CN116041281A - Industrial production method and device of glycidol - Google Patents
Industrial production method and device of glycidol Download PDFInfo
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- CN116041281A CN116041281A CN202211541149.1A CN202211541149A CN116041281A CN 116041281 A CN116041281 A CN 116041281A CN 202211541149 A CN202211541149 A CN 202211541149A CN 116041281 A CN116041281 A CN 116041281A
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- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000009776 industrial production Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 44
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 26
- 230000008020 evaporation Effects 0.000 claims abstract description 23
- 238000007670 refining Methods 0.000 claims abstract description 22
- 239000012074 organic phase Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000010992 reflux Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 42
- 238000010533 azeotropic distillation Methods 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 33
- 238000011084 recovery Methods 0.000 claims description 24
- 239000012071 phase Substances 0.000 claims description 21
- 238000012856 packing Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 10
- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical compound CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 238000007033 dehydrochlorination reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 238000000998 batch distillation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/36—Azeotropic distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses an industrial production method and device of glycidol. The industrial production method comprises the following steps: 3-chloro-1, 2-propanediol and azeotropic solvent are mixed in a reaction kettle in advance according to a certain proportion, then aqueous solution of sodium hydroxide is continuously added into the system in a dropwise manner under the vacuum condition, the system is kept in a boiling reflux state for reaction, and water in the system is continuously removed from the system; after the reaction is finished, the reaction solution is further centrifugally filtered, the obtained filtrate enters a wiped film evaporation device, and the filtrate is evaporated under high vacuum to obtain an organic phase and a heavy component; the heavy component is discharged from the bottom of the wiped film evaporator; and evaporating the organic phase from the top of the wiped film evaporator, and condensing the organic phase to enter a glycidol rectifying, refining and purifying system to obtain a glycidol product. The method has the advantages of simplicity, easiness in operation, easiness in serialization, easiness in obtaining raw materials, low cost, high safety coefficient, environment friendliness, high product purity, high reaction yield and the like.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to an industrial production method and device of glycidol.
Background
Glycidol, namely 2, 3-epoxy-1-propanol, 2, 3-epoxy propanol contains two functional groups of epoxy group and hydroxyl group in the molecule, can be used as an intermediate for synthesizing surfactants, elastomers, plastics, resins, dyes, paint and the like, can be widely used for extracting and separating various solvents, and has derivatives as industrial raw materials of pesticides, plastics, resins, medicines, assistants and the like.
Commercial processes known at home and abroad for preparing glycidol include an allyl alcohol oxidation process and a 3-chloro-1, 2-propanediol low temperature dehydrochlorination process. The allyl alcohol oxidation method adopts allyl alcohol and hydrogen peroxide as raw materials, epoxidation is carried out under the condition of a catalyst to prepare glycidol, but the allyl alcohol required by the route is obtained by epoxidation of propylene into propylene oxide and then isomerization, so that the cost of the glycidol obtained by the route is high, and the initial raw material propylene is a non-renewable resource. The dehydrochlorination method using 3-chloro-1, 2-propanediol as raw material can prepare the raw material 3-chloro-1, 2-propanediol by the reaction of glycerol and hydrogen chloride, the glycerol is a raw material which can be derived from biology, the cost is low, the sustainable development is high, therefore, the glycidol industry development of the route has more and more important green development prospect. The traditional dehydrochlorination method of 3-chloro-1, 2-propanediol uses methylene dichloride as a solvent, solid sodium hydroxide is added for reaction, crude products obtained by the reaction are filtered for desalting, and then reduced pressure distillation is carried out to obtain glycidol. The method relates to the feeding of solid materials in the industrial process, is difficult to realize continuous and large-scale production, and the reaction system relates to solid phase, so that the dissolution of the solid takes time, the reaction time is long, glycidol is easy to self-polymerize in the presence of acid, alkali or salt, and the yield of the glycidol is seriously reduced due to the long reaction time, and even safety accidents occur.
Chinese patent (application No. 201210548907.2) provides a method for synthesizing glycidol, which adopts methylene dichloride as a solvent, 40% sodium hydroxide solution and catalyst amount of tetrabutylammonium chloride are reacted with 3-chloro-1, 2-propanediol at 80 ℃, and anhydrous calcium chloride is used for dehydration and drying after the reaction is finished. Under the temperature condition, the method can lead to obvious ring-opening degradation of glycidol due to the existence of a large amount of water and metal ions, and the dehydration operation of a large amount of anhydrous calcium chloride has no operability of large-scale industrial production, and the production and treatment cost is high. Korean patent (KR 2004/002093) uses fine-grained phosphate instead of sodium hydroxide, and uses methylene chloride as a solvent, and the resulting solution is desalted and distilled under reduced pressure to obtain glycidol. Because water is generated in the reaction process, the crude product still contains a small amount of salt in the reduced pressure distillation process, the problem of ring-opening self-polymerization of glycidol in the presence of the salt in the distillation process is not solved, and meanwhile, the phosphate is still fed in solid form, so that the industrial continuity is difficult to realize. The domestic patent (CN 106588820A) adopts 3-chloro-1, 2-propanediol and 95% ethanol solution of sodium hydroxide to react, and after the reaction is finished, most sodium chloride solid is removed by centrifugal filtration, and then the crude product is concentrated by multiple short-range thin film evaporation to obtain glycidol. Although the method avoids the problem of hydrolysis of glycidol under the existence of a large amount of water and metal salts, a plurality of defects still exist, firstly, the problem of feeding operability of solid sodium hydroxide and the problem of slow dissolution of the solid sodium hydroxide in ethanol still cannot be avoided, secondly, because 95% of ethanol is adopted as a solvent, water is generated in the reaction process, the composition (the water content is more than 5%) of the solution is positioned at one side of the composition of the lowest azeotropic system of ethanol and water (the water content is more than 5%) and the water, the water in the tower kettle cannot be removed completely by adopting common rectification, and finally, the glycerin product still contains about 1% of water after multiple film evaporation concentration, so that a small amount of metal salts still cannot be removed in the glycerin product, not only the yield of the glycidol in the evaporation process is reduced, but also the long-term stable storage of the product is brought into safety risks. The domestic patent (CN 104844463B) adopts 3-chloro-1, 2-propanediol and methanol solution of sodium methoxide to react in a tower reactor, most sodium chloride solid is removed by centrifugal filtration after the reaction is finished, and then the crude product is subjected to batch rectification to obtain a glycidol finished product. The method avoids the problems of feeding and dissolving sodium hydroxide, but the cost of sodium methoxide is higher than that of sodium hydroxide, and because water is generated in the reaction process, methanol is firstly distilled out in the intermittent purification process, and the residual water in the intermittent distillation kettle and the dissolved metal salt in the water can lead to ring-opening self-polymerization of glycidol, thereby reducing the yield of glycidol and having safety risks.
Disclosure of Invention
The invention aims to provide an industrial production method and device of glycidol. The method has the advantages of simplicity, easiness in operation, easiness in serialization, easiness in obtaining raw materials, low cost, high safety coefficient, low reaction temperature, high reaction purity and yield and the like.
An industrial production method of glycidol comprises the following steps:
(1) 3-chloro-1, 2-propanediol and azeotropic solvent are mixed in a reaction kettle in advance according to a certain proportion, then aqueous solution of sodium hydroxide is continuously added into the system in a dropwise manner under the vacuum condition, the system is kept in a boiling reflux state for reaction, and water is removed at the same time;
(2) After the reaction is finished, the reaction solution is further centrifugally filtered, the obtained filtrate enters a wiped film evaporation device, and the filtrate is evaporated under high vacuum to obtain an organic phase and a heavy component; the organic phase is a crude glycidol product and comprises alkali metal chloride, water, azeotropic solvent, residual 3-chloro-1, 2-propanediol, byproducts and the like besides glycidol; the heavy component is mainly sodium chloride and is discharged from the bottom of the wiped film evaporator;
(3) And evaporating the organic phase from the top of the wiped film evaporator, condensing, and refining in a glycidol rectifying system to obtain a glycidol product.
Preferably, the reaction kettle in the step (1) is connected with an azeotropic distillation tower, a gas phase generated during boiling reflux of the system enters the azeotropic distillation tower from the reaction kettle to be further condensed, then enters a liquid-liquid layering device to be layered, an upper organic phase (azeotropic solvent phase) returns into the azeotropic distillation tower in a reflux mode, so that glycidol is prevented from being carried out, and a lower aqueous phase enters a solvent recovery tower to recover azeotropic solvent.
More preferably, the azeotropic distillation tower is a reflux distillation tower with a filler, and the reflux organic phase enters the azeotropic distillation tower from a liquid distributor at the top of the azeotropic distillation tower for reuse.
More preferably, the solvent recovery tower is a continuous rectification tower or a batch rectification tower, and the water after the azeotropic solvent is recovered is discharged into a sewage system or is recycled as reclaimed water.
Preferably, the reaction temperature of the step (1) is 10-40 ℃ and the reaction residence time is 0.5-3 hours. Within the above temperature range, the higher the temperature, the shorter the corresponding desired reaction residence time. If the temperature is below this range, the reaction rate is too slow; above this range, an increase in byproducts results. The residence time of the reaction is too long, which results in a series of cascade reactions of glycidol.
Preferably, the azeotropic solvent of step (1) comprises n-butanol, sec-butanol, isobutanol, methyl isobutyl ketone, benzene, n-heptane, toluene, 1, 2-dichloroethane, cyclohexane or a combination thereof.
The organic solvent has the following advantages: A. forming an azeotrope with water having the lowest azeotropic point, effectively carrying water, and forming an insoluble or partially miscible two-phase system with water; B. the boiling point of the product is obviously different from the boiling point of glycidol (163 ℃) under normal pressure, thus being beneficial to the subsequent separation from the product, and generally, the boiling point difference between the product and the glycidol is not lower than 15 ℃, and an azeotrope is not formed between the product and the glycidol; C. is not reacted with reactants or products under process operating conditions; D. the viscosity is low, the viscosity of the system is favorably adjusted, and the subsequent filtering operation is convenient.
Preferably, the concentration of sodium hydroxide is 30-50%, more preferably, 30% sodium hydroxide solution which is common in industry can be used as the reaction material.
Preferably, the molar ratio of the azeotropic solvent to 3-chloro-1, 2-propanediol in step (1) is 0.50-2.5:1.
Preferably, the molar ratio of 3-chloro-1, 2-propanediol to sodium hydroxide in step (1) is 1.01-1.30:1; more preferably, the molar ratio of the two is 1.05-1.15:1.
Preferably, 3-chloro-1, 2-propanediol in the step (1) has R-type or S-type optical activity, and the corresponding optical activity glycidol product is obtained.
Preferably, the azeotropic solvent and 3-chloro-1, 2-propanediol are recovered in the step (3) and recycled to the reaction system.
The invention also provides a device for the industrial production method of glycidol, which comprises a reaction kettle, a centrifugal filtering device, a wiped film evaporator, a first condenser and a glycidol rectifying system;
the reaction kettle is provided with a mechanical stirring device, the top of the reaction kettle is provided with a liquid-alkali solution continuous feed inlet, and the bottom of the reaction kettle is provided with a reaction solution outlet;
the inlet of the centrifugal filter device is connected with the reaction liquid outlet of the reaction kettle, and the filtrate outlet is connected with the inlet of the wiped film evaporation device;
the top of the film scraping evaporation device is provided with an organic phase outlet which is connected with the inlet of the first condenser, and the bottom of the film scraping evaporation device is provided with a heavy component discharge outlet;
the outlet of the first condenser is connected with the glycidyl rectification system, and the glycidyl rectification system is a glycidyl continuous rectification system or a glycidyl batch rectification tower.
Preferably, the top of the reaction kettle is connected with an azeotropic distillation tower, the top of the azeotropic distillation tower is a gas phase outlet, the azeotropic distillation tower is connected with a second condenser and a liquid-liquid layering device, an organic phase outlet of the liquid-liquid layering device is connected with a liquid distributor at the top of the azeotropic distillation tower, and a water phase outlet of the liquid-liquid layering device is connected with a solvent recovery tower.
Preferably, the glycidol continuous rectification system comprises a light component removing tower, a glycidol refining tower and a chloropropane recovery tower which are connected in sequence; the light component removing tower is used for removing azeotropic solvent, the azeotropic solvent is extracted from the top of the light component removing tower, and the bottom material of the light component removing tower enters the glycidol refining tower; the glycidol refining tower is used for extracting high-purity glycidol from the top, the purity of the glycidol can reach more than 99.0%, the bottom material of the glycidol is fed into the chloropropanol recovery tower, the chloropropanol recovery tower is used for recovering excessive 3-chloro-1, 2-propanediol reactant, and the bottom of the chloropropanol recovery tower is rectification residual liquid.
Preferably, the column internals of the glycidol refining column use low pressure drop structured packing or random packing suitable for high vacuum, including but not limited to structured BX wire mesh packing. Through the selection, the kettle temperature can be reduced, and the yield of glycidol can be improved.
The working principle of the invention is as follows:
the beneficial effects of the invention are as follows:
(1) The invention adopts sodium hydroxide aqueous solution as reaction material, solves the problems of solid sodium hydroxide feeding and dissolution, has convenient operation and easily obtained raw materials, and is easy to realize industrial production continuity.
(2) The water is carried by azeotropic solvent in the reaction process, the water generated in the reaction process and the water carried by liquid alkali solution are removed from the system by the azeotropic solvent, the reaction system is always controlled to maintain low water content, and the side reaction of ring-opening hydrolysis of the glycidol product under the condition is greatly reduced.
(3) The reaction kettle is connected with the azeotropic distillation tower, has low reaction temperature, and effectively inhibits side reactions such as polymerization, hydrolysis and the like of glycidol. Meanwhile, the reaction process is always in a boiling reflux state, and the heat released by the reaction can be used as a heat source of an azeotropic rectification reboiler, so that not only is energy-saving, but also the heat removal capability is strong, the safety coefficient is increased, the hot air risk level of the reaction is reduced, and the possibility of explosion is reduced.
(4) According to the invention, a small amount of alkali metal chloride remained in the crude product is removed by adopting a wiped film evaporator before refining the glycidol, so that the stability of the glycidol in the subsequent rectifying operation stage is greatly improved, and the yield (> 90.0%) of the glycidol is improved.
(5) According to the invention, before refining the glycidol, water and salt are removed, so that the stability of the glycidol under the refining operation condition is increased, and the high-purity glycidol (> 99.0%) can be obtained.
(6) The azeotropic solvent and unreacted 3-chloro-1, 2-propanediol in the process of the invention realize high recycling rate, and a small amount of solvent in the wastewater is recycled before the wastewater is discharged or reclaimed water is recycled, so the whole process is energy-saving and environment-friendly, has little environmental pollution, and can be used for large-scale industrial production.
Drawings
FIG. 1 is a continuous industrial production flow of glycidol.
FIG. 2 shows a batch industrial process flow of glycidol.
Reference numerals:
1 a reaction kettle, 2 an azeotropic distillation tower, 3 a second condenser, 4 a liquid-liquid separator, 5 a centrifugal filter device, 6 a wiped film evaporator, 7 a first condenser, 8 a light component removal tower, 9 a glycidol refining tower, 10 a chloropropane recovery tower, 11 a solvent recovery tower, 12 a glycidol batch distillation tower and 13 a solvent batch recovery tower.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1 Process and apparatus for industrially producing glycidol (continuous process)
The production flow adopted in this example is shown in fig. 1. As shown in FIG. 1, the intermittent industrial production device for glycidol comprises a reaction kettle 1, an azeotropic distillation tower 2, a second condenser 3, a liquid-liquid layering device 4, a centrifugal filter device 5, a scratch film evaporator 6, a first condenser 7, a light component removing tower 8, a glycidol refining tower 9, a chloropropanol recovery tower 10 and a solvent recovery tower 11. The reaction kettle 1 is provided with a mechanical stirring device, and a liquid-alkali solution continuous feed inlet is arranged at the top of the reaction kettle 1. The top of the reaction kettle 1 is connected with an azeotropic distillation tower 2, the top of the azeotropic distillation tower 2 is a gas phase outlet, the gas phase outlet is connected with a second condenser 3 and a liquid-liquid separator 4, an organic phase outlet of the liquid-liquid separator 4 is connected with a liquid distributor at the top of the azeotropic distillation tower 2, and an aqueous phase outlet of the liquid-liquid separator 4 is connected with a solvent recovery tower 11. The bottom of the reaction kettle 1 is provided with a reaction liquid outlet; the inlet of the centrifugal filter device 5 is connected with the reaction liquid outlet of the reaction kettle 1, and the filtrate outlet is connected with the inlet of the wiped film evaporation device 6; the top of the wiped film evaporation device 6 is provided with an organic phase outlet which is connected with the inlet of the first condenser 7, and the bottom of the wiped film evaporation device 6 is provided with a heavy component discharge outlet; the outlet of the first condenser 7 is connected to the light component removal column. The light component removing tower 8 is used for removing azeotropic solvent, the azeotropic solvent is extracted from the top of the light component removing tower 8, and the bottom material of the light component removing tower 8 enters the glycidol refining tower 9; the glycidol refining tower 9 is used for extracting high-purity glycidol from the top, the material at the bottom of the glycidol refining tower 9 enters the chloropropanol recovery tower 10 for recovering excessive 3-chloro-1, 2-propanediol reactant, and the bottom of the glycidol refining tower is rectification residual liquid.
In this example, the azeotropic distillation column 2 had a diameter of 800mm, and 3 m of a regular BX wire gauze packing (packing specific surface area 500m was installed in the column 2 /m 3 ). The diameter of the light component removing tower 8 is 600mm, the packing of the rectifying section is BX structured packing, the height is 2.5 m, and the height of the stripping section BX structured packing is 1.5 m. The diameter of the glycidol refining tower 9 is 700mm, the packing of the rectifying section is BX structured packing, the height is 4 meters, and the height of the stripping section BX structured packing is 2.5 meters. And the chloropropylene glycol recovery tower 10 has a tower diameter of 700mm, the packing of the rectifying section is BX structured packing, the height is 3 meters, and the height of the stripping section BX structured packing is 3 meters.
In the following, according to the flow shown in fig. 1, a specific industrial process comprises the following steps:
(1) After the reaction vessel 1 was inertized with nitrogen, 2000Kg of 3-chloro-1, 2-propanediol was pumped into the reaction vessel 1. The autoclave was cooled to 20℃with 5℃cooling water, and 4200Kg of isobutanol was then pumped into the autoclave 1 by a pump. And (3) opening a cooling water valve at 5 ℃ of a second condenser 3 at the top of the azeotropic distillation tower 2, starting a vacuum pump to reduce the pressure in the reaction kettle 1 to 20mmHg, heating the reaction kettle 1, and maintaining the kettle temperature at 20-25 ℃, wherein isobutanol begins to vaporize and the tower top totally flows back. 2200kg of 30% aqueous alkali is dripped from the overhead tank at 1470kg/hr, the whole dripping process is about 1.5 hours, the kettle temperature is controlled between 20 ℃ and 25 ℃, and the system is kept in a boiling reflux state all the time.
(2) The evaporated gas phase (azeotrope of isobutanol and water) is condensed by a second condenser 3 at the top of the azeotropic distillation tower 2, then enters a liquid-liquid layering device 4 for automatic layering, the organic phase (mainly isobutanol) at the upper layer overflows to a receiving tank with the volume of 2 cubic meters, isobutanol in the receiving tank flows back to the azeotropic distillation tower 2 by a pump, and the liquid level of the receiving tank is constant by controlling the reflux flow. The water phase at the lower layer of the liquid-liquid separator 4 enters a temporary storage tank, and isobutanol in the water phase is recovered by a solvent recovery tower 11 before the water phase is discharged into a sewage system.
(3) After the reaction is finished, the reaction solution is centrifugally filtered, a large amount of generated sodium chloride solids are removed, and the filtrate enters a mother liquor tank. The filter cake was washed with 100kg of isobutanol before each cake discharge. After the completion of the washing, the total amount of isobutanol was 600Kg, and the whole was incorporated into the mother liquor, and the total amount of the mother liquor was 5570Kg. The obtained mother liquor enters a wiped film evaporation device 6 at a feed rate of 300kg/hr per hour, and most of organic matters, namely crude glycidol, also comprises alkali chloride, water, azeotropic solvent, residual 3-chloro-1, 2-propanediol, byproducts and the like are distilled out. The pressure of the wiped film evaporator 6 is 1mmHg, the backwater temperature of the wiped film evaporator 6 is 90 ℃, and the total weight of heavy components (residual liquid) after wiped film evaporation is about 75Kg, and the main components are sodium chloride and a small amount of 3-chloro-1, 2-propanediol.
(4) The crude product after the wiped film evaporation enters a light component removing tower 8 at 1500kg/hr, the operating pressure at the top of the tower is 100mmHg, the temperature at the top of the tower is about 53-54 ℃, and the water content in the isobutanol is about 2.5%. The material coming out of the tower bottom of the light component removing tower 8 enters a glycidol refining tower 9 with a feeding amount of 600kg/hr by a pump, the tower top operation pressure is 5mmHg, the tower top temperature is 44 ℃, and the glycidol content is more than 99.0 percent. The material coming out of the column bottom of the glycidol refining column 9 enters a chloropropanol recovery column 10 with the feeding amount of 120kg/hr, the operation pressure at the top of the column is 1mmHg, the temperature at the top of the column is 71 ℃, and the content of the chloropropanol obtained at the top of the column is about 88%.
The molar yield of glycidol relative to 3-chloro-1, 2-propanediol in this example was calculated to be 93%.
Example 2 Industrial production method and apparatus of glycidol (batch Process)
The production flow adopted in this example is shown in fig. 2. As shown in fig. 2, the glycidol batch industrial production device comprises a reaction kettle 1, an azeotropic distillation tower 2, a second condenser 3, a liquid-liquid separator 4, a centrifugal filter device 5, a wiped film evaporator 6, a first condenser 7, a glycidol batch distillation tower 12 and a solvent batch recovery tower 13. The reaction kettle 1 is provided with a mechanical stirring device, and a liquid-alkali solution continuous feed inlet is arranged at the top of the reaction kettle 1. The top of the reaction kettle 1 is connected with an azeotropic distillation tower 2, the top of the azeotropic distillation tower 2 is a gas phase outlet, the gas phase outlet is connected with a second condenser 3 and a liquid-liquid separator 4, an organic phase outlet of the liquid-liquid separator 4 is connected with a liquid distributor at the top of the azeotropic distillation tower 2, and an aqueous phase outlet of the liquid-liquid separator 4 is connected with a solvent intermittent recovery tower 13. The bottom of the reaction kettle 1 is provided with a reaction liquid outlet; the inlet of the centrifugal filter device 5 is connected with the reaction liquid outlet of the reaction kettle 1, and the filtrate outlet is connected with the inlet of the wiped film evaporation device 6; the top of the wiped film evaporation device 6 is provided with an organic phase outlet which is connected with the inlet of the first condenser 7, and the bottom of the wiped film evaporation device 6 is provided with a heavy component discharge outlet; the outlet of the first condenser 7 is connected with the glycidol batch rectifying tower 12. In this example, the azeotropic distillation column 2 had a diameter of 800mm, and 3 m of a regular BX wire gauze packing (packing specific surface area 500m was installed in the column 2 /m 3 )
In the following, according to the flow shown in fig. 2, a specific industrial process includes the following steps:
(1) After the reaction vessel 1 was inertized with nitrogen, 2000Kg of 3-chloro-1, 2-propanediol was pumped into the reaction vessel 1. The autoclave was cooled to 20℃with 5℃cooling water, and 4200Kg of isobutanol was then pumped into the autoclave 1 by a pump. And (3) opening a cooling water valve at 5 ℃ of a second condenser 3 at the top of the azeotropic distillation tower 2, starting a vacuum pump to reduce the pressure in the reaction kettle 1 to 20mmHg, heating the reaction kettle 1, and maintaining the kettle temperature at 20-25 ℃, wherein isobutanol begins to vaporize and the tower top totally flows back. 2200kg of 30% aqueous alkali is dripped from the overhead tank at 1470kg/hr, the whole dripping process is about 1.5 hours, the kettle temperature is controlled between 20 ℃ and 25 ℃, and the system is kept in a boiling reflux state all the time.
(2) The evaporated gas phase (azeotrope of isobutanol and water) is condensed by a second condenser 3 at the top of the azeotropic distillation tower 2, then enters a liquid-liquid layering device 4 for automatic layering, the organic phase (mainly isobutanol) at the upper layer overflows to a receiving tank with the volume of 2 cubic meters, isobutanol in the receiving tank flows back to the azeotropic distillation tower 2 by a pump, and the liquid level of the receiving tank is constant by controlling the reflux flow. The water phase at the lower layer of the liquid-liquid separator 4 enters a temporary storage tank, and isobutanol in the water phase is recovered by a solvent batch recovery tower 13 before the water phase is discharged into a sewage system.
(3) After the reaction is finished, the reaction solution is centrifugally filtered, a large amount of generated sodium chloride solids are removed, and the filtrate enters a mother liquor tank. The filter cake was washed with 100kg of isobutanol before each cake discharge. After the completion of the washing, the total amount of isobutanol was 600Kg, and the whole was incorporated into the mother liquor, and the total amount of the mother liquor was 5570Kg. The obtained mother liquor enters a wiped film evaporation device 6 at a feed rate of 300kg/hr per hour, and most of organic matters, namely crude glycidol, also comprises alkali chloride, water, azeotropic solvent, residual 3-chloro-1, 2-propanediol, byproducts and the like are distilled out. The pressure of the wiped film evaporator 6 is 1mmHg, the backwater temperature of the wiped film evaporator 6 is 90 ℃, and the total weight of heavy components (residual liquid) after wiped film evaporation is about 75Kg, and the main components are sodium chloride and a small amount of 3-chloro-1, 2-propanediol.
(4) The crude glycidol (about 5495 Kg) obtained was pumped into a glycidol batch rectifying tower 12 for refining. And (3) introducing steam into a jacket of the rectifying kettle, heating materials in the kettle, vacuumizing by using a water ring pump, and recovering the isobutanol under 100 mmHg. When the temperature of the top of the column was 60℃and the vacuum was 100mmHg, isobutanol was recovered at the top of the column, with a water content of 1.1%. When the top temperature starts to rise, a Roots vacuum pump is started, the vacuum is pumped to 10mmHg, and the reflux ratio is 9:1, the fraction obtained in this stage is a front-end fraction. When the top temperature is 56-57 ℃, the vacuum is 10mmHg, and the reflux ratio is 1.5:1, recovering the finished glycidol with the purity of more than 99.0 percent. When the top temperature starts to rise, the vacuum is pumped to be 1mmHg, the whole material is discharged, and the fraction obtained in the stage is a rear fraction. The front and rear fractions were all used for the next batch rectification.
The molar yield of glycidol relative to 3-chloro-1, 2-propanediol in this example was calculated to be 92%.
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (13)
1. An industrial production method of glycidol is characterized by comprising the following steps:
(1) 3-chloro-1, 2-propanediol and azeotropic solvent are mixed in a reaction kettle in advance according to a certain proportion, then aqueous solution of sodium hydroxide is continuously added into the system in a dropwise manner under the vacuum condition, the system is kept in a boiling reflux state for reaction, and water is removed at the same time;
(2) After the reaction is finished, the reaction solution is further centrifugally filtered, the obtained filtrate enters a wiped film evaporation device, and the filtrate is evaporated under high vacuum to obtain an organic phase and a heavy component; the heavy component is discharged from the bottom of the wiped film evaporator;
(3) And evaporating the organic phase from the top of the wiped film evaporator, condensing, and refining in a glycidol rectifying system to obtain a glycidol product.
2. The industrial production method of glycidol according to claim 1, wherein the reaction kettle in the step (1) is connected with an azeotropic distillation tower, a gas phase generated during boiling reflux of the system enters the azeotropic distillation tower from the reaction kettle to be further condensed, then enters a liquid-liquid layering device to be layered, an organic phase at the upper layer returns into the azeotropic distillation tower in a reflux mode, and an aqueous phase at the lower layer enters a solvent recovery tower to recover azeotropic solvent.
3. The method for industrially producing glycidol according to claim 1, wherein the solvent recovery tower is a continuous rectification tower or a batch rectification tower, and the water after recovering the azeotropic solvent is discharged into a sewage system or recycled as reclaimed water.
4. The method for industrially producing glycidol according to claim 1, wherein the reaction temperature in the step (1) is 10 to 40℃and the reaction residence time is 0.5 to 3 hours.
5. The method for industrially producing glycidol according to claim 1, wherein the azeotropic solvent comprises n-butanol, sec-butanol, isobutanol, methyl isobutyl ketone, benzene, n-heptane, toluene, 1, 2-dichloroethane, cyclohexane or a combination thereof.
6. The method for industrially producing glycidol according to claim 1, wherein the concentration of sodium hydroxide is 30 to 50%.
7. The method for industrially producing glycidol according to claim 1, wherein the molar ratio of the azeotropic solvent to 3-chloro-1, 2-propanediol in the step (1) is 0.50 to 2.5:1; the molar ratio of 3-chloro-1, 2-propanediol to sodium hydroxide is 1.01-1.30:1.
8. The method for industrially producing glycidol according to claim 1, wherein 3-chloro-1, 2-propanediol in the step (1) has an R-type or S-type optical activity to obtain a glycidol product corresponding to the optical activity.
9. The method for industrially producing glycidol according to claim 1, wherein the azeotropic solvent and 3-chloro-1, 2-propanediol are recovered in the step (3) and recycled to the reaction system.
10. An apparatus for an industrial production method of glycidol according to any one of claims 1 to 9, characterized in that the apparatus comprises a reaction vessel, a centrifugal filtration apparatus, a wiped film evaporator, a first condenser and a glycidol rectification system;
the reaction kettle is provided with a mechanical stirring device, the top of the reaction kettle is provided with a liquid-alkali solution continuous feed inlet, and the bottom of the reaction kettle is provided with a reaction solution outlet;
the inlet of the centrifugal filter device is connected with the reaction liquid outlet of the reaction kettle, and the filtrate outlet is connected with the inlet of the wiped film evaporation device;
the top of the film scraping evaporation device is provided with an organic phase outlet which is connected with the inlet of the first condenser, and the bottom of the film scraping evaporation device is provided with a heavy component discharge outlet;
the outlet of the first condenser is connected with the glycidyl rectification system, and the glycidyl rectification system is a glycidyl continuous rectification system or a glycidyl batch rectification tower.
11. The device for the industrial production method of glycidol according to claim 10, wherein the top of the reaction kettle is connected with an azeotropic distillation tower, the top of the azeotropic distillation tower is a gas phase outlet, the gas phase outlet is sequentially connected with a second condenser and a liquid-liquid separator, an organic phase outlet of the liquid-liquid separator is connected with a liquid distributor at the top of the azeotropic distillation tower, and a water phase outlet of the liquid-liquid separator is connected with a solvent recovery tower.
12. The apparatus for an industrial production method of glycidol according to claim 10, wherein the glycidol continuous rectification system comprises a light component removal column, a glycidol refining column and a chloropropanol recovery column which are connected in this order.
13. The apparatus according to claim 10, wherein the column internals of the glycidol refining column are structured packing or random packing with low pressure drop suitable for high vacuum.
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