• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to industrial organic synthesis, in particular the production of caprolactam; (CL). To increase the output of KP in the method, another sequence of used reactions is envisaged. First, adipic acid (AA) is mixed with adiponitrile at a ratio of 1:
    公开号:SU1279527A3
    申请号:SU3501768
    申请日:1982-10-13
    公开日:1986-12-23
    发明作者:Кимура Кодзи；Исойя Тосиро
    申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:


    The invention relates to methods for the preparation of caprolactam from adipic acid and adipodonitrile. The aim of the invention is to increase the yield of the target product, which is achieved by a specific sequence of reactions. The method of producing caprolactam (CL) is to conduct a mutual exchange reaction between adipic acid (ADA), adiponitrile (ADN) and dimethyl adipate (DMA) at elevated temperatures in alcohol to form cyanovaleria, a novel acid, which reacts with the alcohol to produce cyanovalerianic acid ester, and restoring it on the catalyst to form aminocaproic acid ester, the latter being heated in a polyhydric alcohol medium having a higher boiling point than caprolactam in order to convert Ether into caprolactam, then the resulting caprodactam is separated by distillation and recycling of the liquid distillation residue into the system. The drawing shows the technology. Ceska diagram illustrating a method -Getting caprolactam by reacting interac many exchange between adipic acid and adiponitrile in methanol-medium by continuous reduction methyl cyanovalerate (SCW) in the absence of solvent and converting metilaminokaproata (MAA) into caprolactam by heating it in tetraethylene glycol (TEG) and removing at this methanol. In the first stage of the preparation of methyl cyanovalerate, adipic acid and adiponitrile, as well as dimethyl adipate and adiponitrile, which are returned from distillation columns, are fed into the reactor 1 for conducting mutual exchange through pipelines 2 and 3. The reciprocal exchange reaction between adipic acid and adiponitrile proceeds in reactor 1, then the reaction mixture is fed to the esterification reactor 4, in which the necessary methanol is also recycled from the distillation column 5 and from the cyclization reactor 6. The liquid reaction mixture containing methyl cyanovalerate formed in the esterification reactor 4 is fed under pressure successively to a distillation column 5 to remove methanol, then to a dehydration column 7 and a column 8 to remove dimethyl adipate. In these columns, methanol, water, and dimethyl adipate are removed by distillation, after which the liquid reaction mixture is fed to the distillation column 9. Distilled methanol is recycled to the ethrification reactor A through line 10. The separated water is removed from the system by line 11. methyl adipate is recycled to reactor 1 to conduct a mutual exchange reaction. In the distillation column 9, the methyl cyanovaler-t is distilled off. The recovered methyl cyano valerate is fed to the hydrogenation reactor 12, and the liquid distillation residue, consisting mainly of adiponitrile, is removed via conduit 13 from the bottom of the distillation column 9 and fed to the reactor 1 for carrying out a reciprocal exchange reaction. In the second stage of producing methylamino caproate, the methyl cyanovalerate supplied from the distillation column 9 via conduit 14 is contacted in the hydrogenation reactor 12 with René cobalt supplied from conduit 15 and hydrogen fed from conduit 16, as a result of which it is reduced to methylamino caproate. Next, the reaction mixture is fed into the reactor 6 cyclization. In the third stage of caprolactam, the methylaminocaproate withdrawn from the hydrogenation reactor 12 is heated in the cyclization reactor 6 together with a polyhydric alcohol with a boiling point higher than that of caprolactam supplied from the distillation column 17, and caprolactam is obtained. A polyhydric alcohol having a boiling point higher than caprolactam containing caprolactam is fed to a distillation column 17, where caprolactam is withdrawn from the top, and the indicated polyhydric alcohol containing unconverted compounds is recirculated to cyclization reactor 6 through line 18. In the reactor 6 cyclization it is heated together with a fresh portion of methylamino caproate to be converted into caprolactam. Example 1. Initially, initial solutions A and B are prepared. Solution A. A 43.8 g (0.300 mol) adipic acid 52j 2 g (0.300 mol) di methyl methipate and 324.0 g (3,000 g) are charged to a liter stainless steel autoclave. mole) adiponitrile at a ratio of 1:10. After purging the system, aethe mix while keeping the contents of 230 ° C. for 2.5 hours. Using liquid chromatography, it is established that 58.6 g (0.54 mol) of cyanovaleric acid is formed. After cooling the reaction mixture, 160.0 g (5,000 mol) of methanol was added. The ratio of alcohol to adipic acid is 17: 1, and the reaction mixture is stirred at 200 ° C for 2 hours. After the completion of ethrification, the reaction mixture is analyzed by gas chromatography and the presence of 76.1 g (0.540 mol) of methyl cyanovalerate and 51.8 g is determined (0,298 mol) of dimethyl adipate. Methanol, water, dimethyl adipate and methyl cyano-naper are separated from the liquid reaction mixture by distillation to form 301.2 g of a liquid distillation residue called solution A. Solution B. A 82.4 g stainless steel autoclave is loaded ( 0.569 mole of metapaminocaproate and 741.6 g of tetraethylene glycol, while its concentration is 10%. After purging the system with nitrogen, the contents are stirred at 230 ° C for 1 hour. After completion of the reaction, the reaction mixture is distilled under reduced pressure to remove methanol and 56 , 5 g (0.500 mol) cap rolactam, resulting in 749.3 g of a liquid distillation residue, which is referred to as solution B. A liter stainless steel autoclave collects 301.2 g of solution A, 39.4 g (0.270 mol) of adipic acid, 51, 8 g (0.298 mol) of dimethyl adipate and 29.2 g (0.270 mol) of adipine dinitr oryl. The contents of the autoclave were mixed at 230 ° C for 2.5 h. After cooling the reaction mixture, 160.0 g of methanol was added, and the resulting mixture was stirred at 200 ° C for 2 hours. Then the liquid reaction mixture was distilled under reduced pressure to form 77.5 g (0.550 mol) novaleryta. Then, in a 300-milliliter steel autoclave, 70.5 g (0.500 nil) of methyl cyanovalerate and Rane’s cobalt methanol slurry, which consists of 20.0 g of Rene cobalt and 20.0 g of methanol, are introduced. After purging the system with nitrogen, hydrogenation is carried out under a hydrogen pressure of 30 kg / cm at 60 ° C, while hydrogen is fed in such a way as to maintain a pressure of 30 kg / cm until the absorption of hydrogen ceases. After completion of the reaction, the liquid reaction mixture is analyzed by gas chromatography. The formation of 69.6 g (0.480 mol) of methyl aminocaproate and 1.9 g (0.017 mol) of caprolactam is detected. The total yield of methylaminocaproate and caprolactam is 99.4%. The liquid reaction mixture was introduced into a 2-liter steel autoclave, washing the catalyst with methanol, after which g of solution B was added, and methanol was removed by distillation under reduced pressure and at room temperature. Next, the autoclave is purged with nitrogen and the contents of the autoclave are stirred at 230 ° C for 1 h. The liquid reaction mixture is analyzed by gas chromatography and the formation of 56.4 g (0.499 mol) of caprolactam is established. Its yield corresponds to 99.8% in terms of methyl cyano-valerate consumed in the reduction reactants, which indicates that the products of the reduction could also be converted into caprolactam. The yield of caprolactam per loaded adipic acid is 78.9%. . Comparative Example 1. In analogy to Example 1, 70.5 g (0.500 mol) of methyl cyanalerate is reduced to form a liquid reaction mixture containing 69.8 g (0.484 mol) of methylamino caproate and 1.9 g (0.017 mol) of caprolactam. The reaction mixture is loaded into a 2-liter stainless steel autoclave together with 652.5 g of ethylene glycol. After the methanol is removed by distillation under reduced pressure and at room temperature, the pressure is brought to normal by introducing nitrogen, after which the contents of the autoclave are stirred
    at 230 ° C for 1 hour. Analysis of the liquid reaction mixture allows the formation of 49.1 g (0.435 mol) of caprolactam to be determined.
    The liquid reaction mixture is then distilled, methanol, ethylene glycol and 48.2 g (0.427 mol) of caprolactam are distilled off. The yield of caprolactam at the stages of hydrogenation and cyclization is 85.4%. In the distillate residue, caprolactam is not identified. The distillation residue, the reaction mixture, obtained by reducing 60.2 g (0.427 mol) of methyl cyanovalerate and 652.5 g of ethylene glycol, was introduced into a 2-liter autoclave made of stainless steel and treated as described. The reaction mixture is analyzed and the presence of 42.5 g (0.376 mol) of caprolactam is determined. The yield of caprolactam corresponds to 88.1% based on the newly added methyl cyano valerate.
    Example 2. Instead of solution B used in Example 1, the entire amount of the liquid distillation residue containing 5 May of Me Tilaminocaproate ether is used. % obtained in Example 1 was removed by distillation of methanol and 56.1 g (0.496 mol) of capro | lactam from caprolactam containing tetraethylene glycol solution (no caprolactam was detected by gas chromatography in the indicated liquid distillate residue). This LIQUID distillation residue is introduced into a 2-liter stainless steel autoclave together with a liquid reaction mixture obtained by reduction of 69.6 g (0.496 mole) of methyl cyanoverate as in Example 1, after which the reaction is carried out under the same conditions. The reaction mixture is analyzed and the presence of 56.3 g (0.498 mol) of caprolactam is determined. The yield of caprolactam is 100.4%, based on the methyl cyanovalerate reused in the reaction, and 94.7% with regard to methyl cyanovalerate in solution B. (repeated experiment 1),
    Then, according to the described procedure, the reaction mixture obtained by reducing the methyl cyanovalerate in an amount equimolar to the distilled caprolactam is added to the distillation residue obtained in the previous experiment, and the reaction and distillation are repeated (repeated experiments 2-6). The results are presented in Table. one .
    Example 3. A 2-liter stainless steel autoclave was charged with 90.0 g (0.62 mol) of adipic acid, 432.0 g (4,000 mol) of adipodine Table 1
    ril with a ratio of 1: 6 and 26.1 g (0.150 mol) of dimethyl adipate. After purging the system with nitrogen, the contents of the autoclave are stirred for 5 hours.
    at. After cooling the reaction mixture, 320.0 g (10,000 mol) of methanol was added to it, then the resulting mixture was stirred for 1 h at 220 ° C, the ratio of alcohol to adipic acid being 17: 1, then the reaction mixture was distilled out. 1, and 692.0 g of tetraethyl glycol were introduced into a liter stainless steel autoclave. The concentration of the ester is 17 May. % After the solvent was completely distilled off at room temperature, reduced pressure, and the autoclave was purged with nitrogen, the contents of the autoclave were stirred at 250 ° C for 3 hours. After completion of the reaction, distillation was carried out under reduced pressure to obtain 18.1 g (0.160 mol) of caprolactam. Then the hydrogenated solution (the solution obtained by stirring the hydrogenated solutions from experiments 2-5 with iio hydrogenation and dividing the mixture into five equal portions) is added to the liquid distillation residue. After distilling off the solvent, the reaction and distillation are repeated according to the described method. The result is caprolactam with yields of 99.6; 101.4; 97.2; 98.1 and 100.8%. Example 4. A 29.2 g (0.200 mol) adipic acid and 324.0 g (3,000 mol) adipodi nitrile are charged to a Liter stainless STEASH autoclave at a ratio of 1:15. After purging the system with nitrogen content
    the mixture to give 141.0. g (1., 000 mol) of methyl cyanovalerate and 26.8 g (0.1 of 54 mol) of dimethyl adipate. Then, 141, 0g of methyl cyanovalerate is reduced under the conditions indicated in table. 2 (experiments 1-5). The pressure of hydrogen / Zg / cm, the reaction temperature is 40 ° C.
    Table 2 of the system is outweighed at 230 ° C for 3 hours and analyzed by high performance liquid chromatography, 11.5 g (0.107 mol) of cyanovaleric acid are determined. After cooling the reaction mixture, 184.0 g (1.5 mol) of ethanol is added, and the alcohol: adipic acid mole ratio is 7.5: 1. The mixture is stirred for 3 hours at 190 ° C. After the completion of the esterification, the reaction mixture was analyzed by gas chromatography, determined to be 60.1 g (0.388 mol) of ethyl cyanovalerate and 1.0 g (0.005 mol) of diethyl adipate. The reaction mixture is distilled in the usual way in order to remove ethanol, water and diethyl adipate, as well as ethyl cyanovalerate. 29.1 g (0.199 mol) of adipic acid and 21.0 g (0.194 mol) of adipodonitrile are added to the liquid distillation residue. The resulting mixture was charged to a liter stainless steel autoclave. After purging the system with nitrogen, the contents are stirred for 3 hours at 240 ° C. After cooling the reaction mixture, 84.0 g (1.5 mol) of ethanol was added, and the mixture was stirred for 3 hours at. As a result of the analysis, 60.3 g (0.398 mol of ethyl cyanalerate and 1.2 g (0.006 mol of diethyl adipate) are determined. 108.5 g (0.700 mol) of ethyl cyanovalerate obtained in the two experiments together with cobalt ethanol Rene (containing 21.7 g of cobalt Rene and 60.0 g of ethanol) and 374.0 g of ethanol. After purging the system with nitrogen, the reaction is carried out under a hydrogen pressure of 60 kg / cm and temperature, supplying hydrogen in such a way as to maintain pressure of 60 kg / cm until the absorption of hydrogen ceases. After completion of the reaction, the resulting pe The mixture is gassed by gas chromatography and the formation of 109.4 g (0.688 mol) of ethylamino caproate and 1.1 g (0.010 mol) of caprolactam is established (the total yield of ethylamino caproate and caprolactam is 99.7%). The catalyst is separated from the reaction mixture and washed with ethanol, after which industrial fluids are added to the reaction mixture with the formation of 700.0 g of ethanol solution. 100.0 of this ethanol solution (O, OH of ethyl cyanalerate used for reduction) and 90.0 g of tetraethylene glycol are introduced into 300 ml three-neck flask (concentration ethics first experience
    82.0 to conduct the reaction Repeated experiment
    Example 5. A 2-liter stainless steel autoclave was charged with 73.0 g (0.500 mol) of adipic acid, 432.0 g (4,000 mol) of adipodonitrile at a ratio of 1: 8 and 26.1 g (0.150 mol) of dimethyl adipate. After purging the system with nitrogen, contents 83, 4
    81.9
    79,8
    the pressure vessel is stirred for 8 hours at 190 ° C. After cooling the reaction mixture, 32.0 g (10,000 mol) of methanol was added thereto at a molar mixture; the ratio of alcohol and adipic acid 1:20. The resulting mixture is then stirred for 1 hour at 220 ° t, 710 nocaproate is 14.7 may. %) ethanol is distilled off by raising the temperature until, after which the contents of the flask are stirred at 200 ° C for 4 hours, ethanol is distilled off. After completion of the reaction, the reaction mixture was distilled under reduced pressure to obtain 9.3 g (0.082 mol) of caprolactam. Its yield corresponds to 82.0% based on the ethyl cyano valerate consumed to recover 82.0 g of the ethanol solution of ethylamino caproate mentioned above (0.082 mol based on the ethyl cyano valerate consumed for recovery) is added to the liquid distillation residue and reacted, and then distillation under the conditions described. 9.2 g (0.081 mol) of caprolactam are obtained. The yield of caprolactam leaves 98.8% on the basis of the ethyl cyano valerate, from which the newly added ethylamino caproate is formed (repeat experiment 1). In the described manner, the ethanolic solution obtained by the reduction of ethyl cyanalerate in an amount. an equimolar distilled caprolactam is added to the previous liquid distillation residue, and the reaction and distillation are repeated again (repeated experiments 2-5). The results are presented in table 3.
    the reaction mixture is then distilled to obtain 114.2 g (0.810 mol) of methyl cyanovalerate and 26.8 g (0.134 mol) of dimethyl adipate.
    59.1 g (0.405 mol) of adipic acid, 43.7 g (0.405 mol) of adipodinitrile and 26.8 g (1.154 mol) of dimethyl adipate are added to the liquid distribution residue. The resulting mixture is introduced into the autoclave. The reaction is carried out in the same manner. As a result
    141.0 g (1.000 mbl) of methyl cyanovalerate is loaded into a 500-million-ton autoclave, together with Rane's cobalt methanol slurry, consisting of Rene 14.1 g and Rn 40.0 g of methanol. After complete distillation of methanol at room temperature and reduced pressure, the pressure in the system is adjusted to atmospheric by adding nitrogen, then the autoclave is additionally purged twice with nitrogen, after which the reaction is carried out under a hydrogen pressure of 20 kg / cm50
    And temperature, supplying hydrogen in such a way as to maintain a pressure of 20 kg / cm until the absorption of hydrogen ceases. The catalyst was removed from the reaction mixture by filtration 55 and scrubbing with methanol, and methanol washes were added to the reaction mixture, to form 200.0 g of a mixed solution. Such
    120.0 g (0.851 mol) of methyl cyanovalerate and 25.6 g (0.147 mol) of dimethyl adipate (repeat experiment 1) are obtained by distillation. Adipic acid and adiponitrile are added to the liquid distillation residue obtained by distilling methyl cyano valerate and dimethyl adipate and repeating reaction and distillation are carried out (repeated experiments 2-5). The results are presented in table 4.
    Table 4
    the solution is analyzed by gas chromatography, 125.0 g (0.862 mol) of methylamino caproate and .15.3 g (0.135 mol) of caprolactam are determined.
    权利要求:
    Claims (1)
    [1]
    100.0 g of the recovered reaction mixture were introduced into a 1-liter trichloride joint with 480.0 g of tetraethylene glycol. Methanol was distilled off, the temperature increased to 70 C. Then the contents of the flask were stirred at 250 ° C for 1 h, methanol was distilled off (the concentration of methylamino caproate is 11 , 4 wt.%). After completion of the reaction, the reaction mixture is distilled under reduced pressure to form 50.9 g (0.450 mol) of caprolactam. The yield of caprolactam is 90.0% in terms of methyl cyano valerate. Then, 90.0 g of the recovered reaction mixture is added to the liquid distillation residue, after which the reaction is carried out in a similar way. The reaction product is distilled under reduced pressure. 50.9 g (0.450 mol) of caprolactam are obtained. The yield of caprolactam is equal to 100.0%, calculated on the mechschian valerate, again added to the reduced reaction mixture. Thus, caprolactam obtained by the proposed method is obtained with a yield of 30-50% higher (70 .100%) than by the method according to which cyanvaleric acid ester is hydrogenated simultaneously with the cyclization of aminocaproic ester (50-70%). The advantage of the proposed method is also the absence of ammonium sulfate by-product. The invention of the method of producing caprolactam using the hydrogenation of cyanvale zyanoic acid ester at elevated temperature and pressure and the cyclization of aminocaproic acid ester at elevated temperature, so that
    chl-rt increases the yield of the target product, adipic acid is mixed with adipodinitrile at 190-230 ° C for 1-3 hours at a ratio of 1: 8-1: 15 in methyl or ethyl alcohol at a molar ratio of alcohol to adipic acid 7.5 : 1–20: 1, the resulting reaction mixture is distilled, the cyanvaleric acid ester is recovered, and the residuals are returned to the synthesis stage, the ester is hydrogenated on Rene cobalt, and the aminocaproic acid ester is mixed with tetraethylene glycol to give 5-17 % solution that cyclized at 200-250 ° C the formation of caprolactam, which is separated by distillation, and the distillation residue is returned to the cyclization stage. Priority on the basis of signs: 15.10.81 g. - use of tetraethylene glycol at the cyclization stage: "at 200-250 ° C with aminocaproic acid ester concentration of 5-17% and recycling of the vat residue, 04.1221 g, other signs indicated in the claims . T
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1279527A3|1986-12-23|Method of producing caprolactam
    KR20000075468A|2000-12-15|Process for the preparation of caprolactam in the absence of catalysts by contacting 6-aminocaproic acid derivatives with superheated steam
    US6723877B1|2004-04-20|Dimethylformamide synthesis via reactive distillation of methyl formate and dimethylamine
    KR100593110B1|2006-06-26|A process for the production of n-methyl pyrrolidone
    US4355181A|1982-10-19|Process for ethanolamines
    KR100727504B1|2007-06-12|Process for the Production of N-Methyl Pyrrolidone Using Gamma Butyrolactone and Mixed Methylamines as Starting Materials
    KR100518073B1|2005-09-28|PROCESS TO CONTINUOUSLY PREPARE AN AQUEOUS MIXTURE OF ε-CAPROLACTAM AND ε-CAPROLACTAM PRECURSORS
    EP0010993B1|1982-11-17|Process for the preparation of tertiary butyl alcohol
    US5717089A|1998-02-10|Process for the preparation of E-caprolactam
    KR20010075697A|2001-08-09|Process to afford gamma butyrolactone and tetrahydrofuran
    EP0501374A1|1992-09-02|Process for purifying dimethyl carbonate
    US3629316A|1971-12-21|Process for the manufacture of adiponitrile
    WO2005087702A1|2005-09-22|Process for producing lactic ester
    US20030105337A1|2003-06-05|Method for producing maleimides
    EP0983993B1|2002-12-18|Process for producing allyl-2-hydroxyisobutyrate
    KR20190064881A|2019-06-11|Method for producing Ethyl 3-Ethoxypropionate
    AU2013234592A1|2014-10-09|Process for making amides
    JP3682805B2|2005-08-17|Method for producing saturated aliphatic carboxylic acid amide
    EP1054864B1|2003-08-13|Process for the preparation of epsilon-caprolactam
    KR20010042773A|2001-05-25|Process for producing dimethylacetamide
    CN214422545U|2021-10-19|Continuous device for producing hexamethylene diamine by 6-aminocapronitrile hydrogenation
    CN1014235B|1991-10-09|Process for prodn. of dialkyl dis-butendioate
    KR100502600B1|2005-11-25|Process for preparing saturated aliphatic carboxylic acid amide
    CN1172898C|2004-10-27|Process for recovery of diacid ester from waste lye from preparation of caprolactam
    SU1004352A1|1983-03-15|Process for producing methyl methacrylate
    同族专利:
    公开号 | 公开日
    DE3235938C2|1988-05-11|
    AU8877282A|1983-05-19|
    FR2514763A1|1983-04-22|
    FR2514763B1|1987-06-05|
    SU1279527A1|1986-12-23|
    AU536959B2|1984-05-31|
    GB2108119B|1986-01-02|
    US4470928A|1984-09-11|
    GB2108119A|1983-05-11|
    DE3235938A1|1983-04-21|
    CA1181398A|1985-01-22|
    DE3249485C2|1988-09-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2377795A|1945-06-05|Synthesis of adiponitrile |
    US2322273A|1940-11-22|1943-06-22|Bell Telephone Labor Inc|Process for manufacture of esters of mononitriles of dicarboxylic acids|
    DE1035139B|1953-11-05|1958-07-31|Huels Chemische Werke Ag|Process for the production of ªŠ-caprolactam|
    US2970997A|1957-02-01|1961-02-07|Hoechst Ag|Process for the manufacture of epsilon-caprolactam|
    US3050547A|1959-07-02|1962-08-21|Dow Chemical Co|1-2 ring cleavage of 2-cyanocyclo-alkanones|
    CH456562A|1963-11-22|1968-07-31|Inventa Ag|Process for the preparation of w-cyanocarboxylic acids|
    US3341567A|1964-02-14|1967-09-12|Kurashiki Rayon Co|Process for the production of benzenedicarboxylic acid and aliphatic dinitrile by exchanging carboxylic group for cyano group|
    US3485821A|1967-05-29|1969-12-23|Techni Chem Co The|Process for preparing caprolactam and its alkyl substituted derivatives|
    IT1043824B|1969-09-12|1980-02-29|Daiichi Seiyaku Co|PROCEDURE FOR PREPARING ACID 4 CYAN CYCLE AND EXANCING LICO|
    NL7216662A|1972-12-08|1974-06-11|
    NL7216661A|1972-12-08|1974-06-11|
    JPS5047927A|1973-08-31|1975-04-28|
    US3988319A|1974-09-16|1976-10-26|Allied Chemical Corporation|Process for producing caprolactam from 6-aminocaproic acid|DE3643010A1|1986-12-17|1988-06-30|Basf Ag|METHOD FOR PRODUCING CAPROLACTAM|
    DE3643011A1|1986-12-17|1988-06-30|Basf Ag|METHOD FOR PRODUCING CAPROLACTAM FROM 6-AMINOCAPRONIC ACID, THEIR ESTERS AND AMIDES|
    DE10028950A1|2000-06-16|2001-12-20|Basf Ag|High yield caprolactam production by catalytic hydrogenation of a cyanovaleric acid derivative, followed by catalytic cyclization of the aminocaproic acid derivative-containing mixture obtained|
    US6365770B1|2000-11-16|2002-04-02|E. I. Du Pont De Nemours And Company|Production of alkyl 6-aminocaproate|
    US6372939B1|2000-11-16|2002-04-16|E.I. Du Pont De Nemours And Company|Production of 6-aminocaproic acid|
    JP2002193927A|2000-12-21|2002-07-10|National Institute Of Advanced Industrial & Technology|Synthetic method of lactam|
    FR2882360B1|2005-02-22|2008-12-26|Rhodia Chimie Sa|PROCESS FOR PRODUCING LACTAMS|
    EP2285946B1|2008-05-09|2017-06-21|Rhodia Opérations|Cleaning compositions incorporating green solvents and methods for use|
    US8222194B2|2008-05-09|2012-07-17|Rhodia Operations|Cleaning compositions incorporating green solvents and methods for use|
    CN102575200B|2009-10-19|2014-09-17|罗地亚管理公司|Auto-emulsifying cleaning systems and methods for use|
    WO2012078193A2|2010-12-10|2012-06-14|Rhodia Operations|Dibasic esters utilized as terpene co-solvents, substitutes and/or carriers in tar sand/bitumen/asphaltene cleaning applications|
    CA2873685C|2012-04-17|2020-06-02|Rhodia Operations|Polysaccharide slurries with environmentally friendly activator solvents|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP16456781A|JPS5867666A|1981-10-15|1981-10-15|Preparation of caprolactam|
    JP56194376A|JPS6021980B2|1981-12-04|1981-12-04|
    [返回顶部]