CN110143882A - The method and separating and extracting process of L-lysine chemical decarboxylation production 1,5- pentanediamine - Google Patents
The method and separating and extracting process of L-lysine chemical decarboxylation production 1,5- pentanediamine Download PDFInfo
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- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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Abstract
The present invention provides the methods and separating and extracting process of a kind of L-lysine chemical decarboxylation production 1,5- pentanediamine, and steps are as follows: (1) L-lysine or L lysine HCL being dissolved in citrate-phosphate disodium hydrogen buffer solution；(2) oxidizing agent solution is added dropwise in step (1), reacts 20-30min at 10-75 DEG C；(3) transition metal salt is added in the reaction solution of step (2), while reducing agent is added and is vigorously stirred and is reacted, reaction time 20-120min obtains 1,5- pentanediamine solution.The present invention reacts to obtain 1,5- pentanediamine by oxidative deamination reaction and cyano reduction, reaction condition is mild, easy to operate and reproducible using L-lysine or its hydrochloride as raw material.The present invention uses cation exchange resin and 1, and 5- pentanediamine solution is contacted, at low cost, environmental-friendly compared to existing 1,5- pentanediamine separation method.
Description
Technical field
The present invention relates to chemical intermediate preparation technical fields, and in particular to a kind of L-lysine chemical decarboxylation production 1,5-
The method and separating and extracting process of pentanediamine.
Background technique
1,5- pentanediamine, similar hexamethylene diamine, with binary acid polymerization nylon 5X(nylon 54, nylon 56 etc.), performance is equal to
Beauty has even surmounted classical nylon66 fiber, and main application fields are fiber (such as clothes, automobile tire cord fabric, carpet and pipelines
Deng) and engineering plastics (such as component of electronic instrument product and automobile).The aggregate demand of global nylon is more than 7,000,000 tons/year,
Hexamethylene diamine alreadys exceed 2,000,000 tons/year as the market demand of nylon raw material.Although the market demand is vigorous, raw material are by state
Outer company monopolizing, the nylon66 fiber in China in development process by numerous obstacles, in order to promote Chinese nylon product to get rid of import
Limitation realizes that bend is overtaken other vehicles, meets the needs of national defence and market, researches and develops nylon 56, and the conjunction of 1,5- pentanediamine is established in especially exploitation
It is crucial at technology.
Lysine can generate pentanediamine with decarboxylation.The domestic serious surplus of lysine production capacity has reached 60%, according to biofermentation
Industry association's data, superfluous situation are possible to be further exacerbated by.Development produces the new technology of pentanediamine using lysine as raw material, has
Help utilize and digest existing lysine production capacity, extend industry value chain, upstream and downstream linkage solves production capacity seriously superfluous bring
Employment crisis, industry crisis, have important Social benefit and economic benefit.
Currently, triumphant match biological utilisation biofermentation technique, develops biology base pentanediamine, and brilliant with this production performance
Series of biologic based polyamide successfully completed industrialization test run in 2014.However, in view of this route in strain, enzyme and work
The selection of skill, culture and service condition require harsh, are faced with that 1,5- pentanediamine productivity is not high and high two disaster of industrial cost
Topic.Simultaneously there is also cadaverine fermentation process complexity, the series of problems such as thallus and separation of fermentative broth difficulty after fermentation.Therefore, at this
A kind of method that chemical method lysine decarboxylation preparation 1,5- pentanediamine easy to operate, pollution is low is found in field, and break Buddhist nun
One of the method for imperial industry foreign technology monopolization pattern, but so far, fresh understatement road.
The separation and Extraction of 1,5- pentanediamine is also the important ring in industrial operation unit.Up to the present, pentanediamine
Separating and extracting process is mainly directed towards biofermentation technique, can conclude are as follows: (1) polar organic solvent extracts；(2) organic film process
It is combined with distillation technique.Although the above method can be separated and recovered 1,5- pentanediamine, environmental pollution is serious for presence,
At high cost, the low defect of separation and recovery rate establishes a kind of 1,5- pentanediamine separation and Extraction efficient, universality is good, environmental-friendly
Method and current urgent problem to be solved.
Summary of the invention
The invention proposes the methods and separating and extracting process of a kind of L-lysine chemical decarboxylation production 1,5- pentanediamine, originally
Inventive technique route and separation method mild condition, be simple to operate and friendly to environment with it is at low cost, and then be 1,5- pentanediamine industry
Change provides a kind of feasible ways for being different from biofermentation technique.
Realize the technical scheme is that
A kind of method of L-lysine chemical decarboxylation production 1,5- pentanediamine, steps are as follows:
(1) L-lysine or L lysine HCL are dissolved in citrate-phosphate disodium hydrogen buffer solution；
(2) oxidizing agent solution is added dropwise in step (1), reacts 20-30min at 10-75 DEG C；
(3) transition metal salt is added in the reaction solution of step (2), while reducing agent is added and is vigorously stirred and is reacted, instead
It is 20-120min between seasonable, obtains 1,5- pentanediamine solution.
L lysine HCL is L-lysine mono-hydrochloric salts or L-lysine dihydrochloride, lemon in the step (1)
Acid-disodium hydrogen phosphate buffer solution pH is 2-9, preferably 4-7.
Oxidizing agent solution is that oxidant is dissolved in solvent to obtain in the step (2), and the oxidant is bromide reagent
And/or any one of chlorinating agent；Bromide reagent include N-bromosuccinimide (NBS), N- bromo acetamide (NBA),
N- bromophthalimide and benzophenone-N- bromine imines, chlorinating agent include trichlorine triazinetrione (TCICA), chlorobenzene
And triazole (CBT) or toluene-sodium-sulfonchloramide (chloramine T)；The solvent is dimethyl sulfoxide, acetonitrile, methanol or dimethyl methyl
Any one of amide；The molar ratio of L-lysine or L lysine HCL and oxidant in step (2) in the step (1)
For 1:(0.5-4.2).
Step (3) transition metal salt is cobalt benzoate, cobalt chloride, nickel chloride, iridous chloride, osmium tetroxide, chlorination
One of sub- platinum, ferric trichloride, zirconium chloride, zinc chloride, copper chloride and alchlor are a variety of；Reduction in the step (3)
Agent is sodium borohydride, and the molar ratio of L-lysine or L lysine HCL is (8.5-12) in reducing agent and step (1): 1, mistake
The molar ratio for crossing metal salt and reducing agent is 1:(1-6).
Reaction atmosphere is any one of nitrogen atmosphere, hydrogen atmosphere and air atmosphere, reaction temperature in the step (3)
It is 0-60 DEG C, preferably 0-40 DEG C, reaction pressure 0.1-10MPa.
In the step (3), sodium borohydride is added in step (2) reaction solution, is restored, there is following manner:
Mode 1: being added in step (2) reaction solution gradually in batches by sodium borohydride is restored；
Mode 2: sodium borohydride is dissolved into aprotic polar solvent and/or any one of ethyl alcohol and/or methanol；
Wherein the aprotic polar solvent preferably includes: dimethylformamide (DMF), acetonitrile and dimethyl sulfoxide (DMSO)
Any one of, more preferably any one of dimethylformamide and acetonitrile.
The separating and extracting process of 1, the 5- pentanediamine, steps are as follows:
A) filter aid is added into obtained 1,5- pentanediamine solution, is filtered, and filtrate is diluted to 500mL；
B) dilution obtained in step a) is adsorbed by cation exchange resin, is adsorbed input rate (0.5-20)
mL/min；
C) it will be adsorbed with the cation exchange resin of 1,5- pentanediamine in step b), eluted.
Filter aid is diatomite or active carbon, preferably Celite diatomite in the step a).
Cation exchange resin is storng-acid cation exchange resin or Subacidity cation exchange tree in the step b)
Any one of rouge, preferably storng-acid cation exchange resin；The volume ratio of cation exchange resin and dilution is
(0.75-4.5): 1；Adsorb input rate (0.5-20) mL/min.
The step c) eluting temperature is 10-60 DEG C, and elution rate is (2-15) mL/min；Eluent includes that weak base is water-soluble
Any one of liquid or strong alkali aqueous solution.
The weak base aqueous solution includes ammonium hydroxide, sodium carbonate or sodium bicarbonate aqueous solution, and strong alkali aqueous solution includes sodium hydroxide
Or potassium hydroxide aqueous solution.The concentration of the weak base aqueous solution is measured with the volume ratio of weak caustic solution and water, and preferably 1:
(0.2-7), more preferably 1:(0.3-3).
The beneficial effects of the present invention are: the present invention is using low-cost L-lysine or its hydrochloride as raw material, through peroxide
Change decarboxylic reaction and cyano reduction reacts to obtain 1,5- pentanediamine, compared to existing biological fermentation process, reaction condition is mild, easily grasps
Make and reproducible；And the present invention uses cation exchange resin and 1,5- pentanediamine solution is contacted, and is adsorbed, eluted
And the processes such as revolving, 1,5- pentanediamine hydrochloride is finally obtained, compared to existing 1,5- pentanediamine separation method, at low cost, ring
Border is friendly.So more crucial that be, the present invention will synthesize 1,5- pentanediamine with chemical method to future, provide wide potential technology valence
It is worth space.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the HPLC-MS spectrogram of 1,5 pentanediamine hydrochloride standard items.
Fig. 2 be L-Lysine dihydrochloride(L- lysine dihydrochloride) standard items HPLC-MS spectrogram.
Fig. 3 is the HPLC-MS spectrogram of 1,5- pentanediamine hydrochloric acid prepared by the embodiment of the present invention 1.
Fig. 4 is the HPLC-MS spectrogram of 1,5- pentanediamine hydrochloric acid prepared by the embodiment of the present invention 2.
Fig. 5 is the HPLC-MS spectrogram of 1,5- pentanediamine hydrochloric acid prepared by the embodiment of the present invention 3.
Fig. 6 is the HPLC spectrogram of 1,5- pentanediamine hydrochloric acid prepared by the embodiment of the present invention 1,2,3.
Fig. 7 is the HPLC-MS spectrogram of 1,5- pentanediamine hydrochloric acid prepared by the embodiment of the present invention 3.
Fig. 8 is the HPLC-MS spectrogram of 1,5- pentanediamine hydrochloric acid prepared by the embodiment of the present invention 3.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
A kind of method of L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
1) the L-lysine dihydrochloride of 15.9mmoL (L-Lysine dihydrochloride) is dissolved in 90mL lemon
In acid-disodium hydrogen phosphate buffer solution (pH 5)；
2) by the dimethylformamide (DMF) solution of 20mL N-bromosuccinimide (NBS), at 25 DEG C, step is added dropwise
In rapid 1) solution, 30min is reacted；
3) Nickel dichloride hexahydrate of 96.5moL is added in step 2 reaction solution, while the boron of 158mmoL is gradually added on a small quantity
Sodium hydride powder, and in ice-water bath, react 1h.
A kind of separating and extracting process of above-mentioned L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
A) solution for containing 1,5- pentanediamine that will acquire uses diatomite as filter aid, is filtered, and filtrate is diluted to
500mL；
B) filtrate after dilution is added to storng-acid cation exchange resin ((25cm × 2cm) of Dowex 50WX8-
200 ion exchange resin) in column, adsorbed, adsorb rate (5-10) mL/min as far as possible；
C) it after absorption terminates, is eluted with the deionized water of 300-500mL, removes remaining impurity；
D) different volumes concentration (V is usedH2O:VAmmonium hydroxide=50:150,100:100,150:50) ammonium hydroxide successively to the highly acid after absorption
Cation exchange resin is eluted, and eluent is rotated, salt acid for adjusting pH to it is acid, again rotate, finally obtain 1,
5- pentanediamine hydrochloride.
L-Lysine dihydrochloride reacts to obtain 1,5- penta through oxidative deamination and cyano reduction in the present embodiment
Diamines, and be isolated to 1,5- pentanediamine hydrochloride, method is simple, mild condition, at low cost and environmental-friendly, reaction result
As shown in table 1.
1 NiCl of table2-NaHB4L-lysine redox decarboxylation system 1, the reaction result of 5- pentanediamine under system
Embodiment 2
A kind of method of L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
1) the L-lysine dihydrochloride of 15.9mmoL (L-Lysine dihydrochloride) is dissolved in 90mL lemon
In acid-disodium hydrogen phosphate buffer solution (pH 5)；
2) by the dimethylformamide (DMF) solution of 20mL N-bromosuccinimide (NBS), at 25 DEG C, step is added dropwise
In rapid 1) solution, 30min is reacted；
3) cobalt chloride hexahydrate of 96.5moL is added in step 2 reaction solution, while the boron of 158mmoL is gradually added on a small quantity
Sodium hydride powder, and in ice-water bath, react 1h.
A kind of separating and extracting process of above-mentioned L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
A) solution for containing 1,5- pentanediamine that will acquire uses diatomite as filter aid, is filtered, and filtrate is diluted to
500mL；
B) filtrate after dilution is added to storng-acid cation exchange resin ((25cm × 2cm) of Dowex 50WX8-
200 ion exchange resin) in column, adsorbed, adsorb rate (5-10) mL/min as far as possible；
C) it after absorption terminates, is eluted with the deionized water of 300-500mL, removes remaining impurity；
With different volumes concentration (VH2O:VAmmonium hydroxide=50:150,100:100,150:50) ammonium hydroxide successively to after absorption highly acid sun
Ion exchange resin is eluted, and eluent is rotated, salt acid for adjusting pH to it is acid, again rotate, finally obtain 1,5-
Pentanediamine hydrochloride.
L-Lysine dihydrochloride reacts to obtain 1,5- penta through oxidative deamination and cyano reduction in the present embodiment
Diamines, and be isolated to 1,5- pentanediamine hydrochloride, method is simple, condition temperature, at low cost and environmental-friendly, and reaction result is such as
Shown in table 2.
2 CoCl of table2-NaHB4L-lysine redox decarboxylation system 1, the reaction result of 5- pentanediamine under system
Embodiment 3
A kind of method of L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
1) the L-lysine dihydrochloride of 15.9mmoL (L-Lysine dihydrochloride) is dissolved in 90mL lemon
In acid-disodium hydrogen phosphate buffer solution (pH 5)；
2) by the dimethylformamide (DMF) solution of 20mL N-bromosuccinimide (NBS), at 25 DEG C, step is added dropwise
In rapid 1) solution, 30min is reacted；
3) ferric trichloride of 96.5moL is added in step 2 reaction solution, while the hydroboration of 158mmoL is gradually added on a small quantity
Sodium powder body, and in ice-water bath, react 1h.
A kind of separating and extracting process of above-mentioned L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
A) solution for containing 1,5- pentanediamine that will acquire uses diatomite as filter aid, is filtered, and filtrate is diluted to
500mL；
B) filtrate after dilution is added to storng-acid cation exchange resin ((25cm × 2cm) of Dowex 50WX8-
200 ion exchange resin) in column, adsorbed, adsorb rate (5-10) mL/min as far as possible；
C) it after absorption terminates, is eluted with the deionized water of 300-500mL, removes remaining impurity；
With different volumes concentration (VH2O:VAmmonium hydroxide=50:150,100:100,150:50) ammonium hydroxide successively to after absorption highly acid sun
Ion exchange resin is eluted, and eluent is rotated, salt acid for adjusting pH to it is acid, again rotate, finally obtain 1,5-
Pentanediamine hydrochloride.
It reacts to obtain 1,5- through oxidative deamination and cyano reduction by L-Lysine dihydrochloride in the present embodiment
Pentanediamine, and be isolated to 1,5- pentanediamine hydrochloride, method is simple, mild condition, at low cost and environmental-friendly, reaction knot
Fruit is as shown in table 3.
3 FeCl of table3-NaHB4L-lysine redox decarboxylation system 1, the reaction result of 5- pentanediamine under system
Embodiment 4
A kind of method of L-lysine chemical decarboxylation production 1,5- pentanediamine, steps are as follows:
1) the L-lysine dihydrochloride of 15.9mmoL (L-Lysine dihydrochloride) is dissolved in 90mL lemon
In acid-disodium hydrogen phosphate buffer solution (pH 2)；
2) by the acetonitrile (CH of 20mLN- bromo acetamide (NBA) (7.95mmol)3CN step is added dropwise at 10 DEG C in) solution
In rapid 1) solution, 20min is reacted；
3) cobalt benzoate of 96.5moL is added in step 2 reaction solution, is passed through nitrogen, while gradually a small amount of addition
The sodium borohydride powder of 158mmoL, and in ice-water bath, react 1h.
A kind of separating and extracting process of above-mentioned L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
A) solution for containing 1,5- pentanediamine that will acquire uses diatomite as filter aid, is filtered, and filtrate is diluted to
500mL；
B) filtrate after diluting 109mL is added to storng-acid cation exchange resin ((25cm × 2cm) of Dowex
50WX8-200 ion exchange resin) in column, adsorbed, adsorb input rate (5-10) mL/min；
C) it after absorption terminates, is eluted with the deionized water of 300-500mL, removes remaining impurity；
D) different volumes concentration (V is usedH2O:VAmmonium hydroxide=50:150,100:100,150:50) ammonium hydroxide successively to the highly acid after absorption
Cation exchange resin is eluted, and eluent is rotated, salt acid for adjusting pH to it is acid, again rotate, finally obtain 1,
5- pentanediamine hydrochloride.
L-Lysine dihydrochloride reacts to obtain 1,5- penta through oxidative deamination and cyano reduction in the present embodiment
Diamines, and be isolated to 1,5- pentanediamine hydrochloride, method is simple, condition temperature, at low cost and environmental-friendly, and reaction result is such as
Shown in table 4.
4 cobalt benzoate of table (II)-NaHB4L-lysine redox decarboxylation system 1 under system, the reaction knot of 5- pentanediamine
Fruit
Embodiment 5
A kind of method of L-lysine chemical decarboxylation production 1,5- pentanediamine, steps are as follows:
1) the L-lysine dihydrochloride of 7.95mmoL (L-Lysine dihydrochloride) is dissolved in 90mL lemon
In acid-disodium hydrogen phosphate buffer solution (pH 9)；
2) by dimethyl sulfoxide (DMSO) solution of 20mL toluene-sodium-sulfonchloramide (chloramine T) (33.39mmol), at 75 DEG C, by
It is added dropwise in step 1) solution, reacts 25min；
3) being added to 48.26moL Nickel dichloride hexahydrate in step 2 reaction solution, while being gradually added 158mmoL's on a small quantity
Sodium borohydride powder, and in 30 DEG C of reaction 20min.
A kind of separating and extracting process of above-mentioned L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
A) solution for containing 1,5- pentanediamine that will acquire uses diatomite as filter aid, is filtered, and filtrate is diluted to
500mL；
B) filtrate after diluting 30mL is added to storng-acid cation exchange resin ((25cm × 2cm) of Dowex
50WX8-200 ion exchange resin) in column, adsorbed, adsorb input rate (5-10) mL/min；
C) it after absorption terminates, is eluted with the deionized water of 300-500mL, removes remaining impurity；
D) different volumes concentration (V is usedH2O:VAmmonium hydroxide=50:150,100:100,150:50) ammonium hydroxide successively to the highly acid after absorption
Cation exchange resin is eluted, and eluent is rotated, salt acid for adjusting pH to it is acid, again rotate, finally obtain 1,
5- pentanediamine hydrochloride.
L-Lysine dihydrochloride reacts to obtain 1,5- penta through oxidative deamination and cyano reduction in the present embodiment
Diamines, and be isolated to 1,5- pentanediamine hydrochloride, method is simple, condition temperature, at low cost and environmental-friendly, and reaction result is such as
Shown in table 5.
5 cobalt benzoate of table (II)-NaHB4L-lysine redox decarboxylation system 1 under system, the reaction knot of 5- pentanediamine
Fruit
Embodiment 6
A kind of method of L-lysine chemical decarboxylation production 1,5- pentanediamine, steps are as follows:
1) the L-lysine dihydrochloride of 7.95mmoL (L-Lysine dihydrochloride) is dissolved in 90mL lemon
In acid-disodium hydrogen phosphate buffer solution (pH 5)；
2) by the acetonitrile (CH of 20mLN- bromosuccinimide (NBS) (33.39mmol)3CN) solution, at 25 DEG C, dropwise plus
Enter in step 1) solution, reacts 30min；
3) being added to 48.26moL zinc chloride in step 2 reaction solution, under air atmosphere, while gradually a small amount of addition
The sodium borohydride powder of 158mmoL, and in 60 DEG C of reaction 2h.
A kind of separating and extracting process of above-mentioned L-lysine chemical decarboxylation production 1,5- pentanediamine, the steps include:
A) solution for containing 1,5- pentanediamine that will acquire uses diatomite as filter aid, is filtered, and filtrate is diluted to
500mL；
B) filtrate after diluting 450mL is added to storng-acid cation exchange resin ((25cm × 2cm) of Dowex
50WX8-200 ion exchange resin) in column, adsorbed, adsorb input rate (5-10) mL/min；
C) it after absorption terminates, is eluted with the deionized water of 300-500mL, removes remaining impurity；
D) different volumes concentration (V is usedH2O:VAmmonium hydroxide=50:150,100:100,150:50) ammonium hydroxide successively to the highly acid after absorption
Cation exchange resin is eluted, and eluent is rotated, salt acid for adjusting pH to it is acid, again rotate, finally obtain 1,
5- pentanediamine hydrochloride.
L-Lysine dihydrochloride reacts to obtain 1,5- penta through oxidative deamination and cyano reduction in the present embodiment
Diamines, and be isolated to 1,5- pentanediamine hydrochloride, method is simple, condition temperature, at low cost and environmental-friendly, and reaction result is such as
Shown in table 6.
6 ZnCl of table2-NaHB4L-lysine redox decarboxylation system 1, the reaction result of 5- pentanediamine under system
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method of L-lysine chemical decarboxylation production 1,5- pentanediamine, which is characterized in that steps are as follows:
(1) L-lysine or L lysine HCL are dissolved in citrate-phosphate disodium hydrogen buffer solution；
(2) oxidizing agent solution is added dropwise in step (1), reacts 20-30min at 10-75 DEG C；
(3) transition metal salt is added in the reaction solution of step (2), while reducing agent is added and is vigorously stirred and is reacted, instead
It is 20-120min between seasonable, obtains 1,5- pentanediamine solution.
2. the method for L-lysine chemical decarboxylation production 1,5- pentanediamine according to claim 1, it is characterised in that: described
L lysine HCL is L-lysine mono-hydrochloric salts or L-lysine dihydrochloride, citrate-phosphate disodium hydrogen in step (1)
The pH of buffer solution is 2-9.
3. the method for L-lysine chemical decarboxylation production 1,5- pentanediamine according to claim 1, it is characterised in that: described
Oxidizing agent solution is that oxidant is dissolved in solvent to obtain in step (2), and the oxidant is bromide reagent and/or chlorinating agent
Any one of；Bromide reagent includes N-bromosuccinimide, N- bromo acetamide, N- bromophthalimide and two
Benzophenone-N- bromine imines, chlorinating agent include trichlorine triazinetrione, chloro benzo triazole or toluene-sodium-sulfonchloramide；The solvent is diformazan
Any one of base sulfoxide, acetonitrile, methanol or dimethylformamide；L-lysine or L-lysine hydrochloric acid in the step (1)
The molar ratio of oxidant is 1:(0.5-4.2 in salt and step (2)).
4. the method for L-lysine chemical decarboxylation production 1,5- pentanediamine according to claim 1, it is characterised in that: described
Step (3) transition metal salt is cobalt benzoate, cobalt chloride, nickel chloride, iridous chloride, osmium tetroxide, platinous chloride, tri-chlorination
One of iron, zirconium chloride, zinc chloride, copper chloride and alchlor are a variety of；Reducing agent is hydroboration in the step (3)
Sodium, the molar ratio of L-lysine or L lysine HCL is (8.5-12) in reducing agent and step (1): 1, transition metal salt with
The molar ratio of reducing agent is 1:(1-6).
5. the method for L-lysine chemical decarboxylation production 1,5- pentanediamine according to claim 1, it is characterised in that: described
Reaction atmosphere is any one of nitrogen atmosphere, hydrogen atmosphere and air atmosphere in step (3), and reaction temperature is 0-60 DEG C, instead
Answering pressure is 0.1-10MPa.
6. the separating and extracting process of described in any item 1, the 5- pentanediamines of claim 1-5, it is characterised in that steps are as follows:
A) filter aid is added into obtained 1,5- pentanediamine solution, is filtered, and filtrate is diluted to 500mL；
B) dilution obtained in step a) is adsorbed by cation exchange resin, is adsorbed input rate (0.5-20)
mL/min；
C) it will be adsorbed with the cation exchange resin of 1,5- pentanediamine in step b), eluted.
7. the separating and extracting process of 1,5- pentanediamine according to claim 6, it is characterised in that: drainage in the step a)
Agent is diatomite or active carbon.
8. the separating and extracting process of 1,5- pentanediamine according to claim 6, it is characterised in that: the step b) middle-jiao yang, function of the spleen and stomach from
Sub-exchange resin is any one of storng-acid cation exchange resin or weak-acid cation-exchange resin, cation exchange tree
The volume ratio of rouge and dilution is (0.75-4.5): 1；Adsorb input rate (0.5-20) mL/min.
9. the separating and extracting process of 1,5- pentanediamine according to claim 6, it is characterised in that: the step c) elution temperature
Degree is 10-60 DEG C, and elution rate is (2-15) mL/min；Eluent includes any in weak base aqueous solution or strong alkali aqueous solution
Kind.
10. the separating and extracting process of 1,5- pentanediamine according to claim 9, it is characterised in that: the weak base aqueous solution
Including ammonium hydroxide, sodium carbonate or sodium bicarbonate aqueous solution, strong alkali aqueous solution includes sodium hydroxide or potassium hydroxide aqueous solution.
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