CN108558589A - The manufacturing method of nitrile and its corresponding amine - Google Patents

The manufacturing method of nitrile and its corresponding amine Download PDF

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Publication number
CN108558589A
CN108558589A CN201810215051.4A CN201810215051A CN108558589A CN 108558589 A CN108558589 A CN 108558589A CN 201810215051 A CN201810215051 A CN 201810215051A CN 108558589 A CN108558589 A CN 108558589A
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nitrile
ammonia
chain
manufacturing
ring
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CN108558589B (en
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孙海龙
魏延雨
陈新华
缪军
李娜
高以龙
阚林
柏基业
陈韶辉
杨爱武
许岳兴
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The present invention relates to the manufacturing methods of nitrile and its corresponding amine.A kind of manufacturing method of nitrile has the characteristics that ammonia source dosage significantly reduces, environmental pressure is small, low energy consumption, production cost is low, the purity and high income of nitrile product, and can obtain the increasingly complex nitrile of structure compared with prior art.The invention further relates to the methods for manufacturing corresponding amine by the nitrile.

Description

The manufacturing method of nitrile and its corresponding amine
The application be application No. is 201410156038.8 (applying date is on April 16th, 2014), it is entitled " nitrile and The divisional application of China's application of the manufacturing method of its corresponding amine ".
Technical field
The present invention relates to a kind of manufacturing method of nitrile and the methods for manufacturing corresponding amine by the nitrile.
Background technology
The such as alicyclic dinitrile of alicyclic polynitriles is very important chemical intermediate, it and its derivative are with non- Normal extensive purposes, for example, the cycloalphatic diamine of one of its derivative just has special property, in dyestuff, medicine, solidification Agent and high molecular polymer etc. extensive application.
The preparation method of alicyclic dinitrile be substantially pass through using existing simple nitrile compounds as raw material it is certain It reacts to obtain, the substrate spectrum that these methods are applicable in is very narrow, severe reaction conditions, is not suitable for industrialized production.
At this stage, the preparation method of aliphatic polybasic nitrile mainly uses carboxylic acid ammoniation process, but related passes through carboxylic acid ammonification Method is then rarely reported to manufacture the technology of alicyclic polynitriles.
But the present inventor by the study found that the prior art by aliphatic polycarboxylic acid's ammoniation process come When manufacturing corresponding aliphatic polybasic nitrile, in order to make aminating reaction fully carry out, which must be in the entire ammonification of carboxylic acid Persistently supply (being passed through) ammonia source (ammonia) is used as raw material, therefore ammonia in journey or within the longer reaction time into reaction system Gas dosage is huge, causes the actual amount of ammonia considerably beyond the dosage needed for aminating reaction, it may be possible to real reaction requirement Thousands of times, thus cause the utilization rate of ammonia extremely low.In addition, the utilization rate due to ammonia is extremely low, which produces It a large amount of waste ammonia liquor but can not recycle, exert heavy pressures on to environment after discharge, with the environmentally protective life followed now Production theory is not inconsistent.Moreover, because the aminating reaction of the technology use overall higher reaction temperature (such as more than 300 DEG C) and The overall longer reaction time, therefore energy consumption is higher, causes production cost higher, and there is also reaction masses in reaction process Loss serious (for example causing reaction mass to be entrained out reaction system because being continually fed into ammonia flow) and side reaction are more and lead The quality and yield for causing nitrile product are difficult the problems such as effectively improving.In addition, in order to obtain higher nitrile yield, the prior art is also wanted It asks the ammonia for using water content extremely low as reaction raw materials, and utilizes the ammonia being continuously passed through during entire aminating reaction As entrainer, the water of the by-product of discharge reaction at any time.
Therefore, the current present situation of the prior art is to be still required for a kind of manufacturing method of alicyclic polynitriles, preparation side Method is simple, is suitble to industrialized production.
Invention content
The present inventor by ammoniation process from carboxylic acid to nitrile on the basis of existing technology by diligent the study found that being turned During change, need the intermediate steps by forming amide, and the intermediate steps only need under lower reaction temperature and It can be completed in the shorter reaction time, and only the intermediate steps just need the supply in ammonia source, thus by the ammoniation process of carboxylic acid Two independent the step of carrying out clearly are decomposed into, and it has furthermore been found that by using the nitrile system with two particular steps Make method, so that it may to solve foregoing problems, and have thus completed the present invention.The appearance of this two-step method new process, for breaking Foreign countries' monopolization, the nitrile compounds and its downstream product for developing China have very important significance.The invention further relates to use The nitrile is come the method that manufactures amine.
Specifically, the present invention relates to the contents of following aspect.
1. a kind of manufacturing method of nitrile, which is characterized in that include the following steps：
First step：Ammonia source without interruption makes carboxylic acid sources with the ammonia source in the reaction temperature T from T1 to T2ALower contact 0.01-2.5 hours reaction time obtained amide intermediate product, wherein the carboxylic acid sources are selected from alicyclic polycarboxylic acid, described The C of alicyclic polycarboxylic acid1-4It is one or more in linear or branched alkyl group ester and the acid anhydrides of the alicyclic polycarboxylic acid, The ammonia source is supplied in a gaseous form, T1 be in 145 DEG C of the fusing point that the carboxylic acid sources are depressed in 1 normal atmosphere and temperature value compared with Big person, T2 are minimum of the alicyclic polycarboxylic acid in the boiling point that 1 normal atmosphere is depressed, sublimation temperature and decomposition temperature Person, on condition that T2>T1,
With
Second step：Stop supplying the ammonia source, by the amide intermediate product in the reaction temperature T from T3 to T4BUnder 0.1 to 4.5 hour reaction time of heat treatment, the fusing point that wherein T3, which is the amide intermediate product, depress in 1 normal atmosphere with The greater in 225 DEG C of temperature value, T4 be the amide intermediate product depressed in 1 normal atmosphere boiling point, sublimation temperature and point The reckling in temperature is solved, on condition that T4>T3,
The first step carries out in open reactive system,
The ammonia source is ammonia, and the ammonia content in the ammonia source is 75-95wt%, remaining is inert diluent, the inertia Diluent is selected from vapor or liquid water,
The alicyclic polycarboxylic acid refers to and the carbon of at least one free carboxy Direct Bonding of polybasic carboxylic acid original Son is the carbon atom in aliphatic ring, but each free carboxy of the polybasic carboxylic acid is not straight with the carbon atom on aromatic ring Bonding is connect, and one or more in the compound of formula selected from having the following structure：
Wherein, groupFor the n valences C optionally replaced3-20Cycloalkanes hydrocarbon ring, the n valences C optionally replaced3-20Cycloolefin Ring or the n valences C optionally replaced2-20Heterocycle；The divalent C that n-1 group B is each independently singly-bound, optionally replaces3-20Cycloalkane Ring, the divalent C optionally replaced3-20Cyclenes hydrocarbon ring, the divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20Hetero-aromatic ring is appointed Choose the divalent C in generation2-20Heterocycle or the divalent combination group optionally replaced；When n-1 group B be each independently singly-bound, appoint Choose the divalent C in generation3-20Cycloalkanes hydrocarbon ring, the divalent C optionally replaced3-20Cyclenes hydrocarbon ring or the divalent C optionally replaced2-20When heterocycle, The divalent aliphatic hydrocarbon chain that n-1 group R is each independently singly-bound or optionally replaces；When n-1 group B is each independently The divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20When hetero-aromatic ring or the divalent combination group optionally replaced, n-1 Group R is each independently the divalent aliphatic hydrocarbon chain optionally replaced；Aliphatic hydrocarbon chain in each definition is each independently selected from C1-15Saturations or undersaturated straight chain or branch hydrocarbon chain；When the carbon atom number of the aliphatic hydrocarbon chain is 2 or more and in its point When in subchain including C -- C single bond, insertion-O- ,-S- or-NR optionally between two carbon atoms of the C -- C single bond1, wherein R1It is H or C1-4Linear or branched alkyl group；N is 2 to 10 integer,
Term " combination group " refers to two or more C3-20Cycloalkanes hydrocarbon ring bonds together via singly-bound or linking group And group, the two or more C formed3-20Cyclenes hydrocarbon ring bond together via singly-bound or linking group and formed group, Two or more C6-20Aromatic ring bonds together via singly-bound or linking group and the group, the two or more C that are formed4-20Heteroaryl Ring bonds together via singly-bound or linking group and the group, the two or more C that are formed2-20Heterocycle is via singly-bound or connection Group bonds together and the group or C that are formed3-20Cycloalkanes hydrocarbon ring, C3-20Cyclenes hydrocarbon ring, C6-20Aromatic ring, C4-20Hetero-aromatic ring and C2-20Two or more groups formed by condensing or bonding together via singly-bound or linking group each other in heterocycle,
Term " linking group " refers to-O-；-S-；-NR1, wherein R1It is H or C1-4Linear or branched alkyl group；Optionally take The C in generation1-4Linear chain or branched chain alkylidene；The C optionally replaced2-4Linear chain or branched chain alkenylene；The C optionally replaced2-4Linear chain or branched chain Alkynylene；Or the arbitrary combination of these linking groups, but-O- ,-S- and-NR1With itself or the case where be bonded directly with one another Except,
Statement " optionally replacing " refers to optionally by one or more selected from halogen, hydroxyl, sulfydryl, amino, amino carbonyl Base, nitro, oxo, thio, cyano, C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-6Linear chain or branched chain (halogen Generation) alkene (oxygen, sulphur, ammonia, carbonyl) base, C2-6Linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Naphthenic base, C3-20Cycloalkanes (oxygen, sulphur, ammonia) base, C3-20Naphthenic base C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Naphthenic base C2-6Straight chain Or branch (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Naphthenic base C2-6Linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group, C3-20Cyclenes (oxygen, sulphur, ammonia) base, C3-20Cycloalkenyl group C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) Base, C3-20Cycloalkenyl group C2-6Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6Linear chain or branched chain (halogen Generation) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl, C6-20Fragrant (oxygen, sulphur, ammonia) base, C6-20Aryl C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Straight chain or Branch (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl, C4-20Heteroaryl (oxygen, sulphur, ammonia) base, C4-20Heteroaryl C1-6Straight chain Or branch (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6Linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocycle, C2-20Heterocycle (oxygen, sulphur, ammonia) Base, C2-20Heterocycle C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocycle C2-6Linear chain or branched chain (halogen Generation) alkene (oxygen, sulphur, ammonia, carbonyl) base and C2-20Heterocycle C2-6The substituent group of linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base Substitution, wherein these substituent groups can bond together between adjacent two substituent groups when there are multiple and form divalent Substituent structure,
Statement " (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base " is meant that：Alkyl, halogenated alkyl, alkoxy, alkylthio group, alkane Amino, alkyl-carbonyl, halogenated alkoxy, halogenated alkylthio, halogenated alkylamino or halogenated alkyl carbonyl state " (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base " is meant that：Alkenyl, halogenated alkenyl, alkenyloxy group, alkenylthio group, enamino, alkenyl carbonyl, haloalkene oxygen Base, halogenated alkenylthio group, halogenated enamino or halogenated alkenyl carbonyl state the meaning of " (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base " It is：Alkynyl, halo alkynyl, alkynyloxy group, alkynes sulfenyl, alkynes amino, alkynylcarbonyl groups, halogenated alkynyloxy group, acetylenic halide sulfenyl, acetylenic halide ammonia Base or halo alkynyl carbonyl, statement " (oxygen, sulphur, ammonia) base " is meant that, oxygroup, sulfenyl or amino, wherein described halogenated Including one halogenated, dihalo, three halogenated or perhalogenos.
2. the manufacturing method of the nitrile described in any preceding aspect, wherein making carboxylic acid sources with the ammonia source anti-from T1 to T2 Answer temperature TAThe reaction time of lower contact 0.05-2 hours.
3. the manufacturing method of the nitrile described in any preceding aspect, wherein making carboxylic acid sources with the ammonia source anti-from T1 to T2 Answer temperature TAThe reaction time of lower contact 0.1-1.5 hours.
4. the manufacturing method of the nitrile described in any preceding aspect, wherein making carboxylic acid sources with the ammonia source anti-from T1 to T2 Answer temperature TAThe reaction time of lower contact 0.2-1 hours.
5. the manufacturing method of the nitrile described in any preceding aspect, wherein making carboxylic acid sources with the ammonia source anti-from T1 to T2 Answer temperature TAThe reaction time of lower contact 0.3-0.8 hours.
6. the manufacturing method of the nitrile described in any preceding aspect, wherein T2-T1 >=10 DEG C.
7. the manufacturing method of the nitrile described in any preceding aspect, wherein by the amide intermediate product anti-from T3 to T4 Answer temperature TBThe reaction time of lower heat treatment 0.2 to 3 hour.
8. the manufacturing method of the nitrile described in any preceding aspect, wherein by the amide intermediate product anti-from T3 to T4 Answer temperature TBThe reaction time of lower heat treatment 0.3 to 2 hour.
9. the manufacturing method of the nitrile described in any preceding aspect, wherein by the amide intermediate product anti-from T3 to T4 Answer temperature TBThe reaction time of lower heat treatment 0.4 to 1.2 hour.
10. the manufacturing method of the nitrile described in any preceding aspect, wherein by the amide intermediate product from T3 to T4 Reaction temperature TBThe reaction time of lower heat treatment 0.4 to 1 hour.
11. the manufacturing method of the nitrile described in any preceding aspect, wherein T4-T3 >=10 DEG C.
12. the manufacturing method of the nitrile described in any preceding aspect, wherein the reaction temperature TAFor from T1' to T2', wherein T1'=T1+5 DEG C or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or T1+60 DEG C or T1+70 DEG C or T1+80 DEG C or T1+90 DEG C, T2'=T2 or T2-5 DEG C or T2-10 DEG C or T2-20 DEG C or T2-30 DEG C or T2-40 DEG C or T2-50 DEG C or 310 DEG C of person, on condition that T2'>T1'；It is described anti- Answer temperature TBFor from T3' to T4', wherein T3'=T3+5 DEG C or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or T3+40 DEG C or T3+50 DEG C or T3+60 DEG C or T3+70 DEG C or T3+80 DEG C, T4'=T4 or T4-5 DEG C or T4-10 DEG C or T4-20 DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C or 350 DEG C of person, on condition that T4' >T3'。
13. the manufacturing method of the nitrile described in any preceding aspect, wherein T1 are 145 DEG C either 150 DEG C or 160 DEG C, Either 170 DEG C of either 180 DEG C of either 190 DEG C of either 200 DEG C of either 210 DEG C of either 220 DEG C either 230 DEG C or 240 DEG C either 250 DEG C of either 260 DEG C of either 270 DEG C of either 280 DEG C either 290 DEG C or 300 DEG C；T2 is 310 DEG C, or 300 DEG C of either 290 DEG C of either 280 DEG C of either 270 DEG C of either 260 DEG C of either 250 DEG C either 240 DEG C or 230 DEG C, Either 220 DEG C of either 210 DEG C of either 200 DEG C either 190 DEG C or 180 DEG C；T3 is 225 DEG C either 230 DEG C or 240 DEG C either 250 DEG C of either 260 DEG C of either 270 DEG C of either 280 DEG C of either 290 DEG C either 300 DEG C or 310 DEG C；T4 is 350 DEG C of either 340 DEG C of either 330 DEG C of either 320 DEG C of either 310 DEG C of either 300 DEG C either 290 DEG C or 280 DEG C, Or 270 DEG C.
14. the manufacturing method of the nitrile described in any preceding aspect, wherein the second step in open reactive system or It is carried out in the closed reaction system of person.
15. the manufacturing method of the nitrile described in any preceding aspect, wherein catalyst, and institute is not used in the first step Second step is stated to carry out in the presence of a catalyst or unused catalyst.
16. the manufacturing method of the nitrile described in any preceding aspect, wherein the ammonia source is industrial waste ammonia gas.
17. the manufacturing method of the nitrile described in any preceding aspect, wherein the carboxylic acid sources are carboxylic acid shown in following table, the carboxylic The acid anhydrides or methyl esters of acid, in the first step, reaction temperature TAAs shown in the table, the reaction time is 0.05-2 hours, In the second step, reaction temperature TBAs shown in the table, the reaction time is 0.2 to 3 hour,
18. the manufacturing method of the nitrile described in any preceding aspect, wherein in the first step, the reaction time is 0.1- 1.5 hour.
19. the manufacturing method of the nitrile described in any preceding aspect, wherein in the first step, the reaction time is 0.2- 1 hour.
20. the manufacturing method of the nitrile described in any preceding aspect, wherein in the first step, the reaction time is 0.3- 0.8 hour.
21. the manufacturing method of the nitrile described in any preceding aspect, wherein in the second step, the reaction time is 0.3 To 2 hours.
22. the manufacturing method of the nitrile described in any preceding aspect, wherein in the second step, the reaction time is 0.4 To 1.2 hours.
23. the manufacturing method of the nitrile described in any preceding aspect, wherein in the second step, the reaction time is 0.4 To 1 hour.
24. the manufacturing method of the nitrile described in any preceding aspect, wherein the aliphatic hydrocarbon chain in each definition is each independently Selected from C1-15Linear chain or branched chain alkane chain, C2-15Linear chain or branched chain alkene chain or C2-15Linear chain or branched chain alkynes chain.
25. the manufacturing method of the nitrile described in any preceding aspect, wherein the aliphatic hydrocarbon chain is each independently selected from C1-9 Linear chain or branched chain alkane chain, C2-9Linear chain or branched chain alkene chain or C2-9Linear chain or branched chain alkynes chain.
26. the manufacturing method of the nitrile described in any preceding aspect, wherein n are 2 to 4 integers.
27. the manufacturing method of the nitrile described in any preceding aspect, wherein the first step is obtaining among the amide Effluent containing ammonia is also obtained while product, and will be used as institute in the circulation-supplied to the first step of effluent containing ammonia State the supplement or a part in ammonia source.
28. the manufacturing method of the nitrile described in any preceding aspect, wherein the effluent containing ammonia is by concentration or drying Supplement or a part in circulation-supplied to the first step as the ammonia source afterwards.
29. the manufacturing method of the nitrile described in any preceding aspect, wherein carboxylic acid sources in terms of carboxyl with NH3Meter The molar ratio minimum 1 in the ammonia source：20, up to 1：500.
30. the manufacturing method of the nitrile described in any preceding aspect, wherein carboxylic acid sources in terms of carboxyl with NH3Meter The molar ratio minimum 1 in the ammonia source：40, up to 1：300.
31. the manufacturing method of the nitrile described in any preceding aspect, wherein carboxylic acid sources in terms of carboxyl with NH3Meter The molar ratio minimum 1 in the ammonia source：50, up to 1：80.
32. the manufacturing method of the nitrile described in any preceding aspect, wherein the carboxylic acid sources use industrial corresponding thick production Product.
33. the manufacturing method of the nitrile described in any preceding aspect, wherein the carboxylic acid sources are biological sources.
34. the manufacturing method of the nitrile described in any preceding aspect, wherein the first step and the second step are same It carries out in one reaction vessel, or is carried out in different reaction vessels.
35. the manufacturing method of the nitrile described in any preceding aspect, wherein the second step is in closed reaction system It carries out.
36. the manufacturing method of the nitrile described in any preceding aspect, wherein the ammonia content in the ammonia source is 85-95wt%.
37. a kind of manufacturing method of amine, which is characterized in that include the following steps：
First step：Nitrile is manufactured according to the manufacturing method described in aforementioned 1 to 36 either side；With
Second step：The nitrile that first step obtains is hydrogenated to manufacture amine.
Technique effect
Compared with prior art, the present invention has the following advantages.
Nitrile manufacturing method according to the present invention only supplies ammonia source (such as ammonia etc.) in the first step, and in second step Stop the supply in ammonia source in rapid completely, therefore the dosage in ammonia source can significantly reduce, and greatly improve the utilization rate in ammonia source.
Nitrile manufacturing method according to the present invention can be effectively reduced anti-since the utilization rate in ammonia source significantly improves Waste ammonia liquor amount caused by answering, environmental pressure is small, is consistent with the environmentally protective production theory followed now.
Nitrile manufacturing method according to the present invention does not have strict requirements to the water content in ammonia source, it might even be possible to directly use Ammonium hydroxide or the ammonium hydroxide of vaporization, also need not be using the ammonia source as the entrainer of by-product water.Moreover, nitrile system according to the present invention Method is made, the waste ammonia liquor or useless ammonia (hereafter referred to collectively as effluent containing ammonia) that aminating reaction generates are found that for the first time in this field It can be introduced directly into the first step of the manufacturing method as the supplement in ammonia source, realize 100% cycle of ammonia-containing water/gas It utilizes, further reduced the environmental pressure of the manufacturing method.
Nitrile manufacturing method according to the present invention, reaction temperature and reaction time generally significantly drop compared with the prior art It is low, thus show the advantage that energy consumption reduces, production cost reduces and manufacturing method is simple.
Nitrile manufacturing method according to the present invention, the reaction mechanism mechanism of reaction is simple, and side reaction is less, aminating reaction by impurity effect compared with Small, thus the manufacturing method is relatively low to the purity requirement in ammonia source and carboxylic acid sources, can directly use respective crude product as anti- Answer raw material.For example, the present invention has found that the nitrile manufacturing method even can directly use industrial waste containing ammonia for the first time in this field Or byproduct, as ammonia source, thus the cycle or recycling for various industrial wastes containing ammonia or byproduct open a new way Diameter meets current environmentally protective production theory.
Nitrile manufacturing method according to the present invention, reaction condition is simple, can be smoothed out (especially not needing catalyst It is first step), this not only reduces the manufacturing cost of nitrile, and also reduces nitrile product later separation or the complexity of purifying Degree.
Nitrile manufacturing method according to the present invention, first step carry out the shorter reaction time under lower reaction temperature, And stop the supply in ammonia source completely in the second step, therefore the reaction mass caused by ammonia source supply etc. can be substantially reduced and damaged Lose (entrainment), according to the difference of nitrile product category, the present invention can obtain 75% or more, 80% or more, 90% or more, 95% with Upper, even 98% or more or higher nitrile yield.
Nitrile manufacturing method according to the present invention, reaction condition is mild, the less generation of side reaction, it is possible thereby to obtain high-purity Nitrile product (such as 97% or more).
Nitrile manufacturing method according to the present invention, can be produced by carboxylic acid ammoniation process the increasingly complex nitrile of structure (such as (polynary) nitrile containing various hetero atoms, unsaturated bond or ring structure or (miscellaneous) aromatic series (polynary) nitrile), this is in the art It is to realize for the first time, to be greatly expanded the application range of carboxylic acid ammoniation process.
Amine manufacturing method according to the present invention is raw material due to the use of high-purity nitrile made according to the present invention, therefore Show the advantage that side reaction is few, product amine purity is accordingly high, production cost is low.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below, it should be noted however that the protection of the present invention Range is not limited to these specific embodiments, but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference. Unless otherwise defined, all technical and scientific terms used herein all has general technology people in fields of the present invention The equivalent that member understands.In case of conflict, including in being defined on, subject to the present specification.
When this specification is come with " well known by persons skilled in the art " or " conventionally known in the art " or similar term When describing material, method, component, device or equipment, which indicates that this specification includes this field routine when proposing the application Those of use, but also include also being of little use at present, but will become art-recognized for suitable for those of similar purpose.
In addition, the various ranges mentioned in this specification is including their endpoint, unless expressly stated otherwise,.This Outside, when to amount, concentration or other values or parameter provide range, one or more preferred scopes or many preferred upper limit values with preferably When lower limiting value, it should be interpreted as specifically disclosing by arbitrarily to any range upper limit value or preferred value and any range lower limiting value Or preferred value is formed by all ranges, whether separately discloses these numerical value pair.
In the context of the present specification, unless otherwise defined explicitly or the meaning has exceeded those skilled in the art Understanding range, more than 3 carbon atoms hydrocarbon or hydrocarbon derivative group (such as propyl, propoxyl group, butyl, butane, butylene, fourth Alkenyl, hexane etc.) identical meaning when being all had with titled with prefix " just " when not titled with prefix " just ".For example, propyl is general It is interpreted as n-propyl, and butyl is generally understood as normal-butyl.
In the context of the present specification, term " ammonia source " refer to can the present invention the nitrile manufacturing method (first step Suddenly any substance as ammonia sources (providing ammonia) in), including ammonia various forms product such as liquid ammonia, gaseous ammonia, Ammonium hydroxide and ammonium hydroxide of vaporization etc. further include (such as anti-by the decomposition such as hydrolyzing or thermally decomposing under the reaction condition of first step Answer) substance (hereinafter referred to as producing ammoniacal substance) of ammonia can be generated, for example the ammonium salt of urea, cyanic acid and inorganic acid can be enumerated (such as ammonium carbonate and ammonium hydrogen carbonate) etc..Nitrile manufacturing method according to the present invention, the reaction mechanism mechanism of reaction is simple, and side reaction is less, ammonification Reaction is smaller by impurity effect, and thus the manufacturing method is relatively low to the purity requirement in ammonia source.In consideration of it, above and below this specification Wen Zhong, term " ammonia source " further include containing ammonia or containing it is aforementioned production ammoniacal substance industrial waste or industry byproduct, including gaseous state, The various industrial wastes or industry byproduct of liquid or solid-state form, for example, it is ammonia-containing exhaust (for example come from ammonia synthesis process), useless Ammonia, waste ammonia liquor (such as nitrile manufacturing method from the prior art), useless urea water, useless ammonium bicarbonate water etc..As long as in general, should The type or content of impurity in industrial waste or byproduct in addition to ammonia and water do not generate the nitrile manufacturing method of the present invention aobvious It writes influence (for example the reduction of nitrile yield is made to be no more than 5%) to can be used directly, without carrying out it advance purification process. This kind of impurity is usually chemically inert for the nitrile manufacturing method of the present invention, for example can enumerate hydrogen, nitrogen, sky Gas and water steam or liquid water etc. are sometimes considered as the inert diluent of the manufacturing method.Certainly, those skilled in the art pass through Simple experiment (such as reduction degree by measuring nitrile yield), it will be able to confirm that a certain industrial waste or industry byproduct are It is no containing or excessively contain on the impurity that makes a significant impact of nitrile manufacturing method of the present invention, thereby confirm that whether it can be with Directly apply to the nitrile manufacturing method of the present invention.In addition, as needed, those skilled in the art can also be by conventionally known This kind of impurity contained in a certain industrial waste or industry byproduct is reduced to the nitrile for not significantly affecting the present invention by technological means The level that manufacturing method is implemented, and as needed, the concentration of ammonia in a certain industrial waste or industry byproduct is concentrated into more Suitable for the present invention nitrile manufacturing method implement level (such as by ammonia or produce ammoniacal substance concentration be concentrated into account for the industrial waste or The 10-95wt% of industry byproduct total amount, preferably 25-95wt%).
In the context of the present specification, term " carboxylic acid sources " refer to can the present invention nitrile manufacturing method (first Step) it is middle as any substance, including carboxylic acid starting material itself of carboxylic acid source (providing carboxylic acid) and in the anti-of first step (for example passing through hydrolysis or ammonolysis etc.) can generate the substance (hereinafter referred to as producing carboxylic acid material) of free carboxy acid under the conditions of answering, such as Carboxylic acid anhydrides and carboxylic acid C can be enumerated1-4Linear or branched alkyl group ester etc..Nitrile manufacturing method according to the present invention, reaction mechanism mechanism of reaction letter Single, side reaction is less, and aminating reaction is smaller by impurity effect, and thus the manufacturing method is relatively low to the purity requirement of carboxylic acid sources (for example it can be 90% that purity is minimum), can directly use industrial corresponding crude product, for example as industry (such as grease Industry) byproduct (mixing) polybasic carboxylic acid product etc..
In the context of the present invention, term " carboxylic acid " using its it is widest define, refer to containing free carboxy (i.e.- COOH compound).
In the context of the present specification, term " polybasic carboxylic acid " refer to containing it is multiple (such as 2 to 10, preferably 2 to 5, more preferable 2 to 4, further preferred 2 or 3) compound of free carboxy.
In the context of the present specification, term " aliphatic polycarboxylic acid " refers to each trip with the polybasic carboxylic acid Carbon atom from carboxyl Direct Bonding is the carbon atom on aliphatic hydrocarbon chain, rather than ring (such as it is aromatic series or alicyclic Ring) on carbon atom.
In the context of the present specification, term " alicyclic polycarboxylic acid " is referred at least one with the polybasic carboxylic acid The carbon atom of free carboxy Direct Bonding is the carbon atom in aliphatic ring (including cycloalkanes hydrocarbon ring, cyclenes hydrocarbon ring and heterocycle), but Each free carboxy of the polybasic carboxylic acid not with the carbon atom Direct Bonding on aromatic ring (including aromatic ring and hetero-aromatic ring).
In the context of the present specification, term " aromatic polycarboxylic acid " is referred at least one with the polybasic carboxylic acid The carbon atom of free carboxy Direct Bonding is the carbon atom on aromatic ring (including aromatic ring and hetero-aromatic ring).
In the context of the present specification, term " open reactive system " refers to that the reaction system is outside from beginning to end Boundary's atmosphere opening (uses open reactive device), at this time pressure (ring of the reaction in the reaction system in (approximation) ambient atmosphere Border pressure) under carry out.
In the context of the present specification, term " closed reaction system " refer to the reaction system from beginning to end with outside Boundary's atmospheric isolation (use closed reactor), the reaction in the reaction system at this time the pressure higher than environmental pressure (such as The self-generated pressure of the reaction system；As long as in the pressure of the upper safety of production, with regard to there is no particular limitation) under carry out, but not (such as pressure release or a part of by-product of discharge etc.) as needed is excluded, the reaction system is outwardly big in entire reaction process The shortness of breath time (for example continuing 0.05-5 minutes, 0.1-4 minutes, 0.3-3 minutes, 0.5-2 minutes or 0.6-1.5 minutes etc.) opens It puts one or many (such as 1-20 times, 1-10 times, 1-5 times, 1-3 times, 1-2 times or 1 inferior).
In the context of the present specification, term " halogen " refers to fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.
In the context of the present specification, statement " optionally replacing " refers to optionally by one or more (such as 1 to 5 It is a, 1 to 4,1 to 3,1 to 2 or 1) selected from halogen, hydroxyl, sulfydryl, amino, amino carbonyl, nitro, oxo, sulphur Generation, cyano, C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-6Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, ammonia, Carbonyl) base, C2-6Linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Naphthenic base, C3-20Cycloalkanes (oxygen, sulphur, ammonia) base, C3-20Naphthenic base C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Naphthenic base C2-6Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Naphthenic base C2-6Linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group, C3-20 Cyclenes (oxygen, sulphur, ammonia) base, C3-20Cycloalkenyl group C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6 Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6Linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, Carbonyl) base, C6-20Aryl, C6-20Fragrant (oxygen, sulphur, ammonia) base, C6-20Aryl C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) Base, C6-20Aryl C2-6Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl, C4-20Heteroaryl (oxygen, sulphur, ammonia) base, C4-20Heteroaryl C1-6Linear chain or branched chain (halogenated) Alkane (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6 Linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocycle, C2-20Heterocycle (oxygen, sulphur, ammonia) base, C2-20Heterocycle C1-6Linear chain or branched chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocycle C2-6Linear chain or branched chain (halogenated) alkene (oxygen, sulphur, Ammonia, carbonyl) base and C2-20Heterocycle C2-6The substituent group of linear chain or branched chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base is (in feasible position Place) substitution.These substituent groups are when there are multiple, (such as the molecule last-in-chain(LIC) of two substituent groups between adjacent two substituent groups End) it can bond together and be formed the substituent structure of divalent.For example, two adjacent C1-6Linear or branched alkyl group can be with that This is bonded and forms corresponding alkylen structures.Alternatively, two adjacent C1-6Straight or branched alkoxyl can such as form phase The alkylidene dioxygen based structures answered, adjacent two C1-6Linear chain or branched chain alkylamino can such as form corresponding alkylidene two Amino structure, adjacent two C1-5Linear chain or branched chain alkylthio group can such as form corresponding alkylidene disulfide group structure, etc. Deng.As preferred substituent group, for example halogen, hydroxyl, sulfydryl, amino, thio, oxo or C can be enumerated1-6Straight chain or branch Chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base etc..
In the context of the present specification, statement " (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base " is meant that：It is alkyl, halogenated Alkyl, alkoxy, alkylthio group, alkylamino, alkyl-carbonyl, halogenated alkoxy, halogenated alkylthio, halogenated alkylamino or alkyl halide Base carbonyl, statement " (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base " are meant that：Alkenyl, halogenated alkenyl, alkenyloxy group, alkenylthio group, alkene ammonia Base, alkenyl carbonyl, haloalkenyloxy, halogenated alkenylthio group, halogenated enamino or halogenated alkenyl carbonyl state " (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base " is meant that：Alkynyl, halo alkynyl, alkynyloxy group, alkynes sulfenyl, alkynes amino, alkynylcarbonyl groups, acetylenic halide oxygen Base, acetylenic halide sulfenyl, acetylenic halide amino or halo alkynyl carbonyl, statement " (oxygen, sulphur, ammonia) base " are meant that, oxygroup, sulfenyl Or amino.Here, it is described it is halogenated include one halogenated, dihalo, three is halogenated or perhalogeno etc..
In the context of the present specification, term " aliphatic hydrocarbon chain " refers to the saturation or unsaturation of straight or branched Hydrocarbon, including alkane chain, alkene chain and alkynes chain.
In the context of the present specification, term " n valences " or its refer to the structure defined by the term similar to term It is obtained after respectively removing (on a carbon) hydrogen atom on n different carbon atoms in (such as group, hydrocarbon chain or compound ring etc.) Group.For example, term " divalent " is referred to from structure defined by the term (such as group, hydrocarbon chain or compound ring etc.) 2 different carbon atoms on respectively remove the group obtained after (on a carbon) hydrogen atom.Specifically for example, divalent aliphatic hydrocarbon chain Refer to aliphatic alkylene or aliphatic hydrocarbon diyl.
In the context of the present specification, term " C3-20Cycloalkanes hydrocarbon ring " refers to the list with carbon atom on 3-20 ring Ring, bicyclic or polycyclic naphthene hydrocarbon ring.As the C3-20Cycloalkanes hydrocarbon ring, for example cyclopropane ring, cyclohexane ring and ring can be enumerated The monocyclic naphthenes such as pentane ring ring and bicyclic penta ring, decahydronaphthalene naphthalene nucleus, adamantane ring, spiral shell [2.4] heptane ring, spiral shell [4.5] last of the ten Heavenly stems Alkane ring, two rings [3.2.1] octane ring, tricyclic [2.2.1.02,6] octane ring, norbornane ring, Equal loop coils, bridged ring or condensed ring formula is bicyclic or polycyclic naphthene hydrocarbon ring.As the C3-20Cycloalkanes hydrocarbon ring, more preferable C3-15Cycloalkanes hydrocarbon ring.
In the context of the present specification, term " C3-20Cyclenes hydrocarbon ring " refers to C above-mentioned3-20Cycloalkanes hydrocarbon ring is at least Group after carbon-carbon single bond (C-C) is replaced by carbon-carbon double bond (C=C) on one ring.As the C3-20Cyclenes hydrocarbon ring, such as can To enumerate cyclobutane ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, cycloheptadiene ring, ring The monocyclic cycloalkenyls such as octatetraene ring hydrocarbon ring and bicyclopentadiene ring, norbornene ring, norbornadiene ring,Equal loop coils, bridged ring or condensed ring formula is bicyclic or polycyclic ring Alkene ring.As the C3-20Cyclenes hydrocarbon ring, more preferable C3-15Cyclenes hydrocarbon ring.
In the context of the present specification, term " C6-20Aromatic ring " refers to the aromatic series with carbon atom on 6-20 ring Hydrocarbon ring.As the C6-20Aromatic ring, for example phenyl ring, biphenyl and terphenyl can be enumerated etc. two or more phenyl ring are direct with singly-bound Group made of two or more phenyl ring such as group and naphthalene nucleus, anthracene nucleus, phenanthrene ring made of being connected are condensed.As the C6-20 Aromatic ring, more preferable phenyl ring and biphenyl.
In the context of the present specification, term " C4-20Hetero-aromatic ring " is referred to carbon atom and 1-3 on 4-20 ring Heteroatomic aromatic series hydrocarbon ring on a ring selected from oxygen, sulphur and nitrogen.As the C4-20Hetero-aromatic ring, for example furans can be enumerated Ring, thiphene ring, pyrrole ring, thiazole ring, benzothiazole ring, Thiadiazole, imidazole ring, benzimidazole ring, triazine ring, triazole ring, Pyridine ring, pyridine ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, pteridine ring and acridine ring etc., wherein it is preferred that furan nucleus, thiophene Pheno ring, imidazole ring, pyridine ring and indole ring etc..
In the context of the present specification, term " C2-20Heterocycle " refers to C above-mentioned3-20Cycloalkanes hydrocarbon ring or C3-20Cyclenes Group after carbon atom is replaced by oxygen atom, sulphur atom or nitrogen-atoms at least one ring of hydrocarbon ring.As the C2-20Heterocycle, For example piperidine ring, piperazine ring, azepine cyclohexene ring, dioxolane ring, dioxane ring, tetrahydrofuran ring, oxa- can be enumerated Cyclobutane ring, a word used for translation ring in heptan ring, pyrrolin ring, tetrahydro pyridine ring, tetrahydro-pyrazole ring, pyrazoline ring, pyranoid ring, thiapyran ring, tetrahydrochysene Pyrrole ring, thiophane ring, aziridine ring, amylene oxide ring, tetrahydric thiapyran ring and morpholine ring etc., wherein it is preferred that piperidine ring, four Hydrogen furan nucleus, amylene oxide ring etc..
In the context of the present specification, term " combination group " refers to two or more C3-20Cycloalkanes hydrocarbon ring is via list Key or linking group bond together and the group, the two or more C that are formed3-20Cyclenes hydrocarbon ring via singly-bound or linking group that The group, two or more C of this bonding and formation6-20Aromatic ring bonds together via singly-bound or linking group and the base that is formed Group, two or more C4-20Hetero-aromatic ring bonds together via singly-bound or linking group and the group, the two or more C that are formed2-20 Heterocycle bonds together via singly-bound or linking group and the group or C that are formed3-20Cycloalkanes hydrocarbon ring, C3-20Cyclenes hydrocarbon ring, C6-20Aromatic ring, C4-20Hetero-aromatic ring and C2-20In heterocycle it is two or more by condense each other or via singly-bound or linking group that The group of this bonding and formation.As the combination group, for example cyclohexyl benzene, tolylthiophene, benzo morpholine, phenyl can be enumerated Morpholine, cyclohexenyl group pentamethylene, naphthalene norbornane, phenyl adamantane, benzofurane, benzcyclobutane, phenyl pyrazines, phenyl Pyrroles, cyclohexenyl group adamantane, cyclohexyl oxetanes, cyclohexyl morpholine, Huan hexyls isoxazole, phenyl-isoxazole azoles, Buddha's warrior attendant Alkane isoxazole, norbornene butylcyclohexane, norbornene benzene, cyclohexyl ring hexane, cyclohexyl methyl hexamethylene, thienyl thiophene Pheno, pyrrole radicals pyrroles, pyrrolidinyl pyrroles, benzyl benzene, phenoxy group benzene, thiophenyl benzene, benzyloxy benzene, benzyloxy methylene Base benzene, styryl benzene, styryl methylene-benzene, phenyl amino phenyl, phenylaminomethyl benzene, hexamethylene methoxycyclohexyl alkane, benzene methoxy Base benzene, Deng.
In the context of the present specification, term " linking group " refers in structure containing there are two be not bonded key (half bond) Any group, for example can be-O-；-S-；-NR1, wherein R1It is H or C1-4Linear or branched alkyl group, preferably hydrogen or methyl； The C optionally replaced1-6Linear chain or branched chain alkylene, the C preferably optionally replaced1-4Linear chain or branched chain alkylidene, the C optionally replaced2-4 Linear chain or branched chain alkenylene or the C optionally replaced2-4Linear chain or branched chain alkynylene, the C more preferably optionally replaced1-4Straight chain or branch Chain alkylidene；Or the arbitrary 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-CH2- O- etc., But-O- ,-S- and-NR1Except with itself or the case where be bonded directly with one another.As the linking group, preferably-O-, optionally Substituted C1-4Linear chain or branched chain alkylidene or its it is arbitrary combine, but-O- with the case where itself Direct Bonding except.
In the context of the present specification, term " effluent containing ammonia " refers to (outstanding in the manufacturing method of the nitrile of the present invention It is first step) in react carry out during from reaction system as by-product or unreacted raw material discharge contain The gaseous state or liquid material (such as water containing ammonia condensing, ammonia-containing water and ammonia-containing exhaust etc.) of ammonia.
Finally, in the case where not clearly indicating, all percentages, number, ratio for being previously mentioned in this specification etc. All it is on the basis of weight, unless not meeting the conventional understanding of those skilled in the art when on the basis of weight.
The present invention relates to a kind of manufacturing methods of nitrile, which is characterized in that including first step and second step as described below Suddenly.
According to first step, in the case of ammonia source without interruption, make carboxylic acid sources with the ammonia source anti-from T1 to T2 Answer temperature TAIn the reaction time of lower contact 0.01-2.5 hours, obtain amide intermediate product, wherein T1 is the carboxylic acid sources 1 The greater in 145 DEG C of the fusing point and temperature value of normal atmosphere pressure, T2 is the alicyclic polycarboxylic acid in 1 standard atmospheric pressure Under boiling point, the reckling in sublimation temperature and decomposition temperature, on condition that T2>T1.Preferably, T2-T1 >=10 DEG C.
According to the present invention, the carboxylic acid sources are selected from the C of alicyclic polycarboxylic acid, the alicyclic polycarboxylic acid1-4Straight chain or Branched alkyl ester (preferably methyl esters) or the acid anhydrides of the alicyclic polycarboxylic acid.These carboxylic acid sources can be used alone, It can also combination of two or more use.
According to the present invention, as the alicyclic polycarboxylic acid, for example the compound such as lower structure can be enumerated.
Wherein, groupFor the n valences C optionally replaced3-20Cycloalkanes hydrocarbon ring, the n valences C optionally replaced3-20Cycloolefin Ring or the n valences C optionally replaced2-20Heterocycle.
According to the present invention, divalent C that n-1 group B is each independently singly-bound, optionally replaces3-20Cycloalkanes hydrocarbon ring, optionally Substituted divalent C3-20Cyclenes hydrocarbon ring, the divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20Hetero-aromatic ring optionally replaces Divalent C2-20Heterocycle or the divalent combination group optionally replaced, are preferably each independently singly-bound.
According to the present invention, as the divalent C that n-1 group B is each independently singly-bound, optionally replaces3-20Cycloalkanes hydrocarbon ring is appointed Choose the divalent C in generation3-20Cyclenes hydrocarbon ring or the divalent C optionally replaced2-20When heterocycle, n-1 group R is each independently singly-bound Or the divalent aliphatic hydrocarbon chain optionally replaced, and when n-1 group B is each independently the divalent C optionally replaced6-20Aromatic ring is appointed Choose the divalent C in generation4-20When hetero-aromatic ring or the divalent combination group optionally replaced, n-1 group R, which is each independently, optionally to be taken The divalent aliphatic hydrocarbon chain in generation.
According to the present invention, the aliphatic hydrocarbon chain in each definition is each independently selected from C1-15(preferably C1-9, such as C1-3) Saturations or undersaturated straight chain or branch hydrocarbon chain.
, according to the invention it is preferred to which the aliphatic hydrocarbon chain in respectively defining is each independently selected from C1-15(preferably C1-9, such as C1-3) linear chain or branched chain alkane chain, C2-15(preferably C2-9, such as C2-3) linear chain or branched chain alkene chain or C2-15(preferably C2-9, than Such as C2-3) linear chain or branched chain alkynes chain, more preferably each independently it is selected from C1-15(preferably C1-9, such as C1-3) linear chain or branched chain alkane Hydrocarbon chain or C2-15(preferably C2-9, such as C2-3) linear chain or branched chain alkene chain.
According to the present invention, when the carbon atom number of the aliphatic hydrocarbon chain is 2 or more and includes C -- C single bond in its strand When, a spacer group is optionally further inserted between two carbon atoms of the C -- C single bond：- O- ,-S- or-NR1, wherein R1 It is H or C1-4Linear or branched alkyl group, preferably hydrogen or methyl.The quantity of the C -- C single bond can be one, can also be it is multiple, than 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(in order to For the sake of facilitating explanation, do not show its valence state) when, it is inserted between two carbon atoms of the C -- C single bond that its strand includes CH can be obtained after one O3-O-CH2-CH2-CH3、CH3-CH2-O-CH2-CH3And CH3-CH2-CH2-O-CH3Deng in two C-C CH can be obtained after being inserted into an O respectively between respective two carbon atoms of singly-bound3-O-CH2-O-CH2-CH3、CH3-CH2-O- CH2-O-CH3And CH3-O-CH2-CH2-O-CH3Deng being inserted into an O respectively between respective two carbon atoms of three C -- C single bonds After can obtain CH3-O-CH2-O-CH2-O-CH3。
According to the present invention, n is 2 to 10 integer, preferably 2 to 5 integer, more preferable 2 to 4 integer, further preferred 2 Or 3.
According to the present invention, aliphatic hydrocarbon chain described here, C3-20Cycloalkanes hydrocarbon ring, C3-20Cyclenes hydrocarbon ring, C6-20Aromatic ring, C4-20Hetero-aromatic ring, C2-20Heterocycle and combination group are defined as previously described.
According to the present invention, as the carboxylic acid sources, alicyclic polycarboxylic acid above-mentioned can be used alone, can also Combination of two or more uses.
According to the present invention, the carboxylic acid sources can be biological source, for example, can enumerate natural polybasic carboxylic acid or As (mixing) polybasic carboxylic acid product etc. of industrial (such as oil prodution industry) byproduct, as long as the impurity contained by it or water impurity The flat reduction for making target nitrile yield is no more than 5%.
According to the present invention, the carboxylic acid sources are in the reaction temperature TAUnder be preferably presented as molten condition or liquid State.In consideration of it, the C of the alicyclic polycarboxylic acid, the alicyclic polycarboxylic acid1-4Linear or branched alkyl group ester is described The acid anhydrides of alicyclic polycarboxylic acid, which preferably has, is equal to or less than the reaction temperature TAThe fusing point (1 of (being typically up to 310 DEG C) Normal atmosphere pressure measures).Those skilled in the art can be by consulting the relevant technologies handbook or passing through conventional determining method Know (and the boiling that the alicyclic polycarboxylic acid depresses in 1 normal atmosphere of fusing point that these carboxylic acid sources depress in 1 normal atmosphere Point, sublimation temperature and decomposition temperature etc.), therefore repeat no more herein.
According to the present invention, as the mode for making carboxylic acid sources be contacted with ammonia source, for example can enumerate to melting in advance The mode in the ammonia source of gaseous form is continuously passed through in carboxylic acid sources.
According to the present invention, the ammonia source is as it was noted above, wherein preferred ammonia or the ammonium hydroxide of vaporization, especially Industry Waste Ammonia or the industrial waste ammonia liquor of vaporization.The ammonia content in the ammonia source such as can be 20-99.9wt%, 25- at this time 99.9wt%, 40-99.9wt%, 60-99.9wt%, 75-99.9wt%, 85-99.9wt% or 95-99.9wt%, remaining It is then previously described inert diluent etc..
According to the present invention, (being passed through) without interruption during the entire process of the first step described ammonia source.As at this time (totality) dosage in the ammonia source is not particularly limited as long as the scheduled nitrile yield of the present invention can be realized.Such as According to real reaction situation, carboxylic acid sources in terms of carboxyl with NH3The minimum molar ratio in the ammonia source of meter can be 1： 20、1：30、1：40 or 1：50 etc., highest is subject to the excess waste for not leading to ammonia source, for example can be 1：500、1：400、 1：300、1：200、1：100 or 1：80 etc., but is not limited thereto.
According to the present invention, the first step carries out in open reactive system (such as open reactive kettle).Ammonia source While being continuously supplied to the reaction system (carboxylic acid sources containing melting), effluent containing ammonia is continuously vented the reaction System., it is preferred according to the present invention that by (after the concentration or drying) circulation-supplied of effluent containing ammonia described in Supplement or a part in first step as the ammonia source.It so can accordingly reduce supplied to the fresh of the first step Thus the dosage in ammonia source improves the utilization rate of ammonia raw material, and realizes effluent containing ammonia (such as ammonia-containing water and ammonia-containing exhaust) Efficient Cycle utilizes.
It was found by the inventors of the present invention that the first step can carry out well without using catalyst.Therefore, According to a preferred embodiment of the present invention, the first step usually makes without using when carrying out carboxylic acid ammoniation process in this field Any catalyst.
According to the present invention, the reaction time of the first step is preferably 0.05-2 hours or 0.1-1.5 hours, or Person 0.2-1 hours either 0.3-0.8 hours or the shorter time.
According to the present invention, after the first step, stop the supply in the ammonia source immediately.
According to the present invention, after the first step, the amide intermediate product that is obtained can directly as raw material into Row second step can also carry out second step again after temporary wait.Although alternatively, not necessarily, among the amide obtained Product can also be washed using weak aqua ammonia etc., to remove possible remaining unreacted carboxylic acid sources.
According to the present invention, the first step and second step can carry out in the same reaction vessel, can also be It carries out, is not particularly limited in different reaction vessels (such as tandem reaction vessel).In the same reaction vessel When progress, after the first step, do not discharge the amide intermediate product, and the reaction condition of first step is directly changed The reaction condition (as described below) for becoming second step, production cost and the production for thus reducing the manufacturing method are complicated Degree.
According to the second step, the amide intermediate product that first step is obtained is in the reaction temperature from T3 to T4 TBThe reaction time of lower heat treatment 0.1 to 4.5 hour, wherein T3 are that the amide intermediate product is melted what 1 normal atmosphere was depressed Point and 225 DEG C of temperature value in the greater, T4 be the amide intermediate product depressed in 1 normal atmosphere boiling point, sublimation temperature With the reckling in decomposition temperature, on condition that T4>T3.Preferably, T4-T3 >=10 DEG C.
According to the present invention, the amide intermediate product is in the reaction temperature TBUnder be preferably presented as molten condition or liquid Body state.In consideration of it, the amide intermediate product, which preferably has, is equal to or less than the reaction temperature TB(it is typically up to 350 DEG C) fusing point (1 normal atmosphere pressure measure).Those skilled in the art can be by consulting the relevant technologies handbook or by normal Rule assay method knows fusing point, boiling point, sublimation temperature and decomposition temperature that these amide intermediate products are depressed in 1 normal atmosphere Deng, therefore repeat no more herein.
According to the present invention, preferably 0.2 to 3 hour reaction time of the second step either 0.3 to 2 hour or 0.4 to 1.2 hour either 0.4 to 1 hour or shorter time.
According to the present invention, stop the supply in the ammonia source completely in the second step.
According to the present invention, the second step can also be in closed reaction system in open reactive system It carries out, is preferably carried out in closed reaction system, to reduce energy consumption.
According to the present invention, the second step can carry out in the presence of a catalyst, can not also use catalyst.Make For the catalyst, for example it can enumerate and those of carry out routinely using catalyst in this field when carboxylic acid ammoniation process, such as five Two phosphorus, phosphoric acid, phosphate, molecular sieve, aluminium oxide, zinc oxide or composite oxide catalysts etc. are aoxidized, wherein it is preferable to use Phosphorus pentoxide or phosphoric acid.When in use, these catalyst can be according to the conventional amount used of this field (such as on the basis of weight Can be the 0.2-10% of the carboxylic acid sources weight, preferably 1-6%) it uses, it is not particularly limited.
According to a further embodiment of the invention, the reaction temperature TAFor from T1' to T2'.At this point, described T1'=T1+5 DEG C or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or T1+60 DEG C or T1+70 DEG C or T1+80 DEG C or T1+90 DEG C.The T2'=T2 or T2-5 DEG C or T2-10 DEG C or T2-20 DEG C or T2-30 DEG C or T2-40 DEG C or T2-50 DEG C, but typically up to be 310 DEG C, on condition that T2'>T1'.Preferably, T2'-T1' >=10 DEG C.
According to a further embodiment of the invention, the reaction temperature TBFor from T3' to T4'.At this point, described T3'=T3+5 DEG C or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or T3+40 DEG C or T3+50 DEG C or T3+60 DEG C or T3+70 DEG C or T3+80 DEG C.The T4'=T4 or T4-5 DEG C or T4-10 DEG C or T4-20 DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C, but typically up to be 350 DEG C.On condition that T4'>T3'.Preferably It is T4'-T3' >=10 DEG C.
According to a further embodiment of the invention, the T1 is 145 DEG C either 150 DEG C or 160 DEG C, or 170 DEG C of person either 180 DEG C of either 190 DEG C of either 200 DEG C of either 210 DEG C of either 220 DEG C either 230 DEG C or 240 DEG C either 250 DEG C of either 260 DEG C of either 270 DEG C of either 280 DEG C either 290 DEG C or 300 DEG C.According to one of the invention Further embodiment, the T2 be 310 DEG C either 300 DEG C either 290 DEG C either 280 DEG C either 270 DEG C or 260 DEG C of either 250 DEG C of either 240 DEG C of either 230 DEG C of either 220 DEG C of either 210 DEG C either 200 DEG C or 190 DEG C, Or 180 DEG C.On condition that T2>T1.Preferably, T2-T1 >=10 DEG C.
According to a further embodiment of the invention, the T3 is 225 DEG C either 230 DEG C or 240 DEG C, or 250 DEG C of person either 260 DEG C of either 270 DEG C of either 280 DEG C of either 290 DEG C either 300 DEG C or 310 DEG C.According to this hair A bright further embodiment, the T4 are 350 DEG C of either 340 DEG C of either 330 DEG C either 320 DEG C or 310 DEG C either 300 DEG C of either 290 DEG C either 280 DEG C or 270 DEG C.On condition that T4>T3.Preferably, T4-T3 >=10 DEG C.
According to a specific embodiment of the invention, the carboxylic acid sources are the acid of carboxylic acid shown in the following table 1, the carboxylic acid Acid anhydride or methyl esters (the preferably described carboxylic acid), in the first step, reaction temperature TAAs shown in table 1 below, the reaction time is 0.05- 2 hours either 0.1-1.5 hours either 0.2-1 hours or 0.3-0.8 hours, in the second step, reaction temperature TBAs shown in table 1 below, the reaction time is 0.2 to 3 hour either 0.3 to 2 hour either 0.4 to 1.2 hour or 0.4 to 1 Hour.
Table 1
According to the present invention, after the second step, by conventional purification or separation methods, you can from second step Suddenly target nitrile is isolated in the reaction mixture obtained as product.As the purifying or separation method, for example can enumerate The way of distillation and extraction etc..
According to the present invention, the way of distillation or extraction can carry out in such a way that this field is conventional, and there is no especially Restriction, as long as target nitrile product can be separated from the reaction mixture.
According to the present invention, as the way of distillation, for example the distillation under vacuum for having used rectifying column can be enumerated, the rectifying The operating condition of tower at this time is such as：Vacuum degree is 25-250mbar, and column bottom temperature is generally 100-320 DEG C, is produced with target nitrile (± 2 DEG C) of boiling point of the product under the vacuum degree is used as cut point, is such as generally 80-290 DEG C, but it is not limited to this but takes Certainly in specific target nitrile product.As needed, the reflux ratio of the rectifying column can be set as the 1.1-4 of minimum reflux ratio Rmin Times, number of actual plates is such as 5-200 blocks, and but it is not limited to this but depends on specific target nitrile product.In addition, the essence The practical operation condition for evaporating tower is not limited to this, those skilled in the art can according to the distillation character of target nitrile product (such as Boiling point and heat decomposition temperature etc.), rectifying tower structure (such as plate number etc.) and actual needs (such as scheduled nitrile purity etc.) Deng selection distillation operation condition appropriate, this is all conventionally known.
According to the present invention, as the extraction, for example can enumerate using the targets nitrile such as ethyl acetate, chloroform, hexane The good solvent of product to the reaction mixture (as needed be added suitable 2-5wt% dilute alkaline aqueous solutions be diluted or After adjusting) method etc. that is directly extracted.
According to the present invention, extraction and the way of distillation can be combined, for example preliminary purifying can be carried out first with extraction Or separation, is then further purified or detached by the way of distillation.
According to the present invention, by the purifying or separation, can obtain purity be 97% or more (preferably 98% or more, more It is preferred that 99% or more) target nitrile product.Nitrile purity at this time such as can be easily measured by gas chromatography etc..
Nitrile manufacturing method according to the present invention, according to the difference of nitrile product category, may be implemented 75% or more, 80% with Upper, 90% or more, 95% or more, even 98% or more or higher nitrile yield.
According to the present invention, the nitrile can be used as raw material for manufacturing corresponding amine.For this purpose, the invention further relates to a kind of amine Manufacturing method, which manufactures corresponding amine by hydrogenating the nitrile.
According to the present invention, the hydrogenation can in hydrogenated nitrile, any mode known to routine carries out according to this field.Than Such as, can be 0.6-5.2MPa in reaction gross pressure, hydrogen partial pressure is 0.4-5MPa (such as 2-4MPa), reaction temperature 70- Under conditions of 130 DEG C (such as 80-120 DEG C), in the presence of a hydrogenation catalyst, make the nitrile raw material hydrogenate 0.2-3 hours it is (excellent Select 0.5-2 hours), but is not limited thereto.
It can be directly using this field conventionally used for hydrogenating nitriles amine as the hydrogenation catalyst according to the present invention Various catalyst, for example the Raney's nickel of the doping such as Raney's nickel, iron or copper can be enumerated, Ni-B or Ni-Co-B amorphous alloys, born Load type Ni-B or Ni-Co-B amorphous alloy, carrier loaded noble metal (such as Pb/C, Pd/C or Rh/C etc.) compound are urged Agent (such as Raney's nickel/eight carbonyl cobalt) etc., wherein facilitating the angle of implementation, preferably Raney's nickel, such as Aladdin from industrialization 50 μm or 150 μm commercially available Raney's nickels of specification are pressed by Reagent Company.These hydrogenation catalysts can be used alone, can also two kinds or Multiple combinations use.
According to the present invention, the dosage of the hydrogenation catalyst such as can be the 2- of the nitrile raw material on the basis of weight 10wt% (such as 2-6wt%), but is not limited thereto.
According to the present invention, the hydrogenation preferably carries out in the presence of solvent (or being diluent), this is ability Known to domain.As the solvent, for example water can be enumerated；The alcohol such as methanol, ethyl alcohol and 2- propyl alcohol；The esters such as methyl acetate；Benzene, first The aromatic hydrocarbon such as benzene, dimethylbenzene；The cycloalkane such as hexamethylene；The alkane such as heptane；Petroleum ether, ether, dioxane and tetrahydrofuran etc. Mixed solvent (the volume ratio of ethyl alcohol and water of ether either arbitrary the combination wherein preferred alcohol or ethyl alcohol and water of these solvents For example it is 0.1:1 to 1:0.1, but it is not limited to this) etc..These solvents can be used alone, can also combination of two or more It uses.
According to the present invention, as the dosage of the solvent, as long as the heat release situation of reaction and not can be effectively improved Excessive burden generated to subsequent product separating step, for example on the basis of volume can be the 1-10 of the nitrile raw material Times, such as 1-5 times, 1-4 times, 1-3 times or 1-2 times etc., but is not limited thereto.
According to the present invention, as needed, the hydrogenation can also carry out in the presence of hydrogenating auxiliary agent.As described Auxiliary agent is hydrogenated, for example the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide can be enumerated.These hydrogenation auxiliary agents It can be used alone, it can also combination of two or more use.
Can be the nitrile raw material as the dosage of the hydrogenation auxiliary agent, such as on the basis of weight according to the present invention 0.3-2wt% (preferably 0.2-1.2wt%), but is not limited thereto.
According to the present invention, after the hydrogenation, by conventional purification or separation methods, you can mixed from reaction It closes in object and isolates targeted amine as product.These purifying or separation method are known in the art, and details are not described herein.
The manufacturing method of amine according to the present invention, according to the difference of nitrile raw material type, may be implemented 85% or more, 90% with Upper, 95% or more, even 98% or more or higher amine yield, and the purity of amine product can reach 97% or more (preferably 98% or more, more preferable 99% or more).
Embodiment
The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.
Amide intermediate prepares embodiment
It is open in reaction kettle in 1L and 500g carboxylic acid starting materials (chemistry is pure) is added, stirring (600r/min) is opened, from reaction kettle Bottom is constantly passed through ammonia (chemistry pure, water content 5.1wt%, flow 100g/min) into carboxylic acid starting material.Reaction is set to exist Reaction temperature TALower carry out TCAfter hour, stopping is passed through ammonia.Content sampling to reaction kettle, does nucleus magnetic hydrogen spectrum and element point Analysis, to characterize amide intermediate.Specific reaction condition and characterization result are shown in following Table A -1, Table A -2, Table A -3, Table A -4 and table A-5.These characterization results show that obtained amide intermediate has high purity (99% or more).
Table A -1
Table A -2
Table A -3
Table A -4
Table A -5
Nitrile product prepares embodiment
It connects amide intermediate and prepares embodiment.The reaction kettle is closed (when the boiling point etc. of amide intermediate under normal pressure In or less than following reaction temperature TBWhen) or keep reaction kettle be open state (when the boiling of amide intermediate under normal pressure Point is higher than following reaction temperature TBWhen), continue to stir (600r/min), reaction temperature is changed into TB, in reaction temperature TB Lower holding TDAfter hour, capping kettle simultaneously connects vacuum pump, and the vacuum degree in reaction kettle is made to reach 20-50mbar (according to nitrile The difference of product species and accordingly adjust), using distillate as nitrile product.The yield of the nitrile product is calculated, and samples and does nuclear-magnetism Hydrogen is composed and elemental analysis, to characterize obtained nitrile product.Specific reaction condition and characterization result see following Table A -6, A-7, A-8, A-9 and A-10.These characterization results show that obtained nitrile product has high purity (99% or more).
In these nitrile products prepare embodiment, in the stage optionally started in reaction, 10g is added at one time into reaction kettle Phosphorus pentoxide is as catalyst.
Table A -6
Table A -7
Table A -8
Table A -9
Table A -10
Amine prepares embodiment
(1) 100g Isosorbide-5-Nitraes-hexamethylene dimethoxy nitrile and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, continuously fills Enter H2, system pressure in reaction process is made to be always maintained at 5MPa.At 95 DEG C of reaction temperature after reaction 0.5h, cooling.It waits for anti- When the temperature in kettle being answered to be down to room temperature, deflate, by filter and be recrystallized to give Isosorbide-5-Nitrae-hexamethylene dimethylamine (purity be 99% with On), yield 90wt%.
1H NMR (300MHz, DMSO) δ 2.54-2.50 (m, 2H), 2.49 (d, J=2.2Hz, 2H), 1.94 (s, 4H), 1.89-1.78 (m, 4H), 1.20-0.87 (m, 6H), Elemental Analysis:C,67.18；H,12.16；N,19.28.
(2) 100g 4- cyclohexene -1,2- dimethoxy nitriles and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, even It is continuous to be filled with H2, system pressure in reaction process is made to be always maintained at 6MPa.At 90 DEG C of reaction temperature after reaction 1h, cooling.It waits for It when temperature in reaction kettle is down to room temperature, deflates, by filtering and being recrystallized to give 4- cyclohexene -1,2- dimethylamine, (purity is 99% or more), yield 91wt%.
1H NMR (300MHz, DMSO) δ 5.69 (d, J=11.0Hz, 1H), 5.74-5.56 (m, 2H), 5.64 (d, J= 4.5Hz,1H),2.77–2.59(m,2H),3.41–2.58(m,2H),2.53–2.42(m,2H),2.55–2.32(m,4H), 2.42-2.32 (m, 2H), 2.07 (ddd, J=12.4,8.3,7.0Hz, 2H), 2.07 (ddd, J=12.4,8.3,7.0Hz, 2H), 1.95 (s, 4H), 1.95 (s, 4H), 1.63-1.50 (m, 1H), 1.62-1.37 (m, 2H), 1.50-1.39 (m, 1H), Elemental Analysis:C,68.17；H,11.05；N,19.24.
(3) 1,3,5- hexamethylene trimethylsilyl nitriles of 100g and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, continuously It is filled with H2, system pressure in reaction process is made to be always maintained at 6MPa.At 100 DEG C of reaction temperature after reaction 1h, cooling.It waits for anti- When the temperature in kettle being answered to be down to room temperature, deflate, by filter and be recrystallized to give 1,3,5- hexamethylene trimethylamines (purity be 99% with On), yield 89wt%.
1H NMR (300MHz, DMSO) δ 2.50 (d, J=7.2Hz, 6H), 1.97-1.90 (m, 8H), 1.88 (s, 1H), 1.26-1.18 (m, 1H), 1.16 (s, 1H), 1.15-1.06 (m, 1H), 0.72 (d, J=7.7Hz, 2H), 0.68 (s, 1H), Elemental Analysis:C,63.01；H,12.14；N,24.19.
(4) 100g 2,3- oxygen Polymorphs dimethoxy nitriles and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, even It is continuous to be filled with H2, system pressure in reaction process is made to be always maintained at 6MPa.At 85 DEG C of reaction temperature after reaction 1h, cooling.It waits for It when temperature in reaction kettle is down to room temperature, deflates, by filtering and being recrystallized to give 2,3- oxygen Polymorphs dimethylamine, (purity is 99% or more), yield 91wt%.
1H NMR (300MHz, DMSO) δ 3.99 (dt, J=9.0,7.3Hz, 1H), 3.89-3.67 (m, 2H), 2.88 (dd, J=12.4,7.3Hz, 1H), 2.66 (ddd, J=19.4,12.4,7.1Hz, 2H), 2.44 (dd, J=12.4,7.0Hz, 1H), 2.15 (s, 2H), 2.08 (s, 2H), 1.91 (ddd, J=13.7,11.7,6.7Hz, 1H), 1.85-1.73 (m, 1H), 1.73- 1.55 (m, 1H), Elemental Analysis:C,55.17；H,10.52；N,21.43.
(5) 1,2,3,4- ring fourths of 100g, four formonitrile HCN and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, even It is continuous to be filled with H2, system pressure in reaction process is made to be always maintained at 8MPa.At 95 DEG C of reaction temperature after reaction 1h, cooling.It waits for It when temperature in reaction kettle is down to room temperature, deflates, by filtering and being recrystallized to give 1,2,3,4- ring fourth tetramethylammoniums, (purity is 99% or more), yield 88wt%.
1H NMR (300MHz, DMSO) δ 2.55-2.46 (m, 8H), 2.24 (s, 8H), 1.80-1.63 (m, 4H), Elemental Analysis:C,55.18；H,11.17；N,32.26.
Although the specific implementation mode of the present invention is described in detail above in conjunction with the embodiments, need to refer to Go out, the scope of protection of the present invention is not limited by these specific embodiments, but by claims of annex Lai It determines.Those skilled in the art can carry out these embodiments in the range of not departing from the technological thought and purport of the present invention Change appropriate, and the embodiment after these changes is obviously also included within protection scope of the present invention.

Claims (10)

1. a kind of manufacturing method of nitrile, which is characterized in that include the following steps：
First step：Ammonia source without interruption makes carboxylic acid sources with the ammonia source in the reaction temperature T from T1 to T2ALower contact 0.01- When the reaction of 2.5 hours (either 0.05-2 hours either 0.1-1.5 hours either 0.2-1 hours or 0.3-0.8 hours) Between, amide intermediate product is obtained, wherein the carboxylic acid sources are selected from the C of alicyclic polycarboxylic acid, the alicyclic polycarboxylic acid1-4 One or more in linear or branched alkyl group ester and the acid anhydrides of the alicyclic polycarboxylic acid, the ammonia source supplies in a gaseous form It answers, T1 is the greater in 145 DEG C of the fusing point that the carboxylic acid sources are depressed in 1 normal atmosphere and temperature value, and T2 is described alicyclic Reckling of the polybasic carboxylic acid in the boiling point that 1 normal atmosphere is depressed, sublimation temperature and decomposition temperature, on condition that T2>T1, preferably T2-T1 >=10 DEG C and second step：Stop supplying the ammonia source, by the amide intermediate product in the reaction temperature from T3 to T4 Spend TBIt is lower heat treatment 0.1 to 4.5 hour (either 0.2 to 3 hour either 0.3 to 2 hour either 0.4 to 1.2 hour or 0.4 to 1 hour) reaction time, wherein T3 is the fusing point and temperature value that the amide intermediate product is depressed in 1 normal atmosphere The greater in 225 DEG C, T4 are boiling point, sublimation temperature and the decomposition temperature that the amide intermediate product is depressed in 1 normal atmosphere In reckling, on condition that T4>T3, preferably T4-T3 >=10 DEG C.
2. the manufacturing method of the nitrile of claim 1, wherein the reaction temperature TAFor from T1' to T2', wherein T1'=T1+5 DEG C (or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or T1+60 DEG C or T1+70 DEG C or T1+80 DEG C or T1+90 DEG C), T2'=T2 (or T2-5 DEG C or T2-10 DEG C or T2-20 DEG C, Or T2-30 DEG C or T2-40 DEG C or T2-50 DEG C or 310 DEG C), on condition that T2'>T1'；The reaction temperature TBFor From T3' to T4', wherein T3'=T3+5 DEG C (or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or T3+40 DEG C or T3+50 DEG C or T3+60 DEG C or T3+70 DEG C or T3+80 DEG C of person), T4'=T4 (or T4-5 DEG C or T4-10 DEG C or T4-20 DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C or 350 DEG C), on condition that T4'>T3'.
3. the manufacturing method of the nitrile of claim 1, wherein T1 be 145 DEG C (either 150 DEG C either 160 DEG C or 170 DEG C, or 180 DEG C of person either 190 DEG C of either 200 DEG C of either 210 DEG C of either 220 DEG C of either 230 DEG C either 240 DEG C or 250 DEG C either 260 DEG C of either 270 DEG C of either 280 DEG C of either 290 DEG C either 300 DEG C) T2 be 310 DEG C (or 300 DEG C, or 290 DEG C of person either 280 DEG C of either 270 DEG C of either 260 DEG C of either 250 DEG C of either 240 DEG C either 230 DEG C or 220 DEG C either 210 DEG C of either 200 DEG C either 190 DEG C or 180 DEG C)；T3 be 225 DEG C (either 230 DEG C or 240 DEG C, or 250 DEG C of person either 260 DEG C of either 270 DEG C of either 280 DEG C of either 290 DEG C either 300 DEG C or 310 DEG C), T4 350 DEG C (either 340 DEG C either 330 DEG C either 320 DEG C either 310 DEG C either 300 DEG C either 290 DEG C either 280 DEG C or 270℃)。
4. the manufacturing method of the nitrile of claim 1, wherein the first step carries out in open reactive system, described second Step carries out in open reactive system or closed reaction system.
5. the manufacturing method of the nitrile of claim 1, wherein catalyst is not used in the first step, and the second step exists Progress or unused catalyst in the presence of catalyst.
6. the manufacturing method of the nitrile of claim 1, wherein the ammonia source is ammonia or the ammonium hydroxide of vaporization, preferably industrial waste ammonia gas Or the industrial waste ammonia liquor of vaporization, ammonia content 20-99.9wt%, preferably 25-99.9wt%.
7. the manufacturing method of the nitrile of claim 1, wherein the carboxylic acid sources are the acid anhydrides or first of carboxylic acid, the carboxylic acid shown in following table Ester, in the first step, reaction temperature TAAs shown in the table, the reaction time is that 0.05-2 hours or 0.1-1.5 are small When either 0.2-1 hours or 0.3-0.8 hours, in the second step, reaction temperature TBAs shown in the table, when reaction Between be 0.2 to 3 hour either 0.3 to 2 hour either 0.4 to 1.2 hour or 0.4 to 1 hour.
8. the manufacturing method of the nitrile of claim 1, wherein the alicyclic polycarboxylic acid is selected from the chemical combination for the formula that has the following structure It is one or more in object：
Wherein, groupFor the n valences C optionally replaced3-20Cycloalkanes hydrocarbon ring, the n valences C optionally replaced3-20Cyclenes hydrocarbon ring or The n valences C optionally replaced2-20Heterocycle；The divalent C that n-1 group B is each independently singly-bound, optionally replaces3-20Cycloalkanes hydrocarbon ring is appointed Choose the divalent C in generation3-20Cyclenes hydrocarbon ring, the divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20Hetero-aromatic ring, optionally substitution Divalent C2-20Heterocycle or the divalent combination group optionally replaced, are preferably each independently singly-bound；When n-1 group B respectively The divalent C for independently being singly-bound, optionally replacing3-20Cycloalkanes hydrocarbon ring, the divalent C optionally replaced3-20Cyclenes hydrocarbon ring optionally replaces Divalent C2-20When heterocycle, divalent aliphatic hydrocarbon chain that n-1 group R is each independently singly-bound or optionally replaces；When n-1 group B is each independently the divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20Hetero-aromatic ring or the divalent group optionally replaced When closing group, n-1 group R is each independently the divalent aliphatic hydrocarbon chain optionally replaced；Aliphatic hydrocarbon chain in each definition is each From independently selected from C1-15(preferably C1-9) saturations or undersaturated straight chain or branch hydrocarbon chain, be preferably each independently selected from C1-15 (preferably C1-9) linear chain or branched chain alkane chain, C2-15(preferably C2-9) linear chain or branched chain alkene chain or C2-15(preferably C2-9) straight chain or Branched alkyne chain is more preferably each independently selected from C1-15(preferably C1-9) linear chain or branched chain alkane chain or C2-15(preferably C2-9) Linear chain or branched chain alkene chain；When the carbon atom number of the aliphatic hydrocarbon chain is 2 or more and includes C -- C single bond in its strand When, insertion-O- ,-S- or-NR optionally between two carbon atoms of the C -- C single bond1-(R1It is H or C1-4Linear chain or branched chain alkane Base)；N is 2 to 10 integer, preferably 2 to 5 integer, more preferable 2 to 4 integer, further preferred 2 or 3.
9. the manufacturing method of the nitrile of claim 1, wherein the first step is gone back while obtaining the amide intermediate product Effluent containing ammonia is obtained, and by the supplement as the ammonia source in the circulation-supplied to the first step of effluent containing ammonia Or a part, the preferably described effluent containing ammonia is in the circulation-supplied to the first step after concentration or drying as described The supplement or a part in ammonia source.
10. a kind of manufacturing method of amine, which is characterized in that include the following steps：
First step：Nitrile is manufactured according to the manufacturing method of any one of claim 1 to 9；With
Second step：The nitrile that first step obtains is hydrogenated to manufacture amine.
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