CN104557610A - Manufacturing method of nitrile and corresponding amine thereof - Google Patents
Manufacturing method of nitrile and corresponding amine thereof Download PDFInfo
- Publication number
- CN104557610A CN104557610A CN201410522472.3A CN201410522472A CN104557610A CN 104557610 A CN104557610 A CN 104557610A CN 201410522472 A CN201410522472 A CN 201410522472A CN 104557610 A CN104557610 A CN 104557610A
- Authority
- CN
- China
- Prior art keywords
- acid
- ammonia
- reaction
- optional
- straight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
Description
Technical field
The present invention relates to a kind of manufacture method of nitrile and manufactured the method for corresponding amine by this nitrile.
Background technology
Nitrile compounds is the organic compound of kind of cyanic (-CN), is important organic synthesis intermediate.Because cyano group has higher reactive behavior, by hydrogenation reaction, corresponding aminated compounds can be obtained, be the important source material manufacturing medicine, agricultural chemicals, dyestuff, spices, tensio-active agent etc., be widely used in the every field of national economy.Such as, the aliphatic mono of one of its derivative is exactly the basic raw material producing positively charged ion, zwitter-ion and nonionogenic tenside.
Aliphatic mono is divided into low-carbon (LC) aliphatic mono and high-carbon aliphatic mono, and the representative of low-carbon (LC) aliphatic mono comprises methylamine, ethamine and Isopropylamine etc.Although low-carbon (LC) aliphatic mono industry is a small specialty industries, involved downstream industry (mainly comprising medicine, pesticide industry) is on a grand scale, and domestic and international accumulated output value expection is more than 1,300 hundred million yuan.So the industrial chain of low-carbon (LC) aliphatic mono industry has extremely strong pushing effect to Economic development.In recent years, the output of low-carbon (LC) aliphatic mono increases substantially, and at the end of cut-off 2012, the throughput of global low-carbon (LC) aliphatic mono is more than 750,000 tons/year, and annual growth more than 5%, the average annual growth rate of China reaches more than 20%.At present, the main manufacturer of domestic and international low-carbon (LC) aliphatic mono has: German BASF, US Air chemistry, U.S.'s Celanese and Chinese Jian Ye organic chemical industry company limited.Higher aliphatic monoamine is one of main intermediate of three large oil chemistries (fatty alcohol, lipid acid and aliphatic amide), it is mainly for the production of tensio-active agent, the demand of people to soap, sanitising agent and family expenses and personal care product has driven tensio-active agent market to occur significant growth, thus make high fatty amine and derivative demand huge, in the recent period some main tensio-active agent manufacturers of the whole world announce one after another to carry out expanding in China can increasing with satisfied local demand.
Up to the present, aliphatics mononitriles, the particularly preparation method of the industrial employing of higher aliphatic mononitriles normally carboxylic acid ammoniation process, widely used technique is carboxylic acid or derivatives thereof heating for dissolving in open system, what then continue passes into ammonia in liquation, system is reacted under the existence of the catalyzer such as zinc oxide or iron cpd, there is NH in this technique
3the problem such as consumption is excessive, loss of material is serious and productive rate is low.
For this reason, the present inventor is found by research, prior art is when manufacturing nitrile by carboxylic acid ammoniation process, fully carry out to make aminating reaction, require to continue to pass into ammonia as raw material in the whole ammonifying process of carboxylic acid or within the longer reaction times in reaction system, therefore ammonia usage is huge, causes the actual amount of ammonia considerably beyond the consumption needed for aminating reaction, may be the thousands of times of real reaction requirement, cause the utilization ratio of ammonia extremely low thus.In addition, because the utilization ratio of ammonia is extremely low, this aminating reaction creates a large amount of deposed ammonias but cannot recycle, exerts heavy pressures on, be not inconsistent with the environmental protection production theory followed now after discharge to environment.And, aminating reaction due to this technology have employed overall higher temperature of reaction (such as more than 300 DEG C) and overall longer reaction times, therefore energy consumption is higher, cause production cost higher, and there is the loss of reaction mass in reaction process serious (such as causing reaction mass to be entrained with reaction system because continue to pass into ammonia flow) and side reaction more and cause the quality of nitrile product and yield to be difficult to the problems such as effective raising.In addition, in order to obtain higher nitrile yield, prior art also requires to use the extremely low ammonia of water content as reaction raw materials, and utilizes the ammonia passed into continuously in whole aminating reaction process as entrainment agent, discharges the water of reaction by-product at any time.
Therefore, the current present situation of prior art still needs a kind of manufacture method of aliphatics mononitriles, and its preparation method is simple, is applicable to suitability for industrialized production, and can overcomes the foregoing problems existed in prior art manufacture method.
Summary of the invention
The process transformed from carboxylic acid to nitrile by carboxylic acid ammoniation process, need through the intermediate steps transformed from carboxylic acid to acid amides and the final step transformed from acid amides to nitrile.The present inventor finds, if the conversion reaction of described intermediate steps is carried out under temperature of reaction low compared with prior art, not only can complete within the shorter reaction times, but also effectively can avoid the generation of side reaction.And the present inventor finds further, even if described final step is in the non-existent situation of ammonia, also can carry out well.The present inventor also finds, by using the nitrile manufacture method with these two particular step, just can solve foregoing problems, and this completes the present invention.The appearance of the two-step approach novel process of this low-cost high-efficiency of the present invention, for breaking external monopolization, nitrile compounds and the derived product thereof of development China have very important significance.The invention still further relates to and use this nitrile to manufacture the method for amine.
Specifically, the present invention relates to the content of following aspect.
1. a manufacture method for nitrile, is characterized in that, comprises the following steps:
First step: make carboxylic acid sources and ammonia source at the temperature of reaction T from T1 to T2
alower contact 0.01-2.5 hour (or 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, or 0.2 to 0.5 hour) reaction times, obtain acid amides intermediate product, wherein said carboxylic acid sources is selected from aliphatics monocarboxylic acid, the monocarboxylic C of described aliphatics
1-4one or more in straight or branched alkyl ester, the monocarboxylic acid anhydrides of described aliphatics and the monocarboxylic ammonium salt of described aliphatics, the greater in the T1 fusing point that to be described carboxylic acid sources depress at 1 standard atmosphere and temperature value 80 DEG C, T2 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described aliphatics monocarboxylic acid is depressed at 1 standard atmosphere, prerequisite is T2>T1, preferred T2-T1>=10 DEG C, and second step: by described acid amides intermediate product at the temperature of reaction T from T3 to T4
blower thermal treatment 0.1 to 4.5 hour (or 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour, or 0.3 to 0.5 hour) reaction times, the greater wherein in the T3 fusing point that to be described acid amides intermediate product depress at 1 standard atmosphere and temperature value 160 DEG C, T4 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described acid amides intermediate product is depressed at 1 standard atmosphere, prerequisite is T4>T3, preferred T4-T3>=10 DEG C.
2. the manufacture method of the nitrile described in any preceding aspect, wherein said temperature of reaction T
afor 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 or T1+100 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 300 DEG C), prerequisite is T2 ' >T1 '; Described temperature of reaction T
bfor 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 or T3+90 DEG C or T3+100 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 400 DEG C), prerequisite is T4 ' >T3 '.
3. the manufacture method of the nitrile described in any preceding aspect, wherein T1 is 80 DEG C (or 100 DEG C, or 110 DEG C, or 120 DEG C, or 130 DEG C, or 140 DEG C, or 150 DEG C, or 160 DEG C, or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C), T2 is 300 DEG C (or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C, or 190 DEG C, or 180 DEG C, or 170 DEG C, or 160 DEG C, or 150 DEG C, or 140 DEG C, or 130 DEG C, or 120 DEG C, or 110 DEG C), T3 is 160 DEG C (or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C, or 300 DEG C), T4 is 400 DEG C (or 390 DEG C, or 380 DEG C, or 370 DEG C, or 360 DEG C, or 350 DEG C, or 340 DEG C, or 330 DEG C, or 320 DEG C, or 310 DEG C, or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C).
4. the manufacture method of the nitrile described in any preceding aspect, wherein said second step carries out at reduced pressure conditions.
5. the manufacture method of the nitrile described in any preceding aspect, wherein said first step does not use catalyzer, and described second step carries out in the presence of a catalyst or do not use catalyzer.
6. the manufacture method of the nitrile described in any preceding aspect, wherein said ammonia source, by without interruption in a gaseous form, is selected from the ammoniacal liquor of ammonia or vaporization, the Industry Waste ammoniacal liquor of preferred Industry Waste ammonia or vaporization, and in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in the described ammonia source of meter is minimum is 1: 20,1: 30,1: 40 or 1: 50, is up to 1: 500,1: 400,1: 300,1: 200,1: 100 or 1: 80; Or described ammonia source is ammonia or produces ammoniacal substance, preferred Industry Waste ammonia, and in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter is 1: 1.1-2.5, preferably 1: 1.2-2.0, more preferably 1: 1.3-1.6; Or described ammonia source is ammoniacal liquor or produces the ammoniacal substance aqueous solution, preferred ammoniacal liquor, more preferably Industry Waste ammoniacal liquor, and in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter is 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.
7. the manufacture method of the nitrile described in any preceding aspect, wherein, described carboxylic acid sources is the carboxylic acid shown in following table 1, the acid anhydrides of described carboxylic acid or methyl esters, wherein preferred described carboxylic acid; In described first step, temperature of reaction is the T shown in following table 1
a, the higher limit more preferably T of this temperature of reaction
a max-5 DEG C, T
a max-10 DEG C, T
a max-15 DEG C or T
a max-20 DEG C, wherein T
a maxrefer to described T
ahigher limit in table 1 below, the reaction times of described first step is 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, or 0.2 to 0.5 hour; Described second step is in open reactive system or when carrying out under pressurized conditions, and temperature of reaction is the T shown in following table 1
b, the higher limit more preferably T of this temperature of reaction
b max-5 DEG C, T
b max-10 DEG C, T
b max-15 DEG C or T
b max-20 DEG C, wherein T
b maxrefer to described T
bhigher limit in table 1 below, the reaction times of described second step is 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour; When described second step carries out at reduced pressure conditions, temperature of reaction is the T ' shown in following table 1-1
b, the higher limit more preferably T ' of this temperature of reaction
b max-5 DEG C, T '
b max-10 DEG C, T '
b max-15 DEG C or T '
b max-20 DEG C, wherein T '
b maxrefer to described T '
bhigher limit in following table 1-1, the reaction times of described second step is 0.1 to 1.5 hour, or 0.1 to 1.2 hour, or 0.2 to 0.8 hour, or 0.2 to 0.6 hour, or 0.3 to 0.5 hour,
Table I
| Carboxylic acid | Temperature of reaction T A，℃ | Temperature of reaction T B，℃ |
| Acetic acid | 80 to 115 | 160 to 220 |
| Acid just | 140 to 185 | 200 to 250 |
| Laurostearic acid | 140 to 225 | 250 to 330 |
| Stearic acid | 140 to 225 | 250 to 400 |
| Vinylformic acid | 100 to 135 | 160 to 230 |
| Toluylic acid | 160 to 215 | 240 to 275 |
| Phenylpropionic acid | 160 to 220 | 240 to 335 |
| Cinnamic acid | 150 to 225 | 250 to 345 |
| Phenoxy acetic acid | 130 to 215 | 250 to 335 |
| 2,2-biphenyl acetic acid | 180 to 225 | 250 to 390 |
| 3-pyridyl acetic acid | 160 to 225 | 250 to 355 |
| 3-indolyl acetic acid | 180 to 225 | 250 to 400 |
| 3 methylvaleric acid | 125 to 180 | 215 to 315 |
| 9-alkene-octadecanoic acid | 150 to 225 | 245 to 305 |
| 10-alkene-undecanoic acid | 150 to 225 | 255 to 305 |
| 14-methyl-pentadecylic acid | 155 to 215 | 245 to 315 |
| 4-alkynes valeric acid | 95 to 155 | 180 to 225 |
| 10-alkynes valeric acid | 95 to 165 | 180 to 225 |
| 2-Padil | 100 to 155 | 185 to 265 |
| 2-Mono Chloro Acetic Acid | 100 to 155 | 175 to 235 |
| Thiovanic acid | 100 to 155 | 175 to 205 |
| Levulinic acid | 145 to 215 | 245 to 300 |
| Sarkosine | 115 to 155 | 185 to 265 |
| 2-methoxyacetic acid | 115 to 145 | 165 to 225 |
| 4-Bromophenylacetic acid | 155 to 225 | 255 to 315 |
| 2 nitrophenyl-acetic acids | 165 to 205 | 245 to 315 |
| Hexamethylene acetic acid | 135 to 200 | 225 to 295 |
| 1-adamantane acetic acid | 155 to 225 | 250 to 305 |
| Cyclopentaneacetic acid | 145 to 215 | 235 to 285 |
| 2-pimelinketone acetic acid | 135 to 200 | 215 to 285 |
| Bank alkane acetic acid falls in 2- | 145 to 205 | 235 to 295 |
| 2-cyclopentenyl-1-acetic acid | 80 to 145 | 175 to 225 |
| 4-methyl 1-tetrahydrobenzene acetic acid | 100 to 155 | 175 to 215 |
| 2-thiophene acetic acid | 115 to 205 | 225 to 265 |
| 3,4-(methylene-dioxy) toluylic acid | 145 to 225 | 250 to 300 |
| Imidazoles-4-acetic acid | 245 to 285 | 300 to 320 |
| 2-furans acetic acid | 115 to 205 | 235 to 300 |
| 4-croak pyridine acetic acid | 125 to 215 | 235 to 300 |
| Tetrahydropyrans-4-acetic acid | 250 to 300 | 305 to 325 |
Table I-1
| Carboxylic acid | Temperature of reaction T ' B，℃ |
| Acetic acid | 100 to 160 |
| N-caproic acid | 150 to 220 |
| Laurostearic acid | 120 to 210 |
| Stearic acid | 170 to 240 |
| Toluylic acid | 150 to 250 |
| Phenylpropionic acid | 150 to 250 |
| Cinnamic acid | 170 to 270 |
| Phenoxy acetic acid | 180 to 245 |
| 2,2-biphenyl acetic acid | 185 to 250 |
| 3-pyridyl acetic acid | 185 to 250 |
| 3-indolyl acetic acid | 165 to 255 |
| 3 methylvaleric acid | 170 to 240 |
| 9-alkene-octadecanoic acid | 185 to 240 |
| 10-alkene-undecanoic acid | 145 to 200 |
| 14-methyl-pentadecylic acid | 170 to 230 |
| 4-alkynes valeric acid | 100 to 180 |
| 10-alkynes valeric acid | 100 to 180 |
| 2-Padil | 130 to 220 |
| 2-Mono Chloro Acetic Acid | 130 to 220 |
| Thiovanic acid | 125 to 200 |
| Levulinic acid | 180 to 235 |
| Sarkosine | 160 to 225 |
| 2-methoxyacetic acid | 135 to 200 |
| 4-Bromophenylacetic acid | 180 to 230 |
| 2 nitrophenyl-acetic acids | 180 to 240 |
| Hexamethylene acetic acid | 175 to 245 |
| 1-adamantane acetic acid | 175 to 235 |
| Cyclopentaneacetic acid | 175 to 235 |
| 2-pimelinketone acetic acid | 175 to 235 |
| Bank alkane acetic acid falls in 2- | 175 to 235 |
| 2-cyclopentenyl-1-acetic acid | 120 to 185 |
| 4-methyl 1-tetrahydrobenzene acetic acid | 120 to 180 |
| 2-thiophene acetic acid | 140 to 220 |
| 3,4-(methylene-dioxy) toluylic acid | 180 to 240 |
| Imidazoles-4-acetic acid | 185 to 250 |
| 2-furans acetic acid | 180 to 240 |
| 4-croak pyridine acetic acid | 180 to 245 |
| Tetrahydropyrans-4-acetic acid | 195 to 270 |
8. the manufacture method of the nitrile described in any preceding aspect, wherein said aliphatics monocarboxylic acid be selected from the compound with following structural formula one or more:
R-COOH，
Wherein, radicals R is C
1-29(preferred C
1-19) saturated or undersaturated straight or branched alkyl, preferred C
1-29(preferred C
1-19) straight or branched alkyl, C
2-29(preferred C
2-19) straight or branched thiazolinyl or C
2-29(preferred C
2-19) straight or branched alkynyl, more preferably C
1-29(preferred C
1-19) straight or branched alkyl or C
2-29(preferred C
2-19) straight or branched thiazolinyl; Described R is optionally selected from halogen, hydroxyl, sulfydryl, amino, aminocarboxyl, nitro, oxo, sulfo-, cyano group, the optional C replaced by one or more (such as 1 to 4,1 to 3,1 to 2 or 1)
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl, the optional C replaced
3-20cycloalkanes (oxygen, sulphur, ammonia) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group, the optional C replaced
3-20cyclenes (oxygen, sulphur, ammonia) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl, the optional C replaced
6-20virtue (oxygen, sulphur, ammonia) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl, the optional C replaced
4-20assorted virtue (oxygen, sulphur, ammonia) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-20heterocyclic radical, the optional C replaced
2-20heterocycle (oxygen, sulphur, ammonia) base, the optional C replaced
2-20heterocyclic radical C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-20heterocyclic radical C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base and the optional C replaced
2-20heterocyclic radical C
1-6the substituting group of straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base replaces; Described R is also optionally selected from-O-,-S-and-NR by one or more (such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1)
1-(R
1h or C
1-4straight or branched alkyl) assorted group interrupt, prerequisite is when existing multiple, not Direct Bonding between any two assorted groups.
9. the manufacture method of the nitrile described in any preceding aspect, wherein said first step also obtains containing ammonia effluent while the described acid amides intermediate product of acquisition, and using described containing in ammonia effluent circulation-supplied to described first step as described ammonia source supplement or a part of, preferably described containing ammonia effluent be fed to through concentrated or dry Posterior circle in described first step as described ammonia source supplement or a part of.
10. a manufacture method for amine, is characterized in that, comprises the following steps:
First step: manufacture nitrile 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 the following advantages.
According to nitrile manufacture method of the present invention, only use ammonia source (such as ammonia etc.) as reactant in a first step, and do not use ammonia source in the second step completely, therefore the consumption in ammonia source can significantly reduce, and drastically increases the utilization ratio in ammonia source.
According to nitrile manufacture method of the present invention, because the utilization ratio in ammonia source significantly improves, therefore effectively can reduce the deposed ammonia amount that reaction produces, environmental stress is little, conforms to the environmental protection production theory followed now.
According to nitrile manufacture method of the present invention, strict requirement be there is no to the water content in ammonia source, even directly can use the ammoniacal liquor of ammoniacal liquor or vaporization, do not need the entrainment agent utilizing this ammonia source as water byproduct yet.And, according to nitrile manufacture method of the present invention, find that the deposed ammonia that aminating reaction produces or useless ammonia (being referred to as below containing ammonia effluent) directly can be introduced in the first step of this manufacture method as the supplementary of ammonia source in this area first time, achieve 100% recycle of ammonia-containing water/gas, reduce further the environmental stress of this manufacture method.
According to nitrile manufacture method of the present invention, temperature of reaction and reaction times significantly reduce generally compared to prior art, show energy consumption reduction, production cost reduction and the simple advantage of manufacture method thus.
According to nitrile manufacture method of the present invention, reaction mechanism is simple, and side reaction is less, and aminating reaction is less by impurity effect, and the purity requirement of this manufacture method to ammonia source and carboxylic acid sources is lower thus, can directly use respective thick product as reaction raw materials.Such as, the present invention found in this area first time, this nitrile manufacture method even can directly use containing ammonia industrial waste or byproduct as ammonia source, thus for the various circulation containing ammonia industrial waste or byproduct or recycling open a new way, meets current environmental protection production theory.
According to nitrile manufacture method of the present invention, reaction conditions is simple, even if do not need catalyzer also can carry out (especially first step) smoothly, this not only reduces the manufacturing cost of nitrile, and also reduces the complexity of nitrile product later separation or purifying.
According to nitrile manufacture method of the present invention, first step carries out the shorter reaction times under lower temperature of reaction, and do not use ammonia source in the second step completely, therefore reaction mass loss (carrying secretly) because ammonia source supply etc. causes can greatly be reduced, according to the difference of nitrile product species, the present invention can obtain more than 75%, more than 80%, more than 90%, the nitrile yield of more than 95%, even more than 98% or higher.
According to nitrile manufacture method of the present invention, reaction conditions is gentle, and the less generation of side reaction, can obtain highly purified nitrile product (such as more than 97%) thus.
According to nitrile manufacture method of the present invention, the more complicated nitrile of structure (such as containing various heteroatomic nitrile) can be produced by carboxylic acid ammoniation process, this is realize first time in the art, thus has greatly expanded the range of application of carboxylic acid ammoniation process.
According to amine manufacture method of the present invention, be raw material owing to employing high purity nitrile constructed in accordance, therefore show that side reaction is few, the corresponding height of product amine purity, advantage that production cost is low.
Embodiment
Below the specific embodiment of the present invention is described in detail, but it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.
All publications, patent application, patent and other reference that this specification sheets is mentioned all draw in this for reference.Unless otherwise defined, all technology that this specification sheets is used and scientific terminology all have the equivalent that in field belonging to the present invention, those skilled in the art understand.In case of conflict, comprise in being defined in, be as the criterion with this specification sheets.
When this specification sheets with " well known by persons skilled in the art " or " this area conventional known " or similar term describes material, method, parts, device or equipment time, this term represent this specification sheets comprise propose the application time this area routine use those, but also comprise and being also of little use at present, but will become art-recognized for being applicable to those of similar object.
In addition, the various scopes that this specification sheets is mentioned include their end points interior, unless expressly stated otherwise.In addition, when providing scope, one or more preferable range or a lot of preferred upper limit value and preferred lower limit value to amount, concentration or other value or parameter, it should be interpreted as specifically discloses by any all scopes formed any range higher limit or preferred value and any range lower value or preferred value, no matter whether separately disclose these numerical value pair.
In the context of the present specification, unless otherwise defined explicitly, or this implication is beyond the understanding scope of those skilled in the art, hydrocarbon more than 3 carbon atoms or hydrocarbon derivative group (such as propyl group, propoxy-, butyl, butane, butylene, butenyl, hexane etc.) not titled with all have time prefix " just " with titled with implication identical time prefix " just ".Such as, propyl group is generally understood as n-propyl, and butyl is generally understood as normal-butyl.
In the context of the present specification, term " ammonia source " refers to can as any material of ammonia sources (namely providing ammonia) in nitrile manufacture method (first step) of the present invention, comprise the various form goods such as liquid ammonia of ammonia, gaseous ammonia, the ammoniacal liquor of vaporization and ammoniacal liquor etc., under being also included in the reaction conditions of first step (as by hydrolysis or the decomposition reaction such as thermolysis) material (hereinafter referred to as product ammoniacal substance) of ammonia can be produced, such as urea can be enumerated, the ammonium salt (such as volatile salt and bicarbonate of ammonia) etc. of cyanic acid and mineral acid.According to nitrile manufacture method of the present invention, reaction mechanism is simple, and side reaction is less, and aminating reaction is less by impurity effect, and the purity requirement of this manufacture method to ammonia source is lower thus.Given this, in the context of the present specification, term " ammonia source " also comprises containing ammonia or the industrial waste or the industry byproduct that contain aforementioned product ammoniacal substance, comprise various industrial waste or the industry byproduct of gaseous state, liquid state or solid-state form, such as ammonia-containing exhaust (such as from ammonia synthesis process), useless ammonia, deposed ammonia (such as from the nitrile manufacture method of prior art), useless urea water, useless carbon ammonium water etc.Generally speaking, as long as the kind of the impurity in this industrial waste or byproduct except ammonia and water or content do not make a significant impact (such as making the reduction of nitrile yield be no more than 5%) to nitrile manufacture method of the present invention and can directly use, and without the need to carrying out purification process in advance to it.This kind of impurity is generally chemically inert for nitrile manufacture method of the present invention, such as can enumerate hydrogen, nitrogen, air, water vapour or liquid water etc., sometimes be regarded as the inert diluent of this manufacture method.Certainly, those skilled in the art are by simple test (the reduction degree as by measuring nitrile yield), just can confirm whether a certain industrial waste or industry byproduct contain or excessively containing the impurity made a significant impact nitrile manufacture method of the present invention, confirm whether it can directly apply to nitrile manufacture method of the present invention thus.In addition, as required, those skilled in the art also can by conventional known technique means, this kind of impurity contained in a certain industrial waste or industry byproduct is reduced to the level that not remarkably influenced nitrile manufacture method of the present invention is implemented, and as required, the concentration of ammonia in a certain industrial waste or industry byproduct is concentrated into the level (such as the concentration of ammonia or product ammoniacal substance being concentrated into the 10-95wt% accounting for this industrial waste or industry byproduct total amount, preferred 25-95wt%) that nitrile manufacture method of the present invention preferably is implemented.
In the context of the present specification, term " carboxylic acid sources " refers to can as any material of carboxylic acid source (namely providing carboxylic acid) in nitrile manufacture method (first step) of the present invention, comprise carboxylic acid starting material itself and (as by hydrolysis or ammonia solution etc.) can produce free carboxy acid under the reaction conditions of first step material (hereinafter referred to as product carboxylic acid material), such as can enumerate carboxylic acid anhydride and carboxylic acid C
1-4straight or branched alkyl esters etc., also comprise carboxylic acid ammonium sometimes.According to nitrile manufacture method of the present invention, reaction mechanism is simple, side reaction is less, aminating reaction is less by impurity effect, this manufacture method to the purity requirement of carboxylic acid sources also lower (such as purity is minimum can be 90%) thus, directly can use industrial corresponding thick product, such as the industry lipid acid of (such as oil prodution industry) byproduct or mixed fatty acid etc.
In the context of the present invention, term " carboxylic acid " uses it to define the most widely, refers to the compound containing free carboxy (i.e.-COOH).
In the context of the present specification, term " monocarboxylic acid " refers to the compound only containing a free carboxy.
In the context of the present specification, term " open reactive system " refers to this reaction system outwardly atmosphere opening (use open reactive device) from start to finish, and the reaction now in this reaction system is carried out under the pressure (environmental stress) of (being similar to) ambient atmosphere.
In the context of the present specification, term " closed reaction system " refers to this reaction system from start to finish with ambient atmosphere isolated (using closed reactor).According to circumstances, the reaction in this reaction system can at pressure (i.e. pressurized conditions, the such as autogenous pressure higher than environmental stress; As long as the pressure range of safety on producing, with regard to there is no particular limitation) under carry out, but do not get rid of (such as pressure release or discharge a part of by product etc.) as required, this reaction system in whole reaction process outwardly the air short period of time (such as continue 0.05-5 minute, 0.1-4 minute, 0.3-3 minute, 0.5-2 minute or 0.6-1.5 minute etc.) open one or many (such as 1-20 time, 1-10 time, 1-5 time, 1-3 time, 1-2 time or 1 inferior).Or according to circumstances, the reaction in this reaction system can be carried out under the pressure (i.e. reduced pressure) lower than environmental stress.Described reduced pressure can keep certain vacuum tightness by making described reaction system (as by connection vacuum pump) and realize.As the numerical range of described vacuum tightness, be generally 5-1000mbar, preferred 20-500mbar or 50-250mbar.
In the context of the present specification, term " halogen " refers to fluorine, chlorine, bromine and iodine, preferred chlorine and bromine.
In the context of the present specification, statement " optional replacement " refers to and is optionally selected from halogen, hydroxyl, sulfydryl, amino, aminocarboxyl, nitro, oxo, sulfo-, cyano group, C by one or more (such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1)
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkyl, C
3-20cycloalkyl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkyl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkyl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkenyl group, C
3-20cycloalkenyl group C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkenyl group C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
3-20cycloalkenyl group C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
6-20aryl, C
6-20aryl C
1-6straight or branched (halo) alkane (oxygen, sulphur,
Ammonia, carbonyl) base, C
6-20aryl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
6-20aryl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
4-20heteroaryl, C
4-20heteroaryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
4-20heteroaryl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, C
4-20heteroaryl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C
2-20heterocyclic radical, C
2-20heterocyclic radical C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, C
2-20heterocyclic radical C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base and C
2-20heterocyclic radical C
1-6the substituting group of straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base replaces.These substituting groups are when existing multiple, and between two adjacent substituting groups, (such as two substituent molecule chain ends) can bond together and form the substituent structure of divalence.Such as, two adjacent C
1-6straight or branched alkyl can bond together and form corresponding alkylen structures.Or, two adjacent C
1-6straight or branched alkoxyl group such as can form corresponding alkylidene dioxygen based structures, two adjacent C
1-6straight or branched alkylamino such as can form corresponding alkylenediamino structure, two adjacent C
1-5straight or branched alkylthio such as can form corresponding alkylidene group disulfide group structure, etc.As preferred substituting group, such as halogen, hydroxyl, sulfydryl, amino, oxo or C can be enumerated
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base etc.
In the context of the present specification, statement " (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base " implication be: alkyl, haloalkyl, alkoxyl group, alkylthio, alkylamino, alkyl-carbonyl, halogenated alkoxy, halogenated alkylthio, haloalkane amino or halogenated alkyl carbonyl, statement " (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base " implication be: thiazolinyl, haloalkenyl group, alkene oxygen base, alkenylthio group, enamino, alkenyl carbonyl, haloalkene oxygen base, haloalkene sulfenyl, haloalkene amino or haloalkenyl group carbonyl, statement " (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base " implication be: alkynyl, halo alkynyl, alkynyloxy group, alkynes sulfenyl, alkynes is amino, alkynylcarbonyl groups, halo alkynyloxy group, acetylenic halide sulfenyl, acetylenic halide amino or halo alkynylcarbonyl groups.
In the context of the present specification, term " C
3-20cycloalkyl " refer to monocycle, dicyclo or the polycyclic naphthene base with carbon atom on 3-20 ring.As described C
3-20cycloalkyl, such as can enumerate the monocyclic cycloalkyls such as cyclopropyl, cyclohexyl and cyclopentyl, and Bicvclopentyl, decahydronaphthalene naphthyl, adamantyl, spiral shell [2.4] heptane base, spiral shell [4.5] decyl, two rings [3.2.1] octyl, three ring [2.2.1.0
2,6] octyl, norborneol alkyl,
with
in volution, bridged ring or condensed ring formula dicyclo or polycyclic naphthene base.As described C
3-20cycloalkyl, more preferably C
3-15cycloalkyl.
In the context of the present specification, term " C
3-20cycloalkenyl group " refer to aforesaid C
3-20on at least one ring of cycloalkyl, carbon-carbon single bond (C-C) is by the group after carbon-carbon double bond (C=C) replacement.As described C
3-20cycloalkenyl group, such as can enumerate the monocyclic cycloalkenyl such as cyclobutene base, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cycloheptadiene base, cyclooctatetraenyl, and dicyclopentadienyl, norbornene, norbornadiene base,
with
in volution, bridged ring or condensed ring formula dicyclo or multi-ringed cycloolefin base.As described C
3-20cycloalkenyl group, more preferably C
3-15cycloalkenyl group.
In the context of the present specification, term " C
6-20aryl " refer to the aromatic hydrocarbyl with carbon atom on 6-20 ring.As described C
6-20aryl, such as can enumerate the group that two or more phenyl ring such as phenyl, xenyl and terphenyl condenses with two or more phenyl ring such as group and naphthyl, anthryl, phenanthryl that singly-bound is directly connected.As described C
6-20aryl, more preferably phenyl and xenyl.
In the context of the present specification, term " C
4-20heteroaryl " refer to there is heteroatomic aromatic hydrocarbyl on ring that carbon atom and 1-3 on 4-20 ring be selected from oxygen, sulphur and nitrogen.As described C
4-20heteroaryl, such as can enumerate furyl, thienyl, pyrryl, thiazolyl, benzothiazolyl, thiadiazolyl group, imidazolyl, benzimidazolyl-, triazinyl, triazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indyl, quinolyl, pteridyl and acridyl etc., wherein preferred furyl, thienyl, imidazolyl, pyridyl and indyl etc.
In the context of the present specification, term " C
2-20heterocyclic radical " refer to aforesaid C
3-20cycloalkyl or C
3-20on at least one ring of cycloalkenyl group, carbon atom is by the group after the replacement of Sauerstoffatom, sulphur atom or nitrogen-atoms.As described C
2-20heterocyclic radical, such as can enumerate piperidyl, piperazinyl, nitrogen heterocyclic hexenyl, dioxolane base, dioxane base, tetrahydrofuran base, oxetanyl, a word used for translation cyclic group in heptan, pyrrolinyl, tetrahydro pyridyl, tetrahydro-pyrazole base, pyrazolinyl, pyranyl, thiapyran base, Pyrrolidine base, tetrahydro-thienyl, '-aziridino, THP trtrahydropyranyl, tetrahydro thiapyran base and morpholinyl etc., wherein preferred piperidyl, tetrahydrofuran base, THP trtrahydropyranyl etc.
In the context of the present specification, term " containing ammonia effluent " to refer in the manufacture method (especially first step) of nitrile of the present invention after reaction to be carried out in process and/or terminated the gaseous state containing ammonia or liquid material (such as containing ammonia condensing water, ammonia-containing water and ammonia-containing exhaust etc.) of discharging as by product or unreacted raw material from reaction system.
Finally, when clearly not indicating, all percentage ratios, number, ratio etc. mentioned in this specification sheets are all benchmark with weight, unless do not met the routine understanding of those skilled in the art when being benchmark with weight.
The present invention relates to a kind of manufacture method of nitrile, it is characterized in that, comprise first step and the second step of the following stated.
According to this first step of the present invention, make carboxylic acid sources and ammonia source at the temperature of reaction T from T1 to T2
athe lower contact reaction times of 0.01-2.5 hour, obtain acid amides intermediate product, wherein, the greater in the T1 fusing point that to be described carboxylic acid sources depress at 1 standard atmosphere and temperature value 80 DEG C, T2 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described aliphatics monocarboxylic acid is depressed at 1 standard atmosphere, and prerequisite is T2>T1.Preferably, T2-T1 >=10 DEG C.
According to the present invention, described carboxylic acid sources is selected from aliphatics monocarboxylic acid, the monocarboxylic C of described aliphatics
1-4straight or branched alkyl ester (preferred methyl esters), the monocarboxylic acid anhydrides of described aliphatics or the monocarboxylic ammonium salt of described aliphatics.These carboxylic acid sources can be used alone one, also can two or more combinationally use.
According to the present invention, as described aliphatics monocarboxylic acid, the compound of following structure such as can be enumerated.
R-COOH，
Wherein, radicals R is C
1-29(preferred C
1-19) saturated or undersaturated straight or branched alkyl.
According to the present invention, as described radicals R, preferred C
1-29(preferred C
1-19) straight or branched alkyl, C
2-29(preferred C
2-19) straight or branched thiazolinyl or C
2-29(preferred C
2-19) straight or branched alkynyl.
According to the present invention, as described radicals R, more preferably C
1-29(preferred C
1-19) straight or branched alkyl or C
2-29(preferred C
2-19) straight or branched thiazolinyl.
According to the present invention, described R optionally can be selected from halogen, hydroxyl, sulfydryl, amino, aminocarboxyl, nitro, oxo, sulfo-, cyano group, the optional C replaced by one or more (such as 1 to 4,1 to 3,1 to 2 or 1)
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl, the optional C replaced
3-20cycloalkanes (oxygen, sulphur, ammonia) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group, the optional C replaced
3-20cyclenes (oxygen, sulphur, ammonia) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl, the optional C replaced
6-20virtue (oxygen, sulphur, ammonia) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl, the optional C replaced
4-20assorted virtue (oxygen, sulphur, ammonia) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-20heterocyclic radical, the optional C replaced
2-20heterocycle (oxygen, sulphur, ammonia) base, the optional C replaced
2-20heterocyclic radical C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-20heterocyclic radical C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base and the optional C replaced
2-20heterocyclic radical C
1-6the substituting group of straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base replaces in feasible position.
Here, statement " cycloalkanes (oxygen, sulphur, ammonia) base " implication be: cycloalkyloxy, cycloalkylthio or naphthene amino, statement " cyclenes (oxygen, sulphur, ammonia) base " implication be: cyclenes oxygen base, cyclenes sulfenyl or cyclenes amino, statement " virtue (oxygen, sulphur, ammonia) base " implication be: aryloxy, arylthio or virtue amino, statement " assorted virtue (oxygen, sulphur, ammonia) base " implication be: heteroaryloxy, heteroarylthio or assorted virtue amino, statement " heterocycle (oxygen, sulphur, ammonia) base " implication be: heterocyclic oxy group, heterocyclethio or heterocyclic amino group.
As described feasible the position of substitution, such as can enumerate in radicals R the optional position that can be substituted (replacing corresponding hydrogen atom), such as be preferably placed at one end relative with described-COOH on radicals R molecular chain.
According to the present invention's special embodiment, described radicals R is C
1-29(preferred C
1-19) straight chained alkyl or C
2-29(preferred C
2-19) straight-chain alkenyl, described substituting group (one or more) is positioned at the ω end of radicals R molecular chain, and-COOH now is then positioned at its α and holds.
According to the present invention, described R is also optionally selected from-O-,-S-and-NR1-(R by one or more (such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1)
1h or C
1-4straight or branched alkyl, preferred H or methyl) assorted group interrupt, prerequisite is when existing multiple, not Direct Bonding between any two assorted groups.Such as, radicals R is CH
3-CH
2-CH
2-CH
2in-time, had no progeny can obtain CH by an O
3-O-CH
2-CH
2-CH
2-, CH
3-CH
2-O-CH
2-CH
2-and CH
3-CH
2-CH
2-O-CH
2-etc., had no progeny can obtain CH by two O
3-O-CH
2-O-CH
2-CH
2-, CH
3-CH
2-O-CH
2-O-CH
2-and CH
3-O-CH
2-CH
2-O-CH
2-etc., had no progeny can obtain CH by three O
3-O-CH
2-O-CH
2-O-CH
2-.
According to the present invention, as described carboxylic acid sources, aforesaid aliphatics monocarboxylic acid can be used alone one, also can two or more combinationally use.
According to the present invention, described carboxylic acid sources can be biogenetic derivation, such as can enumerate natural acid or as the industry lipid acid of (such as oil prodution industry) byproduct or mixed fatty acid etc., as long as the impurity contained by it or impurity level make the reduction of target nitrile yield be no more than 5%.
According to the present invention, described carboxylic acid sources is at described temperature of reaction T
apreferably be rendered as molten state or liquid state down.Given this, described aliphatics monocarboxylic acid, the monocarboxylic C of described aliphatics
1-4straight or branched alkyl ester or the monocarboxylic acid anhydrides of described aliphatics preferably have and are equal to or less than described temperature of reaction T
athe fusing point (1 standard atmosphere pressure measures) of (being generally up to 300 DEG C).Those skilled in the art by consulting correlation technique handbook or knowing fusing point that these carboxylic acid sources depress at 1 standard atmosphere (and described aliphatics monocarboxylic acid depress at 1 standard atmosphere boiling point, sublimation temperature Sum decomposition temperature etc.) by conventional determining method, therefore can not repeat them here herein.
According to an embodiment of the invention, as the described mode making carboxylic acid sources contact with ammonia source, the mode in the ammonia source to (preferably melting in advance) carboxylic acid sources (such as passing into) without interruption gaseous form such as can be enumerated.
According to this embodiment of the present invention, described ammonia source as mentioned before, the Industry Waste ammoniacal liquor of the ammoniacal liquor, particularly Industry Waste ammonia or vaporization of wherein preferably ammonia or vaporization.Now the ammonia content in described ammonia source can be such as 20-99.9wt%, 25-99.9wt%, 40-99.9wt%, 60-99.9wt%, 75-99.9wt%, 85-99.9wt% or 95-99.9wt%, and all the other are then previously described inert diluents etc.
According to this embodiment of the present invention, (passing into) without interruption described ammonia source in the whole process of described first step.As (totally) consumption in now described ammonia source, as long as the predetermined nitrile yield of the present invention can be realized, be not particularly limited.Such as according to real reaction situation, in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter is minimum can be 1: 20,1: 30,1: 40 or 1: 50 etc., the highest not cause the excess waste in ammonia source to be as the criterion, can be such as 1: 500,1: 400,1: 300,1: 200,1: 100 or 1: 80 etc., but sometimes be not limited to this.
According to this embodiment of the present invention, described first step generally carries out in open reactive system (such as open reactive still).Ammonia source, while being continuously supplied to described reaction system (carboxylic acid sources containing melting), is continuously vented described reaction system containing ammonia effluent.
According to another implementation of the invention, as the described mode making carboxylic acid sources contact with ammonia source, such as can also enumerate to (preferably melting in advance) carboxylic acid sources according to the disposable mode adding ammonia source or make the streams of the two be mixed with each other according to predetermined ratio and react of predetermined ratio.Generally speaking, this contact can be carried out according to modes such as continuous, semicontinuous or intervals, not special restriction.
According to this embodiment of the present invention, described ammonia source as mentioned before, wherein preferred ammonia or produce ammoniacal substance, more preferably Industry Waste ammonia.Now, the ammonia content in described ammonia source can be such as 60-99.9wt%, 80-99.9wt%, 85-99.9wt% or 95-99.9wt%, and all the other are then previously described inert diluents etc.Now, as the consumption in described ammonia source, make in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter reaches 1: 1.1-2.5, and preferably 1: 1.2-2.0, more preferably 1: 1.3-1.6.
According to this embodiment of the present invention, as described ammonia source, ammoniacal liquor can also be used or produce the ammoniacal substance aqueous solution, wherein preferred ammoniacal liquor, more preferably Industry Waste ammoniacal liquor.Wherein, the ammonia content of described ammoniacal liquor is generally 10-30wt%, preferred 25-28wt%.Now, as the consumption in described ammonia source, make in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter reaches 1: 1.1-9.5, and preferably 1: 1.2-7.0, more preferably 1: 1.3-5.6,1: 1.3-2.5,1: 1.3-2.0 or 1: 1.3-1.6.
According to this embodiment of the present invention, so-called produce ammoniacal substance, refer to and can decompose under the reaction conditions of described first step and produce the material of ammonia.As described product ammoniacal substance, be preferably selected from urea, cyanic acid, volatile salt, bicarbonate of ammonia and ammonium chloride one or more, be preferably selected from urea and bicarbonate of ammonia one or more, more preferably bicarbonate of ammonia.
According to this embodiment of the present invention, the product ammoniacal substance concentration ratio of the described product ammoniacal substance aqueous solution as can be 20wt% to saturation concentration (preferred saturation concentration) etc., but be not limited to this.As the aqueous solution of described product ammoniacal substance, the industrial waste more preferably containing this product ammoniacal substance or industry byproduct, such as useless urea water and useless carbon ammonium water etc.
According to this embodiment of the present invention, described first step generally carries out in closed reaction system (such as closed reactor).As required, this first step can carry out in complete closed reaction system, that is, this reaction system does not need outwardly air opening in any form in whole reaction process.Given this, described closed reaction system is generally rendered as pressurized conditions (such as the autogenous pressure of described first step).
According to this embodiment of the present invention, while generation acid amides intermediate product, also discharge containing ammonia effluent as by product in mode that is continuous, semicontinuous or interval to reaction system outside.
According to the present invention preferably, aforementioned any embodiment is obtained containing ammonia effluent (preferably through concentrated or dry after) in circulation-supplied to described first step as described ammonia source supplement or a part of.So corresponding minimizing can be supplied to the consumption in the fresh ammonia source of described first step, improve the utilization ratio of ammonia raw material thus, and the Efficient Cycle realized containing ammonia effluent (such as ammonia-containing water and ammonia-containing exhaust) utilizes.
The present inventor finds, even if described first step does not use in this area normally used any catalyzer when carrying out carboxylic acid ammoniation process can carry out well yet.Therefore, according to the present invention one preferred embodiment, described first step does not use catalyzer.
According to the present invention, although and unnecessary, described first step can carry out in the presence of the solvent, to promote the melting of described carboxylic acid sources.As described solvent, such as can enumerate and anyly can dissolve described carboxylic acid sources but the conversion reaction of this first step be there is no to the solvent of disadvantageous effect, more specifically such as can enumerate the halogenated alkanes solvents such as the organic basic such as the intensive polar solvents such as the aromatic hydrocarbon solvent such as toluene or dimethylbenzene, DMF and DMSO, 2-picoline solvent, methylene dichloride, or water.As the consumption of described solvent, be such as generally the 20-50wt% of described carboxylic acid sources weight, but be sometimes not limited to this.
According to the present invention, the reaction times of described first step is preferably 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, or 0.2 to 0.5 hour or shorter time.
According to the present invention, after described first step terminates, stop the described ammonia source of supply immediately, or remove ammonia source from the reaction system of described first step.
According to the present invention, after described first step terminates, the acid amides intermediate product obtained directly can carry out second step as raw material, also after temporary grade, can carry out second step again.Or, although and unnecessary, the acid amides intermediate product obtained also can utilize weak ammonia etc. to wash, to remove the unreacted carboxylic acid sources that may remain.
According to the present invention, described first step and second step can carry out in same reactor, also can carry out in different reactors, be not particularly limited.When carrying out in same reactor, after described first step terminates, acid amides intermediate product described in not discharging, the reaction conditions of first step is directly changed into the reaction conditions (as mentioned below) of second step, reduce production cost and the production complexity of this manufacture method thus.When carrying out in different reactors, can be connected in series between these reactors, wherein, a reactor is using the discharging of last reactor as charging, makes thus successively to continue according to modes such as continuous, semicontinuous or intervals between described first step and described second step.
According to the present invention, as the reactor involved by described first step or described second step, such as reactor, fixed-bed reactor or fluidized-bed reactor etc. can be enumerated.These reactors only can use one, also can two or more combinationally use, not special restriction.
According to described second step, the described acid amides intermediate product obtained by first step is at the temperature of reaction T from T3 to T4
bthe lower thermal treatment reaction times of 0.1 to 4.5 hour, the greater wherein in the T3 fusing point that to be described acid amides intermediate product depress at 1 standard atmosphere and temperature value 160 DEG C, T4 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described acid amides intermediate product is depressed at 1 standard atmosphere, and prerequisite is T4>T3.Preferably, T4-T3 >=10 DEG C.
According to the present invention, described acid amides intermediate product is at described temperature of reaction T
bpreferably be rendered as molten state or liquid state down.Given this, described acid amides intermediate product preferably has and is equal to or less than described temperature of reaction T
bthe fusing point (1 standard atmosphere pressure measures) of (being generally up to 400 DEG C).Therefore those skilled in the art can not repeat them here fusing point, boiling point, sublimation temperature Sum decomposition temperature etc. that these acid amides intermediate products are depressed at 1 standard atmosphere herein by consulting correlation technique handbook or being known by conventional determining method.
According to the present invention, although and unnecessary, described second step can carry out in the presence of the solvent.As described solvent, such as can enumerate and anyly can dissolve described acid amides intermediate product but the conversion reaction of this second step be there is no to the solvent of disadvantageous effect, more specifically such as can enumerate the organic basic such as the intensive polar solvents such as the aromatic hydrocarbon solvent such as toluene or dimethylbenzene, DMF and DMSO and 2-picoline solvent etc.As the consumption of described solvent, be such as generally the 20-50wt% of described acid amides intermediate product weight, but be sometimes not limited to this.
According to the present invention, preferably 0.2 to the 3 hour reaction times of described second step, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour, or 0.3 to 0.5 hour or shorter time.
According to the present invention, in described second step, do not use ammonia source (than any ammonia source as previously described), such as (completely) stops the supply in described ammonia source.In other words, described second step carries out when there is not described ammonia source.
According to the present invention, described second step can carry out in the presence of a catalyst, also can not use catalyzer.As described catalyzer, such as can enumerate in this area conventional those catalyzer used when carrying out carboxylic acid ammoniation process, more specifically such as can enumerate Vanadium Pentoxide in FLAKES, phosphorus oxychloride, thionyl chloride, phosphoric acid, phosphorus pentachloride, Bugess reagent, TFAA-NEt
3reagent, (COCl)
2-NEt
3-DMSO reagent, methylsulfonyl chloride or titanium tetrachloride etc., wherein preferred Vanadium Pentoxide in FLAKES.In use, these catalyzer can use according to the conventional amount used of this area (0.1-10% of to be such as benchmark with weight can be described acid amides intermediate product weight, preferred 0.2-5%), are not particularly limited.
According to the present invention's further embodiment, described temperature of reaction T
afor from T1 ' to T2 '.Now, 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 or T1+100 DEG C.Described 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 be generally up to 300 DEG C.Prerequisite is T2 ' >T1 '.Preferably, T2 '-T1 ' >=10 DEG C.
According to the present invention's further embodiment, described temperature of reaction T
bfor from T3 ' to T4 '.Now, 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 or T3+90 DEG C or T3+100 DEG C.Described 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 be generally up to 400 DEG C.Prerequisite is T4 ' >T3 '.Preferably, T4 '-T3 ' >=10 DEG C.
According to the present invention one further embodiment, described T1 is 80 DEG C, or 100 DEG C, or 110 DEG C, or 120 DEG C, or 130 DEG C, or 140 DEG C, or 150 DEG C, or 160 DEG C, or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C.According to the present invention one further embodiment, described T2 is 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C, or 190 DEG C, or 180 DEG C, or 170 DEG C, or 160 DEG C, or 150 DEG C, or 140 DEG C, or 130 DEG C, or 120 DEG C, or 110 DEG C.Prerequisite is T2>T1.Preferably, T2-T1 >=10 DEG C.
According to the present invention one further embodiment, described T3 is 160 DEG C, or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C, or 300 DEG C.According to the present invention one further embodiment, described T4 is 400 DEG C, or 390 DEG C, or 380 DEG C, or 370 DEG C, or 360 DEG C, or 350 DEG C, or 340 DEG C, or 330 DEG C, or 320 DEG C, or 310 DEG C, or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C.Prerequisite is T4>T3.Preferably, T4-T3 >=10 DEG C.
According to the present invention, described second step also can carry out in open reactive system in closed reaction system.When described second step carries out in closed reaction system, this reaction system can be pressurization or reduced pressure.Wherein, consider from the angle effectively reducing temperature of reaction, preferred reduced pressure.Described reduced pressure can keep certain vacuum tightness by making described reaction system (as by connection vacuum pump) and realize.Now, the concrete numerical value of described vacuum tightness depends on whether target nitrile product distillation effectively can occur under (making a reservation for) temperature of reaction of described second step and separated from described reaction system, therefore cannot specify without exception.Technician can select suitable vacuum values by consulting relevant technical manual for this reason, or is added their confirmation by simple test, there is not technical difficulty.Even so, as the numerical range of described vacuum tightness, be generally 5-1000mbar, preferred 20-500mbar or 50-250mbar.Now, along with the carrying out of the conversion reaction of described second step, the nitrile product generated distills continuously together with water byproduct from the reaction system of described second step, thus is conducive to molecular balance and moves to the direction of product.By the mode adopting this continuous still battery to remove product in described second step, the temperature of reaction of this step significantly can be reduced and the reaction times of remarkable this step of shortening.Due to the reduction of temperature of reaction and the shortening in reaction times, in this second step, side reaction less occurs, favourable to the yield improving nitrile product thus.By adopting this specific reactive mode, each temperature of reaction T that the temperature of reaction of described second step generally can specify in this context
bthe enterprising step-down in basis of (especially its higher limit) is low 40 to 150 DEG C, preferably further reduction by 40,45,50,55,60,65,70,75,80,85,90,95,100,105,110,115,120,125,130,135,140,145,150 DEG C etc.In addition, the reaction times of described second step generally can shorten 40-80% further, preferably shortens 50-70% further.
According to the present invention one preferred embodiment, described carboxylic acid sources is the carboxylic acid shown in following table 1, the acid anhydrides of described carboxylic acid or methyl esters, wherein preferred described carboxylic acid.
According to the present invention one preferred embodiment, in described first step, temperature of reaction is generally the T shown in following table 1
a, the higher limit more preferably T of this temperature of reaction
a max-5 DEG C, T
a max-10 DEG C, T
a max-15 DEG C or T
a max-20 DEG C, wherein T
a maxrefer to described T
ahigher limit in table 1 below.In described first step, the reaction times is generally 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, or 0.2 to 0.5 hour.
According to the present invention one preferred embodiment, described second step is as previously mentioned in open reactive system or when carrying out under pressurized conditions, and temperature of reaction is generally the T shown in following table 1
b, the higher limit more preferably T of this temperature of reaction
b max-5 DEG C, T
b max-10 DEG C, T
b max-15 DEG C or T
b max-20 DEG C, wherein T
b maxrefer to described T
bhigher limit in table 1 below.Now, in described second step, the reaction times is generally 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour.
Table 1
| Carboxylic acid | Temperature of reaction T A，℃ | Temperature of reaction T B，℃ |
| Acetic acid | 80 to 115 | 160 to 220 |
| N-caproic acid | 140 to 185 | 200 to 250 |
| Laurostearic acid | 140 to 225 | 250 to 330 |
| Stearic acid | 140 to 225 | 250 to 400 |
| Vinylformic acid | 100 to 135 | 160 to 230 |
| Toluylic acid | 160 to 215 | 240 to 275 |
| Phenylpropionic acid | 160 to 220 | 240 to 335 |
| Cinnamic acid | 150 to 225 | 250 to 345 |
| Phenoxy acetic acid | 130 to 215 | 250 to 335 |
| 2,2-biphenyl acetic acid | 180 to 225 | 250 to 390 |
| 3-pyridyl acetic acid | 160 to 225 | 250 to 355 |
| 3-indolyl acetic acid | 180 to 225 | 250 to 400 |
| 3 methylvaleric acid | 125 to 180 | 215 to 315 |
| 9-alkene-octadecanoic acid | 150 to 225 | 245 to 305 |
| 10-alkene-undecanoic acid | 150 to 225 | 255 to 305 |
| 14-methyl-pentadecylic acid | 155 to 215 | 245 to 315 |
| 4-alkynes valeric acid | 95 to 155 | 180 to 225 |
| 10-alkynes valeric acid | 95 to 165 | 180 to 225 |
| 2-Padil | 100 to 155 | 185 to 265 |
| 2-Mono Chloro Acetic Acid | 100 to 155 | 175 to 235 |
| Thiovanic acid | 100 to 155 | 175 to 205 |
| Levulinic acid | 145 to 215 | 245 to 300 |
| Sarkosine | 115 to 155 | 185 to 265 |
| 2-methoxyacetic acid | 115 to 145 | 165 to 225 |
| 4-Bromophenylacetic acid | 155 to 225 | 255 to 315 |
| 2 nitrophenyl-acetic acids | 165 to 205 | 245 to 315 |
| Hexamethylene acetic acid | 135 to 200 | 225 to 295 |
| 1-adamantane acetic acid | 155 to 225 | 250 to 305 |
| Cyclopentaneacetic acid | 145 to 215 | 235 to 285 |
| 2-pimelinketone acetic acid | 135 to 200 | 215 to 285 |
| Bank alkane acetic acid falls in 2- | 145 to 205 | 235 to 295 |
| 2-cyclopentenyl-1-acetic acid | 80 to 145 | 175 to 225 |
| 4-methyl 1-tetrahydrobenzene acetic acid | 100 to 155 | 175 to 215 |
| 2-thiophene acetic acid | 115 to 205 | 225 to 265 |
| 3,4-(methylene-dioxy) toluylic acid | 145 to 225 | 250 to 300 |
| Imidazoles-4-acetic acid | 245 to 285 | 300 to 320 |
| 2-furans acetic acid | 115 to 205 | 235 to 300 |
| 4-croak pyridine acetic acid | 125 to 215 | 235 to 300 |
| Tetrahydropyrans-4-acetic acid | 250 to 300 | 305 to 325 |
According to the present invention one preferred embodiment, when described second step carries out as previously mentioned at reduced pressure conditions, temperature of reaction is generally the T ' shown in following table 1-1
b, the higher limit more preferably T ' of this temperature of reaction
b max-5 DEG C, T '
b max-10 DEG C, T '
b max-15 DEG C or T '
b max-20 DEG C, wherein T '
b maxrefer to described T '
bhigher limit in following table 1-1.Now, in described second step, the reaction times is generally 0.1 to 1.5 hour, or 0.1 to 1.2 hour, or 0.2 to 0.8 hour, or 0.2 to 0.6 hour, or 0.3 to 0.5 hour.
Table 1-1
| Carboxylic acid | Temperature of reaction T ' B，℃ |
| Acetic acid | 100 to 160 |
| N-caproic acid | 150 to 220 |
| Laurostearic acid | 120 to 210 |
| Stearic acid | 170 to 240 |
| Toluylic acid | 150 to 250 |
| Phenylpropionic acid | 150 to 250 |
| Cinnamic acid | 170 to 270 |
| Phenoxy acetic acid | 180 to 245 |
| 2,2-biphenyl acetic acid | 185 to 250 |
| 3-pyridyl acetic acid | 185 to 250 |
| 3-indolyl acetic acid | 165 to 255 |
| 3 methylvaleric acid | 170 to 240 |
| 9-alkene-octadecanoic acid | 185 to 240 |
| 10-alkene-undecanoic acid | 145 to 200 |
| 14-methyl-pentadecylic acid | 170 to 230 |
| 4-alkynes valeric acid | 100 to 180 |
| 10-alkynes valeric acid | 100 to 180 |
| 2-Padil | 130 to 220 |
| 2-Mono Chloro Acetic Acid | 130 to 220 |
| Thiovanic acid | 125 to 200 |
| Levulinic acid | 180 to 235 |
| Sarkosine | 160 to 225 |
| 2-methoxyacetic acid | 135 to 200 |
| 4-Bromophenylacetic acid | 180 to 230 |
| 2 nitrophenyl-acetic acids | 180 to 240 |
| Hexamethylene acetic acid | 175 to 245 |
| 1-adamantane acetic acid | 175 to 235 |
| Cyclopentaneacetic acid | 175 to 235 |
| 2-pimelinketone acetic acid | 175 to 235 |
| Bank alkane acetic acid falls in 2- | 175 to 235 |
| 2-cyclopentenyl-1-acetic acid | 120 to 185 |
| 4-methyl 1-tetrahydrobenzene acetic acid | 120 to 180 |
| 2-thiophene acetic acid | 140 to 220 |
| 3,4-(methylene-dioxy) toluylic acid | 180 to 240 |
| Imidazoles-4-acetic acid | 185 to 250 |
| 2-furans acetic acid | 180 to 240 |
| 4-croak pyridine acetic acid | 180 to 245 |
| Tetrahydropyrans-4-acetic acid | 195 to 270 |
According to the present invention, after described second step terminates, by purifying or the separation method of routine, target nitrile can be isolated as product from the reaction mixture that second step obtains.As described purifying or separation method, such as distillation method and extraction process etc. can be enumerated.
According to the present invention, described distillation method or extraction process can carry out according to the mode of this area routine, are not particularly limited, as long as target nitrile product can be separated from described reaction mixture.
According to the present invention, as described distillation method, such as can enumerate the distillation under vacuum employing rectifying tower, this rectifying tower operational condition is now such as: vacuum tightness is 40-100mbar, column bottom temperature is generally 100-320 DEG C, using the boiling point of target nitrile product under described vacuum tightness (± 2 DEG C) as cut point, be such as generally 80-250 DEG C, but be not limited to this but depend on concrete target nitrile product.As required, the reflux ratio of this rectifying tower can be set as the 1.1-3 of minimum reflux ratio Rmin doubly, and number of actual plates is such as 5-200 block, but is not limited to this but depends on concrete target nitrile product.In addition, the actually operating condition of described rectifying tower is not limited to this, those skilled in the art can select suitable distillation operation condition according to the distillation proterties (such as boiling point and heat decomposition temperature etc.) of target nitrile product, rectifying tower structure (such as plate number etc.) and actual needs (such as predetermined nitrile purity etc.) etc., and this is all conventional known.
According to the present invention, as described extraction process, such as can enumerate and use the good solvent of the target nitrile product such as ethyl acetate, chloroform, hexane described reaction mixture (as required add appropriate 2-5wt% dilute alkaline aqueous solution dilutes or regulates after) to be carried out to the method etc. directly extracted.
According to the present invention, extraction process and distillation method can couplings, extraction process such as first can be utilized to carry out preliminary purifying or separation, then carry out further purifying or separation by distillation method.
According to the present invention, by described purifying or separation, the target nitrile product that can to obtain purity be more than 97% (preferably more than 98%, more preferably more than 99%).Nitrile purity now such as can be measured by vapor-phase chromatography etc. easily.
According to nitrile manufacture method of the present invention, according to the difference of nitrile product species, can realize more than 75%, more than 80%, more than 90%, the nitrile yield of more than 95%, even more than 98% or higher.
According to the present invention, compared with the carboxylic acid ammoniation process of prior art, the temperature of reaction of aforementioned first process step significantly reduces, and the reaction times also significantly shortens.When not being bound by any theory, its reason may be as follows.Owing to generally adopting higher temperature and longer reaction times, while there is the conversion reaction from carboxylic acid to acid amides, also there is the conversion reaction from acid amides (it is from last conversion reaction) to nitrile in the carboxylic acid ammoniation process of prior art.And, because temperature of reaction is higher, the molecular balance of these two kinds of conversion reactions, while respective product direction quick travel, also to respective reactant direction quick travel (reversal reaction), creates a large amount of high reactivity midbody compounds thus in reaction system.Due to self or to each other or very high to the chemically reactive of reactant, while the aforesaid conversion reaction of generation or reversal reaction, also there is various undesirable side reaction further in these high reactivity midbody compounds.And along with the prolongation in reaction times, these side reactions will become more and more serious, and intersection occurs.In order to suppress these side reactions, the carboxylic acid ammoniation process of prior art is had to the huge ammonia source of usage quantity.But nonetheless, because temperature of reaction is higher, the reaction times is longer, a large amount of generations of by product are unavoidable, cause the carboxylic acid ammoniation process of prior art to be difficult to improve yield and the quality (such as high product purity) of nitrile product thus.For this problem of prior art, the present inventor is found by diligent research, only needs can realize under compared with prior art significantly reduced temperature of reaction from carboxylic acid to the conversion reaction of acid amides.And this conversion reaction only needs the shorter reaction times to complete.Because temperature of reaction is lower, the reaction times is shorter, and side reaction seldom occurs.In addition, because temperature of reaction is lower, significantly suppressed from acid amides to the conversion reaction of nitrile, show as in the acid amides intermediate product obtained at described first step and almost can't detect nitrile.Simultaneously, relative various side reaction is also significantly suppressed, the acid amides intermediate product showing as the acquisition of described first step has higher product yield (being generally more than 90%) and product purity (being generally more than 95%), lays a good foundation thus for continuing of described second step.Simultaneously, because the conversion reaction of this first step is quantitatively carried out substantially, and even without the restraining effect in ammonia source, side reaction also seldom occurs, therefore the ammonia utilization ratio of first step of the present invention is very high, causes its ammonia consumption compared with prior art can significantly reduce.
According to the present invention, due to the existence of described first step, even if described second step does not use catalyzer, even if or keep normal pressure, even if or initiatively do not take measures (than reduced pressure as the aforementioned) is separated with reaction system to make nitrile product, also can carry out well, finally obtain nitrile product with higher product yield and higher product purity.This is the phenomenon found this area first time.Although its mechanism is not yet clear, but the present inventor thinks that one of reason may be, described first step completes under lower temperature of reaction within the shorter reaction times, generate some other active intermediates except described acid amides intermediate product, and the conversion reaction of this active intermediate to described second step subsequently shows katalysis, thus effectively promote the generation of target nitrile product.And the present inventor is by concrete verification experimental verification, and this active intermediate is not the carboxylic acid sources that uses as reactant or is reacted and the carboxylic acid of fresh generation by reversal.
According to the present invention, can as raw material for the manufacture of corresponding amine according to the nitrile of aforementioned manufacture.For this reason, the invention still further relates to a kind of manufacture method of amine, this manufacture method manufactures corresponding amine by this nitrile of hydrogenation.
According to the present invention, described hydrogenation can be carried out according to this area conventional known any mode when hydrogenated nitrile.Such as, can be 0.6-5.2MPa in reaction total pressure, hydrogen partial pressure is 0.4-5MPa (such as 2-4MPa), temperature of reaction is under the condition of 70-130 DEG C (such as 80-120 DEG C), in the presence of a hydrogenation catalyst, make described nitrile raw material hydrogenation 0.2-3 hour (preferred 0.5-2 hour), but be sometimes not limited to this.
According to the present invention, as described hydrogenation catalyst, directly can use the conventional various catalyzer for hydrogenating nitriles amine in this area, such as Raney's nickel can be enumerated, the Raney's nickel of the doping such as iron or copper, Ni-B or Ni-Co-B amorphous alloy, loading type Ni-B or Ni-Co-B amorphous alloy, carrier loaded precious metal (such as Pb/C, Pd/C or Rh/C etc.) or composite catalyst (such as Raney's nickel/eight cobalt-carbonyl) etc., wherein from the convenient angle implemented of industrialization, preferred Raney's nickel, such as Aladdin Reagent Company is by specification 50 μm or 150 μm of commercially available Raney's nickels.These hydrogenation catalysts can be used alone, and also can two or more combinationally use.
According to the present invention, the 2-10wt% (such as 2-6wt%) of the consumption of described hydrogenation catalyst to take weight as benchmark can be such as described nitrile raw material, but be sometimes not limited to this.
According to the present invention, described hydrogenation preferably carries out under the existence of solvent (or being called thinner), and this is known in the art.As described solvent, such as water can be enumerated; The alcohol such as methyl alcohol, ethanol and 2-propyl alcohol; The esters such as methyl acetate; The aromatic hydrocarbon such as benzene,toluene,xylene; The naphthenic hydrocarbon such as hexanaphthene; The alkane such as heptane; The arbitrary combination of the ethers such as sherwood oil, ether, dioxane and tetrahydrofuran (THF) or these solvents, the wherein mixed solvent (volume ratio of ethanol and water is such as 0.1: 1 to 1: 0.1, but is not limited to this) etc. of preferred alcohol or ethanol and water.These solvents can be used alone, and also can two or more combinationally use.
According to the present invention, as the consumption of described solvent, as long as the heat release situation of reaction effectively can be improved and do not produce excessive burden to follow-up product separation step, with volume be such as benchmark can for the 1-10 of described nitrile raw material doubly, such as 1-5 doubly, 1-4 doubly, 1-3 doubly or 1-2 doubly etc., but be sometimes not limited to this.
According to the present invention, as required, described hydrogenation can also carry out under the existence of hydrogenation auxiliary agent.As described hydrogenation auxiliary agent, such as the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide can be enumerated.These hydrogenation auxiliary agents can be used alone, and also can two or more combinationally use.
According to the present invention, as the consumption of described hydrogenation auxiliary agent, be such as benchmark with weight can be the 0.3-2wt% (preferred 0.2-1.2wt%) of described nitrile raw material, but sometimes be not limited to this.
According to the present invention, after described hydrogenation terminates, by purifying or the separation method of routine, targeted amine can be isolated as product from reaction mixture.These purifying or separation method are known in the art, and do not repeat them here.
According to the manufacture method of amine of the present invention, according to the difference of nitrile raw material type, can realize more than 85%, more than 90%, the amine yield of more than 95%, even more than 98% or higher, and the purity of amine product can reach more than 97% (preferably more than 98%, more preferably more than 99%).
Embodiment
Below adopt embodiment in further detail the present invention to be described, but the present invention is not limited to these embodiments.
Amide intermediate prepares embodiment A
500g carboxylic acid starting material (chemical pure) is added in 1L opening reactor, open stirring (600r/min), constantly to carboxylic acid starting material, ammonia (chemical pure, water content is 5.1wt%, and flow is 100g/min) is passed into from bottom reactor.Make reaction at temperature of reaction T
aunder carry out T
cafter hour, stop passing into ammonia.The content of reactor is sampled, does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize amide intermediate.Concrete reaction conditions and characterization result are shown in following Table A-1, Table A-2, Table A-3, Table A-4, Table A-5 and Table A-6.These characterization results show, the amide intermediate obtained has high purity (more than 99%).
In this embodiment, described ammonia directly can replace with useless ammonia (from raising sub-petrochemical industry chemical plant, containing 50wt% ammonia of having an appointment, all the other are toluene, oxygen, nitrogen, water vapour, carbon monoxide and carbonic acid gas, and the flow of this useless ammonia is 130g/min).
Table A-1
Table A-2
Table A-3
Table A-4
Table A-5
Table A-6
Nitrile product prepares embodiment A
The amide intermediate that continues prepares embodiment A.Close described reactor (when amide intermediate boiling point is at ambient pressure equal to or less than following temperature of reaction T
btime) or keep reactor to be that open state is (when amide intermediate boiling point is at ambient pressure higher than following temperature of reaction T
btime), continue to stir (600r/min), temperature of reaction is changed into T
b, at this temperature of reaction T
blower maintenance T
dafter hour, reaction completes substantially.Then, capping still also connects vacuum pump, makes the vacuum tightness in reactor reach 20-50mbar (according to the difference of nitrile product species and corresponding adjustment), using overhead product as nitrile product.Calculate the yield of this nitrile product, and sampling does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize obtained nitrile product.Concrete reaction conditions and characterization result are shown in following Table A-7, A-8, A-9, A-10, A-11 and A-12.These characterization results show, the nitrile product obtained has high purity (more than 99%).
Prepare in embodiment at these nitrile products, optionally in the stage that reaction starts, in reactor, the disposable 10g Vanadium Pentoxide in FLAKES that adds is as catalyzer.
Table A-7
Table A-8
Table A-9
Table A-10
Table A-11
Table A-12
Nitrile product prepares embodiment A 1
The amide intermediate that continues prepares embodiment A.Close described reactor, open stirring (600r/min), temperature of reaction is changed into T
b.Described reactor is connected to vacuum pump, take 500mbar as starting point, reduces the vacuum tightness in this reactor gradually, until slip out in thing amide intermediate trace (at the most about 0.5wt%) being detected.Maintain this vacuum tightness, reaction times T
dafter hour, reaction completes substantially.Using overhead product as nitrile product.Calculate the yield of this nitrile product, and sampling does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize obtained nitrile product.Concrete reaction conditions and characterization result are shown in following Table A 1-7, A1-8, A1-9, A1-10, A1-11 and A1-12.These characterization results show, the nitrile product obtained has higher purity (more than 92%).
Prepare in embodiment at these nitrile products, optionally in the stage that reaction starts, in reactor, the disposable 10g Vanadium Pentoxide in FLAKES that adds is as catalyzer.
Table A 1-7
Table A 1-8
Table A 1-9
Table A 1-10
Table A 1-11
Table A 1-12
Amide intermediate prepares Embodiment B
In 1L reactor, add 500g carboxylic acid starting material (chemical pure), and be filled with NH
3the ammonia (water content is 0.5wt%, industrial goods) that mole number is carboxylic 1.3 times of this carboxylic acid starting material, capping still, opens stirring (600r/min).Make reaction at temperature of reaction T
aunder carry out T
cafter hour, the content of reactor is sampled, does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize amide intermediate.Concrete reaction conditions and characterization result are shown in following table B-1, table B-2, table B-3, table B-4, table B-5 and table B-6.These characterization results show, the amide intermediate obtained has high purity (more than 99%).
In this embodiment, described ammonia directly can replace with useless ammonia (from raising sub-petrochemical industry chemical plant, containing 50wt% ammonia of having an appointment, all the other are toluene, oxygen, nitrogen, water vapour, carbon monoxide and carbonic acid gas) or the ammonium ion mole number bicarbonate of ammonia powder (chemical pure) that is carboxylic 1.4 times of this carboxylic acid starting material.
Table B-1
Table B-2
Table B-3
Table B-4
Table B-5
Table B-6
Nitrile product prepares Embodiment B
The amide intermediate that continues prepares Embodiment B.Close described reactor (when amide intermediate boiling point is at ambient pressure equal to or less than following temperature of reaction T
btime) or keep reactor to be that open state is (when amide intermediate boiling point is at ambient pressure higher than following temperature of reaction T
btime), continue to stir (600r/min), temperature of reaction is changed into T
b, at this temperature of reaction T
blower maintenance T
dafter hour, reaction completes substantially.Then, capping still also connects vacuum pump, makes the vacuum tightness in reactor reach 20-50mbar (according to the difference of nitrile product species and corresponding adjustment), using overhead product as nitrile product.Calculate the yield of this nitrile product, and sampling does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize obtained nitrile product.Concrete reaction conditions and characterization result are shown in following table B-7, B-8, B-9, B-10, B-11 and B-12.These characterization results show, the nitrile product obtained has high purity (more than 99%).
Prepare in embodiment at these nitrile products, optionally in the stage that reaction starts, in reactor, the disposable 10g Vanadium Pentoxide in FLAKES that adds is as catalyzer.
Table B-7
Table B-8
Table B-9
Table B-10
Table B-11
Table B-12
Nitrile product prepares Embodiment B 1
The amide intermediate that continues prepares Embodiment B.Close described reactor, open stirring (600r/min), temperature of reaction is changed into T
b.Described reactor is connected to vacuum pump, take 500mbar as starting point, reduces the vacuum tightness in this reactor gradually, until slip out in thing amide intermediate trace (at the most about 0.5wt%) being detected.Maintain this vacuum tightness, reaction times T
dafter hour, reaction completes substantially.Using overhead product as nitrile product.Calculate the yield of this nitrile product, and sampling does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize obtained nitrile product.Concrete reaction conditions and characterization result are shown in following table B1-7, B1-8, B1-9, B1-10, B1-11 and B1-12.These characterization results show, the nitrile product obtained has higher purity (more than 92%).
Prepare in embodiment at these nitrile products, optionally in the stage that reaction starts, in reactor, the disposable 10g Vanadium Pentoxide in FLAKES that adds is as catalyzer.
Table B1-7
Table B1-8
Table B1-9
Table B1-10
Table B1-11
Table B1-12
Amide intermediate prepares Embodiment C
500g carboxylic acid starting material (chemical pure) and NH is added in 1L reactor
3mole number is the ammoniacal liquor (NH of carboxylic 1.4 times of this carboxylic acid starting material
3content is 25wt%, industrial goods), capping still, opens stirring (600r/min).Make reaction at temperature of reaction T
aunder carry out T
cafter hour, the content of reactor is sampled, does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize amide intermediate.Concrete reaction conditions and characterization result are shown in following table C-1, table C-2, table C-3, table C-4, table C-5 and table C-6.These characterization results show, the amide intermediate obtained has high purity (more than 99%).
In this embodiment, described ammoniacal liquor directly can replace with deposed ammonia (from raising sub-petrochemical industry chemical plant, containing 20wt% ammonia of having an appointment, all the other are phenol, water, urea, sodium sulfate and carbonic acid gas) or the ammonium ion mole number ammonium bicarbonate aqueous solution (ammonium bicarbonate concentration is 30wt%) that is carboxylic 1.6 times of this carboxylic acid starting material.
Table C-1
Table C-2
Table C-3
Table C-4
Table C-5
Table C-6
Nitrile product prepares Embodiment C
The amide intermediate that continues prepares Embodiment C.Close described reactor (when amide intermediate boiling point is at ambient pressure equal to or less than following temperature of reaction T
btime) or keep reactor to be that open state is (when amide intermediate boiling point is at ambient pressure higher than following temperature of reaction T
btime), continue to stir (600r/min), temperature of reaction is changed into T
b, at this temperature of reaction T
blower maintenance T
dafter hour, reaction completes substantially.Then, capping still also connects vacuum pump, makes the vacuum tightness in reactor reach 20-50mbar (according to the difference of nitrile product species and corresponding adjustment), using overhead product as nitrile product.Calculate the yield of this nitrile product, and sampling does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize obtained nitrile product.Concrete reaction conditions and characterization result are shown in following table C-7, C-8, C-9, C-10, C-11 and C-12.These characterization results show, the nitrile product obtained has high purity (more than 99%).
Prepare in embodiment at these nitrile products, optionally in the stage that reaction starts, in reactor, the disposable 10g Vanadium Pentoxide in FLAKES that adds is as catalyzer.
Table C-7
Table C-8
Table C-9
Table C-10
Table C-11
Table C-12
Nitrile product prepares Embodiment C 1
The amide intermediate that continues prepares Embodiment C.Close described reactor, open stirring (600r/min), temperature of reaction is changed into T
b.Described reactor is connected to vacuum pump, take 500mbar as starting point, reduces the vacuum tightness in this reactor gradually, until slip out in thing amide intermediate trace (at the most about 0.5wt%) being detected.Maintain this vacuum tightness, reaction times T
dafter hour, reaction completes substantially.Using overhead product as nitrile product.Calculate the yield of this nitrile product, and sampling does nucleus magnetic hydrogen spectrum and ultimate analysis, to characterize obtained nitrile product.Concrete reaction conditions and characterization result are shown in following table C1-7, C1-8, C1-9, C1-10, C1-11 and C1-12.These characterization results show, the nitrile product obtained has higher purity (more than 92%).
Prepare in embodiment at these nitrile products, optionally in the stage that reaction starts, in reactor, the disposable 10g Vanadium Pentoxide in FLAKES that adds is as catalyzer.
Table C1-7
Table C1-8
Table C1-9
Table C1-10
Table C1-11
Table C1-12
Amine prepares embodiment
(1) in 1L hydrogenation still, add the own nitrile of 100g and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 6MPa.React 0.5h at temperature of reaction 90 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain hexylamine (purity is more than 99%) by filtration and recrystallization, yield is 92wt%.
1h NMR (300MHz, DMSO) δ 2.69 (q, J=6.2Hz, 2H), 1.68 (s, 2H), 1.06 (t, J=6.2Hz, 3H), ultimate analysis: C, 52.86; H, 15.35; N, 30.85.
(2) in 1L hydrogenation still, add 100g lauronitrile and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 7MPa.React 0.5h at temperature of reaction 95 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain amino dodecane (purity is more than 99%) by filtration and recrystallization, yield is 93wt%.
1h NMR (300MHz, DMSO) δ 2.74 (t, J=7.6Hz, 2H), 1.73 (s, 2H), 1.51 (qd, J=7.6,0.6Hz, 2H), 1.41-1.23 (m, 18H), 0.99-0.89 (m, 3H), ultimate analysis: C, 77.01; H, 13.79; N, 7.07.
(3) in 1L hydrogenation still, add 100g benzyl cyanide and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 7MPa.React 1h at temperature of reaction 105 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain phenylethylamine (purity is more than 99%) by filtration and recrystallization, yield is 91wt%.
1h NMR (300MHz, DMSO) δ 7.25 (s, 1H), 7.21 (d, J=7.3Hz, 1H), 6.90 (t, J=1.8Hz, 1H), 6.87-6.84 (m, 1H), 6.80 (s, 1H), 2.81 (dd, J=11.7,4.1Hz, 2H), 1.82 (s, 2H), ultimate analysis: C, 79.11; H, 8.96; N, 10.88..
(4) in 1L hydrogenation still, add 100g benzene oxygen acetonitrile and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 7MPa.React 1h at temperature of reaction 90 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain phenoxy ethylamine (purity is more than 99%) by filtration and recrystallization, yield is 93wt%.
1h NMR (300MHz, DMSO) δ 7.27 (s, 1H), 7.23 (d, J=7.3Hz, 1H), 6.93 (t, J=1.8Hz, 1H), 6.92-6.90 (m, 1H), 6.90 (s, 1H), 4.16 (t, J=4.2Hz, 2H), 3.37 (t, J=4.2Hz, 2H), 1.92 (s, 2H), ultimate analysis: C, 68.76; H, 8.11; N, 11.80.
(5) in 1L hydrogenation still, add 100g 3-pyridylacetonitrile and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 7MPa.React 1h at temperature of reaction 100 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain 3-PEA (purity is more than 99%) by filtration and recrystallization, yield is 89wt%.
1h NMR (300MHz, DMSO) δ 8.44-8.32 (m, 1H), 8.32-8.24 (m, 1H), 7.57 (dt, J=7.5,1.5Hz, 1H), 7.24 (t, J=7.5Hz, 1H), 3.04 (dd, J=11.6,4.0Hz, 2H), 2.78 (dd, J=11.6,4.0Hz, 2H), 1.82 (s, 2H), ultimate analysis: C, 67.45; H, 8.07; N, 21.43.
(6) in 1L hydrogenation still, add 100g hexamethylene acetonitrile and 3g Raney-Ni, 400mL ethanol, be filled with H continuously
2, make system pressure in reaction process be always maintained at 7MPa.React 1.5h at temperature of reaction 105 DEG C after, cooling.When temperature in question response still is down to room temperature, venting, obtain cyclohexyl amine (purity is more than 99%) by filtration and recrystallization, yield is 94wt%.
1h NMR (300MHz, DMSO) δ 2.73 (t, J=7.7Hz, 2H), 1.76 (d, J=5.7Hz, 2H), 1.74-1.70 (m, 2H), 1.69-1.50 (m, 2H), 1.51-1.39 (m, 2H), 1.38-1.25 (m, 1H), 1.05-0.86 (m, 2H), ultimate analysis: C, 74.28; H, 12.79; N, 10.83.
Nitrile product prepares Comparative examples A
In 1L opening reactor, add 400g n-caproamide (analytical pure), open and stir (600r/min), make temperature of reaction be T
b=225 DEG C, at this temperature of reaction T
blower maintenance T
dafter=1 hour, according to preparing the same mode capping still of embodiment A with nitrile product and connecting vacuum pump, using overhead product as nitrile product.As calculated and analyze, the yield of nitrile-hexyl product is 35%, and purity is 90%.
Nitrile product prepares comparative example B
In 1L opening reactor, add 400g n-caproamide (analytical pure) and 100g n-caproic acid (analytical pure), open and stir (600r/min), make temperature of reaction be T
b=225 DEG C, at this temperature of reaction T
blower maintenance T
dafter=1 hour, according to preparing the same mode capping still of embodiment A with nitrile product and connecting vacuum pump, using overhead product as nitrile product.As calculated and analyze, the yield of nitrile-hexyl product is 40%, and purity is 92%.
Although be described in detail the specific embodiment of the present invention above in conjunction with the embodiments, it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.Those skilled in the art can carry out suitable change to these embodiments in the scope not departing from technological thought of the present invention and purport, and the embodiment after these changes is obviously also included within protection scope of the present invention.
Claims (10)
1. a manufacture method for nitrile, is characterized in that, comprises the following steps:
First step: make carboxylic acid sources and ammonia source at the temperature of reaction T from T1 to T2
alower contact 0.01-2.5 hour (or 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, or 0.2 to 0.5 hour) reaction times, obtain acid amides intermediate product, wherein said carboxylic acid sources is selected from aliphatics monocarboxylic acid, the monocarboxylic C of described aliphatics
1-4one or more in straight or branched alkyl ester, the monocarboxylic acid anhydrides of described aliphatics and the monocarboxylic ammonium salt of described aliphatics, the greater in the T1 fusing point that to be described carboxylic acid sources depress at 1 standard atmosphere and temperature value 80 DEG C, T2 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described aliphatics monocarboxylic acid is depressed at 1 standard atmosphere, prerequisite is T2 > T1, preferred T2-T1>=10 DEG C, and second step: by described acid amides intermediate product at the temperature of reaction T from T3 to T4
blower thermal treatment 0.1 to 4.5 hour (or 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour, or 0.3 to 0.5 hour) reaction times, the greater wherein in the T3 fusing point that to be described acid amides intermediate product depress at 1 standard atmosphere and temperature value 160 DEG C, T4 is boiling point, the reckling in sublimation temperature Sum decomposition temperature that described acid amides intermediate product is depressed at 1 standard atmosphere, prerequisite is T4 > T3, preferred T4-T3>=10 DEG C.
2. the manufacture method of the nitrile of claim 1, wherein said temperature of reaction T
afor 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 or T1+100 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 300 DEG C), prerequisite is T2 ' > T1 '; Described temperature of reaction T
bfor 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 or T3+90 DEG C or T3+100 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 400 DEG C), prerequisite is T4 ' > T3 '.
3. the manufacture method of the nitrile of claim 1, wherein T1 is 80 DEG C (or 100 DEG C, or 110 DEG C, or 120 DEG C, or 130 DEG C, or 140 DEG C, or 150 DEG C, or 160 DEG C, or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C), T2 is 300 DEG C (or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C, or 190 DEG C, or 180 DEG C, or 170 DEG C, or 160 DEG C, or 150 DEG C, or 140 DEG C, or 130 DEG C, or 120 DEG C, or 110 DEG C), T3 is 160 DEG C (or 170 DEG C, or 180 DEG C, or 190 DEG C, or 200 DEG C, or 210 DEG C, or 220 DEG C, or 230 DEG C, or 240 DEG C, or 250 DEG C, or 300 DEG C), T4 is 400 DEG C (or 390 DEG C, or 380 DEG C, or 370 DEG C, or 360 DEG C, or 350 DEG C, or 340 DEG C, or 330 DEG C, or 320 DEG C, or 310 DEG C, or 300 DEG C, or 290 DEG C, or 280 DEG C, or 270 DEG C, or 260 DEG C, or 250 DEG C, or 240 DEG C, or 230 DEG C, or 220 DEG C, or 210 DEG C, or 200 DEG C).
4. the manufacture method of the nitrile of claim 1, wherein said second step carries out at reduced pressure conditions.
5. the manufacture method of the nitrile of claim 1, wherein said first step does not use catalyzer, and described second step carries out in the presence of a catalyst or do not use catalyzer.
6. the manufacture method of the nitrile of claim 1, wherein said ammonia source, by without interruption in a gaseous form, is selected from the ammoniacal liquor of ammonia or vaporization, the Industry Waste ammoniacal liquor of preferred Industry Waste ammonia or vaporization, and in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in the described ammonia source of meter is minimum is 1: 20,1: 30,1: 40 or 1: 50, is up to 1: 500,1: 400,1: 300,1: 200,1: 100 or 1: 80; Or described ammonia source is ammonia or produces ammoniacal substance, preferred Industry Waste ammonia, and in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter is 1: 1.1-2.5, preferably 1: 1.2-2.0, more preferably 1: 1.3-1.6; Or described ammonia source is ammoniacal liquor or produces the ammoniacal substance aqueous solution, preferred ammoniacal liquor, more preferably Industry Waste ammoniacal liquor, and in the described carboxylic acid sources of carboxyl and with NH
3the mol ratio in described ammonia source of meter is 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.
7. the manufacture method of the nitrile of claim 1, wherein, described carboxylic acid sources is the carboxylic acid shown in following table 1, the acid anhydrides of described carboxylic acid or methyl esters, wherein preferred described carboxylic acid; In described first step, temperature of reaction is the T shown in following table 1
a, the higher limit more preferably T of this temperature of reaction
a max-5 DEG C, T
a max-10 DEG C, T
a max-15 DEG C or T
a max-20 DEG C, wherein T
a maxrefer to described T
ahigher limit in table 1 below, the reaction times of described first step is 0.05-2 hour, or 0.1-1.5 hour, or 0.2-1 hour, or 0.3-0.8 hour, or 0.2 to 0.5 hour; Described second step is in open reactive system or when carrying out under pressurized conditions, and temperature of reaction is the T shown in following table 1
b, the higher limit more preferably T of this temperature of reaction
b max-5 DEG C, T
b max-10 DEG C, T
b max-15 DEG C or T
b max-20 DEG C, wherein T
b maxrefer to described T
bhigher limit in table 1 below, the reaction times of described second step is 0.2 to 3 hour, or 0.3 to 2 hour, or 0.4 to 1.2 hour, or 0.4 to 1 hour; When described second step carries out at reduced pressure conditions, temperature of reaction is the T ' shown in following table 1-1
b, the higher limit more preferably T ' of this temperature of reaction
b max-5 DEG C, T '
b max-10 DEG C, T '
b max-15 DEG C or T '
b max-20 DEG C, wherein T '
b maxrefer to described T '
bhigher limit in following table 1-1, the reaction times of described second step is 0.1 to 1.5 hour, or 0.1 to 1.2 hour, or 0.2 to 0.8 hour, or 0.2 to 0.6 hour, or 0.3 to 0.5 hour,
Table 1
Table 1-1
8. the manufacture method of the nitrile of claim 1, wherein said aliphatics monocarboxylic acid be selected from the compound with following structural formula one or more:
R-COOH，
Wherein, radicals R is C
1-29(preferred C
1-19) saturated or undersaturated straight or branched alkyl, preferred C
1-29(preferred C
1-19) straight or branched alkyl, C
2-29(preferred C
2-19) straight or branched thiazolinyl or C
2-29(preferred C
2-19) straight or branched alkynyl, more preferably C
1-29(preferred C
1-19) straight or branched alkyl or C
2-29(preferred C
2-19) straight or branched thiazolinyl; Described R is optionally selected from halogen, hydroxyl, sulfydryl, amino, aminocarboxyl, nitro, oxo, sulfo-, cyano group, the optional C replaced by one or more (such as 1 to 4,1 to 3,1 to 2 or 1)
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl, the optional C replaced
3-20cycloalkanes (oxygen, sulphur, ammonia) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkyl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group, the optional C replaced
3-20cyclenes (oxygen, sulphur, ammonia) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
3-20cycloalkenyl group C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl, the optional C replaced
6-20virtue (oxygen, sulphur, ammonia) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
6-20aryl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl, the optional C replaced
4-20assorted virtue (oxygen, sulphur, ammonia) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
4-20heteroaryl C
1-6straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-20heterocyclic radical, the optional C replaced
2-20heterocycle (oxygen, sulphur, ammonia) base, the optional C replaced
2-20heterocyclic radical C
1-6straight or branched (halo) alkane (oxygen, sulphur, ammonia, carbonyl) base, the optional C replaced
2-20heterocyclic radical C
1-6straight or branched (halo) alkene (oxygen, sulphur, ammonia, carbonyl) base and the optional C replaced
2-20heterocyclic radical C
1-6the substituting group of straight or branched (halo) alkynes (oxygen, sulphur, ammonia, carbonyl) base replaces; Described R is also optionally selected from-O-,-S-and-NR by one or more (such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1)
1-(R
1h or C
1-4straight or branched alkyl) assorted group interrupt, prerequisite is when existing multiple, not Direct Bonding between any two assorted groups.
9. the manufacture method of the nitrile of claim 1, wherein said first step also obtains containing ammonia effluent while the described acid amides intermediate product of acquisition, and using described containing in ammonia effluent circulation-supplied to described first step as described ammonia source supplement or a part of, preferably described containing ammonia effluent be fed to through concentrated or dry Posterior circle in described first step as described ammonia source supplement or a part of.
10. a manufacture method for amine, is characterized in that, comprises the following steps:
First step: manufacture nitrile according to the manufacture method of any one of claim 1 to 9; With
Second step: the nitrile that hydrogenation first step obtains manufactures amine.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810214191.XA CN108586178B (en) | 2013-10-10 | 2014-09-29 | Process for the manufacture of nitriles and their corresponding amines |
| CN201410522472.3A CN104557610B (en) | 2013-10-10 | 2014-09-29 | The manufacture method of nitrile and its corresponding amine |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104743649 | 2013-10-10 | ||
| CN201310474364 | 2013-10-10 | ||
| CN201310474361 | 2013-10-10 | ||
| CN2013104743615 | 2013-10-10 | ||
| CN201310474362X | 2013-10-10 | ||
| CN201310474362 | 2013-10-10 | ||
| CN201410522472.3A CN104557610B (en) | 2013-10-10 | 2014-09-29 | The manufacture method of nitrile and its corresponding amine |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810214191.XA Division CN108586178B (en) | 2013-10-10 | 2014-09-29 | Process for the manufacture of nitriles and their corresponding amines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104557610A true CN104557610A (en) | 2015-04-29 |
| CN104557610B CN104557610B (en) | 2018-04-27 |
Family
ID=53074789
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410522472.3A Active CN104557610B (en) | 2013-10-10 | 2014-09-29 | The manufacture method of nitrile and its corresponding amine |
| CN201810214191.XA Active CN108586178B (en) | 2013-10-10 | 2014-09-29 | Process for the manufacture of nitriles and their corresponding amines |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810214191.XA Active CN108586178B (en) | 2013-10-10 | 2014-09-29 | Process for the manufacture of nitriles and their corresponding amines |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN104557610B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551659A (en) * | 2019-09-16 | 2019-12-10 | 中国农业科学院蔬菜花卉研究所 | Bacillus cereus strain with anti-nematode activity and application thereof |
| CN111004187A (en) * | 2019-12-31 | 2020-04-14 | 扬州天和药业有限公司 | Preparation method of 2, 6-dichloropyrazine |
| CN113444020A (en) * | 2021-06-23 | 2021-09-28 | 常州大学 | Synthesis method of alpha-isopropyl-3, 4-dimethoxyphenylacetonitrile |
| CN114276254A (en) * | 2021-12-31 | 2022-04-05 | 万华化学集团股份有限公司 | Synthetic method of 3-methoxypropylamine |
| CN114890931A (en) * | 2022-04-20 | 2022-08-12 | 湖北第二师范学院 | Extraction method and application of indole-3-acetonitrile in isatis indigotica fort oil |
| CN114934286A (en) * | 2022-06-01 | 2022-08-23 | 中国农业大学 | Method for electrocatalytic carboxylic acid cyanidation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4040253A1 (en) * | 1990-12-17 | 1992-06-25 | Huels Chemische Werke Ag | METHOD FOR NITRILIZING ALIPHATIC DICARBONIC ACIDS IN THE LIQUID PHASE |
| US5965764A (en) * | 1997-08-06 | 1999-10-12 | Toray Industries, Inc. | Process for producing a nitrile |
| US6982342B2 (en) * | 2002-05-16 | 2006-01-03 | Standard Oil Company | Ammoxidation of carboxylic acids to a mixture of nitriles |
| EP1999105A1 (en) * | 2006-03-08 | 2008-12-10 | Kao Corporation | Process for producing aliphatic nitriles |
| US9095631B2 (en) * | 2011-05-24 | 2015-08-04 | Universita Degli Studi Di Bari “Aldo Moro” | Tetrahydroisoquinoline compounds for use in the diagnosis and treatment of neurodegenerative diseases |
-
2014
- 2014-09-29 CN CN201410522472.3A patent/CN104557610B/en active Active
- 2014-09-29 CN CN201810214191.XA patent/CN108586178B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551659A (en) * | 2019-09-16 | 2019-12-10 | 中国农业科学院蔬菜花卉研究所 | Bacillus cereus strain with anti-nematode activity and application thereof |
| CN111004187A (en) * | 2019-12-31 | 2020-04-14 | 扬州天和药业有限公司 | Preparation method of 2, 6-dichloropyrazine |
| CN113444020A (en) * | 2021-06-23 | 2021-09-28 | 常州大学 | Synthesis method of alpha-isopropyl-3, 4-dimethoxyphenylacetonitrile |
| CN114276254A (en) * | 2021-12-31 | 2022-04-05 | 万华化学集团股份有限公司 | Synthetic method of 3-methoxypropylamine |
| CN114276254B (en) * | 2021-12-31 | 2023-09-19 | 万华化学集团股份有限公司 | Synthesis method of 3-methoxypropylamine |
| CN114890931A (en) * | 2022-04-20 | 2022-08-12 | 湖北第二师范学院 | Extraction method and application of indole-3-acetonitrile in isatis indigotica fort oil |
| CN114934286A (en) * | 2022-06-01 | 2022-08-23 | 中国农业大学 | Method for electrocatalytic carboxylic acid cyanidation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108586178B (en) | 2022-02-11 |
| CN108586178A (en) | 2018-09-28 |
| CN104557610B (en) | 2018-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104557610A (en) | Manufacturing method of nitrile and corresponding amine thereof | |
| CN104557357B (en) | The manufacture method of nitrile and its corresponding amine | |
| CN104557356B (en) | The manufacture method of nitrile and its corresponding amine | |
| CN106660935A (en) | Methods of producing compounds from 5-(halomethyl)furfural | |
| WO2009153214A1 (en) | Process for the manufacture of an intermediate in the synthesis of dabigatran | |
| CN105016944A (en) | Preparation methods of nitrile and corresponding amine | |
| CN105001033B (en) | The manufacturing method of nitrile and its corresponding amine | |
| CN105601620A (en) | Method for preparing mereletinib mesylate | |
| CN105016940B (en) | The manufacture method of nitrile and its corresponding amine | |
| CN105001032B (en) | The manufacture method of nitrile and its corresponding amine | |
| CN105016942A (en) | Preparation methods of nitrile and corresponding amine | |
| CN105016941A (en) | Preparation methods of nitrile and corresponding amine | |
| CN105016945A (en) | Preparation methods of nitrile and corresponding amine | |
| CN106946724B (en) | The synthetic method of monoamine base inhibitor class intermediate 2- acetylaminohydroxyphenylarsonic acid 2- benzyl malonic acid mono ethyl ester | |
| CN105016939B (en) | The manufacture method of nitrile and its corresponding amine | |
| CN104447757A (en) | Method for synthesizing epinastine | |
| CN101671296A (en) | New method for obtaining 2-chloro-3-methylpyridine from mixture of 2-chloro-5-methylpyridine and 2-chloro-3-methylpyridine | |
| CN103193666A (en) | Preparation method of 2-amino-3-chlorobenzoic methyl ester | |
| CN110218192B (en) | Preparation method of 2-amino-4, 6-dimethoxypyrimidine | |
| CN102702023A (en) | Synthesis method of trans-alpha-benzoinoxime | |
| CN105016943A (en) | Preparation methods of nitrile and corresponding amine | |
| CN102190619B (en) | Novel synthesis method for levorgyration demethyl phencynonate | |
| CN107628968B (en) | A kind of easy synthesis 1- amino -1- itrile group-cyclopropane method | |
| CN108299236B (en) | Synthetic method of alpha-cyanoacrylate compound | |
| CN103664700A (en) | Synthesis method for 1-ethyl-3-(3-dimethyl amino propyl)-carbonized diimine A iodate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |