CN113754519A - Method for preparing tert-butyl glyceryl ether by using solid acid catalyst - Google Patents
Method for preparing tert-butyl glyceryl ether by using solid acid catalyst Download PDFInfo
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- CN113754519A CN113754519A CN202110918362.9A CN202110918362A CN113754519A CN 113754519 A CN113754519 A CN 113754519A CN 202110918362 A CN202110918362 A CN 202110918362A CN 113754519 A CN113754519 A CN 113754519A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- JPWDLYMEUNBLIR-UHFFFAOYSA-N 3-[(2-methylpropan-2-yl)oxy]propane-1,2-diol Chemical compound CC(C)(C)OCC(O)CO JPWDLYMEUNBLIR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011973 solid acid Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 215
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 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 abstract description 60
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000010926 purge Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- HDXAQJALAKVYTG-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,4,5-triol Chemical compound CC(C)(C)C(O)C(O)C(O)C(C)(C)C HDXAQJALAKVYTG-UHFFFAOYSA-N 0.000 claims description 6
- PPCWIILKZFLSKK-UHFFFAOYSA-N 2,3-ditert-butyl-4,4-dimethylpentane-1,2,3-triol Chemical compound CC(C)(C)C(O)(CO)C(O)(C(C)(C)C)C(C)(C)C PPCWIILKZFLSKK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000012257 stirred material Substances 0.000 claims description 3
- -1 tri-tert-butyl glyceryl Chemical group 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 65
- 238000002360 preparation method Methods 0.000 description 17
- 238000011068 loading method Methods 0.000 description 15
- SBNAQMYJKLIEOC-UHFFFAOYSA-N 4,4-dimethylpentane-1,2,3-triol Chemical class CC(C)(C)C(O)C(O)CO SBNAQMYJKLIEOC-UHFFFAOYSA-N 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003225 biodiesel Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PGQYJNWAXBIJAF-UHFFFAOYSA-N 2-tert-butylpropane-1,2,3-triol Chemical compound C(C)(C)(C)C(CO)(O)CO PGQYJNWAXBIJAF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical class OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- 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
-
- 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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- 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)
Abstract
The invention discloses a method for preparing tert-butyl glyceryl ether by using a solid acid catalyst, which belongs to the technical field of organic synthesis, wherein glycerol and tert-butyl alcohol are used as raw materials, supported phosphotungstic acid solid acid is used as a catalyst, after reaction is carried out for a period of time at a certain temperature in a closed pressure-resistant reactor, the product is subjected to conventional separation to obtain the tert-butyl glyceryl ether, the glycerol conversion rate is 76.3-93.2%, the selectivity of tri-tert-butyl glyceryl ether (TTBG) is 5.5-11.3%, and the selectivity of di-tert-butyl glyceryl ether (DTBG) is 30.1-45.7%. The supported phosphotungstic acid solid acid catalyst is prepared by using phosphotungstic acid as an active component, impregnating a carrier and the phosphotungstic acid for 9-12h by an isometric impregnation method according to a certain mass ratio, drying, and roasting at the temperature of 250-400 ℃ for 2-4 h. According to the invention, through screening the optimal reaction conditions and utilizing the phosphotungstic acid modified catalyst, the conversion rate of glycerol and the selectivity of polysubstituted tert-butyl glyceryl ether during the conversion of glycerol into tert-butyl glyceryl ether can be effectively improved, and the catalyst can be recycled for multiple times.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing tert-butyl glyceryl ether by using a solid acid catalyst.
Background
With the increasing energy crisis and environmental pollution, biodiesel, as a renewable resource, has been researched and produced by more and more countries. However, for every 1 ton of biodiesel produced, 0.1 ton of glycerol is produced as a by-product, and it is therefore necessary to convert it into value-added chemicals by means of appropriate techniques. The development and utilization of the biodiesel byproduct glycerol are improved, and the comprehensive utilization rate and the economical efficiency of the whole process can be improved.
Glyceryl ethers are currently known as valuable alternative fuel additives. The di-substituted tert-butyl glyceryl ether and the tri-substituted tert-butyl glyceryl ether are suitable additives mixed into diesel oil and biodiesel, because the di-substituted tert-butyl glyceryl ether and the tri-substituted tert-butyl glyceryl ether belong to nonpolar substances, have good solubility and low viscosity, and can be mixed and dissolved with the nonpolar substances such as diesel oil and the like. Meanwhile, the oxygen content of the disubstituted tert-butyl glycerol ether and the oxygen content of the trisubstituted tert-butyl glycerol ether are respectively 23.5 percent and 18.5 percent, which are far higher than the oxygen content of 11 percent of the biodiesel. The two can be used as fuel additives, the emission of particulate matters, carbon monoxide and hydrocarbon can be greatly reduced, and the performance of the engine at low temperature can be improved. Therefore, the method for efficiently producing the polysubstituted tert-butyl glycerol ether has great potential in solving the problem of excess glycerol. The etherification reaction of glycerol and tert-butyl alcohol can obtain tert-butyl glycerol ether mixture containing mono-tert-butyl glycerol ether, di-tert-butyl glycerol ether and tri-tert-butyl glycerol ether.
There is currently active research on the conversion of glycerol to tert-butyl glycerol ether. The patent with application number 201310643671.5 discloses a preparation method of a binuclear acidic ionic liquid immobilized SBA-15 molecular sieve catalyst for synthesizing tert-butyl glyceryl ether, which can obtain about 70% of glycerin conversion rate and 40% of multi-substituted tert-butyl glyceryl ether selectivity; however, the method has complicated steps for preparing the catalyst, and increases the complexity of the reaction and the reaction cost. Cristian Miranda et al (Cristian Miranda et al. sulfonated graphene acid catalysts for the glycerol validation [ J ]. Applied Catalysis A, General,2019,580: 167-.
In the existing method, when the tert-butyl glyceryl ether is generated by converting glycerol, the preparation process of the used catalyst is complex, the raw materials are expensive, the glycerol conversion rate is low, the selectivity of the polysubstituted tert-butyl glyceryl ether is low, and in addition, the reaction for generating the tert-butyl glyceryl ether by converting glycerol is carried out at high temperature and high pressure, so that the skeleton structure of the existing catalyst is easy to collapse, the catalyst cannot be recycled for multiple times, and the recovery rate is low.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a method for preparing tert-butyl glyceryl ether by using a solid acid catalyst, aiming at the problems of low glycerol conversion rate, low selectivity of multi-substituted tert-butyl glyceryl ether and low recovery rate of a reaction catalyst at high temperature and high pressure when glycerol is converted to generate tert-butyl glyceryl ether in the prior art.
The technical scheme is as follows: a method for preparing tert-butyl glyceryl ether by using a solid acid catalyst comprises the following steps:
(1) reacting glycerol and tert-butyl alcohol with the mass ratio of substances of 1: 4-1: 12 and a solid acid catalyst accounting for 1-20% of the mass ratio of the glycerol in a closed pressure-resistant reactor to obtain a product;
(2) and (2) separating the product obtained in the step (1) to obtain tert-butyl glyceryl ether.
Further, in the step (1), the specific steps are as follows: adding glycerol, tert-butyl alcohol and a supported phosphotungstic acid solid acid catalyst into a high-pressure reaction kettle by using N2Purging for more than three times, and removing air from the high-pressure reaction kettle to perform reaction.
Further, in the step (1), the reaction conditions are as follows: reacting for 8-12 h at the autogenous pressure of 0-2 MPa and the temperature of 80-120 ℃.
Further, in the step (2), the product comprises tri-tert-butyl glycerol ether, di-tert-butyl glycerol ether and glycerol, wherein the selectivity of the tri-tert-butyl glycerol ether is 5.5-11.3%, and the selectivity of the di-tert-butyl glycerol ether is 30.1-45.7%.
Further, in the step (1), the solid acid catalyst is a supported phosphotungstic acid solid acid catalyst, the supported phosphotungstic acid solid acid catalyst takes phosphotungstic acid as an active component, and the supported phosphotungstic acid solid acid catalyst is obtained by using an isometric impregnation method for a carrier and phosphotungstic acid.
Further, the carrier is one of zirconium dioxide, tin dioxide or silicon dioxide.
Further, the supported phosphotungstic acid solid acid catalyst is obtained by the following method: adding the carrier and phosphotungstic acid into water, and stirring at room temperature; and standing, drying and roasting the stirred material in sequence to obtain the supported phosphotungstic acid solid acid catalyst.
Further, the adding mass ratio of the carrier to the phosphotungstic acid is 1: 0.1-0.3; the volume of the corresponding deionized water was calculated from its water absorption for each 1g of carrier.
Furthermore, the calcination temperature of the catalyst is 250-400 ℃, and the calcination time is 2-4 h.
Has the advantages that: by selecting appropriate reaction substrates, the need for solvents (i.e., dioxane, dimethyl sulfoxide) and the limitations of mass transfer phenomena in the reaction system are avoided. When glycerol is converted to tert-butyl glyceryl ether
The acid sites have higher requirements, and the proportion of the acid sites on the surface of the carrier can be effectively adjusted by loading phosphotungstic acid on the surface of the oxide, so that the etherification reaction can be effectively promoted, and the conversion rate of glycerol and the selectivity of the polysubstituted tert-butyl glyceryl ether are greatly increased; in addition, the modified supported catalyst has stable structure and still has good catalytic effect after being recycled for many times,the economy of the preparation process is improved.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
A method for preparing tert-butyl glyceryl ether by using a solid acid catalyst comprises the following steps:
(1) reacting glycerol and tert-butyl alcohol with the mass ratio of 1: 4-1: 12 and a supported phosphotungstic acid solid acid catalyst accounting for 1-20% of the mass ratio of the glycerol in a closed pressure-resistant reactor to obtain a product;
(2) and (2) separating the product obtained in the step (1) to obtain tert-butyl glyceryl ether.
In the step (1), adding the reaction materials and the supported phosphotungstic acid solid acid catalyst into a 100mL stainless steel high-pressure reaction kettle, and using N2Purging the high-pressure reaction kettle for three times to remove air, and reacting at the autogenous pressure of 0-2 MPa, the temperature of 80-120 ℃ and the time of 8-12 h.
In the step (2), the product is separated conventionally to obtain tert-butyl glyceryl ether. The conversion rate of glycerol is 76.3-93.2%, the selectivity of tri-tert-butyl glycerol ether (TTBG) is 5.5-11.3%, and the selectivity of di-tert-butyl glycerol ether (DTBG) is 30.1-45.7%.
In the step (1), the supported phosphotungstic acid solid acid catalyst takes phosphotungstic acid as an active component, and is obtained by adopting an isometric impregnation method for a carrier and phosphotungstic acid according to a certain mass ratio. Wherein, the carrier is one of zirconium dioxide, tin dioxide or silicon dioxide.
The preparation method of the supported phosphotungstic acid solid acid catalyst comprises the following steps: adding the carrier and phosphotungstic acid into water, and stirring at room temperature; and standing, drying and roasting the stirred materials in sequence to obtain the required catalyst.
The adding mass ratio of the carrier to the phosphotungstic acid is 1: 0.1-0.3; the volume of the corresponding deionized water was calculated from its water absorption for each 1g of carrier.
The roasting temperature of the catalyst is 250-400 ℃, and the roasting time is 2-4 h.
Example 1
The preparation method of the supported phosphotungstic acid solid acid catalyst comprises the following steps:
(1) pretreating the carrier: ZrO 2 is mixed with2Placing the powder in a muffle furnace, roasting for 2 hours at 400 ℃, and removing impurities in the powder to improve the purity of the carrier;
(2) 5g of the calcined ZrO were taken2Adding 0.500g of phosphotungstic acid into 1.5mL of deionized water, and stirring for 1h at normal temperature; loading of phosphotungstic acid to ZrO by stirring2A surface;
(3) standing the material obtained in the step (2) at normal temperature for 8h to completely impregnate the active component, and then drying in a drying oven at 110 ℃ for 12h to completely remove the water;
(4) roasting the dried solid substance in air at 250 ℃ for 4h to obtain a catalyst with 10 wt% of theoretical loading capacity of phosphotungstic acid, which is recorded as (10) HPW/ZrO2。
The (10) HPW/ZrO prepared in example 12Application of the catalyst in preparation of tert-butyl glyceryl ether by catalysis of glycerol:
4.144g of glycerol, 33.354g of tert-butanol and 0.414g of (10) HPW/ZrO2Adding the catalyst into a 100mL stainless steel high-pressure reaction kettle, and adding N2Repeatedly purging the reaction kettle for 3 times to remove air, reacting for 11h at 100 ℃, taking a small amount of reaction solution after the reaction is finished, and measuring the conversion rate of the glycerol to be 74.05 percent and the selectivity of the polysubstituted tert-butyl glycerol ether to be 42.32 percent.
Reacting the (10) HPW/ZrO2The catalyst is recovered after centrifugation, washing, drying and roasting, is continuously used as the catalyst to be applied to the reaction for preparing the tert-butyl glyceryl ether by catalyzing the glycerol, and a small amount of reaction solution is taken after repeated recovery and repeated application for 4 times, and the conversion rate of the glycerol is determined to be 65.14%. The modified supported catalyst still has good catalytic effect after being recycled for many times.
Example 2
The preparation method of the supported phosphotungstic acid solid acid catalyst comprises the following steps:
(1) pretreating the carrier: ZrO 2 is mixed with2Placing in a muffle furnace, roasting at 400 deg.C for 2 hr to removeImpurities in the powder are removed, and the purity of the carrier is improved;
(2) 5g of the calcined ZrO were taken2Adding 0.750g of phosphotungstic acid into 1.5mL of deionized water, and stirring for 1h at normal temperature; loading of phosphotungstic acid to ZrO by stirring2A surface;
(3) standing the material obtained in the step (2) at normal temperature for 8h to completely impregnate the active component, and then drying in an oven at 100 ℃ for 12h to completely remove water;
(4) roasting the dried solid substance in air at 300 ℃ for 3h to obtain a catalyst with 15 wt% of phosphotungstic acid theoretical loading, which is recorded as (15) HPW/ZrO2。
The (15) HPW/ZrO prepared in example 22Application of the catalyst in preparation of tert-butyl glyceryl ether by catalysis of glycerol:
4.144g of glycerol, 33.354g of tert-butanol and 0.414g of (15) HPW/ZrO2Adding the catalyst into a 100mL stainless steel high-pressure reaction kettle, and adding N2Repeatedly purging the reaction kettle for 3 times to remove air, reacting for 8h at 120 ℃, taking a small amount of reaction solution after the reaction is finished, and measuring the conversion rate of the glycerol to be 88.30 percent and the selectivity of the polysubstituted tert-butyl glycerol ether to be 48.39 percent.
Reacting (15) HPW/ZrO2The catalyst is recovered after centrifugation, washing, drying and roasting, is continuously used as the catalyst to be applied to the reaction for preparing the tert-butyl glyceryl ether by the catalysis of the glycerol, and a small amount of reaction solution is taken after repeated recovery and repeated application for 4 times, and the conversion rate of the glycerol is determined to be 77.55%. The modified supported catalyst still has good catalytic effect after being recycled for many times.
Example 3
The preparation method of the supported phosphotungstic acid solid acid catalyst comprises the following steps:
(1) 5g of SnO were sampled2Adding 0.5g of phosphotungstic acid into 5mL of deionized water, and stirring for 12h at normal temperature; loading phosphotungstic acid to SnO by stirring2A surface;
(2) standing the material obtained in the step (1) at normal temperature for 10h to completely impregnate the active component, and then drying the material in a drying oven at the temperature of 110 ℃ for 12h to completely remove the water;
(3) roasting the dried solid substance in air at 400 ℃ for 3h to obtain a catalyst with 10 wt% of phosphotungstic acid theoretical loading, which is recorded as (10) HPW/SnO2。
The (10) HPW/SnO prepared in example 32Application of the catalyst in preparation of tert-butyl glyceryl ether by catalysis of glycerol:
6.216g of glycerol, 30.019g of tert-butanol and 0.932g of (10) HPW/SnO2Adding the catalyst into a 100mL stainless steel high-pressure reaction kettle, and adding N2Repeatedly purging the reaction kettle for 3 times to remove air, reacting for 8h at 110 ℃, taking a small amount of reaction solution after the reaction is finished, and measuring the conversion rate of the glycerol to be 75.24 percent and the selectivity of the polysubstituted tert-butyl glyceryl ether to be 36.11 percent.
Reacting (10) HPW/SnO2The catalyst is recovered after centrifugation, washing, drying and roasting, is continuously used as the catalyst to be applied to the reaction for preparing the tert-butyl glyceryl ether by catalyzing the glycerol, and a small amount of reaction solution is taken after repeated recovery and repeated application for 4 times, and the conversion rate of the glycerol is determined to be 68.52%. The modified supported catalyst still has good catalytic effect after being recycled for many times.
Example 4
The preparation method of the supported phosphotungstic acid solid acid catalyst comprises the following steps:
(1) 5g of SnO were sampled2Adding 1g of phosphotungstic acid into 5mL of deionized water, and stirring for 12h at normal temperature; loading phosphotungstic acid to SnO by stirring2A surface;
(2) standing the material obtained in the step (1) at normal temperature for 12h to completely impregnate the active component, and then drying the material in a drying oven at 100 ℃ for 10h to completely remove the water;
(3) roasting the dried solid substance in air at 300 ℃ for 4h to obtain a catalyst with the theoretical loading of phosphotungstic acid of 20 wt%, which is recorded as (20) HPW/SnO2。
The (20) HPW/SnO prepared in example 42Application of the catalyst in preparation of tert-butyl glyceryl ether by catalysis of glycerol:
5g of glycerol, 32.195g of tert-butanol and 0.75g of (20) HPW/SnO2Adding the catalyst into a 100mL stainless steel high-pressure reaction kettle, and adding N2Repeatedly purging the reaction kettle for 3 times to remove air, reacting at 100 ℃ for 9 hours, taking a small amount of reaction solution after the reaction is finished, and determining that the conversion rate of the glycerol is 82.32% and the selectivity of the polysubstituted tert-butyl glyceryl ether is 38.51%.
Reacting (20) HPW/SnO2The catalyst is recovered after centrifugation, washing, drying and roasting, is continuously used as the catalyst to be applied to the reaction for preparing the tert-butyl glyceryl ether by catalyzing the glycerol, and a small amount of reaction solution is taken after repeated recovery and repeated application for 4 times, and the conversion rate of the glycerol is determined to be 75.30%. The modified supported catalyst still has good catalytic effect after being recycled for many times.
Example 5
The preparation method of the supported phosphotungstic acid solid acid catalyst comprises the following steps:
(1) taking 5g of SiO2Adding 0.75g of phosphotungstic acid into 10mL of deionized water, and stirring for 12h at normal temperature; loading phosphotungstic acid to SiO by stirring2A surface;
(2) standing the material obtained in the step (1) at room temperature for 10h to completely soak the active components, and then drying the material in a drying oven at the temperature of 110 ℃ for 12h to completely remove the water;
(3) roasting the dried solid substance in air at 400 ℃ for 4h to obtain a catalyst with 15 wt% of phosphotungstic acid theoretical loading, which is recorded as (15) HPW/SiO2。
The (15) HPW/SiO prepared in example 52Application of the catalyst in preparation of tert-butyl glyceryl ether by catalysis of glycerol:
4.144g of glycerol, 33.354g of tert-butanol and 0.414g of (15) HPW/SiO2Adding the catalyst into a 100mL stainless steel high-pressure reaction kettle, and adding N2Repeatedly purging the reaction kettle for 3 times to remove air, reacting for 8h at 110 ℃, taking a small amount of reaction solution after the reaction is finished, and measuring the conversion rate of the glycerol to be 90.80 percent and the selectivity of the polysubstituted tert-butyl glycerol ether to be 56.00 percent.
Reacting (15) HPW/SiO2The catalyst is recovered after centrifugation, washing, drying and roasting, and then the catalyst is recoveredThe catalyst is continuously used in the reaction for preparing the tert-butyl glyceryl ether by catalyzing the glycerol, a small amount of reaction solution is taken after repeated recovery and repeated application for 4 times, and the conversion rate of the glycerol is determined to be 83.25%. The modified supported catalyst still has good catalytic effect after being recycled for many times.
Example 6
The preparation method of the supported phosphotungstic acid solid acid catalyst comprises the following steps:
(1) taking 5g of SiO2Adding 1.25g of phosphotungstic acid into 10mL of deionized water, stirring at normal temperature for 12h, and loading the phosphotungstic acid to SiO by stirring2A surface;
(2) standing the material obtained in the step (1) at room temperature for 12h to remove part of water, and then drying in an oven at 110 ℃ for 10h to completely remove the water;
(3) roasting the dried solid substance in air at 350 ℃ for 3h to obtain a catalyst with 25 wt% of phosphotungstic acid theoretical loading, which is recorded as (25) HPW/SiO2。
The (25) HPW/SiO prepared in example 62Application of the catalyst in preparation of tert-butyl glyceryl ether by catalysis of glycerol:
3.5g of glycerol, 33.804g of tert-butanol and 0.525g of (25) HPW/SiO2Adding the catalyst into a 100mL stainless steel high-pressure reaction kettle, and adding N2Repeatedly purging the reaction kettle for 3 times to remove air, reacting for 11h at 100 ℃, taking a small amount of reaction solution after the reaction is finished, and measuring the conversion rate of the glycerol to be 71.69% and the selectivity of the polysubstituted tert-butyl glyceryl ether to be 35.87%.
Reacting (25) HPW/SiO2The catalyst is recovered after centrifugation, washing, drying and roasting, is continuously used as the catalyst to be applied to the reaction for preparing the tert-butyl glyceryl ether by the catalysis of the glycerol, and a small amount of reaction solution is taken after repeated recovery and repeated application for 4 times, and the conversion rate of the glycerol is measured to be 60.34%. The modified supported catalyst still has good catalytic effect after being recycled for many times.
From examples 1 to 6, it is understood that the conversion rate of glycerol increases and then decreases, and the selectivity of polysubstituted tert-butyl glyceryl ether increases and then decreases with the increase of the loading amount of phosphotungstic acid on the carrier, and that the catalytic effect is best when the loading amount of phosphotungstic acid on the carrier is 15% of the mass of the carrier and the addition amount of the catalyst is 10% of the mass of glycerol, that is, the conversion rate of glycerol is the highest, and the selectivity of polysubstituted tert-butyl glyceryl ether is the highest. In addition, when the mass ratio of the catalyst to the reaction substrate glycerol is 1:10, the conversion rate of the obtained glycerol is the highest, and the selectivity of the polysubstituted tert-butyl glycerol ether is the highest.
Comparative examples
Non-modified SiO2Application of the catalyst in preparation of tert-butyl glyceryl ether by catalysis of glycerol:
4.144g of glycerol, 33.354g of tert-butanol and 0.414g of SiO2Adding the catalyst into a 100mL stainless steel high-pressure reaction kettle, and adding N2Repeatedly purging the reaction kettle for 3 times to remove air, reacting for 8h at 110 ℃, taking a small amount of reaction solution after the reaction is finished, and measuring the conversion rate of the glycerol to be 16.55 percent and the selectivity of the polysubstituted tert-butyl glycerol ether to be 1.04 percent.
Reacting the SiO2The catalyst is recovered after centrifugation, washing, drying and roasting, is continuously used as the catalyst to be applied to the reaction for preparing the tert-butyl glyceryl ether by catalyzing the glycerol, a small amount of reaction solution is taken after repeated recovery and repeated application for 2 times, the conversion rate of the glycerol is measured to be 13.93%, and a small amount of reaction solution is taken after repeated recovery and repeated application for 4 times, and the conversion rate of the glycerol is measured to be 10.06%.
From the above results, the glycerol conversion ratios of examples 1, 2, 3, 4, 5, and 6, which demonstrate the effectiveness of the present invention, are: 74.05%, 88.30%, 75.24%, 82.32%, 90.80%, 71.69%, and the selectivity of the multi-substituted tert-butyl glyceryl ether is 42.32%, 48.39%, 36.11%, 38.51%, 56.00%, 35.87%; the conversion of glycerol in the comparative example was 16.55%, and the selectivity to polysubstituted tert-butyl glycerol ether was 1.04%. It is easy to see that the synthetic process route of the invention greatly improves the conversion rate of the glycerol and the selectivity of the polysubstituted tert-butyl glycerol ether.
Claims (9)
1. A method for preparing tert-butyl glyceryl ether by using a solid acid catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) reacting glycerol and tert-butyl alcohol with the mass ratio of substances of 1: 4-1: 12 and a solid acid catalyst accounting for 1-20% of the mass ratio of the glycerol in a closed pressure-resistant reactor to obtain a product;
(2) and (2) separating the product obtained in the step (1) to obtain tert-butyl glyceryl ether.
2. The method for preparing tert-butyl glyceryl ether by using a solid acid catalyst as claimed in claim 1, wherein: in the step (1), the concrete steps are as follows: adding glycerol, tert-butyl alcohol and a supported phosphotungstic acid solid acid catalyst into a high-pressure reaction kettle by using N2Purging for more than three times, and removing air from the high-pressure reaction kettle to perform reaction.
3. The method for preparing tert-butyl glyceryl ether by using a solid acid catalyst as claimed in claim 1, wherein: in the step (1), the reaction conditions are as follows: reacting for 8-12 h at the autogenous pressure of 0-2 MPa and the temperature of 80-120 ℃.
4. The method for preparing tert-butyl glyceryl ether by using a solid acid catalyst as claimed in claim 1, wherein: in the step (2), the product comprises tri-tert-butyl glycerol ether and di-tert-butyl glycerol ether, wherein the selectivity of the tri-tert-butyl glycerol ether is 5.5-11.3%, and the selectivity of the di-tert-butyl glycerol ether is 30.1-45.7%.
5. The method for preparing tert-butyl glyceryl ether by using a solid acid catalyst as claimed in claim 1, wherein: in the step (1), the solid acid catalyst is a supported phosphotungstic acid solid acid catalyst, the supported phosphotungstic acid solid acid catalyst takes phosphotungstic acid as an active component, and the supported phosphotungstic acid solid acid catalyst is obtained by adopting an isometric impregnation method for a carrier and phosphotungstic acid.
6. The method for preparing tert-butyl glyceryl ether by using a solid acid catalyst as claimed in claim 5, wherein: the carrier is one of zirconium dioxide, tin dioxide or silicon dioxide.
7. The method for preparing tert-butyl glyceryl ether by using a solid acid catalyst as claimed in claim 5, wherein: the supported phosphotungstic acid solid acid catalyst is obtained by the following method: adding the carrier and phosphotungstic acid into water, and stirring at room temperature; and standing, drying and roasting the stirred material in sequence to obtain the supported phosphotungstic acid solid acid catalyst.
8. The method for preparing tert-butyl glyceryl ether by using a solid acid catalyst as claimed in claim 5, wherein: the mass ratio of the addition amount of the carrier to the phosphotungstic acid is 1: 0.1-0.3; the volume of the corresponding deionized water was calculated from its water absorption for each 1g of carrier.
9. The method for preparing tert-butyl glyceryl ether by using a solid acid catalyst as claimed in claim 7, wherein: the catalyst calcination temperature is 250-400 ℃, and the calcination time is 2-4 h.
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