CN115304453A - Refining method of 1, 4-butanediol - Google Patents
Refining method of 1, 4-butanediol Download PDFInfo
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- CN115304453A CN115304453A CN202211113470.XA CN202211113470A CN115304453A CN 115304453 A CN115304453 A CN 115304453A CN 202211113470 A CN202211113470 A CN 202211113470A CN 115304453 A CN115304453 A CN 115304453A
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- butanediol
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- sweating
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000007670 refining Methods 0.000 title claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 69
- 230000008025 crystallization Effects 0.000 claims abstract description 69
- 238000004821 distillation Methods 0.000 claims abstract description 26
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 6
- 208000008454 Hyperhidrosis Diseases 0.000 claims description 45
- 230000035900 sweating Effects 0.000 claims description 45
- 239000000155 melt Substances 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 39
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 210000004243 sweat Anatomy 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- -1 polybutylene terephthalate Polymers 0.000 description 6
- NMPJHMFXHISVBR-UHFFFAOYSA-N 4-(oxolan-2-yloxy)butan-1-ol Chemical compound OCCCCOC1CCCO1 NMPJHMFXHISVBR-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000032770 biofilm formation Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical purification, and particularly relates to a refining method of 1, 4-butanediol. The invention provides a refining method of 1, 4-butanediol, which comprises the following steps: and (3) carrying out reduced pressure distillation and crystallization on the 1, 4-butanediol crude product in sequence to obtain the 1, 4-butanediol. The invention adopts the coupling technology of reduced pressure distillation and crystallization to refine the 1, 4-butanediol crude product, and can obtain high-purity 1, 4-butanediol; according to the test results of the examples, the purity of the 1, 4-butanediol obtained by the invention is more than or equal to 99.5 percent. And the process is simple and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical purification, and particularly relates to a refining method of 1, 4-butanediol.
Background
1, 4-butanediol is an important organic chemical product, and is mainly used for producing tetrahydrofuran, gamma-butyrolactone, polybutylene terephthalate, polytetramethylene glycol, polyurethane elastomer and the like.
Currently, the commonly used preparation methods include a cis-anhydride method and an alkynal method, but the purity of 1, 4-butanediol obtained by the above methods is low.
Disclosure of Invention
The invention aims to provide a method for refining 1, 4-butanediol, and the purity of the 1, 4-butanediol obtained by the method is high.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a refining method of 1, 4-butanediol, which comprises the following steps:
and (3) carrying out reduced pressure distillation and crystallization on the 1, 4-butanediol crude product in sequence to obtain the 1, 4-butanediol.
Preferably, the 1, 4-butanediol crude product is a 1, 4-butanediol crude product obtained by preparing 1, 4-butanediol by a maleic anhydride method or an alkyne aldehyde method.
Preferably, the temperature of the reduced pressure distillation is 40-115 ℃, and the pressure is 100-5000 Pa.
Preferably, after the reduced pressure distillation, the method further comprises a cooling treatment; the temperature after the cooling treatment is 20-50 ℃.
Preferably, the crystallization comprises cooling crystallization and heat preservation crystallization in sequence;
the cooling rate of the cooling crystallization is 0.5-5 ℃/h; the time for cooling and crystallizing is 2-10 h; the final temperature of the cooling crystallization is 10-30 ℃;
the temperature of the heat preservation crystallization is the end point temperature of the cooling crystallization, and the time is 10-60 min.
Preferably, the crystallization is carried out in a melt crystallizer;
before the crystallization, the method also comprises the step of performing film forming treatment on the melt crystallizer;
the film forming treatment process comprises the following steps: introducing the molten 1, 4-butanediol into a melt crystallizer for standing, and performing film forming treatment; the temperature of the melt crystallizer is less than or equal to 20 ℃.
Preferably, the standing time is 1-10 min; the temperature of the melt crystallizer after the biofilm formation treatment is-5-20 ℃.
Preferably, after the crystallization, the method further comprises the step of subjecting the obtained crystallized product to sweating treatment and melting treatment in sequence.
Preferably, the sweating treatment comprises heating sweating treatment and heat preservation sweating treatment which are sequentially carried out;
the heating rate of the heating sweating treatment is 0.1-10 ℃/h; the end point temperature of the temperature-rising sweating treatment is 0-20 ℃;
the temperature of the heat preservation sweating treatment is the end point temperature of the temperature rise sweating treatment, and the time is 10-60 min.
Preferably, the temperature of the melt treatment is 30 to 50 ℃.
The invention provides a refining method of 1, 4-butanediol, which comprises the following steps: and (3) carrying out reduced pressure distillation and crystallization on the 1, 4-butanediol crude product in sequence to obtain the 1, 4-butanediol. The invention adopts the coupling technology of reduced pressure distillation and crystallization to refine the 1, 4-butanediol crude product, and can obtain high-purity 1, 4-butanediol; according to the test results of the examples, the purity of the 1, 4-butanediol obtained by the invention is more than or equal to 99.5 percent. And the process is simple and suitable for industrial production.
Detailed Description
The invention provides a refining method of 1, 4-butanediol, which comprises the following steps:
and (3) carrying out reduced pressure distillation and crystallization on the 1, 4-butanediol crude product in sequence to obtain the 1, 4-butanediol.
In the present invention, all the starting materials for the preparation are commercially available products well known to those skilled in the art, unless otherwise specified.
In the present invention, the crude 1, 4-butanediol is preferably crude 1, 4-butanediol obtained by preparing 1, 4-butanediol by a cis-anhydride method or an alkynal method. The preparation process of the cis-anhydride method or the alkynal method is not particularly limited in the present invention, and may be performed by a method known to those skilled in the art.
In the invention, the mass percentage of the 1, 4-butanediol in the 1, 4-butanediol crude product is preferably 90-98%.
In the specific embodiment of the present invention, when the crude 1, 4-butanediol is prepared by the maleic anhydride method, the crude 1, 4-butanediol is preferably discharged from the bottom of the light ends removal column in the maleic anhydride method process.
In the specific embodiment of the invention, when the crude 1, 4-butanediol obtained by the alkyne aldehyde method is prepared, the crude 1, 4-butanediol preferably flows out from the bottom of a lightness-removing column in the alkyne aldehyde method process.
In the invention, the temperature of the reduced pressure distillation is preferably 40-115 ℃, more preferably 50-110 ℃, and more preferably 60-100 ℃; the pressure is preferably 100 to 5000Pa, more preferably 500 to 4000Pa, and still more preferably 1000 to 3000Pa. The time for the distillation under reduced pressure is not particularly limited in the present invention, and those known to those skilled in the art can be used. In the present invention, the reduced pressure distillation is preferably carried out in a reduced pressure distillation still, a reduced pressure distillation pot, a plug flow reactor with a vacuum degassing apparatus, or an extruder with a vacuum degassing apparatus. In the present invention, the flow state of the crude 1, 4-butanediol during the reduced pressure distillation is preferably a fully mixed state or a plug flow state. In the present invention, the feeding manner of the vacuum distillation is preferably a continuous feeding manner or a batch feeding manner. The process of the present invention is not particularly limited, and may be carried out by a process known to those skilled in the art.
After the reduced pressure distillation is finished, the invention also preferably comprises cooling the gas obtained by the reduced pressure distillation to obtain distillate. The cooling process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art. In the present invention, the temperature after the cooling treatment is preferably 20 to 50 ℃, more preferably 25 to 45 ℃, and still more preferably 30 to 40 ℃. The time for the cooling treatment is not particularly limited in the present invention, and those known to those skilled in the art can be used. In a particular embodiment of the invention, the cooling treatment is preferably carried out in a heat exchanger.
In the present invention, the crystallization preferably comprises a temperature-reduction crystallization and a heat-preservation crystallization which are sequentially performed.
In the invention, the cooling rate of the cooling crystallization is preferably 0.5-5 ℃/h, more preferably 1.0-4.5 ℃/h, and more preferably 1.5-4.0 ℃/h; the time for cooling crystallization is preferably 2 to 10 hours, more preferably 3 to 9 hours, and still more preferably 4 to 8 hours. In the present invention, the temperature-decreasing crystallization end point temperature is preferably 10 to 30 ℃, and more preferably 15 to 25 ℃.
In the invention, the temperature of the heat preservation crystallization is preferably the end point temperature of the cooling crystallization; the time is preferably 10 to 60min, more preferably 20 to 50min, and still more preferably 30 to 40min.
In the present invention, the crystallization is preferably carried out in a melt crystallizer.
Before the crystallization, the invention also preferably comprises a film forming treatment on the melt crystallizer.
In the present invention, the process of the biofilm formation treatment is preferably: and introducing the molten 1, 4-butanediol into a melt crystallizer for standing, and performing film forming treatment.
In the invention, the purity of the molten 1, 4-butanediol is preferably not less than 99.5% when the film formation treatment is carried out. In the present invention, the temperature of the melt crystallizer is preferably not more than 20 ℃ and more preferably 10 to 20 ℃ when the biofilm formation treatment is performed. In the present invention, the time for the standing is preferably 1 to 10min, more preferably 2 to 9min, and still more preferably 3 to 8min. The amount of the 1, 4-butanediol in the molten state introduced is not particularly limited, so long as a 1, 4-butanediol crystalline layer can be obtained on the surface of the melt crystallizer. In the present invention, the thickness of the 1, 4-butanediol crystalline layer is preferably 0.1 to 0.5mm.
In the present invention, the temperature of the melt crystallizer after the biofilm formation treatment is preferably-5 to 20 ℃, more preferably-3 to 18 ℃, and still more preferably 0 to 15 ℃.
In the present invention, the crystallization process is preferably: and introducing the distillate obtained by reduced pressure distillation into a melt crystallizer for crystallization.
After passing the distillate into the melt crystallizer, the present invention also preferably comprises subjecting the distillate to a standing treatment; the time of the standing treatment is preferably 30 to 60min.
In the present invention, the crystallization residue obtained after completion of the crystallization is preferably reused as a raw material for distillation under reduced pressure.
After the crystallization is completed, the present invention preferably further comprises subjecting the obtained crystallized product to a sweating treatment and a melting treatment in this order.
In the present invention, the sweating treatment preferably includes a temperature-raising sweating treatment and a heat-retaining sweating treatment which are performed in this order.
In the present invention, the temperature increase rate of the temperature-increasing sweating treatment is preferably 0.1 to 10 ℃/h, more preferably 0.5 to 9 ℃/h, and still more preferably 1 to 8 ℃/h. In the present invention, the end point temperature of the temperature-increasing sweating treatment is preferably 0 to 20 ℃, more preferably 1 to 19 ℃, and still more preferably 2 to 18 ℃.
In the present invention, the temperature of the heat-retaining sweating treatment is preferably the end temperature of the sweating treatment; the time is preferably 10 to 60min, and more preferably 20 to 40min. In the present invention, the sweat obtained by the sweating treatment is preferably reprocessed as a raw material for crystallization.
In the present invention, the temperature of the melting treatment is preferably 30 to 50 ℃, and more preferably 35 to 45 ℃. In the present invention, the time for the melting treatment is not particularly limited as long as the crystalline product can be completely melted.
In the present invention, the purity of the 1, 4-butanediol is preferably 99.5% or more.
In another embodiment of the present invention, it is preferable that the method further comprises refining the obtained 1, 4-butanediol by secondary crystallization after completion of the crystallization. In the present invention, the process of the secondary crystallization refining is the same as the crystallization process described in the above technical solution, and is not described herein again.
In order to further illustrate the present invention, the following examples are provided to describe in detail the purification method of 1, 4-butanediol of the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
1.1kg of 1, 4-butanediol crude product (comprising 95wt% of 1, 4-butanediol) flowing out from the bottom of a light component removal tower in the maleic anhydride method process is put into a reduced pressure distiller and reduced pressure distillation is carried out at the temperature of 40 ℃ and the pressure of 100 Pa; cooling the obtained distilled gas by a heat exchanger to obtain distillate with the temperature of 30 ℃;
introducing molten 1, 4-butanediol with the purity of 99.9% into a melt crystallizer at the temperature of 15 ℃, standing for 10min for film formation, and obtaining a 1, 4-butanediol crystalline layer with the thickness of 0.2mm on the surface of the melt crystallizer; the temperature of the melt crystallizer after the film forming treatment is 20 ℃;
introducing the obtained 30 ℃ distillate into a melt crystallizer after the film forming treatment, standing for 3 hours, then cooling for 5 hours at a cooling rate of 3 ℃/h to 15 ℃ for crystallization, and then preserving heat for 30min at 15 ℃; discharging the residual crystallization liquid out of the melt crystallizer after the crystallization is finished, sweating the obtained crystals at the heating rate of 5 ℃/h, wherein the final temperature of the sweating treatment is 17 ℃, and then preserving the heat for 30min at 17 ℃; after the sweating was completed, the resulting sweating solution was discharged, and the remaining crystals were subjected to a melting treatment at 45 ℃ to obtain purified 1, 4-butanediol.
In this example, the mass of the distillate was 1.0kg, and the purity was 95.0%;
the mass of the purified 1, 4-butanediol was 680.2g, the purity was 99.75%, and the content of 2- (4-hydroxybutoxy) tetrahydrofuran was below the detection limit;
the mass of the perspiration liquid is 52.5g, and the content of 1, 4-butanediol in the perspiration liquid is 97.5 percent;
the mass of the crystallization residue was 267.3g, and the content of 1, 4-butanediol in the crystallization residue was 82.4%.
Example 2
1kg of 1, 4-butanediol crude product (comprising 95wt% of 1, 4-butanediol) flowing out of the bottom of a light component removal tower in the maleic anhydride method process is put into a reduced pressure distiller and subjected to reduced pressure distillation at the temperature of 75 ℃ and the pressure of 1000 Pa; cooling the obtained distillation gas by a heat exchanger to obtain a distillate with the temperature of 28 ℃;
introducing molten 1, 4-butanediol with the purity of 99.9% into a melt crystallizer at the temperature of 10 ℃, standing for 20min for film formation, and obtaining a 1, 4-butanediol crystalline layer with the thickness of 0.5mm on the surface of the melt crystallizer; the temperature of the melt crystallizer after the film hanging treatment is 20 ℃;
introducing the distillate at 28 ℃ into a melt crystallizer after the film forming treatment, cooling for 5 hours at a cooling rate of 3 ℃/h to 13 ℃ for crystallization, and then preserving heat at 13 ℃ for 30min; discharging the residual crystallization liquid out of a melting crystallizer after the crystallization is finished, carrying out sweating treatment on the obtained crystals at the temperature rising rate of 5 ℃/h, wherein the end point temperature of the sweating treatment is 20 ℃, and then carrying out heat preservation for 30min at 20 ℃; after the sweating was completed, the resulting sweating solution was discharged, and the remaining crystals were subjected to a melting treatment at 40 ℃ to obtain purified 1, 4-butanediol.
In this example, the mass of the distillate was 955.3g, and the purity was 96.75%;
the mass of the purified 1, 4-butanediol was 685.2g, the purity was 99.85%, and the content of 2- (4-hydroxybutoxy) tetrahydrofuran was below the detection limit;
the mass of the sweat is 51.2g, and the content of 1, 4-butanediol in the sweat is 97.55%;
the mass of the crystal residue was 218.9g, and the content of 1, 4-butanediol in the crystal residue was 86.86%.
Example 3
Introducing molten 1, 4-butanediol with the purity of 99.9% into a melt crystallizer at the temperature of 15 ℃, standing for 10min for film formation, and obtaining a 1, 4-butanediol crystalline layer with the thickness of 0.2mm on the surface of the melt crystallizer; the temperature of the melt crystallizer after the film hanging treatment is 20 ℃;
introducing 600g of 1, 4-butanediol obtained in the embodiment into a melt crystallizer after film formation treatment, standing for 3 hours, then cooling for 5 hours at a cooling rate of 0.5 ℃/h to 15 ℃ for crystallization, and then preserving heat for 30min at 15 ℃; discharging the residual crystallization liquid out of a melting crystallizer after the crystallization is finished, carrying out sweating treatment on the obtained crystals at the temperature rising rate of 0.2 ℃/h, wherein the end point temperature of the sweating treatment is 20 ℃, and then carrying out heat preservation for 30min at 20 ℃; after the sweating was completed, the obtained sweating solution was discharged, and the remaining crystals were subjected to a melting treatment at 45 ℃ to obtain 1, 4-butanediol refined by secondary crystallization.
The mass of the 1, 4-butanediol refined by secondary crystallization is 450.2g, the purity is 99.992%, and the content of 2- (4-hydroxybutoxy) tetrahydrofuran is lower than the detection limit;
the mass of the sweat is 32.5g, and the content of 1, 4-butanediol in the sweat is 99.92%;
the mass of the crystallization residue was 115.9g, and the content of 1, 4-butanediol in the crystallization residue was 98.77%.
Example 4
1kg of 1, 4-butanediol crude product (comprising 95wt% of 1, 4-butanediol) flowing out of the bottom of a light component removal tower in the alkyne aldehyde method process is put into a reduced pressure distiller and subjected to reduced pressure distillation at the temperature of 55 ℃ and the pressure of 300 Pa; cooling the obtained distilled gas by a heat exchanger to obtain distillate with the temperature of 20 ℃;
introducing molten 1, 4-butanediol with the purity of 99.95% into a melt crystallizer at the temperature of 15 ℃, standing for 60min for film formation, and obtaining a 1, 4-butanediol crystalline layer with the thickness of 0.2mm on the surface of the melt crystallizer; the temperature of the melt crystallizer after the film forming treatment is 25 ℃;
introducing the obtained distillate into a melt crystallizer after film forming treatment, standing for 3 hours, then cooling for 5 hours at a cooling rate of 1.5 ℃/h to 10 ℃ for crystallization, and then preserving heat for 30min at 10 ℃; discharging the residual crystallization liquid out of the melt crystallizer after the crystallization is finished, sweating the obtained crystals at the heating rate of 1 ℃/h, wherein the end point temperature of the sweating treatment is 19 ℃, and then preserving heat for 30min at 19 ℃; after the sweating was completed, the obtained sweating liquid was discharged, and the remaining crystals were subjected to a melting treatment at 50 ℃ to obtain purified 1, 4-butanediol.
In this example, the mass of the distillate was 945.7g, with a purity of 98.72%;
the mass of the purified 1, 4-butanediol was 780.2g, the purity was 99.92%, and the content of 2- (4-hydroxybutoxy) tetrahydrofuran was below the detection limit;
the mass of the sweat is 32.5g, and the content of 1, 4-butanediol in the sweat is 99.5%;
the mass of the residual crystal liquid was 187.3g, and the content of 1, 4-butanediol in the residual crystal liquid was 73.7%.
Example 5
1kg of 1, 4-butanediol crude product (comprising 95wt% of 1, 4-butanediol) flowing out from the bottom of a light component removal tower in the maleic anhydride method process is put into a reduced pressure distiller, and reduced pressure distillation is carried out at the temperature of 100 ℃ and the pressure of 3000Pa (wherein the flowing state of the 1, 4-butanediol crude product in the reduced pressure distiller is a fully mixed flow state); cooling the obtained distilled gas by a heat exchanger to obtain a distillate with the temperature of 15 ℃;
introducing molten 1, 4-butanediol with the purity of 99.9% into a melt crystallizer at the temperature of 5 ℃, standing for 1min for film formation treatment, and obtaining a 1, 4-butanediol crystalline layer with the thickness of 0.3mm on the surface of the melt crystallizer; the temperature of the melt crystallizer after the biofilm culturing treatment is 15 ℃;
introducing the obtained 15 ℃ distillate into a melt crystallizer after the film forming treatment, standing for 3 hours, then cooling for 10 hours at a cooling rate of 0.6 ℃/h to 9 ℃ for crystallization, and then preserving heat for 30min at 9 ℃; discharging the residual crystallization liquid out of a melting crystallizer after the crystallization is finished, carrying out sweating treatment on the obtained crystals at the temperature rising rate of 0.1 ℃/h, wherein the end point temperature of the sweating treatment is 15 ℃, and then carrying out heat preservation for 60min at the temperature of 15 ℃; after the sweating was completed, the obtained sweating liquid was discharged, and the remaining crystals were subjected to a melting treatment at 40 ℃ to obtain purified 1, 4-butanediol.
In this example, the mass of the distillate was 905.6g, the purity was 97.76%;
the mass of the purified 1, 4-butanediol was 650.2g, the purity was 99.75%, and the content of 2- (4-hydroxybutoxy) tetrahydrofuran was below the detection limit;
the mass of the sweat is 42.7g, and the content of 1, 4-butanediol in the sweat is 99.4%;
the mass of the crystallization residue was 307.1g, and the content of 1, 4-butanediol in the crystallization residue was 83.4%.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A method for refining 1, 4-butanediol is characterized by comprising the following steps:
and (3) carrying out reduced pressure distillation and crystallization on the 1, 4-butanediol crude product in sequence to obtain the 1, 4-butanediol.
2. The refining method of claim 1, wherein the crude 1, 4-butanediol is a crude 1, 4-butanediol obtained by preparing 1, 4-butanediol by a cis-anhydride method or an alkynal method.
3. The purification process according to claim 1, wherein the temperature of the reduced pressure distillation is 40 to 115 ℃ and the pressure is 100 to 5000Pa.
4. The refining method according to claim 3, further comprising a cooling treatment after the distillation under reduced pressure; the temperature after the cooling treatment is 20-50 ℃.
5. The refining method according to claim 1, wherein the crystallizing comprises performing cooling crystallization and holding crystallization in this order;
the cooling rate of the cooling crystallization is 0.5-5 ℃/h; the time for cooling and crystallizing is 2-10 h; the final temperature of the cooling crystallization is 10-30 ℃;
the temperature of the heat preservation crystallization is the end point temperature of the cooling crystallization, and the time is 10-60 min.
6. The refining process of claim 5, wherein the crystallization is performed in a melt crystallizer;
before the crystallization, the method also comprises the step of performing film forming treatment on the melt crystallizer;
the film forming treatment process comprises the following steps: introducing the molten 1, 4-butanediol into a melt crystallizer for standing, and performing film forming treatment; the temperature of the melt crystallizer is less than or equal to 20 ℃.
7. The refining method according to claim 6, wherein the time for the standing is 1 to 10min; the temperature of the melt crystallizer after the film forming treatment is-5 to 20 ℃.
8. The purification method as claimed in claim 1, further comprising subjecting the obtained crystalline product to a sweating treatment and a melting treatment in this order after the crystallization.
9. The refining method according to claim 8, wherein the sweating treatment comprises a temperature-raising sweating treatment and a temperature-maintaining sweating treatment which are performed in this order;
the heating rate of the heating sweating treatment is 0.1-10 ℃/h; the end point temperature of the temperature-rising sweating treatment is 0-20 ℃;
the temperature of the heat preservation sweating treatment is the end point temperature of the temperature rise sweating treatment, and the time is 10-60 min.
10. The purification method according to claim 9, wherein the temperature of the melt treatment is 30 to 50 ℃.
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| CN115710159A (en) * | 2022-12-06 | 2023-02-24 | 辽宁鑫隆科技有限公司 | Method for purifying 1-ethynyl cyclohexanol by melt crystallization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11199524A (en) * | 1998-01-08 | 1999-07-27 | Mitsubishi Chemical Corp | Melt crystallization of wall surface falling type |
| US5981810A (en) * | 1997-06-16 | 1999-11-09 | Mitsubishi Chemical Corporation | Process for preparing 1,4-butanediol |
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| US5981810A (en) * | 1997-06-16 | 1999-11-09 | Mitsubishi Chemical Corporation | Process for preparing 1,4-butanediol |
| JPH11199524A (en) * | 1998-01-08 | 1999-07-27 | Mitsubishi Chemical Corp | Melt crystallization of wall surface falling type |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115710159A (en) * | 2022-12-06 | 2023-02-24 | 辽宁鑫隆科技有限公司 | Method for purifying 1-ethynyl cyclohexanol by melt crystallization method |
| CN115710159B (en) * | 2022-12-06 | 2023-11-21 | 辽宁鑫隆科技有限公司 | Method for purifying 1-ethynyl cyclohexanol by using melt crystallization method |
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