丙烯腈装置副产氢氰酸的工业利用

1、丙烯腈装置副产氢氰酸的工业利用This article is contributed by jj200302Pdf documents may experience poor browsing on the WAP side. It is recommended that you first select TXT, or download the source file to the local view.Review onChemical science and technology, 2003, 11 (2): 6063 SCIENCE & TECHNOLO, GY, IN, CHEMIC

2、AL, INDUSTR, YHydrocyanic acid of acrylonitrile plant industrial utilizationZhou Chunyan 1, Zhang Wenwu 2(the 1. Research Institute of PetroChina Jilin Petrochemical Co, Jilin Jilin 132021; research experiment factory of Jilin Chemical Group Corporation Jilin 2., Jilin 132021)Abstract: hydrocyanic a

3、cid is a byproduct of acrylonitrile, the comprehensive utilization of hydrocyanic acid can increase the economic benefits of acrylonitrile plant. Introduces several methods of industrial production to synthesize other chemicals using hydrocyanic acid, to enable enterprises to learn more about the co

4、mprehensive utilization of hydrocyanic acid. Keywords: acrylonitrile; hydrocyanic acid; industrial use 226.61 CLC number: TQ document code: A article number: 100820511 (2003) 0220060204Hydrocyanic acid (HCN) is a colorless liquid, easy to flow, extremely volatile), are highly toxic, the proportion o

5、f 0.6876 20/ (4 - 14 degrees C, melting point, boiling point of 26 DEG C. Miscible with water, ethanol, or ether. Is a weak acid, widely used in industry, agriculture as pesticides, used to fumigation warehouses, fruit trees, seedlings and so on. The industrial production methods using hydrocyanic a

6、cid synthesis of other chemicals, designed to enable enterprises to learn more about the comprehensive utilization of hydrocyanic acid.1.1 2 isobutylene method hydrocyanic acidThe generation of hydrocyanic acid and isobutene, tert butylamine sulfate, then TERT butylamine and ammonia neutralization,

7、and by-product ammonium hydrogen sulfate. The chemical reaction is: (CH3) 2 C CH2 + HCN + H2 + SO4 2 H2 O (CH3) 3 CN H2? 2 SO4 + HCOOH H (CH3) 3 CN H2? 2 SO4 + N H3 (CH3) 3 CN H2 H N H4 (TERT butylamine) + HSO4 the operation process is simple, good product quality, product yield with ISO butene mete

8、r can reach more than 83%, but the high corrosion resistance requirements on equipment, raw materials of cyanide pollutes environment, high production cost. 1.2 2M TB E method using hydrocyanic acid hydrocyanic acid as raw material, the sulfuric acid catalyzed reaction with methyl tert butyl ether,

9、acid reaction after adding methanol and methyl formate production, by-product methyl formate by distillation after neutralization with NaOH, formation of TERT butylamine and sodium sulfate, then distillation of TERT butylamine. The chemical formula is: CH3CH3, CH3, O, CH3 + HCN + H2, SO4 +1 synthesi

10、s of tertiary butyl amineTert butylamine as raw material of organic synthesis 1, 2, for the synthesis of Medicine (anti tuberculosis drug rifampin), pesticides (pesticides, fungicides), high efficiency and safety of rubber accelerator (NS, TBSI), dye stain, also can be used as a solvent. Foreign cou

11、ntries are mainly used in synthetic rubber vulcanizing accelerator NS, instead of NOBS3. The NOBS molecule contains a secondary structure (made from raw morpholine) and is easily formed in the processing, production, storage and use of N2,Carcinogenesis. NS is similar to NOBS in molecular structure,

12、 but NS is the primary amine structure and does not produce N2 nitrosamines. As a raw material for synthesis of NS, tertiary butyl amine has a larger market capacity and development potential. Domestic NS demand is expected to reach 14 thousand T in 2010, about 7000 t of tert butyl amine, in additio

13、n, tertiary butyl amine in medicine, pesticides, dyes and other industries have a wide range of applications. Therefore, from the perspective of development, tert butyl market is very promising. Methods using hydrocyanic acid as raw materials in the synthesis of TERT butylamine with isobutylene meth

14、od and methyl tert butyl ether (M TB E) method 4.Date: 2002212210 accepted the author: Zhou Chunyan (1971 -), female, Sichuan Liangping, engineer Research Institute of Jilin Petrochemical Co, mainly engaged in chemical information research work.OHmethanolH2 O(CH3) 3, CN, H2, 2, SO4 + HCOOCH3, H(CH3)

15、 3, CN, H2, 2, SO4 + 2NaOH, H (CH3) 3, CN, H2 + Na2, SO4 + 2, H2, OThe method has the advantages of simple process, high yield, good product quality, low production cost and no pollution to the environment, and is suitable for the national conditions of our country. Foreign countries have achieved i

16、ndustrial production. Chinas Qilu Petrochemical Industries Co, Fushun Petrochemical Research Institute, Chinese Academy of Sciences, Dalian Institute of physical chemistry, Nanjing chemical industryHttp:/China Academic Journal Electronic Publishing House. All rights reserved.Second issue

17、Zhou Chunyan, et al. Hydrocyanic acid of acrylonitrile plant for industrial use61?Factory, Liaoning, Anshan Xinda Chemical Plant, etc., have also studied the law, and built a small production equipment.2 synthesis of methyl methacrylate (MMA)Methyl methacrylate is one of the most important organic c

18、hemical raw materials. It is the monomer of synthetic acrylic resin. Mainly used in the production of organic glass and PVC impact modifier additives ACR and MBS, as well as the second monomer of acrylic fiber production, ion exchange resin, paper coating agents, textile auxiliaries, leather process

19、ing agent, lubricating oil additive, pour point depressant, wood and soft wood infiltration agent, penetrant, motor coil insulation filling materials and plastic emulsion plasticizer etc. In recent years, with the rapid development of national economy and the improvement of peoples living standards,

20、 the consumption of MMA is growing rapidly, is expected to 2005 the total demand for MMA in China will reach about 168 thousand T, the potential market is still the main organic glass, water-based paint industry and PVC modifier etc. At present, Chinas MMA production capacity and output can not meet

21、 the needs of domestic actual production, and a large number of imports are needed every year. In 1995, the import volume was about 11 thousand T, and import volume reached 65 thousand T in 2001. Acetone cyanohydrin (ACH) method is the first industrialized production of MMA, by the direct addition o

22、f acetone and hydrocyanic acid, such as caustic in the presence of alkaline catalyst can quantitatively generate acetone cyanohydrin.Then at about 100 DEG C to acetone cyanohydrin with concentrated sulfuric acid treatment, which generates methyl acrylamide. It is reacted with methanol at 80 DEG C to

23、 produce a 5, 6 methyl acrylate. The reaction equation is as follows: CH3CH3 C CH3 O CH3 CH3 CH3 + HCN OH CH3 CH2 C COOCH3 H4 HSO4 CN + N + H2 + SO4 CH3 OH CH3 CH3 OH CN (acetone cyanohydrin)The main raw material of hexamethylenediamine also, the production of adipic acid. In 1972 the United States

24、DuPont Co developed using hydrocyanic acid as raw materials, industrial production method of direct hydrogen cyanide production of adiponitrile butadiene 7. At present, the DuPont Co has developed the third generation of butadiene for adiponitrile catalyst 8, the realization of industrialization set

25、 in France on the joint venture Rhodia Inc. Synthesis of adiponitrile butadiene hydrocyanation method is divided into three steps, the reaction is as follows: (1) pentene nitriles reactionCH2, CHCH, CH2 + HCN, CH2NiP (OR 3) 3Solvent, 100 DEG C- NCCH2, CH2, CH - NCCH2, CH - NC - C, HCHCH3 CH2CHCH3(2)

26、 isomerization reaction NC, C, H2, CH, CH3, CH210200 DEG CZnClNiP (PoArCH3) 3 4- NCCH2 CHCHCH3 CH2- NCCH2, CH2, CH(3) adiponitrile formation reactions of HCCH2 CH + 2 HCNZnC1Ni, P (PoArCH3) 3 4 ZnCl 22 TiCl 3 CdI aromatic solventCHCH3 + NCCH2 CH2 CH2NC (CH2) 4 CN (adiponitrile) (4) the synthesis of

27、hexamethylene diamine(methyl methacrylate) process of this method is short, mature technology, high product yield, not only to avoid the toxic sodium cyanide and solves the problem of acrylonitrile byproduct, hydrocyanic acid reduces the pollution of the environment, it is a main method of productio

28、n at home and abroad MMA. The yield of MMA produced by this method is about 80% of the total output of MMA in the world.In the presence of nickel skeleton skeleton cobalt catalyst, catalytic hydrogenation of adiponitrile to hexamethylendiamine 9. The chemical reaction is: NC (CH2) 4 CN + 4 H2 H2 N (

29、CH2) 6 N H2 (hexamethylendiamine) (5) the synthesis of adipic acid in aqueous solution of adiponitrile catalyzed by acid or alkali, hydrolysis of adipic acid and ammonia 10. In concentrated sulfuric acid, water is limited and hydrolysis is stopped at two stages. Chemical reaction formula:NC (CH2) 4,

30、 CN + H2, O, H2, NOC (CH2) 4, CONH2 or HOOC (CH2) 4 COOH + NH3 (adipic acid)H + or OH -3 synthesis of adiponitrileAdiponitrile is a key intermediate for the production of nylon yarn, is the production of4 synthesis of iminodiacetic acid twoIminodiacetic acid, two, used in the synthesis of glyphosate

31、, glyphosate, and GlyphosateHttp:/China Academic Journal Electronic Publishing House. All rights reserved.22 methyl 232 butene CH2Cis -, 32 - ene - trans -42 amyl cyanide62?Chemical TechnologyEleventh volumesIs a kind of important herbicide for weed of cultivated land and non-agricultura

32、l land; in the electroplating industry for chemical plating and preparation of trivalent chromium plating solution; in the water treatment industry, in conjunction with other complexes can chelate calcium and magnesium ions; with its surface active compounds can be used as scale inhibitor of salt wa

33、ter system heat exchanger it will be introduced into the polymerization system; different, chelating cation exchange resin can be use different, these resins for electroless plating wastewater, and industrial waste and nuclear reactor. Iminodiacetic acid two also has a wide range of uses in other wa

34、ys. Hydrocyanic acid synthesis of imino two acetic acid, hydrocyanic acid, is six (Urotropine) and formaldehyde in acidic aqueous solution - methylene four amine should be medium in tube reactor for reaction of imino two acetonitrile, adding caustic soda into the hydrolysis imino two sodium acetate,

35、 with concentrated sulfuric acid acidification and regulation of P H the value of imino two acetic acid crystallized from solution, by centrifugal separation, washing and drying to obtain the product 11. Examples: the reaction in a tubular reactor, the reaction temperature is 120 to 170 DEG C, the r

36、esidence time of 1.5 5 min, the reaction mixture P H value from 6.5 to 9.5, after the completion of the reaction product into the hydrolysis tank, hydrolysis temperature 100 to 102 DEG C, hydrolysis products. The chemical formula is: N 4 (CH2) 6 (six methylene four amines) + 8 HCN + 2CH2 O4N H (CH2

37、CN) 2 + 2 H2 O N H (CH2 CN) 2 + 2NaOH + O 4 H2 N H (CH2 COONa) 2 + 2N H4 OH N H (CH2 COONa) 2 + H2 SO4 N H (CH2 COOH) 2 (imino two acetic acid) + Na2 SO46 Synthetic acrylonitrileEthylene and hydrocyanic acid in acrylonitrile synthesis palladium catalysts, can increase the yield of acrylonitrile. The

38、 technology was developed by Asahi Kasei Corporation 13. The chemical reactions are: CH2, CH2 +, HCN +, 1/, 2O2, CH2, CHCN + H2O(Bing Xijing)7 synthetic hydroxy acetonitrileAs an organic synthesis material, hydroxy acetonitrile can be prepared by condensation with aniline to produce aniline - based

39、acetonitrile. Then, hydrolysis of aniline to produce acetic acid instead of chloroacetic acid to produce indigo dye 14. Formaldehyde and hydrocyanic acid in the presence of a catalyst prepared by hydroxy nitrile 15. The chemical reactions are: HCHO + HCN, HOCH2, CN (hydroxy acetonitrile), C6, H5, N,

40、 H2 (aniline) + HOCH2, CNC6, H5, N, HCH2, CN (aniline, acetonitrile), C6, H5, N, HCH2, CN +, H2, O, C6, H5, N, HCH2, COOH (H3) + N8 conclusion(1) hydrocyanic acid is a by-product of acrylonitrile, comprehensive utilization of hydrogenThe method is mature in technology and easy to be industrialized.

41、The product quality and production cost are very competitive. At present, all foreign companies adopt this method to produce iminodiacetic acid two.5 synthesis of cyanuric chlorideCyanuric chloride is an important fine chemical intermediates, widely used in pesticides, dyes and auxiliaries and other

42、 industries, mainly used in the manufacture of reactive dyes, fluorescent whitening agent BL, pharmaceuticals, herbicides, shrink-resist agent, surface active agent and explosives.Along with the eastward moving of chemical intermediates in Europe, China has become an important base for the supply of

43、 cyanuric chloride, and the continuous development of the downstream products of cyanuric chloride has greatly promoted the development of the industry of cyanuric chloride in china. In 2002, Chinas consumption of cyanuric chloride was about 32 thousand T, and it is expected to reach 50 thousand T i

44、n 2005. Hydrocyanic acid synthesis of cyanuric chloride by the reaction of hydrocyanic acid and chlorine cyanogen chloride in the presence of active carbon, and then polymerized 12. The chemical reaction is: HCN + Cl2 ClCN + HCl = 3ClCN C3 Cl 3 N 3 (cyanuric chloride)Cyanate will increase the econom

45、ic benefits of acrylonitrile plant. (2) hydrocyanic acid is an important organic intermediate, synthesis of TERT butylamine, methyl methacrylate, adiponitrile, hexamethylene diamine and adipic acid, cyanuric chloride. (3) the current production capacity of acrylonitrile plant of Jilin Chemical Group

46、 Company for 100 thousand t/ a, byproduct hydrocyanic acid is about 11 thousand t/ a. The device plans to expand to 210 thousand t/ a, will be the byproduct hydrocyanic acid 22 thousand t/ above a. Comprehensive utilization of byproduct hydrocyanic acid, will bring great benefits to the Jilin Chemic

47、al Group company.Reference documents1 Liang Cheng. TERT butylamine market prospects J. China chemical information, 2000, 5 (20): 7. 2 Chinese chemical products Daquan (Second Edition) M. Beijing: Chemical Industry Press, 1998, 673 674. 3 Yang Qingzhi. Modern rubber technology M. Beijing: Sinopec pre

48、ss, 1997, (6): 96 105. 4. J. Sun Decheng TERT butylamine fine and special chemicals, 2000. (9): 11. 5 Wang Daquan. Fine Chemical Dictionary M. Beijing: Chemical Industry Press, 1998. 6 49. Wei Wende. Encyclopedia of organic chemical materials M Beijing.: Chemical Industry Press, 1990, 147 148. 7 Wei

49、 Wende. Encyclopedia of organic chemical materials M. Beijing: Chemical Industry Press, 1990, 138 139.China Academic Journal Electronic Publishing House. All rights reserved.Http:/Second issueZhou Chunyan, et al. Hydrocyanic acid of acrylonitrile plant for industrial use63?8 Yuanli. News

50、 digest. (Overseas) J. China chemical information, 2002, 1 (4): 26. 9 Wei Wende. Encyclopedia of organic chemical materials M. Beijing: Chemical Industry Press, 1990, 125. 10 Wei Wende. Encyclopedia of organic chemical materials M. Beijing: Chemical Industry Press 1999, 1: 750 751. 11 Shi Lei. Two i

51、mino acetic acid industry situation and development J. Chemical intermediates, 2002, 1 (2): 7 10.12 Chinese chemical products Daquan (Second Edition) M. Beijing: Chemical Industry Press, 1998, 529 530. 13 Wei Wende. Organic chemicals Daquan MBeijing: Chemical Industry Press, 1990, 14. 106. king Pro

52、Chemical Dictionary (Second Edition) M. Beijing: Chemical Industry Press, 1979, 726. 15 China chemical products Daquan (Second Edition) M. Beijing: Chemical Industry Press, 1998, 706.THE, IND, USTRIAL, UTIL, IZATION, OF, HYD, ROCYANIC, ACID, OF, ACRYLONITRIL, E, PLANTZHOU, Chun2yan1, ZHAN, G, Wen2wu

53、2(1., Research, I, nstit, ute, Jili, N, Pet, rochem, Com, pany, Pet, Rochi, Na, Com, L, I, m, ited, Jili, N, Chi, Na, Research, an, D, Testi, ng, Factory, of, J, CGC, ical, Jili, N, of, pany, Na, Chi)Can increase economic benefit of enterprises. This paper discusses t he commercialized production me

54、t hods of sveral chemicals using hydrocyanic acid as raw material. Key words: Acrylonit rile; Hydrocyanic acid; ApplicacationThe nonmetallic mineral resources are one of the four natural resources in nature, and their development and utilization level is one of the marks to measure the modernization

55、 degree of a country. Many modern high-tech and new materials industries and non metallic materials are closely related, such as barite, talc, asbestos, graphite, kaolin, diatomite, Maifanshi, perlite, respectively, with the information, new materials, new energy, bio chemical and aerospace technolo

56、gy, and other related industries. Especially Gao Chunchao fine non-metallic mineral materials, has become an important basic material in the development of the national economy. Experts point out that the key problem of the deep processing of non-metallic minerals is the superfine comminution of mat

57、erials. The general trend of raw materials and mineral materials processing of non metallic minerals in the future is the high purification, refining and function, in order to save energy and reduce cost, deep processing of nonmetal mineral super fine in quite a long period of time will still be usi

58、ng the mechanical method. The non hardness of metal materials are basically in Morse level 5 or above, therefore, the ball mill, the more common Lei Meng grinding grinding equipment has been unable to meet the high pressure jet mill; can smash, but there are fineness is not up to the requirements, high energy consumption, low productivity, large investment in equipment and other defects; has been developed abroad ul