CN117843444A - Process method for refining 1, 4-butanediol - Google Patents
Process method for refining 1, 4-butanediol Download PDFInfo
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- CN117843444A CN117843444A CN202311803833.7A CN202311803833A CN117843444A CN 117843444 A CN117843444 A CN 117843444A CN 202311803833 A CN202311803833 A CN 202311803833A CN 117843444 A CN117843444 A CN 117843444A
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- butanediol
- tetrahydrofuran
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000007670 refining Methods 0.000 title claims abstract description 17
- NMPJHMFXHISVBR-UHFFFAOYSA-N 4-(oxolan-2-yloxy)butan-1-ol Chemical compound OCCCCOC1CCCO1 NMPJHMFXHISVBR-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims abstract description 17
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000010409 thin film Substances 0.000 abstract description 7
- 239000000376 reactant Substances 0.000 abstract description 5
- 238000007259 addition reaction Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- -1 polybutylene terephthalate Polymers 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- IHBCROOGTVEOPK-UHFFFAOYSA-N 4-(oxolan-2-yloxy)butanal Chemical compound O=CCCCOC1CCCO1 IHBCROOGTVEOPK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000000926 separation method 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
-
- 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
-
- 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
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process method for refining 1, 4-butanediol, firstly adding a 1, 4-butanediol crude product containing 2- (4-hydroxy butoxy) -tetrahydrofuran, water and sodium bisulphite into a reaction kettle, and carrying out hydrolysis and addition reaction on the 2- (4-hydroxy butoxy) -tetrahydrofuran under the condition of acidity and water existence to convert the 2- (4-hydroxy butoxy) -tetrahydrofuran into 1, 4-butanediol and organic sodium sulfonate; then carrying out scraping plate thin film evaporation on the reacted reaction liquid to remove organic sodium sulfonate and sodium bisulphite; then, carrying out reduced pressure rectification on distillate evaporated by the scraper film, and extracting water from the top of the tower; finally, carrying out reduced pressure rectification on the dehydrated 1, 4-butanediol crude product, and extracting a 1, 4-butanediol product from the side line of the tower; the invention converts the difficult-to-separate 2- (4-hydroxy butoxy) -tetrahydrofuran into 1, 4-butanediol and the easy-to-separate organic sodium sulfonate by utilizing the reaction, and the introduced reactant is economical, easy to obtain, simple in process and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic solvent purification, and particularly relates to a process method for refining 1, 4-butanediol.
Background
1, 4-butanediol is a saturated carbon tetra straight chain dihydric alcohol, and can be used for producing various derivatives with high added value, such as tetrahydrofuran, gamma-butyrolactone, N-methylpyrrolidone, engineering plastics such as polybutylene terephthalate, degradable plastics such as polybutylene succinate, and the like. The production method of 1, 4-butanediol mainly comprises a Reppe method, a butadiene method, a propylene oxide method, a maleic anhydride method and the like, wherein the Reppe method and the maleic anhydride method are two main industrial production methods of 1, 4-butanediol. The crude 1, 4-butanediol produced by the two methods contains a small amount of cyclic acetal byproduct 2- (4-hydroxy butoxy) -tetrahydrofuran, the 2- (4-hydroxy butoxy) -tetrahydrofuran not only affects the purity of the 1, 4-butanediol product, but also can make the 1, 4-butanediol develop color when the concentration of the 2- (4-hydroxy butoxy) -tetrahydrofuran is higher, so that the chromaticity of the 1, 4-butanediol product is unqualified. Therefore, the content of 2- (4-hydroxybutoxy) -tetrahydrofuran in the 1, 4-butanediol product is subject to stringent requirements. However, 1, 4-butanediol and 2- (4-hydroxybutoxy) -tetrahydrofuran can form the minimum azeotrope, and when purifying 1, 4-butanediol by rectification, it is difficult to completely remove 2- (4-hydroxybutoxy) -tetrahydrofuran even through repeated rectification under reduced pressure.
To remove 2- (4-hydroxybutoxy) -tetrahydrofuran to improve the quality of 1, 4-butanediol, patent publication No. CN1216973A proposes to hydrolyze and hydrogenate 2- (4-hydroxybutoxy) -tetrahydrofuran in 1, 4-butanediol in the presence of a small amount of water and a hydrogenation catalyst to convert the same into 1, 4-butanediol, thereby realizing the purification of 1, 4-butanediol. JP-A-61/197534 proposes a process for purifying crude 1, 4-butanediol by first converting aldehyde and acetal impurities such as 2- (4-hydroxybutoxy) -tetrahydrofuran, 2- (4-oxobutoxy) -tetrahydrofuran, etc., into tetrahydrofuran, 1, 4-butanediol, etc., which are easily separated from 1, 4-butanediol, etc., by catalytic hydrogenation and then removing these products by rectification. Both methods use hydrogenation to remove 2- (4-hydroxy butoxy) -tetrahydrofuran, however, the hydrogenation process has the characteristics of high temperature, high pressure, hydrogen and high material risk, and belongs to the process with high risk; on the other hand, the hydrogenation catalyst is expensive, and has the problem of catalyst poisoning, and the equipment investment and the operation cost are high, so that the method for removing the 2- (4-hydroxy butoxy) -tetrahydrofuran by hydrogenation has no universality.
The patent with publication number CN103044197A proposes a process for purifying 1, 4-butanediol and co-producing gamma-butyrolactone, which includes the first decompression rectifying coarse 1, 4-butanediol containing 2- (4-hydroxy butoxy) -tetrahydrofuran, side extracting 1, 4-butanediol product from the rectifying tower, catalytic dehydrogenation of the enriched tower top and tower bottom material to produce gamma-butyrolactone, and final refining to obtain high purity gamma-butyrolactone byproduct. Dehydrogenation, as opposed to hydrogenation, produces flammable and explosive hydrogen gas and also has problems of catalyst poisoning, high equipment and operating costs.
The patent with publication number CN114874074B proposes that alkyl imidazole ionic liquid, aromatic ether compound containing nitro and furan compound containing benzene ring substituent are used as composite extractant, and selective separation of 1, 4-butanediol and 2- (4-hydroxy butoxy) -tetrahydrofuran is realized by adopting extractive distillation, so that high-purity 1, 4-butanediol product is obtained. However, the composite extractant composition is an unusual chemical, is not easy to obtain in the market, and is not suitable for being widely applied in the production process of 1, 4-butanediol.
Disclosure of Invention
The invention provides a process method for refining 1, 4-butanediol aiming at the defects in the prior art, so as to solve the problems in the prior art.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a process method for refining 1, 4-butanediol comprises the following steps:
(1) Sequentially adding a 1, 4-butanediol crude product containing 2- (4-hydroxy butoxy) -tetrahydrofuran, water and sodium bisulphite into a reaction kettle, stirring and heating to react, hydrolyzing the 2- (4-hydroxy butoxy) -tetrahydrofuran under the condition of acidity and water, converting the 2- (4-hydroxy butoxy) -tetrahydrofuran into 1, 4-butanediol and organic sodium sulfonate, and removing the 2- (4-hydroxy butoxy) -tetrahydrofuran in the 1, 4-butanediol crude product after the reaction;
(2) Delivering the kettle liquid after the reaction in the step (1) into a scraper film evaporator, and carrying out reduced pressure distillation to remove organic sodium sulfonate and sodium bisulphite;
(3) Feeding the distillate obtained in the step (2) through reduced pressure distillation into a dehydration rectifying tower, carrying out reduced pressure rectification, and extracting water from the tower top;
(4) And (3) delivering the tower bottom liquid of the dehydration rectifying tower in the step (3) into a finished product rectifying tower, and carrying out reduced pressure rectification to obtain a 1, 4-butanediol finished product from the side line of the tower.
Further, the water added in the step (1) is 0.5-2 times of the mass of the crude product of the 1, 4-butanediol.
Further, the amount of sodium bisulphite added in the step (1) is 2-4 times of the mass of 2- (4-hydroxy butoxy) -tetrahydrofuran in the crude product of the 1, 4-butanediol.
Further, in the step (1), the reaction pressure is normal pressure, the reaction temperature is 50-90 ℃, and the reaction time is 6-12 hours.
Further, in the step (2), the absolute pressure of the operation of the scraper film evaporator is 0.5-5 kPa.
Further, the absolute pressure of the operation of the dehydration rectifying tower in the step (3) is 0.5-3 kPa.
Further, the absolute pressure of the finished product rectifying tower in the step (4) is 0.2-2 kPa.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1. the invention can convert the 2- (4-hydroxy butoxy) -tetrahydrofuran which is difficult to separate from 1, 4-butanediol into 1, 4-butanediol and organic sodium sulfonate which is easy to separate under the conditions of normal pressure and low temperature.
2. The reactant water introduced by the invention is economical, environment-friendly and harmless, and can be recycled; the introduced reactant sodium bisulphite is a common chemical, and is economical and easy to obtain.
3. The equipment used in the invention is conventional equipment, has simple process and is suitable for industrial production.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to illustrate the problem and to explain the invention, and are not intended to limit the invention.
Example 1:
a process method for refining 1, 4-butanediol comprises the following steps:
step (1), adding 2 kg 1, 4-butanediol crude product containing 2- (4-hydroxy butoxy) -tetrahydrofuran 1.07 wt percent, 1 kg water and 0.043 kg sodium bisulphite into a reaction kettle in sequence under normal pressure, heating and stirring, controlling the reaction temperature to 90 ℃, and keeping the temperature to 6 h. 2- (4-hydroxy butoxy) -tetrahydrofuran in the crude 1, 4-butanediol has 0.0214 kg, 2- (4-hydroxy butoxy) -tetrahydrofuran is subjected to hydrolysis and addition reaction in the presence of acid and water, and is converted into 1, 4-butanediol and organic sodium sulfonate, and the 2- (4-hydroxy butoxy) -tetrahydrofuran in the crude 1, 4-butanediol is removed after the reaction;
step (2), the kettle liquid after the reaction in the step (1) is sent into a scraper thin film evaporator, reduced pressure distillation is carried out under the pressure of 0.5 kPa (A), distilled liquid 2.939 kg mainly contains water and 1, 4-butanediol, a small amount of 1, 4-butanediol, organic sodium sulfonate, sodium bisulphite and other non-evaporated components are discharged from the bottom of the scraper thin film evaporator, and organic sodium sulfonate, sodium bisulphite and other solids are removed;
step (3), delivering the distillate obtained in the reduced pressure distillation in the step (2) into a dehydration rectifying tower, performing reduced pressure rectification under the pressure of 0.5 kPa (A), and extracting water from the tower top;
and (4) feeding the tower bottom liquid 1.944 kg of the dehydration rectifying tower in the step (3) into a finished rectifying tower, carrying out reduced pressure rectification under the pressure of 0.2 kPa (A), discharging a small amount of residual water, 1, 4-butanediol and light component impurities from the tower top, discharging a small amount of 1, 4-butanediol and heavy component impurities from the tower bottom, discharging a 1, 4-butanediol finished product 1.857 kg from the side line of the tower, and carrying out purity 99.809 wt percent, wherein the 2- (4-hydroxybutoxy) -tetrahydrofuran content is 0.093 wt percent, and the water content is 0.021 wt percent.
Example 2:
a process method for refining 1, 4-butanediol comprises the following steps:
step (1), adding 2 kg 1, 4-butanediol crude product containing 2- (4-hydroxy butoxy) -tetrahydrofuran 1.07 wt percent, 2.5 kg water and 0.064 kg sodium bisulphite into a reaction kettle in sequence under normal pressure, heating and stirring, controlling the reaction temperature to 70 ℃, and keeping 9 h. 2- (4-hydroxy butoxy) -tetrahydrofuran in the crude 1, 4-butanediol has 0.0214 kg, 2- (4-hydroxy butoxy) -tetrahydrofuran is subjected to hydrolysis and addition reaction in the presence of acid and water, and is converted into 1, 4-butanediol and organic sodium sulfonate, and the 2- (4-hydroxy butoxy) -tetrahydrofuran in the crude 1, 4-butanediol is removed after the reaction;
step (2), the kettle liquid after the reaction in the step (1) is sent into a scraper thin film evaporator, reduced pressure distillation is carried out under the condition of the pressure of 3 kPa (A), distilled liquid 4.415 kg mainly contains water and 1, 4-butanediol, a small amount of 1, 4-butanediol, organic sodium sulfonate, sodium bisulphite and other non-evaporated components are discharged from the bottom of the scraper thin film evaporator, and organic sodium sulfonate, sodium bisulphite and other solids are removed;
step (3), delivering the distillate obtained in the reduced pressure distillation in the step (2) into a dehydration rectifying tower, performing reduced pressure rectification under the pressure of 1.5 kPa (A), and extracting water from the tower top;
and (4) feeding the tower bottom liquid 1.924 kg of the dehydration rectifying tower in the step (3) into a finished rectifying tower, carrying out reduced pressure rectification under the pressure of 1 kPa (A), discharging a small amount of residual water, 1, 4-butanediol and light component impurities from the tower top, discharging a small amount of 1, 4-butanediol and heavy component impurities from the tower bottom, discharging 1, 4-butanediol finished product 1.836 kg from the side line of the tower, and carrying out purity 99.852 wt percent, 2- (4-hydroxy butoxy) -tetrahydrofuran content of 0.038 wt percent and water content of 0.027 wt percent.
Example 3:
a process method for refining 1, 4-butanediol comprises the following steps:
step (1), adding 2 kg 1, 4-butanediol crude product containing 2- (4-hydroxy butoxy) -tetrahydrofuran 1.07 wt percent, 4 kg water and 0.085 kg sodium bisulphite into a reaction kettle in sequence under normal pressure, heating and stirring, controlling the reaction temperature to 50 ℃, and keeping 12 h. 2- (4-hydroxy butoxy) -tetrahydrofuran in the crude 1, 4-butanediol has 0.0214 kg, 2- (4-hydroxy butoxy) -tetrahydrofuran is subjected to hydrolysis and addition reaction in the presence of acid and water, and is converted into 1, 4-butanediol and organic sodium sulfonate, and the 2- (4-hydroxy butoxy) -tetrahydrofuran in the crude 1, 4-butanediol is removed after the reaction;
step (2), the kettle liquid after the reaction in the step (1) is sent into a scraper thin film evaporator and is subjected to reduced pressure distillation under the pressure of 5 kPa (A), distilled liquid is 5.88 kg, mainly contains water and 1, 4-butanediol, a small amount of 1, 4-butanediol, organic sodium sulfonate, sodium bisulfate and other non-evaporated components are discharged from the bottom of the scraper thin film evaporator, and organic sodium sulfonate, sodium bisulfate and other solids are removed;
step (3), delivering the distillate obtained in the reduced pressure distillation in the step (2) into a dehydration rectifying tower, carrying out reduced pressure rectification under the condition that the pressure is 3 kPa (A), and extracting water from the tower top;
and (4) feeding the tower bottom liquid 1.895 and kg of the dehydration rectifying tower in the step (3) into a finished product rectifying tower, carrying out reduced pressure rectification under the pressure of 2 kPa (A), discharging a small amount of residual water, 1, 4-butanediol and light component impurities from the tower top, discharging a small amount of 1, 4-butanediol and heavy component impurities from the tower bottom, discharging a 1, 4-butanediol finished product 1.797 kg from the side line of the tower, and carrying out purity 99.826 wt percent, wherein the 2- (4-hydroxybutoxy) -tetrahydrofuran content is 0.065 wt percent, and the water content is 0.042 wt percent.
The data summary table of the embodiment of the invention is as follows:
according to the table, the purity of the 1, 4-butanediol finished product prepared by the process method is high, the purity is more than 99.8 and wt percent, and the introduced reactant water is economical, environment-friendly and harmless and can be recycled; the introduced reactant sodium bisulphite is a common chemical, and is economical and easy to obtain.
The specific types of the above-mentioned devices are not limited and described in detail, and the deep connection manner of the above-mentioned devices is not described in detail, as it is common knowledge, and it is understood by those skilled in the art.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A process for refining 1, 4-butanediol, which is characterized by comprising the following steps:
(1) Sequentially adding a 1, 4-butanediol crude product containing 2- (4-hydroxy butoxy) -tetrahydrofuran, water and sodium bisulphite into a reaction kettle, stirring and heating to react, hydrolyzing the 2- (4-hydroxy butoxy) -tetrahydrofuran under the condition of acidity and water, converting the 2- (4-hydroxy butoxy) -tetrahydrofuran into 1, 4-butanediol and organic sodium sulfonate, and removing the 2- (4-hydroxy butoxy) -tetrahydrofuran in the 1, 4-butanediol crude product after the reaction;
(2) Delivering the kettle liquid after the reaction in the step (1) into a scraper film evaporator, and carrying out reduced pressure distillation to remove organic sodium sulfonate and sodium bisulphite;
(3) Feeding the distillate obtained in the step (2) through reduced pressure distillation into a dehydration rectifying tower, carrying out reduced pressure rectification, and extracting water from the tower top;
(4) And (3) delivering the tower bottom liquid of the dehydration rectifying tower in the step (3) into a finished product rectifying tower, and carrying out reduced pressure rectification to obtain a 1, 4-butanediol finished product from the side line of the tower.
2. The process for refining 1, 4-butanediol according to claim 1, wherein the water added in the step (1) is 0.5-2 times of the mass of the 1, 4-butanediol crude product.
3. The process for refining 1, 4-butanediol according to claim 1, wherein the amount of sodium bisulphite added in the step (1) is 2-4 times the mass of 2- (4-hydroxy butoxy) -tetrahydrofuran in the crude product of 1, 4-butanediol.
4. The process for refining 1, 4-butanediol according to claim 1, wherein the reaction pressure in the step (1) is normal pressure, the reaction temperature is 50-90 ℃, and the reaction time is 6-12 hours.
5. The process for refining 1, 4-butanediol according to claim 1, wherein the absolute pressure of the operation of the wiped film evaporator in the step (2) is 0.5-5 kPa.
6. The process for refining 1, 4-butanediol according to claim 1, wherein the absolute pressure of the dehydration rectifying column operation in the step (3) is 0.5-3 kPa.
7. The process for refining 1, 4-butanediol according to claim 1, wherein the absolute pressure of the finished product rectifying tower in the step (4) is 0.2-2 kPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311803833.7A CN117843444A (en) | 2023-12-26 | 2023-12-26 | Process method for refining 1, 4-butanediol |
Applications Claiming Priority (1)
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