CN115304453B - Refining method of 1, 4-butanediol - Google Patents
Refining method of 1, 4-butanediol Download PDFInfo
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- CN115304453B CN115304453B CN202211113470.XA CN202211113470A CN115304453B CN 115304453 B CN115304453 B CN 115304453B CN 202211113470 A CN202211113470 A CN 202211113470A CN 115304453 B CN115304453 B CN 115304453B
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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 53
- 238000007670 refining Methods 0.000 title claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 72
- 230000008025 crystallization Effects 0.000 claims abstract description 72
- 238000004821 distillation Methods 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims description 35
- 238000002844 melting Methods 0.000 claims description 34
- 230000008018 melting Effects 0.000 claims description 34
- 230000035900 sweating Effects 0.000 claims description 22
- 239000000155 melt Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- NMPJHMFXHISVBR-UHFFFAOYSA-N 4-(oxolan-2-yloxy)butan-1-ol Chemical compound OCCCCOC1CCCO1 NMPJHMFXHISVBR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 210000004243 sweat Anatomy 0.000 claims description 6
- 238000000746 purification Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 208000008454 Hyperhidrosis Diseases 0.000 description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- 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
- -1 polybutylene terephthalate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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) sequentially carrying out reduced pressure distillation and crystallization on the crude 1, 4-butanediol to obtain the 1, 4-butanediol. According to the invention, the crude 1, 4-butanediol is refined by adopting a reduced pressure distillation and crystallization coupling process, so that high-purity 1, 4-butanediol can be obtained; according to the test results of the examples, the purity of the 1, 4-butanediol obtained by the method is more than or equal to 99.5 percent. And the process is simple, and is 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.
At present, common preparation methods comprise a maleic anhydride method and an alkynal method, but the purity of the 1, 4-butanediol obtained by the method is lower.
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 object, the present invention provides the following technical solutions:
the invention provides a refining method of 1, 4-butanediol, which comprises the following steps:
and (3) sequentially carrying out reduced pressure distillation and crystallization on the crude 1, 4-butanediol to obtain the 1, 4-butanediol.
Preferably, the 1, 4-butanediol crude product is a1, 4-butanediol crude product obtained by preparing 1, 4-butanediol by a maleic anhydride method or an alkynal 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 cooling crystallization time is 2-10 h; the final temperature of the cooling crystallization is 10-30 ℃;
the temperature of the heat preservation crystallization is the end temperature of the cooling crystallization, and the time is 10-60 min.
Preferably, the crystallization is performed in a melt crystallizer;
before crystallization, film forming treatment is carried out on the melting crystallizer;
The film hanging treatment process comprises the following steps: introducing molten 1, 4-butanediol into a melting crystallizer, standing, and carrying out film forming treatment; the temperature of the melting crystallizer is less than or equal to 20 ℃.
Preferably, the standing time is 1-10 min; the temperature of the melt crystallizer after the film forming treatment is-5-20 ℃.
Preferably, after the crystallization, the method further comprises the step of sequentially performing sweating treatment and melting treatment on the obtained crystallized product.
Preferably, the sweating treatment comprises heating and sweating treatment and heat preservation and sweating treatment in sequence;
The heating rate of the heating sweating treatment is 0.1-10 ℃/h; the temperature of the end point of the heating and sweating treatment is 0-20 ℃;
the temperature of the heat preservation and sweating treatment is the end temperature of the heating and sweating treatment, and the time is 10-60 min.
Preferably, the temperature of the melting treatment is 30 to 50 ℃.
The invention provides a refining method of 1, 4-butanediol, which comprises the following steps: and (3) sequentially carrying out reduced pressure distillation and crystallization on the crude 1, 4-butanediol to obtain the 1, 4-butanediol. According to the invention, the crude 1, 4-butanediol is refined by adopting a reduced pressure distillation and crystallization coupling process, so that high-purity 1, 4-butanediol can be obtained; according to the test results of the examples, the purity of the 1, 4-butanediol obtained by the method is more than or equal to 99.5 percent. And the process is simple, and is suitable for industrial production.
Detailed Description
The invention provides a refining method of 1, 4-butanediol, which comprises the following steps:
and (3) sequentially carrying out reduced pressure distillation and crystallization on the crude 1, 4-butanediol to obtain the 1, 4-butanediol.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
In the invention, the 1, 4-butanediol crude product is preferably a1, 4-butanediol crude product obtained by preparing 1, 4-butanediol by a maleic anhydride method or an alkynal method. The process for preparing the maleic anhydride method or the alkynal method is not particularly limited, and may be carried out by methods well 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 a specific embodiment of the invention, when the crude 1, 4-butanediol product is prepared by adopting a maleic anhydride method, the crude 1, 4-butanediol product preferably flows out from the bottom of a light component removal tower in the maleic anhydride method process.
In a specific embodiment of the invention, when the crude 1, 4-butanediol is prepared by an alkynal method, the crude 1, 4-butanediol preferably flows out of the bottom of a light component removal tower in the alkynal method process.
In the present invention, the temperature of the reduced pressure distillation is preferably 40 to 115 ℃, more preferably 50 to 110 ℃, still more preferably 60 to 100 ℃; the pressure is preferably 100 to 5000Pa, more preferably 500 to 4000Pa, and still more preferably 1000 to 3000Pa. The time of the reduced pressure distillation is not particularly limited, and may be any one known to those skilled in the art. In the present invention, the reduced pressure distillation is preferably performed in a reduced pressure distillation still, a reduced pressure distillation pot, a plug flow reactor with vacuum degassing equipment, or an extruder with vacuum degassing equipment. In the invention, the flow state of the crude 1, 4-butanediol product during reduced pressure distillation is preferably a full mixed state or a plug flow state. In the present invention, the feeding means for the reduced pressure distillation is preferably continuous feeding or batch feeding. The process of the continuous feeding or batch feeding is not particularly limited, and may be performed by a process known to those skilled in the art.
After the reduced pressure distillation is completed, the present invention preferably further includes cooling the gas obtained by the reduced pressure distillation to obtain a distillate. The cooling treatment process is not particularly limited, 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 even more preferably 30 to 40 ℃. The time of the cooling treatment is not particularly limited, and may be known to those skilled in the art. In a specific embodiment of the invention, the cooling treatment is preferably performed in a heat exchanger.
In the present invention, the crystallization preferably includes crystallization by cooling and crystallization by heat preservation in this order.
In the present invention, the cooling rate of the cooling crystallization is preferably 0.5 to 5 ℃/h, more preferably 1.0 to 4.5 ℃/h, still more preferably 1.5 to 4.0 ℃/h; the cooling crystallization time is preferably 2 to 10 hours, more preferably 3 to 9 hours, and even more preferably 4 to 8 hours. In the present invention, the final temperature of the reduced temperature crystallization is preferably 10 to 30 ℃, more preferably 15 to 25 ℃.
In the invention, the temperature of the heat-preserving crystallization is preferably the end temperature of the cooling crystallization; the time is preferably 10 to 60 minutes, more preferably 20 to 50 minutes, and still more preferably 30 to 40 minutes.
In the present invention, the crystallization is preferably performed in a melt crystallizer.
The present invention preferably further includes a film formation treatment of the melt crystallizer prior to the crystallization.
In the present invention, the film forming process is preferably as follows: and (3) introducing the molten 1, 4-butanediol into a melting crystallizer, standing, and carrying out film forming treatment.
In the present invention, the purity of the molten 1, 4-butanediol is preferably not less than 99.5% when the film formation treatment is performed. In the present invention, the temperature of the melt crystallizer is preferably 20℃or less, more preferably 10 to 20 ℃. In the present invention, the time for the standing is preferably 1 to 10 minutes, more preferably 2 to 9 minutes, and still more preferably 3 to 8 minutes. The amount of the molten 1, 4-butanediol introduced in the present invention is not particularly limited as 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 film 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 distilled liquid obtained by reduced pressure distillation into a melting crystallizer for crystallization.
The present invention also preferably includes subjecting the distillate to a standing treatment after passing the distillate into a melt crystallizer; the time of the standing treatment is preferably 30 to 60 minutes.
In the present invention, the residual crystallization liquid 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 also preferably includes subjecting the resulting crystallized product to a sweating treatment and a melting treatment in this order.
In the present invention, the sweating treatment preferably includes sequentially performing a warming sweating treatment and a warming sweating treatment.
In the present invention, the heating rate of the heating 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 temperature of the heating and sweating treatment is preferably 0 to 20 ℃, more preferably 1 to 19 ℃, and even more preferably 2 to 18 ℃.
In the present invention, the temperature of the insulating sweating treatment is preferably the end temperature of the sweating treatment; the time is preferably 10 to 60 minutes, more preferably 20 to 40 minutes. In the present invention, the perspiration obtained by the perspiration treatment is preferably reprocessed as a raw material for crystallization.
In the present invention, the temperature of the melt-processing is preferably 30 to 50 ℃, more preferably 35 to 45 ℃. The time of the melting treatment is not particularly limited in the present invention, as long as the crystalline product can be completely melted.
In the present invention, the purity of the 1, 4-butanediol is preferably not less than 99.5%.
As another embodiment of the present invention, it is preferable that the crystallization is completed further comprises subjecting the obtained 1, 4-butanediol to secondary crystallization purification. In the present invention, the secondary crystallization refining process is identical to the crystallization process described in the above technical scheme, and will not be described herein.
In order to further illustrate the present invention, a method for purifying 1, 4-butanediol provided by the present invention will be described in detail with reference to examples, 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 placed into a reduced pressure distiller, and reduced pressure distillation is carried out under the conditions that the temperature is 40 ℃ and the pressure is 100 Pa; cooling the obtained distilled gas through a heat exchanger to obtain distillate with the temperature of 30 ℃;
Introducing molten 1, 4-butanediol with the purity of 99.9% into a melting crystallizer at 15 ℃, standing for 10min for film forming treatment, and obtaining a 1, 4-butanediol crystallization layer with the thickness of 0.2mm on the surface of the melting crystallizer; the temperature of the melting crystallizer after film forming treatment is 20 ℃;
Introducing the obtained distillate at 30 ℃ into a melt crystallizer after film formation treatment, standing for 3 hours, cooling for 5 hours at a cooling rate of 3 ℃/h to 15 ℃ for crystallization, and then preserving heat at 15 ℃ for 30 minutes; discharging the crystallization residual liquid out of the melting crystallizer after crystallization is completed, performing perspiration treatment on the obtained crystals at a heating rate of 5 ℃/h, wherein the end temperature of the perspiration treatment is 17 ℃, and then preserving the heat for 30min at the temperature of 17 ℃; after the sweating, the obtained sweat was discharged, and the remaining crystals were subjected to a melt treatment at 45℃to obtain purified 1, 4-butanediol.
In this example, the distillate had a mass of 1.0kg and a purity of 95.0%;
the quality of the refined 1, 4-butanediol is 680.2g, the purity is 99.75 percent, and the content of 2- (4-hydroxy butoxy) tetrahydrofuran is lower than the detection limit;
The mass of the perspiration is 52.5g, and the content of 1, 4-butanediol in the perspiration is 97.5%;
the mass of the crystallization raffinate was 267.3g, and the content of 1, 4-butanediol in the crystallization raffinate was 82.4%.
Example 2
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 placed into a reduced pressure distiller, and reduced pressure distillation is carried out under the conditions that the temperature is 75 ℃ and the pressure is 1000 Pa; cooling the obtained distilled gas through a heat exchanger to obtain distillate with the temperature of 28 ℃;
introducing molten 1, 4-butanediol with the purity of 99.9% into a melting crystallizer at the temperature of 10 ℃, standing for 20min for film forming treatment, and obtaining a 1, 4-butanediol crystallization layer with the thickness of 0.5mm on the surface of the melting crystallizer; the temperature of the melting crystallizer after film forming treatment is 20 ℃;
Introducing the obtained distillate at 28 ℃ into a film-forming treated melt crystallizer, cooling at a cooling rate of 3 ℃/h for 5h to 13 ℃ for crystallization, and then preserving heat at 13 ℃ for 30min; discharging the crystallization residual liquid out of the melting crystallizer after crystallization is finished, performing perspiration treatment on the obtained crystals at a heating rate of 5 ℃/h, wherein the end temperature of the perspiration treatment is 20 ℃, and then preserving the heat for 30min at 20 ℃; after the sweating, the obtained sweat was discharged, and the remaining crystals were subjected to a melt treatment at 40℃to obtain purified 1, 4-butanediol.
In this example, the distillate had a mass of 955.3g and a purity of 96.75%;
the quality of the refined 1, 4-butanediol is 685.2g, the purity is 99.85%, and the content of 2- (4-hydroxy butoxy) tetrahydrofuran is lower than the detection limit;
the mass of the perspiration is 51.2g, and the content of 1, 4-butanediol in the perspiration is 97.55%;
The mass of the crystallization raffinate was 218.9g, and the content of 1, 4-butanediol in the crystallization raffinate was 86.86%.
Example 3
Introducing molten 1, 4-butanediol with the purity of 99.9% into a melting crystallizer at 15 ℃, standing for 10min for film forming treatment, and obtaining a 1, 4-butanediol crystallization layer with the thickness of 0.2mm on the surface of the melting crystallizer; the temperature of the melting crystallizer after film forming treatment is 20 ℃;
introducing 600g of the 1, 4-butanediol obtained in the embodiment into a melt crystallizer after film formation treatment, standing for 3 hours, cooling at a cooling rate of 0.5 ℃/h for 5 hours to 15 ℃ for crystallization, and then preserving heat at 15 ℃ for 30 minutes; discharging the crystallization residual liquid out of the melting crystallizer after crystallization is finished, performing perspiration treatment on the obtained crystals at the heating rate of 0.2 ℃/h, wherein the end temperature of the perspiration treatment is 20 ℃, and then preserving the heat for 30min at 20 ℃; after sweating, the obtained sweat is discharged, and the rest crystals are melted at 45 ℃ to obtain the secondary crystallized and refined 1, 4-butanediol.
The mass of the 1, 4-butanediol refined by secondary crystallization is 450.2g, the purity is 99.992 percent, and the content of 2- (4-hydroxy butoxy) tetrahydrofuran is lower than the detection limit;
the mass of the perspiration is 32.5g, and the content of 1, 4-butanediol in the perspiration is 99.92%;
The mass of the crystallization raffinate was 115.9g, and the content of 1, 4-butanediol in the crystallization raffinate was 98.77%.
Example 4
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 an alkynal method process is placed into a reduced pressure distiller, and reduced pressure distillation is carried out under the conditions that the temperature is 55 ℃ and the pressure is 300 Pa; cooling the obtained distilled gas through a heat exchanger to obtain distillate with the temperature of 20 ℃;
Introducing molten 1, 4-butanediol with the purity of 99.95% into a melting crystallizer at 15 ℃, standing for 60min for film forming treatment, and obtaining a 1, 4-butanediol crystallization layer with the thickness of 0.2mm on the surface of the melting crystallizer; the temperature of the melting crystallizer after film forming treatment is 25 ℃;
Introducing the obtained distillate into a melt crystallizer subjected to film forming treatment, standing for 3 hours, cooling at a cooling rate of 1.5 ℃/h for 5 hours to a temperature of 10 ℃ for crystallization, and then preserving heat at the temperature of 10 ℃ for 30 minutes; discharging the crystallization residual liquid out of the melting crystallizer after crystallization is completed, performing perspiration treatment on the obtained crystals at a heating rate of 1 ℃/h, wherein the end temperature of the perspiration treatment is 19 ℃, and then preserving the heat for 30min at 19 ℃; after the sweating, the obtained sweat was discharged, and the remaining crystals were subjected to a melt treatment at 50℃to obtain purified 1, 4-butanediol.
In this example, the distillate had a mass of 945.7g and a purity of 98.72%;
the quality of the refined 1, 4-butanediol is 780.2g, the purity is 99.92%, and the content of 2- (4-hydroxy butoxy) tetrahydrofuran is lower than the detection limit;
the mass of the perspiration is 32.5g, and the content of 1, 4-butanediol in the perspiration is 99.5 percent;
the mass of the crystallization raffinate was 187.3g, and the content of 1, 4-butanediol in the crystallization raffinate 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-ends column 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 full mixed flow state); cooling the obtained distilled gas through 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 melting crystallizer at the temperature of 5 ℃, standing for 1min for film forming treatment, and obtaining a1, 4-butanediol crystallization layer with the thickness of 0.3mm on the surface of the melting crystallizer; the temperature of the melting crystallizer after film forming treatment is 15 ℃;
Introducing the obtained distilled liquid at 15 ℃ into a melt crystallizer after film formation treatment, standing for 3 hours, cooling for 10 hours at a cooling rate of 0.6 ℃/h to 9 ℃ for crystallization, and then preserving heat at 9 ℃ for 30 minutes; discharging the crystallization residual liquid out of the melting crystallizer after crystallization is finished, performing perspiration treatment on the obtained crystals at the heating rate of 0.1 ℃/h, wherein the end temperature of the perspiration treatment is 15 ℃, and then preserving the heat for 60 minutes at 15 ℃; after the sweating, the obtained sweat was discharged, and the remaining crystals were subjected to a melt treatment at 40℃to obtain purified 1, 4-butanediol.
In this example, the distillate had a mass of 905.6g and a purity of 97.76%;
The quality of the refined 1, 4-butanediol is 650.2g, the purity is 99.75 percent, and the content of 2- (4-hydroxy butoxy) tetrahydrofuran is lower than the detection limit;
The mass of the perspiration is 42.7g, and the content of 1, 4-butanediol in the perspiration is 99.4 percent;
the mass of the residue was 307.1g, and the content of 1, 4-butanediol in the residue was 83.4%.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (1)
1. The refining method of the 1, 4-butanediol is characterized by comprising the following steps of:
1kg of 1, 4-butanediol crude product flowing out from the bottom of a light component removal tower in an alkynal method process is placed into a reduced pressure distiller, and reduced pressure distillation is carried out under the conditions that the temperature is 55 ℃ and the pressure is 300 Pa; cooling the obtained distilled gas through a heat exchanger to obtain distillate with the temperature of 20 ℃; the crude 1, 4-butanediol product comprises 95 weight percent of 1, 4-butanediol;
Introducing molten 1, 4-butanediol with the purity of 99.95% into a melting crystallizer at 15 ℃, standing for 60min for film forming treatment, and obtaining a 1, 4-butanediol crystallization layer with the thickness of 0.2mm on the surface of the melting crystallizer; the temperature of the melting crystallizer after film forming treatment is 25 ℃;
Introducing the obtained distillate into a melt crystallizer subjected to film forming treatment, standing for 3 hours, cooling at a cooling rate of 1.5 ℃/h for 5 hours to a temperature of 10 ℃ for crystallization, and then preserving heat at the temperature of 10 ℃ for 30 minutes; discharging the crystallization residual liquid out of the melting crystallizer after crystallization is completed, performing perspiration treatment on the obtained crystals at a heating rate of 1 ℃/h, wherein the end temperature of the perspiration treatment is 19 ℃, and then preserving the heat for 30min at 19 ℃; discharging the obtained sweat after sweating, and carrying out melting treatment on the rest crystals at 50 ℃ to obtain refined 1, 4-butanediol;
the quality of the obtained distillate is 945.7g, and the purity is 98.72%;
the quality of the refined 1, 4-butanediol is 780.2g, the purity is 99.92%, and the content of 2- (4-hydroxy butoxy) tetrahydrofuran is lower than the detection limit;
The mass of the perspiration is 32.5g, and the content of 1, 4-butanediol in the perspiration is 99.5 percent;
The mass of the crystallization raffinate was 187.3g, and the content of 1, 4-butanediol in the crystallization raffinate was 73.7%.
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Citations (2)
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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