CN116947651A - Method for extracting pentanediamine - Google Patents
Method for extracting pentanediamine Download PDFInfo
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- CN116947651A CN116947651A CN202210389737.1A CN202210389737A CN116947651A CN 116947651 A CN116947651 A CN 116947651A CN 202210389737 A CN202210389737 A CN 202210389737A CN 116947651 A CN116947651 A CN 116947651A
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- pentanediamine
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- falling film
- film evaporator
- heating
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- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000000855 fermentation Methods 0.000 claims abstract description 71
- 230000004151 fermentation Effects 0.000 claims abstract description 71
- 238000010438 heat treatment Methods 0.000 claims abstract description 68
- 239000011552 falling film Substances 0.000 claims abstract description 56
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 17
- -1 pentylene diamine carbonate Chemical compound 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 33
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 32
- 238000000354 decomposition reaction Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 16
- 230000008020 evaporation Effects 0.000 claims description 14
- DORYCBOQALEKBP-UHFFFAOYSA-N C(O)(O)=O.C(CCCC)(N)N Chemical compound C(O)(O)=O.C(CCCC)(N)N DORYCBOQALEKBP-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 230000003113 alkalizing effect Effects 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 5
- ABOPCLLUZXTPIQ-UHFFFAOYSA-N carbonic acid;pentane-1,5-diamine Chemical compound OC(O)=O.NCCCCCN ABOPCLLUZXTPIQ-UHFFFAOYSA-N 0.000 abstract 1
- 235000010633 broth Nutrition 0.000 description 41
- 239000000243 solution Substances 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 14
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 13
- 239000004472 Lysine Substances 0.000 description 13
- 238000005979 thermal decomposition reaction Methods 0.000 description 10
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 108090000489 Carboxy-Lyases Proteins 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 125000001288 lysyl group Chemical group 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 108010048581 Lysine decarboxylase Proteins 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RKLJSFSLDCKWPH-UHFFFAOYSA-N C(CCCCC(=O)O)(=O)O.C(CCCC)(N)N Chemical compound C(CCCCC(=O)O)(=O)O.C(CCCC)(N)N RKLJSFSLDCKWPH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010012735 Diarrhoea Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229960000250 adipic acid Drugs 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000004345 fruit ripening Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for extracting pentanediamine, which comprises the following steps: and (3) conveying the pentanediamine fermentation liquor and/or the treatment liquor thereof to a falling film evaporator, heating the pentanediamine fermentation liquor and/or the treatment liquor thereof by using a heating medium at the temperature of 90-195 ℃ to reduce the content of 1, 5-pentanediamine carbonate and/or bicarbonate, and further treating the pentanediamine fermentation liquor and/or the treatment liquor thereof after the heating treatment to obtain the pentanediamine solution. According to the embodiment of the invention, the fermentation liquor which needs to be alkalized and extracted with the pentanediamine can be directly subjected to simple operation, and the consumption of alkali in subsequent treatment can be greatly reduced.
Description
Technical Field
The invention relates to a method for extracting pentanediamine from fermentation liquor.
Background
1, 5-pentanediamine (DN 5, abbreviated as pentanediamine), also known as cadaverine, has wide application in agriculture, medicine and industry. In agriculture, the exogenous application of the pentanediamine can improve fruit setting and promote fruit ripening; in medicine, the pentanediamine can be used as a medicament for effectively treating diarrhea; in industry, the pentanediamine prepared by the biological fermentation method can replace diamine from petrochemical products to carry out polymerization reaction to generate various polymers with different properties, thereby avoiding the defects of high cost and adverse effect on the environment in production of the petrochemical products, and being widely applied to the fields of aerospace, automobile parts, mechanical parts, electronic and electrical appliances, packaging materials and the like.
The following reports are given as the prior art for separating and extracting pentamethylenediamine from a pentamethylenediamine fermentation broth. Patent US7189543B2 discloses a method for preparing a pentanediamine adipate crystal directly from a pentanediamine fermentation broth, specifically, using hexanedioic acid to neutralize pentanediamine generated in the whole cell catalysis process, and cooling to obtain the pentanediamine adipate crystal. Patent application (US 2010/0292429A1, NC 1019812002A and EP1482055A 1) discloses the application of butanol extraction method to separate and extract the pentanediamine from fermentation liquor, specifically, adding sodium hydroxide into the pentanediamine fermentation liquor, refluxing and cracking byproducts in the fermentation liquor at high temperature, extracting for multiple times by using butanol to obtain an organic phase containing the pentanediamine, evaporating a low-boiling point solvent in the organic phase to obtain high-boiling-point pentanediamine, and further rectifying to obtain the high-purity pentanediamine.
In the prior art disclosed above, the yield of the pentylene diamine carboxylate obtained by the crystallization method is low, and impurities such as lysine remain, which is difficult to further refine (e.g. CN101578256 a). The extraction method has the advantages that the organic solvent has large smell, high toxicity, flammability and explosiveness, and the operation difficulty of practical application is increased; and the organic solvent needs to be recovered, thereby increasing the process flow and energy consumption.
In patent application CN105861586a, a protocol is disclosed in which cells expressing lysine decarboxylase are first cultured to obtain a whole cell fermentation broth comprising pentylene diamine, and carbon dioxide is removed from the whole cell fermentation broth prior to the addition of a strong base thereto. However, the scheme has the problems of higher vacuum degree, large loss of the pentanediamine and lower treatment capacity in the heating process, and is difficult to be applied to large-scale industrial production.
The falling film evaporation is to add the feed liquid from the upper pipe box of the heating chamber of the falling film evaporator, uniformly distribute the feed liquid into each heat exchange pipe through the liquid distribution and film forming device, and uniformly flow from top to bottom under the action of gravity, vacuum induction and air flow. In the flowing process, the vapor and the liquid phase generated by the heating vaporization of the shell side heating medium enter the separation chamber of the evaporator together, the vapor and the liquid phase are fully separated, the vapor enters the condenser for condensation (single-effect operation) or enters the next-effect evaporator to serve as the heating medium, and the liquid phase is discharged from the separation chamber. The falling film evaporator is widely used for evaporating and concentrating water or organic solvent solution in the industries of medicine, food, chemical industry, light industry and the like, and can be widely used for treating waste liquid in the industries. The equipment is operated continuously under the vacuum condition, has high evaporation capacity, energy conservation, consumption reduction and low operation cost, and can ensure that materials are not denatured in the evaporation process.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for extracting pentamethylenediamine, comprising: and (3) conveying the glutaric amine fermentation liquor and/or the treatment liquor thereof into a falling film evaporator, heating the fermentation liquor and/or the treatment liquor by using a heating medium at the temperature of 90-195 ℃ to reduce the content of the pentylene diamine carbonate and/or bicarbonate, and then performing alkalization treatment to obtain the pentylene diamine solution.
The invention is directly aimed at fermentation liquor and/or treatment liquor thereof which need to be alkalized and extracted with the pentamethylene diamine, has simple operation and can greatly reduce the consumption of alkali in the subsequent treatment.
Exemplary embodiments that embody features and advantages of the present invention are described in detail in the following description. It is to be understood that the invention is capable of various modifications in the various embodiments, all without departing from the scope of the invention.
The invention provides an extraction method of pentanediamine, which comprises the following steps: and (3) conveying the pentanediamine fermentation liquor and/or the treatment liquor thereof to a falling film evaporator, heating the pentanediamine fermentation liquor and/or the treatment liquor thereof by using a heating medium with the temperature of 90-195 ℃ to reduce the content of the pentanediamine carbonate and/or bicarbonate, and then performing alkalization treatment to obtain the pentanediamine solution.
In one embodiment of the present invention, the pentylene diamine in the pentylene diamine fermentation broth and/or the treatment fluid thereof is mainly in the form of carbonate and/or bicarbonate, and is partly in the form of pentylene diamine sulfate.
The method of the embodiment of the invention solves the problems of high alkalization cost and difficult solid waste treatment caused by excessive solid slag when the pentylene diamine fermentation liquor or the treatment liquor thereof alkalizes in the prior art.
In one embodiment, the pentylene diamine fermentation broth is a pentylene diamine fermentation broth obtained by decarboxylation of lysine or lysine fermentation broth as is conventional in the art.
For example, the pentanediamine fermentation broth is prepared by adopting a preparation method of 1, 5-pentanediamine in Chinese patent CN105164101B or patent application CN 104762336A. Specifically, for example, by using lysine decarboxylase in a lysine fermentation broth or by fermenting a microorganism comprising lysine decarboxylase to form pentamethylene diamine, and simultaneously reacting carbonate and/or bicarbonate (a byproduct of lysine decarboxylation) with a portion of the pentamethylene diamine formed to form carbonate and/or bicarbonate of 1, 5-pentamethylene diamine. Thus, fermentation broths comprising carbonates and/or bicarbonates of pentylenediamine can be prepared.
The pentanediamine fermentation broth may be a fermentation broth containing bacterial cells without any treatment. The pentylene diamine fermentation broth is further treated to obtain a treatment solution, for example, a clarified solution obtained by filtering macromolecular substances such as thalli, proteins and the like by a ceramic membrane or an ultrafiltration membrane, or a solution obtained by simple filtration, a clear solution obtained by centrifugation, or a solution obtained by decoloring and impurity removing by activated carbon. During these processes, insoluble impurities or soluble impurities may be removed, and/or pigment levels may be reduced, and/or solution concentrations may be increased, and 1, 5-pentanediamine and salts thereof may remain in the solution system.
In the present invention, the concentration of the pentanediamine fermentation liquid and/or the treatment liquid thereof is not particularly limited. In one embodiment, the concentration of the pentanediamine fermentation broth and/or the treatment fluid thereof may be 1 to 15%, preferably 5 to 10%, in terms of pentanediamine. For example, the concentration may be 2%, 6%, 8%, 12%, etc.
In one embodiment, the pH of the pentanediamine fermentation broth and/or the treatment solution thereof is from 6 to 12, and may further be from 6 to 10.
In one embodiment, the feed rate of the pentanediamine fermentation broth and/or the treatment broth is from 1 to 300L/(m) based on the unit evaporation area of the falling film evaporator 2 * h) More preferably 30 to 100L/(m) 2 *h)。
The evaporation area of the falling film evaporator refers to the heat exchange area of the falling film evaporator, and the unit is m 2 。
It is well known to those skilled in the art that a feed liquid, such as a pentylene diamine fermentation broth, is passed into a falling film evaporator for heating with a heating medium, and the actual temperature of the feed liquid in the falling film evaporator is related to the temperature of the heating medium and the feed rate. When the temperature of the heating medium is higher and the feeding speed is lower, the material liquid has sufficient time to be heated, and the actual temperature of the material liquid in the falling film evaporator and the temperature difference of the heating medium are smaller. When the temperature of the heating medium is higher and the feeding speed is higher, the heating time of the feed liquid is shorter, and the temperature difference between the actual temperature of the feed liquid in the falling film evaporator and the heating medium is larger. For example, the inventors found that when the heating medium temperature was 155 ℃, the feed rate was 33L/(m) 2 * h) The actual temperature of the pentanediamine fermentation liquid in the falling film evaporator is detected to be 90-95 ℃. When the temperature of the heating medium is 110 ℃, the feeding speed is 3L/(m) 2 * h) The actual temperature of the pentanediamine fermentation liquid in the falling film evaporator is detected to be 90-95 ℃.
In one embodiment, the falling film evaporator exchanges heat with a tube array heat exchanger.
In one embodiment, the temperature of the heating medium is preferably 105 to 195 ℃, and more preferably 125 to 195 ℃.
The heating medium includes, but is not limited to, heat transfer oil.
In one embodiment, the vacuum degree at the time of the heat treatment is 100kPa or less, more preferably 60kPa or less, still more preferably 2 to 40kPa, still more preferably 2 to 25kPa.
In one embodiment, the pentylene diamine is sufficiently dissociated by an alkalization treatment to provide a pentylene diamine solution.
In one embodiment, the residual pentanediamine fermentation broth (aqueous solution containing pentanediamine and/or pentanediamine salt) after the heat treatment is discharged from the falling film evaporator and then subjected to an alkalization treatment.
The specific structure of the falling film evaporator is not particularly limited in the present invention. As known to those skilled in the art, in general, falling film evaporators have a heating chamber, a liquid distribution and film forming device, a separation chamber, a condenser, and the like.
Specifically, in one embodiment, during the heat treatment by the falling film evaporator, the generated vapor and the remaining liquid phase enter the separation chamber of the falling film evaporator together, and after the gas-liquid separation in the separation chamber, the vapor enters the condenser to be condensed. And discharging the residual pentanediamine fermentation liquor after the thermal decomposition treatment from the separation chamber. And then used for the alkalization treatment.
In one embodiment, the alkalization treatment may be performed using an alkali metal oxide, an alkali metal hydroxide, an alkaline earth metal oxide, and an alkaline earth metal hydroxide. Thereby substantially freeing the pentamethylenediamine.
In one embodiment, the alkaline material such as sodium hydroxide or potassium hydroxide, calcium oxide, calcium hydroxide is used to make the alkaline treatment to free the pentylene diamine sufficiently.
In one embodiment, the method comprises: recovering the pentylene diamine from the pentylene diamine solution. The recovery means include, for example, distillation, rectification, extraction, and the like.
According to the invention, the decomposition rate of the pentylene diamine carbonate and/or pentylene diamine bicarbonate is controlled by utilizing the heating treatment of the falling film evaporator, so that the carbonate and bicarbonate contents in the pentylene diamine fermentation liquid are reduced, more pentylene diamine exists in a free form instead of a salt form, the alkali consumption of the subsequent alkalization process for converting pentylene diamine salt into free pentylene diamine through alkaline substances is greatly reduced, the process flow is shortened, and the cost is saved. On the other hand, the falling film evaporator is adopted to decompose the pentanediamine carbonate and/or the pentanediamine bicarbonate, so that the generation amount of salt in the process of extracting the pentanediamine is reduced, the environment is protected, and the cost of enterprises is saved.
In the invention, after the heat treatment, the pentylene diamine carbonate and/or bicarbonate is decomposed, so that the content of the pentylene diamine carbonate and/or bicarbonate is reduced.
In one embodiment, the decomposition rate of the pentylene diamine carbonate and/or bicarbonate is 20% to 70%, further 40% to 70%, further 60% to 70% by heat treatment.
The invention has the positive progress effects that:
in the invention, the falling film decomposition form avoids the risks of kettle type spray can, overflow can and the like, so that the safety of the production process is improved on the basis of guaranteeing the quality of the final product, the generation of alkalization solid slag is obviously reduced, and the resources, labor and cost are saved. The falling film evaporator can form thin layer distribution for materials, and the decomposition efficiency is improved.
Detailed Description
The method for extracting pentamethylenediamine of the present invention is further described below by way of specific examples. The raw materials used herein, unless otherwise specified, are all commercially available. The detection method of the performance parameters related to each embodiment is as follows:
1. the detection method of the pentanediamine comprises the following steps:
the nuclear magnetic detection hydrogen spectrum method uses dimethyl sulfoxide as an internal standard substance.
2. The method for detecting the decomposition rate of the pentanediamine carbonate and/or the pentanediamine bicarbonate comprises the following steps:
taking 100mL of pentanediamine fermentation liquor, adding excessive sulfuric acid, heating to 80 ℃, collecting gas by a drainage method, and measuring the volume V of the gas 1 ；
Taking 100mL of pentanediamine fermentation liquid after being heated by a falling film evaporator, adding excessive sulfuric acid, heating to 80 ℃, collecting gas by a drainage method, and measuring the gas volume V 2 ；
Simultaneously taking 100mL of water as a blank experiment, collecting the gas volume by using a drainage method according to the mode, wherein the measurement volume is V 0 ；
3. Reduction of alkali usage:
taking 100mL of pentanediamine fermentation liquor, adding excessive sulfuric acid, heating to 80 ℃, collecting carbon dioxide gas in raw materials by a drainage method, and measuring the volume V of carbon dioxide 1 Unit L.
Taking 100mL of pentanediamine fermentation liquid after being heated by a falling film evaporator, adding excessive sulfuric acid, heating to 80 ℃, collecting carbon dioxide gas by a drainage method, and measuring the volume V of carbon dioxide 2 Unit L.
Sodium hydroxide mass = { (V 1 -V 2 )/44}*1.977*2*40
44 is carbon dioxide mole, g/mol;
1.977 is carbon dioxide density, g/L;
40 is the molar quantity of sodium hydroxide, g/mol.
4. The calculation method of the loss amount of the pentanediamine comprises the following steps: the concentration of the condensate (calculated as pentanediamine) was measured and the mass of the pentanediamine calculated as m 1 (g) The amount of pentylene diamine lost = m1 (g)/total mass of pentylene diamine broth fed (g) 100%.
The falling film evaporators in the following examples and comparative examples exchange heat by a tube type heat exchanger.
Example 1
The lysine fermentation broth disclosed in example 1 of patent application CN104762336a was subjected to a lysine decarboxylase to produce a pentylene diamine fermentation broth having a concentration of 8.1% (mass percent) as pentylene diamine and a pH of 8.02. Is added into a falling film evaporator (volume 5L, evaporation area 0.45 m) at a feed rate of 33L/h 2 ) A heat treatment is performed to perform a decomposition reaction.
The heating temperature of the conduction oil of the falling film evaporator is controlled to be 135 ℃, and the vacuum degree is controlled to be 10kPa. In the heating treatment process, the generated steam and the residual liquid phase enter a separation chamber of the falling film evaporator together, and the steam enters a condenser for condensation after gas-liquid separation in the separation chamber. The residual fermenting solution of the pentanediamine after the thermal decomposition treatment is discharged from the separating chamber and then collected.
Example 2
Refer to patent applicationThe lysine fermentation broth disclosed in example 1 of CN104762336a was decarboxylated by lysyl decarboxylase to yield a pentylene diamine fermentation broth having a concentration of 8.0% (mass%) as pentylene diamine and a pH of 8.02. Is added into a falling film evaporator (volume 5L, evaporation area 0.45 m) at a feed rate of 33L/h 2 ) A heat treatment is performed to perform a decomposition reaction.
The temperature in the falling film evaporator is controlled to 145 ℃ and the vacuum degree is controlled to 10kPa. In the heating treatment process, the generated steam and the residual liquid phase enter a separation chamber of the falling film evaporator together, and the steam enters a condenser for condensation after gas-liquid separation in the separation chamber. The residual fermenting solution of the pentanediamine after the thermal decomposition treatment is discharged from the separating chamber and then collected.
Example 3
The lysine fermentation broth disclosed in example 1 of patent application CN104762336a was decarboxylated by lysyl decarboxylase to produce a pentylene diamine fermentation broth having a concentration of 8.1% (mass percent) as pentylene diamine and a pH of 8.02. Is added into a falling film evaporator (volume 5L, evaporation area 0.45 m) at a feed rate of 33L/h 2 ) A heat treatment is performed to perform a decomposition reaction.
The heating temperature of the conduction oil of the falling film evaporator is controlled to be 155 ℃, and the vacuum degree is controlled to be 10kPa. In the heating treatment process, the generated steam and the residual liquid phase enter a separation chamber of the falling film evaporator together, and the steam enters a condenser for condensation after gas-liquid separation in the separation chamber. The residual fermenting solution of the pentanediamine after the thermal decomposition treatment is discharged from the separating chamber and then collected.
Example 4
The lysine fermentation broth disclosed in example 1 of patent application CN104762336a was decarboxylated by lysyl decarboxylase to produce a pentylene diamine fermentation broth having a concentration of 8.1% (mass percent) as pentylene diamine and a pH of 8.02. Is added into a falling film evaporator (volume 5L, evaporation area 0.45 m) at a feed rate of 33L/h 2 ) A heat treatment is performed to perform a decomposition reaction.
The heating temperature of the conduction oil of the falling film evaporator is controlled to be 95 ℃ and the vacuum degree is controlled to be 10kPa. In the heating treatment process, the generated steam and the residual liquid phase enter a separation chamber of the falling film evaporator together, and the steam enters a condenser for condensation after gas-liquid separation in the separation chamber. The residual fermenting solution of the pentanediamine after the thermal decomposition treatment is discharged from the separating chamber and then collected.
Example 5
The lysine fermentation broth disclosed in example 1 of patent application CN104762336a was decarboxylated by lysyl decarboxylase to produce a pentylene diamine fermentation broth having a concentration of 8.1% (mass percent) as pentylene diamine and a pH of 8.02. Added to a falling film evaporator (volume 5L, evaporation area 0.45 m) at a feed rate of 33L/h 2 ) A heat treatment is performed to perform a decomposition reaction.
The heating temperature of the conduction oil of the falling film evaporator is controlled to 145 ℃, and the vacuum degree is controlled to 65kPa. In the heating treatment process, the generated steam and the residual liquid phase enter a separation chamber of the falling film evaporator together, and the steam enters a condenser for condensation after gas-liquid separation in the separation chamber. The residual fermenting solution of the pentanediamine after the thermal decomposition treatment is discharged from the separating chamber and then collected.
Example 6
The lysine fermentation broth disclosed in example 1 of patent application CN104762336a was decarboxylated by lysyl decarboxylase to produce a pentylene diamine fermentation broth, the pH of which was adjusted to 9, and the pentylene diamine fermentation broth concentration was 8.05% by mass as pentylene diamine. Is added into a falling film evaporator (volume 5L, evaporation area 0.45 m) at a feed rate of 31L/h 2 ) A heat treatment is performed to perform a decomposition reaction.
The heating temperature of the conduction oil of the falling film evaporator is controlled to 156 ℃, and the vacuum degree is controlled to be 10kPa. In the heating treatment process, the generated steam and the residual liquid phase enter a separation chamber of the falling film evaporator together, and the steam enters a condenser for condensation after gas-liquid separation in the separation chamber. The residual fermenting solution of the pentanediamine after the thermal decomposition treatment is discharged from the separating chamber and then collected.
Comparative example 1
The lysine fermentation broth disclosed in example 1 of patent application CN104762336a was decarboxylated by lysyl decarboxylase to prepare a pentylene diamine fermentation broth, the pH of which was adjusted to 11, and the pentylene diamine fermentation broth concentration was 8.02% (mass%) as pentylene diamine. At a feed rate of 34L/hAdded into a falling film evaporator (volume 5L, evaporation area 0.45 m) 2 ) A heat treatment is performed to perform a decomposition reaction.
The heating temperature of the conduction oil of the falling film evaporator is controlled to 156 ℃, and the vacuum degree is controlled to be 10kPa. In the heating treatment process, the generated steam and the residual liquid phase enter a separation chamber of the falling film evaporator together, and the steam enters a condenser for condensation after gas-liquid separation in the separation chamber. The residual fermenting solution of the pentanediamine after the thermal decomposition treatment is discharged from the separating chamber and then collected.
Example 7
The lysine fermentation broth disclosed in example 1 of patent application CN104762336a was decarboxylated by lysyl decarboxylase to produce a pentylene diamine fermentation broth having a concentration of 8.1% (mass percent) as pentylene diamine and a pH of 8.02. Is added into a falling film evaporator (volume 400L, evaporation area 45 m) at a feed rate of 3300L/h 2 ) And (3) carrying out a decomposition reaction.
The heating temperature of the conduction oil of the falling film evaporator is controlled to be 155 ℃, and the vacuum degree is controlled to be 10kPa. In the heating treatment process, the generated steam and the residual liquid phase enter a separation chamber of the falling film evaporator together, and the steam enters a condenser for condensation after gas-liquid separation in the separation chamber. The residual fermenting solution of the pentanediamine after the thermal decomposition treatment is discharged from the separating chamber and then collected.
The decomposition rate of the pentylene diamine carbonate and/or pentylene diamine bicarbonate, the amount of decrease in the amount of alkali, and the volume of the condensate in the condenser and the pentylene diamine loss of the above examples and comparative examples were measured, respectively. The results are shown in Table 1.
TABLE 1
Note that: the volume percent of condensate refers to the volume percent of condensate volume to the feed.
As is clear from the above table, examples 1 to 3 were falling film type heating solutions for efficiently decomposing pentamethylenediamine, and the decomposition rates were 54.7%, 60.3% and 66.2%, respectively. Under the same control condition, the heat exchange of the glutaric amine fermentation liquor is strong along with the rise of the temperature, and the decomposition rate is gradually increased. Under the condition, the processing capacity of the pentanediamine fermentation liquid is large, the decomposition rate is high, the solid waste is less, and the condensate is less.
Example 4 the heating temperature was 95 ℃, the heating temperature was lower, the heat exchange strength of the pentanediamine broth was low, resulting in a decomposition rate of only 25.4%.
Example 5 the heating temperature was 145℃and the vacuum 65Kpa. The vacuum degree is lower, so that a great amount of moisture in the pentanediamine fermentation liquid is evaporated, and the condensate accounts for 4.61% of the total material. In the whole process, a great amount of energy is consumed by converting moisture from a liquid phase to a gas phase, and the load of a condenser is increased by converting the gas phase to the liquid phase.
In comparative example 1, when ph=11 was adjusted, the form of the pentylene diamine bicarbonate into pentylene diamine carbonate was present, and pentylene diamine carbonate was more difficult to decompose than pentylene diamine bicarbonate, resulting in a sudden drop in the decomposition rate under the same operation conditions.
Example 7 under industrial scale-up conditions, the decomposition rate reached 65.9%. The method of the invention improves the safety of the production process on the basis of guaranteeing the quality of the final product, obviously reduces the generation of alkalized solid slag and saves resources, labor and cost.
The pentylene diamine fermentation broth after the thermal decomposition treatment of examples 1-7 was alkalized with sodium hydroxide or calcium oxide as an alkaline substance to obtain a pentylene diamine solution, and was distilled to recover pentylene diamine having a purity of 99% or higher.
Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention.
Claims (9)
1. An extraction method of pentanediamine, comprising the following steps: and (3) conveying the pentanediamine fermentation liquor and/or the treatment liquor thereof to a falling film evaporator, heating the pentanediamine fermentation liquor and/or the treatment liquor thereof by using a heating medium at 90-195 ℃ to reduce the content of the pentanediamine carbonate and/or bicarbonate, and then performing alkalization treatment to obtain the pentanediamine solution.
2. The method according to claim 1, wherein the concentration of the pentanediamine fermentation broth and/or the treatment broth thereof is 1-15%, preferably 5-10%, by mass of the pentanediamine;
and/or the pH of the pentanediamine fermentation broth and/or the treatment fluid thereof is 6-12, and further 6-10.
3. The method of claim 1, wherein the heating medium has a temperature of 105-195 ℃;
and/or the vacuum degree of the pentanediamine fermentation liquid and/or the treatment liquid thereof is 100kPa or less, more preferably 60kPa or less, still more preferably 2 to 40kPa, still more preferably 2 to 25kPa during the heat treatment;
and/or the heating medium includes, but is not limited to, heat transfer oil.
4. The process according to claim 1, wherein the feed rate of the pentanediamine fermentation broth and/or the treatment liquid thereof is 1 to 300L/(m) based on the unit evaporation area of the falling film evaporator 2 * h) Further 30 to 100L/(m) 2 *h)。
5. The method according to claim 1, wherein the alkalizing treatment is performed with an alkali metal oxide, an alkali metal hydroxide, an alkaline earth metal oxide, an alkaline earth metal hydroxide; further, the alkalization treatment is performed by using sodium hydroxide, potassium hydroxide, calcium oxide and calcium hydroxide.
6. The method of claim 1, wherein the falling film evaporator comprises a heating chamber, a liquid distribution and film forming device, a separation chamber, and a condenser.
7. The method according to claim 1, wherein the decomposition rate of the pentylene diamine carbonate and/or bicarbonate is 20% to 70%, further 40% to 70%, further 60% to 70% by heat treatment.
8. The method according to any one of claims 1 to 7, further comprising the step of recovering the pentamethylenediamine from the pentamethylenediamine solution.
9. The method of claim 8, wherein the recovery means includes, but is not limited to, distillation, rectification, extraction.
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