CN108546224B - Process for the manufacture of nitriles and their corresponding amines - Google Patents

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 201410156037.3 (application date 4/16 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

Aliphatic polynitriles such as aliphatic dinitriles are very important chemical intermediates, and they and their derivatives have very wide applications, for example, aliphatic diamine, one of their derivatives, is a basic raw material for producing nylon 66, nylon 1010, nylon 1212, and the like.

The preparation method of aliphatic dinitrile, especially higher aliphatic dinitrile, adopted in industry is usually carboxylic acid ammoniation method, widely used is that carboxylic acid or its derivative is heated and dissolved in open system, then ammonia gas is continuously introduced into solution to make the system react in the presence of catalyst such as phosphoric acid or phosphate, and NH exists in the process₃Excessive dosage, serious material loss, low yield and the like.

CN101880458A discloses a method for producing nitrile, which comprises adding dodecanedioic acid into a melting acid kettle, heating to 150-. This manufacturing process produces large amounts of waste ammonia water that requires further processing.

Therefore, the inventors of the present invention have found through studies that, in the prior art, when the corresponding aliphatic polynitrile is produced by an ammoniation method of an aliphatic polycarboxylic acid, in order to sufficiently perform the ammoniation reaction, the ammonia source (ammonia gas) must be continuously supplied (fed) to the reaction system during the whole ammoniation process of the carboxylic acid or during a long reaction time, so that the amount of ammonia gas is large, the actual amount of ammonia gas far exceeds the amount required for the ammoniation reaction, and may be ten million times the amount required for the actual reaction, and 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. In addition, 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 carried 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 is that there is still a need for a process for producing an aliphatic polynitrile, which is simple, suitable for industrial production, and can overcome the aforementioned problems in the production processes of the prior art.

Disclosure of Invention

The present inventors have assiduously studied on the basis of the prior art and found that, in the conversion of a carboxylic acid to a nitrile by an amination process, an intermediate step for forming an amide is required, and this intermediate step needs to be completed only at a relatively low reaction temperature and within a relatively short reaction time, and only this intermediate step needs the supply of an ammonia source, whereby the amination process of a carboxylic acid is definitely decomposed into two steps which are carried out independently, and further found that the aforementioned problems can be solved by using a nitrile production process having these two specific steps, and thus completed the present invention. The new two-step process has very important significance for breaking 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 T2_AIs contacted for a reaction time of 0.01 to 2.5 hours to obtain an amide intermediate product, wherein the carboxylic acid source is selected from the group consisting of an aliphatic polycarboxylic acid, C of the aliphatic polycarboxylic acid_1-4One or more of a linear or branched alkyl ester and an anhydride of the aliphatic polycarboxylic acid, the ammonia source being aqueous ammonia or an ammonia-producing substance, T1 being the greater of the melting point and temperature value of the carboxylic acid source at 1 atm of 100 ℃, T2 being the minimum of the boiling point, sublimation temperature and decomposition temperature of the aliphatic polycarboxylic acid at 1 atm, with the proviso that T2>T1, wherein the ammonia generating substance means a substance which can be decomposed under the reaction conditions of the first step to generate ammonia gas, and the ratio of the carboxylic acid source to the ammonia source is such that the carboxylic acid source is in terms of carboxyl groups and NH₃The molar ratio of the ammonia source is up to 1: 1.1-9.5,

and

the second step is as follows: subjecting the amide intermediate to a reaction temperature T of from T3 to T4_BUnder-heat treatment for a reaction time of 0.1 to 4.5 hours, wherein T3 is the greater of the melting point and temperature value of 220 ℃ of the amide intermediate product at 1 atm, 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 is used>T3，

The first step is carried out in a closed reaction system,

the aliphatic polycarboxylic acid means that the carbon atom directly bonded to each free carboxyl group of the polycarboxylic acid is a carbon atom on the aliphatic hydrocarbon chain, not a carbon atom on the ring, and is selected from one or more compounds having the following structural formula:

wherein, the group

Is a single bond, an optionally substituted n-valent aliphatic hydrocarbon chain, an optionally substituted n-valent C_3-20Cycloalkane ring, optionally substituted n-valent C_3-20A cycloalkene ring, optionally substituted n-valent C_6-20Aromatic ring, optionally substituted n-valent C_4-20Heteroaromatic ring, optionally substituted n-valent C_2-20Heterocyclic or optionally substituted n-valent associative groups; radical (I)

In the case of a single bond or an optionally substituted n-valent aliphatic hydrocarbon chain, the n groups R are each independently a single bond or an optionally substituted 2-valent aliphatic hydrocarbon chain

In other definitions, each of the n groups R is independently an optionally substituted 2-valent aliphatic hydrocarbon chain; the aliphatic hydrocarbon chains in each definition are each independently selected from C_1-15A saturated or unsaturated, linear or branched hydrocarbon chain of (a); when the aliphatic hydrocarbon chain has 2 or more carbon atoms and contains a C-C single bond in its molecular chain, optionally-O-, -S-or-NR-is inserted between two carbon atoms of the C-C single bond₁-, wherein R₁Is H or C_1-4A linear or branched alkyl group; n is an integer from 2 to 10; provided that the group

When the number is a single bond, n is 2,

the term "combination group" refers to two or more C_3-20A group in which cycloalkane rings are bonded to each other via a single bond or a linking group, two or more C_3-20A group in which cycloolefin rings are bonded to each other via a single bond or a linking group, two or more C_6-20A group formed by bonding aromatic rings to each other via a single bond or a linking group, two or more C_4-20Heteroaromatic rings via a single ringA group formed by bonding a bond or a linking group to each other, two or more C_2-20A group in which heterocyclic rings are bonded to each other via a single bond or a linking group, or C_3-20Cycloalkane ring, C_3-20Cycloolefin ring, C_6-20Aromatic ring, C_4-20Heteroaromatic ring and C_2-20Two or more groups in the heterocycle formed by being fused to each other or bonded to each other via a single bond or a connecting group,

the term "linking group" refers to-O-; -S-; -NR₁-, wherein R₁Is H or C_1-4A linear or branched alkyl group; optionally substituted C_1-4A linear or branched alkylene group; optionally substituted C_2-4Straight or branched alkenylene; optionally substituted C_2-4Straight or branched alkynylene; or any combination of these linking groups, but-O-, -S-and-NR₁Except in the case of direct bonding to itself or to each other,

the expression "optionally substituted" means optionally substituted by one or more groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_3-20Cycloalkyl radical, C_3-20Cycloalkane (oxy, thio, amino) radical, C_3-20Cycloalkyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_3-20Cycloalkyl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_3-20Cycloalkyl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_3-20Cycloalkenyl radical, C_3-20Cycloalkene (oxy, thio, amino) radical, C_3-20Cycloalkenyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_3-20Cycloalkenyl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_3-20Cycloalkenyl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_6-20Aryl radical, C_6-20Aryl (oxy, thio, amino) radicals, C_6-20Aryl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_6-20Aryl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_6-20Aryl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_4-20Heteroaryl group, C_4-20Heteroaryl (oxy, thio, amino) radical, C_4-20Heteroaryl C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_4-20Heteroaryl C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_4-20Heteroaryl C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_2-20Heterocyclic group, C_2-20Heterocyclic (oxy, thio, amino) radical, C_2-20Heterocyclyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_2-20Heterocyclyl radical C_2-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and C_2-20Heterocyclyl radical C_2-6Linear 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, the expression "(oxy, thio, amino) yl" means oxy, thio or amino, wherein halo includes mono-, di-, tri-or perhalo.

2. The method for producing a nitrile according to any one of the preceding aspectsWherein the carboxylic acid source and ammonia source are reacted at a reaction temperature T from T1 to T2_AThen contacting for a reaction time of 0.05-2 hours to obtain an amide intermediate product.

3. The method for producing a nitrile of any of the preceding aspects, wherein the carboxylic acid source and the ammonia source are allowed to react at a reaction temperature T from T1 to T2_AThen contacting for 0.1-1.5 hours to obtain an amide intermediate product.

4. The method for producing a nitrile of any of the preceding aspects, wherein the carboxylic acid source and the ammonia source are allowed to react at a reaction temperature T from T1 to T2_AAnd then contacted for a reaction time of 0.2 to 1 hour to obtain an amide intermediate product.

5. The method for producing a nitrile of any of the preceding aspects, wherein the carboxylic acid source and the ammonia source are allowed to react at a reaction temperature T from T1 to T2_AThen contacting for 0.3-0.8 h to obtain the amide intermediate product.

6. The method for producing a nitrile of any of the above aspects, wherein the ammonia source is industrial waste aqueous ammonia.

7. The method for producing a nitrile according to any of the preceding aspects, wherein the ratio of the carboxylic acid source to the ammonia source is such that the carboxylic acid source is NH in terms of carboxyl groups₃The molar ratio of the ammonia source is up to 1: 1.3-5.6.

8. The method for producing a nitrile of any of the preceding aspects, wherein the ratio of the carboxylic acid source to the ammonia source is such that the carboxylic acid source is represented by carboxyl groups and NH₃The molar ratio of the ammonia source is up to 1: 1.3-2.5.

9. The method for producing a nitrile of any of the preceding aspects, wherein the ratio of the carboxylic acid source to the ammonia source is such that the carboxylic acid source is represented by carboxyl groups and NH₃The molar ratio of the ammonia source is up to 1: 1.3-1.6.

10. The process for producing a nitrile as described in any of the above aspects, wherein T2-T1 ℃ is 10 ℃ or higher.

11. The method for producing a nitrile of any one of the preceding aspects, wherein the amide intermediate is reacted at a reaction temperature T from T3 to T4_BHeat treatment for a reaction time of 0.2 to 3 hours.

12. Production of the nitrile according to any of the preceding aspectsProcess wherein the amide intermediate is reacted at a reaction temperature T from T3 to T4_BThe lower heat treatment is carried out for a reaction time of 0.3 to 2 hours.

13. The method for producing a nitrile of any one of the preceding aspects, wherein the amide intermediate is reacted at a reaction temperature T from T3 to T4_BThe lower heat treatment is carried out for a reaction time of 0.4 to 1.2 hours.

14. The method for producing a nitrile of any one of the preceding aspects, wherein the amide intermediate is reacted at a reaction temperature T from T3 to T4_BThe lower heat treatment is carried out for a reaction time of 0.4 to 1 hour.

15. The process for producing a nitrile as described in any of the above aspects, wherein T4-T3 ℃ is 10 ℃ or higher.

16. The method for producing a nitrile of any one of the preceding aspects, wherein the reaction temperature T_AFrom 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 315 ℃, provided that T2 'is'>T1'; the reaction temperature T_BFrom 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 440 ℃, provided that T4 'is'>T3'。

17. The method of making a nitrile according to any of the preceding aspects, wherein T1 is 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 ℃, or 260 ℃, or 270 ℃, or 280 ℃, or 290 ℃, or 300 ℃; t2 is 315 ℃, or 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 ℃; t3 is 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃, or 260 ℃, or 270 ℃, or 280 ℃, or 290 ℃, or 300 ℃, or 310 ℃, or 320 ℃; t4 is 440 ℃, or 430 ℃, or 420 ℃, or 410 ℃, or 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 ℃.

18. 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.

19. 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.

20. The method for producing a nitrile of any of the preceding aspects, wherein the ammonia-generating substance is selected from one or more of urea, cyanic acid, ammonium carbonate, ammonium bicarbonate and ammonium chloride.

21. The method for producing a nitrile according to any of the above aspects, wherein the carboxylic acid source is a carboxylic acid, an anhydride or a methyl ester thereof shown in the following table, and in the first step, the reaction temperature T is_AThe reaction time is 0.05-2 hours, as shown in the following table, and the reaction temperature T in the second step_BAs shown in the following table, the reaction time was 0.2 to 3 hours,

。

22. the method for producing a nitrile of any of the preceding aspects, wherein in the first step, the reaction time is 0.1 to 1.5 hours.

23. The method for producing a nitrile of any of the preceding aspects, wherein in the first step, the reaction time is 0.2 to 1 hour.

24. The method for producing a nitrile of any of the preceding aspects, wherein in the first step, the reaction time is 0.3 to 0.8 hours.

25. The method for producing a nitrile of any of the preceding aspects, wherein in the second step, the reaction time is 0.3 to 2 hours.

26. The method for producing a nitrile of any of the preceding aspects, wherein in the second step, the reaction time is 0.4 to 1.2 hours.

27. The method for producing a nitrile of any of the preceding aspects, wherein in the second step, the reaction time is 0.4 to 1 hour.

28. The method for producing a nitrile according to any of the preceding aspects, wherein the aliphatic hydrocarbon chain in each definition is independently selected from C_1-15Straight or branched alkane chain, C_2-15Straight or branched olefin chain or C_2-15Straight or branched alkyne chains.

29. The method for producing a nitrile of any of the preceding aspects, wherein the aliphatic hydrocarbon chains are each independently selected from C_1-9Straight or branched alkane chain, C_2-9Straight or branched olefin chain or C_2-9Straight or branched alkyne chains.

30. The method for producing a nitrile of any of the preceding aspects, wherein n is an integer of 2 to 4.

31. 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.

32. 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.

33. The method for producing a nitrile of any of the preceding aspects, wherein the source of ammonia is metered into the previously melted source of carboxylic acid or mixed therewith in order to bring the source of carboxylic acid into contact with the source of ammonia.

34. The method for producing a nitrile of any of the preceding aspects, wherein the contacting is performed in a batch manner.

35. 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.

36. The method for producing a nitrile of any one of the preceding aspects, wherein the reaction in the closed reaction system is carried out under autogenous pressure.

37. 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.

38. The method for producing a nitrile of any of the above aspects, wherein the carboxylic acid source is an industrially corresponding crude product.

39. The method for producing a nitrile of any of the preceding aspects, wherein the carboxylic acid source is of biological origin.

40. The method for producing a nitrile according to any of the preceding aspects, wherein the first step and the second step are performed in the same reaction vessel, or in different reaction vessels.

41. 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.

42. 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 41; 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 process of the present invention, the supply of the ammonia source (such as ammonia gas or the like) is only performed in the first step, and the supply of the ammonia source is completely stopped in the second step, so that the amount of the ammonia source to be used 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 method for producing a nitrile 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 for 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 compared to 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 the 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 supply of the ammonia source is completely stopped in the second step, 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 yield of a nitrile of 75% or more, 80% or more, 90% or more, 95% or more, or even 98% or more can be obtained 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, it is possible to produce a nitrile having a more complicated structure, such as a (poly) nitrile or a (hetero) aromatic (poly) nitrile containing various hetero atoms, unsaturated bonds or ring structures, by a carboxylic acid amination method, which has been achieved for the first time in the art, thereby greatly expanding the range of applications 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 preferable values and lower preferable 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 are specifically disclosed, regardless of whether such pairs of values are individually 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 (such as propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) has the same meaning when not preceded by the prefix "n". 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 (for example, decrease the yield of nitrile by not more than 5%) the nitrile production process of the present invention. 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 95 wt%, preferably 25 to 95 wt%, 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 mentioned_1-4Linear or branched alkyl esters, and the like. 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 be used as it is as an industrially relevant crude product such as a (mixed) polycarboxylic acid product as an industrially (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 "polycarboxylic acid" refers to a compound containing a plurality (such as 2 to 10, preferably 2 to 5, more preferably 2 to 4, further preferably 2 or 3) of free carboxyl groups.

In the context of the present specification, the term "aliphatic polycarboxylic acid" means that the carbon atom directly bonded to each free carboxyl group of the polycarboxylic acid is a carbon atom on an aliphatic hydrocarbon chain, not on a ring, such as an aromatic or alicyclic ring.

In the context of the present specification, the term "alicyclic polycarboxylic acid" means that the carbon atom directly bonded to at least one free carboxyl group of the polycarboxylic acid is a carbon atom on an alicyclic ring (including cycloalkane rings, cycloalkene rings and heterocyclic rings), but each free carboxyl group of the polycarboxylic acid is not directly bonded to a carbon atom on an aromatic ring (including aromatic rings and heteroaromatic rings).

In the context of the present specification, the term "aromatic polycarboxylic acid" means that the carbon atom directly bonded to at least one free carboxyl group of the polycarboxylic acid is a carbon atom on an aromatic ring (including aromatic and heteroaromatic rings).

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 a reaction system which is isolated from the outside atmosphere throughout (using a closed reactor), in which case the reaction in the reaction system is carried out under a pressure higher than the ambient pressure (e.g., the autogenous pressure of the reaction system; there is no particular limitation as long as it is a pressure safe for production), but does not exclude, as required (e.g., pressure release or discharge of a part of by-products, etc.), 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, 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, 1 time, etc.) throughout the reaction.

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, C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_3-20Cycloalkyl radical, C_3-20Cycloalkane (oxy, thio, amino) radical, C_3-20Cycloalkyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_3-20Cycloalkyl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_3-20Cycloalkyl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_3-20Cycloalkenyl radical, C_3-20Cycloalkene (oxy, thio, amino) radical, C_3-20Cycloalkenyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_3-20Cycloalkenyl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_3-20Cycloalkenyl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_6-20Aryl radical, C_6-20Aryl (oxy, thio, amino) radicals, C_6-20Aryl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_6-20Aryl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_6-20Aryl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_4-20Heteroaryl group, C_4-20Heteroaryl (oxy, thio, amino) radical, C_4-20Heteroaryl C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_4-20Heteroaryl C_2-6Straight or branched chain (halo) alkenes (oxy, thio, amino)Carbonyl group, C)_4-20Heteroaryl C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_2-20Heterocyclic group, C_2-20Heterocyclic (oxy, thio, amino) radical, C_2-20Heterocyclyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_2-20Heterocyclyl radical C_2-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and C_2-20Heterocyclyl radical C_2-6Linear or branched (halo) alkynyl (oxy, thio, amino, carbonyl) substituents, where applicable. 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 C_1-6The linear or branched alkyl groups may be bonded to each other to form a corresponding alkylene structure. Or, two adjacent C_1-6Straight-chain or branched alkoxy radicals may, for example, form the corresponding alkylenedioxy structure, adjacent two C_1-6Straight-chain or branched alkylamino radicals may, for example, form the corresponding alkylenediamino structure, the two adjacent C' s_1-5Straight-chain or branched alkylthio groups, for example, may form the corresponding alkylenedisulfide structures, and the like. Preferred substituents include halogen, hydroxy, mercapto, amino, thio, oxo or C_1-6Straight 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, the expression "(oxy, thio, amino) group" means oxy, thio or amino. Here, the halo includes mono-, di-, tri-, or perhalo, etc.

In the context of the present specification, the term "aliphatic hydrocarbon chain" refers to a straight or branched saturated or unsaturated hydrocarbon, including alkane, alkene and alkyne chains.

In the context of the present specification, the term "n-valent" or the like refers to a group obtained by removing one (on-carbon) hydrogen atom from each of n different carbon atoms in a structure (such as a group, a hydrocarbon chain, or a compound ring, etc.) defined by the term. For example, the term "2-valent" refers to a group obtained by removing one (on-carbon) hydrogen atom from each of 2 different carbon atoms in a structure (e.g., a group, a hydrocarbon chain, or a compound ring, etc.) defined by the term. Specifically, for example, the 2-valent aliphatic hydrocarbon chain refers to an aliphatic alkylene group or an aliphatic hydrocarbon diyl group.

In the context of the present specification, the term "C_3-20The cycloalkane ring "means a monocyclic, bicyclic or polycyclic cycloalkane ring having 3 to 20 ring carbon atoms. As said C_3-20Examples of the cycloalkane ring include monocyclic cycloalkane rings such as cyclopropane ring, cyclohexane ring and cyclopentane ring, and bicyclic pentane ring, decahydronaphthalene ring, adamantane ring and spiro [2.4 ] ring]Heptane cyclo, spiro [4.5 ]]Decane ring, bicyclo [3.2.1]Octane ring, tricyclo [2.2.1.0^2,6]Octane ring, norbornane ring,

And the like are spiro, bridged or fused ring type bicyclic or polycyclic cycloalkane rings. As said C_3-20A cycloalkane ring, more preferably C_3-15A cycloalkane ring.

In the context of the present specification, the term "C_3-20The "cycloolefin ring" refers to the aforementioned C_3-20A group in which a carbon-carbon single bond (C-C) on at least one ring of a cycloalkane ring is replaced with a carbon-carbon double bond (C ═ C). As said C_3-20Cycloolefin ring, ratioExamples thereof include monocyclic cycloalkene rings such as a cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, cycloheptadiene ring and cyclooctatetraene ring, and dicyclopentadiene ring, norbornene ring, norbornadiene ring, norbornene-based ring, and the like,

And spirocyclic, bridged or fused bicyclic or polycyclic cycloalkene rings. As said C_3-20A cycloolefin ring, more preferably C_3-15A cycloalkene ring.

In the context of the present specification, the term "C_6-20Aromatic ring "refers to an aromatic hydrocarbon ring having 6 to 20 ring carbon atoms. As said C_6-20Examples of the aromatic ring include a group in which two or more benzene rings are directly connected to each other by a single bond, such as a benzene ring, biphenyl, terphenyl, and the like, and a group in which two or more benzene rings are condensed, such as a naphthalene ring, an anthracene ring, and a phenanthrene ring. As said C_6-20Aromatic rings, more preferably benzene rings and biphenyls.

In the context of the present specification, the term "C_4-20Heteroaryl ring "refers to an aromatic hydrocarbon ring having 4 to 20 ring carbon atoms and 1 to 3 ring heteroatoms selected from oxygen, sulfur and nitrogen. As said C_4-20Examples of the heteroaromatic ring include furan ring, thiophene ring, pyrrole ring, thiazole ring, benzothiazole ring, thiadiazole ring, imidazole ring, benzimidazole ring, triazine ring, triazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, pteridine ring, and acridine ring, and among them, furan ring, thiophene ring, imidazole ring, pyridine ring, and indole ring are preferable.

In the context of the present specification, the term "C_2-20Heterocycle "refers to the aforementioned C_3-20Cycloalkane ring or C_3-20A group in which at least one ring carbon atom of the cycloolefin ring is replaced with an oxygen atom, a sulfur atom or a nitrogen atom. As said C_2-20Examples of the heterocyclic ring include a piperidine ring, a piperazine ring, an aziridine ring, a dioxolane ring, a dioxane ring, a tetrahydrofuran ring, an oxetane ring, an azepane ring, a pyrroline ring, a tetrahydropyridine ring, a tetrahydropyrazole ring, a pyrazine ring, a piperazine ring, a piperidine ring, a piperazine ring, a piperidine ring, a piperazine ring, a piperidine ring, and a pyridine ringAn oxazoline ring, a pyran ring, a thiopyran ring, a tetrahydropyrrole ring, a tetrahydrothiophene ring, an aziridine ring, a tetrahydropyran ring, a tetrahydrothiopyran ring, a morpholine ring and the like, and among them, a piperidine ring, a tetrahydrofuran ring, a tetrahydropyran ring and the like are preferable.

In the context of the present specification, the term "combination group" refers to two or more C_3-20A group in which cycloalkane rings are bonded to each other via a single bond or a linking group, two or more C_3-20A group in which cycloolefin rings are bonded to each other via a single bond or a linking group, two or more C_6-20A group formed by bonding aromatic rings to each other via a single bond or a linking group, two or more C_4-20A group formed by bonding heteroaromatic rings to each other via a single bond or a linking group, two or more C_2-20A group formed by bonding heterocyclic rings to each other via a single bond or a linking group, or C_3-20Cycloalkane ring, C_3-20Cycloolefin ring, C_6-20Aromatic ring, C_4-20Heteroaromatic ring and C_2-20Two or more of the hetero rings are groups formed by being fused with each other or bonded to each other via a single bond or a connecting group. Examples of the combined group include cyclohexylbenzene, phenylthiophene, benzomorpholine, phenylmorpholine, cyclohexenylcyclopentane, naphthylnorbornane, phenyladamantane, phenylfuran, phenylcyclobutane, phenylpyrazine, phenylpyrrole, cyclohexenyladamantane, cyclohexyloxetane, cyclohexylmorpholine, cyclohexylisoxazole, phenylisoxazole, adamantyisoxazole, norbornenylcyclohexane, norbornenylbenzene, cyclohexylcyclohexane, cyclohexylmethylcyclohexane, thienylthiophene, pyrrolylpyrrole, pyrrolidinylpyrrole, benzylbenzene, phenoxybenzene, phenylthiophenylbenzene, benzyloxybenzene, benzyloxymethylenebenzene, styrylbenzene, styrylmethylbenzene, phenylaminobenzene, phenylaminotoluene, cyclohexylmethoxycyclohexane, benzyloxybenzene, benz-oxybenzene, phenylthiobenzene, phenylisoxazole, phenylmethylisobenzene, phenylmethylidenebenzene, phenylvinylbenzene, phenylvinylmethylbene, phenylmethylidenebenzene, phenylaminobenzene, cyclohexylmethoxycyclohexane, phenylmethoxybenzene, phenylthiobenzene, and the like,

And the like.

In the context of the present specification, the term "linking group" refers to any group in the structure containing two unbonded bonds (half-bonds), such as may be-O-; -S-; -NR₁-, wherein R₁Is H or C_1-4Linear or branched alkyl, preferably hydrogen or methyl; optionally substituted C_1-6Straight or branched alkylene, preferably optionally substituted C_1-4Straight or branched alkylene, optionally substituted C_2-4Straight or branched alkenylene or optionally substituted C_2-4Straight or branched alkynylene, more preferably optionally substituted C_1-4A linear or branched alkylene group; or any combination of these linking groups, such as-O-CH₂-、-O-CH₂-O-、-O-CH₂-CH₂-CH₂-、-O-CH₂-CH₂-CH₂-S-、-CH₂-CH₂-CH₂-NH-、-CH₂-CH₂-CH₂-S-、-O-CH＝CH-CH₂-、-O-CH＝CH-CH₂-O-、-O-CH₂-CH₂-CH₂-NH-、-O-CH₂-O-CH₂-CH₂-、-O-CH₂-O-CH₂-CH₂-O-、-O-CH₂-NH-CH₂-CH₂O-and the like, but-O-, -S-and-NR₁Except in the case of direct bonding to itself or to each other. As said linking group, preference is given to-O-, optionally substituted C_1-4Straight or branched chain alkylene or any combination thereof, except where-O-is directly bonded to itself.

In the context of the present specification, the term "effluent containing ammonia" refers to a gaseous or liquid material containing ammonia (such as condensed water containing ammonia, waste water containing ammonia, tail gas containing ammonia, and the like) discharged from the reaction system as a by-product or unreacted raw material after the end 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 a first step, a carboxylic acid source is reacted with an ammonia source at a reaction temperature T from T1 to T2_A(ii) for a reaction time of from 0.01 to 2.5 hours, to obtain an amide intermediate, wherein T1 is the greater of the melting point and temperature value of the carboxylic acid source at 1 atm, and 100 ℃, and T2 is the minimum of the boiling point, sublimation temperature, and decomposition temperature of the aliphatic polycarboxylic acid at 1 atm, with the proviso that T2>T1. Preferably, T2-T1 is 10 ℃ or higher.

According to the invention, the carboxylic acid source is selected from aliphatic polycarboxylic acids, C of said aliphatic polycarboxylic acids_1-4Linear or branched alkyl esters (preferably methyl esters) or anhydrides of said aliphatic polycarboxylic acids. These carboxylic acid sources may be used singly or in combination of two or more.

According to the present invention, examples of the aliphatic polycarboxylic acid include compounds having the following structures.

Wherein, the group

Is a single bond, an optionally substituted n-valent aliphatic hydrocarbon chain, an optionally substituted n-valent C_3-20Cycloalkane ring, optionally substituted n-valent C_3-20Cycloalkene ring, optionally substituted n-valent C_6-20Aromatic ring, optionally substituted n-valent C_4-20Heteroaromatic ring, optionally substituted n-valent C_2-20Heterocyclic or optionally substituted n-valent combinative groups.

According to the invention, in the group

Is a single bond or an optionally substituted n-valent esterIn the case of an aliphatic hydrocarbon chain, each of the n radicals R is independently a single bond or an optionally substituted 2-valent aliphatic hydrocarbon chain

In other definitions, each of the n groups R is independently an optionally substituted 2-valent aliphatic hydrocarbon chain.

According to the invention, the aliphatic hydrocarbon chain, C, as defined herein_3-20Cycloalkane ring, C_3-20Cycloolefin ring, C_6-20Aromatic ring, C_4-20Heteroaromatic ring, combination group and C_2-20Heterocycles are as defined above.

According to the invention, the aliphatic hydrocarbon chains in each definition are each independently selected from C_1-15(preferably C)_1-9E.g. C_1-3) A saturated or unsaturated straight or branched hydrocarbon chain.

According to the invention, the aliphatic hydrocarbon chains in each definition are preferably each independently selected from C_1-15(preferably C)_1-9E.g. C_1-3) Straight or branched alkane chain, C_2-15(preferably C)_2-9E.g. C_2-3) Straight or branched olefin chain or C_2-15(preferably C)_2-9E.g. C_2-3) Straight or branched alkyne chain, more preferably each independently selected from C_1-15(preferably C)_1-9E.g. C_1-3) Straight or branched alkane chains or C_2-15(preferably C)_2-9E.g. C_2-3) Linear or branched olefin chains.

According to the present invention, when the aliphatic hydrocarbon chain has 2 or more carbon atoms and contains a C — C single bond in its molecular chain, a spacer group is optionally further inserted between two carbon atoms of the C — C single bond: -O-, -S-or-NR₁-, wherein R₁Is H or C_1-4Straight-chain or branched alkyl, preferably hydrogen or methyl. The number of the C-C single bonds may be one or more, such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1. For example, the aliphatic hydrocarbon chain is CH₃-CH₂-CH₂-CH₃(for convenience of explanation, the valence is not shown), a single C-C bond is contained in the molecule chainTo which an O is inserted to obtain CH₃-O-CH₂-CH₂-CH₃、CH₃-CH₂-O-CH₂-CH₃And CH₃-CH₂-CH₂-O-CH₃Etc. by inserting an O between each of the two carbon atoms of the two C-C single bonds to obtain CH₃-O-CH₂-O-CH₂-CH₃、CH₃-CH₂-O-CH₂-O-CH₃And CH₃-O-CH₂-CH₂-O-CH₃Etc. by inserting an O between two carbon atoms of each of the three C-C single bonds to obtain CH₃-O-CH₂-O-CH₂-O-CH₃。

According to the present invention, n is an integer of 2 to 10, preferably an integer of 2 to 5, more preferably an integer of 2 to 4, further preferably 2 or 3.

According to the invention, in the group

In the case of a single bond, n is only 2. In this case, the polycarboxylic acid is a compound represented by HOOC-R-COOH, wherein each group R is as defined above. When both groups R are single bonds, the polycarboxylic acid is oxalic acid.

According to the present invention, as the carboxylic acid source, one kind of the aforementioned aliphatic polycarboxylic acids may be used alone, or two or more kinds may be used in combination.

According to the invention, the carboxylic acid source may be of biological origin, such as natural polycarboxylic acids or (mixed) polycarboxylic acid products as by-products of industry (e.g. the oil and fat industry), provided that 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 T_AIt is preferable that the liquid is in a molten state or a liquid state. In view of this, the aliphatic polycarboxylic acid, C of the aliphatic polycarboxylic acid_1-4The linear or branched alkyl ester or the acid anhydride of the aliphatic polycarboxylic acid preferably has an average molecular weight of not more thanThe reaction temperature T_A(generally up to 315 ℃ C.) as measured at 1 atm. The melting point of these carboxylic acid sources at 1 atm (and the boiling point, sublimation temperature, decomposition temperature, etc. of the aliphatic polycarboxylic 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 the present invention, as the mode of bringing the carboxylic acid source into contact with the ammonia source, there is a mode of, for example, metering the ammonia source into a previously molten carboxylic acid source or mixing the two. The contacting is generally carried out in a batch mode.

According to the invention, the ammonia source is as described hereinbefore, but is preferably aqueous ammonia or an aqueous solution of an ammonia generating substance, of which aqueous ammonia is preferred and industrial waste aqueous ammonia is more preferred. In this case, the ammonia content of the aqueous ammonia is generally 10 to 30% by weight, preferably 25 to 28% by weight.

According to 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. Examples of the aqueous solution of the ammonia-generating substance include industrial waste or industrial by-products containing the ammonia-generating substance, such as waste urea water and waste ammonium carbonate water.

According to the present invention, the ammonia generating substance concentration of the ammonia generating substance aqueous solution may be, for example, 20wt% to a saturated concentration (preferably a saturated concentration) or the like, but is not limited thereto.

According to the invention, the amount of the source of ammonia is such that the source of carboxylic acid, calculated as carboxyl groups, is mixed with 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 the invention, said first step is carried out in a closed reaction system (such as a closed reaction vessel).

According to the invention, after the first step is finished, the reaction system is depressurized to the external atmospheric pressure, and an ammonia-containing effluent is obtained while an amide intermediate product is obtained. It is preferred according to the present invention that the ammonia-containing effluent, preferably after concentration or drying, is recycled to the first step as a supplement or part of the ammonia source. This allows a corresponding reduction in the amount of fresh ammonia source supplied to the first step, thereby increasing the utilization of the ammonia feed and achieving efficient recycling of the ammonia-containing effluent.

The inventors of the present invention have found that the first step can be performed well even without using a catalyst. Thus, according to a preferred embodiment of the present invention, the first step does not use any catalyst commonly used in the art for carrying out the carboxylic acid amination process.

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 or less.

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 performed in the same reaction vessel, or may be performed in different reaction vessels (for example, tandem reaction vessels), and are not particularly limited. When the preparation method is carried out in the same reaction vessel, after the first step is finished, the reaction system is decompressed to the external atmospheric pressure, the amide intermediate product is not discharged, and the reaction system is directly changed into the reaction condition (described below) of the second step, so that the production cost and the production complexity of the preparation method are reduced.

According to the second step, the amide intermediate obtained in the first step is subjected to a reaction temperature T ranging from T3 to T4_BHeat treatment for a reaction time of 0.1 to 4.5 hours, wherein T3 is the amide intermediate product at 1 stThe greater of the melting point and temperature at atmospheric pressure of 220 ℃, T4 being the minimum of the boiling point, sublimation temperature and decomposition temperature of the amide intermediate product at 1 atm, provided that T4>T3. Preferably, T4-T3 is 10 ℃ or higher.

According to the invention, the amide intermediate product is at the reaction temperature T_BIt 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 than_B(typically up to 440 ℃) in the presence of a suitable solvent. The 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 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 or less.

According to the invention, no ammonia source is required in the second step.

According to the present invention, the second step may be carried out in an open reaction system or a closed reaction system, preferably a closed reaction system, to reduce energy consumption for production.

According to the invention, the second step may be carried out in the presence of a catalyst or without a catalyst. Examples of the catalyst include those conventionally used in the art for carboxylic acid amination, such as phosphorus pentoxide, phosphoric acid, phosphate, molecular sieve, alumina, zinc oxide, or a composite oxide catalyst, and among these, phosphorus pentoxide or phosphoric acid is preferably used. When used, these catalysts may be used in an amount conventional in the art (for example, may be 0.2 to 10%, preferably 1 to 6% by weight based on the weight of the carboxylic acid source), and are not particularly limited.

According to a further embodiment of the invention, the reaction temperature T_AFrom T1 'to T2'. In this case, the temperature of T1' is T1+5 ℃ or T1+10 DEG COr 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' is T2, or T2-5 ℃, or T2-10 ℃, or T2-20 ℃, or T2-30 ℃, or T2-40 ℃, or T2-50 ℃, but typically up to 315 ℃. With the proviso that T2'>T1'. Preferably, T2 '-T1'. gtoreq.10 ℃.

According to a further embodiment of the invention, the reaction temperature T_BFrom T3 'to T4'. In this case, 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' is T4, or T4-5 ℃, or T4-10 ℃, or T4-20 ℃, or T4-30 ℃, or T4-40 ℃, or T4-50 ℃, but typically up to 440 ℃. With the proviso that T4'>T3'. Preferably, T4 '-T3'. gtoreq.10 ℃.

According to a further embodiment of the present invention, said T1 is 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 ℃, or 260 ℃, or 270 ℃, or 280 ℃, or 290 ℃, or 300 ℃. According to a further embodiment of the present invention, said T2 is 315 ℃, or 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 ℃. Provided that T2> T1. Preferably, T2-T1 is 10 ℃ or higher.

According to a further embodiment of the present invention, said T3 is 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃, or 260 ℃, or 270 ℃, or 280 ℃, or 290 ℃, or 300 ℃, or 310 ℃, or 320 ℃. According to a further embodiment of the present invention, said T4 is 440 ℃, or 430 ℃, or 420 ℃, or 410 ℃, or 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 ℃. Provided that T4> T3. Preferably, T4-T3 is 10 ℃ or higher.

According to a particular embodiment of the invention, the carboxylic acid source is a carboxylic acid, an anhydride or a methyl ester of said carboxylic acid (preferably said carboxylic acid) as shown in table 1 below, and in said first step, the reaction temperature T is_AAs shown in Table 1 below, the reaction time is 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, and in the second step, the reaction temperature T is_BThe reaction time is 0.2 to 3 hours, alternatively 0.3 to 2 hours, alternatively 0.4 to 1.2 hours, alternatively 0.4 to 1 hour, as shown in table 1 below.

TABLE 1

Carboxylic acids	Reaction temperature TA，℃	Reaction temperature TB，℃
			Malonic acid	100 to 125	220 to 440
Adipic acid	160 to 200	240 to 410
			Dodecanedioic acid	160 to 240	260 to 420
Fumaric acid	290 to 300	320 to 440
			Suberic acid	160 to 240	260 to 310
Sebacic acid	160 to 240	265 to 320
			Eicosanedioic acid	160 to 240	275 to 340
2-Methylmalonic acid	145 to 200	245 to 295
			3-hexynedioic acid	190 to 235	255 to 300
Iminodiacetic acid	220 to 255	285 to 300
			Diglycolic acid	165 to 215	255 to 290
Thiodipropionic acid	155 to 205	245 to 290
			1, 3-Benzenediacetic acid	185 to 245	275 to 300
P-phenyl dipropionic acid	255 to 285	300 to 310
			Anthracene-9, 10-dipropionic acid	275 to 300	310 to 335
Naphthalene-1, 5-diacetic acid	255 to 295	310 to 335
			Pyrazine-2, 5-dipropionic acid	260 to 295	315 to 345
2, 6-Pyridinediacetic acid	175 to 255	280 to 310
			Thiophene-2, 5-diacetic acid	135 to 190	235 to 295
Furan-2, 5-diacetic acid	175 to 205	245 to 290
			Pyrrole-3, 4-dipropionic acid	185 to 215	245 to 295
Pyromellitic acid	235 to 280	300 to 325
			1, 4-Cyclohexanediacetic acid	195 to 255	285 to 305
1, 1-Cyclopentyldiacetic acid	200 to 265	285 to 315
			1, 3-adamantane diacetic acid	275 to 300	315 to 330
1, 3-dioxolane-2, 2-diacetic acid	115 to 175	215 to 285
			1,3, 5-adamantane tripropionic acid	125 to 175	225 to 295
1,2,3, 4-Cyclobutanetetraacetic acid	305 to 315	325 to 345
			1,3, 5-Cyclohexanetriacetic acid	305 to 315	325 to345

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 25-250mbar and the bottom temperature is typically 100-320 ℃ with the boiling point of the target nitrile product at said vacuum (+ -2 ℃) as cut point, typically for example 80-290 ℃, 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 4 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 (such as boiling point and thermal decomposition temperature, etc.) of the objective nitrile product, 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 5 wt% 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 objective 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 separation. 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 invention, the nitriles 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 present invention, the target amine can be separated from the reaction mixture as a product by a conventional purification or separation method after the hydrogenation reaction is completed. 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 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.

Amide intermediate production example

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 material₃25 wt% of industrial product) or an aqueous solution of ammonium hydrogencarbonate (ammonium hydrogencarbonate concentration of 30 wt%) having an ammonium ion molar number 1.6 times as large as that of the carboxyl group contained in the carboxylic acid raw material, the reaction vessel was closed, and stirring was started (600 r/min). The reaction is carried out at a reaction temperature T_ALower run T_CAfter 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 A-1, A-2, A-3, A-4 and A-5. These characterization results indicate that the obtained amide intermediate has very high purity (above 99%).

TABLE A-1

TABLE A-2

TABLE A-3

TABLE A-4

TABLE A-5

Nitrile product preparation examples

The preparation examples of the amide intermediate are connected. 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 below_BWhile 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 T_BAt the reaction temperature T_BLower holding T_DAfter the reaction, the autoclave was closed and connected to a vacuum pump to give a vacuum of 20 to 50mbar (adjusted depending on the kind of 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-6, A-7, A-8, A-9 and A-10. 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 tank, optionally at the start of the reaction.

TABLE A-6

TABLE A-7

TABLE A-8

TABLE A-9

TABLE A-10

Amine preparation examples

(1) 100g of adiponitrile, 3g of Raney-Ni and 400mL of ethanol are added into a 1L hydrogenation kettle, and H is continuously charged₂The system pressure is always maintained at 7MPa during the reaction. After reacting for 1h at the reaction temperature of 95 ℃, cooling. When the temperature in the reaction kettle is reduced to room temperature, the gas is discharged, and the hexamethylene diamine (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)δ2.74(t,J＝7.6Hz,4H),1.73(s,4H),1.51(qd,J＝7.6,0.8Hz,4H),1.42–1.27(m,4H)，Elemental Analysis:C,62.18；H,13.75；N,23.85。

(2) 100g of dodecane dinitrile, 3g of Raney-Ni and 400mL of ethanol are added into a 1L hydrogenation kettle, and H is continuously charged₂The system pressure was always maintained at 8MPa 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 dodecadiamine (with the purity of more than 99 percent) is obtained through filtration and recrystallization, wherein the yield is 94 percent by weight.

¹H NMR(300MHz,DMSO)δ2.74(t,J＝7.6Hz,4H),1.73(s,4H),1.57–1.43(m,4H),1.42–1.26(m,16H)，Elemental Analysis:C,70.84；H,14.01；N,13.81。

(3) 100g of p-phenyl-dipropionitrile, 3g of Raney-Ni and 400mL of ethanol are added into a 1L hydrogenation kettle, and H is continuously charged₂The system pressure was always maintained at 8MPa during the reaction. After reacting for 1.5h at the reaction temperature of 110 ℃, cooling. When the temperature in the reaction kettle is reduced to room temperature, gas is discharged, and the p-phenyl dipropylamine (with the purity of more than 99 percent) is obtained through filtration and recrystallization, wherein the yield is 92 percent by weight.

¹H NMR(300MHz,DMSO)δ7.06(s,4H),2.73(t,J＝7.7Hz,4H),2.66(t,J＝7.9Hz,4H),2.03(p,J＝7.8Hz,4H),1.77(s,4H)，Elemental Analysis:C,74.04；H,10.03；N,14.20。

(4) 100g of 1, 4-cyclohexyldiacetonitrile and 3g of Raney-Ni, 400 g were charged in a 1L hydrogenation vesselmL ethanol, continuously charged with H₂The system pressure was always maintained at 8MPa during the reaction. After reacting for 1.5h at the reaction temperature of 95 ℃, cooling. When the temperature in the reaction kettle is reduced to room temperature, gas is discharged, and the 1, 4-cyclohexyl diethylamine (the purity is more than 99 percent) is obtained by filtration and recrystallization, and the yield is 94 percent by weight.

¹H NMR(300MHz,DMSO)δ2.73(t,J＝7.6Hz,4H),1.75(s,4H),1.67–1.57(m,4H),1.57–1.43(m,4H),1.16–1.06(m,6H)，Elemental Analysis:C,70.21；H,13.07；N,16.89。

(5) 100g of triethyl benzonitrile and 3g of Raney-Ni, 400mL of ethanol were added to a 1L hydrogenation reactor, and H was continuously charged₂The system pressure was always maintained at 8MPa 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, air is discharged, and the phenyl triethylamine (with the purity of more than 99 percent) is obtained through filtration and recrystallization, wherein the yield is 90 percent by weight.

¹H NMR(300MHz,DMSO)δ7.04(s,3H),3.11–2.94(m,6H),2.81(dd,J＝11.7,4.1Hz,6H),1.82(s,6H)，Elemental Analysis:C,69.15；H,10.04；N,20.05。

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 (38)

1. A method for producing a nitrile, comprising the steps of:

the first step is as follows: contacting a carboxylic acid source with an ammonia source to obtain an amide intermediate,

wherein the carboxylic acid source is selected from the group consisting of an aliphatic polycarboxylic acid, C of the aliphatic polycarboxylic acid_1-4One or more of a linear or branched alkyl ester and an anhydride of the aliphatic polycarboxylic acid, the ammonia sourceIs ammonia water or an aqueous solution of an ammonia generating substance which means a substance capable of decomposing to generate ammonia gas under the reaction conditions of the first step,

the first step is carried out in a closed reaction system with the carboxylic acid source and ammonia source at a reaction temperature T from T1 to T2_AFor a reaction time of 0.01 to 2.5 hours under 1 atm to obtain an amide intermediate product, T1 being the greater of the melting point and temperature value of the carboxylic acid source at 1 atm, and T2 being the minimum of the boiling point, sublimation temperature and decomposition temperature of the aliphatic polycarboxylic acid at 1 atm, with the proviso that T2 is>T1，

Further comprising a second step of: subjecting the amide intermediate to a reaction temperature T of from T3 to T4_B(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 220 ℃ of the amide intermediate product at 1 atm, 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,

the aliphatic polycarboxylic acid means that the carbon atom directly bonded to each free carboxyl group of the polycarboxylic acid is a carbon atom on the aliphatic hydrocarbon chain, not a carbon atom on the ring, and is selected from one or more compounds having the following structural formula:

，

wherein, the group

Is a single bond, an optionally substituted n-valent aliphatic hydrocarbon chain, an optionally substituted n-valent C_3-20Cycloalkane ring, optionally substituted n-valent C_3-20Cycloalkene ring, optionally substituted n-valent C_6-20Aromatic ring, optionally substituted n-valent C_4-20Heteroaromatic ring, optionally substituted nValue C_2-20Heterocyclic or optionally substituted n-valent associative groups; radical (I)

In the case of a single bond or an optionally substituted n-valent aliphatic hydrocarbon chain, the n groups R are each independently a single bond or an optionally substituted 2-valent aliphatic hydrocarbon chain

In other definitions, each of the n groups R is independently an optionally substituted 2-valent aliphatic hydrocarbon chain; the aliphatic hydrocarbon chains in each definition are each independently selected from C_1-15A saturated or unsaturated, linear or branched hydrocarbon chain of (a); when the aliphatic hydrocarbon chain has 2 or more carbon atoms and contains a C-C single bond in its molecular chain, optionally-O-, -S-or-NR-is inserted between two carbon atoms of the C-C single bond₁-, wherein R₁Is H or C_1-4A linear or branched alkyl group; n is an integer from 2 to 10; provided that the group

When the group is a single bond, n is 2,

the term "combination group" refers to two or more C_3-20A group in which cycloalkane rings are bonded to each other via a single bond or a linking group, two or more C_3-20A group in which cycloolefin rings are bonded to each other via a single bond or a linking group, two or more C_6-20A group formed by bonding aromatic rings to each other via a single bond or a linking group, two or more C_4-20A group formed by bonding heteroaromatic rings to each other via a single bond or a linking group, two or more C_2-20A group in which heterocyclic rings are bonded to each other via a single bond or a linking group, or C_3-20Cycloalkane ring, C_3-20Cycloolefin ring, C_6-20Aromatic ring, C_4-20Heteroaromatic ring and C_2-20Two or more groups in the heterocycle formed by being fused to each other or bonded to each other via a single bond or a connecting group,

the term "linking group" refers to-O-; -S-; -NR₁-，Wherein R is₁Is H or C_1-4A linear or branched alkyl group; optionally substituted C_1-4A linear or branched alkylene group; optionally substituted C_2-4Straight or branched alkenylene; optionally substituted C_2-4Straight or branched alkynylene; or any combination of these linking groups, but-O-, -S-and-NR₁Except in the case of direct bonding to itself or to each other,

the expression "optionally substituted" means optionally substituted by one or more groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_3-20Cycloalkyl, C_3-20Cycloalkane (oxy, thio, amino) radical, C_3-20Cycloalkyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_3-20Cycloalkyl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_3-20Cycloalkyl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_3-20Cycloalkenyl radical, C_3-20Cycloalkene (oxy, thio, amino) radical, C_3-20Cycloalkenyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_3-20Cycloalkenyl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_3-20Cycloalkenyl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_6-20Aryl radical, C_6-20Aryl (oxy, thio, amino) radicals, C_6-20Aryl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_6-20Aryl radical C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl) group, C_6-20Aryl radical C_2-6Straight-chain or branched (halo) alkyne (oxy, thio, amino, carbonyl), C_4-20Heteroaryl group, C_4-20Heteroaryl (oxy, thio, amino) radical, C_4-20Heteroaryl C_1-6Straight or branched chainChain (halo) alkyl (oxy, thio, amino, carbonyl) radical, C_4-20Heteroaryl C_2-6Straight-chain or branched (halo) ene (oxy, thio, amino, carbonyl), C_4-20Heteroaryl C_2-6Straight-chain or branched (halo) alkynes (oxy, thio, amino, carbonyl), C_2-20Heterocyclic group, C_2-20Heterocyclic (oxy, thio, amino) radical, C_2-20Heterocyclyl radical C_1-6Straight-chain or branched (halo) alk (oxy, thio, amino, carbonyl) yl, C_2-20Heterocyclyl radical C_2-6Straight or branched chain (halo) ene (oxy, thio, amino, carbonyl) and C_2-20Heterocyclyl radical C_2-6Linear 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, the expression "(oxy, thio, amino) yl" means oxy, thio or amino, wherein halo includes mono-, di-, tri-or perhalo.

2. The process of claim 1 wherein the source of ammonia is industrial waste ammonia.

3. The production process according to claim 1, wherein the ratio of the carboxylic acid source to the ammonia source is such that the carboxylic acid source is NH in terms of carboxyl groups₃The ammonia source of the meterTo a molar ratio of 1: 1.1-9.5.

4. The production process according to claim 1, wherein the ratio of the carboxylic acid source to the ammonia source is such that the carboxylic acid source is NH in terms of carboxyl groups₃The molar ratio of the ammonia source is up to 1: 1.3-5.6.

5. The production process according to claim 1, wherein the ratio of the carboxylic acid source to the ammonia source is such that the carboxylic acid source is NH in terms of carboxyl groups₃The molar ratio of the ammonia source is up to 1: 1.3-2.5.

6. The production process according to claim 1, wherein the ratio of the carboxylic acid source to the ammonia source is such that the carboxylic acid source is NH in terms of carboxyl groups₃The molar ratio of the ammonia source is up to 1: 1.3-1.6.

7. The process according to claim 1, wherein T2-T1 ℃ is 10 ℃ or higher.

8. The process according to claim 1, wherein T4-T3 ℃ is 10 ℃ or higher.

9. The production method according to claim 1, wherein the reaction temperature T is_AFrom 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 315 ℃, provided that T2'>T1'。

10. The production method according to claim 1, wherein the reaction temperature T is_BIs from 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 ℃, orT4-20 ℃, or T4-30 ℃, or T4-40 ℃, or T4-50 ℃, or 440 ℃, provided that T4'>T3'。

11. The method of claim 1, wherein T1 is 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 ℃, or 260 ℃, or 270 ℃, or 280 ℃, or 290 ℃, or 300 ℃; t2 is 315 ℃, or 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 ℃.

12. The method of claim 1, wherein T3 is 220 ℃, or 230 ℃, or 240 ℃, or 250 ℃, or 260 ℃, or 270 ℃, or 280 ℃, or 290 ℃, or 300 ℃, or 310 ℃, or 320 ℃; t4 is 440 ℃, or 430 ℃, or 420 ℃, or 410 ℃, or 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 ℃.

13. The production method according to claim 1, wherein the second step is carried out in an open reaction system or a closed reaction system.

14. The manufacturing method of claim 1, wherein the first step does not use a catalyst.

15. The production method of claim 1, wherein the second step is carried out in the presence of a catalyst or without using a catalyst.

16. The production method according to claim 1, wherein the ammonia-producing substance is selected from one or more of urea, cyanic acid, ammonium carbonate, ammonium bicarbonate and ammonium chloride.

17. The production process according to claim 1, wherein the carboxylic acid source is a carboxylic acid, an anhydride or a methyl ester thereof shown in the following table, and in the first step, the reaction temperature T is set to_AThe reaction time is 0.05-2 hours, as shown in the following table, and the reaction temperature T in the second step_BAs shown in the following table, the reaction time was 0.2 to 3 hours,

carboxylic acids Reaction temperature T_A，℃ Reaction temperature T_B，℃ Malonic acid 100 to 125 220 to 440 Adipic acid 160 to 200 240 to 410 Dodecanedioic acid 160 to 240 260 to 420 Fumaric acid 290 to 300 320 to 440 Suberic acid 160 to 240 260 to 310 Sebacic acid 160 to 240 265 to 320 Eicosanedioic acid 160 to 240 275 to 340 2-Methylmalonic acid 145 to 200 245 to 295 3-hexynedioic acid 190 to 235 255 to 300 Iminodiacetic acid 220 to 255 285 to 300 Diglycolic acid 165 to 215 255 to 290 Thiodipropionic acid 155 to 205 245 to 290 1, 3-Benzenediacetic acid 185 to 245 275 to 300 P-phenyl dipropionic acid 255 to 285 300 to 310 Anthracene-9, 10-dipropionic acid 275 to 300 310 to 335 Naphthalene-1, 5-diacetic acid 255 to 295 310 to 335 Pyrazine-2, 5-dipropionic acid 260 to 295 315 to 345 2, 6-Pyridinediacetic acid 175 to 255 280 to 310 Thiophene-2, 5-diacetic acid 135 to 190 235 to 295 Furan-2, 5-diacetic acid 175 to 205 245 to 290 Pyrrole-3, 4-dipropionic acid 185 to 215 245 to 295 Pyromellitic acid 235 to 280 300 to 325 1, 4-Cyclohexanediacetic acid 195 to 255 285 to 305 1, 1-Cyclopentyldiacetic acid 200 to 265 (wt./wt. 200 to/or/200 to 265 (s/or/wt. 285 to 315 1, 3-adamantane diacetic acid 275 to 300 315 to 330 1, 3-dioxolane-2, 2-diacetic acid 115 to 175 215 to 285 1,3, 5-adamantane tripropionic acid 125 to 175 225 to 295 1,2,3, 4-Cyclobutanetetraacetic acid 305 to 315 325 to 345 1,3, 5-Cyclohexanetriacetic acid 305 to 315 325 to 345

。

18. The method of claim 1, wherein the aliphatic hydrocarbon chain in each definition is independently selected from C_1-15Straight or branched alkane chain, C_2-15Straight or branched olefin chain or C_2-15Straight or branched alkyne chains.

19. The method of claim 18, wherein the aliphatic hydrocarbon chains are each independently selected from C_1-9Straight or branched alkane chain, C_2-9Straight or branched olefin chain or C_2-9Straight or branched alkyne chains.

20. The production method of claim 1, wherein n is an integer of 2 to 4.

21. 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.

22. The manufacturing process of claim 21, 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.

23. The production process according to claim 1, wherein the carboxylic acid source is brought into contact with the ammonia source by metering the ammonia source into the previously molten carboxylic acid source or mixing both.

24. The method of claim 1, wherein said contacting is performed in a batch mode.

25. The production method of claim 1, wherein the reaction in the closed reaction system is carried out at a pressure higher than ambient pressure.

26. The production method of claim 1, wherein the reaction in the closed reaction system is carried out under autogenous pressure.

27. 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.

28. The production process according to claim 1, wherein the carboxylic acid source is an industrially corresponding crude product.

29. The method of claim 1, wherein the carboxylic acid source is of biological origin.

30. The production method according to claim 1, wherein the first step and the second step are carried out in the same reaction vessel or in different reaction vessels.

31. The production method of claim 1, 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.

32. The production method according to claim 1, wherein in the first step, the reaction time is 0.1 to 1.5 hours.

33. The production method according to claim 1, wherein in the first step, the reaction time is 0.2 to 1 hour.

34. The production method according to claim 1, wherein in the first step, the reaction time is 0.3 to 0.8 hours.

35. The production method of claim 1, wherein in the second step, the reaction time is 0.3 to 2 hours.

36. The production method of claim 1, wherein in the second step, the reaction time is 0.4 to 1.2 hours.

37. The production method of claim 1, wherein in the second step, the reaction time is 0.4 to 1 hour.

38. 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 37; and

the second step is as follows: the nitrile obtained in the first step is hydrogenated to produce an amine.