CN118063299A - Method for producing acetaldehyde by catalyzing glycol dehydration - Google Patents
Method for producing acetaldehyde by catalyzing glycol dehydration Download PDFInfo
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 106
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 30
- 230000018044 dehydration Effects 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 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 43
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000004898 kneading Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 13
- 238000002791 soaking Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101100112997 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MCM22 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing acetaldehyde by catalyzing glycol dehydration, which comprises the following steps: the catalyst phosphotungstic acid/SiO 2 is adopted to catalyze glycol to dehydrate and produce acetaldehyde in a fixed bed, the phosphotungstic acid/SiO 2 catalyst is prepared by mixing and kneading phosphotungstic acid, deionized water, siO 2 powder and aluminum sol, extruding, drying and calcining, wherein the amount of the phosphotungstic acid is 50-100wt% of the SiO 2 powder, and the amount of the aluminum sol is 25-30wt% of the SiO 2 powder. The conversion rate of glycol and the selectivity of acetaldehyde can reach more than 95 percent; the phosphotungstic acid/SiO 2 catalyst in the invention has simple preparation process, low cost and good catalytic performance, and has better industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for producing acetaldehyde by catalyzing ethylene glycol dehydration.
Background
Acetaldehyde is an important aliphatic compound, is an important raw material for preparing various chemicals such as acetic acid, acetic anhydride, ketene, ethyl acetate, crotonaldehyde, n-butanol, 2-ethylhexanol, pentaerythritol, chloral, pyridine and the like, and has high industrial application value. The current industrial methods for synthesizing acetaldehyde mainly comprise an ethylene direct oxidation method, an ethanol dehydrogenation method and an acetylene direct hydration method. However, these preparation methods have disadvantages: pd catalysts are mostly adopted in the ethylene oxidation method, ag is mostly adopted as a catalyst in the ethanol oxidation method, active components of the catalysts in the two processes are noble metals, and the cost is high. The alcohol dehydrogenation method is to produce acetaldehyde by alcohol dehydrogenation under the action of copper catalyst added with cobalt, chromium, zinc or other compounds. The method has the advantages of by-product of a large amount of water, and high separation energy consumption. The direct hydration method of acetylene has high yield and product purity, but mercury salt has great toxicity and severely pollutes the environment. With the continuous progress of the technology of preparing ethylene glycol from coal, the ethylene glycol is used as a bulk chemical, and has wide sources and low price. The development of the method for producing the acetaldehyde by using the ethylene glycol as the raw material has good economy and broad market prospect.
CN10847010a discloses a method for synthesizing acetaldehyde by gas phase dehydration of ethylene glycol in a fixed bed at a reaction temperature of 200-350 ℃ by using active carbon supported phosphoric acid, sulfuric acid, phosphate or sulfate as catalyst, the conversion rate of ethylene glycol is 70-100%, and the selectivity of acetaldehyde is 50-100%. CN114618580a discloses that one or more of alumina, silica, niobium oxide, phosphoric acid, phosphotungstic acid, etc. are deactivated after a period of time, and an on-line regeneration method of air oxidation and steam blowing is adopted. CN114656344a discloses that the catalyst performance can be improved with molecular sieves or supported Pt molecular sieves. CN116924898a discloses a method for producing acetaldehyde by using a catalyst prepared by modifying MCM22, MCM49 and ZSM5 molecular sieves as active components and adopting a gas phase dehydration reaction of ethylene glycol, wherein the selectivity of glyoxal can reach 95%. The dehydration of ethylene glycol to produce acetaldehyde is a new process route, related mechanism researches are also being carried out, and researches mainly focused on the rearrangement of intermediate products pinacol and the tautomerism of vinyl alcohol are mainly carried out, and the catalyst is mainly focused on solid acid or modification. Since the ethylene glycol dehydration process is quite complex, several processes may occur: breaking carbon-hydrogen bond in ethylene glycol molecule and hydrocarbon bond on carbon atom adjacent to hydroxyl carbon atom to generate vinyl alcohol and finally acetaldehyde; removing one molecule of water from two hydroxyl groups in the ethylene glycol molecule to form ethylene oxide; removing two water molecules in the ethylene glycol molecule, and performing elimination reaction to form acetylene; intermolecular dehydration or polycondensation reactions may also occur to produce side products such as dioxane or diethylene glycol. Therefore, the development of a catalyst with high conversion rate of ethylene glycol and high selectivity and high stability of glyoxal is a key for realizing the industrial production of acetaldehyde by dehydration of ethylene glycol.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for producing acetaldehyde by catalyzing ethylene glycol dehydration.
It is another object of the present invention to provide the use of a phosphotungstic acid/SiO 2 catalyst in the catalytic dehydration of ethylene glycol to acetaldehyde.
The technical scheme of the invention is as follows:
A method for producing acetaldehyde by catalyzing the dehydration of ethylene glycol, comprising: the catalyst phosphotungstic acid/SiO 2 is adopted to catalyze glycol to dehydrate and produce acetaldehyde in a fixed bed, the phosphotungstic acid/SiO 2 catalyst is prepared by mixing and kneading phosphotungstic acid, deionized water, siO 2 powder and aluminum sol, extruding, drying and calcining, wherein the amount of the phosphotungstic acid is 50-100wt% of the SiO 2 powder, and the amount of the aluminum sol is 25-30wt% of the SiO 2 powder.
In a preferred embodiment of the present invention, the preparation method of the phosphotungstic acid/SiO 2 catalyst comprises the following steps: dissolving phosphotungstic acid in part of deionized water, fully stirring and dissolving, adding SiO 2 powder for equal volume impregnation, carrying out ultrasonic treatment for 15-30min, standing for 10-12h, drying, kneading with aluminum sol and the rest deionized water, and then sequentially extruding, drying and calcining to obtain the product.
Further preferably, the volume ratio of the aluminum sol to the rest deionized water is 1:1.
In a preferred embodiment of the present invention, the temperature of the drying is 80-100 ℃; the calcination temperature is 400-450 ℃ and the calcination time is 2-4h.
In a preferred embodiment of the present invention, the reaction conditions of the fixed bed are: the raw material is water and glycol mixed solution, the mol ratio of water to glycol is 0.5-2.5, the liquid hourly space velocity is 5-15h -1, the temperature is 360-420 ℃, and the reaction pressure is normal pressure to 0.2Mpa.
The application of the phosphotungstic acid/SiO 2 catalyst in the production of acetaldehyde by catalyzing glycol dehydration is carried out in a fixed bed, the phosphotungstic acid/SiO 2 catalyst is prepared by kneading, extruding, drying and calcining phosphotungstic acid, deionized water, siO 2 powder and aluminum sol, wherein the amount of the phosphotungstic acid is 50-100wt% of the SiO 2 powder, and the amount of the aluminum sol is 25-30wt% of the SiO 2 powder.
In a preferred embodiment of the present invention, the preparation method of the phosphotungstic acid/SiO 2 catalyst comprises the following steps: dissolving phosphotungstic acid in part of deionized water, fully stirring and dissolving, adding SiO 2 powder for equal volume impregnation, carrying out ultrasonic treatment for 15-30min, standing for 10-12h, drying, kneading with aluminum sol and the rest deionized water, and then sequentially extruding, drying and calcining to obtain the product.
Further preferably, the volume ratio of the aluminum sol to the rest deionized water is 1:1.
In a preferred embodiment of the present invention, the temperature of the drying is 80-100 ℃; the calcination temperature is 400-450 ℃ and the calcination time is 2-4h.
In a preferred embodiment of the present invention, the reaction conditions of the fixed bed are: the raw material is water and glycol mixed solution, the mol ratio of water to glycol is 0.5-2.5, the liquid hourly space velocity is 5-15h -1, the temperature is 360-420 ℃, and the reaction pressure is normal pressure to 0.2Mpa.
The beneficial effects of the invention are as follows:
1. The conversion rate of glycol and the selectivity of acetaldehyde can reach more than 95 percent.
2. The phosphotungstic acid/SiO 2 catalyst in the invention has simple preparation process, low cost and good catalytic performance, and has better industrial application prospect.
Detailed Description
The technical scheme of the invention is further illustrated and described through the following specific embodiments.
Example 1
(1) Dissolving 51.8g of phosphotungstic acid in 100mL of deionized water, fully stirring and dissolving, adding 100g of SiO 2 powder for soaking, carrying out ultrasonic treatment for 15min, standing for 12h, drying at 80-100 ℃,
(2) And putting the dried powder into a kneader, adding 30g of aluminum sol and 30mL of deionized water for kneading, extruding strips, drying and calcining to obtain the formed phosphotungstic acid/SiO 2 catalyst. Wherein, the catalyst is dried at 80-100 ℃, and finally baked for 4 hours at 450 ℃ to obtain the molded strip phosphotungstic acid/SiO 2 catalyst with the diameter of 2-3mm, the length of 5-10mm and the mechanical strength of more than 40N. The catalyst was labeled HPW50/SiO 2.
The HPW50/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 96.6% and the average selectivity of acetaldehyde was 97.0%.
Example 2
(1) Dissolving 37.4g of phosphotungstic acid in 100mL of deionized water, fully stirring and dissolving, adding 100g of SiO 2 powder for soaking, carrying out ultrasonic treatment for 15min, standing for 12h, drying at 80-100 ℃,
Step (2) was the same as in example 1; the catalyst was labeled HPW30/SiO 2.
The HPW30/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 76.5% and the average selectivity of acetaldehyde was 90.0%.
Example 3
(1) 62.14G of phosphotungstic acid is dissolved in 100mL of deionized water and is fully stirred and dissolved, 100g of SiO 2 powder is added for soaking, the mixture is kept stand for 12 hours after ultrasonic treatment for 15 minutes, and is dried at 80-100 ℃,
Step (2) was the same as in example 1; the catalyst was labeled HPW60/SiO 2.
The HPW60/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 90.6% and the average selectivity of acetaldehyde was 93.8%.
Example 4
(1) Dissolving 72.5g of phosphotungstic acid in 100mL of deionized water, fully stirring and dissolving, adding 100g of SiO 2 powder for soaking, carrying out ultrasonic treatment for 15min, standing for 12h, drying at 80-100 ℃,
Step (2) was the same as in example 1; the catalyst was labeled HPW70/SiO 2.
The HPW70/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 90.5% and the average selectivity of acetaldehyde was 91.3%.
Example 5
(1) Dissolving 93.2g of phosphotungstic acid in 100mL of deionized water, fully stirring and dissolving, adding 100g of SiO 2 powder for soaking, carrying out ultrasonic treatment for 15min, standing for 12h, drying at 80-100 ℃,
Step (2) was the same as in example 1; the catalyst was labeled HPW90/SiO 2.
The HPW90/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 85.5% and the average selectivity of acetaldehyde was 93.7%.
Example 6
Step (1) is the same as in example 5.
(2) And putting the dried powder into a kneader, adding 30g of aluminum sol and 30mL of deionized water for kneading, extruding strips, drying and calcining to obtain the formed phosphotungstic acid/SiO 2 catalyst. Wherein, the catalyst is dried at 80-100 ℃, and finally baked for 4 hours at 400 ℃ to obtain the molded strip phosphotungstic acid/SiO 2 catalyst with the diameter of 2-3mm, the length of 5-10mm and the mechanical strength of more than 40N. The catalyst was labeled HPW90/SiO 2 -400.
The HPW90/SiO2-400 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 86.3% and the average selectivity of acetaldehyde was 95.1%.
Example 7
Step (1) is the same as in example 5.
(2) And putting the dried powder into a kneader, adding 30g of aluminum sol and 30mL of deionized water for kneading, extruding strips, drying and calcining to obtain the formed phosphotungstic acid/SiO 2 catalyst. Wherein, the catalyst is dried at 80-100 ℃, and finally baked for 4 hours at 500 ℃ to obtain the molded strip phosphotungstic acid/SiO 2 catalyst with the diameter of 2-3mm, the length of 5-10mm and the mechanical strength of more than 40N. The catalyst was labeled HPW90/SiO 2 -500.
The HPW90/SiO 2 -500 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 72.5% and the average selectivity of acetaldehyde was 97.2%.
Example 8
Step (1) and step (2) are the same as in example 1; the catalyst was labeled HPW50/SiO 2.
The HPW50/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 360 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 85.5% and the average selectivity of acetaldehyde was 86.3%.
Example 9
Step (1) and step (2) are the same as in example 1; the catalyst was labeled HPW50/SiO 2.
The HPW50/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 420 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 92.5% and the average selectivity of acetaldehyde was 94.3%.
Example 10
Step (1) and step (2) are the same as in example 1; the catalyst was labeled HPW50/SiO 2.
The HPW50/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 4.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 92.5% and the average selectivity of acetaldehyde was 94.3%.
Example 11
Step (1) and step (2) are the same as in example 1; the catalyst was labeled HPW50/SiO 2.
The HPW50/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 1, the liquid hourly space velocity is 10.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 85.5% and the average selectivity of acetaldehyde was 90.5%.
Example 12
Step (1) and step (2) are the same as in example 1; the catalyst was labeled HPW50/SiO 2.
The HPW50/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 0.5, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 88.3% and the average selectivity of acetaldehyde was 88.9%.
Example 13
Step (1) and step (2) are the same as in example 1; the catalyst was labeled HPW50/SiO 2.
The HPW50/SiO 2 catalyst prepared in the embodiment is used for the reaction of producing acetaldehyde by fixed bed glycol catalytic dehydration, the molar ratio of raw material water to alcohol is 2.5, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the reaction temperature is 380 ℃, and the reaction time is 8h.
The evaluation results are as follows: the average conversion of ethylene glycol was 93.5% and the average selectivity of acetaldehyde was 93.8%.
In summary, the reaction for producing acetaldehyde by adopting the fixed bed ethylene glycol catalytic dehydration has the following reaction conditions: the molar ratio of the raw material water to the alcohol is 1, the liquid hourly space velocity is 7.5h -1, the reaction pressure is 0.1Mpa, the HPW50/SiO 2 catalyst shows the best catalytic performance at the reaction temperature of 380 ℃, the average conversion rate of ethylene glycol is 96.6%, and the average selectivity of acetaldehyde is 97.0%.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Claims (10)
1. A method for producing acetaldehyde by catalyzing glycol dehydration is characterized in that: comprising the following steps: the catalyst phosphotungstic acid/SiO 2 is adopted to catalyze glycol to dehydrate and produce acetaldehyde in a fixed bed, the phosphotungstic acid/SiO 2 catalyst is prepared by mixing and kneading phosphotungstic acid, deionized water, siO 2 powder and aluminum sol, extruding, drying and calcining, wherein the amount of the phosphotungstic acid is 50-100wt% of the SiO 2 powder, and the amount of the aluminum sol is 25-30wt% of the SiO 2 powder.
2. The method of claim 1, wherein: the preparation method of the phosphotungstic acid/SiO 2 catalyst comprises the following steps: dissolving phosphotungstic acid in part of deionized water, fully stirring and dissolving, adding SiO 2 powder for equal volume impregnation, carrying out ultrasonic treatment for 15-30min, standing for 10-12h, drying, kneading with aluminum sol and the rest deionized water, and then sequentially extruding, drying and calcining to obtain the product.
3. The method of claim 2, wherein: the volume ratio of the aluminum sol to the rest deionized water is 1:1.
4. The method of claim 1, wherein: the temperature of the drying is 80-100 ℃; the calcination temperature is 400-450 ℃ and the calcination time is 2-4h.
5. The method of any one of claims 1 to 4, wherein: the reaction conditions of the fixed bed are as follows: the raw material is water and glycol mixed solution, the mol ratio of water to glycol is 0.5-2.5, the liquid hourly space velocity is 5-15h -1, the temperature is 360-420 ℃, and the reaction pressure is normal pressure to 0.2Mpa.
6. The application of the phosphotungstic acid/SiO 2 catalyst in catalyzing glycol dehydration to produce acetaldehyde is characterized in that: the phosphotungstic acid/SiO 2 catalyst is prepared by mixing and kneading phosphotungstic acid, deionized water, siO 2 powder and aluminum sol, extruding, drying and calcining, wherein the amount of the phosphotungstic acid is 50-100wt% of the SiO 2 powder, and the amount of the aluminum sol is 25-30wt% of the SiO 2 powder.
7. The use according to claim 6, wherein: the preparation method of the phosphotungstic acid/SiO 2 catalyst comprises the following steps: dissolving phosphotungstic acid in part of deionized water, fully stirring and dissolving, adding SiO 2 powder for equal volume impregnation, carrying out ultrasonic treatment for 15-30min, standing for 10-12h, drying, kneading with aluminum sol and the rest deionized water, and then sequentially extruding, drying and calcining to obtain the product.
8. The use according to claim 7, wherein: the volume ratio of the aluminum sol to the rest deionized water is 1:1.
9. The use according to claim 6, wherein: the temperature of the drying is 80-100 ℃; the calcination temperature is 400-450 ℃ and the calcination time is 2-4h.
10. Use according to any one of claims 6 to 9, characterized in that: the reaction conditions of the fixed bed are as follows: the raw material is water and glycol mixed solution, the mol ratio of water to glycol is 0.5-2.5, the liquid hourly space velocity is 5-15h -1, the temperature is 360-420 ℃, and the reaction pressure is normal pressure to 0.2Mpa.
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