CN108276292A - A kind of separation method of 1,5- pentanediamines - Google Patents
A kind of separation method of 1,5- pentanediamines Download PDFInfo
- Publication number
- CN108276292A CN108276292A CN201710011198.7A CN201710011198A CN108276292A CN 108276292 A CN108276292 A CN 108276292A CN 201710011198 A CN201710011198 A CN 201710011198A CN 108276292 A CN108276292 A CN 108276292A
- Authority
- CN
- China
- Prior art keywords
- pentanediamines
- solution
- resin
- cation
- pentanediamine
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Abstract
The present invention provides a kind of separation method of 1,5 pentanediamines, which includes the following steps：(1) solution of 1,5 pentanediamine is contacted with resin cation, is adsorbed；(2) elution is adsorbed on 1,5 pentanediamines on resin.Compared with conventional method, the 1 of the present invention, 5 pentanediamine separation and recovery methods, the yield of 1,5 pentanediamines is improved, 1 is substantially free of in the treatment fluid after resin adsorption, 5 pentanediamines remain, and the impurity such as tetrahydropyridine, thalline, protein will not be adsorbed in resin, 1,5 pentanediamine purity are high because obtained from, it is miscellaneous low to contain.And the processing solution obtained by resin adsorption does not contain polar organic solvent yet, environmental sound is simultaneously easily processed, and reduces the pollution to environment and separation costs.Meanwhile 1 afforded using binary acid, 5 pentanediamine binary acid solutions can be used directly as the raw material of synthesized high-performance polyamide.
Description
Technical field
The present invention relates to the fields that isolates and purifies of organic matter, the more particularly to separation method of one kind 1,5- pentanediamines.
Background technology
All the time, chemical industry is relied on produces polymer product using oil and natural gas as raw material, becomes modern text
The mainstay of bright society.But with petering out for oil and natural gas resource, petroleum product produces and uses caused temperature
Room effect is on the rise, and finds the substitute products of fossil resources, is based particularly on the green products of renewable resource, becomes current
The important development direction of chemical industry.
Polyamide is a kind of very important polymer material, is had in multiple fields such as automobile, high-grade weavings important
Purposes, whole world polyamide polymer annual output is at 6,000,000 tons or more at present, and the consumption figure of China accounts for global polyamide yield
30%.
In this context, 1,5- pentanediamines, the exploitations of especially 1,5- pentanediamines just seem very desirable.From
1,5- pentanediamine sets out, can be with synthesizing polyamides 5X series of products, such as the polyamide 510 of polyamide 56 or full biology base, this
A little products can apply many aspects in the daily production and living such as electronic apparatus, mechanical equipment, automobile component.
Bioanalysis, which prepares 1,5- pentanediamines, at present mainly direct fermentation and lysyl oxidase conversion method.The production of pentanediamine
With purifying patent, report below can be enumerated：
Patent EP1482055A1 is disclosed during enzymatic conversion, with adipic acid control enzymatic conversion pH value, 100% turn
Change lysine；Then with the activated carbon decolorizing of pentanediamine amount 20%, 70~77% nylon salinity are concentrated into；Nylon salt solution temperature
Degree is reduced to 10 DEG C from 60 DEG C, crystallizes the method for obtaining pentanediamine nylon salt.But pentanediamine enzymatic conversion is controlled by organic acid
The method of liquid pH value, because of the addition of zymoprotein, even if obtaining pentanediamine acylate as raw material using the lysine of high-purity
Also it can contain impurity, this kind of impurity usually brings illeffects to polymerizing polyamide, influences the quality of final polyamide product.Together
When, this technique is also faced with that polyamide salt crystallization yield is low, the difficulty of unstable product quality.
Patent CN101981202A is disclosed obtains pentanediamine solution, pentanediamine concentration 72g/L by direct fermentation.Then
At 103 DEG C, flow back zymotic fluid 5h, cracks the by-product in zymotic fluid；It is repeatedly extracted with butanol, evaporation organic solvent obtains penta
The method of two amine products.Pentanediamine is extracted using organic solvent, because of the influence of pentanediamine characteristic, commonly uses polar organic solvent extraction
It takes.Polar organic solvent unavoidably has solvent volatilization in extraction process, causes environmental pollution, increase simultaneously such as chloroform or butanol
Add extraction cost.Toxic organic solvent also damages the body of operating personnel.
Patent CN200980121108 discloses organic film process pentanediamine enzyme reaction solution with UF12000 molecular weight, drop
Trifunctional organic matter in low reaction liquid, trifunctional content of organics are 0.0063 with respect to pentanediamine.Pentanediamine solution heats
To 100 DEG C or more decomposition pentanediamine carbonate, the method that pentanediamine obtains product is then distilled.But the decomposition of carbonate need compared with
High temperature and long-time heating, meanwhile, it cannot be guaranteed that the whole of carbonate decompose, shadow is caused to rectification process and product quality
It rings.
It also discloses in the prior art and 1,5- penta 2 is refining to obtain by 1,5- pentanediamines salt (for example, 1,5- pentanediamine sulfate)
When amine, to remove the impurity such as tetrahydropyridine, thalline, protein present in 1,5- pentanediamine salt, add in 1,5- pentanediamine salt
Enter alkaline matter (for example, sodium hydroxide) improve pH value and to keep 1,5- pentanediamines free and forms 1, the 5- pentanediamines that dissociate, it is right
The salt (for example, sodium sulphate) formed after alkaline matter is added, then free 1,5- pentanediamines are detached to obtain by operations such as extractions, then leads to
It crosses distillation and carries out refined method.Equally, it when being detached 1,5- pentanediamines with salt by extracting operation, needs a large amount of organic
Solvent (for example, aniline, chloroform etc.) unavoidably has solvent volatilization in extraction process, causes environmental pollution, while increasing separation
Cost.Toxic organic solvent also damages the body of operating personnel.
In addition, also useful NF membrane handles 1, the 5- pentanediamine aqueous solutions of alkalization in the prior art, salinity is filtered out.Though
Right cost can decline to a great extent, but a large amount of 1,5- pentanediamines can be wrapped or be mixed in solid inorganic salt, lead to free 1,
5- pentanediamines can not be recycled effectively, for example, after using solid salt is removed by suction filtration under vacuum, the distillation recovery efficiency of 1,5- pentanediamine
Highest only has 20% or so, and yield is low, and large-tonnage product is wasted.
The method of above-mentioned various 1,5- pentanediamines separation and recovery, that there are the rate of recovery is low, finished product impurity content is high, it is of high cost,
The defect that energy consumption is big, environmental pollution is serious etc., therefore, this field find it is a kind of efficiently, low 1, the 5- penta 2 of low cost, pollution
The separation and recovery method of amine becomes urgent problem to be solved in the prior art.
Invention content
For the defect of existing 1,5- pentanediamines (following 1,5- pentanediamines are all 1,5- pentanediamines) separation method, inventor
By long-term further investigation, proposes a kind of method detaching 1,5- pentanediamines from the solution of 1,5- pentanediamines, is simple and efficient,
It is high to obtain 1,5- pentanediamines product purity, impurity content is low, and the separation method of 1, the 5- pentanediamines of the present invention is at low cost, to ring
Border is pollution-free.
The present invention provides the separation method of one kind 1,5- pentanediamines, and the separation method includes the following steps：
(1) solution of 1,5- pentanediamines is contacted with resin cation, is adsorbed；
(2) elution is adsorbed on the 1,5- pentanediamines on the resin cation.
The further preferred technical solution of above-mentioned technical proposal is described in detail below：
In an embodiment of the separation method of the present invention, the pH value of solution 3-12 of the pentanediamine, preferably pH5-9.
In an embodiment of the separation method of the present invention, the solution of 1, the 5- pentanediamines includes：Ionic state
1,5- pentanediamines (mainly with the form presence of the salt of 1,5- pentanediamines) and/or ionic state 1,5- pentanediamines, wherein big portion
Divide and exists in the form of the 1,5- pentanediamines of ionic state.
In an embodiment of the separation method of the present invention, the solution of 1, the 5- pentanediamines is 1 containing impurity,
The solution of 5- pentanediamines.
In an embodiment of the separation method of the present invention, the impurity includes：Tetrahydropyridine, thalline and protein
In it is one or more.
In an embodiment of the separation method of the present invention, the solution of 1, the 5- pentanediamines can pass through bioanalysis
And/or organic synthesis method obtains, the solution of 1, the 5- pentanediamines can be：1,5- pentanediamine enzymatic conversion solution and/or its at
Liquid is managed, and/or, 1,5- pentanediamine fermentation liquid and/or its treatment fluid.
In an embodiment of the separation method of the present invention, the resin cation includes：Highly acidic cation tree
Fat, or, acidulous cation resin.
In an embodiment of the separation method of the present invention, the cation exchange resin includes：Hydrogen form cation
Resin, or, sodium form resin cation or other suitable types.
In an embodiment of the separation method of the present invention, the cation exchange resin includes：Hydrogen type strong acid
In resin cation, Hydrogen acidulous cation resin, sodium form strong acidic ion resin or sodium form acidulous cation resin
One kind.
In an embodiment of the separation method of the present invention, in step (1), solution and the sun of 1, the 5- pentanediamines
Ion exchange resin contacts, and is adsorbed, preferred 10-90 DEG C, more preferable 20-70 DEG C of the adsorption temp.
In an embodiment of the separation method of the present invention, in step (1), solution and the sun of 1, the 5- pentanediamines
Ion exchange resin contacts, and is adsorbed, may include following manner：
Mode one：The solution of resin cation and 1,5- pentanediamines is uniformly mixed, is adsorbed；
And/or
Mode two：By the solution of 1,5- pentanediamines by ion exchange resin column, adsorbed.
In an embodiment of the separation method of the present invention, in mode one, the uniformly mixed method is ability
Resin cation is preferably added in the solution of 1,5- pentanediamines by the method for domain routine, the present invention, is uniformly mixed.
In an embodiment of the separation method of the present invention, in mode one, the dosage of the resin cation with 1,
The solution of 5- pentanediamines and the volume basis of resin, the solution of 1, the 5- pentanediamines and the volume ratio of the resin cation are excellent
Select 6.5 or less.Wherein, the volume ratio of the solution of 1, the 5- pentanediamines and the strong acidic ion resin preferably (0.5-
2.7)：1；Wherein, the volume ratio of the solution of 1, the 5- pentanediamines and the acidulous cation resin is preferred (1-5)：1.
In an embodiment of the separation method of the present invention, in mode one, by resin cation and 1,5- pentanediamines
Solution be uniformly mixed, after being adsorbed, then by one or more modes in the modes such as concussion, stirring or standing, make suction
It is attached more abundant.
In an embodiment of the separation method of the present invention, in mode two, the feed flow rate of the absorption is preferred
0.1-30BV/h, more preferable 0.5-5BV/h.
In an embodiment of the separation method of the present invention, in mode two, when 1,5- in the solution of 1,5- pentanediamines
When a concentration of 1wt% or more of pentanediamine, the feed flow rate preferred 0.1-10BV/h, more preferable 1-5BV/h of the absorption；When 1,
In the solution of 5- pentanediamines when a concentration of 1wt% or less of 1,5- pentanediamines, the preferred 5-20BV/h of feed flow rate of the absorption,
More preferable 8-15BV/h.
In an embodiment of the separation method of the present invention, the ratio of height to diameter of the ion exchange resin column can be
(1-20)：1, preferably (3-8)：1, more preferable (4-6)：1.
In an embodiment of the separation method of the present invention, in mode two, the absorption is with cation exchange resin
The form of fixed bed, moving bed or Simulation moving bed carries out.
In an embodiment of the separation method of the present invention, in mode two, after the absorption, washed.It is described
Washing is preferably washed with distilled water.The flow velocity when washing is preferably 1-10BV/h, more preferable 2-5BV/h.
In an embodiment of the separation method of the present invention, in step (2), the elution is according to this field routine
Elution process is eluted.The eluent when elution can be any of following type：
Type one：Strong alkali aqueous solution and its mixed solution；
Or, type two：The mixed aqueous solution of highly basic and weak base；
Or, type three：Acidic aqueous solution.
Wherein, the highly basic preferably includes：Alkali metal hydroxide and/or alkaline earth metal hydroxide more preferably include：
It is one or more in sodium hydroxide, potassium hydroxide and calcium hydroxide.
Wherein, the preferred 1-12wt% of the concentration of the strong alkali aqueous solution, more preferable 2-8wt%, most preferably 3-5wt%.
Wherein, the weak base preferably includes ammonium hydroxide.
Wherein, the acidic aqueous solution preferably includes inorganic acid and/or organic acid；Wherein, the inorganic acid is preferably inorganic
Strong acid, more preferable sulfuric acid and/or hydrochloric acid；The preferred organic dibasic acid of organic acid, in more preferable oxalic acid, succinic acid and adipic acid
It is one or more.Wherein, the concentration of the aqueous solution of the inorganic acid preferred 1-12wt%, more preferable 2-8wt%.Wherein,
The saturated aqueous solution of the preferred organic acid of aqueous solution of the organic acid is (when the concentration of the saturated aqueous solution of the organic acid is more than
10wt% then selects the aqueous solution of the organic acid of 2-10wt%).
In an embodiment of the separation method of the present invention, in step (2), the preferred 10-90 of temperature of the elution
DEG C, more preferable 30-60 DEG C.
In an embodiment of the separation method of the present invention, in step (2), the mode of the elution is with lower section
Formula it is any：
Mode one：The cation exchange resin is mixed with the eluent, is eluted；
Or,
Mode two：The eluent is flowed through into the resin cation.
Wherein, in mode one, the mode of the mixing preferably stirs.
Wherein, in mode two, the flow velocity preferred 0.5-8BV/h, more preferable 1-4BV/h of the eluent of the elution.
In an embodiment of the separation method of the present invention, after step (2), the processing of eluent is also carried out.Institute
The processing mode stated may include：Evaporation and/or rectifying.
In the present invention, if having carried out primary above elution and/or washing, routinely merge washing lotion according to this field,
Subsequent processing as described above is carried out again.
1, the 5- pentanediamine separation and recovery methods of the present invention, improve the yield of 1,5- pentanediamines, after resin adsorption
It is substantially free of 1,5- pentanediamines residual in treatment fluid, and the impurity such as tetrahydropyridine, thalline, protein will not be adsorbed in resin,
The 1,5- pentanediamines purity because obtained from is high, it is miscellaneous low to contain.And also have without polarized by the processing solution that resin adsorption obtains
Solvent, environmental sound are simultaneously easily processed, and reduce the pollution to environment and separation costs.Meanwhile it being eluted using binary acid
Obtained 1,5- pentanediamine binary acid solution can be used directly as the raw material of synthesized high-performance polyamide.
Specific implementation mode
Technical scheme of the present invention is described further below according to specific embodiment.Protection scope of the present invention is unlimited
In following embodiment, these examples are enumerated merely for exemplary purpose without limiting the invention in any way.
The present invention provides the separation method of one kind 1,5- pentanediamines, which includes the following steps：
(1) solution of 1,5- pentanediamines is contacted with resin cation, is adsorbed；
(2) elution is adsorbed on the 1,5- pentanediamines on resin.
The solution of 1,5-- pentanediamines：
In the present invention, the pH value of solution 3-12 of the pentanediamine, preferably pH5-9.
In the present invention, the solution of 1, the 5- pentanediamines includes：The 1,5- pentanediamines of ionic state are (mainly with 1,5- penta 2
The form presence of the salt of amine) and/or ionic state 1,5- pentanediamines, wherein most is in the form of 1, the 5- pentanediamines of ionic state
In the presence of.
In the present invention, the solution of 1, the 5- pentanediamines is the solution of 1, the 5- pentanediamines containing impurity.
In the present invention, the impurity includes：It is one or more in tetrahydropyridine, thalline and protein.
In the present invention, the solution of 1, the 5- pentanediamines can be obtained by bioanalysis and/or organic synthesis method, and described 1,5-
The solution of pentanediamine can be：
(1) 1,5- pentanediamine enzymatic conversion solution and/or its treatment fluid, and/or,
(2) 1,5- pentanediamine fermentation liquid and/or its treatment fluid, and/or,
(3) pentanediamine sterling reacts the solution of 1,5- pentanediamines obtained with acid.
Industrially, first two is generally used.
Wherein, (1) 1,5- pentanediamine enzymatic conversion solution and/or its treatment fluid：
1,5- pentanediamine enzymatic conversion solution refers to lysine or lysine salt solution under the action of lysine decarboxylase,
1,5- pentanediamines enzymatic conversion solution obtained by the reaction.The present invention does not have the specific preparation method of 1,5- pentanediamine enzymatic conversion solution
Special to limit, those skilled in the art can determine to select specific raw material according to the prior art, determine specific enzymatic conversion
The technological parameter of process.
Lysine salt in the present invention refers to the inorganic salts or organic salt of lysine, preferably relies the sour sulfate of acid.
The salting liquid of lysine, can be market purchasing or homemade dry lysine salt be dissolved in water to be formed it is molten
Liquid, such as lysine hydrochloride available on the market, lysine sulphate commodity are dissolved in water the lysine salt solution of generation.
For another example homemade lysine hydrochloride, lysine sulphate finished product are dissolved in water the lysine salt solution of generation.
The salting liquid of lysine can also be the zymotic fluid of lysine.In industrial-scale fermentation, culture medium uses sulphur
Sour ammonium contains a large amount of sulfate radical as one of nitrogen source in zymotic fluid.
The salting liquid of lysine can also be that lysine fermentation liquor further cleans obtained liquid, as fermentation obtains
Lysine fermentation liquor removes obtained clear solution after thalline by centrifugation, filtering or membrane filtration, or, relying of obtaining of fermentation
Propylhomoserin zymotic fluid adds activated carbon decolorizing, the lysine salt solution being obtained by filtration.
Lysine decarboxylase (LDC) in the present invention refers to that can act on lysine, generates the enzyme of 1,5- pentanediamines.Rely ammonia
Acid decarboxylase can be lysine decarboxylase zymotic fluid, or the zymotic fluid by centrifuging or filtering or other technologies means obtain
Cell, or broken cell or zymotic fluid filter out the zymotic fluid clear liquid obtained after cell or refined enzyme.Can also be two kinds with
The mixture of upper enzyme.
Generate lysine decarboxylase microorganism can be wild strain, can also be mutagenic strain, can also be by
The bacterial strain of genetic recombination.
The present invention is not particularly limited the technique of lysine decarboxylic reaction, and existing any enzymatic conversion skill can be used
Art.
Such as：Zhu Jing (" microorganism conversion L-lysine is the research of cadaverine ", Master's thesis, University Of Science and Technology Of Tianjin, 2009
March in year) propose following four method：
(1), it directly reacts：Lysine hydrochloride is directly appended in lysine decarboxylase zymotic fluid extremely to arrive concentration of substrate
0.05mol/kg reacts 2h, molar yield 36.05%.
(2), buffer system enzyme reaction：Changed with 0.6N acetate buffer buffering reaction systems pH, lysine hydrochloride exists
Final concentration of 0.22mol/kg in buffer solution reacts 2h, molar yield 81.30%.
(3), pH enzyme reactions are controlled：Strong acid, which controls, reacts pH5-6, lysine hydrochloric acid salinity 0.22mol/ in enzyme reaction system
Kg reacts 2h, molar yield 94.97%.
(4), pH enzyme reactions in batches are controlled：Strong acid, which controls, reacts pH5-6, initial lysine hydrochloric acid salinity in reaction system
0.22mol/kg, reaction certain time separation product constantly in situ and enzyme, whole conversion of substrate 0.87mol/kg, cadaverine yield are
94.61%.
Chinese patent literature (application number 201180010677.8) discloses before enzymatic conversion to expression lysine decarboxylase
Microorganism carries out the modes such as freeze-thaw, heat treatment, lysine salt and handles, to improve efficiency.
Japanese documentation JP20050147171 is disclosed using lysine carbonate aqueous solution as substrate and is urged to carry out enzyme
Change, and pH is adjusted with carbon dioxide.
, can be as needed in lysine decarboxylic reaction, additional addition other compositions, as inorganic salts, vitamin or
Other contribute to the additive of enzyme reaction process.
In lysine decarboxylic reaction, reaction temperature is generally at 20 DEG C or more, at 60 DEG C or less.
Wherein, (2) 1,5- pentanediamines fermentation liquid and/or its treatment fluid：
1,5- pentanediamine fermentation liquids refer to：By gene technology, is raised in the bacterial strain that can generate lysine and rely ammonia
The expression of acid decarboxylase, or recombinant expression lysine decarboxylase, can make the lysine of generation synchronize conversion during the fermentation
For pentanediamine, pentanediamine zymotic fluid is obtained.The present invention does not require recombinant bacterium particularly, as long as pentanediamine can be obtained.
Such as " One-step production 1, the structure of 5- pentanediamine Corynebacterium glutamicum gene engineering bacterias " (ox great waves etc., Chinese biological engineering are miscellaneous
Will, 2010,30 (8)：One plant 93-99) is disclosed using hafnia alvei (Hafnia alvei) genome, as template, to pass through
PCR amplification obtains lysine decarboxylase gene ldc, and with Escherichia coli (Escherichia coli)/Corynebacterium glutamicum
(Corynebacterium glutamicum) shuttle plasmid is carrier, and the target gene fragment that amplification obtains is cloned into paddy ammonia
Sour bar bacterium, the recombinant bacterial strain of acquisition.It will be obvious to one with ordinary skill in the art that how according to specific recombinant bacterium Optimal Medium
Component, ratio and fermentation parameter.Also, 1, the 5- penta obtained by the way that alkali metal is added in past 1,5- pentanediamine zymotic fluids
Diamines fermentation treatment fluid (can refer to CN101981202A).
Further include anion in the solution of 1, the 5- pentanediamines in the present invention.Anion species are not particularly limited,
As long as corresponding 1,5- pentanediamines salt can be dissolved in water.The anion, including but not limited to, sulfate radical, carbonate,
It is one or more in phosphate radical, adipic acid root, decanedioic acid root, chlorion or carbanion.
Resin cation：
In the present invention, the resin cation includes：Strong acidic ion resin or acidulous cation resin；Including：
Hydrogen form cation resin, or, sodium form resin cation or other suitable types.
In the present invention, the cation exchange resin includes：Hydrogen type strong acid resin cation, Hydrogen Subacidity cation
One kind in resin, sodium form strong acidic ion resin or sodium form acidulous cation resin.
In the present invention, the cation exchange resin includes：Styrene type cation exchange resin or acrylic acid series sun from
The cation exchange resin of the cation exchange resin optimization styrene system of sub-exchange resin or other systems.
In one embodiment of the invention, the resin cation is 732 storng-acid cation exchange resins；In this hair
In bright one embodiment, the resin cation is 732 strong acidic ion resins of regeneration of hydrochloric acid, at the resin is most of
In H-type state；In one embodiment of the invention, the resin cation is 732 highly acids of sodium hydroxide and water process
Resin cation, the resin are mostly in Na type states；In one embodiment of the invention, the resin cation is
D110 weak-acid cation-exchange resins；In one embodiment of the invention, the resin cation is 001*7 polystyrenes
Macroporous type strong acid type cationic resin；In one embodiment of the invention, the resin cation is solidifying for 001*7 polystyrenes
Glue-type strong acid type cationic resin；In one embodiment of the invention, the resin cation is that D113 type acrylic acid series is big
Pass weak-type resin cation.
In the present invention, the resin cation either gel-type, can also be macroporous type or other forms
Cation exchange resin.
In the present invention, before absorption, according to this field routine, ion exchange resin can be activated or be regenerated.It is living
The cation exchange resin changed, pH value are generally 11 hereinafter, preferable ph 3-9.
1,5-- pentanediamines are adsorbed using resin cation：
In step (1), the solution of 1, the 5- pentanediamines is contacted with resin cation, is adsorbed；
In step (1), preferred 10-90 DEG C of the adsorption temp, more preferable 20-70 DEG C, most preferably 20-40 DEG C.
In step (1), the solution of 1, the 5- pentanediamines is contacted with resin cation, is adsorbed, and may include following
Mode：
Mode one：The solution of resin cation and 1,5- pentanediamines is uniformly mixed, is adsorbed；And/or mode two：
By the solution of 1,5- pentanediamines by ion exchange resin column, adsorbed.
Wherein, in mode one：
Uniformly mixed method is：Resin cation is added in the solution of 1,5- pentanediamines, is uniformly mixed.
The dosage of the resin cation is with the volume basis of the solution of 1,5- pentanediamines and resin, 1, the 5- pentanediamines
Solution and the resin cation volume ratio preferably 6.5 or less.Wherein, the solution and highly acidic cation of 1,5- pentanediamines
The volume ratio of resin is preferably (0.5-2.7)：1.Wherein, the solution of 1,5- pentanediamines and the volume ratio of acidulous cation resin are excellent
It selects (1-5)：1.
The solution of resin cation and 1,5- pentanediamines is uniformly mixed, it, can be again by shaking, stirring after being adsorbed
Or one or more modes in the modes such as standing, keep absorption more abundant.
In some embodiments, by resin cation and 1, the solution of 5- pentanediamines is mixed, is stirred under room temperature (20 DEG C)
Then 10min is filtered, obtain absorption 1, the resin of 5- pentanediamines.
In mode one, the pentanediamine ion in the adsorbent solution of resin cation selectivity and other cations, and penta
Impurity in diamines salting liquid, such as sugar, pigment fermentating metabolism product, do not act on resin cation, still remain in original solution
In.After the completion of absorption, by simply detaching, such as filtering, centrifugation the methods of, can by be adsorbed with pentanediamine resin and other
Impurity separates, and pentanediamine product is effectively purified.
Wherein, in mode two：
The feed flow rate preferred 0.1-30BV/h, more preferable 0.5-5BV/h of the absorption；When in the solution of 1,5- pentanediamines
When a concentration of 1wt% or more of 1,5- pentanediamine, the feed flow rate preferred 0.1-10BV/h, more preferable 1-5BV/h of the absorption；
As a concentration of 1wt% or less of 1,5- pentanediamines in the solution of 1,5- pentanediamines, the preferred 5- of feed flow rate of the absorption
20BV/h, more preferable 8-15BV/h.
In an embodiment of the separation method of the present invention, the ratio of height to diameter of the ion exchange resin column can be
(1-20)：1, preferably (3-8)：1, more preferable (4-6)：1.
The absorption is carried out in the form of cation exchange resin fixed bed, moving bed or Simulation moving bed.
After the absorption, washed.The washing is preferably washed with distilled water.Resin cation absorption penta 2
After amine aqueous solution, the remaining impurity of interlaminar resin can be further separated out by modes such as washings, is that the desorption of pentanediamine is accurate
Standby condition.The flow velocity when washing is preferably 1-10BV/h, more preferable 2-5BV/h.
In some embodiments, resin cation can be loaded into splitter, the solution of 1,5- pentanediamine is with speed
2BV/h passes through splitter.In some embodiments, resin cation can be loaded into the company for including 30 root polypropylene chromatographic columns
In continuous ion-exchange system, 1,5- pentanediamine aqueous solution obtains the solution of 1,5- pentanediamines by continuous ion-exchange system.
In mode two, adsorption process using by the way of resin column, i.e., resin is fixed in splitter, 1,5- pentanediamine
Solution stayed resin column, 1,5- pentanediamine and partial cation to be adsorbed, other impurities are reserved with solution and are detached outside column.Sun
After ion exchange resin adsorbs 1,5- pentanediamine solution, the remaining impurity of interlaminar resin can further be detached by modes such as washings
It goes out, is the desorption preparatory condition of 1,5- pentanediamines.
In step (1), 1, the 5- pentanediamines ion in the adsorbent solution of resin cation selectivity and other cations, and
Impurity in the solution of 1,5- pentanediamine, such as sugar, pigment fermentating metabolism product and 2, the by-products such as 3,4,5- tetrahydropyridines
It does not act on then, is still remained in original solution with resin cation.
1,5- pentanediamines after absorption are eluted (desorption)：
In step (2), the elution is to be eluted according to this field routine elution process.The eluent when elution
Can be any of following type：
Type one：Strong alkali aqueous solution and its mixed solution；
Or, type two：The mixed aqueous solution of highly basic and weak base；
Or, type three：Acidic aqueous solution.
Wherein, the highly basic preferably includes：Alkali metal hydroxide and/or alkaline earth metal hydroxide more preferably include：
It is one or more in sodium hydroxide, potassium hydroxide and calcium hydroxide.
Wherein, the preferred 1-12wt% of the concentration of the strong alkali aqueous solution, more preferable 2-8wt%, most preferably 3-5wt%.
Wherein, the weak base preferably includes ammonium hydroxide.
Wherein, the acidic aqueous solution preferably includes inorganic acid and/or organic acid；Wherein, the inorganic acid is preferably inorganic
Strong acid, more preferable sulfuric acid and/or hydrochloric acid；The preferred organic dibasic acid of organic acid, in more preferable oxalic acid, succinic acid and adipic acid
It is one or more.Wherein, the concentration of the aqueous solution of the inorganic acid preferred 1-12wt%, more preferable 2-8wt%.Wherein,
The saturated aqueous solution of the preferred organic acid of aqueous solution of the organic acid is (when the concentration of the saturated aqueous solution of the organic acid is more than
10wt% then selects the aqueous solution of the organic acid of 2-10wt%).
Specifically, the eluent can be the aqueous solution of sodium hydroxide, or, the aqueous solution of potassium hydroxide, or, hydrogen-oxygen
The aqueous solution for changing calcium, or, the mixed liquor of the aqueous solution of sodium hydroxide and potassium hydroxide.The eluent can be sodium hydroxide and
The mixed solution etc. of ammonium hydroxide.Alternatively, the eluent can also be the mixed solution of acidic aqueous solution or acidic aqueous solution.
In step (2), preferred 10-90 DEG C, more preferable 30-60 DEG C of the temperature of the elution.
In step (2), the mode of the elution is any of following manner：
Mode one：The cation exchange resin is mixed with the eluent, is eluted；
Or,
Mode two：The eluent is flowed through into the resin cation.
Wherein, in mode one, the mode of the mixing preferably stirs.
Wherein, in mode two, the flow velocity preferred 0.5-8BV/h, more preferable 1-4BV/h of the eluent of the elution.
After step (2), suitable water rinse resin can also be used, remaining pentanediamine in resin is fully washed, to the greatest extent
Amount recycling pentanediamine product, obtains pentanediamine aqueous solution.
The embodiment that the present invention most has after the mode one in step (1), carries out the mode one in step (2)；
After mode two in step (1), the mode two in step (2) is carried out.
Eluent is further processed：
Including but not limited to the following method is further processed to the eluents of 1,5- pentanediamines：
For the eluent eluted with the aqueous solution of alkali, can evaporate, rectifying, the modes such as concentration obtain 1,5- pentanediamines；
For the eluent eluted with the aqueous solution of inorganic acid, basification is first carried out, then re-evaporation concentration, rectifying obtains
Obtain 1,5- pentanediamines；
For the eluent eluted with the aqueous solution of organic dibasic acid, it can further concentrate and carry out polymerizing polyamide.
1,5- pentanediamine solution is evaporated, is the mistake for being further separated out water from 1,5- pentanediamine solution
Journey.Because the boiling temperature of water is far below 1,5- pentanediamines, so by the way of evaporation, it is easy to by water and 1,5- pentanediamines point
It leaves.The equipment of evaporation can select conventional distilling apparatus, can also select multi-effect evaporator, rectifying can also be selected to set
It is standby, it can evaporate, can also be evaporated under reduced pressure under normal pressure.
To 1,5- pentanediamine concentrates carry out rectifying, preferred 50-250 DEG C of the temperature of rectifying, further preferred 70-185 DEG C,
Still more preferably 70-120 DEG C.The pressure of rectifying be preferable over 0.5MPa (gauge pressure) hereinafter, further preferably 0MPa (gauge pressure) with
Under, still more preferably 0.02MPa (absolute pressure) is hereinafter, i.e. -0.08MPa (gauge pressure).
In the present invention, if having carried out primary above elution and/or washing, routinely merge washing lotion according to this field,
Subsequent processing as described above is carried out again.
The present inventor may also contain considerable part it is emphasized that after evaporation in obtained evaporation residue
Remaining 1,5- pentanediamines and inorganic salts, this part salt can by subsequent processes technique, such as repeat the present invention separation work
Skill process, or existing technical process, such as extraction process are used, it is further processed, improves entire process recovery ratio.
The present inventor it is specifically that, during realizing present invention process, the technique actually used can not
It is only limited to above description, according to the difference of technological requirement, process can be increased, increased process portion will not be to work
The main body of skill generates change substantially, has only carried out supplement or perfect to main process in some aspects.
Compared with conventional method, separation method of the invention can be completed at the same time extraction with a step and purify 1,5- pentanediamines
Step, 1, the 5- pentanediamines ion in the adsorbent solution of resin cation selectivity and other cations, and 1,5- pentanediamine water
Impurity in solution, such as sugar, pigment fermentating metabolism product and 2, the by-products such as 3,4,5- tetrahydropyridines then not with cation
Resin acts on, and still remains in original solution, and the solution of pure 1,5- pentanediamines can be obtained, no in the mode ratio with alkali is directly added
With particularly across decolourizing and remove thalline step, obtained 1,5- pentanediamines sterling quality is more preferable, and impurity is less, purer.
In the present invention, 1,5- pentanediamines in original solution are substantially all to be adsorbed by resin cation, and it is molten to remain in processing
The level that the concentration of 1,5- pentanediamines in liquid can reach trace or even can not be detected.Because 1,5- pentanediamines are moderate toxicities
Compound, the processing for remaining the waste water solution of 1,5- pentanediamines is the ultimate challenge faced in 1,5- pentanediamine production technologies.It adopts
With the technique of the present invention, 1,5- pentanediamine high income is produced in waste water and is remained without 1,5- pentanediamines, is easy to give birth to 1,5- pentanediamines
Produce that waste water is innoxious, thus the method for the present invention is not only suitably applied in extraction 1,1 in 5- pentanediamine solution, 5- pentanediamines,
It is also applied for processing 1,1, the 5- pentanediamine waste water in 5- pentanediamine production processes, 1,5- pentanediamine waste water after processing carries out
After biochemical treatment can direct emission, and eluting the eluent for containing 1,5- pentanediamines that resin obtains also can directly recycle.
After the present invention removes the substances such as sugar, the pigment in the solution of 1,5- pentanediamines, make subsequent separating step, such as extracts
Take, evaporate become it is simpler be easy, eluted in particular with binary aqueous acid, eluent can directly concentrate into
The further polymerizing polyamide of row.
In addition, the separation method industrial automatization of the present invention is high, production efficiency is high, and 1,5- pentanediamine high income contains
Miscellaneous low, environmental sound is simultaneously easily processed, and is conducive to the large-scale production of 1,5- pentanediamines, while reducing and even avoiding polarity
The application of organic solvent reduces the pollution to environment and separation costs.
Unless otherwise defined, term used herein is the normally understood meaning of those skilled in the art.
The present invention is described in further detail by the following examples.
Embodiment
In embodiment, 2, the relative concentrations of 3,4,5- tetrahydropyridines refer in solution 2,3,4,5- tetrahydropyridines relative to
The Mole percent specific concentration of 1,5- pentanediamines.
The preparation method of the substances such as sample and assay method used in embodiment and comparative example are as described below：
The detection method of the detection method of 1.1,5- pentanediamines and 2,3,4,5- tetrahydropyridines：
Referring to CN102782146A, using gas phase normalization method.
<Purity (the unit of 1,5- pentanediamines：Quality %)>
Use the purifying 1 obtained in aftermentioned (distillation of 1,5- pentanediamine), 5- pentanediamines, using by gas below
Standard curve made of the area value of the gas chromatogram obtained under phase chromatographic conditions calculates the purity of 1,5- pentanediamines.
Device：GC-6890 (Agilent Technologies corporations)
Column：WCOT FUSED SILICA CP-SIL 8CB FOR AMINES (VARIAN corporations)
Column temperature：3min is kept at 40 DEG C, 300 DEG C is warming up to from 40 DEG C with the rate of 10 DEG C/min, is kept at 300 DEG C
11min
Inlet temperature：250℃
Detector temperature：280℃
Carrier gas：Helium
Detection method：FID
Embodiment 1
(1) 1, the 5- pentanediamine enzymatic conversion liquid of 50g is added in 250mL triangular flasks, 1,5- pentanediamine concentration 2.5wt%,
PH value 8.1, it is 2.7 to measure its absorbance at 340nm；30mL732 storng-acid cation exchange resins are added in solution
(pH3.0), stir 10min under the conditions of 25 DEG C, filter paper filtering, obtained clear liquid sample detection, 1, the 5- pentanediamines of solution it is dense
Spend 2000ppm；
(2) resin will be obtained by filtration to be added in 150mL sodium hydrate aqueous solutions (concentration 2%), will be stirred under the conditions of 60 DEG C,
After 10min, a concentration of 7000ppm of 1,5- pentanediamines in solution is measured；Filter paper filters, and obtains containing the clear of 1,5- pentanediamines
Liquid, it is 0.15 to measure absorbance of the clear liquid of 1,5- pentanediamines at 340nm, most of color quilt during adsorption-desorption
Removing.
Embodiment 2
(1) 1, the 5- pentanediamines of 1g are added in 250mL triangular flasks, 30g water are added, extremely with 30% sulphur acid for adjusting pH
Water is added to the total 50g of solution in pH10；30mLD110 (Shanghai Hua Zhen) weak-acid cation-exchange resin is added in solution
(pH7.1), 10min is stirred under room temperature, and filter paper filters, obtained clear liquid sample detection, 1,5- pentanediamine concentration in solution
3000ppm；
(2) resin will be obtained by filtration to be added in 150mL sodium hydrate aqueous solutions (concentration 2%), will be stirred under the conditions of 60 DEG C
10min, filter paper filtering, measures a concentration of 7000ppm of 1,5- pentanediamines in filtrate.
Embodiment 3
(1) 1, the 5- pentanediamine enzymatic conversion liquid of 100mL, 15min is centrifuged in centrifuge with 4000rpm, and separating thallus obtains
Supernatant；60g supernatants are taken, a concentration of 3.1wt% of its 1,5- pentanediamine, pH value 7.8 are measured；Under room temperature, by supernatant
With the feed flow rate of 2BV/h be added to diameter 3cm, high 60cm, be filled with 200mL strong acid type cationic resins (Su Qing, 001*7,
Polystyrene macroporous type pH3.5) splitter in, after charging, with the water washing resin column of 2BV；Merge absorption efflux
And cleaning solution, gas Chromatographic Determination can not detect 1,5- pentanediamines；
(2) it uses the sodium hydroxide solution of 60mL3% to flow through resin under the conditions of 60 DEG C with the speed of 1BV/h, then uses
The water of 600mL washs resin with the speed of 2BV/h, collects the total 653g of all effluxes, measuring its 1,5- pentanediamine content is
2700ppm；
(3) obtained filtrate is evaporated in the evaporating kettle of pressure -0.095MPa, heating temperature is stepped up from 70 DEG C
To 150 DEG C, distillation to substantially no liquid steams；The evaporation yield 79.4wt% of 1,5- pentanediamines.
Embodiment 4
(1) 1, the 5- pentanediamine enzymatic conversion liquid of 100mL, 15min is centrifuged in centrifuge with 4000rpm, and separating thallus obtains
Supernatant；60g supernatants are taken, a concentration of 3.1wt% of its 1,5- pentanediamine is measured, pH to pH5.1 is adjusted with 30% sulfuric acid solution；
Under the conditions of 60 DEG C, supernatant is added to diameter 3cm, high 60cm with the charging rate of 2BV/h, is filled with 200mL strong-acid type sun
In the splitter of ion exchange resin (Su Qing, 001*7, polystyrene macroporous type, pH3.5), after charging, with the water washing of 2BV
Resin column；1,5- pentanediamines can not be detected by merging absorption efflux and cleaning solution, gas chromatographic detection；
(2) potassium hydroxide solution of 40g 6% is used to flow through resin at 60 DEG C with the speed of 1BV/h, then use 600mL
Water resin is washed with the speed of 2BV/h, collect the total 635g of all effluxes, measuring its 1,5- pentanediamine content is
2800ppm；
(3) obtained filtrate is evaporated in the evaporating kettle of pressure -0.095MPa, heating temperature from 70 DEG C step up to
150 DEG C, distillation to basic no liquid steams；The evaporation yield of 1,5- pentanediamines is 81.0wt%.
Embodiment 5
(1) 1, the 5- pentanediamine enzymatic conversion liquid of 100mL, 15min is centrifuged in centrifuge with 4000rpm, and separating thallus obtains
Supernatant；60g supernatants are taken, a concentration of 3.1wt% of its 1,5- pentanediamine is measured, pH to pH5.1 is adjusted with 30% sulfuric acid solution；
Under the conditions of 60 DEG C, supernatant with the charging rate of 2BV/h be added to diameter 3cm, high 60cm, be filled with 200mL strong-acid types sun from
In the splitter of subtree fat (Su Qing, 001*7, polystyrene gel-type, pH4.5), after charging, with the water washing tree of 2BV
Fat column；1,5- pentanediamines can not be detected by merging absorption efflux and cleaning solution, gas chromatographic detection；
(2) it uses the potassium hydroxide solution of 40g 6% to flow through resin under the conditions of 60 DEG C with the speed of 1BV/h, then uses
The water of 600mL washs resin with the speed of 2BV/h, collects the total 635g of all effluxes, measures its 1,5- pentanediamine content
2700ppm；
(3) obtained filtrate is evaporated in the evaporating kettle of pressure -0.095MPa, heating temperature from 70 DEG C step up to
150 DEG C, distillation to substantially no liquid steams；The evaporation yield of 1,5- pentanediamines is 80.1wt%.
Embodiment 6
(1) 1, the 5- pentanediamine enzymatic conversion liquid of 100mL, 15min is centrifuged in centrifuge with 4000rpm, and separating thallus obtains
Supernatant；60g supernatants are taken, a concentration of 3.1wt% of its 1,5- pentanediamine is measured, pH is adjusted with the sodium hydroxide solution of 30wt%
To pH9.5；Under the conditions of 30 DEG C, supernatant is added to that diameter 3cm, high 60cm, to be filled with 200mL weak with the charging rate of 2BV/h
In the splitter of acid type resin cation (Su Qing, D113 type, acrylic acid series macroporous type, pH6.5), after charging, with 2BV's
Water washing resin column；Merge absorption efflux and cleaning solution, gas chromatographic detection, a concentration of 5ppm of 1,5- pentanediamine；
(2) mixed solution for using the sodium hydroxide of 40g 4% and 3% potassium hydroxide, under the conditions of 60 DEG C, with 1BV/h
Speed flow through resin, then with the water of 600mL resin is washed with the speed of 2BV/h, collects the total 636g of all effluxes, survey
Its fixed 1,5- pentanediamine content is 2500ppm；
(3) obtained filtrate is evaporated in the evaporating kettle of pressure -0.095MPa, heating temperature from 70 DEG C step up to
150 DEG C, distillation to basic no liquid steams；The evaporation yield of 1,5- pentanediamines is 78.3wt%.
Embodiment 7
(1) 1, the 5- pentanediamine salt enzymatic conversion liquid of 700L, under the conditions of 60 DEG C, with ceramic membrane (SanDa film Science (Xiamen)
Co., Ltd) filtering, thalline is removed, 1,5- pentanediamine salt clear liquids are obtained, detects a concentration of 3.3wt% of 1,5- pentanediamines, solution
pH7.8；Feeding liquid of this clear liquid as continuous ion-exchange；
(2) sodium hydroxide solution of 3wt% is prepared as alkali wash water；The hydrochloric acid solution of 0.5wt% is prepared as pickle；
(3) it is poly- that 24L strong acidic ion resins (732 types, polystyrene macroporous type) are uniformly packed into 30 diameter 3.3cm
In propylene chromatographic column together with automatic control system and feed pump, continuous ion-exchange system is formed；Pillar rotates successively around central shaft,
It is rotated forward once per 24min, each cycle (whole pillars are rotated back to original position) takes 12h；
Continuously the raw material of ion-exchange is：
Continuous ion-exchange system feeding situation is as follows：
No. 1 to No. 3 column series connection is feed zone, and the speed of No. 1 column into raw material is 40ml/min；
No. 4 to No. 10 column series connection, the speed for the areas washing I, the water inlet of No. 4 columns is 120ml/min；
O.11 is connected to No. 15 column, is alkali cleaning area, the speed of No. 11 columns into alkali is 40ml/min, and alkali is concentration
The sodium hydroxide solution of 3.0wt%；
No. 16 to No. 25 column series connection, the speed for the areas washing II, the water inlet of No. 21 columns is 80ml/min；
No. 26 to No. 27 column series connection is acid-washing region, and the speed of No. 28 columns into acid is 40ml/min, and acid is 0.5wt%
Hydrochloric acid solution；
No. 28 to No. 30 column series connection is water wash zone, and the speed of No. 21 columns water inlet is 80ml/min；
Continuous ion-exchange system discharging situation is as follows：
Merge alkali cleaning area and washing II areas liquid is product discharge end, discharge end flow velocity 120mL/min, 1,5- pentanediamine is dense
Degree is 1.1wt%；
(4) obtained 200kg filtrates are evaporated in the evaporating kettle of pressure -0.095MPa, heating temperature from 70 DEG C gradually
It improves to 150 DEG C, distillation to basic no liquid steams；The evaporation yield of 1,5- pentanediamines is 89.3wt%；
(5) obtained aqueous solution is evaporated with rectifier unit, collection pressure is -0.095MPa, and 92 DEG C or so of temperature evaporates
Point, obtain 1, the 5- pentanediamine finished products of purity 99.2wt%.
Comparative example 1
1, the 5- pentanediamine enzymatic conversion liquid of 50g is added in 250mL triangular flasks, 1,5- pentanediamine concentration 2.5wt%, pH value
8.1, it is 2.7 to measure its absorbance at 340nm.30mL732 storng-acid cation exchange resins are added in solution
(pH3.0), 10min, filter paper filtering, obtained clear liquid sample detection, 1, the 5- pentanediamine concentration of solution are stirred at 25 DEG C
2000ppm。
Resin will be obtained by filtration to be added in 150mL sodium hydrate aqueous solutions (concentration 2%), stirred under the conditions of 20 DEG C
After 10min, 1, the 5- pentanediamine concentration 5000ppm in solution is measured.
Comparative example 2
1, the 5- pentanediamine enzymatic conversion liquid of 50g is added in 250mL triangular flasks, 1,5- pentanediamine concentration 2.5wt%, pH value
8.1, it is 2.7 to measure its absorbance at 340nm.30mL732 storng-acid cation exchange resins are added in solution
(pH3.0), it stirs at 60 DEG C, filter paper filters after 10min, obtained clear liquid sample detection, 1, the 5- pentanediamine concentration of solution
4000ppm。
Resin will be obtained by filtration to be added in 150mL sodium hydrate aqueous solutions (concentration 2%), stirred under the conditions of 60 DEG C
After 10min, 1, the 5- pentanediamine concentration 5000ppm in solution is measured.
Comparative example 3
1, the 5- pentanediamine sulfate enzymatic conversion liquid of 200L, at room temperature, with stack centrifuge (the Nanjing oasis Zhong Chuan machine
Co., Ltd) centrifugation, thalline is removed, 1,5- pentanediamine sulfate clear liquids are obtained.The clear liquid has with 10000 Dalton molecular weights
Machine rolled film (Sandamo Science and Technology (Xiamen) Co., Ltd.) filters, and obtains clear filtrate.
1, the 5- pentanediamine sulfate enzymatic conversion liquid for taking above-mentioned 1000g, measures a concentration of 4.9wt% of its 1,5- pentanediamine,
Absorbance of the solution at 340nm is 3.7.31% (w/w) sodium hydroxide solution of 140g is added at 40 DEG C, stirs 2h, makes 1,
5- pentanediamines sulfate is fully reacted with sodium hydroxide, after reaction, pH value of solution ＞ 12.6.Solution is in 50-70 DEG C of temperature, pressure
It is concentrated by evaporation on power -0.085MPa Rotary Evaporators, stops when being concentrated into without obviously evaporating distillate.In pressure-
Under 0.095MPa, oil bath temperature is stepped up from 70 DEG C to 180 DEG C, is stopped when being evaporated to no apparent distillate.It evaporated
Cheng Zhong, residual solids substance gradually becomes glutinous in flask, and brown high viscosity slurry influences the further progress of evaporation.Evaporation knot
Shu Hou, remaining a large amount of blocky half dry solids in flask, hardness is high, large viscosity.
Merge evaporation liquid, obtains the aqueous solution that 1032g contains 1,5- pentanediamines 2.1%.1,5- pentanediamine evaporation yields
44wt%.
Those skilled in the art should be noted that embodiment described in the invention is only exemplary, can be
Various other replacements, changes and improvements are made in the scope of the present invention.Thus, the present invention is not limited to the above embodiments, and only
It is defined by the claims.
Claims (10)
1. one kind 1, the separation method of 5- pentanediamines, it is characterised in that：The separation method includes the following steps：
(1) solution of 1,5- pentanediamines is contacted with resin cation, is adsorbed；
(2) elution is adsorbed on the 1,5- pentanediamines on the resin cation.
2. separation method as described in claim 1, it is characterised in that：The pH of the solution of 1, the 5- pentanediamines is 3-12, excellent
It is 5-9 to select pH；
And/or the solution that the solution of 1, the 5- pentanediamines is 1, the 5- pentanediamines containing impurity；The impurity includes：Tetrahydrochysene
It is one or more in pyridine, thalline and protein；
And/or the solution of 1, the 5- pentanediamines is：1,5- pentanediamine enzymatic conversion solution and/or its treatment fluid, and/or, 1,5-
Pentanediamine fermentation liquid and/or its treatment fluid.
3. separation method as described in claim 1, it is characterised in that：The resin cation includes：Highly acidic cation tree
Fat, or, acidulous cation resin；
And/or the cation exchange resin includes：Hydrogen form cation resin, or, sodium form resin cation.
4. separation method as described in any one of claims 1-3, it is characterised in that：
In step (1), preferred 10-90 DEG C, more preferable 20-70 DEG C of the adsorption temp；
And/or in step (1), the solution of 1, the 5- pentanediamines is contacted with resin cation, is adsorbed, may include with
Under type：
Mode one：The solution of resin cation and 1,5- pentanediamines is uniformly mixed, is adsorbed；
And/or
Mode two：By the solution of 1,5- pentanediamines by ion exchange resin column, adsorbed.
5. separation method as claimed in claim 4, it is characterised in that：
In mode one, the uniformly mixed method is to be added to resin cation in the solution of 1,5- pentanediamines, and mixing is equal
It is even；
In mode one, the dosage of the resin cation is with the volume basis of the solution of 1,5- pentanediamines and resin, and described 1,5-
The volume ratio of the solution of pentanediamine and the resin cation preferably 6.5 or less；Wherein, the solution of 1, the 5- pentanediamines and institute
State the volume ratio of strong acidic ion resin preferably (0.5-2.7)：1；Wherein, the solution of 1, the 5- pentanediamines and the weak acid
Property resin cation volume ratio preferably (1-5)：1；
In mode one, the solution of resin cation and 1,5- pentanediamines is uniformly mixed, after being adsorbed, preferably passes through shake again
It one or more modes in modes such as swings, stir or stands, keep absorption more abundant.
6. separation method as claimed in claim 4, it is characterised in that：
In mode two, the feed flow rate of the absorption is 0.1-30BV/h, preferably 0.5-5BV/h；
And/or in mode two, as a concentration of 1wt% or more of 1,5- pentanediamines in the solution of 1,5- pentanediamines, the absorption
Feed flow rate preferred 0.1-10BV/h, more preferable 1-5BV/h；When in the solution of 1,5- pentanediamines 1,5- pentanediamines it is a concentration of
When 1wt% or less, the feed flow rate preferred 5-20BV/h, more preferable 8-15BV/h of the absorption；
And/or the ratio of height to diameter of the ion exchange resin column is (1-20)：1, preferably (3-8)：1, more preferable (4-6)：1；
And/or in mode two, after the absorption, washed；The washing is preferably washed with distilled water；It is described to wash
Flow velocity when washing is preferably 1-10BV/h, more preferable 2-5BV/h.
7. separation method as claimed in any one of claims 1 to 6, it is characterised in that：In step (2), the elution when elution
Liquid can be any of following type：
Type one：Strong alkali aqueous solution and its mixed solution；
Or, type two：The mixed aqueous solution of highly basic and weak base；
Or, type three：Acidic aqueous solution；
The wherein described highly basic preferably includes：Alkali metal hydroxide and/or alkaline earth metal hydroxide more preferably include：Hydrogen-oxygen
Change one or more in sodium, potassium hydroxide and calcium hydroxide；
And/or the weak base preferably includes ammonium hydroxide；
And/or the acidic aqueous solution preferably includes inorganic acid and/or organic acid；Wherein, the inorganic acid is preferably inorganic strong
Acid, more preferable sulfuric acid and/or hydrochloric acid；The preferred organic dibasic acid of organic acid, in more preferable oxalic acid, succinic acid and adipic acid
It is one or more；
And/or the concentration preferred 1-12wt%, more preferable 2-8wt% of the strong alkali aqueous solution；
And/or the preferred 1-12wt% of concentration of the aqueous solution of the inorganic acid, more preferable 2-8wt%；
And/or the aqueous solution of the organic acid be organic acid saturated aqueous solution, when the organic acid saturated aqueous solution it is dense
For degree more than 10wt%, the aqueous solution of the organic acid is the aqueous solution of the organic acid of concentration 2-10wt%.
8. separation method as claimed in claim 7, it is characterised in that：In step (2), the mode of the elution is with lower section
Formula it is any：
Mode one：The cation exchange resin is mixed with the eluent, is eluted；
Or,
Mode two：The eluent is flowed through into the resin cation；
Wherein, in mode one, the mode of the mixing preferably stirs；
Wherein, in mode two, the flow velocity preferred 0.5-8BV/h, more preferable 1-4BV/h of the eluent of the elution.
9. such as claim 1-8 any one of them separation methods, it is characterised in that：
In step (2), the temperature of the elution is 10-90 DEG C, preferably 30-60 DEG C.
10. such as claim 1-9 any one of them separation methods, it is characterised in that：
After step (2), the processing of eluent is also carried out；The processing mode includes：Evaporation and/or rectifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710011198.7A CN108276292B (en) | 2017-01-06 | 2017-01-06 | Separation method of 1, 5-pentanediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710011198.7A CN108276292B (en) | 2017-01-06 | 2017-01-06 | Separation method of 1, 5-pentanediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108276292A true CN108276292A (en) | 2018-07-13 |
| CN108276292B CN108276292B (en) | 2020-09-22 |
Family
ID=62800963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710011198.7A Active CN108276292B (en) | 2017-01-06 | 2017-01-06 | Separation method of 1, 5-pentanediamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108276292B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143882A (en) * | 2019-06-25 | 2019-08-20 | 郑州中科新兴产业技术研究院 | The method and separating and extracting process of L-lysine chemical decarboxylation production 1,5- pentanediamine |
| CN110563594A (en) * | 2019-09-05 | 2019-12-13 | 南京工业大学 | Method for refining pentamethylene diamine by separation-separation coupling process |
| WO2020060970A1 (en) * | 2018-09-18 | 2020-03-26 | Invista North America S.A.R.L. | Systems and methods for recovering amines and their derivates from aqueous mixtures |
| US10974168B2 (en) | 2015-04-08 | 2021-04-13 | Inv Nylon Chemicals Americas, Llc | Materials and methods for the selective recovery of monovalent products from aqueous solutions using continuous ion exchange |
| CN114057582A (en) * | 2021-11-16 | 2022-02-18 | 南京工业大学 | Method for continuously separating and purifying pentanediamine hydrochloride crystals |
| CN115594594A (en) * | 2021-07-08 | 2023-01-13 | 上海凯赛生物技术股份有限公司（Cn） | Pentanediamine chromatographic separation method and pentanediamine product |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023141455A2 (en) * | 2022-01-20 | 2023-07-27 | Archer Daniels Midland Company | E to 1.5 pentanediamine and separation of diamines from amino and carboxylic acids |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102131845A (en) * | 2008-06-30 | 2011-07-20 | 东丽株式会社 | Polyamide resin, composition containing polyamide resin, and molded articles of polyamide resin and composition |
| CN102732578A (en) * | 2006-03-30 | 2012-10-17 | 巴斯夫欧洲公司 | Process for the production of cadaverine |
| US20160168075A1 (en) * | 2013-08-23 | 2016-06-16 | Ajinomoto Co., Inc. | Method for Producing 1,5-Pentanediamine |
| CN106146318A (en) * | 2015-04-24 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | A kind of nylon salt of the purification process of the nylon salt containing 2,3,4,5-tetrahydropyridine and thus gained |
-
2017
- 2017-01-06 CN CN201710011198.7A patent/CN108276292B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732578A (en) * | 2006-03-30 | 2012-10-17 | 巴斯夫欧洲公司 | Process for the production of cadaverine |
| CN102131845A (en) * | 2008-06-30 | 2011-07-20 | 东丽株式会社 | Polyamide resin, composition containing polyamide resin, and molded articles of polyamide resin and composition |
| US20160168075A1 (en) * | 2013-08-23 | 2016-06-16 | Ajinomoto Co., Inc. | Method for Producing 1,5-Pentanediamine |
| CN106146318A (en) * | 2015-04-24 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | A kind of nylon salt of the purification process of the nylon salt containing 2,3,4,5-tetrahydropyridine and thus gained |
Non-Patent Citations (1)
| Title |
|---|
| 邓洁 等: "生物酶法合成1,5-戊二胺的研究进展", 《广西科学》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10974168B2 (en) | 2015-04-08 | 2021-04-13 | Inv Nylon Chemicals Americas, Llc | Materials and methods for the selective recovery of monovalent products from aqueous solutions using continuous ion exchange |
| WO2020060970A1 (en) * | 2018-09-18 | 2020-03-26 | Invista North America S.A.R.L. | Systems and methods for recovering amines and their derivates from aqueous mixtures |
| CN113015578A (en) * | 2018-09-18 | 2021-06-22 | 英威达纺织（英国）有限公司 | System and method for recovering amines and derivatives thereof from aqueous mixtures |
| CN113015578B (en) * | 2018-09-18 | 2023-11-21 | 英威达纺织（英国）有限公司 | System and method for recovering amines and derivatives thereof from aqueous mixtures |
| CN110143882A (en) * | 2019-06-25 | 2019-08-20 | 郑州中科新兴产业技术研究院 | The method and separating and extracting process of L-lysine chemical decarboxylation production 1,5- pentanediamine |
| CN110563594A (en) * | 2019-09-05 | 2019-12-13 | 南京工业大学 | Method for refining pentamethylene diamine by separation-separation coupling process |
| CN110563594B (en) * | 2019-09-05 | 2022-09-23 | 南京工业大学 | Method for refining pentamethylene diamine by separation-separation coupling process |
| CN115594594A (en) * | 2021-07-08 | 2023-01-13 | 上海凯赛生物技术股份有限公司（Cn） | Pentanediamine chromatographic separation method and pentanediamine product |
| CN114057582A (en) * | 2021-11-16 | 2022-02-18 | 南京工业大学 | Method for continuously separating and purifying pentanediamine hydrochloride crystals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108276292B (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108276292A (en) | A kind of separation method of 1,5- pentanediamines | |
| KR101543199B1 (en) | Method for Production of L-Methionine and Related Products | |
| Sun et al. | Salting-out extraction and crystallization of succinic acid from fermentation broths | |
| Boonmee et al. | Improved lactic acid production by in situ removal of lactic acid during fermentation and a proposed scheme for its recovery | |
| CN111269107A (en) | L-lactic acid purification and refining method | |
| CN108299278B (en) | Method for extracting and separating L-tryptophan | |
| CN107043330A (en) | A kind of method that 1,5- pentanediamines are extracted from the solution system of the salt of pentanediamine containing 1,5- | |
| CN102363594B (en) | Method for separating and purifying succinic acid from fermentation broth | |
| CN102911070A (en) | Technology for separating and extacting L-threonine from fermentation broth | |
| CN104529755B (en) | A kind of method being separated α-ketoglutaric acid from conversion fluid | |
| WO1997008332A1 (en) | A process for production of citric acid and monovalent citrate salts | |
| CN116813447A (en) | Method for co-producing inositol and disodium hydrogen phosphate by using corn soaking water | |
| CN103058877B (en) | A kind of method of utilizing chromatographic isolation GABA and glutamic acid | |
| CN108276293A (en) | A kind of separation method of 1,5- pentanediamines | |
| CN112266362B (en) | Method for extracting tetrahydropyrimidine by combining aqueous two-phase extraction with ion exchange chromatography | |
| CN105612257A (en) | Purification of cadaverine using high boiling point solvent | |
| TW201610164A (en) | A process for preparing succinic acid and succinate ester | |
| CN107032983B (en) | Method for extracting and separating succinic acid from fermentation liquor by using macroporous adsorption resin | |
| CN115772549A (en) | Preparation method for extracting nicotinamide containing trace nicotinic acid from fermentation liquor | |
| CN110372521B (en) | Method for stripping and recovering pentanediamine from aqueous phase containing pentanediamine | |
| Boonkong et al. | Comparison of an Ion Exchanger and an In‐House Electrodialysis Unit for Recovery of L‐Lactic Acid from Fungal Fermentation Broth | |
| CN103554065B (en) | A kind of method using succinic acid fermentation liquor to prepare tetrahydrofuran (THF) | |
| CN102249889B (en) | Method for extracting succinic acid from citric acid mother solution | |
| CN104974054A (en) | Method and apparatus for preparing iminodiacetic acid by using iminodiacetonitrile to produce mother liquor | |
| CN113121329B (en) | Method for coupling conversion and extraction of lactic acid from aqueous lactate raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 201203 floor 4, building 5, No. 1690, Cailun Road, Shanghai pilot Free Trade Zone Applicant after: Shanghai Kaisai Biotechnology Co., Ltd. Address before: 201203 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 1690 Building 5 Floor 4 Applicant before: Shanghai Cathay Biotechnology Research and Development Center Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |