阅读说明：本技术 一种二元酸胺盐的提取纯化方法 (Method for extracting and purifying diamine salt ) 是由 董筱雯 杨晨 秦兵兵 刘修才 于 2018-05-29 设计创作，主要内容包括：本发明公开了二元酸胺盐溶液的纯化方法,包括以下步骤：(1)将包括杂质的二元酸胺盐溶液固液分离,得上层清液；(2)使步骤(1)中得到的上层清液进入色谱分离系统,进行连续色谱分离,连续色谱分离系统包括多个分离单元,分离单元内填充有树脂,分离单元构成连续色谱分离系统的吸附区、分离区、洗脱区和再生区；所述洗脱区的流速为0.3-8BV/h。本发明的方法,操作简单,能够得到高质量的聚酰胺聚合前体。(The invention discloses a purification method of diamine salt solution, which comprises the following steps: (1) carrying out solid-liquid separation on the diamine salt solution containing impurities to obtain supernatant; (2) enabling the supernatant obtained in the step (1) to enter a chromatographic separation system for continuous chromatographic separation, wherein the continuous chromatographic separation system comprises a plurality of separation units, the separation units are filled with resin, and the separation units form an adsorption area, a separation area, an elution area and a regeneration area of the continuous chromatographic separation system; the flow rate of the elution area is 0.3-8 BV/h. The method of the invention is simple to operate and can obtain the high-quality polyamide polymerization precursor.)

1. a method for purifying a diamine salt solution, the method comprising the steps of:

(1) Carrying out solid-liquid separation on the diamine salt solution containing impurities to obtain supernatant;

(2) Enabling the supernatant obtained in the step (1) to enter a chromatographic separation system for continuous chromatographic separation, wherein the continuous chromatographic separation system comprises a plurality of separation units, the separation units are filled with resin, and the separation units form an adsorption area, a separation area, an elution area and a regeneration area of the continuous chromatographic separation system; the flow rate of the elution area is 0.3-8 BV/h.

2. The method of claim 1, wherein: the diamine salt comprises: a salt of a C4-C18 aliphatic or aromatic diamine and a C4-C18 aliphatic or aromatic dicarboxylic acid; the structural formula of the diamine is as follows: -OOC (CH2) nCOO- + H3N- (CH2) m-NH3+, wherein 6. ltoreq. n.ltoreq.18 and 4. ltoreq. m.ltoreq.6.

In the step (1), the diamine dibasic acid salt solution is obtained after fermentation liquor of dibasic acid or treatment liquid thereof participates in a pentanediamine fermentation process or a process of obtaining pentanediamine by lysine fermentation-enzyme conversion.

3. the method of claim 1 or 2, wherein: the resin comprises: ion exchange resins, preferably: the weak base ion exchange resin and/or strong acid ion exchange resin, more preferably weak base acrylic acid gel ion exchange resin, weak base styrene macroporous ion exchange resin and strong acid styrene macroporous ion exchange resin in one or more.

4. The method of claim 1 or 2, wherein: in the step (2), the eluent in the separation area is water; the flow rate of the separation area is 0.3-6BV/h, preferably 1-3 BV/h;

And/or the eluent in the elution area is water, and the flow rate of the elution area is 0.3-6BV/h, preferably 1-3 BV/h.

And/or, in step (2), the flow rate of the elution zone is equal to the flow rate of the separation zone.

5. the method of claim 1 or 2, wherein: the temperature of the continuous chromatographic separation is 15-50 ℃, preferably 20-30 ℃.

6. The method of claim 1 or 2, wherein: continuously feeding in said adsorption zone; separating impurities in the separation zone; obtaining a diamine salt solution in the elution zone; resin regeneration is performed in the regeneration zone.

7. The method of claim 1 or 2, wherein: in the step (2), continuous chromatographic separation is carried out, and after T1 time, the long-chain diamine salt solution is collected, wherein T1 is the residence time of the diamine salt in a single separation unit;

and/or, in the step (2), the time T1 for starting to collect the solution of the long-chain diamine salt is obtained by the following method: obtaining a solution in the elution area, detecting that the conductivity of the solution is more than 2300, and collecting the long-chain diamine salt solution;

And/or, in step (2), the time T2 for starting to obtain the impurity is obtained in the following manner: obtaining a solution in the separation zone, and detecting that the solution has an absorbance at 428nm of 0.26 or more.

8. the method of claim 1 or 2, wherein: the feeding speed V1 of the supernatant in the adsorption zone is 0.5-8 BV/h;

And/or the eluent in the regeneration zone is acid, preferably hydrochloric acid; the flow rate of the regeneration area is 1-15 BV/h.

9. The method of claim 1 or 2, wherein: in the step (2), the separation unit is arranged on a rotary turntable which rotates; the separation units are connected in sequence through a pipeline and used for flowing of eluent in the pipeline.

10. The method of claim 1 or 2, wherein: in the step (1), the solid-liquid separation method comprises one or more of filtration, centrifugation or ceramic membrane separation.

11. The diamine salt solution prepared by the process according to any one of claims 1 to 10.

12. A method for preparing diamine comprises the following steps:

(A) The process according to any one of claims 1 to 10 to obtain a solution of the amine salt of a dibasic acid,

(B) Crystallizing in water to obtain diamine diacid; the mass ratio of the water to the diamine salt is (0.2-0.4): 1, preferably (0.25-0.35): 1; the cooling rate of the crystal is 1 ℃/3-12 min.

13. The solution of the diamine of claim 12, wherein the solution of the diamine salt has a UV index of 0.8X 10-3 or less, preferably (0.3-0.8). times.10-3, or preferably (0.1-0.5). times.10-3, measured at 279nm at a concentration of 0.1% (m/V) and an absorption cell thickness of 5 cm.

14. A solution of a salt of a dibasic acid amine, which has a UV index of 0.8X 10-3 or less, preferably (0.3-0.8). times.10-3, or preferably (0.1-0.5). times.10-3, as measured at 279nm at a concentration of 0.1% (m/V) and an absorption cell thickness of 5 cm.

Technical Field

The invention relates to a method for extracting and purifying diamine salt.

Background

Amine salts of dibasic acids (also known as polyamide salts or nylon salts) are precursors for the synthesis of polyamides. Polyamide is generally prepared by mixing amine and dibasic acid serving as monomer raw materials to form dibasic acid amine salt and then polymerizing the dibasic acid amine salt and the dibasic acid amine salt to obtain a polymer; the preparation process has the premise that: the monomeric amine and the dibasic acid are both necessarily polymerization-grade products, so that the obtained polyamide has industrial application value.

However, the preparation of polymer-grade dibasic acid and amine is complex in process and high in cost. Taking dibasic acid as an example, most of the existing dibasic acids are prepared by a biological fermentation method, and the polymer-grade dibasic acid is extracted from fermentation liquor by various complicated extraction and purification means. In general, obtaining conventional polymer grade diacids from fermentation broths requires the following complex steps: the fermentation liquor is processed by demulsification (such as alkali demulsification or heating demulsification), standing to remove substrate (such as alkane), crystallization (such as acidification crystallization) to obtain coarse product crystallized liquid of binary acid containing a large amount of thalli, filtering supernatant to obtain binary acid filter cake containing thalli, low-temperature drying the filter cake, washing to remove water-soluble impurities, adding organic solvent for extraction (simultaneously decoloring), filtering to remove decolorant, thalli, inorganic salt and the like to obtain organic solvent containing binary acid, and crystallizing, filtering and drying the binary acid to obtain binary acid product with high purity.

In addition, the fermentation liquor contains various impurities such as thalli, culture medium, unfermented substrate, a large amount of inorganic salt, protein, water and the like, and the fermentation liquor coexists in multiple phases, has complex composition and thick medium, has higher operation requirements of each step, consumes a large amount of energy, has high cost and low yield.

On the basis, Chinese patent CN00110713.5 is improved. CN00110713.5 indicates that: the main problems of the method for preparing the amine salt of the dibasic acid by using the long-chain dicarboxylic acid produced by the conventional fermentation method are that: (1) the pretreatment process of the fermentation liquor is complicated, and particularly, the drying of the crude acid filter cake containing bacteria and the final drying step of the dicarboxylic acid product are carried out at a lower temperature, so that the drying period is long, and the energy consumption is high; (2) the used extraction solvent has higher boiling point and is dried at low temperature, the solvent contained in the dicarboxylic acid product is difficult to completely remove, and the preparation of the diamine salt of the dibasic acid is adversely affected; (3) dicarboxylic acid extraction and diamine salt preparation use two different types of solvents, and the regeneration and recovery of the solvents require two different sets of processes and equipment, which further complicates the process. Therefore, the steps of drying the crude acid filter cake containing bacteria in the pretreatment process and crystallizing, filtering and drying the dicarboxylic acid product in the extraction process are omitted, the same solvent is used in the solvent extraction process and the preparation of the diamine salt, the process is simplified, the operation period and the energy consumption are shortened, and the product cost is reduced.

however, the technical scheme of CN00110713.5 is to treat the fermentation broth of long-chain dibasic acid, and then add diamine to form salt, but omits some steps in the treatment process of long-chain dibasic acid.

The method still has the problems of complex operation, high cost and low yield.

Disclosure of Invention

The invention provides a method for separating and purifying diacid amine salt containing various impurities, which aims to solve the problems that the preparation method of polymer-grade diacid and amine monomers is complex in operation, high in cost and low in yield, and the cost of the obtained industrially applied polymerization product is very high in the prior art. The method of the invention is simple to operate and can obtain the high-quality polyamide polymerization precursor.

considering the inventive concept of the present invention, the conventional thinking of the prior art firstly obtains the high-quality polymerized monomers, namely, the dibasic acid and the amine, and then the dibasic acid and the amine are subjected to salt formation and polymerization to obtain various polymers. The object of the present invention is to remove various impurities from a complex system by using a mixed solution of a dibasic acid containing various impurities and a fermentation solution of an amine (equivalent to a mixed solution obtained by two fermentations or a treatment solution thereof) to obtain a polymer grade, and then polymerizing the salt solution of the polymer grade to obtain various polymers. None of the prior publications mention such a concept.

In practice, such a method is not only difficult to conceive, but also difficult to implement, requiring a number of technical difficulties to be overcome. The amine salt of dibasic acid fermentation broth or its treated solution contains a large amount of impurities such as: thalli, protein, a culture medium, an unfermented substrate, a large amount of inorganic salt, pigment, sugar, water and the like, and not only comprises various impurities in the dibasic acid fermentation process, but also various impurities in the pentamethylenediamine production process, and the whole system comprises multiphase substances such as gas, oil, water, solid and the like, and certain specific impurities need to be removed in the complex system, so that the high purity is ensured, and meanwhile, the high yield is also needed, and the difficulty is very high. In order to solve the problems, the inventor researches for many years and finds that various impurities can be synergistically removed through specific process steps and conditions, and further impurities such as thalli, pigments and the like can be well removed within a specific parameter range, so that a diamine salt solution can reach a polymerization level, and the performances of the polymer obtained by polymerization, such as purity, chromaticity and the like, can be comparable to those of the polymer obtained by polymerization of the existing polymerization level monomer, thereby obtaining the technical scheme of the invention.

One of the objects of the present invention is to provide a method for purifying a diamine salt solution, comprising the steps of:

(1) Carrying out solid-liquid separation on the diamine salt solution containing impurities to obtain supernatant;

(2) enabling the supernatant obtained in the step (1) to enter a chromatographic separation system for continuous chromatographic separation, wherein the continuous chromatographic separation system comprises a plurality of separation units, the separation units are filled with resin, and the separation units form an adsorption area, a separation area, an elution area and a regeneration area of the continuous chromatographic separation system; the flow rate of the elution area is 0.3-8 BV/h.

Further preferable embodiments of the above-described technical means will be described below.

In a preferred embodiment of the present invention, the amine salt of dibasic acid may include: the salt is formed by aliphatic or aromatic diamine of C4-C18 and aliphatic or aromatic dicarboxylic acid of C4-C18, and the amine group of the diamine and the carboxyl group of the dicarboxylic acid are positioned at the terminal group.

In a preferred technical scheme of the present invention, in the amine salt of dibasic acid, the structural formula of the dibasic acid is: HOOC (CH2) nCOOH, where n is 4. ltoreq. n.ltoreq.18, preferably 6. ltoreq. n.ltoreq.18, and may be 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18; the amine has the structural formula: H2N- (CH2) m-NH2, where 4. ltoreq. m.ltoreq.18, preferably 4. ltoreq. m.ltoreq.6, i.e. m can be 4, 5 or 6; the structural formula of the diamine is as follows: -OOC (CH2) nCOO- + H3N- (CH2) m-NH3+, wherein 6. ltoreq. n.ltoreq.18 and 4. ltoreq. m.ltoreq.6.

For example: the amine salt of a dibasic acid may be: glutaric acid ethylenediamine succinate, adipic acid glutaric acid diamine, sebacic acid glutaric acid diamine, dodecanedicarboxylic acid glutaric acid diamine, and the like. Amine salts of diacids may also include amine salts of diacids containing aromatic structures, such as: pentamethylene terephthalate, and the like. In order to obtain copolymers having different properties, diamine salts of polyamides of different types or diamine salts of polyamides and a monomer to be polymerized may be obtained as required. For example: the amine salt of dibasic acid of the present invention may further include nylon 66 salt, caprolactam, 6-aminocaproic acid, and the like. The amine salt of a dibasic acid of the invention may also be a mixture of different amine salts of dibasic acids.

In a preferred technical scheme of the invention, the diamine salt solution is prepared by a fermentation method or prepared by a fermentation method and an enzyme conversion method.

According to a preferable technical scheme of the invention, the dibasic acid is prepared by a fermentation method.

In a preferred embodiment of the present invention, the amine is prepared by fermentation, or by fermentation and enzymatic conversion.

According to a preferable technical scheme of the invention, the diamine dibasic acid salt solution is obtained after fermentation liquor of dibasic acid or treatment liquid thereof participates in a pentamethylene diamine fermentation process or participates in a process of lysine fermentation-enzyme conversion to obtain pentamethylene diamine.

according to a preferable technical scheme of the invention, after the diacid amine salt solution is prepared by a fermentation method, before the method is carried out, the polymer-grade diacid and the polymer-grade amine are obtained by various methods and then dissolved to obtain the diacid amine salt, but the polymer-grade diacid amine salt is directly prepared from the fermentation liquor.

the concentration of the diamine salt solution of the present invention is not particularly limited as long as the diamine salt can be uniformly dissolved in the solution. According to a preferable technical scheme of the invention, in the step (1), the content of the diamine salt in the diamine salt solution is 10-30%, preferably 12-20%, and the percentage is the mass percentage of the diamine salt solution.

In a preferred embodiment of the present invention, in the step (2), the chromatographic separation is a continuous chromatographic separation. The continuous chromatographic separation can be used to separate impurities and amine salts of dibasic acids. The impurities include pigments.

In a preferred embodiment of the present invention, in the step (2), the eluent in the separation zone is water. The flow rate of the separation zone is 0.3-6BV/h, preferably 1-3BV/h, and can be: 0.5BV/h, 1BV/h, 1.5BV/h, 2BV/h, 2.5BV/h, 3BV/h, 3.5BV/h, 4BV/h, 4.5BV/h, 5BV/h, 5.5BV/h, 6BV/h, 6.5BV/h, 7BV/h, 7.5BV/h, 8 BV/h.

in a preferred embodiment of the present invention, in step (2), the eluent in the elution zone is water. The flow rate of the elution zone is 0.3-6BV/h, preferably 1-3BV/h and can be: 0.5BV/h, 1BV/h, 1.5BV/h, 2BV/h, 2.5BV/h, 3BV/h, 3.5BV/h, 4BV/h, 4.5BV/h, 5BV/h, 5.5BV/h, 6BV/h, 6.5BV/h, 7BV/h, 7.5BV/h, 8 BV/h.

In a preferred embodiment of the present invention, in the step (2), the flow rate of the elution zone is equal to the flow rate of the separation zone.

in a preferred embodiment of the present invention, the temperature of the continuous chromatographic separation is 15 ℃ to 50 ℃, preferably 20 ℃ to 30 ℃.

in a preferred embodiment of the present invention, the adsorption zone is continuously fed with the feed; separating impurities in the separation zone; obtaining a diamine salt solution in the elution zone; resin regeneration is performed in the regeneration zone.

In a preferred embodiment of the present invention, in the step (2), the resin includes: ion exchange resins, preferably: a weakly basic ion exchange resin and/or a strongly acidic ion exchange resin, more preferably one or more of a weakly basic acrylic gel ion exchange resin, a weakly basic styrene macroporous ion exchange resin and a strongly acidic styrene macroporous ion exchange resin, most preferably one or more of SQD817 resin (threo), LX67 resin (sienna blue dawn) and LX108 resin (sienna blue dawn).

According to a preferable technical scheme of the invention, in the step (2), continuous chromatographic separation is carried out, and after T1 time, the long-chain diamine salt solution is collected, wherein T1 is the residence time of the diamine salt in a single separation unit.

In a preferred embodiment of the present invention, in the step (2), the time T1 for starting the collection of the solution of the long-chain diamine salt may be obtained as follows: and (3) obtaining a solution in the elution area, detecting that the conductivity of the solution is more than 2300, and collecting the solution of the long-chain diamine salt.

In a preferred technical scheme of the invention, in the step (2), continuous chromatographic separation is carried out, and after T1 time, the long-chain diamine acid salt solution starts to be collected in the elution area; the time T1 for starting to collect the solution of the long-chain diamine salt meets the following conditions:

34*V3≤T1≤40*V3

wherein V3 is the flow rate of the elution zone, BV/h.

in a preferred embodiment of the present invention, in the step (2), the time T1 for starting the collection of the long-chain diamine salt solution is preferably 10 to 180min, and more preferably 15 to 120 min.

The time T1 for the start of the collection of the solution of the long chain diamine salt is more than one third of the rotation period of the continuous chromatographic separation system, preferably more than one half of the rotation period.

For example: and the rotation period of the continuous chromatographic separation system is 180min, and the long-chain diamine salt solution can be collected after 60min or 90 min.

For another example: and the rotation period of the continuous chromatographic separation system is 75min, and the long-chain diamine salt solution can be collected after 37.5min or 50 min.

The end time of collecting the long-chain diamine salt solution is not limited, and generally, the end time can be the complete end of the continuous chromatographic separation method, and can also be any time point of the continuous chromatographic separation.

In a preferred technical scheme of the invention, in the step (2), the solution of the long-chain diamine salt is continuously collected, and the solution obtained in the elution area meets the following conditions within the continuous time: the conductivity is above 2300.

In a preferred embodiment of the present invention, in step (2), the time T2 for starting obtaining the impurities can be obtained as follows: obtaining a solution in the separation zone, and detecting that the solution has an absorbance at 428nm of 0.26 or more.

In the step (2), chromatographic separation is carried out, after time T2, the collection of the impurities is started in the separation area, and the time T2 for starting the collection of the impurities meets the following conditions:

20*V2≤T1≤25*V2

Wherein V2 is the flow rate of the separation zone, BV/h.

In a preferred embodiment of the present invention, in step (2), the time T2 for starting to collect the impurities is preferably 5 to 90min, and more preferably 7.5 to 60 min.

the time T2 for the start of the collection of the impurities is less than half, preferably less than one third, of the rotation cycle of the continuous chromatographic separation system.

For example: and the rotation period of the continuous chromatographic separation system is 180min, and the long-chain diamine salt solution can be collected after 90min or 60 min.

For another example: and the rotation period of the continuous chromatographic separation system is 75min, and the long-chain diamine salt solution can be collected after 50min or 25 min.

In a preferred embodiment of the present invention, in the step (2), the impurities are continuously collected, and the solution obtained in the separation zone satisfies the following conditions for the continuous time: an absorbance at 428nm of 0.26 or more.

In a preferred embodiment of the present invention, in step (2), the time T1 for starting collection of the long-chain diamine salt solution is greater than the time T2 for starting collection of the impurities.

In a preferred technical scheme of the invention, the feeding speed V1 of the supernatant in the adsorption zone is 0.5-8 BV/h.

in a preferred embodiment of the present invention, the eluent in the regeneration zone is an acid, preferably hydrochloric acid. The flow rate of the regeneration area is 1-15 BV/h.

In a preferred embodiment of the present invention, in the step (2), the separation unit is disposed on a rotating turntable.

in a preferred embodiment of the present invention, in step (2), the separation units are connected in sequence through a pipeline, and are used for flowing eluent in the pipeline.

In a preferred technical scheme of the invention, in the step (2), the time of one cycle of the rotating disc is 20-200 min.

in a preferred embodiment of the present invention, in the step (2), the supernatant obtained in the step (1) is fed at the feed inlet of the adsorption zone.

In a preferred technical scheme of the present invention, in the step (1), the solution of diamine salt is: a solution obtained by mixing a fermentation liquid and/or a treatment liquid of dibasic acid obtained by fermentation and an amine fermentation liquid and/or a treatment liquid of amine obtained by fermentation and conventional in the field; or the following steps: a solution obtained by mixing a fermentation solution and/or a treated solution thereof of a dibasic acid obtained by fermentation and an enzyme-converted solution and/or a treated solution thereof of an amine obtained by fermentation and enzyme conversion, which are conventional in the art. The impurities include: bacteria, proteins, culture medium, unfermented substrate, inorganic salts, pigment, reducing sugar and water. The impurities include at least bacteria. The impurities include at least a pigment.

in a preferred embodiment of the present invention, in step (1), the solid-liquid separation method includes one or more of filtration, centrifugation, or ceramic membrane separation. The filtration may be filter aid filtration or membrane filtration, etc.

In a preferred technical scheme of the invention, in the step (1), before the solid-liquid separation, the pH of the diamine dibasic acid salt solution is 6-10, preferably 7-9.

In a preferred technical scheme of the invention, in the step (1), before the solid-liquid separation, the diamine dibasic acid salt solution containing impurities is heated. The heating temperature is 70-100 deg.C, preferably 80-95 deg.C. The heating time is 30-120 min.

In a preferred embodiment of the present invention, in the step (1), the temperature of the solid-liquid separation is room temperature or higher, preferably 60 ℃ or higher, more preferably 70 ℃ or higher, and most preferably 70 to 90 ℃.

in a preferred technical scheme of the invention, in the step (1), the rotation speed of the centrifugation is 4000-.

In a preferred embodiment of the present invention, in step (1), the centrifugation time is 1-10 min.

The invention also aims to provide the long-chain diamine salt solution prepared by the preparation method.

the third purpose of the invention is: a method for preparing diamine comprises the following steps:

(A) The diamine salt solution is prepared by the method described above,

(B) Crystallizing to obtain diamine diacid.

In a preferred embodiment of the present invention, in the step (B), the crystallization is crystallization in water.

in a preferred technical scheme of the invention, in the step (B), the mass ratio of the water to the diamine salt is (0.2-0.4): 1, preferably (0.25-0.35): 1. the above proportion can be obtained by rotary evaporation, but is not limited to rotary evaporation.

In a preferred embodiment of the present invention, in the step (B), the crystallization is preferably a temperature-decreasing crystallization. The cooling rate of the crystal is 1 ℃/3-12 min.

In a preferred embodiment of the present invention, in step (B), the temperature-reducing crystallization includes the following steps: preparing aqueous solution of diamine salt, cooling to 20-40 deg.C at 1 deg.C/3-10 min, and maintaining for 0.3-5 h; then the temperature is reduced by 5 to 20 ℃ at the speed of 1 ℃/6 to 15min, and the temperature is preserved for 0.2 to 5 hours.

the fourth object of the present invention is to provide diamine dibasic acid prepared by the above preparation method.

fifth object of the present invention is a diamine, wherein a solution of a salt of the diamine has a UV index of 0.8X 10-3 or less, preferably (0.3-0.8). times.10-3, or preferably (0.1-0.5). times.10-3, as measured at 279nm at a concentration of 0.1% (m/V) and an absorption cell thickness of 5 cm.

the diacid amine salt is not prepared by mixing polymer-grade diacid and polymer-grade amine. According to the common knowledge in the art, in general, the polymer-grade dibasic acid is a dibasic acid with a total acid content of more than 98%, or a dibasic acid with a total acid content of more than 98.5%, or a dibasic acid with a total acid content of more than 99%, or a dibasic acid with a total acid content of more than 99.5%; the polymer-grade pentamethylene diamine is pentamethylene diamine with the purity of more than 98 percent, or pentamethylene diamine with the purity of more than 99 percent, and pentamethylene diamine with the purity of more than 99.5 percent, and the percentage is mass percent.

The amine salt of a dibasic acid as described above, which is a solution having a concentration of 0.1% (m/V) and has a UV index of 0.8X 10-3, 0.75X 10-3, 0.7X 10-3, 0.65X 10-3, 0.6X 10-3, 0.55X 10-3, 0.5X 10-3, 0.45X 10-3, 0.4X 10-3, 0.35X 10-3, 0.3X 10-3, 0.25X 10-3, 0.2X 10-3, 0.15X 10-3, 0.1X 10-3 as measured at a cell thickness of 5cm at 279 nm.

The invention directly aims at the solution of diacid amine salt which contains various impurities and has a complex system, generally is the mixed solution of diamine and diacid fermentation liquor, or the mixed solution of diacid fermentation liquor and diamine enzyme conversion liquor, and can effectively reduce some special proteins (such as valine) in the diacid amine salt by processing the complex system, and can reduce the chroma, and the performance of the polymer obtained by polymerizing the prepared product can be comparable with the performance of the product obtained by polymerizing the existing polymer-grade diacid and diacid. Compared with the conventional method for preparing the polymer-grade dibasic acid and the polymer-grade diamine in advance, the method has two completely different process ideas, greatly reduces the steps of extraction and purification in the prior art on the basis of ensuring the quality of the final product, and saves energy, labor and cost.

drawings

Fig. 1 a continuous chromatographic separation system wherein:

1 represents: a separation unit;

21 denotes: an adsorption zone;

22 denotes: a separation zone;

23 denotes: an elution zone;

and 24 represents: a regeneration zone.

Detailed Description

According to one embodiment of the present invention, the diamine forming the diamine salt of the dibasic acid at least comprises pentamethylenediamine, that is, the diamine forming the diamine salt of the dibasic acid is pentamethylenediamine or a mixed diamine of pentamethylenediamine and one or more of the following diamines: butanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, p-phenylenediamine, and o-phenylenediamine.

In a preferred embodiment, one of the components of the diamine diacid salt is pentanediamine containing impurities, which may be typically a pentanediamine fermentation broth, an enzyme conversion broth, a salt solution, or the like.

In the present invention, the pentamethylene diamine is not limited in source, and can be produced by any conventional biological method. For example, Hexanzhen et al (decarboxylation of amino acids (4 th report), J.Pharma, Vol.85(6), P531-533, 1965) disclose the preparation of pentanediamine by boiling lysine in cyclohexanol with tetralin peroxide; japanese patent laid-open No. 60-23328 discloses a process for producing pentamethylenediamine from lysine as a raw material using a ketene compound of 2-cyclic vinyl ester as a catalyst; obtaining an enzyme conversion solution by reacting pentamethylene diamine decarboxylase with lysine, and further extracting pentamethylene diamine (refer to JP 200400114A); through a genetic technology, the expression of lysine decarboxylase is up-regulated or the lysine decarboxylase is expressed in a recombinant mode in a strain capable of generating lysine, the produced lysine can be synchronously converted into pentanediamine in the fermentation process, and pentanediamine fermentation liquor can be obtained through direct fermentation (refer to the construction of a one-step method for producing 1, 5-pentanediamine corynebacterium glutamicum genetic engineering bacteria, such as Takara and the like, China journal of bioengineering, 2010, 30 (8): 93-99), and the like.

In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The detection method of the performance parameters related to the embodiments of the present invention is as follows:

1. The method for detecting the purity of the diamine salt solution comprises the following steps:

characterizing by a UV index; the absorbance A was measured at 279nm using a KONICA MINOLTA CM-3600A apparatus, and the UV index was 0.1% (m/V) of the concentration of the dibasic acid amine salt and 5CM of the thickness of the cell.

2. The method for detecting the color (chroma) of the diamine salt solution comprises the following steps:

and the visual detection method refers to GB/T605-2006 for detection.

3. Detection method of polyamide color:

According to GB-T2409-1980 standard, detection was carried out using a KONICA MINOLTA CM-3600A device.

4. tensile strength and elongation at break

Measured according to ASTM D638.

5. bending strength

Measured according to ASTM D790.

6. notched impact strength of cantilever beam

measured according to ASTM D256.

7. Viscosity number

Concentrated sulfuric acid method with Ubbelohde viscometer: the dried nylon sample was accurately weighed at 0.25. + -. 0.0002g, dissolved by adding 50mL of concentrated sulfuric acid (96%), and the concentrated sulfuric acid flow time t0 and the nylon solution flow time t were measured and recorded in a constant temperature water bath at 25 ℃.

Viscosity number calculation formula: viscosity number VN ═ t/t 0-1/C

t- -time of solution flow

t0- -time of solvent flow through

C- -concentration of Polymer (g/mL)