CN109867587B - Preparation method of 3-chloro-1,2-propanediol - Google Patents
Preparation method of 3-chloro-1,2-propanediol Download PDFInfo
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- CN109867587B CN109867587B CN201711249740.9A CN201711249740A CN109867587B CN 109867587 B CN109867587 B CN 109867587B CN 201711249740 A CN201711249740 A CN 201711249740A CN 109867587 B CN109867587 B CN 109867587B
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- hydrogen peroxide
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- propanediol
- epichlorohydrin
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- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 29
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 18
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000011973 solid acid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 if it is two Inorganic materials 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims 4
- PVYDNJADTSAQQU-UHFFFAOYSA-N prop-1-ene;hydrochloride Chemical compound Cl.CC=C PVYDNJADTSAQQU-UHFFFAOYSA-N 0.000 claims 3
- 238000005292 vacuum distillation Methods 0.000 claims 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IJOMNBGOXZTBBJ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl.OCC(O)CCl IJOMNBGOXZTBBJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供的一种3氯‑1,2‑丙二醇的制备方法，是以过氧化氢为氧源、反应控制相转移催化剂催化氯丙烯生成环氧氯丙烷再经过水解制备3氯‑1,2‑丙二醇，制备过程主要包含以环氧化反应、水解反应及产品提纯下三个步骤，得到含量为99.9％以上产品3氯‑1,2‑丙二醇，该方法工艺简单、产品纯度高、易于生产。The present invention provides a method for preparing 3-chloro-1,2-propanediol, which uses hydrogen peroxide as an oxygen source, a reaction-controlled phase-transfer catalyst catalyzes chloropropene to generate epichlorohydrin, and then undergoes hydrolysis to prepare 3-chloro-1,2-propanediol. Propanediol, the preparation process mainly includes the next three steps of epoxidation reaction, hydrolysis reaction and product purification, to obtain the product 3-chloro-1,2-propanediol with a content of more than 99.9%, the method has simple process, high product purity, and easy production .
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a preparation method of 3-chloro-1, 2-propanediol.
Background
3-chloro-1,2-propanediol (3-chloro-1,2-propanediol), commonly known as 3-chloro-1, 2-dihydroxypropane, having the molecular formula C3H7CIO2And the molecular weight is 110.55. Can be used as an organic synthesis intermediate to synthesize pesticides, medicines, coatings, plasticizers, surfactants and the like; at present, the synthesis of 3-chloro-1,2-propanediol mainly comprises an epichlorohydrin hydrolysis method and a glycerol chlorination method.
The glycerol chlorination method is to add glycerol and acetic acid into a reaction kettle, stir and heat the mixture to 90-95 ℃, introduce dry hydrogen chloride gas until the weight of the reaction liquid is increased to 150% (theoretical value), and the end point is obtained. And carrying out reduced pressure distillation to obtain a crude product. Then the 3-chloro-1,2-propanediol is obtained by collecting the 128-phase 132 ℃ (1.33-2.67kPa) fraction. The glycerol method has the disadvantages that more byproducts are produced, the content and purity of the product are difficult to reach more than 99.5 percent, and hydrogen chloride gas has high requirements on equipment and large investment.
The epoxy chloropropane hydrolysis method is to add epoxy chloropropane into a reaction pot, stir, add dilute sulphuric acid to make the reaction solution acidic, heat up, reflux for 1h, and rectify the obtained product under reduced pressure to obtain the finished product. Although the epichlorohydrin hydrolysis method is a mature method at home and abroad, the defects are that the traditional chlorohydrin method production of raw material epichlorohydrin is difficult to meet the national requirements of energy conservation, emission reduction and environmental protection, in addition, organic acid is used as a catalyst, side reaction is generated to reduce the yield, and the subsequent process is easily affected by the addition of alkali to adjust the pH value, so that the process parameters are difficult to adjust and control, the solid waste is increased, and the like.
CN201010011544.X discloses a production method of high-purity 3-chloro-1,2-propanediol, which comprises the following steps: (1) respectively dissolving sulfuric acid, benzenesulfonic acid and succinic acid in deionized water to prepare a sulfuric acid solution, a benzenesulfonic acid solution and a succinic acid solution; (2) mixing and reacting part of sulfuric acid solution, part of benzenesulfonic acid solution and part of epichlorohydrin for a period of time, raising the temperature, adding the rest of epichlorohydrin, sequentially adding the rest of benzenesulfonic acid solution and sulfuric acid solution in different periods of time, adding succinic acid solution at one time, and raising the temperature to continue reacting; (3) after the hydrolysis reaction is finished, adding an alkali solution, and stirring to ensure that the reaction is uniform; (4) dehydrating the hydrolysate after the alkali is added, adding the alkali solution after the dehydration, and heating under the stirring condition; (5) heating the material under vacuum condition, transferring into a distillation system, and distilling to obtain the product 3-chloro-1,2-propanediol when the vacuum degree is more than or equal to 0.1 MPa. The method has the defects that in the hydrolysis process of the epichlorohydrin, organic acid is used as a catalyst, side reaction can occur until the yield is reduced, and the addition of alkali after the hydrolysis reaction is finished to adjust the pH value easily causes adverse effects such as difficult adjustment and control of process parameters, increase of solid wastes and the like on a subsequent process.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects of the existing 3-chloro-1,2-propanediol production technology, the preparation method of the 3-chloro-1,2-propanediol with few byproducts, simple, green and environment-friendly process and high product purity is provided.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the method takes hydrogen peroxide as an oxygen source, controls a reaction and controls a phase transfer catalyst to catalyze chloropropene to generate epichlorohydrin, and then prepares the 3-chloro-1,2-propanediol by hydrolysis. The preparation process mainly comprises the following three steps of epoxidation reaction, hydrolysis reaction and product purification:
epoxidation reaction: in the presence of a reaction control phase transfer catalyst, performing chloropropene epoxidation reaction to prepare epoxy chloropropane, wherein the molar ratio of chloropropene to hydrogen peroxide is 1.5-4.5: 1; the reaction temperature is
40-65 ℃; the reaction time is 2-6 h; the reaction pressure is 0.1-1 MPa; the hydrogen peroxide is a hydrogen peroxide solution with the mass concentration of 15-50%.
And (3) hydrolysis reaction: continuously adding hydrogen peroxide, deionized water and a solid acid catalyst into the obtained epoxidation reaction material for reaction, wherein the molar ratio of the epoxidation product epoxy chloropropane to the hydrogen peroxide is 1.5-4.5: 1; the mol ratio of epoxy chloropropane of an epoxidation product to deionized water is 0.5-1.5: 1, and the reaction temperature is 45-95 ℃; the reaction time is 2-4 h; the reaction pressure is 0.1-1.5 MPa.
And (3) product purification: washing the hydrolysis reaction material by chloropropene, and then carrying out reduced pressure distillation to remove chloropropene, water and epichlorohydrin in the reaction liquid to obtain the product 3 chloro-1, 2-propanediol. The adding mass of the washing chloropropene is 0.5-2 times of that of the solid acid catalyst hydrolysis reaction material separated by filtering, the vacuum degree of reduced pressure distillation is 1000-200 KPa, and the temperature of reduced pressure distillation is 65-120 ℃.
Separating the reaction control phase transfer catalyst from reaction liquid after the epoxidation reaction of generating epoxy chloropropane by catalyzing chloropropene by the reaction control phase transfer catalyst, and recycling the reaction control phase transfer catalyst for the epoxidation reaction; the reaction-controlled phase transfer catalyst is [ pi-C5H5NC16H33]3(PO4)(WO3)4]。
The solid acid catalyst used in the hydrolysis reaction is commercial SiO2-Al2O3Or B2O3-Al2O3One or two, if two, SiO2-Al2O3And B2O3-Al2O3The mass ratio is 0.5-2: 1.
The product purification hydrolysis reaction material is a solid acid catalyst reaction material which is obtained by filtering and separating after the hydrolysis reaction is finished, and the solid acid catalyst is recycled for the hydrolysis reaction.
By adopting the technical scheme, the invention has the beneficial effects that:
1. hydrogen peroxide is used as an oxygen source, and a phase transfer catalyst is controlled to react to catalyze chloropropene to generate epichlorohydrin, so that the pollution influence of the traditional chlorohydrin method production process of epichlorohydrin is overcome, and the requirements of energy conservation, emission reduction and environmental protection advocated by the state are met;
2. the solid acid catalyst is used for replacing inorganic acid, carboxylic acid or benzene sulfonic acid for hydrolysis of epoxy chloropropane, so that the conversion rate of epoxy chloropropane is improved, hydrolysis by-products are reduced, waste acid discharge is reduced, and the solid acid catalyst can be recycled.
3. Alkali is not needed to be added for adjusting the pH value, the production process is simplified, and the solid waste discharge is reduced.
4. The purity of the obtained 3-chloro-1,2-propanediol product is more than or equal to 99.9 percent.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Example 1
300g of chloropropene and 90g of 50% aqueous hydrogen peroxide solution are added into a 1000ml reaction kettle, and 20g of reaction control phase transfer catalyst [ pi-C ] is added5H5NC16H33]3(PO4)(WO3)4]The reaction temperature is 45 ℃, the reaction pressure is 0.5MPa, and after 2.5 hours of reaction, the reaction materials are centrifugally separated and recovered to control the phase transfer catalyst.
Continuously adding 90g of aqueous solution of hydrogen peroxide with the mass concentration of 50%, 400g of deionized water and a solid acid catalyst B into the material containing the epoxy chloropropane2O3-Al2O35g of the mixture is reacted for 2 hours at the temperature of 75 ℃, and the reaction pressure is 1.5 MPa.
And after the hydrolysis reaction is finished, filtering and separating out solid acid catalyst reaction materials, washing the filtrate by 300g of chloropropene, and then carrying out reduced pressure distillation, wherein the vacuum degree of the reduced pressure distillation is 400KPa, the reduced pressure distillation temperature is 110 ℃, 290g of 3-chloro-1,2-propanediol product is obtained, the chroma of the product is less than or equal to 15, the purity of the product is 99.97% by GC analysis, the low-boiling content is less than or equal to 0.01%, the high-boiling content is less than or equal to 0.02%, and the moisture is less than or equal to 300 ppm.
Example 2
300g of chloropropene and 90g of 50% aqueous hydrogen peroxide solution are added into a 1000ml reaction kettle, and 20g of reaction control phase transfer catalyst [ pi-C ] is added5H5NC16H33]3(PO4)(WO3)4]The reaction temperature is 45 ℃, the reaction pressure is 0.5MPa, and after 2.5 hours of reaction, the reaction materials are centrifugally separated and recovered to control the phase transfer catalyst.
The preparation method comprises the steps ofAdding 120g of 50% hydrogen peroxide aqueous solution, 300g of deionized water and a solid acid catalyst SiO into the alkane material2-Al2O35g of the mixture is reacted for 1.5h at the temperature of 75 ℃, and the reaction pressure is 1.0 MPa.
And filtering and separating solid acid catalyst reaction materials after the hydrolysis reaction is finished, washing the filtrate by 350g of chloropropene, and then carrying out reduced pressure distillation, wherein the vacuum degree of the reduced pressure distillation is 200KPa, the reduced pressure distillation temperature is 120 ℃, 320g of 3-chloro-1,2-propanediol product is obtained, the chroma of the product is less than or equal to 15, the purity of the product is 99.98 percent by GC analysis, the low-boiling content is 0.00 percent, the high-boiling content is less than or equal to 0.02 percent, and the moisture is less than or equal to 200 ppm.
Claims (3)
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| CN112899315B (en) * | 2019-12-12 | 2022-11-18 | 上海安谱实验科技股份有限公司 | Synthesis method of stable isotope labeled 3-chloro-1, 2-propylene glycol fatty acid diester |
| CN111943805A (en) * | 2020-09-16 | 2020-11-17 | 安徽工业大学 | Preparation method of (R) -3-chloro-1, 2-propanediol |
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2017
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