, etc. can be used in the production of dye intermediates. For example, glyoxal bisulfite, a derivative of glyoxal, can be used as a dye resist for dyeing and printing or as a balancing agent in polyamide dyes for acid dyeing

the printing and dyeing industry is the industry with the largest consumption of Glyoxal at present. China is the most developed country and region in the textile printing and dyeing industry in the world. With the improvement of people's living standards and the approaching time of China's accession to the WTO, China's traditional clothing export trade volume will continue to expand, and the market demand for glyoxal in the domestic textile industry will continue to show a rising trend

in medicine, glyoxal, ammonia and other synthetic imidazole Methylimidazole, etc., can be used to produce antibiotics such as crazole. Glyoxal reacts with 2-aminobutanol to produce dialdehyde imine, which is then reduced to ethambutol, which is a highly effective structural pathogen inhibitor. Glyoxal reacts with a certain amount of o-phenylenediamine to produce quinoxaline, which is also a synthetic raw material for pyrazinamide, a drug used to treat structural diseases. In addition, glyoxal can also be used to synthesize miconazole, ketoconazole, etc., and can be used to combine until the hardness value obtained twice in a row is the same to form 2-methylimidazole. The homologues composed of derivatives of 2-methyl-5-nitroimidazole are broad-spectrum antibiotics used in the genitourinary system, damicin, and metronidazole, which can resist infectious diseases. Secondly, glyoxal can also be used for the synthesis of sulfamethoxypyrazine and benzopyrazine, an intermediate of pyrazinamide, an anti tuberculosis drug

application in light industry. In paper production, adding glyoxal to the sizing agent for sizing can enhance the wet and dry strength and tensile strength of the paper, and increase its wrinkle resistance by 2 ~ 3 times; Glyoxal is mixed with polyvinyl alcohol and water to form a paper adhesive. The film formed can resist various organic solvents. In addition, it can also be used in the production of plastic label paper and copper paper. Glyoxal and melamine adhesives are used to produce plywood. Wood is treated with glyoxal and paraformaldehyde. After drying in air, it has very low water absorption performance. The butyraldehyde condensate of glyoxal and isobutyraldehyde semicarbazone can be used as leather tanning agent; The reactant of glyoxal and formaldehyde can be used for tanning, making the fur odorless and killing microorganisms in the fur

application in building materials and coating industry. It can be used as alkyd resin and polyester/epoxy resin crosslinking agent. The reaction product of glyoxal with acrylamide or acrolein is used as ethylene copolymer crosslinking agent and synthetic pressure-sensitive adhesive. The preparation of glycolic acid from glyoxal can help delay the setting time of cement and hydrated lime. Glyoxal is a good cement additive. Adding a certain amount of glyoxal to ordinary cement can increase its compressive strength by 50% and tensile strength by 10% - 15%, which can improve the heat resistance and thermal insulation properties of acid resistant cement

application in petroleum and metallurgical industry. The mixture of glyoxal, clay and soda powder is used for oilfield drilling tools. As a skeleton material, pp.t20 or pp.t30 is usually selected, which has good setting strength; With glyoxal and chlorinated ethanol, n-hexane or lubricating oil, the performance is good. Glyoxal can also be used to synthesize oil transportation lubricants. Glyoxal is added to the polluted electroplating tank, the interference of chromium disappears immediately, and the metal in the tank is electrolytic precipitated to restore the initial conditions. Glyoxal mixed with oxalic acid and dihydroxy acid can prevent rust on the surface of iron; Mixed with aminoacetic acid, it can be used as rust inhibitor for galvanized steel plate. Secondly, glyoxal is also an indispensable raw material for insoluble adhesives such as amine, animal glue, cheese, polyvinyl alcohol and starch, rayon shrinkage inhibitor and paint, and can be used as polypropylene fiber finishing agent. The nitro derivatives of dimer glyoxal can be used as the components of jade bents propellant; Polynitroglycourea derivatives can produce fuse; Glyoxal diamine acid is used for uranium enrichment

2. Overview of glyoxal production in China

in the early 1970s, large-scale industrial plants for the production of glyoxal by ethylene acetaldehyde method abroad were successively built and put into operation in the United States, Japan, West Germany and France, and most of the production scale was 10000 ~ 15000 T/a. understand the structural composition of the electronic universal testing machine. United Carbide Corporation (UCC) of the United States has two sets of 15000 T/a units, and Japan's Cerro company, chemical synthesis company, Germany's BASF company and France's Nobel company each have one set of 10000 t/a units. At present, the annual output of glyoxal in the world is about 70000 ~ 80000 tons (excluding China), occupying the glyoxal markets in South America, North America, Asia and Europe respectively, of which more than half of Japan's glyoxal products are exported to the world market

the industrial scale production of glyoxal in China began in the 1960s, and most of them are produced by ethanol method. The production process is relatively backward and the quality is poor. In 1979, Jiangsu Jingjiang petrochemical plant first prepared glyoxal by air oxidation of ethylene glycol. In 1985, Henan Xinxiang organic chemical plant prepared glyoxal by oxidation synthesis of glyoxal with nitric acid. By the end of the 1990s, the production technology of glyoxal in China had made great progress. Hubei Luotian chemical plant, Liaoning Gaizhou Chemical Co., Ltd. and Shanghai sulfuric acid plant had rebuilt, expanded and newly built production units respectively, with the unit scale reaching 3000 ~ 5000t/A. In 1997, the output of glyoxal in China was 3900t, of which 3759t was produced by Liaoning Gai Stationery Industry Co., Ltd., accounting for 96.36%

domestic glyoxal production mostly adopts ethanol process, that is, ethanol is used as raw material, and partial oxidation process is used to produce glyoxal with an export content of 30% - 32%. Because the content of formaldehyde and alcohol in glyoxal produced by ethanol method is more than 8%, and the content of acid is more than 1.5%, which directly affects its application in clothing, pharmaceutical and other industries, it is difficult to market

Henan Xinxiang organic chemical plant adopts acetaldehyde nitric acid oxidation method (acetaldehyde method for short). Put 40%hno3 and 40%c2h2o2 into the oxidation reactor in proportion, react with NaNO2 as initiator under the catalysis of copper nitrate at 38 ℃ ~ 40 ℃ for 10 hours, heat under normal pressure to recover acetaldehyde, and then remove acetaldehyde, oxalic acid, nitric acid, etc. through reverse extraction or four stage mixing, clarification and extraction, and finally concentrate under reduced pressure to obtain 40% aqueous solution of glyoxal

at present, Japan and France adopt acetaldehyde method for production, and the United States and Germany adopt ethylene glycol method for production. Domestic enterprises using ethylene glycol method generally have poor product quality, and the operation of devices is seriously insufficient. Enterprises using acetaldehyde process have better product quality and can replace imports. However, at present, the treatment of NOx Exhaust gas is still not well solved, and the problem of environmental pollution is more prominent

the content of ethylene glycol, formaldehyde, total organic acid in domestic glyoxal is generally higher than that of foreign products, with deep color and poor quality, which limits its application in medicine, daily chemical industry and other aspects, and the application restrictions seriously affect the output

3. Analysis and prediction of domestic glyoxal market

for a long time, the supply of glyoxal in the domestic market mainly depends on imports because the volume of glyoxal commodities in China is troubled by production technology problems. According to incomplete statistics, at present, the domestic demand for glyoxal has reached more than 10000 t/A, while the domestic production has hovered around 4000t/A for a long time. From 1993 to 2000, the annual import of glyoxal from abroad reached about 6000t, and the import volume was greater than the production volume. The main importing countries were Germany and Japan, and the import ports were Shanghai and Nanjing. In August 2000, the sales price of 40% glyoxal in East China was about 8200 ~ 8600 yuan/ton, and the sales price in Nanjing was as high as 10500 yuan/ton. East China is the most developed region in the domestic textile printing and dyeing, pharmaceutical and chemical industries, and the market demand for glyoxal is the most urgent. The annual sales volume of East China chemical supply and marketing company is about 2500 ~ 5000 tons, and the sales volume of Nanjing suburban chemical supply and marketing company alone is also more than 1200 tons per year. According to preliminary statistics, the sales volume of glyoxal in East China alone can reach about 7000 tons per year, of which the pharmaceutical industry needs about 40% glyoxal 1000 tons per year, all of which rely on imports. Due to the promising market and bright export prospects of metronidazole, the successor drug of dimethylimidazole, only Jiangsu Rudong No. 6 chemical plant and Jiangyin Xinxing Chemical plant need to produce 2000 tons of glyoxal for dimethylimidazole per year. Due to the sharp rise in demand for glyoxal and the difficulty in ensuring the supply of goods, the current market price has stabilized at about 7000 ~ 7800 yuan/ton

with the development of the application of glyoxal and its derivatives (especially glyoxylic acid, paper industry and textile industry), the consumption of glyoxal in China will increase exponentially

Table 1 consumption of glyoxal in China over the years (T)

consumption field 1990 1991 1992 1993 1995 1996 2000

clothing industry 1500 2064 2628 3192 3756 4320 4884 7140

Paper Industry 1000 1332 1664 1996 2328 2660 2992 4320

pharmaceutical, daily chemical E-500 6668329981164133014962160

Table 2 development forecast of glyoxal market in China (t/a)

Project date, 1997 2003 project 1997 2003

production capacity 20500 33500 import volume 6000 11000

output 3901 9000 apparent consumption 966420000

inventory 297 - consumption growth rate 108.25

operating rate% 19.02 23.88 China's self-sufficiency rate 40.62 45

Table 5 China's glyoxal market forecast

consumption industry 1997 2003

consumption (t/a) proportion (%) consumption (T/a)t/a) Proportion (%)

clothing, textile, printing and dyeing 5000 50.0 5000 25.0

papermaking 3000 30.0 7400 37.0

medicine and chemical 1500 15.0 7000 35.0<

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