CN105001032B - The manufacture method of nitrile and its corresponding amine - Google Patents
The manufacture method of nitrile and its corresponding amine Download PDFInfo
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- CN105001032B CN105001032B CN201410155943.1A CN201410155943A CN105001032B CN 105001032 B CN105001032 B CN 105001032B CN 201410155943 A CN201410155943 A CN 201410155943A CN 105001032 B CN105001032 B CN 105001032B
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Abstract
The present invention relates to a kind of manufacture method of nitrile, compared with prior art, has the characteristics that ammonia source dosage significantly reduces, environmental pressure is small, energy consumption is low, production cost is low, the purity and high income of nitrile product, and can obtain the increasingly complex nitrile of structure.The invention further relates to the method that corresponding amine is manufactured by the nitrile.
Description
Technical field
The method that corresponding amine is manufactured the present invention relates to a kind of manufacture method of nitrile and by the nitrile.
Background technology
Aromatic polyvalent nitrile such as aromatic dicarboxylic nitrile is the fine-chemical intermediate for having extensive use, utilizes its cyano group
Chemical activity, a series of agricultural chemicals, medicine, dyestuff, spices etc. can be synthesized, be widely used in each neck of national economy
Domain.
The traditional preparation method of aromatic dicarboxylic nitrile include sandmeyer reactions, halogenated hydrocarbons and the direct cyaniding of cyanide and
Aromatic aldehyde is dehydrated through aldoxime or gas phase catalysis ammonification etc., and these method General reactions routes are longer, complex process, difficult separation are pure
Change, be seriously polluted, particularly raw material is more difficult to get or need to use reagent costly, thus production cost is higher, is not suitable for work
Industry metaplasia is produced.
At this stage, the main method that the production of aromatic dicarboxylic nitrile uses is aromatic hydrocarbon ammoxidation technology, and ammonia oxidation is with passing
System method is compared, although having the advantages such as raw material is cheap and easy to get, reaction scheme is short, product is disposable, still there is following four
The problem of individual serious：(1) in order that yield improves, NH3 dosages are excessive；(2) a large amount of deposed ammonias are produced in course of reaction, to environment
And post processing causes very big pressure；(3) reaction substrate narrow scope, prepare selectively low during alkyl mononitriles；(4) reaction temperature
Spend higher (more than 410 DEG C), very high is required to catalyst preparation.
The preparation method of aliphatic polybasic nitrile mainly uses carboxylic acid ammoniation process, but relevant is manufactured by carboxylic acid ammoniation process
The technology of aromatic polyvalent nitrile is then rarely reported.
But the present inventor by study find, prior art by aliphatic polycarboxylic acid's ammoniation process come
When manufacturing corresponding aliphatic polybasic nitrile, in order that aminating reaction is fully carried out, the technology must be in the whole 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 dosage needed for the actual amount considerably beyond aminating reaction of ammonia, it may be possible to real reaction requirement
Thousands of times, thus cause the utilization rate of ammonia extremely low.Further, since the utilization rate of ammonia is extremely low, the aminating reaction generates
It substantial amounts of deposed ammonia but can not recycle, environment be exerted heavy pressures on after discharge, with the green life followed now
Production theory is not inconsistent.Be additionally, since the technology aminating reaction employ 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 also deposit reaction mass during the course of the reaction
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, prior art will also
The ammonia for using water content extremely low is sought as reaction raw materials, and utilizes the ammonia being continuously passed through during whole aminating reaction
As entrainer, the water of the by-product of discharge reaction at any time.
Therefore, the current present situation of prior art is to be still required for a kind of manufacture method of aromatic polyvalent nitrile, its preparation side
Method is simple, is adapted to industrialized production, and can overcome foregoing problems present in prior art manufacture method.
The content of the invention
The present inventor has found by diligent research on the basis of existing technology, is being turned by ammoniation process from carboxylic acid to nitrile
, it is necessary to intermediate steps by forming acid amides during change, and the intermediate steps only need under relatively low 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, it is possible to solve foregoing problems, and this completes the present invention.The appearance of this two-step method new technology, 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 manufactures the method for amine.
Specifically, the present invention relates to the content of following aspect.
1. a kind of manufacture method of nitrile, it is characterised in that comprise the following steps：
First step：Make carboxylic acid sources with ammonia source in the reaction temperature T from T1 to T2ALower contact 0.01-2.5 hours (or
0.05-2 hours, either 0.1-1.5 hours or 0.2-1 hours, or 0.3-0.8 hours) reaction time, obtain acid amides
Intermediate product, wherein the carboxylic acid sources are selected from aromatic polycarboxylic acid, the C of the aromatic polycarboxylic acid1-4Straight or branched alkane
One or more in the acid anhydrides of base ester and the aromatic polycarboxylic acid, the ammonia source are ammoniacal liquor or the production ammoniacal substance aqueous solution
(preferably ammoniacal liquor, more preferably industrial deposed ammonia), T1 is 245 DEG C of the fusing point that the carboxylic acid sources are depressed in 1 normal atmosphere and temperature value
In the greater, T2 is the aromatic polycarboxylic acid in boiling point, sublimation temperature and the decomposition temperature that 1 normal atmosphere is depressed
Reckling, on condition that T2 ＞ T1, preferably T2-T1 >=10 DEG C, wherein the production ammoniacal substance refers to the reaction bar in first step
It can be decomposed under part and produce the material of ammonia, and the carboxylic acid sources and the ratio in the ammonia source cause described in terms of carboxyl
Carboxylic acid sources with NH3The mol ratio in the ammonia source of meter reach 1: 1.1-9.5 (preferably 1: 1.2-7.0, more preferably 1: 1.3-5.6,
, and second step 1: 1.3-2.5,1: 1.3-2.0 or 1: 1.3-1.6)：By the acid amides intermediate product in the reaction from T3 to T4
Temperature TBIt is lower heat treatment 0.1 to 4.5 hour (either 0.2 to 3 hour or 0.3 to 2 hour, or 0.4 to 1.2 hour, or
Person 0.4 to 1 hour) reaction time, wherein T3 is the fusing point and temperature value that the acid amides intermediate product is depressed in 1 normal atmosphere
The greater in 300 DEG C, T4 are boiling point, sublimation temperature and the decomposition temperature that the acid amides intermediate product is depressed in 1 normal atmosphere
In reckling, on condition that T4 ＞ T3, preferably T4-T3 >=10 DEG C.
2. the manufacture 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 325 DEG C), on condition that T2 ' ＞ T1 '；Institute
State 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), 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 440 DEG C), it is preceding
It is T4 ' ＞ T3 ' to carry.
3. the manufacture method of the nitrile described in any preceding aspect, wherein T1 be 245 DEG C (either 250 DEG C or 260 DEG C, or
270 DEG C of person, either 280 DEG C or 290 DEG C, either 300 DEG C or 310 DEG C, or 320 DEG C), T2 is 325 DEG C (or 320
DEG C, either 310 DEG C or 300 DEG C, either 290 DEG C or 280 DEG C)；T3 be 300 DEG C (either 310 DEG C or 320 DEG C, or
330 DEG C of person, either 340 DEG C or 350 DEG C), T4 is 440 DEG C (either 430 DEG C or 420 DEG C, either 410 DEG C or 400
DEG C, either 390 DEG C or 380 DEG C, either 370 DEG C or 360 DEG C, either 350 DEG C or 340 DEG C, either 330 DEG C or
320℃)。
4. the manufacture method of the nitrile described in any preceding aspect, wherein the first step enters in closed reaction system
OK, the second step is carried out in open reactive system or closed reaction system.
5. the manufacture method of the nitrile described in any preceding aspect, wherein catalyst, and institute is not used in the first step
State second step and carry out or be not used in the presence of a catalyst catalyst.
6. the manufacture method of the nitrile described in any preceding aspect, wherein the ammonia content of the ammoniacal liquor is 10-30wt%, preferably
25-28wt%, and the one kind or more of the production ammoniacal substance in urea, cyanic acid, ammonium carbonate, ammonium hydrogen carbonate and ammonium chloride
Kind, the one or more being preferably selected from urea and ammonium hydrogen carbonate, more preferably ammonium hydrogen carbonate.
7. the manufacture method of the nitrile described in any preceding aspect, wherein the carboxylic acid sources are carboxylic acid, carboxylic shown in following table
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, or
Person's 0.1-1.5 hours, either 0.2-1 hours or 0.3-0.8 hours, in the second step, reaction temperature TBSuch as following table
Shown, the reaction time is 0.2 to 3 hour, either 0.3 to 2 hour or 0.4 to 1.2 hour, or 0.4 to 1 hour.
| Carboxylic acid | Reaction temperature TA, DEG C | Reaction temperature TB, DEG C |
| Terephthalic acid (TPA) | 310 to 325 | 340 to 430 |
| Phthalic acid | 245 to 325 | 345 to 430 |
| 3,4- pyridinedicarboxylic acids | 270 to 300 | 320 to 440 |
| 1,2,4,5- benzene tetracarboxylic acid | 290 to 310 | 320 to 440 |
| Chloro- 1, the 3- phthalic acids of 2- amino -5- | 255 to 295 | 305 to 330 |
| 2- itrile groups-Isosorbide-5-Nitrae-phthalic acid | 250 to 285 | 300 to 325 |
| 2- amino -5- methoxyl group -1,3- phthalic acids | 260 to 300 | 315 to 335 |
| 2,7- naphthalenedicarboxylic acids | 265 to 305 | 315 to 330 |
| 1,2,3,5,6- benzene pentacarbonic acid | 295 to 315 | 330 to 345 |
| NDA | 265 to 305 | 315 to 335 |
| 5- nitro -1,3- phthalic acids | 275 to 300 | 315 to 335 |
| 5- hydroxyl -1,3- phthalic acids | 270 to 305 | 320 to 345 |
| Isosorbide-5-Nitrae-naphthalenedicarboxylic acid | 305 to 325 | 335 to 350 |
| 1,3,5- benzenetricarboxylic acid | 290 to 315 | 335 to 350 |
| 1,2,4- benzenetricarboxylic acid | 290 to 315 | 330 to 345 |
| Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics | 310 to 325 | 345 to 355 |
| M-phthalic acid | 295 to 310 | 325 to 335 |
| 5,6- quinolinedicarboxylic acids | 275 to 300 | 315 to 335 |
| 6- Ethyl-2-Methyl -3,4- pyridinedicarboxylic acids | 285 to 310 | 325 to 350 |
| 5- amino -3- methyl -2,4- thiophenedicarboxylic acids | 255 to 290 | 315 to 335 |
| 8- methyl -2,3- quinolinedicarboxylic acids | 255 to 290 | 310 to 335 |
| 2- methyl -4,5- sulphur pyrrole dioctyl phthalate | 260 to 295 | 315 to 340 |
| 2- amino -4,5- sulphur pyrrole dioctyl phthalate | 265 to 295 | 315 to 345 |
| NDA | 245 to 290 | 310 to 335 |
| 2- (2- pyridine radicals) -4,5- imidazoles dioctyl phthalate | 255 to 300 | 315 to 345 |
| 4- acetoxy-benzoic acids | 310 to 325 | 340 to 430 |
| 4- propionic acid yl benzoic acids | 310 to 325 | 340 to 430 |
| 4- caproic acid yl benzoic acids | 310 to 325 | 340 to 430 |
| 4- lauric acid yl benzoic acids | 310 to 325 | 340 to 430 |
| 2- nitro -4- caproic acid yl benzoic acids | 315 to 325 | 340 to 400 |
8. the manufacture method of the nitrile described in any preceding aspect, wherein the aromatic polycarboxylic acid, which is selected from, has following knot
One or more in the compound of structure formula：
Wherein, groupFor the n valencys C optionally substituted6-20Aromatic ring or the n valencys C optionally substituted4-20Hetero-aromatic ring；
N-1 group R be each independently singly-bound, optionally substitutes divalent aliphatic hydrocarbon chain, the divalent C optionally substituted3-20Cycloalkanes hydrocarbon ring,
The divalent C optionally substituted3-20Cyclenes hydrocarbon ring, the divalent C optionally substituted6-20Aromatic ring, the divalent C optionally substituted4-20Hetero-aromatic ring, optionally take
The divalent C in generation2-20Heterocycle or the divalent combination group optionally substituted；Aliphatic hydrocarbon chain in each definition is each independently selected from
C1-15(preferably C1-9) saturation or undersaturated straight or branched hydrocarbon chain, be preferably each independently selected from C1-15(preferably C1-9) straight
Chain or branched alkane hydrocarbon chain, C2-15(preferably C2-9) straight or branched alkene chain or C2-15(preferably C2-9) straight or branched alkynes chain,
More preferably each independently it is selected from C1-15(preferably C1-9) straight or branched alkane chain or C2-15(preferably C2-9) straight or branched alkene
Hydrocarbon chain；When the carbon number of the aliphatic hydrocarbon chain is more than 2 and when including C -- C single bond in its strand, optionally in the C-C
Insertion-O- ,-S- or-NR between two carbon atoms of singly-bound1-(R1It is H or C1-4Straight or branched alkyl)；N be 2 to 10 it is whole
Number, preferably 2 to 5 integer, more preferably 2 to 4 integer, further preferred 2 or 3.
9. the manufacture method of the nitrile described in any preceding aspect, wherein the first step produces among the acquisition acid amides
Effluent containing ammonia is also obtained while thing, and incites somebody to action the circulation-supplied of effluent containing ammonia into the first step as described
The supplement or a part in ammonia source, preferably described effluent containing ammonia are being fed to the first step by concentrating or drying Posterior circle
Middle supplement or a part as the ammonia source.
10. a kind of manufacture method of amine, it is characterised in that comprise the following steps：
First step：Nitrile is manufactured according to the manufacture method described in any preceding aspect；With
Second step：The nitrile that hydrogenation first step obtains manufactures amine.
Technique effect
Compared with prior art, the present invention has advantages below.
According to the nitrile manufacture method of the present invention, ammonia source (such as ammonia etc.) only is supplied 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 drastically increase the utilization rate in ammonia source.
According to the nitrile manufacture method of the present invention, because the utilization rate in ammonia source significantly improves, therefore can be effectively reduced anti-
Deposed ammonia amount caused by answering, environmental pressure is small, is consistent with the green production theory followed now.
According to the nitrile manufacture method of the present invention, there is no strict requirements to the water content in ammonia source, it might even be possible to directly use
Ammoniacal liquor or the ammoniacal liquor of vaporization, it is not required that the entrainer of water byproduct is used as by the use of the ammonia source.Moreover, the nitrile system according to the present invention
Method is made, deposed ammonia caused by aminating reaction or useless ammonia (hereafter referred to collectively as effluent containing ammonia) are found that for the first time in this area
It can be introduced directly into as the supplement in ammonia source in the first step of the manufacture method, realize 100% circulation of ammonia-containing water/gas
Utilize, reduce further the environmental pressure of the manufacture method.
According to the nitrile manufacture method of the present invention, reaction temperature and reaction time generally significantly drop compared to prior art
It is low, thus show the advantages of energy consumption reduces, production cost reduces and manufacture method is simple.
According to the present invention nitrile manufacture method, the reaction mechanism mechanism of reaction is simple, and side reaction is less, aminating reaction by impurity effect compared with
Small, thus purity requirement of the manufacture method to ammonia source and carboxylic acid sources is relatively low, can directly use respective crude product as anti-
Answer raw material.For example the present invention has found that the nitrile manufacture method even can directly use industrial waste containing ammonia for the first time in this area
Or byproduct opens a new way as ammonia source, the thus circulation for various industrial wastes containing ammonia or byproduct or recycling
Footpath, meet current green production theory.
According to the nitrile manufacture method of the present invention, reaction condition is simple, can be also smoothed out (especially even if catalyst is not needed
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.
According to the nitrile manufacture method of the present invention, first step carries out the shorter reaction time under relatively low 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 more than 75%, more than 80%, more than 90%, 95% with
Upper, even more than 98% or higher nitrile yield.
According to the nitrile manufacture method of the present invention, reaction condition is gentle, the less generation of side reaction, it is possible thereby to obtain high-purity
Nitrile product (such as more than 97%).
According to the present invention nitrile manufacture method, 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, so as to be greatly expanded the application of carboxylic acid ammoniation process.
It is raw material due to having used high-purity nitrile made according to the present invention, therefore according to the amine manufacture method of the present invention
Show the advantages of side reaction is few, product amine purity is corresponding high, production cost is low.
Embodiment
The embodiment of the present invention is described in detail below, it should be noted however that the protection of the present invention
Scope is not limited to these specific embodiments, but is determined by claims of annex.
All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference.
Unless otherwise defined, all technologies used in this specification and scientific terminology all have general technology people in art of the present invention
The equivalent that member understands.In case of conflict, including in being defined on, it is defined by this 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, part, device or equipment, the term represents that this specification includes proposing that this area is conventional during the application
Those used, but also include also being of little use at present, but will become art-recognized is suitable for those similar to purpose.
In addition, the various scopes that this specification is mentioned are including their end points, unless expressly stated otherwise,.This
Outside, when amount, concentration or other values or parameter are provided scope, one or more preferred scopes or many preferred upper limit values with it is preferred
During lower limit, it should be interpreted as specifically disclosing by arbitrarily to any range higher limit or preferred value and any range lower limit
Or all scopes that preferred value is formed, whether separately disclose these numerical value pair.
In the context of the present specification, unless otherwise defined explicitly, or the implication is beyond those skilled in the art
Understanding scope, more than 3 carbon atoms hydrocarbon or hydrocarbon derivative group (such as propyl group, propoxyl group, butyl, butane, butylene, fourth
Alkenyl, hexane etc.) identical implication during with titled with prefix " just " is respectively provided with when not titled with prefix " just ".For example propyl group is general
N-propyl is interpreted as, 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 manufacture method (first step
Suddenly any material as ammonia sources (providing ammonia) in), including ammonia various form products such as liquid ammonia, gaseous ammonia,
Ammoniacal liquor and ammoniacal liquor of vaporization etc., be additionally included under the reaction condition of first step (such as it is anti-by the decomposition such as hydrolyzing or thermally decomposing
Should) material (hereinafter referred to as producing ammoniacal substance) of ammonia can be produced, for example the ammonium salt of urea, cyanic acid and inorganic acid can be enumerated
(such as ammonium carbonate and ammonium hydrogen carbonate) etc..According to the nitrile manufacture method of 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 purity requirement of the manufacture method to ammonia source is relatively low.In consideration of it, above and below this specification
Wen Zhong, term " ammonia source " also include containing ammonia or containing it is foregoing 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 (such as from ammonia synthesis process), useless
Ammonia, deposed ammonia (such as nitrile manufacture method from prior art), useless urea water, useless carbon ammonium water etc..As long as in general, should
The species or content of impurity in industrial waste or byproduct in addition to ammonia and water do not produce aobvious to the nitrile manufacture method of the present invention
Write influence (for example making the reduction of nitrile yield 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 manufacture method of the present invention, for example can enumerate hydrogen, nitrogen, sky
Gas and water steam or aqueous water etc., it is sometimes considered as the inert diluent of the manufacture method.Certainly, those skilled in the art pass through
Simple experiment (such as by determining the reduction degree of nitrile yield), it becomes possible to confirm that a certain industrial waste or industry byproduct are
It is no containing or excessively contain the impurity that makes a significant impact of nitrile manufacture method on the present invention, thereby confirm that whether it can be with
Directly apply to the nitrile manufacture method of the present invention.In addition, as needed, those skilled in the art can also be by conventionally known
Technological means, 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
The level that manufacture method is implemented, and as needed, the concentration of ammonia in a certain industrial waste or industry byproduct is concentrated into more
Level that the nitrile manufacture method of the suitable present invention is implemented (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 manufacture method (first
Step) middle any material as carboxylic acid source (providing carboxylic acid), including carboxylic acid starting material is in itself and in the anti-of first step
(such as by hydrolysis or ammonolysis etc.) can produce the material (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 enumerated1-4Straight or branched alkyl ester etc..According to the nitrile manufacture method of the present invention, reaction mechanism mechanism of reaction letter
Single, side reaction is less, and aminating reaction is smaller by impurity effect, and thus purity requirement of the manufacture method to carboxylic acid sources is relatively low
(for example it can be 90% that purity is minimum), can be directly using 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 preferably 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 aromatic series or alicyclic
Ring) on carbon atom.
In the context of the present specification, term " alicyclic polycarboxylic acid " refers 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 " refers 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), now 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 (uses closed reactor), the now reaction in the reaction system the pressure higher than environmental pressure (such as
The self-generated pressure of the reaction system；As long as the safe pressure in production, with regard to there is no particular limitation) under carry out, but not
(such as pressure release or a part of accessory substance of discharge etc.) as needed is excluded, the reaction system is outwardly big in whole course of reaction
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
Put 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 substituting " is referred to optionally by one or more (such as 1 to 5
It is individual, 1 to 4,1 to 3,1 to 2 or 1) selected from halogen, hydroxyl, sulfydryl, amino, amino carbonyl, nitro, oxo, sulphur
Generation, cyano group, C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-6Straight or branched (halo) alkene (oxygen, sulphur, ammonia,
Carbonyl) base, C2-6Straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl, C3-20Cycloalkanes (oxygen, sulphur, ammonia) base,
C3-20Cycloalkyl C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl C2-6Straight or branched (halo) alkene
(oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl C2-6Straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group, C3-20
Cyclenes (oxygen, sulphur, ammonia) base, C3-20Cycloalkenyl group C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6
Straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6Straight or branched (halo) alkynes (oxygen, sulphur, ammonia,
Carbonyl) base, C6-20Aryl, C6-20Fragrant (oxygen, sulphur, ammonia) base, C6-20Aryl C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl)
Base, C6-20Aryl C2-6Straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Straight or branched (halo) alkynes
(oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl, C4-20Heteroaryl (oxygen, sulphur, ammonia) base, C4-20Heteroaryl C1-6Straight or branched (halo)
Alkane (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6Straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6
Straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocyclic radical, C2-20Heterocycle (oxygen, sulphur, ammonia) base, C2-20Heterocyclic radical
C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocyclic radical C2-6Straight or branched (halo) alkene (oxygen, sulphur,
Ammonia, carbonyl) base and C2-20Heterocyclic radical C2-6The substituent of straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base is (in feasible position
Place) substitution.These substituents are when multiple being present, (such as the molecule last-in-chain(LIC) of two substituents between adjacent two substituents
End) it can bond together and form the substituent structure of divalence.Such as two adjacent C1-6Straight or branched alkyl can be with that
This is bonded and forms corresponding alkylen structures.Or two adjacent C1-6Straight or branched alkoxyl can such as form phase
The alkylidene dioxygen based structures answered, adjacent two C1-6Straight or branched alkylamino can such as form corresponding alkylidene two
Amino structure, adjacent two C1-5Straight or branched alkylthio group can such as form corresponding alkylidene disulfide group structure, etc.
Deng.As preferable substituent, for example halogen, hydroxyl, sulfydryl, amino, thio, oxo or C can be enumerated1-6Straight chain or branch
Chain (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base etc..
In the context of the present specification, statement " (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base " is meant that：Alkyl, halo
Alkyl, alkoxy, alkylthio group, alkylamino, alkyl-carbonyl, halogenated alkoxy, halogenated alkylthio, halo alkylamino or alkyl halide
Base carbonyl, statement " (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base " are meant that：Alkenyl, haloalkenyl group, alkenyloxy group, alkenylthio group, alkene ammonia
Base, alkenyl carbonyl, halo alkenyloxy group, halo alkenylthio group, halo enamino or haloalkenyl group carbonyl, state " (halo) 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, epoxide, sulfenyl
Or amino.Here, the halo includes a halo, dihalo, three halos 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 valencys " or its structure for referring to being limited from the term similar to term
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 in the structure (such as group, hydrocarbon chain or compound ring etc.) that is limited from the term
2 different carbon atoms on respectively remove the group that obtains 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 ring such as pentane 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, three ring [2.2.1.02,6] octane ring, norbornane ring,With
Deng loop coil, bridged ring or condensed ring formula is bicyclic or polycyclic naphthene hydrocarbon ring.As the C3-20Cycloalkanes hydrocarbon ring, more preferably C3-15Cycloalkanes hydrocarbon ring.
In the context of the present specification, term " C3-20Cyclenes hydrocarbon ring " refers to foregoing C3-20Cycloalkanes hydrocarbon ring
Group after carbon-carbon single bond (C-C) is replaced by carbon-carbon double bond (C=C) at least one ring.As the C3-20Cycloolefin
Ring, for example cyclobutane ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, ring can be enumerated
The monocyclic cycloalkenyl hydrocarbon rings such as heptadiene ring, cyclo-octatetraene ring, and bicyclopentadiene ring, norbornene ring, norbornadiene ring,It is bicyclic or polycyclic Deng loop coil, bridged ring or condensed ring formula
Cyclenes hydrocarbon ring.As the C3-20Cyclenes hydrocarbon ring, more preferably 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 can to enumerate two or more phenyl ring such as phenyl ring, biphenyl and terphenyl direct with singly-bound
Be connected the group that two or more phenyl ring fusions such as the group formed and naphthalene nucleus, anthracene nucleus, phenanthrene ring form.As the C6-20
Aromatic ring, more preferably 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 the individual 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, pyrazine ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, pteridine ring and acridine ring etc., wherein it is preferred that furan nucleus, thiophene
Fen ring, imidazole ring, pyridine ring and indole ring etc..
In the context of the present specification, term " C2-20Heterocycle " refers to foregoing C3-20Cycloalkanes 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
Group that key or linking group bond together and formed, two or more C3-20Cyclenes hydrocarbon ring via singly-bound or linking group that
This group, two or more C for being bonded and being formed6-20The base that aromatic ring bonds together and formed via singly-bound or linking group
Group, two or more C4-20Group that hetero-aromatic ring bonds together and formed via singly-bound or linking group, two or more C2-20
The group or C that heterocycle bonds together and formed via singly-bound or linking group3-20Cycloalkanes hydrocarbon ring, C3-20Cyclenes hydrocarbon ring,
C6-20Aromatic ring, C4-20Hetero-aromatic ring and C2-20It is two or more by condensing each other or via singly-bound or linker in heterocycle
The group that group bonds together and formed.As the combination group, for example cyclohexyl benzene, tolylthiophene, benzo can be enumerated
Quinoline, phenylmorpholine, cyclohexenyl group pentamethylene, naphthyl norbornane, phenyl adamantane, benzofurane, benzcyclobutane, benzene
Base pyrazine, phenylpyrrole, cyclohexenyl group adamantane, cyclohexyl oxetanes, cyclohexyl morpholine, Huan hexyls isoxazole, benzene
Isoxazole, adamantane isoxazole, ENB butylcyclohexane, norbornene benzene, cyclohexyl ring hexane, cyclohexyl methyl hexamethylene
Alkane, thienyl thiophene, pyrrole radicals pyrroles, pyrrolidinyl pyrroles, benzyl benzene, phenoxy group benzene, thiophenyl benzene, benzyloxy benzene,
Benzyloxy methylene-benzene, styryl benzene, styryl methylene-benzene, phenyl amino phenyl, phenylaminomethyl benzene, hexamethylene methoxy basic ring
Hexane, benzyloxy benzene,
In the context of the present specification, term " linking group " refers to not being bonded key (half bond) containing two in structure
Any group, for example can be-O-；-S-；-NR1-, wherein R1It is H or C1-4Straight or branched alkyl, preferably hydrogen or methyl；
The C optionally substituted1-6Straight or branched alkylene, the C preferably optionally substituted1-4Straight or branched alkylidene, the C optionally substituted2-4
Straight or branched alkenylene or the C optionally substituted2-4Straight or branched alkynylene, the C more preferably optionally substituted1-4Straight chain or branch
Chain alkylidene；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-CH2- O- etc.,
But-O- ,-S- and-NR1Except-situation about being bonded with itself or directly with one another.As the linking group, preferably-O-, optionally
Substituted C1-4Straight or branched alkylidene or its any combination, but except the situation of-O- and itself Direct Bonding.
In the context of the present specification, term " effluent containing ammonia " refers to that the manufacture method in the nitrile of the present invention is (outstanding
It is first step) in after the completion of reaction from reaction system as accessory substance or unreacted raw material discharge containing ammonia
Gaseous state or liquid material (such as water containing ammonia condensing, ammonia-containing water and ammonia-containing exhaust etc.).
Finally, in the case where not clearly indicating, all percentages for being previously mentioned in this specification, number, ratio 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 manufacture method of nitrile, it is characterised in that including first step and second step as described below
Suddenly.
According to first step, make carboxylic acid sources with ammonia source in the reaction temperature T from T1 to T2ALower contact 0.01-2.5 hours
In the reaction time, acid amides intermediate product is obtained, wherein T1 is the fusing point that the carboxylic acid sources are depressed in 1 normal atmosphere and temperature value 245
The greater in DEG C, T2 are the aromatic polycarboxylic acids in boiling point, sublimation temperature and the decomposition temperature that 1 normal atmosphere is depressed
Reckling, on condition that T2 ＞ T1.Preferably, T2-T1 >=10 DEG C.
According to the present invention, the carboxylic acid sources are selected from aromatic polycarboxylic acid, the C of the aromatic polycarboxylic acid1-4Straight chain or
The acid anhydrides of branched alkyl ester (preferably methyl esters) or the aromatic polycarboxylic acid.These carboxylic acid sources can be used alone,
Can also combination of two or more use.
According to the present invention, as the aromatic polycarboxylic acid, for example the compound of following structure can be enumerated.
Wherein, groupFor the n valencys C optionally substituted6-20Aromatic ring or the n valencys C optionally substituted4-20Hetero-aromatic ring.
According to the present invention, n-1 group R be each independently singly-bound, the divalent aliphatic hydrocarbon chain that optionally substitutes, optionally takes
The divalent C in generation3-20Cycloalkanes hydrocarbon ring, the divalent C optionally substituted3-20Cyclenes hydrocarbon ring, the divalent C optionally substituted6-20Aromatic ring, optionally substitute
Divalent C4-20Hetero-aromatic ring, the divalent C optionally substituted2-20Heterocycle or optionally substitute divalent combination group, wherein it is preferred that singly-bound or
The divalent aliphatic hydrocarbon chain optionally substituted.
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)
Saturation or undersaturated straight or branched hydrocarbon chain.
, according to the invention it is preferred to the aliphatic hydrocarbon chain in respectively defining is each independently selected from C1-15(preferably C1-9, such as
C1-3) straight or branched alkane chain, C2-15(preferably C2-9, such as C2-3) straight or branched alkene chain or C2-15(preferably C2-9, than
Such as C2-3) straight or branched alkynes chain, more preferably each independently selected from C1-15(preferably C1-9, such as C1-3) straight or branched alkane
Hydrocarbon chain or C2-15(preferably C2-9, such as C2-3) straight or branched alkene chain.
According to the present invention, when the carbon number of the aliphatic hydrocarbon chain is more than 2 and C -- C single bond is included 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 C1-4Straight or branched alkyl, preferably hydrogen or methyl.The quantity of the C -- C single bond can be one or 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 convenient explanation, do not show its valence state) when, 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 inserting 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 inserting 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 preferably 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, foregoing aromatic polycarboxylic acid 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
(mixing) polybasic carboxylic acid product as industrial (such as oil prodution industry) byproduct etc., as long as impurity or water impurity contained by it
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 aromatic polycarboxylic acid, the C of the aromatic polycarboxylic acid1-4Straight or branched alkyl ester is described
The acid anhydrides of aromatic polycarboxylic acid, which preferably has, is equal to or less than the reaction temperature TAThe fusing point (1 of (being typically up to 325 DEG C)
Normal atmosphere pressure measure).Those skilled in the art can be by consulting correlation technique handbook or passing through conventional determining method
Know (and the boiling that the aromatic polycarboxylic acid is depressed 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
Metered ammonia source or the mode for mixing the two in carboxylic acid sources.The contact is carried out generally according to the mode of interval.
According to the present invention, the ammonia source as it was noted above, but preferably ammoniacal liquor or production the ammoniacal substance aqueous solution, wherein it is preferred that ammonia
Water, more preferably industrial deposed ammonia.Now, the ammonia content of the ammoniacal liquor is generally 10-30wt%, preferably 25-28wt%.
According to the present invention, so-called production ammoniacal substance, refer to decompose and producing under the reaction condition of the first step
The material of ammonifying gas.As the production ammoniacal substance, one be preferably selected from urea, cyanic acid, ammonium carbonate, ammonium hydrogen carbonate and ammonium chloride
Kind or a variety of, the one or more being preferably selected from urea and ammonium hydrogen carbonate, more preferably ammonium hydrogen carbonate.As the production ammoniacal substance
The aqueous solution, for example industrial waste or industry byproduct containing the production ammoniacal substance can be enumerated, such as useless urea water and useless carbon
Ammonium water etc..
According to the present invention, the production ammoniacal substance concentration of the production ammoniacal substance aqueous solution can be such as 20wt% to saturated concentration
(preferably saturated concentration) etc., but it is not limited to this.
According to the present invention, the dosage as the ammonia source so that carboxylic acid sources in terms of carboxyl with NH3That counts is described
The mol ratio in ammonia source reach 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 present invention, the first step is carried out in closed reaction system (such as closed reactor).
According to the present invention, after the first step terminates, by reaction system pressure release to external atmospheric pressure, acid amides is being obtained
Effluent containing ammonia is also obtained while intermediate product., it is preferred according to the present invention that by the effluent containing ammonia (preferably through dense
After contracting or drying) supplement or a part of the circulation-supplied into the first step as the ammonia source.So can accordingly it subtract
Less supplied to the dosage in the fresh ammonia source of the first step, the utilization rate of ammonia raw material is thus improved, and realizes effluent containing ammonia
Efficient Cycle utilize.
It was found by the inventors of the present invention that the first step can also be carried out well even if without using catalyst.Therefore,
According to one preferred embodiment of the invention, the first step generally makes without using when carrying out carboxylic acid ammoniation process in this area
Any catalyst.
According to the present invention, reaction time of the first step is preferably 0.05-2 hours, or 0.1-1.5 hours, or
Person's 0.2-1 hours, either 0.3-0.8 hours or shorter time.
According to the present invention, after the first step terminates, the acid amides intermediate product obtained can enter directly as raw material
Row second step, second step can also be carried out again after temporary wait.Or although not necessarily, among the acid amides obtained
Product can also be washed using weak aqua ammonia etc., to remove the unreacted carboxylic acid sources that may be remained.
According to the present invention, the first step and second step can be carried out in same reaction vessel, can also be
Carry out, be not particularly limited in different reaction vessels (such as tandem reaction vessel).In same reaction vessel
During progress, after the first step terminates, reaction system pressure release to external atmospheric pressure is produced among the acid amides that do not discharge
Thing, reaction system is directly changed into the reaction condition (as described below) of second step, thus reduces the manufacture method
Production cost and production complexity.
According to the second step, the acid amides 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 acid amides intermediate product melts what 1 normal atmosphere was depressed
Point and 300 DEG C of temperature value in the greater, T4 be the acid amides 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 acid amides intermediate product is in the reaction temperature TBUnder be preferably presented as molten condition or liquid
Body state.In consideration of it, the acid amides intermediate product, which preferably has, is equal to or less than the reaction temperature TB(it is typically up to 440
DEG C) fusing point (1 normal atmosphere pressure measure).Those skilled in the art can be by consulting correlation technique handbook or by normal
Rule assay method knows fusing point, boiling point, sublimation temperature and decomposition temperature that these acid amides intermediate products are depressed in 1 normal atmosphere
Deng, therefore repeat no more herein.
According to the present invention, preferably 0.2 to the 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, ammonia source need not be used in the second step.
According to the present invention, the second step can also be in closed reaction system in open reactive system
Carry out, preferably carried out in closed reaction system, to reduce energy consumption.
According to the present invention, the second step can be carried out in the presence of a catalyst, can also be without using catalyst.Make
For the catalyst, for example those conventional use of catalyst when carboxylic acid ammoniation process is carried out in this area can be enumerated, such as five
Two phosphorus, phosphoric acid, phosphate, molecular sieve, aluminum oxide, zinc oxide or composite oxide catalysts etc. are aoxidized, wherein it is preferred that using
Phosphorus pentoxide or phosphoric acid.When in use, these catalyst can be according to the conventional amount used of this area (such as on the basis of weight
Can be the 0.2-10% of the carboxylic acid sources weight, preferably 1-6%) use, it is not particularly limited.
According to a further embodiment of the invention, the reaction temperature TAFor from T1 ' to T2 '.Now, it is 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 325 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 '.Now, it is 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 440 DEG C.On condition that T4 ' ＞ T3 '.It is preferred that
, T4 '-T3 ' >=10 DEG C.
According to a further embodiment of the invention, the T1 is 245 DEG C, either 250 DEG C or 260 DEG C, or
270 DEG C of person, either 280 DEG C or 290 DEG C, either 300 DEG C or 310 DEG C, or 320 DEG C.According to the present invention, one is more entered
The embodiment of one step, the T2 are 325 DEG C, either 320 DEG C or 310 DEG C, either 300 DEG C or 290 DEG C, or 280
℃.On condition that T2 ＞ T1.Preferably, T2-T1 >=10 DEG C.
According to a further embodiment of the invention, the T3 is 300 DEG C, either 310 DEG C or 320 DEG C, or
330 DEG C of person, either 340 DEG C or 350 DEG C.According to a further embodiment of the invention, the T4 is 440 DEG C, or
430 DEG C of person, either 420 DEG C or 410 DEG C, either 400 DEG C or 390 DEG C, either 380 DEG C or 370 DEG C, or 360
DEG C, either 350 DEG C or 340 DEG C, either 330 DEG C or 320 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 carboxylic acid, the acid of the carboxylic acid shown in table 1 below
Acid anhydride or methyl esters (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 or 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 or 0.4 to 1.2 hour, or 0.4 to 1
Hour.
Table 1
| Carboxylic acid | Reaction temperature TA, DEG C | Reaction temperature TB, DEG C |
| Terephthalic acid (TPA) | 310 to 325 | 340 to 430 |
| Phthalic acid | 245 to 325 | 345 to 430 |
| 3,4- pyridinedicarboxylic acids | 270 to 300 | 320 to 440 |
| 1,2,4,5- benzene tetracarboxylic acid | 290 to 310 | 320 to 440 |
| Chloro- 1, the 3- phthalic acids of 2- amino -5- | 255 to 295 | 305 to 330 |
| 2- itrile groups-Isosorbide-5-Nitrae-phthalic acid | 250 to 285 | 300 to 325 |
| 2- amino -5- methoxyl group -1,3- phthalic acids | 260 to 300 | 315 to 335 |
| 2,7- naphthalenedicarboxylic acids | 265 to 305 | 315 to 330 |
| 1,2,3,5,6- benzene pentacarbonic acid | 295 to 315 | 330 to 345 |
| NDA | 265 to 305 | 315 to 335 |
| 5- nitro -1,3- phthalic acids | 275 to 300 | 315 to 335 |
| 5- hydroxyl -1,3- phthalic acids | 270 to 305 | 320 to 345 |
| Isosorbide-5-Nitrae-naphthalenedicarboxylic acid | 305 to 325 | 335 to 350 |
| 1,3,5- benzenetricarboxylic acid | 290 to 315 | 335 to 350 |
| 1,2,4- benzenetricarboxylic acid | 290 to 315 | 330 to 345 |
| Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics | 310 to 325 | 345 to 355 |
| M-phthalic acid | 295 to 310 | 325 to 335 |
| 5,6- quinolinedicarboxylic acids | 275 to 300 | 315 to 335 |
| 6- Ethyl-2-Methyl -3,4- pyridinedicarboxylic acids | 285 to 310 | 325 to 350 |
| 5- amino -3- methyl -2,4- thiophenedicarboxylic acids | 255 to 290 | 315 to 335 |
| 8- methyl -2,3- quinolinedicarboxylic acids | 255 to 290 | 310 to 335 |
| 2- methyl -4,5- sulphur pyrrole dioctyl phthalate | 260 to 295 | 315 to 340 |
| 2- amino -4,5- sulphur pyrrole dioctyl phthalate | 265 to 295 | 315 to 345 |
| NDA | 245 to 290 | 310 to 335 |
| 2- (2- pyridine radicals) -4,5- imidazoles dioctyl phthalate | 255 to 300 | 315 to 345 |
| 4- acetoxy-benzoic acids | 310 to 325 | 340 to 430 |
| 4- propionic acid yl benzoic acids | 310 to 325 | 340 to 430 |
| 4- caproic acid yl benzoic acids | 310 to 325 | 340 to 430 |
| 4- lauric acid yl benzoic acids | 310 to 325 | 340 to 430 |
| 2- nitro -4- caproic acid yl benzoic acids | 315 to 325 | 340 to 400 |
According to the present invention, after the second step terminates, purifying or separation method by routine, you can from second step
Suddenly target nitrile is isolated in the reactant 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 be carried out in the way of this area is conventional, not special
Restriction, as long as target nitrile product can be separated from the reactant 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 now is such as：Vacuum is 25-250mbar, and column bottom temperature is generally 100-320 DEG C, is produced with target nitrile
Boiling point (± 2 DEG C) of the product under the vacuum is used as cut point, is typically such as 80-290 DEG C, but be not limited to this but take
Certainly in specific target nitrile product.As needed, the reflux ratio of the rectifying column can be set as minimum reflux ratio Rmin 1.1-4
Times, number of actual plates is such as 5-200 blocks, but 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 be actually needed (such as predetermined nitrile purity etc.)
Deng the appropriate distillation operation condition of selection, this is all conventionally known.
According to the present invention, as the extraction, for example can enumerate using the target nitrile such as ethyl acetate, chloroform, hexane
The good solvent of product to the reactant mixture (as needed add appropriate 2-5wt% dilute alkaline aqueous solutions be diluted or
After regulation) method that is directly extracted etc..
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, then further purified or separated by the way of distillation.
According to the present invention, by the purifying or separation, can obtain purity for more than 97% (preferably more than 98%, more
It is preferred that more than 99%) target nitrile product.Nitrile purity now such as can be easily measured by gas chromatography etc..
According to the present invention nitrile manufacture method, according to the difference of nitrile product category, it is possible to achieve more than 75%, 80% with
Upper, more than 90%, more than 95%, even more than 98% or higher nitrile yield.
According to the present invention, the nitrile can be used as raw material to be used to manufacture corresponding amine.Therefore, the invention further relates to a kind of amine
Manufacture method, the manufacture method manufactures corresponding amine by hydrogenating the nitrile.
According to the present invention, the hydrogenation can in hydrogenated nitrile, any mode be carried out known to routine according to this area.Than
Such as, can reaction gross pressure be 0.6-5.2MPa, hydrogen partial pressure be 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 hydrogenation 0.2-3 hours (excellent
Select 0.5-2 hours), but this is not limited to sometimes.
, can be directly using this area 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, Ni-B or Ni-Co-B amorphous alloys can be enumerated, 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 from the convenient angle implemented of industrialization, preferably Raney's nickel, such as Aladdin
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 this is not limited to sometimes.
According to the present invention, the hydrogenation is preferably carried out in the presence of solvent (or being diluent), and this is ability
Known to domain.As the solvent, for example water can be enumerated；The alcohol such as methanol, ethanol 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.
The mixed solvent of any combination of ether or these solvents, the wherein preferred alcohol or ethanol and water (volume ratio of ethanol and water
For example be 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
Use.
According to the present invention, as the dosage of the solvent, as long as can effectively improve the heat release situation of reaction and not
Excessive burden is produced to follow-up 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 this is not limited to sometimes.
According to the present invention, as needed, the hydrogenation can also be carried out in the presence of auxiliary agent is hydrogenated.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, 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 this is not limited to sometimes.
According to the present invention, after the hydrogenation terminates, purifying or separation method by routine, you can mixed from reaction
Targeted amine is isolated in compound as product.These purifying or separation method are known in the art, and will not be repeated here.
According to the present invention amine manufacture method, according to the difference of nitrile raw material type, it is possible to achieve more than 85%, 90% with
Upper, more than 95%, even more than 98% or higher amine yield, and the purity of amine product can reach more than 97% (preferably
More than 98%, more preferably more than 99%).
Embodiment
The present invention is illustrated using embodiment in further detail below, but the present invention is not limited to these embodiments.
Amide intermediate prepares embodiment
500g carboxylic acid starting materials (chemistry is pure) and NH are added in 1L reactors3Molal quantity is carboxylic for the carboxylic acid starting material
1.4 times of ammoniacal liquor (NH3Content is 25wt%, industrial goods) or ammonium ion molal quantity carboxylic for the carboxylic acid starting material 1.6
Ammonium bicarbonate aqueous solution (ammonium bicarbonate concentration 30wt%) again, capping kettle, open stirring (600r/min).Make reaction
In reaction temperature TALower carry out TCAfter hour, the content of reactor is sampled, nucleus magnetic hydrogen spectrum and elementary analysis are done, to characterize acyl
Amine intermediate.Specific reaction condition and characterization result are shown in following Table A -1, Table A -2, Table A -3 and Table A -4.These characterization results
Show, the amide intermediate obtained has high purity (more than 99%).
Table A -1
Table A -2
Table A -3
Table A -4
Nitrile product prepares embodiment
The amide intermediate that continues prepares embodiment.The reactor is closed (when the boiling point of amide intermediate at ambient pressure etc.
In or less than following reaction temperature TBWhen) or keep reactor be open state (when the boiling of amide intermediate at ambient 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 vavuum pump, the vacuum in reactor is reached 20-50mbar (according to nitrile
Product species different and accordingly adjust), nitrile product is used as using distillate.The yield of the nitrile product is calculated, and samples and does nuclear-magnetism
Hydrogen is composed and elementary analysis, to characterize obtained nitrile product.Specific reaction condition and characterization result see following Table A -5, A-6,
A-7 and A-8.These characterization results show that the nitrile product obtained has high purity (more than 99%).
In these nitrile products prepare embodiment, in the stage optionally in reaction beginning, 10g is disposably added into reactor
Phosphorus pentoxide is as catalyst.
Table A -5
Table A -6
Table A -7
Table A -8
Amine prepares embodiment
(1) it is hydrogenated with 1L in kettle and adds 100g para-Phthalonitriles and 3g Raney-Ni, 400mL ethanol, is continuously filled with H2,
System pressure in course of reaction is set to be always maintained at 7MPa.After 1h being reacted at 95 DEG C of reaction temperature, cooling.In question response kettle
When temperature is down to room temperature, deflate, by filtering and being recrystallized to give p dimethylamine's (purity is more than 99%), yield is
92wt%.
1H NMR (300MHz, DMSO) δ 7.24 (s, 4H), 4.04 (s, 4H), 1.93 (s, 4H), Elemental
Analysis：C, 70.27；H, 8.53；N, 20.53.
(2) it is hydrogenated with 1L in kettle and adds 100g2,7- naphthalenes dimethoxy nitrile and 3g Raney-Ni, 400mL ethanol, is continuously filled with
H2, system pressure in course of reaction is always maintained at 8MPa.After 1h being reacted at 100 DEG C of reaction temperature, cooling.Question response kettle
When interior temperature is down to room temperature, deflate, by filtering and being recrystallized to give 2,7- naphthalenes dimethylamine (purity is more than 99%), yield
For 93wt%.
1H NMR (300MHz, DMSO) δ 7.64 (s, 0H), 7.62 (s, 0H), 7.49 (d, J=0.8Hz, 1H), 7.38 (s,
0H), 7.36 (s, 0H), 4.02 (s, 4H), 2.01 (s, 4H), Elemental Analysis：C, 77.07；H, 7.18；N,
15.01。
(3) it is hydrogenated with 1L in kettle and adds 100g1,3,5- benzene trimethylsilyl nitriles and 3g Raney-Ni, 400mL ethanol, is continuously filled with
H2, system pressure in course of reaction is always maintained at 8MPa.After 1.5h being reacted at 110 DEG C of reaction temperature, cooling.Question response
When temperature in kettle is down to room temperature, deflate, by filtering and being recrystallized to give 1,3,5- benzene trimethylamines (purity is more than 99%),
Yield is 88wt%.
1H NMR (300MHz, DMSO) δ 7.24 (s, 3H), 4.05 (s, 6H), 1.95 (s, 6H), Elemental
Analysis：C, 65.17；H, 9.05；N, 25.13.
(4) it is hydrogenated with 1L in kettle and adds 100g2- methyl -4,5- sulphur pyrrole dimethoxy nitrile and 3gRaney-Ni, 400mL second
Alcohol, continuously it is filled with H2, system pressure in course of reaction is always maintained at 7MPa.After 1.5h being reacted at 95 DEG C of reaction temperature,
Cooling.When temperature in question response kettle is down to room temperature, deflate, by filtering and being recrystallized to give 2- methyl -4,5- sulphur pyrroles
Dimethylamine (purity is more than 99%), yield 93wt%.
1H NMR (300MHz, DMSO) δ 4.24 (s, 2H), 3.96 (s, 2H), 2.63 (s, 3H), 2.09 (s, 2H), 2.06
(s, 2H), Elemental Analysis：C, 45.4；H, 7.02；N, 26.57.
(5) it is hydrogenated with 1L in kettle and adds 100g4- acetonitrile-bases benzonitrile and 3g Raney-Ni, 400mL ethanol, is continuously filled with
H2, system pressure in course of reaction is always maintained at 8MPa.After 1.5h being reacted at 105 DEG C of reaction temperature, cooling.Question response
When temperature in kettle is down to room temperature, deflate, by filtering and being recrystallized to give 4- ethylamino-s benzene methanamine (purity is more than 99%),
Yield is 88wt%.
1H NMR (300MHz, DMSO) δ 7.23 (s, 1H), 7.21 (s, 1H), 7.10 (s, 1H), 7.07 (s, 1H), 4.04
(s, 2H), 3.13-2.98 (m, 2H), 2.92-2.59 (m, 2H), 1.93 (s, 2H), 1.82 (s, 2H), Elemental
Analysis：C, 71.76；H, 9.35；N, 18.51.
Although the embodiment of the present invention is described in detail above in conjunction with the embodiments, need to refer to
Go out, protection scope of the present invention is not limited to these specific embodiments, but by claims of annex Lai
It is determined that.Those skilled in the art can be carried out in the range of the technological thought of the present invention and purport is not departed to these embodiments
Appropriate change, and the embodiment after these changes is obviously also included within protection scope of the present invention.
Claims (42)
1. a kind of manufacture method of nitrile, it is characterised in that comprise the following steps：
First step：Make carboxylic acid sources with ammonia source in the reaction temperature T from T1 to T2AThe reaction time of lower contact 0.01-2.5 hours,
Acid amides intermediate product is obtained, wherein the carboxylic acid sources are selected from aromatic polycarboxylic acid, the C of the aromatic polycarboxylic acid1-4Straight chain
Or the one or more in the acid anhydrides of branched alkyl ester and the aromatic polycarboxylic acid, the ammonia source are ammoniacal liquor or production ammonia thing
The matter aqueous solution, the greater that T1 is the carboxylic acid sources in 245 DEG C of the fusing point and temperature value that 1 normal atmosphere is depressed, T2 is described
Reckling of the aromatic polycarboxylic acid in boiling point, sublimation temperature and the decomposition temperature that 1 normal atmosphere is depressed, on condition that T2 ＞
T1, wherein the production ammoniacal substance refers to decompose under the reaction condition of first step and producing the material of ammonia, and
The carboxylic acid sources and the ratio in the ammonia source cause carboxylic acid sources in terms of carboxyl with NH3The mol ratio in the ammonia source of meter
Reach 1: 1.1-9.5,
With
Second step：By the acid amides intermediate product in the reaction temperature T from T3 to T4B0.1 to 4.5 hour anti-of lower heat treatment
Between seasonable, the greater that wherein T3 is the acid amides intermediate product in 300 DEG C of the fusing point and temperature value that 1 normal atmosphere is depressed,
T4 is reckling of the acid amides intermediate product in boiling point, sublimation temperature and the decomposition temperature that 1 normal atmosphere is depressed, on condition that
T4 ＞ T3,
The first step is carried out in closed reaction system,
The aromatic polycarboxylic acid refers to
Carbon atom on aromatic ring, and the one or more in the compound with following structural formula：
Wherein, groupFor the n valencys C optionally substituted6-20Aromatic ring or the n valencys C optionally substituted4-20Hetero-aromatic ring；N-1
Group R is each independently singly-bound, optionally substitutes divalent aliphatic hydrocarbon chain, the divalent C optionally substituted3-20Cycloalkanes hydrocarbon ring, optionally
Substituted divalent C3-20Cyclenes hydrocarbon ring, the divalent C optionally substituted6-20Aromatic ring, the divalent C optionally substituted4-20Hetero-aromatic ring, optionally substitute
Divalent C2-20Heterocycle or the divalent combination group optionally substituted；Aliphatic hydrocarbon chain in each definition is each independently selected from C1-15's
Saturation or undersaturated straight or branched hydrocarbon chain；When the carbon number of the aliphatic hydrocarbon chain is more than 2 and in its strand
During comprising 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 C1-4
Straight or branched alkyl；N is 2 to 10 integer,
Term " combination group " refers to two or more C3-20Cycloalkanes hydrocarbon ring bonds together and formed via singly-bound or linking group
Group, two or more C3-20Group that cyclenes hydrocarbon ring bonds together and formed via singly-bound or linking group, two or
Multiple C6-20Group that aromatic ring bonds together and formed via singly-bound or linking group, two or more C4-20Hetero-aromatic ring via
Group that singly-bound or linking group bond together and formed, two or more C2-20Heterocycle via singly-bound or linking group that
This group or C for being bonded and being formed3-20Cycloalkanes hydrocarbon ring, C3-20Cyclenes hydrocarbon ring, C6-20Aromatic ring, C4-20Hetero-aromatic ring and C2-20Heterocycle
In it is two or more by condensing or being bonded together via singly-bound or linking group and the group formed each other,
Term " linking group " refers to-O-；-S-；-NR1-, wherein R1It is H or C1-4Straight or branched alkyl；Optionally substitute
C1-4Straight or branched alkylidene；The C optionally substituted2-4Straight or branched alkenylene；The C optionally substituted2-4Straight or branched Asia alkynes
Base；Or any combination of these linking groups, but-O- ,-S- and-NR1Except-situation about being bonded with itself or directly with one another,
Statement " optionally substituting " is referred to optionally by one or more selected from halogen, hydroxyl, sulfydryl, amino, amino carbonyl, nitre
Base, oxo, thio, cyano group, C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-6Straight or branched (halo) alkene
(oxygen, sulphur, ammonia, carbonyl) base, C2-6Straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl, C3-20Cycloalkanes (oxygen,
Sulphur, ammonia) base, C3-20Cycloalkyl C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl C2-6Straight chain or branch
Chain (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl C2-6Straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20
Cycloalkenyl group, C3-20Cyclenes (oxygen, sulphur, ammonia) base, C3-20Cycloalkenyl group C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base,
C3-20Cycloalkenyl group C2-6Straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6Straight or branched (halo) alkynes
(oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl, C6-20Fragrant (oxygen, sulphur, ammonia) base, C6-20Aryl C1-6Straight or branched (halo) alkane (oxygen,
Sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Straight or branched
(halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl, C4-20Heteroaryl (oxygen, sulphur, ammonia) base, C4-20Heteroaryl C1-6Straight chain or branch
Chain (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6Straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C4-20
Heteroaryl C2-6Straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocyclic radical, C2-20Heterocycle (oxygen, sulphur, ammonia) base,
C2-20Heterocyclic radical C1-6Straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocyclic radical C2-6Straight or branched (halo) alkene
(oxygen, sulphur, ammonia, carbonyl) base and C2-20Heterocyclic radical C2-6The substituent substitution of straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base,
Wherein these substituents can bond together between adjacent two substituents when having multiple and form the substituent of divalence
Structure,
Statement " (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base " is meant that：Alkyl, haloalkyl, alkoxy, alkylthio group, alkylamino,
Alkyl-carbonyl, halogenated alkoxy, halogenated alkylthio, halo alkylamino or halogenated alkyl carbonyl, statement " (halo) alkene (oxygen,
Sulphur, ammonia, carbonyl) base " it is meant that：Alkenyl, haloalkenyl group, alkenyloxy group, alkenylthio group, enamino, alkenyl carbonyl, halo alkenyloxy group,
Halo alkenylthio group, halo enamino or haloalkenyl group carbonyl, statement " (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base " are meant that：
Alkynyl, halo alkynyl, alkynyloxy group, alkynes sulfenyl, alkynes amino, alkynylcarbonyl groups, halo alkynyloxy group, acetylenic halide sulfenyl, acetylenic halide amino
Or halo alkynyl carbonyl, statement " (oxygen, sulphur, ammonia) base " is meant that, epoxide, sulfenyl or amino, wherein the halo bag
Include a halo, dihalo, three halos or perhalogeno.
2. the manufacture method of the nitrile of claim 1, wherein making carboxylic acid sources with ammonia source in the reaction temperature T from T1 to T2ALower contact
In the reaction time of 0.05-2 hours, obtain acid amides intermediate product.
3. the manufacture method of the nitrile of claim 1, wherein making carboxylic acid sources with ammonia source in the reaction temperature T from T1 to T2ALower contact
In the reaction time of 0.1-1.5 hours, obtain acid amides intermediate product.
4. the manufacture method of the nitrile of claim 1, wherein making carboxylic acid sources with ammonia source in the reaction temperature T from T1 to T2ALower contact
In the reaction time of 0.2-1 hours, obtain acid amides intermediate product.
5. the manufacture method of the nitrile of claim 1, wherein making carboxylic acid sources with ammonia source in the reaction temperature T from T1 to T2ALower contact
In the reaction time of 0.3-0.8 hours, obtain acid amides intermediate product.
6. the manufacture method of the nitrile of claim 1, wherein the ammonia source is industrial deposed ammonia.
7. the manufacture method of the nitrile of claim 1, wherein the carboxylic acid sources and the ratio in the ammonia source cause the institute in terms of carboxyl
State carboxylic acid sources and with NH3The mol ratio in the ammonia source of meter reaches 1: 1.3-5.6.
8. the manufacture method of the nitrile of claim 1, wherein the carboxylic acid sources and the ratio in the ammonia source cause the institute in terms of carboxyl
State carboxylic acid sources and with NH3The mol ratio in the ammonia source of meter reaches 1: 1.3-2.5.
9. the manufacture method of the nitrile of claim 1, wherein the carboxylic acid sources and the ratio in the ammonia source cause the institute in terms of carboxyl
State carboxylic acid sources and with NH3The mol ratio in the ammonia source of meter reaches 1: 1.3-1.6.
10. the manufacture method of the nitrile of claim 1, wherein T2-T1 >=10 DEG C.
11. the manufacture method of the nitrile of claim 1, wherein by the acid amides intermediate product in the reaction temperature T from T3 to T4BUnder
The reaction time of heat treatment 0.2 to 3 hour.
12. the manufacture method of the nitrile of claim 1, wherein by the acid amides intermediate product in the reaction temperature T from T3 to T4BUnder
The reaction time of heat treatment 0.3 to 2 hour.
13. the manufacture method of the nitrile of claim 1, wherein by the acid amides intermediate product in the reaction temperature T from T3 to T4BUnder
The reaction time of heat treatment 0.4 to 1.2 hour.
14. the manufacture method of the nitrile of claim 1, wherein by the acid amides intermediate product in the reaction temperature T from T3 to T4BUnder
The reaction time of heat treatment 0.4 to 1 hour.
15. the manufacture method of the nitrile of claim 1, wherein T4-T3 >=10 DEG C.
16. the manufacture 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 325 DEG C of person, 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, 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 440 DEG C of person, on condition that T4 ' ＞ T3 '.
17. the manufacture method of the nitrile of claim 1, wherein T1 are 245 DEG C, either 250 DEG C or 260 DEG C, or 270 DEG C, or
280 DEG C of person, either 290 DEG C or 300 DEG C, either 310 DEG C or 320 DEG C；T2 is 325 DEG C, either 320 DEG C or 310
DEG C, either 300 DEG C or 290 DEG C, or 280 DEG C；T3 be 300 DEG C, either 310 DEG C or 320 DEG C, either 330 DEG C or
340 DEG C, or 350 DEG C；T4 be 440 DEG C, either 430 DEG C or 420 DEG C, either 410 DEG C or 400 DEG C, or 390 DEG C,
Either 380 DEG C or 370 DEG C, either 360 DEG C or 350 DEG C, either 340 DEG C or 330 DEG C, or 320 DEG C.
18. the manufacture method of the nitrile of claim 1, wherein the second step is in open reactive system or closed reaction
Carried out in system.
19. the manufacture method of the nitrile of claim 1, wherein catalyst, and the second step is not used in the first step
Progress or unused catalyst in the presence of a catalyst.
20. the manufacture method of the nitrile of claim 1, wherein the production ammoniacal substance is selected from urea, cyanic acid, ammonium carbonate, ammonium hydrogen carbonate
With the one or more in ammonium chloride.
21. the manufacture method of the nitrile of claim 1, wherein the carboxylic acid sources be carboxylic acid shown in following table, the carboxylic acid acid anhydrides or
Methyl esters, in the first step, reaction temperature TAAs shown in the table, the reaction time is 0.05-2 hours, in the second step
In rapid, reaction temperature TBAs shown in the table, the reaction time is 0.2 to 3 hour,
22. the manufacture method of the nitrile of claim 21, wherein in the first step, the reaction time is 0.1-1.5 hours.
23. the manufacture method of the nitrile of claim 21, wherein in the first step, the reaction time is 0.2-1 hours.
24. the manufacture method of the nitrile of claim 21, wherein in the first step, the reaction time is 0.3-0.8 hours.
25. the manufacture method of the nitrile of claim 21, wherein in the second step, the reaction time is 0.3 to 2 hour.
26. the manufacture method of the nitrile of claim 21, wherein in the second step, the reaction time is 0.4 to 1.2 hour.
27. the manufacture method of the nitrile of claim 21, wherein in the second step, the reaction time is 0.4 to 1 hour.
28. the manufacture method of the nitrile of claim 1, wherein the aliphatic hydrocarbon chain in each definition is each independently selected from C1-15Straight chain
Or branched alkane hydrocarbon chain, C2-15Straight or branched alkene chain or C2-15Straight or branched alkynes chain.
29. the manufacture method of the nitrile of claim 28, wherein the aliphatic hydrocarbon chain is each independently selected from C1-9Straight or branched
Alkane chain, C2-9Straight or branched alkene chain or C2-9Straight or branched alkynes chain.
30. the manufacture method of the nitrile of claim 1, wherein n are 2 to 4 integers.
31. the manufacture method of the nitrile of claim 1, wherein the first step is gone back while the acid amides intermediate product is obtained
Obtain effluent containing ammonia, and using the circulation-supplied of effluent containing ammonia into the first step as the supplement in the ammonia source
An or part.
32. the manufacture method of the nitrile of claim 31, wherein the effluent containing ammonia is by concentrating or drying Posterior circle supply
Supplement or a part into the first step as the ammonia source.
33. the manufacture method of the nitrile of claim 1, wherein in order that described make carboxylic acid sources be contacted with the ammonia source, to molten in advance
The metered ammonia source or make the two mixing in the carboxylic acid sources melted.
34. the manufacture method of the nitrile of claim 1, wherein the contact is carried out in the way of interval.
35. the manufacture method of the nitrile of claim 1, wherein the reaction in the closed reaction system is higher than environmental pressure
Carried out under pressure.
36. the manufacture method of the nitrile of claim 1, wherein the reaction in the closed reaction system is entered at autogenous pressures
OK.
37. the manufacture method of the nitrile of claim 1, wherein the ammonia source is the Industry Waste containing ammonia or containing the production ammoniacal substance
Material or industry byproduct.
38. the manufacture method of the nitrile of claim 1, wherein the carboxylic acid sources use industrial corresponding crude product.
39. the manufacture method of the nitrile of claim 1, wherein the carboxylic acid sources are biological sources.
40. the manufacture method of the nitrile of claim 1, wherein the first step and the second step are in same reaction vessel
Middle progress, or carried out in different reaction vessels.
41. the manufacture method of the nitrile of claim 1, wherein the ammonia content of the ammoniacal liquor is 10-30wt%, and the production ammonia thing
The production ammoniacal substance concentration of the matter aqueous solution is 20wt% to saturated concentration.
42. a kind of manufacture method of amine, it is characterised in that comprise the following steps：
First step：Nitrile is manufactured according to the manufacture method of any one of Claims 1-4 1；With
Second step：The nitrile that hydrogenation first step obtains manufactures amine.
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| CN201810215043.XA CN108164381B (en) | 2014-04-16 | 2014-04-16 | Process for the manufacture of nitriles and their corresponding amines |
| CN201410155943.1A CN105001032B (en) | 2014-04-16 | 2014-04-16 | The manufacture method of nitrile and its corresponding amine |
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| US4973746A (en) * | 1988-10-24 | 1990-11-27 | General Electric Company | Process for converting pet scrap to diamine monomers |
| CN1139668A (en) * | 1995-03-09 | 1997-01-08 | 西巴-盖尔基股份公司 | Preparation for aromatic nitrile compound |
| CN1210852A (en) * | 1997-08-06 | 1999-03-17 | 东丽株式会社 | Process for producing nitrile |
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