CN113831304A - Method for efficiently preparing epoxy chloropropane through biomass glycerol - Google Patents
Method for efficiently preparing epoxy chloropropane through biomass glycerol Download PDFInfo
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- CN113831304A CN113831304A CN202111178292.4A CN202111178292A CN113831304A CN 113831304 A CN113831304 A CN 113831304A CN 202111178292 A CN202111178292 A CN 202111178292A CN 113831304 A CN113831304 A CN 113831304A
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- epichlorohydrin
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002028 Biomass Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000000523 sample Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 43
- 238000002604 ultrasonography Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 26
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 19
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 19
- 229940045803 cuprous chloride Drugs 0.000 claims description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 19
- 239000004246 zinc acetate Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000001361 adipic acid Substances 0.000 claims description 13
- 235000011037 adipic acid Nutrition 0.000 claims description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 12
- 229910000278 bentonite Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003225 biodiesel Substances 0.000 abstract description 10
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 abstract description 5
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 abstract description 4
- 235000011187 glycerol Nutrition 0.000 description 21
- 239000002994 raw material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FLTSEOGWHPJWRV-UHFFFAOYSA-N 1,2-dichloropropan-1-ol Chemical compound CC(Cl)C(O)Cl FLTSEOGWHPJWRV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for efficiently preparing epichlorohydrin by using biomass glycerol, which comprises the following steps: 1) mixing the components in a mass ratio of 1: 0.06-0.08 of biomass glycerol and a composite catalyst are poured into a reaction kettle, and then an ultrasonic probe is used for extending into the reaction kettle, 2) after the reaction in the step 1) is finished, the obtained material is cooled to room temperature and then transferred into a reaction container, the temperature is kept at 15-30 ℃, and then an alkaline cyclizing agent is added for reaction; 3) filtering the generated solid after the reaction is finished, wherein the filtrate is the epichlorohydrin solution; the glycerol can be completely converted, the yield of the intermediate dichloropropanol is high, the selectivity of collecting the 1, 3-dichloropropanol is improved, and the reaction rate is accelerated; and the process can be used for industrial co-production of biodiesel and chlor-alkali, and has good industrial prospect.
Description
Technical Field
The invention relates to the technical field of chemical intermediate epichlorohydrin, in particular to a method for efficiently preparing epichlorohydrin by using biomass glycerol.
Background
Epichlorohydrin is an important fine chemical raw material and chemical product intermediate, and has quite common use. It is used for producing adhesive, positive ion exchange resin, glass fiber reinforced plastic, chlorohydrin rubber, epoxy resin, insulating product and explosive. Before the development of the biodiesel, epichlorohydrin is used for synthesizing glycerin with relatively high price, and due to the improvement of the process, the glycerin serving as the biodiesel product is up to more than 90%, the price of the glycerin is rapidly reduced due to the large supply, the biodiesel is favored by scientists, the glycerin is taken as the raw material to prepare the dichloropropanol and the epichlorohydrin, and the development of other chemical product production processes taking the glycerin as the raw material is suitable for climbing the historical stage at any time, so that the problem of surplus by-products in the biodiesel production can be solved, and the environmental and economic benefits of the biodiesel can be increased.
The preparation of dichloropropanol and epichlorohydrin by using glycerol as a raw material relates to a chlorination reaction process and an epoxidation reaction process. During the chlorination reaction, 2-products were produced, one being 1, 2-dichloropropanol and one being 1, 3-dichloropropanol. In the prior art, more 1, 2-dichloropropanol appears in the chlorination reaction process, the requirement on reaction temperature is high, the reaction speed is low, and the working efficiency is reduced.
The prior patent No. CN105272946A discloses a preparation method of epichlorohydrin, which is a continuous reaction and has high efficiency. But the raw materials are chloropropene and peroxide, so the cost is higher.
Disclosure of Invention
The invention provides a method for efficiently preparing epichlorohydrin by using biomass glycerol.
The scheme of the invention is as follows:
a method for efficiently preparing epichlorohydrin by biomass glycerol comprises the following steps:
1) mixing the components in a mass ratio of 1: pouring 0.06-0.08 of biomass glycerol and a composite catalyst into a reaction kettle, then extending into the reaction kettle by using an ultrasonic probe, carrying out intermittent ultrasound for 3-5 min, and oscillating; the intermittent ultrasound comprises an ultrasound time period and a non-ultrasound time period which are alternately circulated, wherein the ultrasound time period is not more than 0.1 second; the time used in the non-ultrasonic time period is 5-10 times of the time used in the ultrasonic time period, the ultrasonic power of the ultrasonic time period is 5-20W, and the ultrasonic frequency is 30-50 KH; heating to 80-110 ℃, and then carrying out heat preservation; introducing hydrogen chloride gas into the system to start a bubbling reaction, wherein the reaction time lasts for 45-60 h, tail gas is absorbed by using alkali liquor, the composite catalyst comprises a catalyst A and a catalyst B, the mass ratio of the catalyst A to the catalyst B is 7: 2-3, the catalyst A comprises adipic acid and n-octanoic acid, and the catalyst B comprises phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite;
2) after the reaction in the step 1) is finished, cooling the obtained material to room temperature, transferring the cooled material into a reaction container, keeping the temperature at 15-30 ℃, and then adding an alkaline cyclizing agent for reaction;
3) and filtering the generated solid after the reaction is finished, wherein the filtrate is the epichlorohydrin solution.
As a preferred technical scheme, the mass ratio of phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite in the catalyst B is 1-5: 3-6: 0.5-2: 0.1-1: 0.8 to 2.
As a preferable technical scheme, the modified bentonite is bentonite: and (2) adding water into the bentonite according to the mass ratio of 1:35, soaking for 24 hours, stirring, sieving by a 80-mesh sieve, adding 10% by mass of dilute hydrochloric acid into the filtrate to adjust the pH value to 3-6, standing for 24 hours, washing to be neutral, performing centrifugal separation, drying at 120 ℃, and roasting for 3 hours at 360-420 ℃ to obtain the modified bentonite.
According to a preferable technical scheme, the preparation method of the catalyst B comprises the steps of mixing phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite according to a mass ratio to form a mixture, adding deionized water and absolute ethyl alcohol into the mixture, mixing and stirring at 50 ℃ to form gel, aging for 24 hours, drying at 120-140 ℃ for 5-7 hours, and roasting at 260-300 ℃ for 3-6 hours to obtain the catalyst B, wherein the mass ratio of the mixture to the deionized water to the absolute ethyl alcohol is 15-22: 25-35: 20 to 25.
According to a preferable technical scheme, the alkaline cyclizing agent comprises sodium carbonate, sodium sulfide, ferrous sulfide, sodium hydroxide and deionized water, and the mass ratio of the sodium carbonate to the ferrous sulfide to the sodium hydroxide to the deionized water is 20-30: 1-3: 4-8: 2-5: 110 to 120.
As a preferable technical scheme, the introduction flow rate of the hydrogen chloride gas in the step 1) is 200-600 mL/min.
Preferably, the mass ratio of the adipic acid to the n-octanoic acid is 3: 2.
As a preferable technical scheme, the mass-to-volume ratio of the material in the step 1) to the alkaline cyclizing agent in the step 2) is 1 kg: 1.4-1.58L.
Due to the adoption of the technical scheme, the method for efficiently preparing the epichlorohydrin by using the biomass glycerol comprises the following steps: 1) mixing the components in a mass ratio of 1: pouring 0.06-0.08 of biomass glycerol and a composite catalyst into a reaction kettle, then extending into the reaction kettle by using an ultrasonic probe, carrying out intermittent ultrasound for 3-5 min, and oscillating; the intermittent ultrasound comprises an ultrasound time period and a non-ultrasound time period which are alternately circulated, wherein the ultrasound time period is not more than 0.1 second; the time used in the non-ultrasonic time period is 5-10 times of the time used in the ultrasonic time period, the ultrasonic power of the ultrasonic time period is 5-20W, and the ultrasonic frequency is 30-50 KH; heating to 80-110 ℃, and then carrying out heat preservation; introducing hydrogen chloride gas into the system to start a bubbling reaction, wherein the reaction time lasts for 45-60 h, tail gas is absorbed by using alkali liquor, the composite catalyst comprises a catalyst A and a catalyst B, the mass ratio of the catalyst A to the catalyst B is 7: 2-3, the catalyst A comprises adipic acid and n-octanoic acid, and the catalyst B comprises phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite; 2) after the reaction in the step 1) is finished, cooling the obtained material to room temperature, transferring the cooled material into a reaction container, keeping the temperature at 15-30 ℃, and then adding an alkaline cyclizing agent for reaction; 3) and filtering the generated solid after the reaction is finished, wherein the filtrate is the epichlorohydrin solution.
The invention has the beneficial effects that:
1. the invention has the advantages of easily obtained raw materials, lower cost and higher safety, can be co-produced with biodiesel and chlor-alkali industries in a large scale, and reduces the production cost.
2. The invention has simple working steps, can completely convert glycerol, has higher yield of intermediate dichloropropanol, improves the selectivity of collecting 1, 3-dichloropropanol and accelerates the reaction rate.
3. After the catalyst is recycled for 8 times, the catalytic activity is not obviously reduced.
4. The invention adopts the alkali cyclizing agent to carry out epoxidation reaction, the reaction rate is high, and the byproducts are few.
5. The invention solves the problem of surplus by-products in the production of the biodiesel, can change waste into valuable, increases the environmental and economic benefits of the biodiesel, can be co-produced with the biodiesel and chlor-alkali industries, and has good industrialization prospect.
Detailed Description
In order to make up for the defects, the invention provides a method for efficiently preparing epichlorohydrin by using biomass glycerol so as to solve the problems in the background art.
A method for efficiently preparing epichlorohydrin by biomass glycerol comprises the following steps:
1) mixing the components in a mass ratio of 1: pouring 0.06-0.08 of biomass glycerol and a composite catalyst into a reaction kettle, then extending into the reaction kettle by using an ultrasonic probe, carrying out intermittent ultrasound for 3-5 min, and oscillating; the intermittent ultrasound comprises an ultrasound time period and a non-ultrasound time period which are alternately circulated, wherein the ultrasound time period is not more than 0.1 second; the time used in the non-ultrasonic time period is 5-10 times of the time used in the ultrasonic time period, the ultrasonic power of the ultrasonic time period is 5-20W, and the ultrasonic frequency is 30-50 KH; heating to 80-110 ℃, and then carrying out heat preservation; introducing hydrogen chloride gas into the system to start a bubbling reaction, wherein the reaction time lasts for 45-60 h, tail gas is absorbed by using alkali liquor, the composite catalyst comprises a catalyst A and a catalyst B, the mass ratio of the catalyst A to the catalyst B is 7: 2-3, the catalyst A comprises adipic acid and n-octanoic acid, and the catalyst B comprises phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite;
2) after the reaction in the step 1) is finished, cooling the obtained material to room temperature, transferring the cooled material into a reaction container, keeping the temperature at 15-30 ℃, and then adding an alkaline cyclizing agent for reaction;
3) and filtering the generated solid after the reaction is finished, wherein the filtrate is the epichlorohydrin solution.
The mass ratio of phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite in the catalyst B is 1-5: 3-6: 0.5-2: 0.1-1: 0.8 to 2.
The modified bentonite is bentonite: and (2) adding water into the bentonite according to the mass ratio of 1:35, soaking for 24 hours, stirring, sieving by a 80-mesh sieve, adding 10% by mass of dilute hydrochloric acid into the filtrate to adjust the pH value to 3-6, standing for 24 hours, washing to be neutral, performing centrifugal separation, drying at 120 ℃, and roasting for 3 hours at 360-420 ℃ to obtain the modified bentonite.
The preparation method of the catalyst B comprises the steps of mixing phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite according to the mass ratio to form a mixture, adding deionized water and absolute ethyl alcohol into the mixture, mixing and stirring at 50 ℃ to form gel, aging for 24 hours, drying at 120-140 ℃ for 5-7 hours, and roasting at 260-300 ℃ for 3-6 hours to obtain the catalyst B, wherein the mass ratio of the mixture to the deionized water to the absolute ethyl alcohol is 15-22: 25-35: 20 to 25.
The alkaline cyclizing agent comprises sodium carbonate, sodium sulfide, ferrous sulfide, sodium hydroxide and deionized water, and the mass ratio of the alkaline cyclizing agent to the deionized water is 20-30: 1-3: 4-8: 2-5: 110 to 120.
The introduction flow of the hydrogen chloride gas in the step 1) is 200-600 mL/min.
The mass ratio of the adipic acid to the n-octanoic acid is 3: 2.
The mass volume ratio of the material in the step 1) in the step 2) to the alkaline cyclizing agent is 1 kg: 1.4-1.58L.
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1:
1) mixing the components in a mass ratio of 1: 0.06 of biomass glycerol and a composite catalyst are poured into a reaction kettle, and then an ultrasonic probe is used for stretching into the reaction kettle to carry out intermittent ultrasound for 3-5 min and oscillation; the intermittent ultrasound comprises an ultrasound time period and a non-ultrasound time period which are alternately circulated, wherein the ultrasound time period is not more than 0.1 second; the time used in the non-ultrasonic time period is 5-10 times of the time used in the ultrasonic time period, the ultrasonic power of the ultrasonic time period is 5-20W, and the ultrasonic frequency is 30-50 KH; heating to 80-110 ℃, and then carrying out heat preservation; introducing hydrogen chloride gas into the system to start a bubbling reaction, wherein the reaction time lasts for 45-60 h, tail gas is absorbed by using alkali liquor, the composite catalyst comprises a catalyst A and a catalyst B, the mass ratio of the catalyst A to the catalyst B is 7:2, the catalyst A comprises adipic acid and n-octanoic acid, and the catalyst B comprises phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite;
2) after the reaction in the step 1) is finished, cooling the obtained material to room temperature, transferring the cooled material into a reaction container, keeping the temperature at 15-30 ℃, and then adding an alkaline cyclizing agent for reaction;
3) and filtering the generated solid after the reaction is finished, wherein the filtrate is the epichlorohydrin solution.
The mass ratio of phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite in the catalyst B is 1: 3: 0.5: 0.1: 0.8.
the modified bentonite is bentonite: and (2) adding water into the bentonite according to the mass ratio of 1:35, soaking for 24 hours, stirring, sieving by a 80-mesh sieve, adding 10% by mass of dilute hydrochloric acid into the filtrate to adjust the pH value to 3-6, standing for 24 hours, washing to be neutral, performing centrifugal separation, drying at 120 ℃, and roasting for 3 hours at 360-420 ℃ to obtain the modified bentonite.
The preparation method of the catalyst B comprises the steps of mixing phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite according to the mass ratio to form a mixture, adding deionized water and absolute ethyl alcohol into the mixture, mixing and stirring at 50 ℃ to form gel, aging for 24 hours, drying at 120-140 ℃ for 5-7 hours, and roasting at 260-300 ℃ for 3-6 hours to obtain the catalyst B, wherein the mass ratio of the mixture to the deionized water to the absolute ethyl alcohol is 15: 25: 20.
the alkaline cyclizing agent comprises sodium carbonate, sodium sulfide, ferrous sulfide, sodium hydroxide and deionized water, and the mass ratio of the sodium carbonate to the ferrous sulfide to the sodium hydroxide is 20:1:4: 2: 110.
the introduction flow of the hydrogen chloride gas in the step 1) is 200-600 mL/min.
The mass ratio of the adipic acid to the n-octanoic acid is 3: 2.
The mass volume ratio of the material in the step 1) in the step 2) to the alkaline cyclizing agent is 1 kg: 1.4L.
Example 2
1) Mixing the components in a mass ratio of 1: pouring 0.08 of biomass glycerol and a composite catalyst into a reaction kettle, then extending into the reaction kettle by using an ultrasonic probe, carrying out intermittent ultrasound for 3-5 min, and oscillating; the intermittent ultrasound comprises an ultrasound time period and a non-ultrasound time period which are alternately circulated, wherein the ultrasound time period is not more than 0.1 second; the time used in the non-ultrasonic time period is 5-10 times of the time used in the ultrasonic time period, the ultrasonic power of the ultrasonic time period is 5-20W, and the ultrasonic frequency is 30-50 KH; heating to 80-110 ℃, and then carrying out heat preservation; introducing hydrogen chloride gas into the system to start a bubbling reaction, wherein the reaction time lasts for 45-60 h, tail gas is absorbed by using alkali liquor, the composite catalyst comprises a catalyst A and a catalyst B, the mass ratio of the catalyst A to the catalyst B is 7:3, the catalyst A comprises adipic acid and n-octanoic acid, and the catalyst B comprises phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite;
2) after the reaction in the step 1) is finished, cooling the obtained material to room temperature, transferring the cooled material into a reaction container, keeping the temperature at 15-30 ℃, and then adding an alkaline cyclizing agent for reaction;
3) and filtering the generated solid after the reaction is finished, wherein the filtrate is the epichlorohydrin solution.
The mass ratio of phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite in the catalyst B is 5: 6: 2: 1: 2.
the modified bentonite is bentonite: and (2) adding water into the bentonite according to the mass ratio of 1:35, soaking for 24 hours, stirring, sieving by a 80-mesh sieve, adding 10% by mass of dilute hydrochloric acid into the filtrate to adjust the pH value to 3-6, standing for 24 hours, washing to be neutral, performing centrifugal separation, drying at 120 ℃, and roasting for 3 hours at 360-420 ℃ to obtain the modified bentonite.
The preparation method of the catalyst B comprises the steps of mixing phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite according to the mass ratio to form a mixture, adding deionized water and absolute ethyl alcohol into the mixture, mixing and stirring at 50 ℃ to form gel, aging for 24 hours, drying at 120-140 ℃ for 5-7 hours, and roasting at 260-300 ℃ for 3-6 hours to obtain the catalyst B, wherein the mass ratio of the mixture to the deionized water to the absolute ethyl alcohol is 22: 35: 25.
the alkaline cyclizing agent comprises sodium carbonate, sodium sulfide, ferrous sulfide, sodium hydroxide and deionized water, and the mass ratio of the sodium carbonate to the ferrous sulfide to the sodium hydroxide is 30:3:8: 5: 120.
the introduction flow of the hydrogen chloride gas in the step 1) is 200-600 mL/min.
The mass ratio of the adipic acid to the n-octanoic acid is 3: 2.
The mass volume ratio of the material in the step 1) in the step 2) to the alkaline cyclizing agent is 1 kg: 1.4-1.58L.
Example 3
1) Mixing the components in a mass ratio of 1: pouring 0.07 mass of biomass glycerol and a composite catalyst into a reaction kettle, then extending into the reaction kettle by using an ultrasonic probe, carrying out intermittent ultrasound for 3-5 min, and oscillating; the intermittent ultrasound comprises an ultrasound time period and a non-ultrasound time period which are alternately circulated, wherein the ultrasound time period is not more than 0.1 second; the time used in the non-ultrasonic time period is 5-10 times of the time used in the ultrasonic time period, the ultrasonic power of the ultrasonic time period is 5-20W, and the ultrasonic frequency is 30-50 KH; heating to 80-110 ℃, and then carrying out heat preservation; introducing hydrogen chloride gas into the system to start a bubbling reaction, wherein the reaction time lasts for 45-60 h, tail gas is absorbed by using alkali liquor, the composite catalyst comprises a catalyst A and a catalyst B, the mass ratio of the catalyst A to the catalyst B is 7:2, the catalyst A comprises adipic acid and n-octanoic acid, and the catalyst B comprises phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite;
2) after the reaction in the step 1) is finished, cooling the obtained material to room temperature, transferring the cooled material into a reaction container, keeping the temperature at 15-30 ℃, and then adding an alkaline cyclizing agent for reaction;
3) and filtering the generated solid after the reaction is finished, wherein the filtrate is the epichlorohydrin solution.
The mass ratio of phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite in the catalyst B is 2: 3: 1: 0.3: 1.
the modified bentonite is bentonite: and (2) adding water into the bentonite according to the mass ratio of 1:35, soaking for 24 hours, stirring, sieving by a 80-mesh sieve, adding 10% by mass of dilute hydrochloric acid into the filtrate to adjust the pH value to 3-6, standing for 24 hours, washing to be neutral, performing centrifugal separation, drying at 120 ℃, and roasting for 3 hours at 360-420 ℃ to obtain the modified bentonite.
The preparation method of the catalyst B comprises the steps of mixing phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite according to the mass ratio to form a mixture, adding deionized water and absolute ethyl alcohol into the mixture, mixing and stirring at 50 ℃ to form gel, aging for 24 hours, drying at 120-140 ℃ for 5-7 hours, and roasting at 260-300 ℃ for 3-6 hours to obtain the catalyst B, wherein the mass ratio of the mixture to the deionized water to the absolute ethyl alcohol is 17: 28: 23.
the alkaline cyclizing agent comprises sodium carbonate, sodium sulfide, ferrous sulfide, sodium hydroxide and deionized water in a mass ratio of 24:2:5: 3: 110.
the introduction flow of the hydrogen chloride gas in the step 1) is 200-600 mL/min.
The mass ratio of the adipic acid to the n-octanoic acid is 3: 2.
The mass volume ratio of the material in the step 1) in the step 2) to the alkaline cyclizing agent is 1 kg: 1.4-1.58L.
After the composite catalyst in the embodiment 3 is recycled for eight times, the catalytic activity is not obviously reduced, and the use is not influenced.
The following table shows the examples of the present invention:
as can be seen from the table, glycerol can be completely converted, the yield of the intermediate dichloropropanol is high, the selectivity of collecting 1, 3-dichloropropanol is improved, and the reaction rate is accelerated.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The method for efficiently preparing epichlorohydrin by using biomass glycerol is characterized by comprising the following steps:
1) mixing the components in a mass ratio of 1: pouring 0.06-0.08 of biomass glycerol and a composite catalyst into a reaction kettle, then extending into the reaction kettle by using an ultrasonic probe, carrying out intermittent ultrasound for 3-5 min, and oscillating; the intermittent ultrasound comprises an ultrasound time period and a non-ultrasound time period which are alternately circulated, wherein the ultrasound time period is not more than 0.1 second; the time used in the non-ultrasonic time period is 5-10 times of the time used in the ultrasonic time period, the ultrasonic power of the ultrasonic time period is 5-20W, and the ultrasonic frequency is 30-50 KH; heating to 80-110 ℃, and then carrying out heat preservation; introducing hydrogen chloride gas into the system to start a bubbling reaction, wherein the reaction time lasts for 45-60 h, tail gas is absorbed by using alkali liquor, the composite catalyst comprises a catalyst A and a catalyst B, the mass ratio of the catalyst A to the catalyst B is 7: 2-3, the catalyst A comprises adipic acid and n-octanoic acid, and the catalyst B comprises phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite;
2) after the reaction in the step 1) is finished, cooling the obtained material to room temperature, transferring the cooled material into a reaction container, keeping the temperature at 15-30 ℃, and then adding an alkaline cyclizing agent for reaction;
3) and filtering the generated solid after the reaction is finished, wherein the filtrate is the epichlorohydrin solution.
2. The process for the efficient production of epichlorohydrin by biomass glycerol according to claim 1, characterized in that: the mass ratio of phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite in the catalyst B is 1-5: 3-6: 0.5-2: 0.1-1: 0.8 to 2.
3. The process for the efficient production of epichlorohydrin by biomass glycerol according to claim 1 or 2, characterized in that: the modified bentonite is bentonite: and (2) adding water into the bentonite according to the mass ratio of 1:35, soaking for 24 hours, stirring, sieving by a 80-mesh sieve, adding 10% by mass of dilute hydrochloric acid into the filtrate to adjust the pH value to 3-6, standing for 24 hours, washing to be neutral, performing centrifugal separation, drying at 120 ℃, and roasting for 3 hours at 360-420 ℃ to obtain the modified bentonite.
4. The process for the efficient production of epichlorohydrin by biomass glycerol according to claim 1 or 2, characterized in that: the preparation method of the catalyst B comprises the steps of mixing phosphotungstic acid, zinc acetate, cuprous chloride, ferric trichloride and modified bentonite according to the mass ratio to form a mixture, adding deionized water and absolute ethyl alcohol into the mixture, mixing and stirring at 50 ℃ to form gel, aging for 24 hours, drying at 120-140 ℃ for 5-7 hours, and roasting at 260-300 ℃ for 3-6 hours to obtain the catalyst B, wherein the mass ratio of the mixture to the deionized water to the absolute ethyl alcohol is 15-22: 25-35: 20 to 25.
5. The process for the efficient production of epichlorohydrin by biomass glycerol according to claim 1, characterized in that: the alkaline cyclizing agent comprises sodium carbonate, sodium sulfide, ferrous sulfide, sodium hydroxide and deionized water, and the mass ratio of the alkaline cyclizing agent to the deionized water is 20-30: 1-3: 4-8: 2-5: 110 to 120.
6. The process for the efficient production of epichlorohydrin by biomass glycerol according to claim 1, characterized in that: the introduction flow of the hydrogen chloride gas in the step 1) is 200-600 mL/min.
7. The process for the efficient production of epichlorohydrin by biomass glycerol according to claim 1, characterized in that: the mass ratio of the adipic acid to the n-octanoic acid is 3: 2.
8. The process for the efficient production of epichlorohydrin by biomass glycerol according to claim 1, characterized in that: the mass volume ratio of the material in the step 1) in the step 2) to the alkaline cyclizing agent is 1 kg: 1.4-1.58L.
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