CN108276292B - Separation method of 1, 5-pentanediamine - Google Patents
Separation method of 1, 5-pentanediamine Download PDFInfo
- Publication number
- CN108276292B CN108276292B CN201710011198.7A CN201710011198A CN108276292B CN 108276292 B CN108276292 B CN 108276292B CN 201710011198 A CN201710011198 A CN 201710011198A CN 108276292 B CN108276292 B CN 108276292B
- Authority
- CN
- China
- Prior art keywords
- pentanediamine
- solution
- resin
- separation method
- acid
- 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.)
- Active
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a separation method of 1, 5-pentanediamine, which comprises the following steps: (1) contacting the solution of 1, 5-pentanediamine with cation resin for adsorption; (2) eluting the 1, 5-pentanediamine adsorbed on the resin. Compared with the traditional method, the method for separating and recovering the 1, 5-pentanediamine improves the yield of the 1, 5-pentanediamine, basically does not contain 1, 5-pentanediamine residue in the treatment solution after resin adsorption, and does not adsorb impurities such as tetrahydropyridine, thalli, protein and the like in the resin, so that the obtained 1, 5-pentanediamine has high purity and low impurity content. The treatment solution obtained by resin adsorption does not contain polar organic solvent, is harmless to the environment and easy to treat, and reduces the pollution to the environment and the separation cost. Meanwhile, the 1, 5-pentanediamine diacid solution obtained by using diacid to elute can be directly used as a raw material for synthesizing high-performance polyamide.
Description
Technical Field
The invention relates to the field of separation and purification of organic matters, in particular to a separation method of 1, 5-pentanediamine.
Background
The chemical industry has long relied on petroleum and natural gas as raw materials to produce polymeric articles, which has become an important backbone of modern civilized society. However, with the gradual depletion of petroleum and natural gas resources, the greenhouse effect caused by the production and use of petroleum products is becoming more serious, and the search for alternative products of petrochemical resources, especially green products based on renewable resources, becomes an important development direction of the chemical industry at present.
Polyamide is a very important polymer material and has important application in a plurality of fields such as automobiles, high-grade textiles and the like, the annual output of the global polyamide polymer is over 600 million tons at present, and the consumption of China accounts for 30 percent of the global polyamide output.
Under such circumstances, the development of 1, 5-pentanediamine, particularly 1, 5-pentanediamine, has been desired. Starting from 1, 5-pentanediamine, polyamide 5X series products, such as polyamide 56 or all-bio-based polyamide 510, can be synthesized, and the products can be applied to various aspects of daily production and life of electronic and electric appliances, mechanical equipment, automobile parts and the like.
At present, the biological method for preparing 1, 5-pentanediamine mainly comprises a direct fermentation method and a lysine enzyme conversion method. Patents on the production and purification of pentamethylenediamine include the following reports:
patent EP1482055a1 discloses that during the enzymatic conversion, adipic acid is used to control the pH of the enzymatic conversion, 100% converting lysine; then, decolorizing with activated carbon with the content of 20% of the pentamethylene diamine, and concentrating to 70-77% of the concentration of the nylon salt; the temperature of the nylon salt solution is reduced from 60 ℃ to 10 ℃, and the pentamethylene diamine nylon salt is obtained by crystallization. However, the method of controlling the pH of the pentanediamine enzyme conversion solution by the organic acid, even if high-purity lysine is used as a raw material due to the addition of the enzyme protein, the obtained pentanediamine organic acid salt may contain impurities, which generally have a harmful effect on the polymerization of polyamide and affect the quality of the final polyamide product. Meanwhile, the process also has the difficulties of low crystallization yield of the polyamide salt and unstable product quality.
Patent CN101981202A discloses the direct fermentation of a solution of pentanediamine with a pentanediamine concentration of 72 g/L. Then refluxing the fermentation liquor for 5 hours at 103 ℃, and cracking by-products in the fermentation liquor; extracting with butanol for several times, and evaporating the organic solvent to obtain pentamethylene diamine product. The organic solvent is adopted to extract the pentanediamine, and the polar organic solvent is commonly used for extraction due to the influence of the characteristics of the pentanediamine. Polar organic solvents, such as chloroform or butanol, inevitably volatilize during the extraction process, causing environmental pollution and increasing the extraction cost. Toxic organic solvents also cause physical damage to the operator.
Patent CN200980121108 discloses treating the pentanediaminase reaction liquid by an organic membrane with UF12000 molecular weight, and reducing trifunctional organic matters in the reaction liquid, wherein the content of the trifunctional organic matters is 0.0063 relative to that of pentanediamine. Heating the solution of pentanediamine to above 100 deg.C to decompose the carbonate of pentanediamine, and distilling the pentanediamine to obtain the product. However, the decomposition of carbonate requires high temperature and long-time heating, and simultaneously, the complete decomposition of carbonate cannot be ensured, thereby influencing the rectification process and the product quality.
In the case of purifying 1, 5-pentanediamine from a1, 5-pentanediamine salt (e.g., 1, 5-pentanediamine sulfate), a method has been disclosed in which, in order to remove impurities such as tetrahydropyridine, bacterial cells, and proteins present in the 1, 5-pentanediamine salt, an alkaline substance (e.g., sodium hydroxide) is added to the 1, 5-pentanediamine salt to raise the pH and release the 1, 5-pentanediamine to form free 1, 5-pentanediamine, and the salt (e.g., sodium sulfate) formed by adding the alkaline substance is separated by an extraction operation to obtain free 1, 5-pentanediamine, which is then purified by distillation. Also, in the separation of 1, 5-pentanediamine from salts by an extraction operation, a large amount of organic solvent (e.g., aniline, chloroform, etc.) is required, and solvent volatilization during the extraction process is inevitable, causing environmental pollution, and increasing the separation cost. Toxic organic solvents also cause physical damage to the operator.
In addition, in the prior art, the alkalized 1, 5-pentanediamine aqueous solution is treated by a nanofiltration membrane, and the salt is filtered. Although the cost can be greatly reduced, a large amount of 1, 5-pentanediamine can be wrapped or included in the solid inorganic salt, so that the free 1, 5-pentanediamine can not be effectively recovered, for example, after the solid salt is removed by vacuum filtration, the distillation recovery efficiency of the 1, 5-pentanediamine is only about 20 percent at most, the yield is low, and a large amount of products are wasted.
The above methods for separating and recovering 1, 5-pentanediamine have the defects of low recovery rate, high impurity content of finished products, high cost, high energy consumption, serious environmental pollution and the like, so that the method for separating and recovering 1, 5-pentanediamine with high efficiency, low cost and low pollution is sought in the field, and becomes a problem to be solved urgently in the prior art.
Disclosure of Invention
Aiming at the defects of the existing separation method of 1, 5-pentanediamine (the following 1, 5-pentanediamine is 1, 5-pentanediamine), the inventor provides a method for separating 1, 5-pentanediamine from a solution of the 1, 5-pentanediamine, which is simple and efficient, and the obtained 1, 5-pentanediamine product has high purity and low impurity content, and the separation method of the 1, 5-pentanediamine has low cost and no pollution to the environment.
The invention provides a separation method of 1, 5-pentanediamine, which comprises the following steps:
(1) contacting the solution of 1, 5-pentanediamine with cation resin for adsorption;
(2) eluting the 1, 5-pentanediamine adsorbed on the cationic resin.
Further preferred embodiments of the above-described embodiments are described in detail below:
in one embodiment of the separation process of the present invention, the solution of pentanediamine has a pH of 3-12, preferably a pH of 5-9.
In one embodiment of the separation method of the present invention, the solution of 1, 5-pentanediamine comprises: 1, 5-pentanediamine in an ionic state (mainly existing in the form of a salt of the 1, 5-pentanediamine) and/or 1, 5-pentanediamine in an ionic state, wherein most of the 1, 5-pentanediamine exists in the form of the ionic state.
In one embodiment of the separation method of the present invention, the solution of 1, 5-pentanediamine is a solution of 1, 5-pentanediamine containing impurities.
In one embodiment of the separation method of the present invention, the impurities comprise: one or more of tetrahydropyridine, thallus and protein.
In one embodiment of the separation method of the present invention, the solution of 1, 5-pentanediamine may be obtained by a biological method and/or an organic synthesis method, and the solution of 1, 5-pentanediamine may be: 1, 5-pentanediamine enzyme conversion solution and/or treatment solution thereof, and/or 1, 5-pentanediamine fermentation solution and/or treatment solution thereof.
In one embodiment of the separation method of the present invention, the cationic resin comprises: a strongly acidic cation resin, or a weakly acidic cation resin.
In one embodiment of the separation method of the present invention, the cation exchange resin comprises: a hydrogen type cationic resin, or a sodium type cationic resin, or other suitable types.
In one embodiment of the separation method of the present invention, the cation exchange resin comprises: one of a hydrogen type strongly acidic cation resin, a hydrogen type weakly acidic cation resin, a sodium type strongly acidic cation resin or a sodium type weakly acidic cation resin.
In one embodiment of the separation method of the present invention, in the step (1), the solution of 1, 5-pentanediamine is contacted with a cationic resin to perform adsorption, and the adsorption temperature is preferably 10 to 90 ℃, more preferably 20 to 70 ℃.
In one embodiment of the separation method of the present invention, the contacting of the solution of 1, 5-pentanediamine with the cationic resin for adsorption in step (1) may include the following:
the first method is as follows: uniformly mixing the cationic resin and the solution of the 1, 5-pentanediamine, and adsorbing;
and/or the presence of a gas in the gas,
the second method comprises the following steps: passing the solution of the 1, 5-pentanediamine through an ion exchange resin column for adsorption.
In one embodiment of the separation method of the present invention, in the first embodiment, the method of uniformly mixing is a method conventional in the art, and the present invention preferably adds a cationic resin to a solution of 1, 5-pentanediamine and uniformly mixes.
In one embodiment of the separation method of the present invention, in the first embodiment, the cationic resin is used in a volume ratio of the solution of 1, 5-pentanediamine to the resin, and the volume ratio of the solution of 1, 5-pentanediamine to the cationic resin is preferably 6.5 or less. Wherein the volume ratio of the solution of the 1, 5-pentanediamine to the strong acid cation resin is preferably (0.5-2.7): 1; wherein, the volume ratio of the 1, 5-pentanediamine solution to the weak acidic cation resin is preferably (1-5): 1.
in one embodiment of the separation method of the present invention, in the first embodiment, the cationic resin and the solution of 1, 5-pentanediamine are uniformly mixed and adsorbed, and then the adsorption is further performed by one or more of shaking, stirring, standing or the like.
In one embodiment of the separation process of the present invention, mode two, the feed flow rate for the adsorption is preferably 0.1 to 30BV/h, more preferably 0.5 to 5 BV/h.
In one embodiment of the separation process of the present invention, in the second embodiment, when the concentration of 1, 5-pentanediamine in the solution of 1, 5-pentanediamine is 1 wt% or more, the feed flow rate of the adsorption is preferably 0.1 to 10BV/h, more preferably 1 to 5 BV/h; when the concentration of 1, 5-pentanediamine in the solution of 1, 5-pentanediamine is 1 wt% or less, the feed flow rate of the adsorption is preferably 5 to 20BV/h, more preferably 8 to 15 BV/h.
In one embodiment of the separation method of the present invention, the aspect ratio of the ion exchange resin column may be (1 to 20): 1, preferably (3-8): 1, more preferably (4-6): 1.
in one embodiment of the separation process of the present invention, mode two, the adsorption is carried out in the form of a fixed bed of cation exchange resin, a moving bed or a simulated moving bed.
In one embodiment of the separation method of the present invention, in the second embodiment, after the adsorption, washing is performed. The washing is preferably carried out with distilled water. The flow rate at the time of washing is preferably 1 to 10BV/h, more preferably 2 to 5 BV/h.
In one embodiment of the separation method of the present invention, in step (2), the elution is performed according to a conventional elution method in the art. The eluent in the elution may be any one of the following types:
the first kind: strong alkaline aqueous solution and mixed solution thereof;
or, type two: a mixed aqueous solution of a strong base and a weak base;
or, type three: an acidic aqueous solution.
Wherein the strong base preferably comprises: alkali metal hydroxides and/or alkaline earth metal hydroxides, more preferably including: one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
Among them, the concentration of the strong alkali aqueous solution is preferably 1 to 12 wt%, more preferably 2 to 8 wt%, most preferably 3 to 5 wt%.
Wherein the weak base preferably comprises ammonia.
Wherein the acidic aqueous solution preferably comprises an inorganic acid and/or an organic acid; wherein the inorganic acid is preferably strong inorganic acid, more preferably sulfuric acid and/or hydrochloric acid; the organic acid is preferably an organic dibasic acid, more preferably one or more of oxalic acid, succinic acid and adipic acid. Among them, the concentration of the aqueous solution of the inorganic acid is preferably 1 to 12% by weight, more preferably 2 to 8% by weight. The aqueous solution of the organic acid is preferably a saturated aqueous solution of the organic acid (when the concentration of the saturated aqueous solution of the organic acid exceeds 10 wt%, an aqueous solution of the organic acid of 2 to 10 wt% is selected).
In one embodiment of the separation method of the present invention, in the step (2), the temperature of the elution is preferably 10 to 90 ℃, more preferably 30 to 60 ℃.
In one embodiment of the separation method of the present invention, in the step (2), the elution mode is any one of the following modes:
the first method is as follows: mixing the cation exchange resin with the eluent to carry out elution;
or the like, or, alternatively,
the second method comprises the following steps: flowing the eluent through the cationic resin.
In the first embodiment, the mixing is preferably performed by stirring.
Wherein, in the second mode, the flow rate of the elution liquid is preferably 0.5-8BV/h, and more preferably 1-4 BV/h.
In one embodiment of the separation method of the present invention, after the step (2), the treatment of the eluate is further performed. The processing mode may include: evaporation and/or rectification.
In the present invention, if more than one elution and/or washing is performed, the washing solutions are combined as usual in the art, and the subsequent treatment as described above is performed.
The method for separating and recovering 1, 5-pentanediamine improves the yield of 1, 5-pentanediamine, basically does not contain 1, 5-pentanediamine residue in a treatment solution after resin adsorption, and does not adsorb impurities such as tetrahydropyridine, thalli, protein and the like in the resin, so that the obtained 1, 5-pentanediamine has high purity and low impurity content. The treatment solution obtained by resin adsorption does not contain polar organic solvent, is harmless to the environment and easy to treat, and reduces the pollution to the environment and the separation cost. Meanwhile, the 1, 5-pentanediamine diacid solution obtained by using diacid to elute can be directly used as a raw material for synthesizing high-performance polyamide.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The invention provides a separation method of 1, 5-pentanediamine, which comprises the following steps:
(1) contacting the solution of 1, 5-pentanediamine with cation resin for adsorption;
(2) eluting the 1, 5-pentanediamine adsorbed on the resin.
Solution of 1, 5-pentanediamine:
in the present invention, the solution of pentamethylene diamine has a pH of 3-12, preferably 5-9.
In the present invention, the solution of 1, 5-pentanediamine comprises: 1, 5-pentanediamine in an ionic state (mainly existing in the form of a salt of the 1, 5-pentanediamine) and/or 1, 5-pentanediamine in an ionic state, wherein most of the 1, 5-pentanediamine exists in the form of the ionic state.
In the present invention, the solution of 1, 5-pentanediamine is a solution of 1, 5-pentanediamine containing impurities.
In the present invention, the impurities include: one or more of tetrahydropyridine, thallus and protein.
In the present invention, the solution of the 1, 5-pentanediamine may be obtained by a biological method and/or an organic synthesis method, and the solution of the 1, 5-pentanediamine may be:
(1) a1, 5-pentanediamine enzyme conversion solution and/or a treatment solution thereof, and/or,
(2)1, 5-pentanediamine fermentation solution and/or a treatment solution thereof, and/or,
(3) the solution of the 1, 5-pentanediamine is prepared by the reaction of the pure product of the pentanediamine and acid.
In industry, the first two are generally used.
Wherein, (1) the 1, 5-pentanediamine enzyme conversion solution and/or the treatment solution thereof:
the 1, 5-pentanediaminase conversion solution is 1, 5-pentanediaminase conversion solution obtained by the reaction of lysine or lysine salt solution under the action of lysine decarboxylase. The specific preparation method of the 1, 5-pentanediamine enzymatic conversion solution is not particularly limited, and a person skilled in the art can select specific raw materials and determine the process parameters of a specific enzymatic conversion process according to the prior art.
Lysine salt in the present invention means an inorganic salt or an organic salt of lysine, and preferably lysine sulfate.
The lysine salt solution may be a commercially available or self-made solution of solid lysine salt dissolved in water, such as commercially available lysine hydrochloride, lysine sulfate, or lysine salt solution formed by dissolving lysine salt in water. And as the self-made lysine hydrochloride and lysine sulfate finished product, the lysine salt solution generated by dissolving in water.
The salt solution of lysine may be a fermentation broth of lysine. In industrial large-scale fermentation, the medium employs ammonium sulfate as one of the nitrogen sources, and thus the fermentation broth contains a large amount of sulfate.
The lysine salt solution can also be a liquid obtained by further removing impurities from the lysine fermentation liquor, such as a clear solution obtained by removing bacteria from the fermented lysine fermentation liquor through centrifugation, filtration or membrane filtration, or a lysine salt solution obtained by decoloring the fermented lysine fermentation liquor by adding activated carbon and filtering.
Lysine Decarboxylase (LDC) in the present invention refers to an enzyme which acts on lysine to produce 1, 5-pentanediamine. The lysine decarboxylase can be lysine decarboxylase fermentation liquor, or fermentation liquor cells obtained by centrifugation, filtration or other technical means, or broken cells, or fermentation liquor clear liquid obtained after the cells of the fermentation liquor are filtered, or refined enzyme. Or a mixture of two or more enzymes.
The lysine decarboxylase-producing microorganism may be a wild strain, a mutant strain, or a strain subjected to gene recombination.
The process of the decarboxylation of lysine in the present invention is not particularly limited, and any of the existing enzymatic conversion techniques can be used.
For example: zhu Jing (research on the transformation of L-lysine into cadaverine by microorganisms, Master thesis, Tianjin science and technology university, 3 months 2009) proposes the following four methods:
(1) and (3) direct reaction: lysine hydrochloride is directly added into lysine decarboxylase fermentation liquor until the concentration of the substrate is 0.05mol/kg, the reaction lasts for 2 hours, and the molar conversion rate is 36.05 percent.
(2) And buffer system enzyme reaction: the pH change of the reaction system is buffered by 0.6N acetic acid buffer solution, the final concentration of lysine hydrochloride in the buffer solution is 0.22mol/kg, the reaction is carried out for 2h, and the molar conversion rate is 81.30 percent.
(3) Controlling pH enzyme reaction: the pH of the reaction is controlled by strong acid to 5-6, the concentration of lysine hydrochloride in an enzyme reaction system is 0.22mol/kg, the reaction lasts for 2 hours, and the molar conversion rate is 94.97%.
(4) Controlling pH and carrying out batch enzyme reaction: the pH value of the reaction is controlled by strong acid to be 5-6, the initial lysine hydrochloride concentration in the reaction system is 0.22mol/kg, the product and the enzyme are continuously separated in situ after the reaction is carried out for a certain time, the final conversion substrate is 0.87mol/kg, and the yield of the cadaverine is 94.61%.
Chinese patent document (application No. 201180010677.8) discloses that efficiency is improved by subjecting a lysine decarboxylase-expressing microorganism to freeze thawing, heat treatment, lysine salt treatment, and the like before the enzymatic conversion.
Japanese patent document JP20050147171 discloses carrying out enzyme catalysis with an aqueous lysine carbonate solution as a substrate and adjusting the pH with carbon dioxide.
In the decarboxylation of lysine, other components such as inorganic salts, vitamins, or other additives that contribute to the enzymatic reaction process may be additionally added as necessary.
In the decarboxylation of lysine, the reaction temperature is generally 20 ℃ or higher and 60 ℃ or lower.
Wherein, (2) the 1, 5-pentanediamine fermentation solution and/or the treatment solution thereof:
the 1, 5-pentanediamine fermentation solution refers to: by means of gene technology, the expression of lysine decarboxylase is up-regulated or recombinant expressed in the strain capable of producing lysine, and produced lysine can be synchronously converted into pentanediamine in the fermentation process to obtain the pentanediamine fermentation liquor. The invention has no special requirements on the recombinant bacteria as long as the pentamethylene diamine can be obtained. For example, "construction of a genetically engineered bacterium for producing 1, 5-pentanediamin Corynebacterium glutamicum by one-step method" (Tan et al, J. China bioengineering, 2010, 30 (8): 93-99) discloses a recombinant strain obtained by using a genome of Hafnia alvei (Hafnia alvei) as a template, performing PCR amplification to obtain a lysine decarboxylase gene ldc, and using shuttle plasmids of Escherichia coli (Escherichia coli)/Corynebacterium glutamicum (Corynebacterium glutamicum) as vectors to clone a target gene fragment obtained by amplification to the Corynebacterium glutamicum. One skilled in the art would know how to optimize the media components, ratios, and fermentation process parameters for a particular recombinant bacterium. Further, a1, 5-pentamethylenediamine fermentation treatment liquid (refer to CN101981202A) obtained by adding an alkali metal to a1, 5-pentamethylenediamine fermentation liquid was obtained.
In the present invention, the solution of the 1, 5-pentanediamine further includes an anion. The kind of the anion is not particularly limited as long as the corresponding 1, 5-pentanediamine salt can be dissolved in water. The anion includes, but is not limited to, one or more of sulfate, carbonate, phosphate, adipate, sebacate, chloride, or carbonate.
Cationic resin:
in the present invention, the cationic resin includes: a strongly acidic cation resin or a weakly acidic cation resin; the method comprises the following steps: a hydrogen type cationic resin, or a sodium type cationic resin, or other suitable types.
In the present invention, the cation exchange resin comprises: one of a hydrogen type strongly acidic cation resin, a hydrogen type weakly acidic cation resin, a sodium type strongly acidic cation resin or a sodium type weakly acidic cation resin.
In the present invention, the cation exchange resin comprises: the cation exchange resin is preferably styrene cation exchange resin.
In one embodiment of the invention, the cation resin is 732 strong acid cation exchange resin; in one embodiment of the invention, the cation resin is a 732 strong acid cation resin regenerated by hydrochloric acid, and the majority of the resin is in an H-type state; in one embodiment of the invention, the cation resin is a 732 strong acid cation resin treated with sodium hydroxide and water, which is mostly in the Na-type state; in one embodiment of the invention, the cation resin is a D110 weakly acidic cation exchange resin; in one embodiment of the invention, the cationic resin is a 001 × 7 styrene macroporous strong acid type cationic resin; in one embodiment of the invention, the cationic resin is a 001 x 7 styrene-based gel type strong acid type cationic resin; in one embodiment of the present invention, the cationic resin is a D113 type acrylic macroporous weak acid type cationic resin.
In the present invention, the cation exchange resin may be a gel type, a macroporous type, or another type of cation exchange resin.
In the present invention, the ion exchange resin may be activated or regenerated prior to adsorption as is conventional in the art. The activated cation exchange resin has a pH of generally 11 or less, preferably 3 to 9.
Adsorbing 1, 5-pentanediamine by using cation resin:
in the step (1), the solution of the 1, 5-pentanediamine is contacted with cation resin for adsorption;
in step (1), the adsorption temperature is preferably 10 to 90 ℃, more preferably 20 to 70 ℃, and most preferably 20 to 40 ℃.
In the step (1), the solution of 1, 5-pentanediamine is contacted with a cationic resin for adsorption, which may include the following ways:
the first method is as follows: uniformly mixing the cationic resin and the solution of the 1, 5-pentanediamine, and adsorbing; and/or, mode two: passing the solution of the 1, 5-pentanediamine through an ion exchange resin column for adsorption.
Wherein, in the first mode:
the method for uniformly mixing comprises the following steps: adding the cationic resin into the solution of the 1, 5-pentanediamine, and uniformly mixing.
The dosage of the cation resin is calculated by the volume ratio of the solution of the 1, 5-pentanediamine to the resin, and the volume ratio of the solution of the 1, 5-pentanediamine to the cation resin is preferably less than 6.5. Among them, the volume ratio of the solution of 1, 5-pentanediamine to the strongly acidic cation resin is preferably (0.5 to 2.7): 1. among them, the volume ratio of the solution of 1, 5-pentanediamine to the weakly acidic cationic resin is preferably (1-5): 1.
the cation resin and the solution of the 1, 5-pentanediamine are uniformly mixed and adsorbed, and then the adsorption can be more fully realized by one or more of the modes of oscillation, stirring or standing and the like.
In some examples, the cationic resin is mixed with a solution of 1, 5-pentanediamine, stirred at room temperature (20 ℃) for 10min, and then filtered to provide a resin that adsorbs 1, 5-pentanediamine.
In the first mode, the cation resin selectively adsorbs the pentanediamine ions and other cations in the solution, and impurities in the pentanediamine salt solution, such as fermentation metabolites of sugar, pigment and the like, do not react with the cation resin and remain in the original solution. After the adsorption is finished, the resin adsorbed with the pentamethylene diamine can be separated from other impurities by simple separation methods such as filtration, centrifugation and the like, and the pentamethylene diamine product is effectively purified.
Wherein, in the second mode:
the feed flow rate for the adsorption is preferably 0.1-30BV/h, more preferably 0.5-5 BV/h; when the concentration of 1, 5-pentanediamine in the solution of 1, 5-pentanediamine is 1 wt% or more, the feed flow rate of the adsorption is preferably 0.1 to 10BV/h, more preferably 1 to 5 BV/h; when the concentration of 1, 5-pentanediamine in the solution of 1, 5-pentanediamine is 1 wt% or less, the feed flow rate of the adsorption is preferably 5 to 20BV/h, more preferably 8 to 15 BV/h.
In one embodiment of the separation method of the present invention, the aspect ratio of the ion exchange resin column may be (1 to 20): 1, preferably (3-8): 1, more preferably (4-6): 1.
the adsorption is carried out in the form of a fixed bed of cation exchange resin, a moving bed or a simulated moving bed.
After the adsorption, washing was performed. The washing is preferably carried out with distilled water. After the cationic resin adsorbs the pentamethylenediamine solution, impurities remaining between the resins can be further separated by means of water washing or the like, and conditions are prepared for desorption of pentamethylenediamine. The flow rate at the time of washing is preferably 1 to 10BV/h, more preferably 2 to 5 BV/h.
In some embodiments, the cationic resin may be loaded into a separation column through which a solution of 1, 5-pentanediamine is passed at a rate of 2 BV/h. In some embodiments, the cationic resin may be loaded into a continuous ion-exchange system comprising 30 polypropylene chromatography columns through which an aqueous solution of 1, 5-pentanediamine is passed to produce a solution of 1, 5-pentanediamine.
In the second mode, the adsorption process adopts a mode of passing through a resin column, namely, the resin is fixed in the separation column, the solution of the 1, 5-pentanediamine passes through the resin column, the 1, 5-pentanediamine and part of cations are adsorbed, and other impurities are separated along with the solution outside the column. After the cationic resin adsorbs the 1, 5-pentanediamine solution, impurities remaining between the resins can be further separated by means of washing with water or the like, and conditions are prepared for desorption of the 1, 5-pentanediamine.
In the step (1), the cation resin selectively adsorbs 1, 5-pentanediamine ions and other cations in the solution, while impurities in the solution of the 1, 5-pentanediamine, such as fermentation metabolites of sugar, pigment and the like, and byproducts of 2,3,4, 5-tetrahydropyridine and the like do not react with the cation resin and remain in the original solution.
Elution (desorption) of the adsorbed 1, 5-pentanediamine:
in the step (2), the elution is performed according to the conventional elution method in the field. The eluent in the elution may be any one of the following types:
the first kind: strong alkaline aqueous solution and mixed solution thereof;
or, type two: a mixed aqueous solution of a strong base and a weak base;
or, type three: an acidic aqueous solution.
Wherein the strong base preferably comprises: alkali metal hydroxides and/or alkaline earth metal hydroxides, more preferably including: one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
Among them, the concentration of the strong alkali aqueous solution is preferably 1 to 12 wt%, more preferably 2 to 8 wt%, most preferably 3 to 5 wt%.
Wherein the weak base preferably comprises ammonia.
Wherein the acidic aqueous solution preferably comprises an inorganic acid and/or an organic acid; wherein the inorganic acid is preferably strong inorganic acid, more preferably sulfuric acid and/or hydrochloric acid; the organic acid is preferably an organic dibasic acid, more preferably one or more of oxalic acid, succinic acid and adipic acid. Among them, the concentration of the aqueous solution of the inorganic acid is preferably 1 to 12% by weight, more preferably 2 to 8% by weight. The aqueous solution of the organic acid is preferably a saturated aqueous solution of the organic acid (when the concentration of the saturated aqueous solution of the organic acid exceeds 10 wt%, an aqueous solution of the organic acid of 2 to 10 wt% is selected).
Specifically, the eluent may be an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of calcium hydroxide, or a mixture of aqueous solutions of sodium hydroxide and potassium hydroxide. The eluent can be a mixed solution of sodium hydroxide and ammonia water, and the like. Alternatively, the eluent may be an acidic aqueous solution or a mixed solution of acidic aqueous solutions.
In the step (2), the temperature of the elution is preferably 10 to 90 ℃, more preferably 30 to 60 ℃.
In the step (2), the elution mode is any one of the following modes:
the first method is as follows: mixing the cation exchange resin with the eluent to carry out elution;
or the like, or, alternatively,
the second method comprises the following steps: flowing the eluent through the cationic resin.
In the first embodiment, the mixing is preferably performed by stirring.
Wherein, in the second mode, the flow rate of the elution liquid is preferably 0.5-8BV/h, and more preferably 1-4 BV/h.
After the step (2), the resin can be washed by using a proper amount of water, the residual pentamethylene diamine in the resin is fully washed, and the pentamethylene diamine product is recycled as much as possible to obtain the pentamethylene diamine aqueous solution.
In the most preferable embodiment of the present invention, after the first embodiment in step (1), the first embodiment in step (2) is performed; after the second mode in step (1), the second mode in step (2) is performed.
Further treatment of the eluate:
further processing of the eluate of 1, 5-pentanediamine includes, but is not limited to, the following methods:
for the eluent eluted by the aqueous solution of alkali, 1, 5-pentanediamine can be obtained by evaporation, rectification, concentration and other modes;
carrying out alkalization treatment on an eluent eluted by an aqueous solution of inorganic acid, and then carrying out evaporation concentration and rectification to obtain 1, 5-pentanediamine;
the eluate eluted with the aqueous solution of the organic dibasic acid may be further concentrated and subjected to polyamide polymerization.
The evaporation of the 1, 5-pentanediamine solution is a process for further separating water from the 1, 5-pentanediamine solution. Since the boiling temperature of water is much lower than that of 1, 5-pentanediamine, the water and the 1, 5-pentanediamine can be easily separated by evaporation. The evaporation equipment can be a conventional distillation device, a multi-effect evaporator or a rectification equipment, and can be used for evaporation under normal pressure or reduced pressure.
The concentrated solution of 1, 5-pentanediamine is rectified, and the rectifying temperature is preferably 50-250 ℃, more preferably 70-185 ℃, and still more preferably 70-120 ℃. The pressure of the rectification is preferably 0.5MPa (gauge pressure) or less, more preferably 0MPa (gauge pressure) or less, and still more preferably 0.02MPa (absolute pressure) or less, that is, -0.08MPa (gauge pressure).
In the present invention, if more than one elution and/or washing is performed, the washing solutions are combined as usual in the art, and the subsequent treatment as described above is performed.
The inventors have specifically pointed out that after the evaporation is complete, the evaporation residue obtained may contain a considerable portion of residual 1, 5-pentanediamine and inorganic salts, which may be further treated by subsequent treatment processes, such as repetition of the separation process of the present invention, or by using existing processes, such as extraction processes, etc., to increase the overall process yield.
The inventor also specifically points out that in the process of implementing the invention, the actually adopted process may not be limited to the above description, and according to different process requirements, a process procedure may be added, and the added process part may not substantially change the main body of the process, but only supplement or improve the main body process in some aspects.
Compared with the traditional method, the separation method can simultaneously complete the steps of extracting and purifying the 1, 5-pentanediamine in one step, the cation resin selectively adsorbs 1, 5-pentanediamine ions and other cations in the solution, impurities in the 1, 5-pentanediamine aqueous solution, such as fermentation metabolites of sugar, pigment and the like, and byproducts of 2,3,4, 5-tetrahydropyridine and the like do not react with the cation resin and are still remained in the original solution, compared with the mode of directly adding alkali, the pure 1, 5-pentanediamine solution can be obtained, the pure 1, 5-pentanediamine product obtained does not need to be specially subjected to decoloration and bacteria removal, and has better quality, less impurities and purer purity.
In the present invention, substantially all of the 1, 5-pentanediamine in the original solution is adsorbed by the cationic resin, and the concentration of the 1, 5-pentanediamine remaining in the treatment solution can reach a level of trace amount or even undetectable amount. Since 1, 5-pentanediamine is a moderately toxic compound, the treatment of the waste aqueous solution of the residual 1, 5-pentanediamine is the biggest challenge in the production process of 1, 5-pentanediamine. By adopting the process, the yield of the 1, 5-pentanediamine is high, no 1, 5-pentanediamine residue exists in the production wastewater, and the 1, 5-pentanediamine production wastewater is easy to be innoxious, so the method is not only suitable for extracting the 1, 5-pentanediamine in the 1, 5-pentanediamine solution, but also suitable for treating the 1, 5-pentanediamine wastewater in the 1, 5-pentanediamine production process, the treated 1, 5-pentanediamine wastewater can be directly discharged after biochemical treatment, and the 1, 5-pentanediamine-containing eluent obtained by resin elution can be directly recovered.
The invention removes sugar, pigment and other substances in the solution of the 1, 5-pentanediamine, makes the subsequent separation steps such as extraction and evaporation simpler and easier, and particularly uses dibasic acid aqueous solution for elution, and the eluent can be directly concentrated to further polyamide polymerization.
In addition, the separation method has high industrial automation degree, high production efficiency, high yield of the 1, 5-pentanediamine, low impurity content, no harm to the environment, easy treatment, contribution to large-scale production of the 1, 5-pentanediamine, reduction and even avoidance of the application of a polar organic solvent, and reduction of environmental pollution and separation cost.
Unless otherwise defined, all terms used herein have the meanings that are commonly understood by those skilled in the art.
The present invention will be described in further detail with reference to examples.
Examples
In the examples, the relative concentration of 2,3,4, 5-tetrahydropyridine refers to the molar percentage concentration of 2,3,4, 5-tetrahydropyridine in solution relative to 1, 5-pentanediamine.
The preparation methods and measurement methods of the samples and the like used in the examples and comparative examples are as follows:
the detection method of 1, 5-pentanediamine and 2,3,4, 5-tetrahydropyridine comprises the following steps:
see CN102782146A, using gas phase normalization.
< purity of 1, 5-Pentanediamine (% by mass) >
The purity of 1, 5-pentanediamine was calculated from a calibration curve prepared from the area value of a gas chromatogram obtained under the following gas chromatography analysis conditions, using purified 1, 5-pentanediamine obtained in (distillation of 1, 5-pentanediamine) described later.
The device comprises the following steps: GC-6890(Agilent Technologies Co., Ltd.)
Column: WCOT FUSED SILICA CP-SIL 8CB FOR AMINES (manufactured by VARIAN Co., Ltd.)
Column temperature: maintaining at 40 deg.C for 3min, heating from 40 deg.C to 300 deg.C at a rate of 10 deg.C/min, and maintaining at 300 deg.C for 11min
Injection port temperature: 250 deg.C
Detector temperature: 280 deg.C
Carrier gas: helium gas
Detection method: FID
Example 1
(1)50g of the 1, 5-pentanediamine enzyme conversion solution is added into a 250mL triangular flask, the concentration of the 1, 5-pentanediamine is 2.5 wt%, the pH value is 8.1, and the absorbance of the solution at 340nm is 2.7; adding 30mL732 strong acid cation exchange resin (pH3.0) into the solution, stirring at 25 deg.C for 10min, filtering with filter paper, and sampling the obtained clear solution to obtain a solution with a concentration of 1, 5-pentanediamine of 2000 ppm;
(2) adding the filtered resin into 150mL of sodium hydroxide aqueous solution (the concentration is 2%), stirring at 60 ℃, and after 10min, determining the concentration of 1, 5-pentanediamine in the solution to be 7000 ppm; filtering with filter paper to obtain clear solution containing 1, 5-pentanediamine, and measuring the absorbance of the clear solution containing 1, 5-pentanediamine at 340nm to be 0.15, wherein most of color is removed in the process of adsorption and desorption.
Example 2
(1) Adding 1g of 1, 5-pentanediamine into a 250mL triangular flask, adding 30g of water, adjusting the pH to 10 with 30% sulfuric acid, and adding water to the solution to obtain 50g of solution; adding 30mLD110 (Shanghai Huazheng) weakly acidic cation exchange resin (pH7.1) into the solution, stirring at room temperature for 10min, filtering with filter paper, sampling the obtained clear solution, and detecting to obtain 1, 5-pentanediamine with concentration of 3000 ppm;
(2) the resin obtained by filtration was added to 150mL of an aqueous solution of sodium hydroxide (concentration: 2%), stirred at 60 ℃ for 10min, filtered through filter paper, and the concentration of 1, 5-pentanediamine in the filtrate was measured to be 7000 ppm.
Example 3
(1) Centrifuging 100mL of 1, 5-pentanediamine enzyme conversion solution in a centrifuge at 4000rpm for 15min, and separating thalli to obtain supernatant; 60g of supernatant is taken, and the concentration of the 1, 5-pentanediamine is measured to be 3.1wt percent, and the pH value is 7.8; adding the supernatant into a separation column with the diameter of 3cm and the height of 60cm and filled with 200mL of strong acid type cation resin (Suqing, 001 × 7, styrene macroporous type pH3.5) at the feeding flow rate of 2BV/h at room temperature, and washing the resin column with 2BV water after the feeding is finished; combining the adsorption effluent and the washing liquid, and detecting by gas chromatography, wherein 1, 5-pentanediamine cannot be detected;
(2) 60mL of 3% sodium hydroxide solution was passed through the resin at 60 ℃ at a rate of 1BV/h, followed by 600mL of water at a rate of 2BV/h to wash the resin, and all the effluent was collected and found to have a1, 5-pentanediamine content of 2700 ppm;
(3) evaporating the obtained filtrate in an evaporation kettle with the pressure of-0.095 MPa, heating the filtrate to 150 ℃ from 70 ℃, and distilling until no liquid is evaporated; the evaporation yield of 1, 5-pentanediamine was 79.4 wt%.
Example 4
(1) Centrifuging 100mL of 1, 5-pentanediamine enzyme conversion solution in a centrifuge at 4000rpm for 15min, and separating thalli to obtain supernatant; 60g of supernatant was taken, the concentration of 1, 5-pentanediamine was measured to be 3.1 wt%, and the pH was adjusted to pH5.1 with 30% sulfuric acid solution; adding the supernatant into a separation column with a diameter of 3cm and a height of 60cm and filled with 200mL of strong acid type cation resin (Suqing, 001 × 7, styrene macroporous type, pH3.5) at a feeding speed of 2BV/h at 60 ℃, and washing the resin column with 2BV of water after the addition; combining the adsorption effluent and the washing liquid, and detecting by gas chromatography until the 1, 5-pentanediamine cannot be detected;
(2) a total of 635g of the effluent was collected by passing 40g of 6% potassium hydroxide solution at 60 ℃ over the resin at a rate of 1BV/h, followed by washing the resin with 600mL of water at a rate of 2BV/h, and the 1, 5-pentanediamine content was determined to be 2800 ppm;
(3) evaporating the obtained filtrate in an evaporation kettle with the pressure of-0.095 MPa, gradually increasing the heating temperature from 70 ℃ to 150 ℃, and distilling until no liquid is evaporated out basically; the evaporation yield of 1, 5-pentanediamine was 81.0 wt%.
Example 5
(1) Centrifuging 100mL of 1, 5-pentanediamine enzyme conversion solution in a centrifuge at 4000rpm for 15min, and separating thalli to obtain supernatant; 60g of supernatant was taken, the concentration of 1, 5-pentanediamine was measured to be 3.1 wt%, and the pH was adjusted to pH5.1 with 30% sulfuric acid solution; adding the supernatant into a separation column with a diameter of 3cm and a height of 60cm and filled with 200mL of strong acid type cation resin (Suqing, 001 × 7, styrene gel type, pH4.5) at a feeding speed of 2BV/h at 60 ℃, and washing the resin column with 2BV of water after the addition; combining the adsorption effluent and the washing liquid, and detecting by gas chromatography until the 1, 5-pentanediamine cannot be detected;
(2) 40g of 6% potassium hydroxide solution was passed through the resin at 60 ℃ at a rate of 1BV/h, followed by washing the resin with 600mL of water at a rate of 2BV/h, collecting a total of 635g of all the effluents and determining the 1, 5-pentanediamine content at 2700 ppm;
(3) evaporating the obtained filtrate in an evaporation kettle with the pressure of-0.095 MPa, gradually increasing the heating temperature from 70 ℃ to 150 ℃, and distilling until no liquid is evaporated; the evaporation yield of 1, 5-pentanediamine was 80.1 wt%.
Example 6
(1) Centrifuging 100mL of 1, 5-pentanediamine enzyme conversion solution in a centrifuge at 4000rpm for 15min, and separating thalli to obtain supernatant; 60g of the supernatant was taken, the concentration of 1, 5-pentanediamine was measured to be 3.1 wt%, and the pH was adjusted to pH9.5 with 30 wt% sodium hydroxide solution; adding the supernatant into a separation column with a diameter of 3cm and a height of 60cm and filled with 200mL of weak acid type cation resin (Suqing, D113 type, acrylic acid series macroporous type, pH6.5) at a feeding speed of 2BV/h at 30 ℃, and washing the resin column with 2BV of water after the addition is finished; combining the adsorption effluent and the washing liquid, and detecting by gas chromatography, wherein the concentration of the 1, 5-pentanediamine is 5 ppm;
(2) 40g of a mixed solution of 4% sodium hydroxide and 3% potassium hydroxide was passed through the resin at 60 ℃ at a rate of 1BV/h, followed by washing the resin with 600mL of water at a rate of 2BV/h, and all the effluent was collected in total of 636g and the 1, 5-pentanediamine content was determined to be 2500 ppm;
(3) evaporating the obtained filtrate in an evaporation kettle with the pressure of-0.095 MPa, gradually increasing the heating temperature from 70 ℃ to 150 ℃, and distilling until no liquid is evaporated out basically; the evaporation yield of 1, 5-pentanediamine was 78.3 wt%.
Example 7
(1)700L of the 1, 5-pentanediamine salt enzyme conversion solution is filtered by a ceramic membrane (Sanda membrane technology (Xiamen) Co., Ltd.) at the temperature of 60 ℃ to remove thalli, so as to obtain a1, 5-pentanediamine salt clear solution, the concentration of the 1, 5-pentanediamine is detected to be 3.3 wt%, and the pH value of the solution is 7.8; this clear solution was used as feed for continuous ion-exchange;
(2) preparing 3 wt% of sodium hydroxide solution as alkaline washing solution; preparing 0.5 wt% hydrochloric acid solution as pickling solution;
(3) uniformly loading 24L of strong acid cation resin (732 type, styrene macroporous type) into 30 polypropylene chromatographic columns with diameter of 3.3cm, and forming a continuous ion exchange system together with an automatic control system and a feed pump; the columns were rotated sequentially around the central axis, once every 24min forward, and each cycle (all columns rotated back to the home position) took 12 h;
the raw materials for continuous ion exchange are as follows:
the feeding conditions of the continuous ion exchange system are as follows:
the columns from No. 1 to No. 3 are connected in series and are used as a feeding area, and the feeding speed of the column from No. 1 is 40 ml/min;
the No. 4 to No. 10 columns are connected in series and are used as a washing I area, and the water inlet speed of the No. 4 column is 120 ml/min;
the 11 th to 15 th columns are connected in series and are used as an alkali washing area, the alkali feeding speed of the 11 th column is 40ml/min, and the alkali is 3.0 wt% sodium hydroxide solution;
the No. 16 to No. 25 columns are connected in series and are used as a water washing II area, and the water inlet speed of the No. 21 column is 80 ml/min;
the columns 26 to 27 are connected in series and are used as an acid washing area, the acid feeding speed of the column 28 is 40ml/min, and the acid is 0.5 wt% hydrochloric acid solution;
the No. 28 to No. 30 columns are connected in series and are used as a water washing area, and the water inlet speed of the No. 21 column is 80 ml/min;
the discharging condition of the continuous ion exchange system is as follows:
combining the liquid in the alkali washing area and the liquid in the water washing area II to be the discharge end of the product, wherein the flow rate of the discharge end is 120mL/min, and the concentration of 1, 5-pentanediamine is 1.1 wt%;
(4) evaporating 200kg of the obtained filtrate in an evaporation kettle with the pressure of-0.095 MPa, gradually increasing the heating temperature from 70 ℃ to 150 ℃, and distilling until no liquid is evaporated out basically; the evaporation yield of 1, 5-pentanediamine was 89.3 wt%;
(5) evaporating the obtained aqueous solution by using a rectifying device, and collecting fractions with the pressure of-0.095 MPa and the temperature of about 92 ℃ to obtain a finished product of the 1, 5-pentanediamine with the purity of 99.2 wt%.
Comparative example 1
50g of the 1, 5-pentanediamine enzyme-converted solution was charged into a 250mL Erlenmeyer flask, and the 1, 5-pentanediamine concentration was 2.5% by weight, pH was 8.1, and its absorbance at 340nm was measured to be 2.7. 30mL of 732 strongly acidic cation exchange resin (pH3.0) was added to the solution, and the mixture was stirred at 25 ℃ for 10min, filtered through filter paper, and the resulting clear solution was sampled and examined to find that the concentration of 1, 5-pentanediamine in the solution was 2000 ppm.
The resin obtained by filtration was added to 150mL of an aqueous solution of sodium hydroxide (concentration: 2%), and after stirring at 20 ℃ for 10 minutes, the concentration of 1, 5-pentanediamine in the solution was determined to be 5000 ppm.
Comparative example 2
50g of the 1, 5-pentanediamine enzyme-converted solution was charged into a 250mL Erlenmeyer flask, and the 1, 5-pentanediamine concentration was 2.5% by weight, pH was 8.1, and its absorbance at 340nm was measured to be 2.7. 30mL of 732 strong-acid cation exchange resin (pH3.0) was added to the solution, the mixture was stirred at 60 ℃ and filtered through a filter paper after 10 minutes, and the obtained clear solution was sampled and tested to have a1, 5-pentanediamine concentration of 4000 ppm.
The resin obtained by filtration was added to 150mL of an aqueous solution of sodium hydroxide (concentration: 2%), and after stirring at 60 ℃ for 10 minutes, the concentration of 1, 5-pentanediamine in the solution was determined to be 5000 ppm.
Comparative example 3
200L of the 1, 5-pentanediamine sulfatase conversion solution was centrifuged at room temperature by a lamination centrifuge (Nanjing Zhonghai oasis machine Co., Ltd.) to remove the cells, thereby obtaining a clear solution of 1, 5-pentanediamine sulfate. The clear solution was filtered through an organic spiral-wound membrane (Sanda Membrane technology, Xiamen, Inc.) of 10000 Dalton molecular weight to obtain a clear filtrate.
1000g of the above-mentioned 1, 5-pentanediamine sulfatase-converted solution was taken, and it was determined that the concentration of 1, 5-pentanediamine was 4.9% by weight and the absorbance of the solution at 340nm was 3.7. 140g of 31% (w/w) sodium hydroxide solution is added at 40 ℃, and stirred for 2h to ensure that the 1, 5-pentanediamine sulfate and the sodium hydroxide fully react, and the pH value of the solution is more than 12.6 after the reaction is finished. Evaporating and concentrating the solution on a rotary evaporator at 50-70 deg.C and-0.085 MPa until no distillate is evaporated. The oil bath temperature was gradually increased from 70 ℃ to 180 ℃ at a pressure of-0.095 MPa and was stopped by evaporation until no distillate was evident. In the evaporation process, the solid substances remained in the flask gradually become sticky and brown high-viscosity slurry, so that the further evaporation is influenced. After evaporation is finished, a large amount of blocky semi-dry solids are left in the flask, and the hardness and viscosity are high.
The evaporations were combined to give 1032g of a 2.1% aqueous solution containing 1, 5-pentanediamine. The evaporation yield of 1, 5-pentanediamine was 44 wt%.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (22)
1. A method for separating 1, 5-pentanediamine is characterized in that: the separation method comprises the following steps:
(1) contacting the solution of 1, 5-pentanediamine with cation resin for adsorption;
(2) eluting the 1, 5-pentanediamine adsorbed on the cationic resin;
the solution of the 1, 5-pentanediamine is a solution of 1, 5-pentanediamine containing impurities; the impurities include: one or more of tetrahydropyridine, thalli and protein; and/or the solution of the 1, 5-pentanediamine is: 1, 5-pentanediamine enzyme conversion solution and/or treatment solution thereof, and/or 1, 5-pentanediamine fermentation solution and/or treatment solution thereof;
in the step (1), the adsorption temperature is 20-40 ℃;
the solution of the 1, 5-pentanediamine is contacted with a cation resin for adsorption, and the method comprises the following steps:
the first method is as follows: uniformly mixing the cationic resin and the solution of the 1, 5-pentanediamine, and adsorbing;
and/or the presence of a gas in the gas,
the second method comprises the following steps: adsorbing the solution of the 1, 5-pentanediamine by an ion exchange resin column;
in the second mode, the feeding flow rate of the adsorption is 0.1-30 BV/h;
in the step (2), the elution temperature is 30-60 ℃;
the cation resin comprises 732 strong-acid cation exchange resin, D110 weak-acid cation exchange resin, 001 × 7 styrene macroporous strong acid cation resin, 001 × 7 styrene gel strong acid cation resin or D113 acrylic macroporous weak acid cation resin;
the pH value of the cationic resin is 3-9.
2. The separation method of claim 1, wherein: the pH of the solution of the 1, 5-pentanediamine is 3-12.
3. The separation method of claim 1, wherein: the pH of the solution of the 1, 5-pentanediamine is 5-9.
4. The separation method of claim 1, wherein:
in the first mode, the uniform mixing method comprises the steps of adding the cationic resin into a solution of 1, 5-pentanediamine, and uniformly mixing;
in the first embodiment, the cationic resin is used in a volume ratio of the solution of 1, 5-pentamethylenediamine to the resin, and the volume ratio of the solution of 1, 5-pentamethylenediamine to the cationic resin is 6.5 or less; wherein the volume ratio of the solution of the 1, 5-pentanediamine to the strong acid cation resin is (0.5-2.7): 1; wherein the volume ratio of the 1, 5-pentanediamine solution to the weakly acidic cationic resin is (1-5): 1;
in the first mode, the cation resin and the solution of the 1, 5-pentanediamine are uniformly mixed and adsorbed, and then the adsorption is more sufficient through one or more modes of oscillation, stirring or standing.
5. The separation method of claim 1, wherein:
in the second mode, when the concentration of the 1, 5-pentanediamine in the solution of the 1, 5-pentanediamine is more than 1 wt%, the feeding flow rate of the adsorption is 0.1-10 BV/h; when the concentration of the 1, 5-pentanediamine in the solution of the 1, 5-pentanediamine is less than 1 weight percent, the feeding flow rate of the adsorption is 5-20 BV/h;
and/or the aspect ratio of the ion exchange resin column is (1-20): 1;
and/or, in the second mode, washing is performed after the adsorption; the washing is washing by using distilled water; the flow rate during washing is 1-10 BV/h.
6. The separation method of claim 5, wherein:
in the second mode, when the concentration of the 1, 5-pentanediamine in the solution of the 1, 5-pentanediamine is more than 1 wt%, the feeding flow rate of the adsorption is 1-5 BV/h; when the concentration of the 1, 5-pentanediamine in the solution of the 1, 5-pentanediamine is less than 1 weight percent, the feeding flow rate of the adsorption is 8-15BV/h
And/or the aspect ratio of the ion exchange resin column is (3-8): 1;
and/or, the washing is washing with distilled water; the flow rate during washing is 2-5 BV/h.
7. The separation method of claim 6, wherein: the height-diameter ratio of the ion exchange resin column is (4-6): 1.
8. the separation method of any one of claims 1 to 7, wherein: in the step (2), the eluent in the elution may be any one of the following types:
the first kind: strong alkaline aqueous solution and mixed solution thereof;
or, type two: a mixed aqueous solution of a strong base and a weak base;
or, type three: an acidic aqueous solution;
wherein the strong base comprises: alkali metal hydroxides and/or alkaline earth metal hydroxides;
and/or, the weak base comprises ammonia;
and/or, the acidic aqueous solution comprises an inorganic acid and/or an organic acid; wherein the inorganic acid is strong inorganic acid; the organic acid is organic dibasic acid;
and/or, the concentration of the strong alkali aqueous solution is 1-12 wt%;
and/or the concentration of the aqueous solution of the inorganic acid is 1-12 wt%;
and/or the aqueous solution of the organic acid is a saturated aqueous solution of the organic acid, and when the concentration of the saturated aqueous solution of the organic acid exceeds 10 wt%, the aqueous solution of the organic acid is an aqueous solution of the organic acid with the concentration of 2-10 wt%.
9. The separation method of claim 8, wherein:
the strong base comprises: one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide;
and/or, the inorganic acid is sulfuric acid and/or hydrochloric acid; the organic acid is one or more of oxalic acid, succinic acid and adipic acid;
and/or, the concentration of the strong alkali aqueous solution is 2-8 wt%;
and/or the concentration of the aqueous solution of the inorganic acid is 2-8 wt%.
10. The separation method of claim 8, wherein: in the step (2), the elution mode is any one of the following modes:
the first method is as follows: mixing the cation exchange resin with the eluent to carry out elution;
or the like, or, alternatively,
the second method comprises the following steps: flowing the eluent over the cationic resin;
in the first mode, the mixing mode is stirring;
wherein, in the second mode, the flow rate of the eluted eluent is 0.5-8 BV/h.
11. The separation method of claim 10, wherein: in the second mode, the flow rate of the eluted eluent is 1-4 BV/h.
12. The separation method of claim 1, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
13. The separation method of claim 2, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
14. The separation method of claim 3, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
15. The separation method of claim 4, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
16. The separation method of claim 5, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
17. The separation method of claim 6, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
18. The separation method of claim 7, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
19. The separation method of claim 8, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
20. The separation method of claim 9, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
21. The separation method of claim 10, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
22. The separation method of claim 11, wherein:
after the step (2), treating the eluent; the processing mode comprises the following steps: evaporation and/or rectification.
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 CN108276292A (en) | 2018-07-13 |
| CN108276292B true 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023141455A3 (en) * | 2022-01-20 | 2023-10-26 | Archer Daniels Midland Company | E to 1.5 pentanediamine and separation of diamines from amino and carboxylic acids |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016164748A1 (en) | 2015-04-08 | 2016-10-13 | Invista North America S.A.R.L. | Materials and methods for the selective recovery of monovalent products from aqueous solutions using continuous ion exchange |
| 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 |
| CN110143882B (en) * | 2019-06-25 | 2022-02-22 | 郑州中科新兴产业技术研究院 | Method for producing 1, 5-pentanediamine by chemical decarboxylation of L-lysine and separation and extraction method |
| CN110563594B (en) * | 2019-09-05 | 2022-09-23 | 南京工业大学 | Method for refining pentamethylene diamine by separation-separation coupling process |
| CN114057582A (en) * | 2021-11-16 | 2022-02-18 | 南京工业大学 | Method for continuously separating and purifying pentanediamine hydrochloride crystals |
Citations (3)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015025896A1 (en) * | 2013-08-23 | 2015-02-26 | 味の素株式会社 | Method for producing 1,5-pentadiamine |
-
2017
- 2017-01-06 CN CN201710011198.7A patent/CN108276292B/en active Active
Patent Citations (3)
| 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 |
| 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 |
|---|
| 生物酶法合成1,5-戊二胺的研究进展;邓洁 等;《广西科学》;20170116;第24卷(第1期);第40-47页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023141455A3 (en) * | 2022-01-20 | 2023-10-26 | Archer Daniels Midland Company | E to 1.5 pentanediamine and separation of diamines from amino and carboxylic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108276292A (en) | 2018-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108276292B (en) | Separation method of 1, 5-pentanediamine | |
| CN107043330B (en) | Method for extracting 1, 5-pentamethylene diamine from solution system containing 1, 5-pentamethylene diamine salt | |
| EP0822989B1 (en) | Process for producing calcium d-pantothenate | |
| CN109593034B (en) | Method for preparing shikimic acid from ginkgo leaf extraction waste liquid | |
| OA11315A (en) | Method for the separation of acid from sugars. | |
| CN106928323B (en) | Preparation method of high-purity oritavancin key intermediate A82846B | |
| EP2847342B1 (en) | Purification of succinic acid | |
| Esteves et al. | A study on lupin beans process wastewater nanofiltration treatment and lupanine recovery | |
| CN110330538B (en) | Separation and purification method of isomeric product in sophorolipid fermentation liquor | |
| CN105198732A (en) | Method for extracting alpha-ketoglutaric acid from fermentation liquor | |
| CN106565425B (en) | Method for recovering catechol and levodopa from levodopa mother liquor | |
| CN107032983B (en) | Method for extracting and separating succinic acid from fermentation liquor by using macroporous adsorption resin | |
| JPS5852999B2 (en) | Stevioside Noseiseihou | |
| CN113121329B (en) | Method for coupling conversion and extraction of lactic acid from aqueous lactate raw material | |
| CN100509757C (en) | Purification method of *N-L-arginine | |
| CN101085749A (en) | Method for separating terramycin | |
| CN112125842A (en) | Method for separating and purifying nicotinic acid from 3-cyanopyridine wastewater | |
| CN102952008A (en) | Method for extracting succinic acid from anaerobic fermentation broth | |
| CN114436816B (en) | Method for efficiently extracting shikimic acid by ion exchange technology | |
| CN107739307B (en) | Method for purifying protocatechuic acid by using dilute alkali solution extraction-solid phase extraction column | |
| CN110590586A (en) | Method for separating and purifying lysine fermentation liquor | |
| CN110787472B (en) | Pentanediamine concentration system and concentration method | |
| CN109851514B (en) | Separation and purification method of L-isoleucine | |
| CN110787638A (en) | Pentanediamine concentration system and method | |
| CN114805103B (en) | Extraction method of L-alanine |
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 |
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. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |