CN111774051A - Catalyst for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration and preparation method thereof - Google Patents
Catalyst for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000005977 Ethylene Substances 0.000 title claims abstract description 32
- 230000018044 dehydration Effects 0.000 title claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 235000019441 ethanol Nutrition 0.000 claims description 28
- 230000007547 defect Effects 0.000 claims description 17
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229910003091 WCl6 Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 60
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 10
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Images
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J35/39—
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
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- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
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- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/34—Manganese
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- 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
- Y02P20/10—Process efficiency
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- 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
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- 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
Abstract
The invention provides a catalyst for preparing ethylene and organic products by alcohol dehydration under photo-thermal catalysis and a preparation method thereof. The method is characterized in that the metal oxide photo-thermal catalyst generates heat under the irradiation of electromagnetic waves to drive alcohol dehydration reaction to generate ethylene and other organic products. The method can utilize sunlight to drive the reaction of preparing ethylene and organic matters by methanol dehydration, simultaneously, the used catalyst has strong absorption in visible and infrared light regions, solar energy can be effectively utilized, higher photo-thermal conversion efficiency can be obtained, and simultaneously, compared with the industrial methanol dehydration reaction, the reaction has the advantages of low cost, simple preparation method, environmental protection and the like, and belongs to the technical field of ethylene preparation.
Description
Technical Field
The invention relates to a catalyst for preparing ethylene and organic products by alcohol dehydration under photo-thermal catalysis and a preparation method thereof, belonging to the technical field of ethylene preparation.
Background
The industrial synthesis capacity of the low-carbon olefin such as ethylene, propylene and the like which are used as important raw materials in the chemical industry is an important index for measuring the national comprehensive strength. The traditional ethylene production process is by petroleum cracking, however, with increasing global energy demand and decreasing crude oil reserves, the cost of producing light olefins via the petroleum route is increasing. In recent years, research and development of chemical routes for obtaining olefins from non-petroleum have been paid attention from various countries in the world, and particularly for our country, petroleum resources are relatively deficient and coal resources are relatively abundant, so that the technology of preparing methanol from coal and natural gas and then preparing olefins (MTO) from methanol is very competitive in economy, and the research enthusiasm of vast researchers is brought up. From the consideration of national safety and energy strategy, the development and research of the chemical process for preparing olefin from methanol also have extremely important significance.
The reaction for preparing the olefin from the methanol is a very complex reaction system, most of the reactions are thermodynamically favorable and belong to strong exothermic reactions, and the total reaction heat is 34-22 kJ/mol. The reaction temperature has obvious influence on the activity of the reaction, and the reaction rate is favorably improved by increasing the reaction temperature, but the reaction temperature is not favorable for obtaining high olefin selectivity, so the temperature control of a reaction system is particularly important, and the reaction temperature generally selected industrially is 325-425 ℃.
Although the reaction for producing olefins from methanol is an exothermic reaction, the reaction still needs to be carried out at a high temperature, and in industrial reactions, fossil fuels need to be burned to provide heat for the reaction and the reaction temperature needs to be kept at a certain temperature. If the heat of the reaction can be provided by the photothermal effect of sunlight, a great deal of energy can be saved, and the reaction process is cleaner.
Tungsten-based oxides have been extensively studied and synthesized in various morphological structures over the past decades due to their unique physical and electronic properties, and due to their structural versatility, have a variety of oxide phases, the most common of which is tungsten trioxide, and have been extensively studied as a classical photocatalytic water-oxidized semiconductor material. Tungsten trioxide is a typical indirect semiconductor with a narrow band gap, the forbidden band width of the tungsten trioxide is 2.6-2.8 eV, the tungsten trioxide can absorb part of visible light, and W in tungsten oxide6+The tungsten oxide semiconductor with oxygen vacancies of different concentrations has great adjustability of surface properties and electronic structures, gradually becomes a material which is very concerned in the field of defect engineering, and is widely applied to the fields of photoelectricity and photo-thermal catalysis. The absorption of non-stoichiometric tungsten oxides in the visible and infrared regions is very pronounced. Because the light in the wave band has strong photothermal effect, the compound has great application potential in photothermal catalytic reaction. Meanwhile, photo-thermal catalysis can convert low-density solar energy into high-density chemical energy, thus showing more unique advantages than conventional photo-catalysis and thermal catalysis.
Disclosure of Invention
The invention provides a method for preparing ethylene and organic products by alcohol dehydration through photo-thermal catalysis, the method can utilize sunlight to drive the reaction of preparing ethylene and organic products by methanol dehydration, simultaneously, the used catalyst has strong absorption in visible and infrared light regions, solar energy can be effectively utilized, higher photo-thermal conversion efficiency can be obtained, and simultaneously, compared with the industrial methanol dehydration reaction, the reaction has the advantages of low cost, simple preparation method, environmental protection and the like.
To achieve the above object, a catalyst for the photothermal catalytic dehydration of alcohols to ethylene and organic products is intended to be used, which catalyst is a defect-containing acidic metal oxide, preferably a defect-containing tungsten-based oxide.
The preparation method of the catalyst adopts a hydrothermal-high temperature annealing method and comprises the following steps:
(1) mixing WCl6Dissolving in absolute ethyl alcohol, stirring after ultrasonic treatment until the solution becomes yellow transparent solution, pouring the solution into a polytetrafluoroethylene lining, putting the solution into a stainless steel hydrothermal reaction kettle, reacting at the temperature of 150-200 ℃ for 6-15 hours, naturally cooling to room temperature after the reaction is finished, washing for 4-6 times by using absolute ethyl alcohol, drying in a vacuum drying oven at the temperature of 40-80 ℃, and collecting to obtain W18O49Sample (a WO containing defects3-x)，WCl6Concentration of ethanol solution, influence formation of WO3-xThe formed catalyst has little influence on the photo-thermal reaction;
(2) to obtain WO with different defect contents3-xW prepared in (1)18O49Respectively annealing at 200 ℃ and 500 ℃ to obtain two kinds of WO with different defect contents3-xA photo-thermal catalyst.
As a preferable embodiment of the present invention, in the step (1), WCl is contained in a yellow transparent solution6The concentration of (A) is 0.01-0.05mol/L, the hydrothermal temperature is set to 180 ℃, and the reaction time is 12 hours
In the method, the reaction heat is completely generated by the photo-thermal conversion of the surface of the metal oxide, the light source is sunlight, focused sunlight, an infrared lamp or a xenon lamp, and the temperature of the surface of the catalyst is 100-500 ℃;
preferably, the temperature of the catalyst surface is 300-.
The invention also provides a method for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration, which is characterized in that a metal oxide photo-thermal catalyst generates heat under the irradiation of electromagnetic waves to drive alcohol dehydration reaction to generate ethylene and other organic products, the alcohol can be directly dehydrated to produce ethylene and ether organic products, no additional heating is needed, and main products of methanol dehydration are ethylene and methyl ether.
In the foregoing method, the active component of the metal oxide photo-thermal catalyst is a defect-containing acidic metal oxide, specifically a tungsten-based oxide, a molybdenum-based oxide, a titanium-based oxide, or a manganese-based oxide, and the defect-containing acidic metal oxide has two functions: firstly, the electromagnetic radiation generates heat through photo-thermal conversion to provide heat for reaction; the second is catalytic action, which improves the conversion rate of the reaction and the selectivity of ethylene.
Compared with the prior art, the invention utilizes the acid metal oxide containing defects as a photo-thermal catalyst, particularly the tungsten-based oxide containing defects, the oxide material containing defects has wider sunlight spectral response and can realize higher photo-thermal conversion efficiency, in addition, the oxide has catalytic action on alcohol dehydration reaction, can obviously reduce the reaction temperature of the alcohol dehydration reaction, and has two functions: 1) electromagnetic radiation generates heat through photo-thermal conversion to provide heat for reaction; 2) the catalytic action improves the conversion rate and the selectivity of ethylene of the reaction, can utilize sunlight to drive methanol to dehydrate to prepare ethylene and organic matters, simultaneously, the used catalyst has strong absorption in visible and infrared light regions, can effectively utilize solar energy to obtain higher photothermal conversion efficiency, can directly dehydrate alcohols to produce ethylene and ether organic products, does not need additional heating, and has the advantages of low cost, simple preparation method, environmental protection and the like compared with the industrial methanol dehydration reaction.
The implementation of the invention can obviously reduce the energy consumption of the alcohol dehydration reaction, improve the reaction activity of the alcohol reaction and the selectivity of the alcohol reaction to ethylene, provide a new thought for the reaction of preparing olefin by high-efficiency energy-saving photo-thermal alcohol dehydration, and simultaneously, the preparation of the photo-thermal catalyst has the following characteristics:
(1) preparing WO by adopting a hydrothermal method3-xThe photo-thermal catalyst has the advantages of low reaction temperature, simple technical process, simple equipment and low cost.
(2) The method by heat treatment is described in WO3The method has the advantages of simple process, simple equipment, and rapid reactionAnd the cost is low.
(3) The defective tungsten-based oxide has obvious light absorption in ultraviolet, visible and infrared light regions, and can efficiently utilize sunlight. The material is used as a catalyst to drive alcohol dehydration reaction, and other energy sources such as heat energy, electric energy and the like are not consumed.
(4) The defective tungsten-based oxide not only can be used for photo-thermal conversion, but also has a catalytic action, and improves the reaction activity of the alcohol dehydration reaction and the selectivity of a specific product.
(5) Compared with the traditional methanol dehydration reaction, the olefin product of the catalyst only contains ethylene, so that the steps of separating ethylene and propylene gases and energy consumption can be saved.
Drawings
FIG. 1 shows W prepared by hydrothermal method18O49Scanning photo of photo-thermal catalyst;
FIG. 2 is W18O49Adsorption and desorption curves of the photo-thermal catalyst;
FIG. 3 is W18O49A graph comparing the ultraviolet-visible absorption spectrum of the photothermal catalyst with the solar spectrum;
FIG. 4 is a schematic diagram of a photothermal methanol dehydration reactor;
FIG. 5 is W18O49The surface temperature of the photo-thermal catalyst under the irradiation of a 300W xenon lamp;
FIG. 6 is W18O49And W after annealing at 200 DEG C18O49The activity of methanol dehydration reaction.
Detailed Description
To make the objects, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail with reference to the accompanying drawings, and it should be understood that the specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention.
Example 1
Referring to fig. 1-6, this example provides a method for preparing ethylene and organic products by alcohol dehydration with photo-thermal catalysis, which comprises the following steps:
1)WO3preparing a photo-thermal catalyst: 0.6g of chlorine are weighed outDissolving tungsten oxide in 60mL of ethanol solution, and performing ultrasonic treatment for 200 minutes to obtain a transparent clear solution. And pouring the solution into a 100mL hydrothermal reaction kettle, reacting at 180 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is finished. Washed with absolute ethyl alcohol for 5 times, and then dried in a vacuum drying oven at 60 ℃. Obtaining a deep blue W18O49And (3) sampling. The particle size of the sample is about 1 micron (see figure 1) observed by a scanning electron microscope, the specific surface area of the sample is 163 square meters/gram (see figure 2), and W18O49The catalyst has obvious light absorption in ultraviolet, visible and infrared regions (see figure 3), because of the existence of a large number of oxygen vacancies and low-valent tungsten ions W in the catalyst body and on the surface5+. In order to prepare WO with different defects3-xSample, W to be collected18O49The sample was annealed in a muffle furnace at 200 ℃ and 500 ℃ for 2 hours, respectively, to obtain a pale yellow WO3-xSample, noted W18O49-200 and W18O49-500。
2) The methanol dehydration reaction was carried out in a closed vessel (see FIG. 4). 0.2g of catalyst is weighed, laid flat and placed in a sample tank, a quartz cover is covered on the reactor, and four fastening clamps are clamped tightly to seal the reactor and isolate air. The reactor was purged with argon through two sample ports for 10 minutes to remove air from the reactor, and then the sample ports were sealed with a sample pad. 50 microliter of liquid methanol (1.24mmol) is filled into the reactor by a sample injection needle, and the reactor is wrapped by tinfoil for dark reaction for 10 hours to reach absorption and desorption equilibrium. During the photothermal reaction, a 300W xenon lamp is used as a light source, different optical filters are matched, the light intensity is adjusted to the maximum value, the light irradiates the surface of the catalyst from the top of the reactor, the light source can completely cover the catalyst, and the distance from the xenon lamp to the top cover of the reactor is fixed at 10cm so as to ensure that the light intensity of each reaction is consistent. The strong light absorption of the catalyst enables the temperature of the catalyst surface to reach 300 ℃ rapidly under the irradiation of a xenon lamp (see figure 5), and the generation of alcohol dehydration reaction is driven. The main products of the methanol dehydration reaction are dimethyl ether and ethylene (see figure 6), the conversion rate of methanol can reach 75%, the selectivity of ethylene is 9.5%, and the selectivity of dimethyl ether is 90.5%.
Example 2
The amount of tungsten chloride in step 1) of example 1 was changed to 0.2g, and the other conditions were kept unchanged.
Example 3
The amount of tungsten chloride in step 1) of example 1 was changed to 0.4g, and the other conditions were kept unchanged.
Example 4
The amount of tungsten chloride in step 1) of example 1 was changed to 0.8g, and the other conditions were kept unchanged.
Example 5
The amount of tungsten chloride in step 1) of example 1 was changed to 1g, and the other conditions were kept unchanged.
Example 6
The tungsten chloride of step 1) of example 1 was exchanged for molybdenum chloride, the other conditions remaining unchanged.
Example 7
The tungsten chloride of step 1) of example 1 was changed to titanium chloride, the other conditions being kept unchanged.
Example 8
The tungsten chloride of step 1) of example 1 was changed to manganese chloride, and the other conditions were kept unchanged.
Example 9
The hydrothermal reaction temperature in step 1) of example 1 was changed to 150 ℃ and the other conditions were kept unchanged.
Example 10
The hydrothermal reaction temperature in step 1) of example 1 was changed to 200 ℃ and the other conditions were kept unchanged.
Example 11
The methanol of step 2) in example 1 was changed to ethanol, propanol or other alcohols, and other conditions were kept unchanged.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The catalyst for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration is characterized in that the catalyst is an acidic metal oxide containing defects.
2. The catalyst for preparing ethylene and organic products by alcohol dehydration through photo-thermal catalysis according to claim 1, which is characterized in that: the catalyst is a tungsten-based oxide containing defects.
3. The method for preparing the catalyst according to claim 2, wherein a hydrothermal-high temperature annealing method is adopted, comprising the steps of:
(1) mixing WCl6Dissolving in absolute ethyl alcohol, stirring after ultrasonic treatment until the solution becomes yellow transparent solution, pouring the solution into a polytetrafluoroethylene lining, putting the solution into a stainless steel hydrothermal reaction kettle, reacting at the temperature of 150-200 ℃ for 6-15 hours, naturally cooling to room temperature after the reaction is finished, washing for 4-6 times by using absolute ethyl alcohol, drying in a vacuum drying oven at the temperature of 40-80 ℃, and collecting to obtain W18O49A sample;
(2) to obtain WO with different defect contents3-xW prepared in (1)18O49Respectively annealing at 200 ℃ and 500 ℃ to obtain two kinds of WO with different defect contents3-xA photo-thermal catalyst.
4. The method according to claim 3, wherein: in the step (1), WCl is in the yellow transparent solution6The concentration of (A) is 0.01-0.05mol/L, the hydrothermal temperature is set to 180 ℃, and the reaction time is 12 hours.
5. The method according to claim 3, wherein: the reaction heat is generated by photo-thermal conversion of the surface of the metal oxide, the light source is sunlight, focused sunlight, an infrared lamp or a xenon lamp, and the temperature of the surface of the catalyst is 100-500 ℃.
6. The method according to claim 5, wherein: the method is characterized in that: the temperature of the catalyst surface is 300-350 ℃.
7. The method for preparing ethylene and organic products by alcohol dehydration under photo-thermal catalysis is characterized by comprising the following steps: the method is characterized in that the metal oxide photo-thermal catalyst generates heat under the irradiation of electromagnetic waves to drive alcohol dehydration reaction to generate ethylene and other organic products.
8. The method of claim 7 for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration, wherein the method comprises the following steps: the active component of the metal oxide photo-thermal catalyst is a defect-containing acidic metal oxide, specifically a defect-containing tungsten-based oxide, molybdenum-based oxide, titanium-based oxide or manganese-based oxide.
9. The method of claim 8 for preparing ethylene and organic products by photo-thermal catalysis of alcohol dehydration, wherein the method comprises the following steps: the metal oxide photo-thermal catalyst is a tungsten-based oxide containing defects.
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