CN110540511B - Extraction and purification method of diamine salt - Google Patents
Extraction and purification method of diamine salt Download PDFInfo
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- CN110540511B CN110540511B CN201810528886.5A CN201810528886A CN110540511B CN 110540511 B CN110540511 B CN 110540511B CN 201810528886 A CN201810528886 A CN 201810528886A CN 110540511 B CN110540511 B CN 110540511B
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- salt solution
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- diamine salt
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000000605 extraction Methods 0.000 title description 7
- 238000000746 purification Methods 0.000 title description 6
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- 239000006228 supernatant Substances 0.000 claims abstract description 45
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
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- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 3
- YDCMTALHFLXJKA-UHFFFAOYSA-N C(CCCC)(N)N.C(CCCCCCCCC(=O)O)(=O)O Chemical compound C(CCCC)(N)N.C(CCCCCCCCC(=O)O)(=O)O YDCMTALHFLXJKA-UHFFFAOYSA-N 0.000 description 3
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- VJCJAQSLASCYAW-UHFFFAOYSA-N azane;dodecanoic acid Chemical compound [NH4+].CCCCCCCCCCCC([O-])=O VJCJAQSLASCYAW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a method for purifying a diamine salt solution of dibasic acid, which comprises the following steps: (1) Solid-liquid separation is carried out on the diamine salt solution containing impurities to obtain supernatant; (2) And (3) adsorbing the supernatant obtained in the step (1) by resin to obtain a diamine salt solution. The method directly separates and purifies the diamine salt containing various impurities, has simple operation, can well remove the impurities such as thalli, pigments and the like, and ensures that the diamine salt solution can reach a high-quality polymerization grade, so that the polymer obtained by polymerization has the performances of purity, chromaticity and the like which are comparable with those of the polymer obtained by polymerization of the existing polymerization grade monomer, and the yield of the diamine is high.
Description
Technical Field
The invention relates to a method for extracting and purifying diamine salts.
Background
Diamine salts (also known as polyamide salts or nylon salts) are precursors for the synthesis of polyamides. The polyamide is generally prepared by mixing amine and dibasic acid serving as monomer raw materials to form diamine salt of dibasic acid, and polymerizing to obtain a polymer; the preparation process is characterized in that: both monomeric amines and dibasic acids must be polymeric grade products to ensure that the polyamide obtained has industrial application value.
But the preparation of polymeric dibasic acids and amines is complex and costly. Taking dibasic acid as an example, most of the existing dibasic acids are prepared by a biological fermentation method, and polymeric dibasic acid is extracted from fermentation broth by various complex extraction and purification means. In general, obtaining conventional polymeric grade dibasic acids from fermentation broths requires the following complex steps: the fermentation liquid is demulsified (for example, alkali is added for demulsification or heating for demulsification) and stands for removing a substrate (for example, alkane), a crude product crystal precipitation liquid of the dibasic acid containing a large amount of thalli is obtained through crystallization (for example, acidification crystallization), a supernatant liquid is filtered, a dibasic acid filter cake containing thalli is obtained, the filter cake is dried at a low temperature, water-soluble impurities are removed through washing, an organic solvent is added for extraction (simultaneously decolorization can be carried out), a decolorizer, thalli, inorganic salt and the like are filtered, an organic solvent containing dibasic acid is obtained, and the dibasic acid is crystallized, filtered and dried, so that a dibasic acid product with higher purity is obtained.
In addition, the fermentation liquor contains a plurality of impurities such as thalli, a culture medium, unfermented substrates, a large amount of inorganic salts, proteins, water and the like, and the fermentation liquor coexists in a multiphase manner, has complex composition, viscous medium, high operation requirements of each step, high cost and low yield, and consumes a large amount of energy.
On the basis, china patent CN00110713.5 is improved. CN00110713.5 indicates that: the main problems of the method for preparing the diamine salt from the long-chain dicarboxylic acid produced by the conventional fermentation method are as follows: (1) The pretreatment process of the fermentation liquor is complicated, especially the drying of the bacterial-containing crude acid filter cake and the final drying step of the dicarboxylic acid product are all required to be carried out at a lower temperature, 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, so that the solvent contained in the dicarboxylic acid product is difficult to completely remove, and the preparation of diamine salt can be adversely affected; (3) Two different kinds of solvents are used for dicarboxylic acid extraction and diamine salt preparation, and two different processes and equipment are required for regeneration and recovery of the solvents, so that the process is further complicated. Therefore, the steps of drying the bacterial-containing crude acid filter cake in the pretreatment process and crystallizing, filtering and drying the dicarboxylic acid product in the extraction process are omitted, and the same solvent is used in the solvent extraction process and the preparation of the diamine salt, so that the process is simplified, the operation period is shortened, the energy consumption is reduced, and the product cost is reduced.
However, the technical scheme of CN00110713.5 is to treat the fermentation liquor of long-chain diacid, and then add diamine to form salt, so that only some steps in the treatment process of long-chain diacid are omitted.
The method still has the problems of complex operation, high cost and lower yield.
Disclosure of Invention
The invention provides a separation and purification method directly aiming at diamine salts containing various impurities, aiming at solving the problems of complex operation, high cost and low yield of a preparation method of polymerization grade diacid and amine monomers, which lead to high cost of an obtained polymerization product for industrial application in the prior art. The method of the invention has simple operation and can obtain high-quality polyamide polymerization precursor.
Considering the inventive concept of the present invention, the conventional thinking of the prior art is to obtain high-quality polymerization monomers, namely dibasic acid and amine, which are salified and polymerized to obtain various polymers. The treatment object of the invention is a mixed solution of fermentation liquid of dibasic acid and amine containing various impurities (corresponding to mixed solution of two fermentations or treatment liquid thereof), various impurities are removed in a complex system, so that the mixed solution reaches a polymerization grade, and salt solution of the polymerization grade is polymerized to obtain various polymers. None of the prior publications mention such a concept.
In fact, such a method is not only difficult to envisage, but also difficult to implement, requiring a great deal of technical difficulty to be overcome. The fermentation broth or the treatment broth of the diamine salt contains a large amount of impurities, such as: thallus, protein, culture medium, unfermented substrate, a large amount of inorganic salt, pigment, saccharide, water and the like, and not only comprises various impurities in the process of binary acid fermentation, but also comprises various impurities in the process of pentanediamine production, and the whole system comprises multiphase substances such as gas, oil, water, solid and the like, so that certain specific impurities need to be removed in the complex system, high purity is ensured, high yield is also required, and the difficulty is very high. In the face of such problems, the inventors have studied for many years, and found that various impurities can be cooperatively removed through specific process steps and conditions, and further, in a specific parameter range, impurities such as thalli, pigments and the like can be well removed, so that a diamine salt solution can reach a polymerization grade, and the properties such as purity, chromaticity and the like of a polymer obtained by polymerization can be comparable to those of a polymer obtained by polymerization of the conventional polymerization grade monomer, thereby obtaining the technical scheme of the invention.
It is an object of the present invention to provide a method for purifying a diamine salt solution, the method comprising the steps of:
(1) Solid-liquid separation is carried out on the diamine salt solution containing impurities to obtain supernatant;
(2) And (3) adsorbing the supernatant obtained in the step (1) by resin to obtain a diamine salt solution.
Further preferred embodiments of the above-described embodiments will be described below.
According to a preferred embodiment of the present invention, the diamine salt may include: salts of C4-C6 aliphatic or aromatic diamines and C4-C18 aliphatic or aromatic dicarboxylic acids. Both the amine groups of the diamine and the carboxyl groups of the dicarboxylic acid are at the end groups.
In a preferred technical scheme of the invention, in the diamine salt of dibasic acid, the structural formula of the dibasic acid is as follows: HOOC (CH 2)n COOH, where 4.ltoreq.n.ltoreq.18, preferably 6.ltoreq.n.ltoreq.18, may be 4,5,6,7,8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18), the amine having the formula H 2N-(CH2)m-NH2, where 4.ltoreq.m.ltoreq.18, preferably 4.ltoreq.m.ltoreq.6, i.e. m may be 4,5 or 6, the diamine having the formula-OOC (CH 2)nCOO-+H3N-(CH2)m-NH3 +, where 4.ltoreq.n.ltoreq.18 and 4.ltoreq.m.ltoreq.6.
For example: the diamine salt may be: glutaric amine succinate, glutaric amine adipate, glutaric amine sebacate, glutaric amine dodecadicarboxylate, and the like. The diamine salts may also include diamine salts containing aromatic structures, such as: and glutarimide terephthalate. In order to obtain copolymers having different properties, it is also possible to obtain diamine salts of polyamides of different types or diamine salts of polyamides and polymerized monomers, as required. For example: the diamine salts of the present invention may also include nylon 66 salts, caprolactam, 6-aminocaproic acid, and the like. The diamine salts of the present invention may also be mixtures of different diamine salts.
In a preferred technical scheme of the invention, in the step (1), the diamine salt solution is obtained by taking the fermentation liquor of the dibasic acid or the treatment liquor thereof into the process of fermenting the pentanediamine or the process of fermenting and enzyme converting the lysine into the pentanediamine.
According to a preferred technical scheme of the invention, the diamine salt solution is prepared by a fermentation method or by a fermentation method and an enzyme conversion method.
According to a preferred technical scheme of the invention, the dibasic acid is prepared by a fermentation method.
According to a preferred embodiment of the invention, the amine is prepared by fermentation or by fermentation and enzymatic conversion.
According to a preferred technical scheme of the invention, after the diamine salt solution is prepared by a fermentation method, before the method of the invention is carried out, polymeric diamine and polymeric diamine are not obtained by various methods, and then are dissolved to obtain diamine salt, but polymeric diamine salt is directly prepared from fermentation liquor.
The concentration of the diamine salt solution is not particularly required, so long as the diamine salt can be uniformly dissolved in the solution. According to a preferred 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 technical scheme of the invention, in the step (1), the diamine salt solution is: the fermentation liquor and/or the treatment liquor of the dibasic acid obtained by fermentation and the solution obtained by mixing the fermentation liquor and/or the treatment liquor of the amine obtained by fermentation and the treatment liquor of the amine obtained by fermentation are conventional in the field; or is: the fermentation broth of dibasic acid obtained by fermentation and/or the treatment fluid thereof, which are conventional in the art, and the enzymatic conversion broth of amine obtained by fermentation and enzymatic conversion and/or the treatment fluid thereof, which are conventional in the art, are mixed to obtain the solution. The impurities include: cells, proteins, a culture medium, an unfermented substrate, inorganic salts, pigments, reducing sugars, water, and the like. The impurities include at least cells. The impurities include at least pigments.
In the present invention, the reducing sugar comprises: saccharides containing free aldehyde or ketone groups include, inter alia, glucose.
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 a filter aid filtration or a membrane filtration, etc.
In a preferred embodiment of the present invention, in step (1), the pH of the diamine salt solution is 6 to 10, preferably 7 to 9, before the solid-liquid separation.
In a preferred embodiment of the present invention, in step (1), the diamine salt solution containing the impurities is heated before the solid-liquid separation. The heating temperature is 70-100 ℃, preferably 80-95 ℃. The heating time is 30-120min.
In a preferred embodiment of the present invention, in the step (1), the solid-liquid separation temperature is at least room temperature, preferably at least 60 ℃, more preferably at least 70 ℃, and most preferably from 70 to 90 ℃.
In a preferred embodiment of the invention, in step (1), the rotational speed of the centrifugation is 4000-5500rpm, preferably 4500-5000rpm.
According to a preferred technical scheme of the invention, in the step (1), the centrifugation time is 1-10min.
In a preferred technical scheme of the invention, in the step (2), the adsorption method comprises the following steps: and (3) contacting the supernatant obtained in the step (1) with macroporous adsorption resin to adsorb.
In a preferred embodiment of the present invention, in the step (2), the pore diameter of the macroporous adsorbent resin is 2-10nm, preferably 3-8nm; the macroporous adsorption resin comprises: the macroporous adsorption resin with the pore diameter of 3-6nm, the macroporous adsorption resin with the pore diameter of 6-8nm and the macroporous adsorption resin with the pore diameter of 3-4nm preferably comprises: one or more of XDA-1G macroporous adsorbent resin, XDA-5 macroporous adsorbent resin and DA201-C macroporous adsorbent resin.
In a preferred embodiment of the present invention, in step (2), the method of contacting includes any one of the following methods:
Mode one: uniformly mixing the supernatant with macroporous adsorption resin, and adsorbing; and/or the number of the groups of groups,
Mode two: and (3) passing the supernatant through a macroporous adsorption resin column for adsorption.
Among the above modes, the second mode is preferable, and the second mode has a more remarkable effect in removing the reducing sugar than the first mode.
In one preferable technical scheme of the invention, in the first mode, the dosage of the macroporous adsorption resin is as follows: the volume ratio of the supernatant to the macroporous adsorption resin is (0.5-7): 1, preferably (1-5): 1, more preferably (1-3): 1, a step of;
In a preferred embodiment of the present invention, in the first mode, the adsorption time is 5-72 hours, preferably 12-48 hours;
In a preferred embodiment of the present invention, in the first embodiment, the temperature of the adsorption is 10 to 95 ℃, preferably 20 to 60 ℃, preferably 30 to 50 ℃;
In one preferred technical scheme of the invention, in the first mode, the supernatant and the macroporous adsorption resin are uniformly mixed, and after adsorption, the adsorption is more sufficient by one or more modes of vibration, stirring or standing.
In a preferred embodiment of the present invention, in the second mode, the feeding flow rate of the supernatant is 0.5-5BV/h, preferably 0.5-2BV/h.
In the second mode, the macroporous adsorption resin is in the form of macroporous adsorption resin columns, and the aspect ratio of the macroporous adsorption resin columns is (10-20): 1.
In a preferred technical scheme of the invention, in the second mode, washing is performed after the adsorption; the washing is preferably performed with distilled water, ammonia water or an acid solution; the flow rate at the time of washing is preferably 1 to 10BV/h, more preferably 5 to 8BV/h; the acid solution is preferably hydrochloric acid solution; the temperature of the washing is preferably 20 to 95 ℃, more preferably 60 to 90 ℃.
In a preferred embodiment of the present invention, in step (2), after the adsorption, the resin is separated from the diamine salt solution. The obtained diamine salt solution can be directly used for polymerization to obtain various polymers.
The second object of the present invention is to provide a diamine salt solution of dibasic acid prepared by the above method.
The third object of the present invention is to provide a diamine salt, wherein the solution of the diamine salt has a concentration of 0.1% (m/V) and a UV index of not more than 0.8X10 -3, preferably (0.3-0.8). Times.10 -3, or preferably (0.1-0.8). Times.10 -3, or preferably (0.1-0.3). Times.10 -3, as measured at 279nm when the thickness of the absorption cell is 5 cm.
The diamine salt is prepared without mixing the polymer grade diacid and the polymer grade amine. According to the general knowledge in the art, the polymeric dibasic acid is dibasic acid with total acid content of more than 98%, or dibasic acid with total acid content of more than 98.5%, or dibasic acid with total acid content of more than 99%, or dibasic acid with total acid content of more than 99.5%; the polymerization grade pentanediamine is the pentanediamine with the purity of more than 98 percent or the pentanediamine with the purity of more than 99 percent and the pentanediamine with the purity of more than 99.5 percent, and the percentages are mass percentages.
The diamine salt of the above-mentioned dibasic acid has a concentration of 0.1% (m/V) and a UV index of 5cm in the absorption cell at 279nm 0.8×10-3,0.8×10-3,0.75×10-3,0.7×10-3,0.65×10-3,0.6×10-3,0.55×10-3,0.5×10-3,0.45×10-3,0.4×10-3,0.35×10-3,0.3×10-3,0.25×10-3,0.2×10-3,0.15×10-3,0.1×10-3.
The invention provides a preparation method of diamine salt, which comprises the following steps:
(A) Obtaining a diamine salt solution according to the purification method of the diamine salt solution;
(B) Separating the diamine salt from the diamine salt solution in step (a).
In a preferred embodiment of the present invention, in step (B), the separation method comprises crystallization. The crystallization is preferably a cooling crystallization. The cooling rate of the crystallization is preferably 1 ℃/3-15min.
According to a preferred technical scheme of the invention, the cooling crystallization comprises the following steps: cooling the diamine salt solution to 20-40 ℃ at a speed of 1 ℃/3-10min, and preserving heat for 0.3-5h; then cooling by 5-20 ℃ at the speed of 1 ℃/6-15min, and preserving heat for 0.2-5h.
According to a preferred technical scheme of the invention, the water content in the diamine salt solution before crystallization is 25-40%, and the percentage is the mass percentage of water in the diamine salt solution. The water content can be achieved by means of rotary steaming.
The method directly separates and purifies the diamine salt containing various impurities, has simple operation, can well remove the impurities such as thalli, pigments and the like, and ensures that the diamine salt solution can reach a high-quality polymerization grade, so that the polymer obtained by polymerization has the performances of purity, chromaticity and the like which are comparable with those of the polymer obtained by polymerization of the existing polymerization grade monomer.
Detailed Description
In one embodiment of the present invention, the diamine forming the diamine salt comprises at least pentanediamine, that is, the diamine forming the diamine salt is pentanediamine or a mixed diamine of pentanediamine 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 salt is an impurity-containing pentanediamine, which may generally be a fermentation broth of pentanediamine, an enzyme conversion broth, a salt solution, or the like.
In the present invention, the pentylene diamine is not limited in source and can be prepared by any existing biological method. For example, an enzymatic conversion solution is obtained by reacting a lysine with a pentylene diamine decarboxylase to thereby obtain an enzymatic conversion solution containing pentylene diamine (refer to JP 200400114A); through genetic technology, the expression of lysine decarboxylase is up-regulated in a strain capable of producing lysine, or the lysine decarboxylase is expressed in a recombinant way, so that the produced lysine can be synchronously converted into the pentanediamine in the fermentation process, and the pentanediamine fermentation broth is obtained through direct fermentation (refer to construction of a genetic engineering bacterium for producing the 1, 5-pentanediamine corynebacterium glutamicum by a one-step method, niu Tao and the like, journal of Chinese bioengineering, 2010, 30 (8): 93-99), and the like.
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The detection method of the performance parameters related to each embodiment of the invention is as follows:
1. the method for detecting the purity of the diamine salt solution comprises the following steps:
characterized by UV index; using KONICA MINOLTA CM-3600A apparatus, the absorbance A was measured at 279nm with a UV index of 0.1% (m/V) diamine salt and an absorption cell thickness of 5 cm.
2. The method for detecting the color (chromaticity) of the diamine salt solution comprises the following steps:
visual inspection was performed with reference to GB/T605-2006.
3. The method for detecting the content of the reducing sugar comprises the following steps:
detection was performed according to DNS colorimetry using KONICA MINOLTA CM-3600A apparatus.
4. The detection method of the color of the polyamide comprises the following steps:
Detection was performed using KONICA MINOLTA CM-3600A equipment according to the GB-T2409-1980 standard.
Preparation example 1
Preparation of pentanediamine sebacate fermentation liquor
1. Preparation of ammonium sebacate fermentation liquor
1.1 Strain activation:
Inoculating candida glycerinum strain into a seed bottle filled with YPD culture, and shake culturing at 29 ℃ for 1 day at 220rpm under natural pH; YPD medium included: 20g/L glucose, 10g/L yeast extract, 20g/L peptone; pH7.0;
1.2 seed tank culture, preparing seed liquid:
taking seed bottle seeds, inoculating the seed bottle seeds into a seed tank filled with a seed culture medium, wherein the initial pH value of a fermentation system after inoculation is 6.0, the ventilation ratio is 0.5vvm at 29 ℃, the tank pressure is 0.1MPa, a certain stirring speed is kept, the dissolved oxygen in the seed culture process is controlled to be more than or equal to 10%, the culture is carried out for 18-20h, and the OD620 of the mature seeds after the culture is diluted 30 times is 15;
The seed medium comprises: 20g/L sucrose, 8g/L corn steep liquor, 5g/L yeast extract, 8g/L KH 2PO4, 3g/L urea, prepared with water, and sterilized at 121℃for 20min; urea is sterilized separately, sterilized for 15min at 110 ℃, cooled and mixed with other sterilized components;
1.3 fermentation:
Inoculating a seed solution into the fermentation tank containing a fermentation medium, wherein the fermentation medium comprises: 40g/L of glucose, 3g/L of potassium nitrate, 5g/L of monopotassium phosphate, 4g/L of ammonium sulfate and 1g/L of magnesium sulfate;
Controlling the temperature at 29 ℃ in the fermentation process, the ventilation ratio is 0.3vvm, the tank pressure is 0.1MPa (gauge pressure), a certain stirring speed is maintained to control dissolved oxygen to be more than or equal to 10%, the pH is controlled to be 6.0 in the initial fermentation, the pH is controlled to be 4.0-5.0 in the initial fermentation 18h, and the pH is controlled to be 5.0-8.0 in the fermentation 18h until the fermentation is finished; adding substrate n-decalin in batch for the first time during fermentation for 18h, and adding substrate again when the substrate content in the fermentation liquid is lower than 2%; in the fermentation process, 0-5 h of ammonia water (ammonia gas content is 25%) is continuously fed at a speed of 0.5g/h/L, 5-18 h of ammonia water (ammonia gas content is 25%) is continuously fed at a speed of 2g/h/L, 18-48 h of ammonia water (ammonia gas content is 25%) is continuously fed at a speed of 1.5g/h/L, 48-120 h of ammonia water (ammonia gas content is 25%) is continuously fed at a speed of 0.4g/h/L, and the feeding amount of ammonia water is 100g/L.
The total fermentation period is 165h; the concentration of the sebacic acid ammonium salt solution is 120g/L.
2. Preparation of pentanediamine sebacate fermentation liquor
2.1 Seed tank culture: 10L fermentors (working volume 5.5L), fermentation strain CIB132-3 (construction method, see PCT application No. PCT/CN2015/094121, published application No. WO2017/079872A1, published application No. 2017, 5 month and 18 days, see, for example, examples 16 and 17 in the specification of the patent application), inoculation ratio of 2%, ventilation ratio of 0.4vvm, temperature of 37 ℃, rotation speed of 700rpm, tank pressure of 0.10MPa, ammonia water control pH of 6.5, and after bacterial concentration OD562 reaches 1.00, inoculating into the fermentors; seed culture medium: KH 2PO4 0.4％,MgSO4·7H2O 0.25％,MnSO4·H2 O13.5 ppm, ammonium sebacate (prepared in 1 above, added in the form of ammonium sebacate solution, percentage of ammonium sebacate salt as active ingredient) 0.58%, glucose 15%, corn steep liquor 0.27%, threonine 0.035%, leucine 0.025%;
2.2 fermenter culture: 10L of fermentation tank (working volume 6L), wherein the fermentation strain is CIB132-3, the inoculation ratio is 20%, the aeration ratio is 0.4vvm, the temperature is 37 ℃, the rotating speed is 800rpm, the tank pressure is 0.10MPa, the pH is controlled to be 6.5 by ammonia water, the feeding culture medium is fed after fermentation for 5h, and the fermentation period is 35h; fermentation medium: KH 2PO4 0.04％,MgSO4·7H2O 0.25％,MnSO4·H2 O0.017%, ammonium sebacate 0.3%, glucose 3.5%, corn steep liquor 0.50%, threonine 0.022%; feed medium: glucose 50%, ammonium sebacate 25%.
The concentration of the glutarimide sebacate salt in the final fermentation broth was 235.33g/kg.
Preparation example 2
Preparation of dodecandioic acid-pentanediamine salt fermentation liquor
1. Preparation of ammonium dodecadibasic acid fermentation liquor
1.1 Strain activation:
Inoculating candida glycerinum strain into a seed bottle filled with YPD culture, and performing shake culture at 29 ℃ at 220rpm with the amplitude of 26-50 mm for 1 day; YPD medium included: 20g/L glucose, 10g/L yeast extract, 20g/L peptone; pH7.0-7.5;
1.2 seed tank culture, preparing seed liquid:
Taking seed bottle seeds, inoculating the seed bottle seeds into a seed tank filled with a seed culture medium, wherein the initial pH value of a fermentation system after inoculation is 6.0, the ventilation ratio is 0.5vvm at 29 ℃, the tank pressure is 0.1MPa, a certain stirring speed is kept, the dissolved oxygen in the seed culture process is controlled to be more than or equal to 10%, the culture is carried out for 18 hours, and the OD620 of the mature seeds after the culture is diluted 30 times is 15; the seed medium comprises: 20g/L sucrose, 8g/L corn steep liquor, 5g/L yeast extract, 8g/L KH 2PO4, 3g/L urea, 15mL/L substrate, prepared with water, and sterilized at 121℃for 20min; urea is sterilized separately, sterilized for 15min at 110 ℃, cooled and mixed with other sterilized components;
1.3 fermentation:
Inoculating a seed solution into the fermentation tank containing a fermentation medium, wherein the fermentation medium comprises: 30g/L of glucose, 2g/L of potassium nitrate, 3g/L of monopotassium phosphate, 1g/L of ammonium sulfate and 0.5g/L of magnesium sulfate;
Controlling the temperature at 29 ℃ in the fermentation process, the ventilation ratio is 0.5vvm, the tank pressure is 0.1MPa (gauge pressure), a certain stirring speed is maintained to control dissolved oxygen to be more than or equal to 10%, the pH is controlled to be 6.0 in the initial fermentation, the pH is controlled to be 4.0-5.0 in the initial fermentation 18h, and the pH is controlled to be 5.0-8.0 in the fermentation 18 h; adding substrate n-dodecane in batches for the first time during fermentation for 18 hours, and adding substrate in batches when the substrate content in the fermentation liquid is lower than 5%; continuously supplementing ammonia water (ammonia gas content is 25%) at a speed of 0.7g/h/L in the fermentation process, and supplementing 100g/L ammonia water after the fermentation is finished, wherein the total addition amount of the ammonia water is 210g/L;
The total fermentation period is 155h; obtaining the dodecandioic acid ammonium salt solution with the concentration of 180g/L.
2. Preparation of dodecandioic acid-pentanediamine salt fermentation liquor
2.1 Seed tank culture: 10L of fermentation tank (7L), wherein the fermentation strain is corynebacterium glutamicum (Corynebacteriumglutamicum), the inoculation ratio is 2%, the aeration ratio is 0.8vvm, the temperature is 39 ℃, the rotating speed is 400rpm, the tank pressure is 0.05MPa, the pH is controlled to be 7.0 by ammonia water, and the fermentation tank is accessed after the bacterial concentration OD562 reaches 1.00; seed culture medium: KH 2PO4 0.5％,MgSO4·7H2O0.35％,MnSO4·H2 O16 ppm, dodecandioic acid ammonium salt (prepared in the above 1, added in the form of dodecandioic acid ammonium salt solution, the percentage is the percentage of the effective component dodecandioic acid ammonium salt), glucose 5%, corn steep liquor 0.30%, threonine 0.045%, leucine 0.025%;
(2) Culturing in a fermentation tank: 10L fermentation tank (working volume 7L), inoculation ratio 20%, aeration ratio 0.8vvm, temperature 39 ℃, rotating speed 500rpm, tank pressure 0.05MPa, ammonia water pH control 7.0, after fermentation for 6h, feeding prepared feed medium, fermentation period 40h, obtaining lysine fermentation liquor, wherein the lysine content in the lysine fermentation liquor is 31.8%, and pH value is 6.7; fermentation medium: KH 2PO4 0.04％,MgSO4·7H2O 0.30％,MnSO4·H2 O0.010%, ammonium salt of dodecandioic acid 0.4%, glucose 2.0%, corn steep liquor 0.50% and threonine 0.030%; feed medium: 20% of glucose and 5% of ammonium dodecanoate.
(3) Adding a certain amount of the lysine decarboxylase prepared in the way above into the lysine fermentation broth, wherein the ratio of the adding weight of the lysine decarboxylase (calculated according to the dry basis of lysine decarboxylase cells) to the weight of lysine in the lysine fermentation broth (calculated according to lysine dodecadibasic acid salt) is 1:255, the adding amount of the coenzyme 5' -pyridoxal phosphate is 0.2mmol/L based on the weight of the reaction system; decarboxylation reaction is carried out for 12 hours at 100rpm and 35 ℃, lysine is converted into pentanediamine, the conversion rate of lysine is more than 99 percent, and the reaction is finished to form a solution of dodecandioic acid-pentanediamine salt;
in the final solution of the dodecandioic acid-glutaramide salt (enzyme conversion solution), the concentration of the dodecandioic acid-glutaramide salt is 270.63g/kg; the sulfate ion concentration was 0.43g/kg.
Example 1
The preparation method of the glutarimide sebacate comprises the following steps:
(1) Taking the pentamethylene diamine sebacate salt solution prepared in the preparation example 1, wherein the content of the pentamethylene diamine sebacate salt (-OOC(CH2)8COO-+H3N-(CH2)5-NH3+) is 15% (mass percent), heating for 30min at 80 ℃, the pH value of the pentamethylene diamine sebacate salt solution is 7.7, and centrifuging at the temperature of 70 ℃ for 5min at the rotating speed of 4800rpm to obtain supernatant;
(2) Uniformly mixing the supernatant obtained in the step (1) with XDA-1G macroporous adsorption resin (Xishan blue dawn technology), vibrating, and adsorbing; the volume ratio of the supernatant to the macroporous adsorption resin is 3:1, the adsorption time is 10 hours, and the adsorption temperature is 45 ℃; separating after adsorption to obtain a diamine salt solution of dibasic acid;
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 30 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 10 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the solid product of the diamine salt.
And (3) detecting:
the pentamethylenediamine sebacate salt solution (stock solution) prepared in preparation example 1 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
The pentamethylenediamine sebacate solid product was dissolved in water to give a solution with a concentration of 0.1% (m/V) and a UV index measured at 279nm at an absorption cell thickness of 5 cm: 0.558×10 -3;
The solid product of the pentamethylene diamine sebacate is dissolved in water to prepare the pentamethylene diamine sebacate salt solution, and the chromaticity of the pentamethylene diamine sebacate salt solution is as follows: and color comparison 27.
Example 2
The preparation method of the dodecadiacid-glutarimide salt comprises the following steps:
(1) Taking the dodecandioic acid pentanediamine salt solution prepared in the preparation example 2, wherein the content of the dodecandioic acid pentanediamine salt (-OOC(CH2)10COO-+H3N-(CH2)5-NH3+) is 12 percent (mass percent), heating for 35min at 90 ℃, and centrifuging for 5min at a rotation speed of 5000rpm at the temperature of 90 ℃ to obtain a supernatant;
(2) Uniformly mixing the supernatant obtained in the step (1) with DA201-C macroporous adsorption resin (Jiangsu Su Qing), stirring, and adsorbing; the volume ratio of the supernatant to the macroporous adsorption resin is 4:1, the adsorption time is 20 hours, and the adsorption temperature is 50 ℃; separating after adsorption to obtain a diamine salt solution of dibasic acid;
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 35 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 10 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the solid product of the diamine salt.
And (3) detecting:
The solution (stock solution) of the pentanediamine salt of dodecadibasic acid prepared in preparation example 2 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
The solid product of the dodecanedioic acid, pentanediamine, is dissolved in water to obtain a solution with the concentration of 0.1% (m/V), and the UV index of the solution detected at 279nm when the thickness of an absorption tank is 5cm is as follows: 0.574×10 -3;
the solid product of the dodecyl dibasic acid and the amyl diamine is dissolved in water to prepare the dodecyl dibasic acid and the amyl diamine salt solution, the chromaticity of which is as follows: and color comparison 27.
Example 3
The preparation method of the glutarimide sebacate comprises the following steps:
(1) Taking the pentamethylene diamine sebacate salt solution prepared in the preparation example 1, wherein the content of the pentamethylene diamine sebacate salt (-OOC(CH2)8COO-+H3N-(CH2)5-NH3+) is 12% (mass percent), heating at 90 ℃ for 35min, the pH value of the pentamethylene diamine sebacate salt solution is 6, and centrifuging at the temperature of 65 ℃ for 8min at the rotating speed of 4000rpm to obtain supernatant;
(2) Uniformly mixing the supernatant obtained in the step (1) with XDA-5 macroporous adsorption resin (Xishan blue dawn technology), vibrating and adsorbing; the volume ratio of the supernatant to the macroporous adsorption resin is 1:1, the adsorption time is 17h, and the adsorption temperature is 45 ℃; separating after adsorption to obtain a diamine salt solution of dibasic acid;
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 30 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 5 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the solid product of the diamine salt.
And (3) detecting:
the pentamethylenediamine sebacate salt solution (stock solution) prepared in preparation example 1 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
The pentamethylenediamine sebacate solid product was dissolved in water to give a solution with a concentration of 0.1% (m/V) and a UV index measured at 279nm at an absorption cell thickness of 5 cm: 0.8X10 -3;
the solid product of the pentamethylene diamine sebacate is dissolved in water to prepare the pentamethylene diamine sebacate salt solution, and the chromaticity of the pentamethylene diamine sebacate salt solution is as follows: and (5) colorimetric 30.
Example 4
The preparation method of the glutarimide sebacate comprises the following steps:
(1) Taking the pentamethylene diamine sebacate salt solution prepared in the preparation example 1, wherein the content of the pentamethylene diamine sebacate salt (-OOC(CH2)8COO-+H3N-(CH2)5-NH3+) is 15% (mass percent), heating for 35min at 90 ℃, centrifuging for 10min at the rotation speed of 4900rpm at the temperature of 75 ℃ to obtain supernatant;
(2) Passing the supernatant obtained in the step (1) through a macroporous adsorption resin column, wherein the macroporous adsorption resin is XDA-1G macroporous adsorption resin (Xiyan Xiao technology), and the aspect ratio of the macroporous adsorption resin column is 15:1, the feeding flow rate of the supernatant is 2BV/h; obtaining a diamine salt solution of dibasic acid; after adsorption, washing with distilled water, wherein the flow rate during washing is 2BV/h, and the washing temperature is 60 ℃;
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 35 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 10 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the solid product of the diamine salt.
And (3) detecting:
the pentamethylenediamine sebacate salt solution (stock solution) prepared in preparation example 1 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
the pentamethylenediamine sebacate solid product was dissolved in water to give a solution with a concentration of 0.1% (m/V) and a UV index measured at 279nm at an absorption cell thickness of 5 cm: 0.348×10 -3;
The solid product of the pentamethylene diamine sebacate is dissolved in water to prepare the pentamethylene diamine sebacate salt solution, and the chromaticity of the pentamethylene diamine sebacate salt solution is as follows: colorimetric 21;
reducing sugar content: stock solution: 5.12g/kg, end product: 0.07g/kg.
Example 5
The preparation method of the dodecadiacid-glutarimide salt comprises the following steps:
(1) Taking the dodecandioic acid pentanediamine salt solution prepared in preparation example 2, wherein the content of the dodecandioic acid pentanediamine salt (-OOC(CH2)10COO-+H3N-(CH2)5-NH3+) is 12 percent (mass percent), heating for 35min at 90 ℃, and centrifuging for 4min at a rotation speed of 5000rpm at a temperature of 85 ℃ to obtain a supernatant;
(2) Passing the supernatant obtained in the step (1) through a macroporous adsorption resin column, wherein the macroporous adsorption resin is DA201-C macroporous adsorption resin (Jiangsu Su Qing), and the height-diameter ratio of the macroporous adsorption resin column is 16:1, the feeding flow rate of the supernatant is 1BV/h; obtaining a diamine salt solution of dibasic acid; after adsorption, washing with hydrochloric acid solution, wherein the flow rate during washing is 1BV/h, and the washing temperature is 75 ℃;
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 28 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 8 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the solid product of the diamine salt.
And (3) detecting:
The solution (stock solution) of the pentanediamine salt of dodecadibasic acid prepared in preparation example 2 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
The solid product of the dodecanedioic acid, pentanediamine, is dissolved in water to obtain a solution with the concentration of 0.1% (m/V), and the UV index of the solution detected at 279nm when the thickness of an absorption tank is 5cm is as follows: 0.281×10 -3;
the solid product of the dodecyl dibasic acid and the amyl diamine is dissolved in water to prepare the dodecyl dibasic acid and the amyl diamine salt solution, the chromaticity of which is as follows: colorimetric 21;
Reducing sugar content: stock solution: 5.12g/kg, end product: 0.15g/kg.
Example 6
The preparation method of the glutarimide sebacate comprises the following steps:
(1) Taking the pentamethylene diamine sebacate salt solution prepared in the preparation example 1, wherein the content of the pentamethylene diamine sebacate salt (-OOC(CH2)8COO-+H3N-(CH2)5-NH3+) is 10% (mass percent), heating for 35min at 85 ℃, and centrifuging for 3min at 5500rpm at 68 ℃ to obtain supernatant;
(2) Passing the supernatant obtained in the step (1) through a macroporous adsorption resin column, wherein the macroporous adsorption resin is XDA-5 macroporous adsorption resin (Xian blue dawn technology), and the height-diameter ratio of the macroporous resin column is 10:1, the feeding flow rate of the supernatant is 1BV/h; obtaining a diamine salt solution of dibasic acid; after adsorption, washing was performed with a hydrochloric acid solution at a flow rate of 1BV/h and a washing temperature of 20 ℃.
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 30 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 10 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the solid product of the diamine salt.
And (3) detecting:
the pentamethylenediamine sebacate salt solution (stock solution) prepared in preparation example 1 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
the pentamethylenediamine sebacate solid product was dissolved in water to give a solution with a concentration of 0.1% (m/V) and a UV index measured at 279nm at an absorption cell thickness of 5 cm: 0.378 x 10 -3;
The solid product of the pentanediamine sebacate is dissolved in water to prepare a diamine salt solution, the chromaticity of which is as follows: colorimetric 23;
reducing sugar content: stock solution: 5.12g/kg, end product: 0.31g/kg.
Comparative example 1
The preparation method of the glutarimide sebacate comprises the following steps:
(1) Taking the pentamethylene diamine sebacate salt solution prepared in the preparation example 1, wherein the content of the pentamethylene diamine sebacate salt (-OOC(CH2)8COO-+H3N-(CH2)5-NH3+) is 15% (mass percent), heating for 30min at 80 ℃, the pH value of the pentamethylene diamine sebacate salt solution is 7.7, and centrifuging at the temperature of 70 ℃ for 5min at the rotating speed of 4800rpm to obtain supernatant;
(2) Uniformly mixing the supernatant obtained in the step (1) with LX67 resin (the technology of Xian blue), vibrating and adsorbing; the volume ratio of the supernatant to the macroporous adsorption resin is 3:1, the adsorption time is 10 hours, and the adsorption temperature is 45 ℃; separating after adsorption to obtain a diamine salt solution of dibasic acid;
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 30 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 10 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the solid product of the diamine salt.
And (3) detecting:
the pentamethylenediamine sebacate salt solution (stock solution) prepared in preparation example 1 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
the pentamethylenediamine sebacate solid product was dissolved in water to give a solution with a concentration of 0.1% (m/V) and a UV index measured at 279nm at an absorption cell thickness of 5 cm: 1.128×10 -3;
The solid product of the pentamethylene diamine sebacate is dissolved in water to prepare the pentamethylene diamine sebacate salt solution, and the chromaticity of the pentamethylene diamine sebacate salt solution is as follows: and (5) colorimetric 35.
Comparative example 2
The preparation method of the glutarimide sebacate comprises the following steps:
(1) Taking the pentamethylene diamine sebacate salt solution prepared in the preparation example 1, wherein the content of the pentamethylene diamine sebacate salt (-OOC(CH2)8COO-+H3N-(CH2)5-NH3+) is 15% (mass percent), heating for 35min at 90 ℃, centrifuging for 10min at the rotation speed of 4900rpm at the temperature of 75 ℃ to obtain supernatant;
(2) Passing the supernatant obtained in the step (1) through a macroporous adsorption resin column, wherein the macroporous adsorption resin is XDA-1G macroporous adsorption resin (Xiyan blue dawn technology), and the height-diameter ratio of the macroporous adsorption resin column is 5:1, the feeding flow rate of the supernatant is 2BV/h; obtaining a diamine salt solution of dibasic acid; after adsorption, washing with distilled water, wherein the flow rate during washing is 2BV/h, and the washing temperature is 60 ℃;
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 30 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 10 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the solid product of the diamine salt.
And (3) detecting:
the pentamethylenediamine sebacate salt solution (stock solution) prepared in preparation example 1 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
The pentamethylenediamine sebacate solid product was dissolved in water to give a solution with a concentration of 0.1% (m/V) and a UV index measured at 279nm at an absorption cell thickness of 5 cm: 2.598X 10 -3;
the solid product of the pentamethylene diamine sebacate is dissolved in water to prepare the pentamethylene diamine sebacate salt solution, and the chromaticity of the pentamethylene diamine sebacate salt solution is as follows: and a color comparison 38.
Reducing sugar content: stock solution: 5.12g/kg, end product: 3.85g/kg.
Comparative example 3
The preparation method of the dodecadiacid-glutarimide salt comprises the following steps:
(1) Taking the dodecandioic acid pentanediamine salt solution prepared in preparation example 2, wherein the content of the dodecandioic acid pentanediamine salt (-OOC(CH2)10COO-+H3N-(CH2)5-NH3+) is 12 percent (mass percent), heating for 35min at 90 ℃, and centrifuging for 4min at a rotation speed of 5000rpm at a temperature of 85 ℃ to obtain a supernatant;
(2) Passing the supernatant obtained in the step (1) through a macroporous adsorption resin column, wherein the macroporous adsorption resin is DA201-C macroporous adsorption resin (Jiangsu Su Qing), and the height-diameter ratio of the macroporous adsorption resin column is 16:1, the feeding flow rate of the supernatant is 3BV/h; obtaining a diamine salt solution of dibasic acid; after adsorption, washing with hydrochloric acid solution, wherein the flow rate during washing is 1BV/h, and the washing temperature is 75 ℃;
(3) The diamine salt solution obtained in the step (2) is subjected to rotary evaporation, wherein the water content is 30 percent (the percentage is the mass percentage of the diamine salt solution), the temperature is reduced to 28 ℃ at the speed of 1 ℃/5min from 55 ℃, and the heat is preserved for 1h; then cooling to 8 ℃ at a speed of 1 ℃/10min, and preserving heat for 0.5h; obtaining the dodecyl dibasic acid pentanediamine solid product.
And (3) detecting:
The solution (stock solution) of the pentanediamine salt of dodecadibasic acid prepared in preparation example 2 was adjusted to a concentration of 0.1% (m/V) and the UV index measured at 279nm at an absorption cell thickness of 5cm was: 4.0X10 -3;
The solid product of the dodecanedioic acid, pentanediamine, is dissolved in water to obtain a solution with the concentration of 0.1% (m/V), and the UV index of the solution detected at 279nm when the thickness of an absorption tank is 5cm is as follows: 2.732×10 -3;
the solid product of the dodecyl dibasic acid and the amyl diamine is dissolved in water to prepare the dodecyl dibasic acid and the amyl diamine salt solution, the chromaticity of which is as follows: brown turbidity;
reducing sugar content: stock solution: after 5.12g/kg experiment: 4.85g/kg.
Effect examples
The solid salts of dibasic acid amine obtained in examples 1 to 6 and comparative examples 1 to 3 were used to prepare polyamides as follows:
And (3) replacing air with nitrogen in a 100-liter polymerization kettle, polymerizing a solution of diamine salt in the polymerization kettle, heating the oil bath to 230 ℃, starting exhausting when the pressure in the kettle is raised to 1.73MPa, vacuumizing to-0.06 MPa (vacuum gauge pressure) when the temperature in the kettle is up to 265 ℃, and maintaining the vacuum degree for 20min to obtain the corresponding polyamide.
Nitrogen was charged into the polymerizer to a pressure of 0.5MPa, and the melt discharge was started, and the mixture was granulated by a granulator, dried at 80 ℃ and vacuum-dried for 8 hours, and then tested, and the test results are shown in table 1.
Comparative example 1
Polymeric grade dibasic acid (purity 99.9%, commercially available, kaiser Biotechnology Co., ltd.) and polymeric grade pentanediamine (purity 99.9%, commercially available, kaiser Biotechnology materials Co., ltd.) were dissolved to form a diamine salt solution, and a polyamide was prepared as described above.
Purity of the diamine salt solution: 0.3X10 -3;
Chromaticity of the diamine salt solution: and (5) colorimetric 15.
TABLE 1 yellow index of polyamides
| Group of | Yellow index |
| Polyamides prepared from diamine salts of example 1 | 5 |
| Polyamides prepared from diamine salts of example 2 | 5 |
| Polyamide obtained from diamine salt of example 3 | 6 |
| Polyamide obtained from diamine salt of example 4 | 3 |
| Polyamides prepared from the diamine salts of example 5 | 3 |
| Polyamide obtained from diamine salt of example 6 | 4 |
| Polyamide obtained from diamine salt of comparative example 1 | 10 |
| Polyamide obtained from diamine salt of comparative example 2 | 15 |
| Polyamide obtained from diamine salt of comparative example 3 | 15 |
| Comparative example 1 | 3 |
As can be seen from the above examples, comparative examples and comparative examples, the diamine salt purified by the purification method of the present invention has high purity and low impurity content, and the prepared polyamide has high quality and can meet the requirements of industrial application.
Claims (12)
1. A process for the preparation of an amine salt of a dibasic acid, the process comprising the steps of:
(1) Solid-liquid separation is carried out on the diamine salt solution containing impurities to obtain supernatant;
(2) Adsorbing the supernatant obtained in the step (1) by resin to obtain a diamine salt solution;
(3) Separating the diamine salt from the diamine salt solution in step (2); the separation method is cooling crystallization; the cooling crystallization comprises the following steps: cooling the diamine salt solution to 20-40 ℃ at a speed of 1 ℃/3-10min, and preserving heat for 0.3-5h; then cooling by 5-20 ℃ at the speed of 1 ℃/6-15min, and preserving heat for 0.2-5h;
in the step (1), the diamine salt solution is obtained after fermentation broth or treatment fluid of dibasic acid participates in the process of fermenting the pentanediamine or the process of fermenting and enzyme converting the lysine to obtain the pentanediamine; the diamine salt solution comprises impurities, wherein the impurities at least comprise thalli and pigments;
In the step (1), before solid-liquid separation, heating the diamine salt solution containing impurities; the heating temperature is 70-100 ℃; the heating time is 30-120min; in the step (2), the adsorption method comprises the following steps: contacting the supernatant obtained in the step (1) with macroporous adsorption resin for adsorption; the macroporous adsorption resin comprises: one or more of XDA-1G macroporous adsorption resin, XDA-5 macroporous adsorption resin and DA201-C macroporous adsorption resin;
In step (2), the method of contacting includes one or two of the following modes:
Mode one: uniformly mixing the supernatant with macroporous adsorption resin for adsorption, wherein the volume ratio of the supernatant to the macroporous adsorption resin is (1-5): 1, a step of; the adsorption time is 12-48h; the temperature of the adsorption is 30-50 ℃;
mode two: passing the supernatant through a macroporous adsorption resin column for adsorption; the feeding flow rate of the supernatant fluid is 0.5-2BV/h; the macroporous adsorption resin is in the form of macroporous adsorption resin columns, and the height-to-diameter ratio of the macroporous adsorption resin columns is (10-20): 1, a step of;
In the step (1), the diamine salt is a salt formed by pentanediamine and C4-C18 aliphatic dicarboxylic acid; the structural formula of the diamine is as follows: -OOC(CH2)nCOO-+H3N-(CH2)5-NH3 + Wherein n is more than or equal to 4 and less than or equal to 18.
2. The method of manufacturing according to claim 1, wherein: in step (1), the solid-liquid separation method comprises one or more of filtration, centrifugation or ceramic membrane separation;
and/or, in the step (1), the temperature of the solid-liquid separation is above room temperature.
3. The preparation method according to claim 2, characterized in that:
In the step (1), the rotational speed of the centrifugation is 4000-5500rpm;
and/or, in the step (1), the centrifugation time is 1-10min.
4. The preparation method according to claim 2, characterized in that: the temperature of the solid-liquid separation is above 60 ℃;
and/or, in the step (1), the rotational speed of the centrifugation is 4500-5000rpm.
5. The method according to claim 4, wherein: the solid-liquid separation temperature is above 70 ℃.
6. The method according to claim 5, wherein: the temperature of the solid-liquid separation is 70-90 ℃.
7. The method of any one of claims 1-6, wherein:
in the step (2), the pore diameter of the macroporous adsorption resin is 2-10nm.
8. The method of manufacturing according to claim 7, wherein: in the step (2), the pore diameter of the macroporous adsorption resin is 3-8nm.
9. The method of claim 7, wherein: in step (2), the macroporous adsorption resin is selected from the group consisting of: macroporous adsorption resin with the aperture of 3-6 nm.
10. The method of claim 7, wherein: in step (2), the macroporous adsorption resin is selected from the group consisting of: macroporous adsorption resin with the aperture of 6-8 nm.
11. The method of claim 7, wherein: in step (2), the macroporous adsorption resin is selected from the group consisting of: macroporous adsorption resin with the aperture of 3-4 nm.
12. The method of any one of claims 1-6, wherein: the water content in the diamine salt solution before crystallization is 25-40%, and the percentage is the mass percentage of water in the diamine salt solution.
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| CN105753718A (en) * | 2014-12-17 | 2016-07-13 | 上海凯赛生物技术研发中心有限公司 | Method for removing impurity 2,3,4,5-tetrahydropyridine in nylon salt and purified nylon salt |
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