CN116410094A - Polymer grade bio-based pentylene diamine refining and purifying process - Google Patents
Polymer grade bio-based pentylene diamine refining and purifying process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 229920000642 polymer Polymers 0.000 title claims abstract description 11
- -1 pentylene diamine Chemical class 0.000 title claims description 37
- 238000007670 refining Methods 0.000 title claims description 13
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000004821 distillation Methods 0.000 claims abstract description 37
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 17
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- 238000000638 solvent extraction Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 68
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- 238000006243 chemical reaction Methods 0.000 claims description 9
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 8
- NGVDGCNFYWLIFO-UHFFFAOYSA-N pyridoxal 5'-phosphate Chemical compound CC1=NC=C(COP(O)(O)=O)C(C=O)=C1O NGVDGCNFYWLIFO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000855 fermentation Methods 0.000 claims description 7
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- 238000006555 catalytic reaction Methods 0.000 claims description 6
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000007682 pyridoxal 5'-phosphate Nutrition 0.000 claims description 4
- 239000011589 pyridoxal 5'-phosphate Substances 0.000 claims description 4
- 229960001327 pyridoxal phosphate Drugs 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 claims description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
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- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a purification process method of polymer grade bio-based pentanediamine after liquid-liquid extraction, which is characterized in that non-volatile impurities in an extraction phase are preferentially removed by utilizing a weight removing procedure before distillation/rectification, interference in the subsequent distillation/rectification process is reduced, physical and chemical changes in the distillation/rectification process are avoided, so that loss of the bio-based pentanediamine is reduced, and finally the polymer grade bio-based pentanediamine with the purity more than 99.5% is obtained by a distillation/rectification means.
Description
Technical Field
The invention belongs to the technical field of biology, and particularly relates to a process for refining and purifying bio-based pentanediamine, which is used for obtaining polymer-grade bio-based pentanediamine.
Background
1, 5-pentanediamine is an important precursor material with wide industrial application, and is widely applied to various production processes of polyamide, polyurethane, chelating agent, additive and the like. The method for synthesizing high-quality high-molecular material nylon 5X by using the biotechnology to produce the high-quality high-molecular material nylon 5X in large quantity is an environment-friendly sustainable production mode and has wide application prospect.
Although the production of bio-based pentanediamine by microbiological techniques opens up a new way for its mass production, it presents difficulties in the isolation, extraction and purification of the pentanediamine due to the complexity of the components of the fermentation broth. To ensure efficient polymerization using bio-based pentalene diamine, it is necessary to obtain a purity of > 99.5% of the pentalene diamine, while the presence of unreacted lysine (or lysine hydrochloride), inorganic salt ions, unused medium, microbial cells (debris), and metabolites in the fermentation broth places higher demands on downstream processing of bio-based pentalene diamine. If the purity of the bio-based pentylene diamine product is not standard, the polymerization effect and the product quality are seriously affected.
At present, the high-yield pentylene diamine monomer is obtained by separating and purifying fermentation liquor, which is generally a separation means by rapid extraction. Firstly, removing microbial cells by means of centrifugation, flocculation or filtration; then adding sodium hydroxide, potassium hydroxide or calcium hydroxide to adjust the pH value of the system to be more than 13.5; incubating the fermentation broth at a temperature to remove the possible by-product N-acetyl-diaminopentane; extracting with organic solvent (such as n-butanol) which can be stabilized under alkaline condition to obtain crude product of pentylene diamine. Purifying the pentanediamine by using a chromatographic method, a distillation/rectification method or an acid precipitation method, and using the purified pentanediamine monomer for producing polyamide after reaching the polymerization grade requirement.
Distillation/rectification is an economical and well-established separation means and has been widely used in the industrial production of various compounds. The organic extractant (such as n-butanol and the like) applied at present has larger relative volatility difference with the target product of the pentanediamine and obvious boiling point difference, and the distillation/rectification refining of the pentanediamine is a simple and economic means. However, in the extracted phase containing the pentylene diamine, there are still non-volatile impurities which interfere with the distillation/rectification of the pentylene diamine, and may prolong the distillation/rectification time, and may cause the pentylene diamine to be converted into other substances or introduce new impurities during the distillation/rectification separation process for a long time.
Disclosure of Invention
The invention provides a purification process method of polymer grade bio-based pentanediamine after liquid-liquid extraction, which is characterized in that non-volatile impurities in an extraction phase are removed preferentially by utilizing a weight removing procedure before distillation/rectification, interference in the subsequent distillation/rectification process is reduced, physical and chemical changes in the distillation/rectification process are avoided, so that loss of the bio-based pentanediamine is reduced, and finally the polymer grade bio-based pentanediamine with purity more than 99.5% is obtained by a distillation/rectification means. The method for refining the polymer-grade bio-based pentanediamine specifically comprises the following steps:
the solution containing high concentration of the pentanediamine is obtained through liquid-liquid extraction separation, the non-volatile impurities are removed from the extract phase through a weight removing procedure preferentially, the weight removed product is obtained, and then the polymerization grade bio-pentanediamine is obtained through distillation/rectification for further refining the pentanediamine.
In a first aspect, in the process of the present invention, a process is provided for the production of polymer grade bio-based pentylene diamine for preferential removal of non-volatile impurities in the extract phase, avoiding subsequent interference with the distillation/rectification process, ensuring yield and quality of bio-based pentylene diamine product.
The extracted solution is an extraction phase obtained by separating after the liquid-liquid extraction reaction is finished. The solvent used for extraction includes, but is not limited to, one of n-butanol, n-pentanol, n-hexanol and the like which exist stably under alkaline conditions and have a significant difference in relative volatility with pentanediamine.
The original liquid-liquid extraction solution is derived from a solution after reaction for preparing the pentanediamine by a biological method.
Preferably, the reaction solution for preparing the bio-based pentanediamine by enzyme catalysis or whole cell catalysis is adopted.
The content of the pentanediamine in the solution after the higher concentration of the pentanediamine is extracted is more than 0.2mol/L, and the content of the pentanediamine in the solution after the extraction is preferably more than 0.5mol/L, for example, 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 2mol/L and the like.
The de-weighting process is to quickly gasify the extracted solution, and quickly condense and recycle the gasified solution to remove non-volatile impurities.
The weight removing operation can be flash evaporation, rotary evaporation and other operations.
The weight removing equipment can be a flash tank, a rotary evaporator or a thin film evaporator and the like.
The thin film evaporator that can be used includes a wiped film evaporator (wiped film evaporator), a rising film evaporator, or a falling film evaporator.
The non-volatile impurities removed include, but are not limited to, inorganic salts in the fermentation broth, pyridoxal phosphate (PLP) as a coenzyme used in the enzymatic/whole cell catalytic reaction, excess sodium hydroxide or calcium hydroxide or potassium hydroxide added during liquid-liquid extraction, sodium chloride or calcium chloride or potassium chloride formed during conditioning, and the like.
According to the difference of the extracted samples, the heavy removal operation can be carried out for more than or equal to 1 time, and the non-volatile impurities in the heavy removal operation can be removed.
In the method, the product after the de-duplication treatment is further refined by a distillation/rectification mode to obtain the polymer grade bio-based pentanediamine.
Said distillation/rectification operation is carried out under normal pressure or reduced pressure; preferably, it is carried out under reduced pressure.
The rectification operation mode is batch operation or continuous operation.
The pressure of the reduced pressure distillation/rectification operation is 2kPa to 101.325kPa (absolute pressure), preferably, the operating pressure is 2kPa to 20kPa; more preferably, the operating pressure is from 2kPa to 10kPa.
The equipment for realizing the refining of the bio-based pentanediamine is distillation/rectification equipment such as a rotary evaporator or a rectification tower and the like.
The rectification tower is a plate tower or a packed tower, and the preferred rectification tower is a packed tower.
The packing method of the packed tower is structured packing or bulk packing.
The type of packing material of the packed tower is metal, ceramic or glass.
The structured packing is a grid packing, a corrugated packing or a pulse packing.
The bulk packing type is Raschig ring packing, pall ring packing, theta ring packing, stepped ring packing or spring packing, etc.
The size of the rectifying tower is specifically determined according to the size of the sample amount of the pentylene diamine to be treated.
The components with different temperatures obtained by distillation/rectification operation are collected respectively, and the extractant in the components is further recovered while refining the bio-based pentylene diamine.
The refined bio-based pentylene diamine is quantitatively analyzed by gas chromatography, liquid chromatography or gas chromatography-mass spectrometry.
Detailed Description
The technical solution of the present invention will be further described with reference to the following specific embodiments, and it should be apparent to those skilled in the art that the following examples are only simple examples of the present invention and do not represent or limit the scope of the claims of the present invention.
Example 1
Converting the pentylene diamine salt in the pentylene diamine aqueous solution into free pentylene diamine. Sodium hydroxide solid is added into 1L of aqueous solution of the pentanediamine with the concentration of 2.3mol/L in batches, and stirring is carried out while adding, so that the temperature is prevented from being higher than 50 ℃ until the pH is more than 13.5. The desalting reaction was carried out by heating in a water bath at 80℃and 100rpm in a water bath shaker and shaking for 4 hours.
And (5) extracting and separating the free pentanediamine. After the desalting reaction is finished, filtering off excessive solids, cooling the solution to room temperature, adding n-butanol with the volume of the neopentanediamine solution, extracting for 1h in a constant-temperature shaking box at 200rpm at 50 ℃, then subpackaging in a separating funnel, standing and extracting at normal temperature for 6h, and obtaining an upper n-butanol phase and a lower water phase.
The n-butanol phase is subjected to de-weighting. The n-butanol phase is distilled off rapidly under reduced pressure in a rotary evaporator to remove most of the soluble salts, the operating pressure is 2kPa (absolute pressure), the heating temperature is 55 ℃, the cooling water temperature is 5 ℃, the rotating speed is 30rpm, and the liquid is kept in a continuous boiling state by continuously adjusting the heating temperature during heating until the liquid is thoroughly evaporated.
And separating the de-heavy pentylene diamine solution in a rectifying tower. The distillation tower adopts a packing type, the heating mode is to use a constant temperature oil bath pot with a magnetic stirring function for gradient heating, the operating pressure is 10kPa (absolute pressure), the cooling water temperature is 10 ℃, and a stirring magnet is added into a tower kettle to prevent bumping. Firstly, total reflux is carried out at the tower bottom temperature of 100 ℃, at the moment, the tower top temperature is 40 ℃, the reflux time is adjusted to be 5s, the extraction time is 10s, and the component is collected to be component 1; then the temperature of the tower top is increased from 40 ℃ to 60 ℃, the reflux time is adjusted to be 5s, the extraction time is adjusted to be 5s, and the component is collected to be component 2; then the temperature of the tower top is stabilized at 60 ℃, the reflux time is adjusted to be 5s, the extraction time is 15s, and the component is collected to be component 3; then the temperature of the tower top is increased from 60 ℃ to 105 ℃, the reflux time is adjusted to be 5s, the extraction time is adjusted to be 5s, and the component is collected to be component 4; the overhead temperature will then stabilize at 105 ℃, and this component is collected as component 5; heating until the tower kettle is evaporated to dryness, and the temperature of the tower top is not increased any more.
Through analysis, the component 1 is an azeotrope of water and n-butanol, the component 2 is a transition component of water and n-butanol, the component 3 is n-butanol, the component 4 is a transition component of n-butanol and pentanediamine, the component 5 is pentanediamine, and the residue at the bottom of the tower is the pentanediamine after the weight is removed.
Example 2
Converting the pentylene diamine salt in the pentylene diamine aqueous solution into free pentylene diamine. More than 400g of sodium hydroxide solid is added into 1L of pentanediamine salt solution with the concentration of 2.3mol/L at one time, and the sodium hydroxide is completely dissolved by stirring, and the temperature is controlled by tap water during the process, so that the overhigh temperature is avoided. Stirring for 4h to carry out desalination reaction.
And (5) extracting and separating the free pentanediamine. Cooling to room temperature after desalting reaction, adding n-butanol with equal volume, stirring in water bath at 50deg.C for 1 hr, mixing, packaging in separating funnel, standing at room temperature, and extracting for 6 hr to obtain upper n-butanol phase and lower water phase.
The n-butanol phase is then subjected to de-weighting. The aqueous phase was centrifuged to obtain a solid, and the n-butanol phase was subjected to weight removal. The n-butanol phase is subjected to reduced pressure rapid distillation in a rotary evaporator to remove most of soluble salts, the operating pressure is 2kPa (absolute pressure), the heating temperature is 55 ℃, the cooling water temperature is 5 ℃, the rotating speed of a distillation sample bottle is 30rpm, and the liquid is in a continuous boiling state by continuously adjusting the vacuum degree during heating, but the bumping is avoided, and the liquid is heated until the liquid is thoroughly evaporated.
Separating the de-heavy pentylene diamine solution in a rectifying tower, wherein the rectifying tower adopts a packing type, the heating mode is constant boiling heating by using an electric heating sleeve, the operating pressure is 10kPa (absolute pressure), the cooling water is tap water, and zeolite is added into a tower kettle to prevent bumping. Firstly, carrying out total reflux for 30min, wherein the temperature of the tower top is 40 ℃, the reflux time is adjusted to be 5s, the extraction time is 15s, and the component is collected to be component 1; then the temperature of the top of the tower is increased from 40 ℃ to 60 ℃, at the moment, the components of the tower are transition components of water and n-butanol, the reflux time is adjusted to be 5s, the extraction time is 10s, and the components are collected to be component 2; then the temperature of the tower top is stabilized at 60 ℃, the reflux time is adjusted to be 5s, the extraction time is 20s, and the component is collected to be component 3; then the temperature of the tower top is increased from 60 ℃ to 105 ℃, the reflux time is adjusted to be 5s, the extraction time is 10s, and the component is collected to be component 4; the liquid left in the tower kettle contains a small amount of impurities, and is subjected to rotary evaporation and heavy removal to obtain the pentanediamine.
Through analysis, the component 1 is an azeotrope of water and n-butanol, the component 2 is a transition component of water and n-butanol, the component 3 is n-butanol, the component 4 is a transition component of n-butanol and pentanediamine, and the residue at the bottom of the tower is the pentanediamine after the weight is removed. The components 1,2 and 4 are added into the next batch of samples to continue rectification.
Example 3
The salt of the pentylene diamine salt in the aqueous solution of pentylene diamine is converted into free pentylene diamine. Adding more than 400g of sodium hydroxide solid into 100mL of tap water, continuously stirring to completely dissolve the sodium hydroxide solid, cooling to about 50 ℃, mixing with 1L of a pentanediamine water solution with the concentration of 2.3mol/L, fully stirring and uniformly mixing, sealing, heating in a water bath with the temperature of 50 ℃ and magnetically stirring for 4 hours to carry out desalination reaction.
The free pentanediamine is extracted and separated. After the desalination reaction is completed, adding n-butanol with the volume twice that of the pentanediamine solution, oscillating for 1h in a water bath at 50 ℃, then sub-packaging in a separating funnel, standing and extracting at normal temperature for 6h, and obtaining an upper n-butanol phase and a lower water phase.
The n-butanol phase is subjected to de-weighting. And (3) rapidly distilling to remove most of soluble salts in a rotary evaporator, wherein the heating temperature of an oil bath is 230 ℃, the temperature of cooling water is 5 ℃, the rotating speed is 50rpm, adding zeolite to avoid bumping, and heating until thoroughly evaporating.
And separating the de-heavy pentylene diamine solution in a rectifying tower. The distillation tower adopts a packing type, the heating mode is to use a constant-temperature water bath kettle with a magnetic stirring function for gradient heating, the operating pressure is 3kPa (absolute pressure), the cooling water temperature is 5 ℃, and stirring magnetons and zeolite are added into the tower kettle to prevent bumping. Firstly, total reflux is carried out at the tower bottom temperature of 100 ℃, at the moment, the tower top temperature is 40 ℃, the reflux time is adjusted to be 1s, the extraction time is 2s, and the component is collected to be component 1; then the temperature of the tower top is increased from 40 ℃ to 60 ℃, the reflux time is adjusted to be 1s, the extraction time is 1s, and the component is collected to be component 2; then the temperature of the tower top is stabilized at 60 ℃, the temperature is adjusted to be fully extracted, and the component is collected as component 3; heating is carried out until the temperature at the top of the column is not increased any more. And (3) a small amount of liquid left in the tower kettle is pentyenediamine with a small amount of impurities, and rotary evaporation and heavy removal are carried out.
Through analysis, the component 1 and the component 2 are a mixture of water and n-butanol, the component 3 is n-butanol, and the residue at the bottom of the tower is subjected to weight removal to obtain the pentanediamine. The components 1 and 2 are added into the next batch of samples to continue rectification.
Example 4
Converting the pentylene diamine salt in the pentylene diamine aqueous solution into free pentylene diamine. Dissolving sodium hydroxide solid in tap water according to the mass ratio of 4:1, continuously stirring to completely dissolve the sodium hydroxide solid, cooling to about 50 ℃, adding a pentanediamine aqueous solution with the concentration of 2.3mol/L into the sodium hydroxide solution, fully stirring and uniformly mixing, stopping adding the pentanediamine aqueous solution when the pH value is 13.5, and carrying out desalination reaction.
The pentylene diamine solution was de-weighted. Filtering out solid impurities after the desalination reaction is finished, and performing reduced pressure rapid distillation in a rotary evaporator to remove most of soluble salts, wherein the operation pressure is 5kPa (absolute pressure), the heating temperature is 75 ℃, the cooling water temperature is 5 ℃, the rotating speed is 50rpm, and the liquid is in a continuous boiling state by continuously adjusting the heating temperature and the operation pressure during heating, but the bumping is avoided, and the liquid is heated until the liquid is thoroughly evaporated.
The free pentanediamine is extracted and separated. Adding n-butanol with equal volume after the weight removal, stirring, shaking, mixing, packaging in a separating funnel, standing at normal temperature for extraction, and layering to obtain upper n-butanol phase and lower water phase.
The n-butanol phase is separated in a rectification column. The distillation tower adopts a packing type, the heating mode is heating by using an electric heating sleeve, the temperature of cooling water is 5 ℃, and zeolite is added into the tower kettle to prevent bumping. After total reflux for 30min, the reflux time was set to 1s and the extraction time was set to 2s. At this time, the temperature of the top of the column was 40 ℃, and the component was collected as component 1; subsequently, the temperature of the top of the column is increased from 40 ℃ to 60 ℃, and the component is collected to be component 2; the overhead temperature will then stabilize at 60 ℃, and this component is collected as component 3; then the temperature of the top of the tower is increased from 60 ℃ to 105 ℃, the temperature is adjusted to be fully extracted, and the component is collected as component 4; the overhead temperature will then stabilize at 105 ℃, and this component is collected as component 5; heating until the tower kettle is evaporated to dryness, and the temperature of the tower top is not increased any more.
Through analysis, the component 1 is an azeotrope of water and n-butanol, the component 2 is a transition component of water and n-butanol, the component 3 is pure n-butanol, the component 4 is a transition component of n-butanol and pentanediamine, and the component 5 is pure pentanediamine. The components 1,2 and 4 are added into the next batch of samples to continue rectification.
The applicant states that the process of the invention for extracting purified pentanediamine from a fermentation broth is illustrated by the above examples, but the invention is not limited to, i.e. it is not meant that the invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials and addition of auxiliary components, selection of specific modes, and change of operating conditions, etc. of the present invention fall within the scope of the present invention and the scope of disclosure.
Claims (9)
1. The invention provides a purification process method of polymer grade bio-based pentanediamine after liquid-liquid extraction, which is characterized in that non-volatile impurities in an extraction phase are removed preferentially by utilizing a weight removing procedure before distillation/rectification, interference in the subsequent distillation/rectification process is reduced, physical and chemical changes in the distillation/rectification process are avoided, so that loss of the bio-based pentanediamine is reduced, and finally the polymer grade bio-based pentanediamine with purity more than 99.5% is obtained by a distillation/rectification means. The method for refining the polymer-grade bio-based pentanediamine specifically comprises the following steps:
the solution containing high concentration of the pentanediamine is obtained through liquid-liquid extraction separation, the non-volatile impurities are removed from the extract phase through a weight removing procedure preferentially, the weight removed product is obtained, and then the polymerization grade bio-based pentanediamine which can be used for polymerization reaction is obtained through further refining of the pentanediamine through distillation/rectification.
2. The post-extraction solution of claim 1 is an extract phase obtained by separation after completion of the liquid-liquid extraction reaction. The solvent used for extraction includes, but is not limited to, one of n-butanol, n-pentanol, n-hexanol and the like which exist stably under alkaline conditions and have a significant difference in relative volatility with pentanediamine.
3. The liquid-liquid extraction starting solution according to claim 2, which is derived from a post-reaction solution of a biological process for the preparation of pentylene diamine.
Preferably, the reaction solution for preparing the bio-based pentanediamine by enzyme catalysis or whole cell catalysis is adopted.
4. The content of pentamethylenediamine in the solution after pentamethylenediamine extraction according to claim 2 should be more than 0.2mol/L, preferably the content of pentamethylenediamine in the solution after extraction should be more than 0.5mol/L, for example, 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 2mol/L, etc.
5. The de-duplication process of claim 1 is to gasify the extracted solution fast, and the gasified solution is condensed fast to recover non-volatile impurity.
The weight removing operation can be flash evaporation, rotary evaporation and other operations.
The weight removing equipment can be a flash tank, a rotary evaporator or a thin film evaporator and the like.
The thin film evaporator that can be used includes a wiped film evaporator (wiped film evaporator), a rising film evaporator, or a falling film evaporator.
6. According to claim 5, the non-volatile impurities removed include, but are not limited to, inorganic salts in the fermentation broth, pyridoxal phosphate (PLP) as a coenzyme used in the enzymatic/whole cell catalytic reaction, excessive sodium hydroxide or calcium hydroxide or potassium hydroxide added during liquid-liquid extraction, sodium chloride or calcium chloride or potassium chloride generated during conditioning, and the like.
7. According to the method, according to the difference of the extracted samples, the heavy removal operation can be carried out for more than or equal to 1 time, and the non-volatile impurities in the heavy removal operation can be removed.
8. The process according to claim 1, wherein the polymer grade bio-based pentylene diamine is obtained by further refining the de-duplication treated product by distillation/rectification.
9. The distillation/rectification operation of claim 8, carried out under atmospheric or reduced pressure conditions; preferably, it is carried out under reduced pressure.
The rectification operation mode is batch operation or continuous operation.
The pressure of the reduced pressure distillation/rectification operation is 2.5kPa to 101.325kPa (absolute pressure), preferably the operating pressure is 2.5kPa to 20kPa; more preferably, the operating pressure is from 2.5kPa to 10kPa.
The equipment for realizing the refining of the bio-based pentanediamine is distillation/rectification equipment such as a rotary evaporator or a rectification tower and the like.
The rectification tower is a plate tower or a packed tower, and the preferred rectification tower is a packed tower.
The packing method of the packed tower is structured packing or bulk packing.
The type of packing material of the packed tower is metal, ceramic or glass.
The structured packing is a grid packing, a corrugated packing or a pulse packing.
The bulk packing type is Raschig ring packing, pall ring packing, theta ring packing, stepped ring packing or spring packing, etc.
The size of the rectifying tower is specifically determined according to the size of the sample amount of the pentylene diamine to be treated.
The components with different temperatures obtained by distillation/rectification operation are collected respectively, and the extractant in the components is further recovered while refining the bio-based pentylene diamine.
The refined bio-based pentylene diamine is quantitatively analyzed by gas chromatography, liquid chromatography and gas chromatography-mass spectrometry.
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