CN108586178B - Process for the manufacture of nitriles and their corresponding amines - Google Patents

Process for the manufacture of nitriles and their corresponding amines Download PDF

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CN108586178B
CN108586178B CN201810214191.XA CN201810214191A CN108586178B CN 108586178 B CN108586178 B CN 108586178B CN 201810214191 A CN201810214191 A CN 201810214191A CN 108586178 B CN108586178 B CN 108586178B
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ammonia
amino
thio
oxy
straight
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CN108586178A (en
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孙海龙
魏延雨
高以龙
陈新华
缪军
李娜
阚林
柏基业
陈韶辉
杨爱武
许岳兴
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The present invention relates to a process for the production of nitriles and their corresponding amines. Compared with the prior art, the method for preparing the nitrile has the characteristics of obviously reduced ammonia source consumption, small environmental pressure, low energy consumption, low production cost, high purity and yield of nitrile products and the like, and can obtain the nitrile with a more complex structure. The invention also relates to a method for producing the corresponding amine from the nitrile.

Description

Process for the manufacture of nitriles and their corresponding amines
The present application is a divisional application of chinese application having application number 201410522472.3 (application date: 9/29/2014) and entitled "method for producing nitrile and corresponding amine".
Technical Field
The present invention relates to a method for producing a nitrile and a method for producing a corresponding amine from the nitrile.
Background
Nitrile compounds are organic compounds containing cyano (-CN) groups and are important organic synthesis intermediates. The cyano group has high reaction activity, so that the corresponding amine compound can be prepared through hydrogenation reaction, is an important raw material for preparing medicines, pesticides, dyes, spices, surfactants and the like, and is widely applied to various fields of national economy. For example, aliphatic monoamines, one of their derivatives, are basic raw materials for the production of cationic, zwitterionic and nonionic surfactants.
The aliphatic monoamine is classified into low-carbon aliphatic monoamine and high-carbon aliphatic monoamine, and representatives of the low-carbon aliphatic monoamine comprise methylamine, ethylamine, isopropylamine and the like. Although the low-carbon aliphatic monoamine industry is a special industry with small scale, the related downstream industries (mainly comprising the pharmaceutical and pesticide industries) have large scale, and the accumulated domestic and foreign output value is expected to exceed 1300 billion yuan. Therefore, the industrial chain of the low-carbon aliphatic monoamine industry has a strong pushing effect on economic development. In recent years, the yield of low-carbon aliphatic monoamine has increased greatly, and by the end of 2012, the production capacity of low-carbon aliphatic monoamine has exceeded 75 ten thousand tons per year globally, the annual growth rate is more than 5%, and the average annual growth rate in china is more than 20%. Currently, the main manufacturers of low-carbon aliphatic monoamines at home and abroad include: basf, us aerochemistry, us selanis and china organic chemical industries ltd. The higher aliphatic monoamine is one of the main intermediates of the three major grease chemistry (fatty alcohol, fatty acid and fatty amine), and is mainly used for producing the surfactant, the demand of people on soap, detergent and household and personal care products drives the remarkable growth of the surfactant market, so that the demand of the higher aliphatic amine and the derivative thereof is huge, and some major surfactant manufacturers in the world recently have been announced to expand the energy in China to meet the growth of local demand.
Up to now, the industrially employed process for producing aliphatic mononitriles, particularly higher aliphatic mononitriles, is usually a carboxylic acid ammonification process, in which a carboxylic acid or a derivative thereof is dissolved by heating in an open system, and then ammonia gas is continuously introduced into the melt to react the system in the presence of a catalyst such as zinc oxide or an iron compound in the presence of NH3Excessive dosage, serious material loss, low yield and the like.
Therefore, the inventors of the present invention have found through studies that, in the prior art, when nitrile is produced by a carboxylic acid amination method, in order to sufficiently perform the amination reaction, ammonia gas is required to be continuously fed into a reaction system as a raw material during the whole amination process of carboxylic acid or for a long reaction time, and therefore, the amount of ammonia gas is large, which may be tens of millions of times as large as the amount required for the amination reaction because the actual amount of ammonia gas is far more than the amount required for the amination reaction, and thus the utilization rate of ammonia gas is extremely low. In addition, because the utilization rate of ammonia gas is extremely low, a large amount of waste ammonia water is generated in the ammoniation reaction but cannot be recycled, and huge pressure is caused to the environment after the ammonia gas is discharged, so that the ammonia gas is not in accordance with the current popular green environmental protection production concept. Moreover, the ammoniation reaction of the technology adopts overall higher reaction temperature (such as over 300 ℃) and overall longer reaction time, so the energy consumption is higher, the production cost is higher, and the problems of serious reaction material loss (such as reaction material is entrained out of the reaction system because of continuous ammonia gas flow) in the reaction process, more side reactions, difficult effective improvement of the quality and yield of nitrile products and the like exist. In addition, in order to obtain a high nitrile yield, the prior art also requires that ammonia gas with an extremely low water content be used as a reaction raw material, and ammonia gas continuously introduced during the whole ammoniation reaction process be used as an entrainer to discharge water as a by-product of the reaction at any time.
Therefore, the present state of the art still needs a method for producing aliphatic mono-nitriles, which is simple, suitable for industrial production, and can overcome the aforementioned problems of the production methods of the prior art.
Disclosure of Invention
In the conversion of a carboxylic acid to a nitrile by a carboxylic acid amination process, it is necessary to go through an intermediate step of conversion of the carboxylic acid to an amide and a final step of conversion of the amide to a nitrile. The present inventors have found that the conversion reaction in the intermediate step can be completed in a shorter reaction time and can effectively prevent side reactions if it is carried out at a lower reaction temperature than the prior art. Furthermore, the inventors have further found that the final step can be performed well even in the absence of ammonia. The present inventors have also found that the aforementioned problems can be solved by using a nitrile production process having the two specific steps, and thus have completed the present invention. The appearance of the new process of the two-step method with low cost and high efficiency has very important significance for breaking through the monopoly abroad and developing nitrile compounds and downstream products thereof in China. The invention also relates to a method for producing amines using the nitriles.
Specifically, the present invention relates to the following aspects.
1. A method for producing a nitrile, comprising the steps of:
the first step is as follows: reacting a carboxylic acid source with an ammonia source at a reaction temperature T from T1 to T2A(ii) for a reaction time of from 0.01 to 2.5 hours to obtain an amide intermediate, wherein the carboxylic acid source is selected from the group consisting of an aliphatic monocarboxylic acid, C of the aliphatic monocarboxylic acid1-4One or more of a linear or branched alkyl ester, an anhydride of the aliphatic monocarboxylic acid, and an ammonium salt of the aliphatic monocarboxylic acid, T1 being the greater of the melting point and temperature value 80 ℃ of the carboxylic acid source at 1 standard atmosphere, T2 being the minimum of the boiling point, sublimation temperature, and decomposition temperature of the aliphatic monocarboxylic acid at 1 standard atmosphere, with the proviso that T2>T1，
Said ammonia source being continuously supplied in gaseous form, selected from ammonia gas, said ammonia source having an ammonia content of from 75 to 95% by weight, the remainder being an inert diluent selected from water vapour or liquid water, and said first step being carried out in an open reaction system,
or the ammonia source is ammonia gas or an ammonia generating substance, or the ammonia source is aqueous ammonia or an aqueous ammonia generating substance solution, and the first step is carried out in a closed reaction system,
and
the second step is as follows: subjecting the amide intermediate to a reaction temperature T of from T3 to T4B(ii) an under-heat treatment for a reaction time of from 0.1 to 4.5 hours, wherein T3 is the greater of the melting point and temperature value of the amide intermediate product at 1 atm and 160 ℃, and T4 is the minimum of the boiling point, sublimation temperature, and decomposition temperature of the amide intermediate product at 1 atm, with the proviso that T4>T3，
The aliphatic monocarboxylic acid is selected from one or more of the compounds having the following structural formula:
R-COOH，
wherein the radical R is C1-29Straight or branched alkyl, C2-29Straight or branched alkenyl or C2-29Straight or branched chain alkynyl; said R is optionally substituted by one or more groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, optionally substituted C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C2-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C2-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C3-20Cycloalkyl, optionally substituted C3-20Cycloalkane (oxy, thio, amino) radicals, optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C3-20Cycloalkenyl, optionally substituted C3-20Cycloalkene (oxy, thio, amino) radical, optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C6-20Aryl, optionally substituted C6-20Aryl (oxy, thio, amino) radicals, optionally substituted C6-20Aryl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C6-20Aryl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C6-20Aryl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C4-20Heteroaryl, optionally substituted C4-20Heteroaryl (oxy, thio, amino) radical, optionally substituted C4-20Heteroaryl C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C4-20Heteroaryl C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C4-20Heteroaryl C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C2-20Heterocyclyl, optionally substituted C2-20Heterocyclic (oxy, thio, amino) radical, optionally substituted C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and optionally substituted C2-20Heterocyclyl radical C1-6Linear or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, wherein the expression "cycloalkane (oxy, thio, amino) group" means: cycloalkoxy, cycloalkylthio or cycloalkylamino, the expression "cycloalkene (oxy, thio, amino) group" means: cycloalkenyloxy, cycloalkenylthio or cycloalkenylamino, the expression "aryl (oxy, thio, amino) group" means: aryloxy, arylthio or arylamino, the expression "heteroaryl (oxy, thio, amino) group" means: heteroaryloxy, heteroarylthio or heteroarylamino, the expression "heterocyclic (oxy, thio, amino) group" means: a heterocyclic oxy group, a heterocyclic thio group or a heterocyclic amino group,
said R is optionally further substituted by one or more groups selected from-O-, -S-and-NR1Interruption of a hetero group of (A) wherein R1Is H or C1-4Straight or branched chain alkyl, provided that when a plurality is present, there is no direct linkage between any two hetero groups,
the expression "optionally substituted" means optionally substituted by one or more groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C3-20Cycloalkyl radical, C3-20Cycloalkyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C3-20Cycloalkyl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C3-20Cycloalkyl radical C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C3-20Cycloalkenyl radical, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C6-20Aryl radical, C6-20Aryl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C6-20Aryl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C6-20Aryl radical C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C4-20Heteroaryl group, C4-20Heteroaryl C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C4-20Heteroaryl C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C4-20Heteroaryl C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C2-20Heterocyclic group, C2-20Heterocyclyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and C2-20Heterocyclyl radical C1-6Linear or branched (halo) alkynyl (oxy, thio, amino, carbonyl) substituents, where when a plurality of such substituents are present, adjacent two substituents may be bonded to each other to form a divalent substituent structure,
the expression "(halo) alk (oxy, thio, amino, carbonyl) yl" means: alkyl, haloalkyl, alkoxy, alkylthio, alkylamino, alkylcarbonyl, haloalkoxy, haloalkylthio, haloalkylamino or haloalkylcarbonyl, the expression "(halo) ene (oxy, thio, amino, carbonyl) group" means: alkenyl, haloalkenyl, alkenyloxy, alkenylthio, alkenylamino, alkenylcarbonyl, haloalkenyloxy, haloalkenylthio, haloalkenylamino or haloalkenylcarbonyl, the expression "(halo) alkyne (oxy, thio, amino, carbonyl)" means: alkynyl, haloalkynyl, alkynyloxy, alkynylthio, alkynylamino, alkynylcarbonyl, haloalkynyloxy, haloalkynylthio, haloalkynylamino or haloalkynylcarbonyl.
2. The method for producing a nitrile of any one of the preceding aspects, wherein in the first step, a carboxylic acid source and an ammonia source are reacted at a reaction temperature T from T1 to T2AAnd the reaction time is 0.05-2 hours.
3. The method for producing a nitrile of any one of the preceding aspects, wherein in the first step, a carboxylic acid source and an ammonia source are reacted at a reaction temperature T from T1 to T2AAnd the reaction time is 0.3-0.8 hour.
4. The method for producing a nitrile of any one of the preceding aspects, wherein in the first step, a carboxylic acid source and an ammonia source are reacted at a reaction temperature T from T1 to T2AAnd a reaction time of 0.2 to 0.5 hours.
5. The method for producing a nitrile of any one of the preceding aspects, wherein in the second step, the amide intermediate is subjected to a reaction temperature T of from T3 to T4BThe lower heat treatment is carried out for a reaction time of 0.2 to 3 hours.
6. The method for producing a nitrile of any one of the preceding aspects, wherein in the second step, the amide intermediate is subjected to a reaction temperature T of from T3 to T4BThe lower heat treatment is carried out for a reaction time of 0.4 to 1 hour.
7. The method for producing a nitrile of any one of the preceding aspects, wherein in the second step, the amide intermediate is subjected to a reaction temperature T of from T3 to T4BThe lower heat treatment is carried out for a reaction time of 0.3 to 0.5 hours.
8. The method for producing a nitrile of any of the above aspects, wherein T2-T1 ℃ C. is 10 ℃ or higher, and T4-T3 ℃ C. is 10 ℃ or higher.
9. The method for producing a nitrile of any one of the preceding aspects, wherein the reaction temperature TAIs from T1 'to T2', wherein T1 ═ T1+5 ℃, or T1+10 ℃, or T1+20 ℃, or T1+30 ℃, or T1+40 ℃, or T1+50 ℃, or T1+60 ℃, or T1+70 ℃, or T1+80 ℃, or T1+90 ℃, or T1+100 ℃, T2 ═ T2, or T2-5 ℃, or T2-10 ℃, or T2-20 ℃ or T2-30 ℃ or T2-40 ℃ or T2-50 ℃ or 300 ℃ provided that T2'>T1'; the reaction temperature TBFrom T3' to T4', wherein T3' ═ T3+5 ℃, or T3+10 ℃, or T3+20 ℃, or T3+30 ℃, or T3+40 ℃, or T3+50 ℃, or T3+60 ℃, or T3+70 ℃, or T3+80 ℃, or T3+90 ℃, or T3+100 ℃, T4' ═ T4, or T4-5 ℃, or T4-10 ℃, or T4-20 ℃, or T4-30 ℃, or T4-40 ℃, or T4-50 ℃, or 400 ℃, provided that T4'>T3'。
10. The method of making a nitrile of any of the preceding aspects, wherein T1 is 80 ℃, or 100 ℃, or 110 ℃, or 120 ℃, or 130 ℃, or 140 ℃, or 150 ℃, or 160 ℃, or 170 ℃, or 180 ℃, or 190 ℃, or 200 ℃, or 210 ℃, or 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃; t2 is 300 ℃, or 290 ℃, or 280 ℃, or 270 ℃, or 260 ℃, or 250 ℃, or 240 ℃, or 230 ℃, or 220 ℃, or 210 ℃, or 200 ℃, or 190 ℃, or 180 ℃, or 170 ℃, or 160 ℃, or 150 ℃, or 140 ℃, or 130 ℃, or 120 ℃, or 110 ℃; t3 is 160 ℃, or 170 ℃, or 180 ℃, or 190 ℃, or 200 ℃, or 210 ℃, or 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃, or 300 ℃; t4 is 400 ℃, or 390 ℃, or 380 ℃, or 370 ℃, or 360 ℃, or 350 ℃, or 340 ℃, or 330 ℃, or 320 ℃, or 310 ℃, or 300 ℃, or 290 ℃, or 280 ℃, or 270 ℃, or 260 ℃, or 250 ℃, or 240 ℃, or 230 ℃, or 220 ℃, or 210 ℃, or 200 ℃.
11. The method for producing a nitrile of any of the preceding aspects, wherein the second step is performed under reduced pressure.
12. The method for producing a nitrile of any of the preceding aspects, wherein the first step does not use a catalyst, and the second step is performed in the presence of a catalyst or does not use a catalyst.
13. The process for producing a nitrile according to any of the preceding aspects,wherein the ammonia source is continuously supplied in gaseous form, selected from ammonia gas, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is at least 1: 20, max 1: 500, a step of; or the ammonia source is ammonia gas or an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.1-2.5; or the ammonia source is ammonia water or an ammonia-generating substance aqueous solution, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.1-9.5.
14. The method for producing a nitrile of any of the preceding aspects, wherein the first step is carried out in a closed reaction system, and in order to contact the carboxylic acid source and the ammonia source, the ammonia source is added to the carboxylic acid source at a time in a predetermined ratio or streams of both are mixed with each other in a predetermined ratio to react.
15. The method for producing a nitrile of any of the preceding aspects, wherein the ammonia source is continuously supplied in a gaseous form, selected from ammonia gas, and the ammonia content of the ammonia source is 85 to 95 wt%.
16. The method for producing a nitrile of any of the above aspects, wherein the ammonia source is industrial waste ammonia gas or industrial waste aqueous ammonia.
17. The method for producing a nitrile of any of the preceding aspects, wherein the ammonia source is continuously supplied in a gaseous form, the ammonia source is ammonia gas, and the carboxylic acid source in terms of carboxyl groups is mixed with NH3The molar ratio of the ammonia source calculated is at least 1: 30, max 1: 300.
18. the method for producing a nitrile of any of the preceding aspects, wherein the ammonia source is continuously supplied in a gaseous form, the ammonia source is ammonia gas, and the carboxylic acid source in terms of carboxyl groups is mixed with NH3The molar ratio of the ammonia source calculated is at least 1: 40, up to 1: 200.
19. the method for producing a nitrile of any of the preceding aspects, wherein the ammonia source is continuously supplied in a gaseous form, the ammonia source is ammonia gas, and the carboxylic acid source in terms of carboxyl groups is mixed with NH3The molar ratio of the ammonia source calculated is at least 1: 50, max 1: 80.
20. the method for producing a nitrile of any of the above aspects, wherein the ammonia source is ammonia gas or an ammonia-generating substance, and the carboxylic acid source is reacted with NH in terms of carboxyl groups3The molar ratio of the ammonia source calculated is 1: 1.2-2.0.
21. The method for producing a nitrile of any of the above aspects, wherein the ammonia source is ammonia gas or an ammonia-generating substance, and the carboxylic acid source is reacted with NH in terms of carboxyl groups3The molar ratio of the ammonia source calculated is 1: 1.3-1.6.
22. The method for producing a nitrile of any of the above aspects, wherein the ammonia source is aqueous ammonia or an aqueous solution of an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.3-5.6.
23. The method for producing a nitrile of any of the above aspects, wherein the ammonia source is aqueous ammonia or an aqueous solution of an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.3-2.5.
24. The method for producing a nitrile of any of the above aspects, wherein the ammonia source is aqueous ammonia or an aqueous solution of an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.3-1.6.
25. The method for producing a nitrile of any of the above aspects, wherein the carboxylic acid source is a carboxylic acid, an anhydride or a methyl ester of the carboxylic acid shown in table 1 below; in the first step, the reaction temperature was T shown in Table 1 belowAThe reaction time of the first step is 0.05 to 2 hours; when the second step is carried out in an open reaction system or under pressurized conditions, the reaction temperature is T shown in Table 1 belowBThe reaction time of the second step is 0.2 to 3 hours; when the second step is carried out under reduced pressure, the reaction temperature is T 'shown in the following Table 1-1'BThe reaction time of the second step is 0.1 to 1.5 hours,
TABLE 1
Carboxylic acids Reaction temperature TA，℃ Reaction temperature TB，℃
Acetic acid 80 to 115 160 to 220
Hexanoic acid 140 to 185 200 to 250
Dodecanoic acid 140 to 225 250 to 330
Stearic acid 140 to 225 250 to 400
Acrylic acid 100 to 135 160 to 230
Phenylacetic acid 160 to 215 240 to 275
Phenylpropionic acid 160 to 220 240 to 335
PhenylpropanoneAcid(s) 150 to 225 250 to 345 of
Phenoxyacetic acids 130 to 215 250 to 335
2, 2-Biphenyl acetic acid 180 to 225 250 to 390
3-pyridylacetic acid 160 to 225 250 to 355
3-indoleacetic acid 180 to 225 250 to 400
3-Methylpentanoic acid 125 to 180 215 to 315
9-alkene-octadecanoic acid 150 to 225 245 to 305
10-alkene-undecanoic acid 150 to 225 255 to 305
14-methyl-pentadecanoic acid 155 to 215 245 to 315
4-alkynylpentanoic acid 95 to 155 180 to 225
10-alkynylpentanoic acid 95 to 165 180 to 225
2-amino acetic acid 100 to 155 185 to 265
2-Chloroacetic acid 100 to 155 175 to 235
Thioglycollic acid 100 to 155 175 to 205
Levulinic acid 145 to 215 245 to 300
Sarcosine 115 to 155 185 to 265
2-methoxy acetic acid 115 to 145 165 to 225
4-bromophenylacetic acid 155 to 225 255 to 315
2 Nitrophenylacetic acid 165 to 205 245 to 315
Cyclohexaneacetic acid 135 to 200 225 to 295
1-adamantane acetic acid 155 to 225 250 to 305
Cyclopentaacetic acid 145 to 215 235 to 285
2-Cyclohexanoneacetic acid 135 to 200 215 to 285
2-norkaneacetic acid 145 to 205 235 to 295
2-cyclopentenyl-1-acetic acid 80 to 145 175 to 225
4-methyl-1-cyclohexeneacetic acid 100 to 155 175 to 215
2-Thiopheneacetic acid 115 to 205 225 to 265
3,4- (methylenedioxy) phenylacetic acid 145 to 225 250 to 300
Imidazole-4-acetic acid 245 to 285 300 to 320
2-Furanoacetic acid 115 to 205 235 to 300
4-Piperidineacetic acid 125 to 215 235 to 300
Tetrahydropyran-4-acetic acid 250 to 300 305 to 325
TABLE 1-1
Figure BDA0001598104130000101
26. The method for producing a nitrile of any of the above aspects, wherein in the first step, the upper limit of the reaction temperature is TA max-5℃、TA max-10℃、TA max-15 ℃ or TA max-20 ℃ of which TA maxRefer to said TAUpper limit values in said table 1.
27. The method for producing a nitrile of any of the preceding aspects, wherein the reaction time of the first step is 0.1 to 1.5 hours.
28. The method for producing a nitrile of any of the preceding aspects, wherein the reaction time of the first step is 0.2 to 0.5 hours.
29. The process for producing a nitrile in accordance with any one of the preceding aspects, wherein when the second step is carried out in an open reaction system or under pressurized conditions, the upper limit of the reaction temperature is TB max-5℃、TB max-10℃、TB max-15 ℃ or TB max-20 ℃ of which TB maxRefer to said TBUpper limit values in said table 1.
30. The method for producing a nitrile according to any of the preceding aspects, wherein when the second step is carried out in an open reaction system or under pressurized conditions, the reaction time of the second step is 0.3 to 2 hours.
31. The method for producing a nitrile according to any of the preceding aspects, wherein when the second step is carried out in an open reaction system or under pressurized conditions, the reaction time of the second step is 0.4 to 1 hour.
32. The process for producing a nitrile of any one of the above aspects, wherein when the second step is carried out under reduced pressure, the upper limit of the reaction temperature is T'B max-5℃、T'B max-10℃、T'B max-15 ℃ or T'B max-20 ℃ of T'B maxIs referred to as T'BThe upper limit value in said Table 1-1.
33. The method for producing a nitrile of any of the preceding aspects, wherein when the second step is performed under reduced pressure, the reaction time of the second step is 0.2 to 0.8 hours.
34. The method for producing a nitrile of any of the preceding aspects, wherein when the second step is performed under reduced pressure, the reaction time of the second step is 0.3 to 0.5 hours.
35. The method for producing a nitrile according to any of the preceding aspects, whereinThe group R is C1-19Straight or branched alkyl, C2-19Straight or branched alkenyl or C2-19Straight or branched alkynyl.
36. The method for producing a nitrile of any of the preceding aspects, wherein the first step obtains an ammonia-containing effluent simultaneously with the amide intermediate product, and the ammonia-containing effluent is recycled to be supplied to the first step as a supplement to or a part of the ammonia source.
37. The method for producing a nitrile of any of the preceding aspects, wherein the effluent containing ammonia is recycled to be supplied to the first step as a supplement to or a part of the ammonia source after being concentrated or dried.
38. The method for producing a nitrile of any of the preceding aspects, wherein the carboxylic acid source is of biological origin.
39. The method for producing a nitrile of any of the above aspects, wherein the carboxylic acid source is directly used as an industrially corresponding crude product.
40. The method for producing a nitrile of any of the above aspects, wherein the ammonia source is an industrial waste or an industrial byproduct containing ammonia or the ammonia-producing substance.
41. The method for producing a nitrile of any of the preceding aspects, wherein the contacting is performed in a continuous, semi-continuous or batch manner.
42. The method for producing a nitrile of any of the preceding aspects, wherein the reaction in the closed reaction system is carried out at a pressure higher than ambient pressure.
43. The method for producing a nitrile of any of the preceding aspects, wherein the first step and the second step are performed in the same reactor or different reactors.
44. The method for producing a nitrile of any one of the preceding aspects, wherein the second step is carried out in an open reaction system or a closed reaction system.
45. The method for producing a nitrile of any of the preceding aspects, wherein the first step is performed under autogenous pressure.
46. The method for producing a nitrile of any of the preceding aspects, wherein no ammonia source is used in the second step.
47. The method for producing a nitrile of any of the above aspects, wherein the decompression condition is achieved by maintaining the reaction system of the second step at a degree of vacuum, and the degree of vacuum has a value ranging from 5 to 1000 mbar.
48. The method for producing a nitrile as described in any of the preceding aspects, wherein the vacuum degree has a value in the range of 20 to 500 mbar.
49. The method for producing a nitrile as described in any of the preceding aspects, wherein the degree of vacuum is in the range of 50 to 250 mbar.
50. The method for producing a nitrile of any of the above aspects, wherein the reaction temperature T of the second step is brought to the reaction temperature T by the reduced pressure conditionBFurther reduction of 40 to 150 ℃ and further reduction of the reaction time of the second step by 40-80%.
51. The method for producing a nitrile of any of the preceding aspects, wherein the ammonia content of the aqueous ammonia solution is 10 to 30wt%, and the ammonia generator concentration of the ammonia generator aqueous solution is 20wt% to the saturated concentration.
52. A method for producing an amine, comprising the steps of:
the first step is as follows: producing a nitrile according to the production method described in any one of the foregoing aspects 1 to 51; and
the second step is as follows: the nitrile obtained in the first step is hydrogenated to produce an amine.
Technical effects
Compared with the prior art, the invention has the following advantages.
According to the nitrile production method of the present invention, an ammonia source (such as ammonia gas or the like) is used as a reactant only in the first step, and no ammonia source is used at all in the second step, so that the amount of the ammonia source can be significantly reduced, and the utilization rate of the ammonia source can be greatly improved.
According to the nitrile manufacturing method, the utilization rate of the ammonia source is obviously improved, so that the amount of waste ammonia water generated by the reaction can be effectively reduced, the environmental pressure is low, and the method conforms to the current popular green and environment-friendly production concept.
According to the nitrile production method of the present invention, there is no strict requirement for the water content of the ammonia source, and even ammonia water or vaporized ammonia water can be used as it is without using the ammonia source as an entrainer of water as a by-product. Furthermore, according to the nitrile production method of the present invention, it was found for the first time in the art that waste ammonia water or waste ammonia gas (hereinafter, collectively referred to as ammonia-containing effluent) generated by the ammoniation reaction can be directly introduced into the first step of the production method as a supplement to the ammonia source, thereby achieving 100% recycling of ammonia-containing wastewater/gas and further reducing the environmental pressure of the production method.
According to the nitrile production method of the present invention, the reaction temperature and the reaction time are significantly reduced as a whole as compared with the prior art, thereby exhibiting advantages of reduced energy consumption, reduced production costs, and simple production process.
According to the method for producing a nitrile of the present invention, the reaction process is simple, the side reaction is less, and the influence of impurities on the amination reaction is less, so that the production method has a low requirement on the purity of the ammonia source and the carboxylic acid source, and can use the respective crude products as the reaction raw materials. For example, the invention finds for the first time in the field that the nitrile production method can even directly use ammonia-containing industrial waste or by-products as ammonia sources, thereby opening up a new way for recycling or reusing various ammonia-containing industrial waste or by-products and meeting the current green and environment-friendly production concept.
According to the nitrile production method of the present invention, the reaction conditions are simple, and the process can be smoothly carried out even without a catalyst (especially the first step), which not only reduces the production cost of the nitrile but also reduces the complexity of subsequent separation or purification of the nitrile product.
According to the method for producing a nitrile of the present invention, the first step is carried out at a relatively low reaction temperature for a relatively short reaction time, and the second step does not use any ammonia source at all, so that the loss (entrainment) of the reaction material due to the supply of the ammonia source and the like can be greatly reduced, and the method can obtain a nitrile yield of 75% or more, 80% or more, 90% or more, 95% or more, or even 98% or more, depending on the kind of the nitrile product.
According to the method for producing a nitrile of the present invention, the reaction conditions are mild, and side reactions occur less frequently, whereby a high-purity nitrile product (for example, 97% or more) can be obtained.
According to the nitrile production method of the present invention, nitriles with more complex structures (for example, nitriles containing various heteroatoms) can be produced by a carboxylic acid amination method, which is achieved for the first time in the art, thereby greatly expanding the application range of the carboxylic acid amination method.
According to the amine production method of the present invention, since the high-purity nitrile produced according to the present invention is used as a raw material, there are advantages in that side reactions are less, the purity of the amine product is correspondingly high, and the production cost is low.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When the specification describes materials, methods, components, devices, or apparatus as "known to one of ordinary skill in the art" or "known conventionally in the art" or the like, that term means that the specification includes those conventionally used in the art at the time of filing the present application, but also includes those not currently used, but which will become known in the art to be suitable for a similar purpose.
In addition, all ranges mentioned in this specification are inclusive of their endpoints unless explicitly stated otherwise. Further, when a range, one or more preferred ranges, or a plurality of upper preferred values and lower preferred values are given for an amount, concentration, or other value or parameter, it is to be understood that all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, whether or not such pairs of values are disclosed, are specifically disclosed.
In the context of this specification, unless explicitly defined otherwise, or the meaning is beyond the understanding of those skilled in the art, a hydrocarbon or hydrocarbon derivative group of 3 or more carbon atoms (e.g., propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) when not headed "plus" has the same meaning as when headed "plus". For example, propyl is generally understood to be n-propyl, and butyl is generally understood to be n-butyl.
In the context of the present specification, the term "ammonia source" refers to any substance that can be used as a source of ammonia gas (i.e., supply ammonia) in the nitrile production process (first step) of the present invention, including various forms of products of ammonia such as liquid ammonia, gaseous ammonia, vaporized aqueous ammonia, and the like, and also including substances that can generate ammonia gas (hereinafter referred to as ammonia-producing substances) under the reaction conditions of the first step (such as decomposition reaction by hydrolysis or thermal decomposition or the like), such as urea, cyanic acid, and ammonium salts of inorganic acids (such as ammonium carbonate and ammonium bicarbonate), and the like. According to the nitrile production method of the present invention, the reaction process is simple, side reactions are less, and the ammoniation reaction is less affected by impurities, and thus the production method has a low requirement for the purity of the ammonia source. In view of this, in the context of the present specification, the term "ammonia source" also includes industrial waste or industrial by-products containing ammonia or containing the aforementioned ammonia-producing substances, including various industrial waste or industrial by-products in gaseous, liquid or solid form, such as ammonia-containing off-gases (such as from a synthetic ammonia process), waste ammonia gas, waste ammonia water (such as from a prior art nitrile production process), waste urea water, waste ammonium carbonate water, and the like. In general, the industrial waste or by-product can be used as it is without being subjected to a prior purification treatment as long as the kind or content of impurities other than ammonia and water in the industrial waste or by-product does not significantly affect the nitrile production process of the present invention (for example, the reduction in the nitrile yield is not more than 5%). Such impurities are generally chemically inert to the nitrile production process of the present invention, and include, for example, hydrogen, nitrogen, air, water vapor, liquid water, and the like, and may be considered as inert diluents for the production process. Of course, a person skilled in the art can confirm whether or not a certain industrial waste or industrial by-product contains or excessively contains impurities that significantly affect the method for producing a nitrile of the present invention by a simple test (for example, by measuring the degree of decrease in the nitrile yield), and thus confirm whether or not it can be directly applied to the method for producing a nitrile of the present invention. In addition, according to need, those skilled in the art can also reduce such impurities contained in a certain industrial waste or industrial by-product to a level that does not significantly affect the practice of the nitrile production process of the present invention by conventionally known technical means, and, according to need, concentrate the concentration of ammonia in a certain industrial waste or industrial by-product to a level more suitable for the practice of the nitrile production process of the present invention (for example, concentrate the concentration of ammonia or an ammonia-producing substance to 10 to 95wt%, preferably 25 to 95wt%, based on the total amount of the industrial waste or industrial by-product).
In the context of the present specification, the term "carboxylic acid source" refers to any substance that can be used as a carboxylic acid source (i.e., to provide a carboxylic acid) in the nitrile production process (first step) of the present invention, including the carboxylic acid starting material itself and a substance capable of producing a free carboxylic acid under the reaction conditions of the first step (such as by hydrolysis or aminolysis, etc.) (hereinafter referred to as a carboxylic acid-producing substance), such as carboxylic anhydride and carboxylic acid C, for example, may be mentioned1-4Linear or branched alkyl esters, and the like, and sometimes ammonium carboxylates. The process for producing a nitrile of the present invention has a simple reaction process, less side reactions, and less influence of impurities on the amination reaction, and therefore, the process has a low requirement for the purity of the carboxylic acid source (for example, the purity may be 90% at the minimum), and can directly use an industrially relevant crude product such as a fatty acid or a mixed fatty acid as an industrial (for example, oil and fat industry) by-product.
In the context of the present invention, the term "carboxylic acid" is used in its broadest definition to refer to a compound containing a free carboxyl group (i.e., -COOH).
In the context of the present specification, the term "monocarboxylic acid" refers to a compound containing only one free carboxyl group.
In the context of the present specification, the term "open reaction system" means that the reaction system is open to the outside atmosphere throughout (using an open reactor), when the reaction in the reaction system is carried out at (approximately) the pressure of the outside atmosphere (ambient pressure).
In the context of the present specification, the term "closed reaction system" means that the reaction system is isolated from the outside atmosphere throughout (using an enclosed reactor). According to circumstances, the reaction in the reaction system may be carried out under a pressure higher than the ambient pressure (i.e., a pressurization condition such as autogenous pressure; there is no particular limitation as long as it is a pressure range safe in production), but it is not excluded that the reaction system is opened to the outside atmosphere for a short time (e.g., for 0.05 to 5 minutes, 0.1 to 4 minutes, 0.3 to 3 minutes, 0.5 to 2 minutes, or 0.6 to 1.5 minutes, etc.) once or more (e.g., 1 to 20 times, 1 to 10 times, 1 to 5 times, 1 to 3 times, 1 to 2 times, or 1 time, etc.) throughout the entire reaction process (e.g., pressure relief or discharge of a part of by-products, etc.). Alternatively, the reaction in the reaction system may be carried out under a pressure lower than the ambient pressure (i.e., reduced pressure condition), as the case may be. The reduced pressure condition may be achieved by maintaining the reaction system at a certain degree of vacuum, for example, by connecting a vacuum pump. The value of the vacuum is generally 5 to 1000mbar, preferably 20 to 500mbar or 50 to 250 mbar.
In the context of the present specification, the term "halogen" refers to fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.
In the context of the present specification, the expression "optionally substituted" means optionally substituted by one or more (such as 1 to 5,1 to 4, 1 to 3, 1 to 2 or 1) groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C3-20Cycloalkyl radical, C3-20Cycloalkyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C3-20Cycloalkyl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C3-20Cycloalkyl radical C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C3-20Cycloalkenyl radical, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C6-20Aryl radical, C6-20Aryl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C6-20Aryl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C6-20Aryl radical C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C4-20Heteroaryl group, C4-20Heteroaryl C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C4-20Heteroaryl C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C4-20Heteroaryl C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C2-20Heterocyclic group, C2-20Heterocyclyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and C2-20Heterocyclyl radical C1-6Linear or branched (halo) alkynyl (oxy, thio, amino, carbonyl) substituents. When a plurality of these substituents are present, two adjacent substituents (for example, molecular chain ends of two substituents) may be bonded to each other to form a divalent substituent structure. For example, two adjacent C1-6The linear or branched alkyl groups may be bonded to each other to form a corresponding alkylene structure. Or, two adjacent C1-6Straight-chain or branched alkoxy radicals may, for example, form the corresponding alkylenedioxy structure, adjacent two C1-6Straight-chain or branched alkylamino radicals may, for example, form the corresponding alkylenediamino structure, two adjacent C1-5Straight-chain or branched alkylthio groups, for example, may form the corresponding alkylenedisulfide structures, and the like. Preferred substituents include halogen, hydroxy, mercapto, amino, oxo or C1-6Straight or branched chain (halo) alkyl (oxy, thio, amino, carbonyl) groups, and the like.
In the context of the present specification, the expression "(halo) alk (oxy, thio, amino, carbonyl) yl" means: alkyl, haloalkyl, alkoxy, alkylthio, alkylamino, alkylcarbonyl, haloalkoxy, haloalkylthio, haloalkylamino or haloalkylcarbonyl, the expression "(halo) ene (oxy, thio, amino, carbonyl) group" means: alkenyl, haloalkenyl, alkenyloxy, alkenylthio, alkenylamino, alkenylcarbonyl, haloalkenyloxy, haloalkenylthio, haloalkenylamino or haloalkenylcarbonyl, the expression "(halo) alkyne (oxy, thio, amino, carbonyl)" means: alkynyl, haloalkynyl, alkynyloxy, alkynylthio, alkynylamino, alkynylcarbonyl, haloalkynyloxy, haloalkynylthio, haloalkynylamino or haloalkynylcarbonyl.
In the context of the present specification, the term "C3-20Cycloalkyl "refers to monocyclic, bicyclic or polycyclic cycloalkyl groups having 3 to 20 ring carbon atoms. As said C3-20Examples of the cycloalkyl group include monocyclic cycloalkyl groups such as cyclopropyl, cyclohexyl and cyclopentyl, and dicyclopentyl, decahydronaphthyl, adamantyl and spiro [2.4 ]]Heptylalkyl, spiro [4.5 ]]Decyl, bicyclo [3.2.1]Octyl, tricyclo [2.2.1.0 ]2,6]Octyl, norbornyl, and the like,
Figure BDA0001598104130000181
And spirocyclic, bridged or fused ring bicyclic or polycyclic cycloalkyl groups. As said C3-20Cycloalkyl, more preferably C3-15A cycloalkyl group.
In the context of the present specification, the term "C3-20Cycloalkenyl "refers to the aforementioned C3-20A group in which at least one ring carbon-carbon single bond (C-C) of the cycloalkyl group is replaced by a carbon-carbon double bond (C ═ C). As said C3-20Examples of the cycloalkenyl group include monocyclic cycloalkenyl groups such as cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cycloheptadienyl and cyclooctatetraenyl, and dicyclopentadienyl, norbornenyl, norbornadiyl, and the like,
Figure BDA0001598104130000182
And spirocyclic, bridged or fused cyclic bicyclic or polycyclic cycloalkenyl groups. As said C3-20Cycloalkenyl group, more preferably C3-15A cycloalkenyl group.
In the context of the present specification, the term "C6-20Aryl "refers to an aromatic hydrocarbon group having 6 to 20 ring carbon atoms. As said C6-20Examples of the aryl group include a group in which two or more benzene rings are directly connected by a single bond, such as a phenyl group, a biphenyl group, and a terphenyl group, and a group in which two or more benzene rings are condensed, such as a naphthyl group, an anthryl group, and a phenanthryl group. As said C6-20Aryl, more preferably phenyl and biphenyl.
In the context of the present specification, the term "C4-20Heteroaryl "refers to an aromatic hydrocarbon group having 4 to 20 ring carbon atoms and 1 to 3 ring heteroatoms selected from oxygen, sulfur and nitrogen. As said C4-20Examples of the heteroaryl group include furyl, thienyl, pyrrolyl, thiazolyl, benzothiazolyl, thiadiazolyl, imidazolyl, benzimidazolyl, triazinyl, triazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl, pteridinyl, and acridinyl groups, and among them, furyl, thienyl, imidazolyl, pyridyl, and indolyl groups are preferable.
In the context of the present specification, the term "C2-20Heterocyclyl "refers to C as described above3-20Cycloalkyl or C3-20A group in which at least one of the ring carbon atoms of the cycloalkenyl group is replaced with an oxygen atom, a sulfur atom, or a nitrogen atom. As said C2-20Examples of the heterocyclic group include a piperidyl group, a piperazinyl group, an azacyclohexenyl group, a dioxolanyl group, a dioxanyl group, a tetrahydrofuryl group, an oxetanyl group, an azepinyl group, a pyrrolinyl group, a tetrahydropyridinyl group, a tetrahydropyrazolyl group, a pyrazolinyl group, a pyranyl group, a thiopyranyl group, a tetrahydropyrrolyl group, a tetrahydrothienyl group, an aziridinyl group, a tetrahydropyranyl group, a tetrahydrothiopyranyl group and a morpholinyl group, and among them, a piperidyl group, a tetrahydrofuryl group, a tetrahydropyranyl group and the like are preferable.
In the context of the present specification, the term "ammonia-containing effluent" refers to a gaseous or liquid material containing ammonia (such as ammonia-containing condensed water, ammonia-containing waste water, ammonia-containing off-gas, and the like) discharged from the reaction system as a by-product or unreacted raw material during and/or after the progress and/or completion of the reaction in the process for producing a nitrile of the present invention (particularly, the first step).
Finally, unless otherwise expressly indicated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless otherwise generally recognized by those skilled in the art.
The present invention relates to a method for producing a nitrile, which is characterized by comprising a first step and a second step described below.
According to this first step of the invention, the carboxylic acid source and the ammonia source are brought to a reaction temperature T ranging from T1 to T2A(ii) for a reaction time of from 0.01 to 2.5 hours, to obtain an amide intermediate product, wherein T1 is the greater of the melting point and temperature value 80 ℃ of the carboxylic acid source at 1 atm, and T2 is the minimum of the boiling point, sublimation temperature, and decomposition temperature of the aliphatic monocarboxylic acid at 1 atm, provided that T2>T1. Preferably, T2-T1 is 10 ℃ or higher.
According to the invention, the carboxylic acid source is selected from the group consisting of aliphatic monocarboxylic acids, C of said aliphatic monocarboxylic acids1-4A linear or branched alkyl ester (preferably methyl ester), an anhydride of the aliphatic monocarboxylic acid, or an ammonium salt of the aliphatic monocarboxylic acid. These carboxylic acid sources may be used singly or in combination of two or more.
According to the present invention, examples of the aliphatic monocarboxylic acid include compounds having the following structures.
R-COOH，
Wherein the radical R is C1-29(preferably C)1-19) A saturated or unsaturated linear or branched hydrocarbon group.
According to the invention, as said group R, C is preferred1-29(preferably C)1-19) Straight or branched alkyl, C2-29(preferably C)2-19) Straight or branched alkenyl or C2-29(preferably C)2-19) Straight or branched alkynyl.
According toIn the present invention, as the group R, C is more preferable1-29(preferably C)1-19) Straight or branched alkyl or C2-29(preferably C)2-19) Straight or branched alkenyl.
According to the invention, said R may be optionally substituted by one or more (such as 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, optionally substituted C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C2-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C2-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C3-20Cycloalkyl, optionally substituted C3-20Cycloalkane (oxy, thio, amino) radicals, optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C3-20Cycloalkenyl, optionally substituted C3-20Cycloalkene (oxy, thio, amino) radical, optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C6-20Aryl, optionally substituted C6-20Aryl (oxy, thio, amino) radicals, optionally substituted C6-20Aryl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C6-20Aryl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C6-20Aryl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C4-20Heteroaryl, optionally substituted C4-20Heteroaromatic (oxy, thio, amino) groups,Optionally substituted C4-20Heteroaryl C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C4-20Heteroaryl C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C4-20Heteroaryl C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C2-20Heterocyclyl, optionally substituted C2-20Heterocyclic (oxy, thio, amino) radical, optionally substituted C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and optionally substituted C2-20Heterocyclyl radical C1-6The substituents of the straight-chain or branched (halo) alkynyl (oxy, thio, amino, carbonyl) groups are substituted at the feasible positions.
Here, the expression "cycloalkane (oxy, thio, amino) group" means: cycloalkoxy, cycloalkylthio or cycloalkylamino, the expression "cycloalkene (oxy, thio, amino) group" means: cycloalkenyloxy, cycloalkenylthio or cycloalkenylamino, the expression "aryl (oxy, thio, amino) group" means: aryloxy, arylthio or arylamino, the expression "heteroaryl (oxy, thio, amino) group" means: heteroaryloxy, heteroarylthio or heteroarylamino, the expression "heterocyclic (oxy, thio, amino) group" means: heterocyclic oxy, heterocyclic thio or heterocyclic amino.
Examples of the possible substitution position include any position on the group R that can be substituted (by a corresponding hydrogen atom), and is preferably located at an end of the molecular chain of the group R opposite to the-COOH.
According to a particular embodiment of the invention, the radical R is C1-29(preferably C)1-19) Straight chain alkyl or C2-29(preferably C)2-19) Linear alkenyl, the substituent(s) (1 or more) being located at the ω -terminus of the molecular chain of the group R, in which case the-COOH is located at its α -terminus.
According to the invention, said R is optionally also selected by one or more (such as 1 to 5,1 to 4, 1 to 3, 1 to 2 or 1) from-O-, -S-and-NR1-(R1is H or C1-4Straight-chain or branched alkyl, preferably H or methyl), provided that when a plurality is present, there is no direct linkage between any two of the hetero groups. For example, the radical R is CH3-CH2-CH2-CH2When interrupted by an O, CH is available3-O-CH2-CH2-CH2-、CH3-CH2-O-CH2-CH2-and CH3-CH2-CH2-O-CH2-etc., CH can be obtained after interruption by two O3-O-CH2-O-CH2-CH2-、CH3-CH2-O-CH2-O-CH2-and CH3-O-CH2-CH2-O-CH2-etc., CH can be obtained after interruption by three O3-O-CH2-O-CH2-O-CH2-。
According to the present invention, as the carboxylic acid source, one of the above aliphatic monocarboxylic acids may be used alone, or two or more of them may be used in combination.
According to the present invention, the carboxylic acid source may be of biological origin, such as natural fatty acids or mixed fatty acids as by-products of industry (e.g., the oil and fat industry), as long as it contains impurities or impurity levels that reduce the yield of the target nitrile by no more than 5%.
According to the invention, the carboxylic acid source is at the reaction temperature TAIt is preferable that the liquid is in a molten state or a liquid state. In view of this, the aliphatic monocarboxylic acid, C of the aliphatic monocarboxylic acid1-4The linear or branched alkyl ester or the anhydride of the aliphatic monocarboxylic acid preferably has the reaction temperature T equal to or less thanA(typically up to 300 ℃) in the presence of a base. The melting point of these carboxylic acid sources at 1 atm (and the boiling point, sublimation temperature, decomposition temperature, etc. of the aliphatic monocarboxylic acid at 1 atm) can be known to those skilled in the art by referring to the relevant technical manuals or by conventional measurement methods, and therefore, will not be described herein in detail.
According to an embodiment of the present invention, the carboxylic acid source and the ammonia source are contacted with each other, for example, by continuously supplying (for example, feeding) the ammonia source in a gaseous form to the (preferably previously melted) carboxylic acid source.
According to this embodiment of the invention, the ammonia source is as described above, wherein ammonia gas or vaporized ammonia water, in particular industrial waste ammonia gas or vaporized industrial waste ammonia water, is preferred. In this case, the ammonia content of the ammonia source may be, for example, 20 to 99.9 wt%, 25 to 99.9 wt%, 40 to 99.9 wt%, 60 to 99.9 wt%, 75 to 99.9 wt%, 85 to 99.9 wt%, or 95 to 99.9 wt%, with the balance being the inert diluent or the like as described above.
According to this embodiment of the invention, the ammonia source is supplied (fed) continuously throughout the first step. The amount of the ammonia source to be used (as a whole) in this case is not particularly limited as long as the nitrile yield to be achieved in the present invention can be achieved. For example, the carboxylic acid source in terms of carboxyl groups and NH according to actual reaction conditions3The molar ratio of the ammonia source may be at least 1: 20. 1: 30. 1: 40 or 1: 50, etc., up to no excessive waste of the ammonia source, such as may be 1: 500. 1: 400. 1: 300. 1: 200. 1: 100 or 1: 80, etc., but may not be limited thereto.
According to this embodiment of the invention, the first step is generally carried out in an open reaction system, such as an open reaction kettle. The ammonia source is continuously supplied to the reaction system (containing the molten carboxylic acid source) while the ammonia-containing effluent is continuously withdrawn from the reaction system.
According to another embodiment of the present invention, the carboxylic acid source and the ammonia source may be contacted with each other by, for example, adding the ammonia source to the (preferably previously melted) carboxylic acid source at a time in a predetermined ratio or mixing the streams of the two with each other in a predetermined ratio to react. In general, the contact may be carried out continuously, semi-continuously, or intermittently, and is not particularly limited.
According to this embodiment of the invention, the source of ammonia is as described above, with ammonia gas or ammonia-generating being preferredSubstance, more preferably industrial waste ammonia gas. In this case, the ammonia content of the ammonia source may be, for example, 60 to 99.9 wt%, 80 to 99.9 wt%, 85 to 99.9 wt%, or 95 to 99.9 wt%, with the remainder being the inert diluent or the like as described above. In this case, the amount of the carboxylic acid source is such that the amount of the carboxylic acid source in terms of carboxyl groups is equal to the amount of NH3The molar ratio of the ammonia source is up to 1: 1.1-2.5, preferably 1: 1.2-2.0, more preferably 1: 1.3-1.6.
According to this embodiment of the present invention, as the ammonia source, it is also possible to use aqueous ammonia or an aqueous solution of an ammonia generating substance, with aqueous ammonia being preferred and industrial waste aqueous ammonia being more preferred. Wherein the ammonia content of the aqueous ammonia is generally 10 to 30% by weight, preferably 25 to 28% by weight. In this case, the amount of the carboxylic acid source is such that the amount of the carboxylic acid source in terms of carboxyl groups is equal to the amount of NH3The molar ratio of the ammonia source is up to 1: 1.1-9.5, preferably 1: 1.2-7.0, more preferably 1: 1.3-5.6, 1: 1.3-2.5, 1: 1.3-2.0 or 1: 1.3-1.6.
According to this embodiment of the present invention, the ammonia generating substance refers to a substance that can be decomposed under the reaction conditions of the first step to generate ammonia gas. As the ammonia generating substance, one or more selected from urea, cyanic acid, ammonium carbonate, ammonium bicarbonate and ammonium chloride are preferable, one or more selected from urea and ammonium bicarbonate are preferable, and ammonium bicarbonate is more preferable.
According to this embodiment of the present invention, the ammonia generator concentration of the ammonia generator aqueous solution may be, for example, 20wt% to a saturated concentration (preferably a saturated concentration) or the like, but is not limited thereto. As the aqueous solution of the ammonia-producing substance, an industrial waste or an industrial by-product containing the ammonia-producing substance, such as waste urea water and waste ammonium carbonate water, is more preferable.
According to this embodiment of the invention, the first step is generally carried out in a closed reaction system (such as a closed reaction vessel). If desired, this first step can be carried out in a completely closed reaction system, i.e. the reaction system does not need to be open to the outside atmosphere in any way during the entire reaction. In view of this, the closed reaction system generally exhibits pressurized conditions (such as the autogenous pressure of the first step).
According to this embodiment of the present invention, while the amide intermediate product is produced, an effluent containing ammonia is also discharged as a by-product to the outside of the reaction system in a continuous, semi-continuous or batch manner.
It is preferred according to the present invention that the ammonia-containing effluent obtained in any of the preceding embodiments, preferably after concentration or drying, is recycled to be fed to the first step as a supplement or part of the ammonia source. This can correspondingly reduce the amount of fresh ammonia source supplied to the first step, thereby increasing the utilization of ammonia raw material and achieving effective recycling of ammonia-containing effluent (such as ammonia-containing wastewater and ammonia-containing tail gas).
The inventors of the present invention have found that the first step can be carried out well even without using any catalyst which is generally used in the art for carrying out a carboxylic acid amination process. Thus, according to a preferred embodiment of the invention, no catalyst is used in the first step.
According to the invention, although not essential, the first step may be carried out in the presence of a solvent to promote melting of the carboxylic acid source. Examples of the solvent include any solvent which can dissolve the carboxylic acid source but does not adversely affect the conversion reaction in the first step, and more specifically, examples thereof include an aromatic hydrocarbon solvent such as toluene or xylene, a strongly polar solvent such as DMF and DMSO, an organic basic solvent such as 2-methylpyridine, a halogenated alkane solvent such as dichloromethane, and water. The amount of the solvent is, for example, generally 20 to 50% by weight based on the weight of the carboxylic acid source, but is not limited thereto in some cases.
According to the invention, the reaction time of the first step is preferably 0.05 to 2 hours, alternatively 0.1 to 1.5 hours, alternatively 0.2 to 1 hour, alternatively 0.3 to 0.8 hour, alternatively 0.2 to 0.5 hour or less.
According to the present invention, the supply of the ammonia source is stopped or the ammonia source is removed from the reaction system of the first step immediately after the end of the first step.
According to the invention, after the first step is completed, the obtained amide intermediate product can be directly used as a raw material to carry out the second step, or can be temporarily stored and then carried out in the second step. Alternatively, although not necessarily, the obtained amide intermediate product may be washed with dilute aqueous ammonia or the like to remove a possibly remaining unreacted carboxylic acid source.
According to the present invention, the first step and the second step may be carried out in the same reactor or in different reactors, and are not particularly limited. When the reaction is carried out in the same reactor, the amide intermediate product is not discharged after the first step, and the reaction conditions in the first step are directly changed to those in the second step (described below), thereby reducing the production cost and production complexity of the production process. When carried out in different reactors, these reactors may be connected in series, with the latter reactor being fed by the discharge of the former reactor, so that the first step and the second step may be continued one after the other in a continuous, semi-continuous or batch-like manner.
According to the present invention, examples of the reactor in the first step or the second step include a reaction vessel, a fixed bed reactor, a fluidized bed reactor, and the like. These reactors may be used alone or in combination of two or more kinds, and are not particularly limited.
According to the second step, the amide intermediate obtained in the first step is subjected to a reaction temperature T ranging from T3 to T4B(ii) an under-heat treatment for a reaction time of from 0.1 to 4.5 hours, wherein T3 is the greater of the melting point and temperature value of the amide intermediate product at 1 atm and 160 ℃, and T4 is the minimum of the boiling point, sublimation temperature, and decomposition temperature of the amide intermediate product at 1 atm, with the proviso that T4>T3. Preferably, T4-T3 is 10 ℃ or higher.
According to the invention, the amide intermediate product is at the reaction temperature TBIt is preferable that the liquid is in a molten state or a liquid state. In view of this, the amide intermediate product preferably has the reaction temperature T equal to or less thanB(typically up to 400 ℃) in the presence of a suitable solvent. In the field ofThe melting point, boiling point, sublimation temperature, decomposition temperature, etc. of these amide intermediates at 1 atm can be known to those skilled in the art by referring to the relevant technical manuals or by conventional measurement methods, and therefore, will not be described herein in detail.
According to the present invention, although not essential, the second step may be carried out in the presence of a solvent. Examples of the solvent include any solvent which can dissolve the amide intermediate without adversely affecting the conversion reaction in the second step, and more specifically, aromatic hydrocarbon solvents such as toluene and xylene, strongly polar solvents such as DMF and DMSO, and organic basic solvents such as 2-methylpyridine. As the solvent, for example, 20 to 50% by weight based on the weight of the amide intermediate is generally used, but it is sometimes not limited thereto.
According to the invention, the reaction time of the second step is preferably 0.2 to 3 hours, alternatively 0.3 to 2 hours, alternatively 0.4 to 1.2 hours, alternatively 0.4 to 1 hour, alternatively 0.3 to 0.5 hours or less.
According to the invention, no ammonia source (such as any of the ammonia sources described hereinbefore) is used in the second step, such as (completely) stopping the supply of the ammonia source. In other words, the second step is carried out in the absence of the ammonia source.
According to the invention, the second step may be carried out in the presence of a catalyst or without a catalyst. The catalyst may be, for example, one conventionally used in the art for the carboxylic acid amination, and more specifically, phosphorus pentoxide, phosphorus oxychloride, thionyl chloride, phosphoric acid, phosphorus pentachloride, Bugess reagent, TFAA-NEt3Reagent, (COCl)2-NEt3DMSO reagents, methanesulfonyl chloride or titanium tetrachloride, etc., among which phosphorus pentoxide is preferred. When used, these catalysts may be used in amounts customary in the art (for example, from 0.1 to 10%, preferably from 0.2 to 5%, by weight based on the weight of the amide intermediate), without particular limitation.
According to a further embodiment of the invention, the reaction temperature TAFrom T1 'to T2'. At this time, the T1' is T1+5 ℃, or T1+10 ℃, or T1+20 ℃, or T1+30 ℃, or T1+40 ℃, or T1+50 ℃, or T1+60 ℃, or T1+70 ℃, or T1+80 ℃, or T1+90 ℃, or T1+100 ℃. T2' ═ T2, or T2-5 ℃, or T2-10 ℃, or T2-20 ℃, or T2-30 ℃, or T2-40 ℃, or T2-50 ℃, but generally up to 300 ℃. With the proviso that T2'>T1'. Preferably, T2 '-T1'. gtoreq.10 ℃.
According to a further embodiment of the invention, the reaction temperature TBFrom T3 'to T4'. At this time, the T3' is T3+5 ℃, or T3+10 ℃, or T3+20 ℃, or T3+30 ℃, or T3+40 ℃, or T3+50 ℃, or T3+60 ℃, or T3+70 ℃, or T3+80 ℃, or T3+90 ℃, or T3+100 ℃. T4' ═ T4, or T4-5 ℃, or T4-10 ℃, or T4-20 ℃, or T4-30 ℃, or T4-40 ℃, or T4-50 ℃, but generally up to 400 ℃. With the proviso that T4'>T3'. Preferably, T4 '-T3'. gtoreq.10 ℃.
According to a further embodiment of the present invention, said T1 is 80 ℃, or 100 ℃, or 110 ℃, or 120 ℃, or 130 ℃, or 140 ℃, or 150 ℃, or 160 ℃, or 170 ℃, or 180 ℃, or 190 ℃, or 200 ℃, or 210 ℃, or 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃. According to a further embodiment of the present invention, said T2 is 300 ℃, or 290 ℃, or 280 ℃, or 270 ℃, or 260 ℃, or 250 ℃, or 240 ℃, or 230 ℃, or 220 ℃, or 210 ℃, or 200 ℃, or 190 ℃, or 180 ℃, or 170 ℃, or 160 ℃, or 150 ℃, or 140 ℃, or 130 ℃, or 120 ℃, or 110 ℃. Provided that T2> T1. Preferably, T2-T1 is 10 ℃ or higher.
According to a further embodiment of the present invention, said T3 is 160 ℃, or 170 ℃, or 180 ℃, or 190 ℃, or 200 ℃, or 210 ℃, or 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃, or 300 ℃. According to a further embodiment of the present invention, said T4 is 400 ℃, or 390 ℃, or 380 ℃, or 370 ℃, or 360 ℃, or 350 ℃, or 340 ℃, or 330 ℃, or 320 ℃, or 310 ℃, or 300 ℃, or 290 ℃, or 280 ℃, or 270 ℃, or 260 ℃, or 250 ℃, or 240 ℃, or 230 ℃, or 220 ℃, or 210 ℃, or 200 ℃. Provided that T4> T3. Preferably, T4-T3 is 10 ℃ or higher.
According to the present invention, the second step may be carried out in an open reaction system or a closed reaction system. When the second step is carried out in a closed reaction system, the reaction system may be under a pressurized or depressurized condition. Among them, the reduced pressure condition is preferable from the viewpoint of effectively reducing the reaction temperature. The reduced pressure condition may be achieved by maintaining the reaction system at a certain degree of vacuum, for example, by connecting a vacuum pump. At this time, the specific value of the degree of vacuum depends on whether or not the objective nitrile product can be efficiently separated from the reaction system by distillation at the (predetermined) reaction temperature of the second step, and thus cannot be specified in general. The skilled person can select a suitable value for the vacuum degree for this purpose by consulting the relevant technical manual or can confirm it by simple tests without technical difficulties. Nevertheless, the value range of the vacuum is generally 5 to 1000mbar, preferably 20 to 500mbar or 50 to 250 mbar. At this time, as the conversion reaction of the second step proceeds, the nitrile product formed is continuously distilled out of the reaction system of the second step together with by-product water, thereby facilitating the shift of the reaction equilibrium toward the product. By using this way of continuous distillation to remove the product in the second step, the reaction temperature of this step can be significantly reduced and the reaction time of this step can be significantly shortened. Side reactions occur less frequently in this second step due to the reduction in reaction temperature and the reduction in reaction time, thereby contributing to an increase in the yield of the nitrile product. By employing this particular reaction regime, the reaction temperature of the second step can generally be at each reaction temperature T as defined in the context of the present specificationB(especially the upper limit value thereof) of 40 to 150 ℃ and preferably by 40, 45, 50, 55. 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150 ℃, etc. In addition, the reaction time of the second step can be further shortened generally by 40 to 80%, preferably by 50 to 70%.
According to a preferred embodiment of the present invention, the carboxylic acid source is a carboxylic acid, an anhydride or a methyl ester of the carboxylic acid shown in table 1 below, wherein the carboxylic acid is preferred.
According to a preferred embodiment of the present invention, in said first step, the reaction temperature is generally T as shown in Table 1 belowAThe upper limit of the reaction temperature is more preferably TA max-5℃、TA max-10℃、TA max-15 ℃ or TA max-20 ℃ of which TA maxRefer to said TAUpper limit values in table 1 below. In the first step, the reaction time is generally from 0.05 to 2 hours, alternatively from 0.1 to 1.5 hours, alternatively from 0.2 to 1 hour, alternatively from 0.3 to 0.8 hour, alternatively from 0.2 to 0.5 hour.
According to a preferred embodiment of the present invention, when the second step is carried out in an open reaction system or under pressurized conditions as described above, the reaction temperature is generally T shown in Table 1 belowBThe upper limit of the reaction temperature is more preferably TB max-5℃、TB max-10℃、TB max-15 ℃ or TB max-20 ℃ of which TB maxRefer to said TBUpper limit values in table 1 below. At this time, in the second step, the reaction time is generally 0.2 to 3 hours, alternatively 0.3 to 2 hours, alternatively 0.4 to 1.2 hours, alternatively 0.4 to 1 hour.
TABLE 1
Carboxylic acids Reaction temperature TA，℃ Reaction temperature TB，℃
Acetic acid 80 to 115 160 to 220
Hexanoic acid 140 to 185 200 to 250
Dodecanoic acid 140 to 225 250 to 330
Stearic acid 140 to 225 250 to 400
Acrylic acid 100 to 135 160 to 230
Phenylacetic acid 160 to 215 240 to 275
Phenylpropionic acid 160 to 220 240 to 335
Phenylpropanoic acid 150 to 225 250 to 345 of
Phenoxyacetic acids 130 to 215 250 to 335
2, 2-Biphenyl acetic acid 180 to 225 250 to 390
3-pyridylacetic acid 160 to 225 250 to 355
3-indoleacetic acid 180 to 225 250 to 400
3-Methylpentanoic acid 125 to 180 215 to 315
9-alkene-octadecanoic acid 150 to 225 245 to 305
10-alkene-undecanoic acid 150 to 225 255 to 305
14-methyl-pentadecanoic acid 155 to 215 245 to 315
4-alkynylpentanoic acid 95 to 155 180 to 225
10-alkynylpentanoic acid 95 to 165 180 to 225
2-amino acetic acid 100 to 155 185 to 265
2-Chloroacetic acid 100 to 155 175 to 235
Thioglycollic acid 100 to 155 175 to 205
Levulinic acid 145 to 215 245 to 300
Sarcosine 115 to 155 185 to 265
2-methoxy acetic acid 115 to 145 165 to 225
4-bromophenylacetic acid 155 to 225 255 to 315
2 Nitrophenylacetic acid 165 to 205 245 to 315
Cyclohexaneacetic acid 135 to 200 225 to 295
1-adamantane acetic acid 155 to 225 250 to 305
Cyclopentaacetic acid 145 to 215 235 to 285
2-Cyclohexanoneacetic acid 135 to 200 215 to 285
2-norkaneacetic acid 145 to 205 235 to 295
2-cyclopentenyl-1-acetic acid 80 to 145 175 to 225
4-methyl-1-cyclohexeneacetic acid 100 to 155 175 to 215
2-Thiopheneacetic acid 115 to 205 225 to 265
3,4- (methylenedioxy)) Phenylacetic acid 145 to 225 250 to 300
Imidazole-4-acetic acid 245 to 285 300 to 320
2-Furanoacetic acid 115 to 205 235 to 300
4-Piperidineacetic acid 125 to 215 235 to 300
Tetrahydropyran-4-acetic acid 250 to 300 305 to 325
According to a preferred embodiment of the present invention, when the second step is carried out under reduced pressure as described above, the reaction temperature is generally T 'as shown in tables 1 to 1 below'BThe upper limit of the reaction temperature is more preferably T'B max-5℃、T'B max-10℃、T'B max-15 ℃ or T'B max-20 ℃ of T'B maxIs referred to as T'BThe upper limit values in the following Table 1-1. At this time, in the second step, the reaction time is generally 0.1 to 1.5 hours, alternatively 0.1 to 1.2 hours, alternatively 0.2 to 0.8 hours, alternatively 0.2 to 0.6 hours, alternatively 0.3 to 0.5 hours.
TABLE 1-1
Figure BDA0001598104130000291
Figure BDA0001598104130000301
According to the present invention, after the second step is completed, the objective nitrile can be separated as a product from the reaction mixture obtained in the second step by a conventional purification or separation method. Examples of the purification or separation method include a distillation method and an extraction method.
According to the present invention, the distillation or extraction method may be carried out in a manner conventional in the art, and is not particularly limited as long as the objective nitrile product can be separated from the reaction mixture.
According to the present invention, as the distillation method, for example, a vacuum distillation method using a rectifying column under the following operating conditions: the vacuum is 40-100mbar and the bottom temperature is generally 100-320 ℃ with the boiling point of the target nitrile product at said vacuum (+ -2 ℃) as cut point, generally for example 80-250 ℃, but is not limited thereto and depends on the particular target nitrile product. The reflux ratio of the rectifying column may be set to 1.1 to 3 times the minimum reflux ratio Rmin as required, and the actual number of plates is, for example, 5 to 200, but is not limited thereto and depends on the specific target nitrile product. In addition, the actual operating conditions of the rectification column are not limited thereto, and those skilled in the art can select appropriate rectification operating conditions according to the distillation properties of the objective nitrile product (such as boiling point and thermal decomposition temperature, etc.), the rectification column structure (such as the number of trays, etc.), and the actual requirements (such as a predetermined nitrile purity, etc.), etc., which are conventionally known.
According to the present invention, the extraction method includes, for example, a method of directly extracting the reaction mixture (after diluting or adjusting the reaction mixture by adding an appropriate amount of a 2 to 5wt% dilute aqueous alkali solution as necessary) with a good solvent for the target nitrile product such as ethyl acetate, chloroform, hexane, and the like.
According to the invention, extraction and distillation can be combined, for example, by first carrying out a preliminary purification or separation by extraction and then carrying out a further purification or separation by distillation.
According to the present invention, the target nitrile product having a purity of 97% or more (preferably 98% or more, more preferably 99% or more) can be obtained by the purification or isolation. The nitrile purity in this case can be measured conveniently by gas chromatography or the like.
According to the method for producing a nitrile of the present invention, a nitrile yield of 75% or more, 80% or more, 90% or more, 95% or more, or even 98% or more can be achieved depending on the kind of the nitrile product.
According to the present invention, the reaction temperature in the first step is significantly reduced and the reaction time is significantly shortened as compared with the prior art carboxylic acid amination method. Without being bound by any theory, the reason for this may be as follows. The prior art processes for the amination of carboxylic acids generally employ relatively high temperatures and relatively long reaction times, so that the conversion of the carboxylic acid into the amide takes place simultaneously with the conversion of the amide (which results from the previous conversion) into the nitrile. Moreover, due to the high reaction temperature, the reaction equilibrium of these two conversion reactions rapidly moves toward the respective products and also toward the respective reactants (reversion reaction), thereby producing a large amount of highly reactive intermediate compounds in the reaction system. These highly reactive intermediate compounds, by themselves or with each other or with the reactants, are very chemically reactive, and, at the same time, undergo the aforementioned conversion or reversion reactions, various undesired side reactions also occur. Moreover, these side reactions become more severe and cross-occur as the reaction time increases. In order to suppress these side reactions, the prior art carboxylic acid amination process has to use a large number of ammonia sources. However, even in this case, since the reaction temperature is high and the reaction time is long, the generation of a large amount of by-products is unavoidable, thereby making it difficult to improve the yield and quality (e.g., high product purity) of the nitrile product by the prior art carboxylic acid amination method. In response to the problem of the prior art, the present inventors have found through diligent studies that the conversion reaction from carboxylic acid to amide can be achieved only at a significantly reduced reaction temperature compared to the prior art. Moreover, the conversion reaction requires only a short reaction time to complete. Because the reaction temperature is lower, the reaction time is shorter, and side reactions rarely occur. In addition, due to the lower reaction temperature, the conversion reaction from amide to nitrile is significantly inhibited, as evidenced by the fact that almost no nitrile is detectable in the amide intermediate product obtained in the first step. At the same time, the various side reactions associated therewith are also significantly suppressed, as evidenced by the high product yield (generally above 90%) and product purity (generally above 95%) of the amide intermediate obtained in the first step, thus laying a good foundation for the continuation of the second step. Meanwhile, since the conversion reaction of the first step is substantially quantitatively performed and side reactions are rarely generated even without the inhibitory effect of the ammonia source, the ammonia utilization rate of the first step of the present invention is very high, resulting in that the ammonia consumption amount thereof can be significantly reduced as compared with the prior art.
According to the present invention, due to the presence of the first step, the second step can be carried out well even without using a catalyst, or even while maintaining normal pressure, or even without actively taking measures such as the aforementioned reduced pressure conditions to separate the nitrile product from the reaction system, and finally the nitrile product can be obtained with higher product yield and higher product purity. This was the first phenomenon discovered in the art. Although the mechanism thereof is not clear, the present inventors considered that one of the reasons may be that the first step is completed at a lower reaction temperature within a shorter reaction time to produce some other reactive intermediates than the amide intermediate, which exhibit a catalytic effect on the conversion reaction of the second step to be carried out later, thereby effectively promoting the production of the objective nitrile product. Further, the present inventors confirmed by specific experiments that the reactive intermediate was not a carboxylic acid source used as a reactant or a carboxylic acid freshly produced by a reverse conversion reaction.
According to the present invention, the nitriles produced as described above can be used as starting materials for the production of the corresponding amines. To this end, the invention also relates to a process for the preparation of amines by hydrogenation of the nitrile to give the corresponding amines.
According to the invention, the hydrogenation can be carried out in any manner conventionally known in the art for the hydrogenation of nitriles. For example, the nitrile feed may be hydrogenated in the presence of a hydrogenation catalyst for 0.2 to 3 hours (preferably 0.5 to 2 hours) at a total reaction pressure of 0.6 to 5.2MPa, a hydrogen partial pressure of 0.4 to 5MPa (e.g., 2 to 4MPa), and a reaction temperature of 70 to 130 ℃ (e.g., 80 to 120 ℃), although it is sometimes not limited thereto.
According to the present invention, as the hydrogenation catalyst, various catalysts conventionally used in the art for producing amine by hydrogenation of nitrile can be directly used, and examples thereof include raney nickel, iron or copper doped raney nickel, Ni-B or Ni-Co-B amorphous alloy, supported Ni-B or Ni-Co-B amorphous alloy, carrier-supported noble metal (e.g., Pb/C, Pd/C or Rh/C, etc.), or composite catalyst (e.g., raney nickel/cobalt octacarbonyl), etc., wherein raney nickel is preferable from the viewpoint of easy industrial implementation, such as raney nickel sold by aladin reagent company under the specification of 50 μm or 150 μm. These hydrogenation catalysts may be used alone or in combination of two or more.
According to the invention, the hydrogenation catalyst may be used in an amount of, for example, 2 to 10 wt% (e.g., 2 to 6 wt%) on a weight basis, but is sometimes not limited thereto, of the nitrile feedstock.
According to the present invention, the hydrogenation reaction is preferably carried out in the presence of a solvent (otherwise known as a diluent), as is known in the art. As the solvent, for example, water; alcohols such as methanol, ethanol and 2-propanol; esters such as methyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; cycloalkanes such as cyclohexane; alkanes such as heptane; petroleum ether, diethyl ether, dioxane, tetrahydrofuran, and other ethers, or any combination of these solvents, and among them, ethanol or a mixed solvent of ethanol and water (a volume ratio of ethanol to water is, for example, 0.1:1 to 1:0.1, but not limited thereto) and the like are preferable. These solvents may be used alone or in combination of two or more.
According to the present invention, the solvent may be used in an amount effective to improve the exothermic reaction without imposing an excessive burden on the subsequent product separation step, and may be, for example, 1 to 10 times, such as 1 to 5 times, 1 to 4 times, 1 to 3 times, 1 to 2 times, or the like, based on the volume of the nitrile raw material, but is not limited thereto in some cases.
According to the present invention, the hydrogenation reaction may also be carried out in the presence of a hydrogenation aid, if necessary. Examples of the hydrogenation aid include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide. These hydrogenation assistants may be used alone or in combination of two or more.
According to the invention, the hydrogenation aid may be used in an amount of, for example, 0.3 to 2 wt% (preferably 0.2 to 1.2 wt%) on a weight basis of the nitrile raw material, but is not limited thereto in some cases.
According to the invention, the target amine can be isolated from the reaction mixture as the product by conventional purification or separation methods after the hydrogenation reaction has ended. Such purification or isolation methods are known in the art and will not be described in detail herein.
According to the method for producing an amine of the present invention, an amine yield of 85% or more, 90% or more, 95% or more, or even 98% or more can be achieved depending on the kind of the nitrile raw material, and the purity of the amine product can be 97% or more (preferably 98% or more, more preferably 99% or more).
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Preparation of amide intermediate example A
500g of carboxylic acid raw material (chemical purity) is added into a 1L open reaction kettle, stirring is started (600r/min), and ammonia gas (chemical purity, the water content is 5.1 wt%, and the flow is 100g/min) is continuously introduced into the carboxylic acid raw material from the bottom of the reaction kettle. The reaction is carried out at a reaction temperature TALower run TCAfter hours, the introduction of ammonia was stopped. The contents of the reactor were sampled for nuclear magnetic hydrogen spectroscopy and elemental analysis to characterize the amide intermediate. The specific reaction conditions and the results of characterization are shown in the following tables A-1, A-2, A-3, A-4, A-5 and A-6. These characterization results indicate that the obtained amide intermediate has an extremely high purity (99)% or more).
In this example, the ammonia gas can be directly replaced by spent ammonia gas (from a winnowing chemical plant, containing about 50 wt% ammonia, the remainder being toluene, oxygen, nitrogen, water vapour, carbon monoxide and carbon dioxide, the spent ammonia gas having a flow rate of 130 g/min).
TABLE A-1
Figure BDA0001598104130000341
TABLE A-2
Figure BDA0001598104130000351
TABLE A-3
Figure BDA0001598104130000361
TABLE A-4
Figure BDA0001598104130000371
TABLE A-5
Figure BDA0001598104130000381
TABLE A-6
Figure BDA0001598104130000391
Nitrile product preparation example A
Example a was prepared following the amide intermediate. The reaction vessel was closed (when the boiling point of the amide intermediate at atmospheric pressure was equal to or lower than the reaction temperature T described belowBWhile the reaction vessel is kept open (when the boiling point of the amide intermediate at normal pressure is higher than the reaction temperature T described below)BAt the time),stirring was continued (600r/min) and the reaction temperature was changed to TBAt the reaction temperature TBLower holding TDAfter hours, the reaction was substantially complete. Then, the reaction vessel was closed and connected to a vacuum pump to make the degree of vacuum in the reaction vessel 20 to 50mbar (adjusted depending on the kind of the nitrile product), and the distillate was used as the nitrile product. The yield of the nitrile product was calculated and sampled for nuclear magnetic hydrogen spectroscopy and elemental analysis to characterize the nitrile product obtained. The specific reaction conditions and characterization results are shown in the following tables A-7, A-8, A-9, A-10, A-11 and A-12. These characterization results indicate that the nitrile product obtained is of very high purity (above 99%).
In these nitrile product production examples, 10g of phosphorus pentoxide as a catalyst was added in one portion to the reaction vessel, optionally at the stage of initiation of the reaction.
TABLE A-7
Figure BDA0001598104130000401
TABLE A-8
Figure BDA0001598104130000411
TABLE A-9
Figure BDA0001598104130000421
TABLE A-10
Figure BDA0001598104130000431
TABLE A-11
Figure BDA0001598104130000441
TABLE A-12
Figure BDA0001598104130000451
Nitrile product preparation example A1
Example a was prepared following the amide intermediate. The reaction kettle is closed, the stirring is opened (600r/min), and the reaction temperature is changed into TB. The reactor was connected to a vacuum pump and the vacuum in the reactor was gradually reduced starting at 500mbar until a trace amount (up to about 0.5 wt%) of the amide intermediate was detected in the bleed. Maintaining the vacuum degree and the reaction time TDAfter hours, the reaction was substantially complete. The distillate was taken as the nitrile product. The yield of the nitrile product was calculated and sampled for nuclear magnetic hydrogen spectroscopy and elemental analysis to characterize the nitrile product obtained. The specific reaction conditions and characterization results are shown in the following tables A1-7, A1-8, A1-9, A1-10, A1-11 and A1-12. These characterization results indicate that the obtained nitrile product has a high purity (above 92%).
In these nitrile product production examples, 10g of phosphorus pentoxide as a catalyst was added in one portion to the reaction vessel, optionally at the stage of initiation of the reaction.
TABLE A1-7
Figure BDA0001598104130000461
TABLE A1-8
Figure BDA0001598104130000471
TABLE A1-9
Figure BDA0001598104130000481
TABLE A1-10
Figure BDA0001598104130000491
TABLE A1-11
Figure BDA0001598104130000501
TABLE A1-12
Figure BDA0001598104130000511
Preparation of amide intermediate example B
500g of carboxylic acid starting material (chemically pure) was charged into a 1L reactor, and NH was introduced3Ammonia gas (containing 0.5 wt% of water and being an industrial product) in a molar amount 1.3 times that of the carboxyl group contained in the carboxylic acid raw material was added to the reaction vessel, and the reaction vessel was closed and stirred (600 r/min). The reaction is carried out at a reaction temperature TALower run TCAfter hours, the contents of the autoclave were sampled for nuclear magnetic hydrogen spectroscopy and elemental analysis to characterize the amide intermediate. The specific reaction conditions and the results of characterization are shown in the following tables B-1, B-2, B-3, B-4, B-5 and B-6. These characterization results indicate that the obtained amide intermediate has very high purity (above 99%).
In this example, the ammonia gas can be directly replaced by spent ammonia gas (from the winnowing chemical plant, containing about 50 wt% ammonia, the remainder being toluene, oxygen, nitrogen, water vapor, carbon monoxide and carbon dioxide) or ammonium bicarbonate powder (chemically pure) having a molar number of ammonium ions of 1.4 times the number of carboxyl groups contained in the carboxylic acid feedstock.
TABLE B-1
Figure BDA0001598104130000521
TABLE B-2
Figure BDA0001598104130000531
TABLE B-3
Figure BDA0001598104130000541
TABLE B-4
Figure BDA0001598104130000551
TABLE B-5
Figure BDA0001598104130000561
TABLE B-6
Figure BDA0001598104130000571
Nitrile product preparation example B
Example B was prepared following the amide intermediate. The reaction vessel was closed (when the boiling point of the amide intermediate at atmospheric pressure was equal to or lower than the reaction temperature T described belowBWhile the reaction vessel is kept open (when the boiling point of the amide intermediate at normal pressure is higher than the reaction temperature T described below)BAt this time), stirring was continued (600r/min) to change the reaction temperature to TBAt the reaction temperature TBLower holding TDAfter hours, the reaction was substantially complete. Then, the reaction vessel was closed and connected to a vacuum pump to make the degree of vacuum in the reaction vessel 20 to 50mbar (adjusted depending on the kind of the nitrile product), and the distillate was used as the nitrile product. The yield of the nitrile product was calculated and sampled for nuclear magnetic hydrogen spectroscopy and elemental analysis to characterize the nitrile product obtained. The specific reaction conditions and the results of characterization are shown in the following tables B-7, B-8, B-9, B-10, B-11 and B-12. These characterization results indicate that the nitrile product obtained is of very high purity (above 99%).
In these nitrile product production examples, 10g of phosphorus pentoxide as a catalyst was added in one portion to the reaction vessel, optionally at the stage of initiation of the reaction.
TABLE B-7
Figure BDA0001598104130000591
TABLE B-8
Figure BDA0001598104130000601
TABLE B-9
Figure BDA0001598104130000611
TABLE B-10
Figure BDA0001598104130000621
TABLE B-11
Figure BDA0001598104130000631
TABLE B-12
Figure BDA0001598104130000641
Nitrile product preparation example B1
Example B was prepared following the amide intermediate. The reaction kettle is closed, the stirring is opened (600r/min), and the reaction temperature is changed into TB. The reactor was connected to a vacuum pump and the vacuum in the reactor was gradually reduced starting at 500mbar until a trace amount (up to about 0.5 wt%) of the amide intermediate was detected in the bleed. Maintaining the vacuum degree and the reaction time TDAfter hours, the reaction was substantially complete. The distillate was taken as the nitrile product. The yield of the nitrile product was calculated and sampled for nuclear magnetic hydrogen spectroscopy and elemental analysis to characterize the nitrile product obtained. The specific reaction conditions and characterization results are shown in the following tables B1-7, B1-8, B1-9, B1-10, B1-11 and B1-12. These characterization results indicate that the nitrile obtained is producedThe product has high purity (more than 92%).
In these nitrile product production examples, 10g of phosphorus pentoxide as a catalyst was added in one portion to the reaction vessel, optionally at the stage of initiation of the reaction.
TABLE B1-7
Figure BDA0001598104130000651
TABLE B1-8
Figure BDA0001598104130000661
TABLE B1-9
Figure BDA0001598104130000671
TABLE B1-10
Figure BDA0001598104130000681
TABLE B1-11
Figure BDA0001598104130000691
TABLE B1-12
Figure BDA0001598104130000701
Preparation of amide intermediate example C
500g of carboxylic acid starting material (chemically pure) and NH were charged in a 1L reactor3Ammonia water (NH) having a molar number 1.4 times that of the carboxyl group contained in the carboxylic acid raw material3Content 25 wt%, industrial product), the reaction kettle is closed, and the stirring is opened (600 r/min). The reaction is carried out at a reaction temperature TALower run TCAfter hours, the contents of the autoclave were sampled and nucleatedMagnetic hydrogen spectroscopy and elemental analysis to characterize the amide intermediate. The specific reaction conditions and the results of characterization are shown in the following tables C-1, C-2, C-3, C-4, C-5 and C-6. These characterization results indicate that the obtained amide intermediate has very high purity (above 99%).
In this example, the aqueous ammonia can be directly replaced with spent aqueous ammonia (from a Yankee petrochemical plant, containing about 20wt% ammonia, the remainder being phenol, water, urea, sodium sulfate and carbon dioxide) or an aqueous ammonium bicarbonate solution having 1.6 times the molar number of ammonium ions as the carboxyl groups contained in the carboxylic acid starting material (30 wt% ammonium bicarbonate concentration).
TABLE C-1
Figure BDA0001598104130000711
TABLE C-2
Figure BDA0001598104130000721
TABLE C-3
Figure BDA0001598104130000731
TABLE C-4
Figure BDA0001598104130000741
TABLE C-5
Figure BDA0001598104130000751
TABLE C-6
Figure BDA0001598104130000761
Nitrile product preparation example C
Example C was prepared following the amide intermediate. The reaction vessel was closed (when the boiling point of the amide intermediate at atmospheric pressure was equal to or lower than the reaction temperature T described belowBWhile the reaction vessel is kept open (when the boiling point of the amide intermediate at normal pressure is higher than the reaction temperature T described below)BAt this time), stirring was continued (600r/min) to change the reaction temperature to TBAt the reaction temperature TBLower holding TDAfter hours, the reaction was substantially complete. Then, the reaction vessel was closed and connected to a vacuum pump to make the degree of vacuum in the reaction vessel 20 to 50mbar (adjusted depending on the kind of the nitrile product), and the distillate was used as the nitrile product. The yield of the nitrile product was calculated and sampled for nuclear magnetic hydrogen spectroscopy and elemental analysis to characterize the nitrile product obtained. The specific reaction conditions and characterization results are shown in the following tables C-7, C-8, C-9, C-10, C-11 and C-12. These characterization results indicate that the nitrile product obtained is of very high purity (above 99%).
In these nitrile product production examples, 10g of phosphorus pentoxide as a catalyst was added in one portion to the reaction vessel, optionally at the stage of initiation of the reaction.
TABLE C-7
Figure BDA0001598104130000781
TABLE C-8
Figure BDA0001598104130000791
TABLE C-9
Figure BDA0001598104130000801
TABLE C-10
Figure BDA0001598104130000811
TABLE C-11
Figure BDA0001598104130000821
TABLE C-12
Figure BDA0001598104130000831
Nitrile product preparation example C1
Example C was prepared following the amide intermediate. The reaction kettle is closed, the stirring is opened (600r/min), and the reaction temperature is changed into TB. The reactor was connected to a vacuum pump and the vacuum in the reactor was gradually reduced starting at 500mbar until a trace amount (up to about 0.5 wt%) of the amide intermediate was detected in the bleed. Maintaining the vacuum degree and the reaction time TDAfter hours, the reaction was substantially complete. The distillate was taken as the nitrile product. The yield of the nitrile product was calculated and sampled for nuclear magnetic hydrogen spectroscopy and elemental analysis to characterize the nitrile product obtained. The specific reaction conditions and characterization results are shown in the following tables C1-7, C1-8, C1-9, C1-10, C1-11 and C1-12. These characterization results indicate that the obtained nitrile product has a high purity (above 92%).
In these nitrile product production examples, 10g of phosphorus pentoxide as a catalyst was added in one portion to the reaction vessel, optionally at the stage of initiation of the reaction.
TABLE C1-7
Figure BDA0001598104130000841
TABLE C1-8
Figure BDA0001598104130000851
TABLE C1-9
Figure BDA0001598104130000861
TABLE C1-10
Figure BDA0001598104130000871
TABLE C1-11
Figure BDA0001598104130000881
TABLE C1-12
Figure BDA0001598104130000891
Amine preparation examples
(1) 100g of hexanenitrile, 3g of Raney-Ni and 400mL of ethanol are added into a 1L hydrogenation kettle, and H is continuously charged2The system pressure is always kept at 6MPa in the reaction process. Reacting at 90 deg.c for 0.5 hr, and cooling. When the temperature in the reaction kettle is reduced to room temperature, the gas is discharged, and the hexylamine (with the purity of more than 99 percent) is obtained through filtration and recrystallization, wherein the yield is 92 weight percent.
1H NMR (300MHz, DMSO) δ 2.69(q, J ═ 6.2Hz,2H),1.68(s,2H),1.06(t, J ═ 6.2Hz,3H), elemental analysis: C, 52.86; h, 15.35; and N, 30.85.
(2) 100g of dodecanonitrile, 3g of Raney-Ni and 400mL of ethanol are added into a 1L hydrogenation kettle, and H is continuously filled into the kettle2The system pressure is always maintained at 7MPa during the reaction. After the reaction is carried out for 0.5h at the reaction temperature of 95 ℃, the temperature is reduced. When the temperature in the reaction kettle is reduced to room temperature, gas is discharged, and dodecylamine (with the purity of more than 99%) is obtained through filtration and recrystallization, wherein the yield is 93 wt%.
1H NMR (300MHz, DMSO) δ 2.74(t, J ═ 7.6Hz,2H),1.73(s,2H),1.51(qd, J ═ 7.6,0.6Hz,2H), 1.41-1.23 (m,18H), 0.99-0.89 (m,3H), elemental analysis: C, 77.01; h, 13.79; and N, 7.07.
(3) 100g of benzyl cyanide and 3g of Raney-Ni, 400mL of ethanol are added into a 1L hydrogenation kettle, and H is continuously filled into the hydrogenation kettle2The system pressure is always maintained at 7MPa during the reaction. After reacting at the reaction temperature of 105 ℃ for 1h, the temperature is reduced. When the temperature in the reaction kettle is reduced to room temperature, the gas is discharged, and the phenylethylamine (with the purity of more than 99 percent) is obtained through filtration and recrystallization, wherein the yield is 91wt percent.
1H NMR (300MHz, DMSO) δ 7.25(s,1H),7.21(d, J ═ 7.3Hz,1H),6.90(t, J ═ 1.8Hz,1H), 6.87-6.84 (m,1H),6.80(s,1H),2.81(dd, J ═ 11.7,4.1Hz,2H),1.82(s,2H), elemental analysis: C, 79.11; h, 8.96; n,10.88.
(4) Adding 100g of phenoxyacetonitrile, 3g of Raney-Ni and 400mL of ethanol into a 1L hydrogenation kettle, and continuously charging H2The system pressure is always maintained at 7MPa during the reaction. After reacting for 1h at the reaction temperature of 90 ℃, cooling. When the temperature in the reaction kettle is reduced to room temperature, the gas is discharged, and the phenoxyethylamine (with the purity of more than 99 percent) is obtained through filtration and recrystallization, wherein the yield is 93 percent by weight.
1H NMR (300MHz, DMSO) δ 7.27(s,1H),7.23(d, J ═ 7.3Hz,1H),6.93(t, J ═ 1.8Hz,1H), 6.92-6.90 (m,1H),6.90(s,1H),4.16(t, J ═ 4.2Hz,2H),3.37(t, J ═ 4.2Hz,2H),1.92(s,2H), elemental analysis: C, 68.76; h, 8.11; n, 11.80.
(5) 100g of 3-pyridine acetonitrile and 3g of Raney-Ni, 400mL of ethanol are added into a 1L hydrogenation kettle, and H is continuously filled2The system pressure is always maintained at 7MPa during the reaction. After reacting for 1h at the reaction temperature of 100 ℃, cooling. When the temperature in the reaction kettle is reduced to room temperature, the gas is discharged, and the 3-pyridine ethylamine (with the purity of more than 99 percent) is obtained through filtration and recrystallization, wherein the yield is 89 percent by weight.
1H NMR (300MHz, DMSO) δ 8.44-8.32 (m,1H), 8.32-8.24 (m,1H),7.57(dt, J ═ 7.5,1.5Hz,1H),7.24(t, J ═ 7.5Hz,1H),3.04(dd, J ═ 11.6,4.0Hz,2H),2.78(dd, J ═ 11.6,4.0Hz,2H),1.82(s,2H), elemental analysis: C, 67.45; h, 8.07; n, 21.43.
(6) Adding 100g of cyclohexylacetonitrile and 3g of Raney-Ni into a 1L hydrogenation kettle, and continuously charging H into the hydrogenation kettle2The system pressure is always maintained at 7MPa during the reaction. After reacting at the reaction temperature of 105 ℃ for 1.5h, the temperature is reduced. When the temperature in the reaction kettle is reduced to room temperature, the gas is discharged,the cyclohexylethylamine (purity over 99%) was obtained in 94 wt% yield by filtration and recrystallization.
1H NMR (300MHz, DMSO) δ 2.73(t, J ═ 7.7Hz,2H),1.76(d, J ═ 5.7Hz,2H), 1.74-1.70 (m,2H), 1.69-1.50 (m,2H), 1.51-1.39 (m,2H), 1.38-1.25 (m,1H), 1.05-0.86 (m,2H), elemental analysis: C, 74.28; h, 12.79; n, 10.83.
Nitrile product preparation comparative example A
400g of n-caproamide (analytically pure) is added into a 1L open reaction kettle, and stirring is started (600r/min) to ensure that the reaction temperature is TBAt the reaction temperature T ═ 225 ℃BLower holding TDAfter 1 hour, the reaction vessel was closed and a vacuum pump was connected in the same manner as in nitrile product production example a, and the distillate was taken as a nitrile product. The n-hexanenitrile product was calculated and analyzed to have a yield of 35% and a purity of 90%.
Nitrile product preparation comparative example B
400g of n-caproamide (analytically pure) and 100g of n-caproic acid (analytically pure) are added into a 1L open reaction kettle, and stirring is started (600r/min) to ensure that the reaction temperature is TBAt the reaction temperature T ═ 225 ℃BLower holding TDAfter 1 hour, the reaction vessel was closed and a vacuum pump was connected in the same manner as in nitrile product production example a, and the distillate was taken as a nitrile product. The n-hexanenitrile product was calculated and analyzed to have a yield of 40% and a purity of 92%.
Although the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims. Those skilled in the art can appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.

Claims (50)

1. A method for producing a nitrile, comprising the steps of:
the first step is as follows: the carboxylic acid source and the ammonia source are mixed from T1 toReaction temperature T of T2A(ii) for a reaction time of from 0.01 to 2.5 hours to obtain an amide intermediate, wherein the carboxylic acid source is selected from the group consisting of an aliphatic monocarboxylic acid, C of the aliphatic monocarboxylic acid1-4One or more of a linear or branched alkyl ester, an anhydride of the aliphatic monocarboxylic acid, and an ammonium salt of the aliphatic monocarboxylic acid, wherein T1 is the greater of the melting point and temperature value 80 ℃ of the carboxylic acid source at 1 standard atmosphere pressure, T2 is the minimum of the boiling point, sublimation temperature, and decomposition temperature of the aliphatic monocarboxylic acid at 1 standard atmosphere pressure, provided that T2>T1，
Further comprising a second step of: subjecting the amide intermediate to a reaction temperature T of from T3 to T4B(ii) an under-heat treatment for a reaction time of from 0.1 to 4.5 hours, wherein T3 is the greater of the melting point and temperature value of the amide intermediate product at 1 atm and 160 ℃, and T4 is the minimum of the boiling point, sublimation temperature, and decomposition temperature of the amide intermediate product at 1 atm, with the proviso that T4>T3，
After the end of the second step, separating the nitrile product from the reaction mixture obtained in the second step by purification or isolation,
said ammonia source being continuously supplied in gaseous form, selected from ammonia gas, said ammonia source having an ammonia content of from 75 to 95% by weight, the remainder being an inert diluent selected from water vapour or liquid water, and said first step being carried out in an open reaction system,
or the ammonia source is ammonia gas or an ammonia generating substance, or the ammonia source is aqueous ammonia or an aqueous ammonia generating substance solution, and the first step is carried out in a closed reaction system,
the aliphatic monocarboxylic acid is selected from one or more of the compounds having the following structural formula:
R-COOH，
wherein the radical R is C1-29Straight or branched alkyl, C2-29Straight or branched alkenyl or C2-29Straight or branched chain alkynyl; said R is optionally substituted by one or more groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, optionallySubstituted C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C2-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C2-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C3-20Cycloalkyl, optionally substituted C3-20Cycloalkane (oxy, thio, amino) radicals, optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C3-20Cycloalkyl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C3-20Cycloalkenyl, optionally substituted C3-20Cycloalkene (oxy, thio, amino) radical, optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C3-20Cycloalkenyl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C6-20Aryl, optionally substituted C6-20Aryl (oxy, thio, amino) radicals, optionally substituted C6-20Aryl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C6-20Aryl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C6-20Aryl radical C1-6Straight or branched (halo) alkynyl (oxy, thio, amino, carbonyl) group, optionally substituted C4-20Heteroaryl, optionally substituted C4-20Heteroaryl (oxy, thio, amino) radical, optionally substituted C4-20Heteroaryl C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C4-20Heteroaryl C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl), optionally substituted C4-20Heteroaryl C1-6Straight chain orBranched (halo) alkynes (oxy, thio, amino, carbonyl), optionally substituted C2-20Heterocyclyl, optionally substituted C2-20Heterocyclic (oxy, thio, amino) radical, optionally substituted C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) alk (oxy, thio, amino, carbonyl) yl, optionally substituted C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and optionally substituted C2-20Heterocyclyl radical C1-6Linear or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, wherein the expression "cycloalkane (oxy, thio, amino) group" means: cycloalkoxy, cycloalkylthio or cycloalkylamino, the expression "cycloalkene (oxy, thio, amino) group" means: cycloalkenyloxy, cycloalkenylthio or cycloalkenylamino, the expression "aryl (oxy, thio, amino) group" means: aryloxy, arylthio or arylamino, the expression "heteroaryl (oxy, thio, amino) group" means: heteroaryloxy, heteroarylthio or heteroarylamino, the expression "heterocyclic (oxy, thio, amino) group" means: a heterocyclic oxy group, a heterocyclic thio group or a heterocyclic amino group,
said R is optionally further substituted by one or more groups selected from-O-, -S-and-NR1Interruption of a hetero group of (A) wherein R1Is H or C1-4Straight or branched chain alkyl, provided that when a plurality is present, there is no direct linkage between any two hetero groups,
the expression "optionally substituted" means optionally substituted by one or more groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C3-20Cycloalkyl radical, C3-20Cycloalkyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C3-20Cycloalkyl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C3-20Cycloalkyl radical C1-6Straight or branched chain (halo) alkynes (oxy),Sulfur, ammonia, carbonyl) group, C3-20Cycloalkenyl radical, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C3-20Cycloalkenyl radical C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C6-20Aryl radical, C6-20Aryl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C6-20Aryl radical C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C6-20Aryl radical C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C4-20Heteroaryl group, C4-20Heteroaryl C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C4-20Heteroaryl C1-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C4-20Heteroaryl C1-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C2-20Heterocyclic group, C2-20Heterocyclyl radical C1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C2-20Heterocyclyl radical C1-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and C2-20Heterocyclyl radical C1-6Linear or branched (halo) alkynyl (oxy, thio, amino, carbonyl) substituents, where when a plurality of such substituents are present, adjacent two substituents may be bonded to each other to form a divalent substituent structure,
the expression "(halo) alk (oxy, thio, amino, carbonyl) yl" means: alkyl, haloalkyl, alkoxy, alkylthio, alkylamino, alkylcarbonyl, haloalkoxy, haloalkylthio, haloalkylamino or haloalkylcarbonyl, the expression "(halo) ene (oxy, thio, amino, carbonyl) group" means: alkenyl, haloalkenyl, alkenyloxy, alkenylthio, alkenylamino, alkenylcarbonyl, haloalkenyloxy, haloalkenylthio, haloalkenylamino or haloalkenylcarbonyl, the expression "(halo) alkyne (oxy, thio, amino, carbonyl)" means: alkynyl, haloalkynyl, alkynyloxy, alkynylthio, alkynylamino, alkynylcarbonyl, haloalkynyloxy, haloalkynylthio, haloalkynylamino or haloalkynylcarbonyl.
2. The process according to claim 1, wherein T2-T1 ℃ is 10 ℃ or higher.
3. The process according to claim 1, wherein T4-T3 ℃ is 10 ℃ or higher.
4. The production method according to claim 1, wherein the reaction temperature T isAFrom T1' to T2', wherein T1' = T1+5 ℃, or T1+10 ℃, or T1+20 ℃, or T1+30 ℃, or T1+40 ℃, or T1+50 ℃, or T1+60 ℃, or T1+70 ℃, or T1+80 ℃, or T1+90 ℃, or T1+100 ℃, T2' = T2, or T2-5 ℃, or T2-10 ℃, or T2-20 ℃, or T2-30 ℃, or T2-40 ℃, or T2-50 ℃, or 300 ℃, provided that T2'>T1'。
5. The production method according to claim 1, wherein the reaction temperature T isBFrom T3' to T4', wherein T3' = T3+5 ℃, or T3+10 ℃, or T3+20 ℃, or T3+30 ℃, or T3+40 ℃, or T3+50 ℃, or T3+60 ℃, or T3+70 ℃, or T3+80 ℃, or T3+90 ℃, or T3+100 ℃, T4' = T4, or T4-5 ℃, or T4-10 ℃, or T4-20 ℃, or T4-30 ℃, or T4-40 ℃, or T4-50 ℃, or 400 ℃, provided that T4'>T3'。
6. The method of claim 1, wherein T1 is 80 ℃, or 100 ℃, or 110 ℃, or 120 ℃, or 130 ℃, or 140 ℃, or 150 ℃, or 160 ℃, or 170 ℃, or 180 ℃, or 190 ℃, or 200 ℃, or 210 ℃, or 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃; t2 is 300 ℃, or 290 ℃, or 280 ℃, or 270 ℃, or 260 ℃, or 250 ℃, or 240 ℃, or 230 ℃, or 220 ℃, or 210 ℃, or 200 ℃, or 190 ℃, or 180 ℃, or 170 ℃, or 160 ℃, or 150 ℃, or 140 ℃, or 130 ℃, or 120 ℃, or 110 ℃.
7. The method of claim 1, wherein T3 is 160 ℃, or 170 ℃, or 180 ℃, or 190 ℃, or 200 ℃, or 210 ℃, or 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃, or 300 ℃; t4 is 400 ℃, or 390 ℃, or 380 ℃, or 370 ℃, or 360 ℃, or 350 ℃, or 340 ℃, or 330 ℃, or 320 ℃, or 310 ℃, or 300 ℃, or 290 ℃, or 280 ℃, or 270 ℃, or 260 ℃, or 250 ℃, or 240 ℃, or 230 ℃, or 220 ℃, or 210 ℃, or 200 ℃.
8. The production process according to claim 1, wherein the second step is carried out under reduced pressure.
9. The manufacturing method of claim 1, wherein the first step does not use a catalyst.
10. The production method of claim 1, wherein the second step is carried out in the presence of a catalyst or without using a catalyst.
11. The production process according to claim 1, wherein the ammonia source is continuously supplied in gaseous form, selected from ammonia gas, and the carboxylic acid source in terms of carboxyl groups is mixed with NH3The molar ratio of the ammonia source calculated is at least 1: 20, max 1: 500, a step of; or the ammonia source is ammonia gas or an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.1-2.5; or the ammonia source is ammonia water or an ammonia-generating substance aqueous solution, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.1-9.5.
12. The production process according to claim 1, wherein the first step is carried out in a closed reaction system, and in order to contact the carboxylic acid source with the ammonia source, the reaction is carried out by adding the ammonia source to the carboxylic acid source at a time in a predetermined ratio or by mixing streams of both with each other in a predetermined ratio.
13. The production method of claim 1, wherein the ammonia source is continuously supplied in gaseous form, selected from ammonia gas, and the ammonia content of the ammonia source is 85 to 95 wt%.
14. The production method of claim 1, wherein the ammonia source is industrial waste ammonia gas or industrial waste ammonia water.
15. The production method of claim 11, wherein the ammonia source is continuously supplied in a gaseous form, the ammonia source is ammonia gas, and the carboxylic acid source in terms of carboxyl groups is mixed with NH3The molar ratio of the ammonia source calculated is at least 1: 30, max 1: 300.
16. the production method of claim 11, wherein the ammonia source is continuously supplied in a gaseous form, the ammonia source is ammonia gas, and the carboxylic acid source in terms of carboxyl groups is mixed with NH3The molar ratio of the ammonia source calculated is at least 1: 40, up to 1: 200.
17. the production method of claim 11, wherein the ammonia source is continuously supplied in a gaseous form, the ammonia source is ammonia gas, and the carboxylic acid source in terms of carboxyl groups is mixed with NH3The molar ratio of the ammonia source calculated is at least 1: 50, max 1: 80.
18. the production process according to claim 11, wherein the ammonia source is ammonia gas or an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.2-2.0.
19. The production process according to claim 11, wherein the ammonia source is ammonia gas or an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3Of metersThe molar ratio of the ammonia source is 1: 1.3-1.6.
20. The production process according to claim 11, wherein the ammonia source is aqueous ammonia or an aqueous solution of an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.3-5.6.
21. The production process according to claim 11, wherein the ammonia source is aqueous ammonia or an aqueous solution of an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.3-2.5.
22. The production process according to claim 11, wherein the ammonia source is aqueous ammonia or an aqueous solution of an ammonia-generating substance, and the carboxylic acid source in terms of carboxyl groups is reacted with NH3The molar ratio of the ammonia source calculated is 1: 1.3-1.6.
23. The production process according to claim 1, wherein the carboxylic acid source is a carboxylic acid, an anhydride or a methyl ester of the carboxylic acid shown in the following table 1; in the first step, the reaction temperature was T shown in Table 1 belowAThe reaction time of the first step is 0.05 to 2 hours; when the second step is carried out in an open reaction system or under pressurized conditions, the reaction temperature is T shown in Table 1 belowBThe reaction time of the second step is 0.2 to 3 hours; when the second step is carried out under reduced pressure, the reaction temperature is T 'shown in the following Table 1-1'BThe reaction time of the second step is 0.1 to 1.5 hours,
TABLE 1
Figure DEST_PATH_IMAGE001
TABLE 1-1
Carboxylic acids Reaction temperature T'B，℃ Acetic acid 100 to 160 Hexanoic acid 150 to 220 Dodecanoic acid 120 to 210 Stearic acid 170 to 240 Phenylacetic acid 150 to 250 Phenylpropionic acid 150 to 250 Phenylpropanoic acid 170 to 270 Phenoxyacetic acids 180 to 245 2, 2-Biphenyl acetic acid 185 to 250 3-pyridylacetic acid 185 to 250 3-indoleacetic acid 165 to 255 3-Methylpentanoic acid 170 to 240 9-alkene-octadecanoic acid 185 to 240 10-alkene-undecanoic acid 145 to 200 14-methyl-pentadecanoic acid 170 to 230 4-alkynylpentanoic acid 100 to 180 10-alkynylpentanoic acid 100 to 180 2-amino acetic acid 130 to 220 2-Chloroacetic acid 130 to 220 Thioglycollic acid 125 to 200 Levulinic acid 180 to 235 Sarcosine 160 to 225 2-methoxy acetic acid 135 to 200 4-bromophenylacetic acid 180 to 230 2-Nitrophenylacetic acid 180 to 240 Cyclohexaneacetic acid 175 to 245 1-adamantane acetic acid 175 to 235 Cyclopentaacetic acid 175 to 235 2-Cyclohexanoneacetic acid 175 to 235 2-norkaneacetic acid 175 to 235 2-cyclopentenyl-1-acetic acid 120 to 185 4-methyl-1-cyclohexeneacetic acid 120 to 180 2-Thiopheneacetic acid 140 to 220 3,4- (methylenedioxy) phenylacetic acid 180 to 240 Imidazole-4-acetic acid 185 to 250 2-Furanoacetic acid 180 to 240 4-Piperidineacetic acid 180 to 245 Tetrahydropyran-4-acetic acid 195 to 270
。
24. The production method of claim 23, wherein in the first step, the upper limit value of the reaction temperature is TA max-5℃、TA max-10℃、TA max-15 ℃ or TA max-20 ℃ of which TA maxRefer to said TAUpper limit values in said table 1.
25. The production process according to claim 23, wherein when the second step is carried out in an open reaction system or under pressurized conditions, the upper limit of the reaction temperature is TB max-5℃、TB max-10℃、TB max-15 ℃ or TB max-20 ℃ of which TB maxRefer to said TBUpper limit values in said table 1.
26. The production process according to claim 23, wherein when the second step is carried out under reduced pressure, the upper limit of the reaction temperature is T'B max-5℃、T'B max-10℃、T'B max-15 ℃ or T'B max-20 ℃ of T'B maxIs referred to as T'BThe upper limit value in said Table 1-1.
27. The method of claim 1 wherein said group R is C1-19Straight or branched alkyl, C2-19Straight or branched alkenyl or C2-19Straight or branched alkynyl.
28. The production process according to claim 1, wherein the first step obtains an ammonia-containing effluent at the same time as the amide intermediate product, and the ammonia-containing effluent is recycled to be supplied to the first step as a supplement to or a part of the ammonia source.
29. The manufacturing process of claim 28, wherein the ammonia-containing effluent is recycled to the first step after concentration or drying as a supplement to or part of the ammonia source.
30. The method of claim 1, wherein the carboxylic acid source is of biological origin.
31. The production process according to claim 1, wherein the carboxylic acid source is directly used as an industrially corresponding crude product.
32. The production method of claim 1, wherein the ammonia source is an industrial waste or an industrial byproduct containing ammonia or the ammonia-producing substance.
33. The method of claim 1, wherein the contacting is performed in a continuous, semi-continuous, or batch manner.
34. The production method of claim 1, wherein the reaction in the closed reaction system is carried out at a pressure higher than ambient pressure.
35. The manufacturing method of claim 1, wherein the first step and the second step are performed in the same reactor or different reactors.
36. The production method according to claim 1, wherein the second step is carried out in an open reaction system or a closed reaction system.
37. The manufacturing method of claim 1, wherein the first step is performed under autogenous pressure.
38. The production method of claim 1, wherein no ammonia source is used in the second step.
39. The production process according to claim 8, wherein the reduced pressure condition is achieved by maintaining the reaction system of the second step at a degree of vacuum, and the degree of vacuum has a value in the range of 5 to 1000 mbar.
40. The manufacturing method of claim 39, wherein the vacuum degree has a value ranging from 20 to 500 mbar.
41. The manufacturing process of claim 39, wherein the vacuum has a value in the range of 50 to 250 mbar.
42. The production process according to claim 8, wherein the reaction temperature T in the second step is controlled by the reduced pressure conditionBFurther reduction of 40 to 150 ℃ and further reduction of the reaction time of the second step by 40-80%.
43. The production method of claim 11, wherein the ammonia content of the aqueous ammonia solution is 10 to 30% by weight, and the ammonia generating substance concentration of the ammonia generating substance aqueous solution is 20% by weight to a saturated concentration.
44. The production method according to claim 1, wherein the reaction time of the first step is 0.1 to 1.5 hours.
45. The production method of claim 1, wherein the reaction time of the first step is 0.2 to 0.5 hours.
46. The production method according to claim 1, wherein when the second step is carried out in an open reaction system or under pressurized conditions, the reaction time of the second step is 0.3 to 2 hours.
47. The production method according to claim 1, wherein when the second step is carried out in an open reaction system or under pressurized conditions, the reaction time of the second step is 0.4 to 1 hour.
48. The production process according to claim 1, wherein when the second step is carried out under reduced pressure, the reaction time of the second step is 0.2 to 0.8 hours.
49. The production process according to claim 1, wherein when the second step is carried out under reduced pressure, the reaction time of the second step is 0.3 to 0.5 hours.
50. A method for producing an amine, comprising the steps of:
the first step is as follows: producing a nitrile according to the production method of any one of claims 1 to 49; and
the second step is as follows: the nitrile obtained in the first step is hydrogenated to produce an amine.
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