CN112206765B - Preparation method of bimetallic catalyst and application of bimetallic catalyst in synthesis of allyl ether - Google Patents
Preparation method of bimetallic catalyst and application of bimetallic catalyst in synthesis of allyl ether Download PDFInfo
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Abstract
The invention discloses a preparation method of a bimetallic catalyst and application thereof in synthesis of allyl ether, wherein the molecular formula of the bimetallic catalyst is TiMo x O y The present invention uses allyl alcohol and one or several kinds selected from monohydric alcohol, polyhydric alcohol and monohydric phenol as raw material, and can prepare allyl ether compound by using Wilson synthesis method in the presence of bimetallic catalyst. The use of the bimetallic catalyst overcomes the defects that the catalyst is difficult to recover and the byproduct halogen acid corrodes equipment, no solvent is needed to be added in the synthesis process, and the product yield is more than 96 percent, thereby greatly reducing the production cost.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a preparation method of a bimetallic catalyst and application of the bimetallic catalyst in synthesis of allyl ether.
Background
Allyl ethers are well known to be useful components in industrial and laboratory synthesis, and the allyl ether structure has isomerization, oxygen binding and polymerization properties, and is commonly used in the fields of protecting groups, polymer monomers or crosslinking agents, photocuring, thermal curing, free radical curing coatings, air-drying unsaturated polyester coatings, flame retardant resins, and the like.
There are roughly three methods for producing allyl ethers: (1) reacting allyl halide with corresponding alcohol under the catalysis of alkali to generate allyl ether; (2) under the condition that Ru and Pd are used as catalysts, allyl alcohol and alcohol directly react to generate allyl ether; (3) in CSmhnPW 12 O 40 /ZrO 2 The catalyst is allyl alcohol as raw material and aromatic alcohol. However, the above methods have disadvantages, such as: the first production method can generate a large amount of hydrogen chloride to corrode equipment, so that the cost is greatly increased; the catalyst of the second production method cannot be reused; the third production method is applicable only to aromatic alcohols.
In addition, Japanese patent JP60252400 describes a process for preparing trimethylolpropane diallyl ether from trimethylolpropane and allyl chloride, but the yield is low and is not suitable for industrial production; U.S. Pat. No. 3,33, 502 describes a process for preparing allyl ethers from hydroxyalkanes and allyl alcohol, using Hg + BF is used as a catalyst, and benzene is used as a reaction medium, but the reaction catalyst and the reaction medium are toxic, and the subsequent separation can increase the production cost.
At present, the prior art does not have a method for solving the problems, and the production cost of the allyl ether is high, so a new process is urgently needed for solving the problems.
Disclosure of Invention
The invention provides a preparation method of a bimetallic catalyst and application thereof in synthesizing allyl ether, aiming at solving the problems in the prior art, the use of the bimetallic catalyst overcomes the defects that the catalyst is difficult to recover and the byproduct halogen acid corrodes equipment, no solvent is needed to be added in the synthesis process, and the product yield is more than 98 percent, thereby greatly reducing the production cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a bimetallic catalyst comprises the following steps: adding a titanium-containing compound into a dilute aqueous solution of molybdenum salt, soaking for a period of time, and drying at 50-150 ℃ for 2-5 hours; then heating to 450-600 ℃ at a heating rate of 3-10 ℃/min in an air environment, and continuously calcining for 2-5 hours at a constant temperature after the temperature reaches 450-600 ℃ to obtain the bimetallic catalyst.
In particular embodiments, the titanium-containing compound is Ti (NO) 3 ) 4 、TiO 2 、Ti(OH) 4 、Ti(Cl) 4 、TiOSO 4 Preferably TiO, one or more of the above components 2 。
In a particular embodiment, the molybdenum salt is (NH) 4 ) 6 (Mo 7 )O 24 (H 2 O) 4 、Na 2 MoO 4 、MgMoO 4 、Al 2 (MoO 4 ) 3 Preferably (NH) 4 ) 6 (Mo 7 )O 24 (H 2 O) 4 The mass concentration range of the dilute aqueous solution is 10-20%.
In a particular embodiment of the bimetallic catalyst according to the invention, the ratio of the molar amount of molybdenum to the molar amount of titanium added is 1 (1-20), preferably 1 (3-10).
In a particular embodiment of the bimetallic catalyst according to the invention, the impregnation time is between 0.5 and 10h, preferably between 3 and 4 h.
In a specific embodiment, the drying temperature is preferably 110 ℃ to 120 ℃, and the temperature rise rate is preferably 5 to 7 ℃/min.
The bimetallic catalyst prepared by adopting the parameters has high batch stability and good catalytic performance.
The second aspect of the invention provides a bimetallic catalyst with the molecular formula of TiMo prepared by the preparation method x O y X has a value of 0.2 to 1.0, preferably 0.5 to 1.0; y has a value of 2 to 4, preferably 2 to 3; the preferable Mo content can stabilize the crystal structure of Ti-O on one hand, and can prevent the activity of Ti from being reduced by too large Mo content on the other hand.
In a third aspect, the present invention provides the use of the bimetallic catalyst prepared by the above-mentioned preparation method for synthesizing an allyl ether compound.
The fourth aspect of the present invention provides a method for synthesizing an allyl ether compound, comprising the steps of:
allyl alcohol is used as a first raw material, one or more of monohydric alcohol, polyhydric alcohol and monohydric phenol are used as a second raw material, and the allyl ether compound is prepared and synthesized by a Wilson synthesis method in the presence of a catalyst, wherein the catalyst is a bimetallic catalyst TiMo prepared by the method x O y 。
According to the synthesis method of the present invention, in a specific embodiment, the monohydric alcohol is selected from one or more of ethanol, propanol, butanol, pentanol, isopentanol, hexanol, heptanol, and octanol; the polyalcohol is one or more selected from trimethylolpropane, pentaerythritol, glycerol, diethylene glycol and ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and butanediol; the monohydric phenol is selected from one or more of bisphenol a, phenol and derivatives thereof, for example, alkylated substituents of bisphenol a or phenol.
According to the synthesis method of the present invention, in a specific embodiment, allyl alcohol is added in an amount of 1.5 to 10.0 times, preferably 1.5 to 5.0 times the molar amount of the hydroxyl group contained in the second raw material added.
According to the synthesis method of the present invention, in a specific embodiment, the mass of the bimetallic catalyst added is 10% to 50%, preferably 10% to 30% of the mass of the second raw material added.
The parameter setting in the synthesis method can improve the yield of the allyl ether.
In accordance with the synthetic method of the present invention, in a specific embodiment, a synthetic method of an allyl ether compound comprises the steps of:
adding the bimetallic catalyst into allyl alcohol and one or more raw materials selected from monohydric alcohol, polyhydric alcohol and monohydric phenol to obtain reactants; under the protection of inert gas, heating the reactant to 140-160 ℃, reacting for 2-5 hours, cooling to room temperature, pouring out the reactant, filtering out the catalyst, washing and drying to obtain the allyl ether compound.
In the synthesis method of the allyl ether compound, the catalytic mechanism of the bimetallic catalyst is that hydroxyl oxygen in allyl alcohol forms a hydrogen bond with an acid site in the bimetallic catalyst and then removes one molecule of water to form a double bond, meanwhile, hydroxyl hydrogen in another reaction substrate (monohydric alcohol, polyhydric alcohol and/or monohydric phenol) forms a hydrogen bond with oxygen in the bimetallic catalyst, and then an oxygen atom forming the hydrogen bond provides electrons to shift the double bond of the removed water molecule, so that two molecules are connected to form the allyl ether.
"more" of "one or more" as used herein means "two or more". As used herein, "room temperature" means the same ambient temperature, typically 15-35 ℃.
The technical scheme provided by the invention has the following beneficial effects: the allyl ether compound synthesized by the bimetallic catalyst has simple process route, the catalyst can be recycled and is easy to recover, the maximum application of the catalyst can reach 15 times, and the requirement of long-period production can be met. In addition, no solvent is required to be added in the synthesis process, no corrosive by-product is generated, the product yield is more than 96%, the production cost is low, and the method is suitable for large-scale industrial production; and solves the problems that the catalyst is difficult to recover and the byproduct hydrohalogen acid corrodes equipment in the prior art, thereby being difficult to realize industrial production.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. For example, butanol, trimethylolpropane, bisphenol A, 1, 3-propanediol, titanium dioxide, titanium hydroxide, allyl alcohol, (NH) 4 ) 6 (Mo 7 )O 24 (H 2 O) 4 Were purchased from Sigma-Aldrich reagent.
The above reagents were purchased and used directly.
The test methods used in the examples of the invention and the comparative examples are as follows:
the product structure was determined by an elemental analyzer, Vario EL cube Analyzer, Elementar, Germany.
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
Preparation of the catalyst
80.0g (1.0mol) of TiO 2 To (NH) containing 4 ) 6 (Mo 7 )O 24 (H 2 O) 4 (49.0g, 0.04mol) in a 10% dilute aqueous solution, after 30 minutes the impregnated mixture was dried at 110 ℃ for 3 hours and then at 5 ℃ for 5 min in an air atmosphere -1 The temperature rise rate is increased from 110 ℃ to 500 ℃ for calcination, the calcination is continued at the temperature for 3 hours after the temperature is increased to 500 ℃, and 87.32g of the bimetallic catalyst is finally obtained, and the chemical formula of the bimetallic catalyst is TiMoO according to element analysis 4 。
Elemental analysis: ti: 23.0%, O: 30.8%, Mo: 46.2 percent;
synthesis of 1, 3-propanediol diallyl ether (Wilson Synthesis)
760.0g (10mol) of 1, 3-propanediol and 1740.0g (30mol) of allyl alcohol were charged into a 5L reactor, then 76.0g of the above bimetallic catalyst was added, the reactor was sealed after 3 times of nitrogen substitution, the reactor was heated to 145 ℃ to react for 3 hours, cooled to room temperature, the reaction product was poured out, the catalyst was filtered off, washed with pure water and dried to finally obtain 1483.14g of a product with a yield of 95%.
Elemental analysis: c: 65.75%, H: 9.83%, O: 24.42 percent
Example 2
Preparation of the catalyst
80.0g (1.0mol) of TiO 2 Adding into a container containing MgMoO 4 (18.4g, 0.1mol) in a 15% dilute aqueous solution, after 5h of impregnation, the impregnated mixture is dried at 50 ℃ for 5 hours and then at 10 ℃ for 10 min in an air atmosphere -1 The temperature rise rate of the catalyst is increased from 50 ℃ to 600 ℃ for calcination, and the calcination is continued after the temperature is increased to 600 DEG CCalcining at the temperature for 3 hours to finally obtain 91.4g of bimetallic catalyst, wherein the chemical formula obtained by element analysis is TiMo 0.5 O 2 。
Elemental analysis: ti: 37.6%, O: 25.0%, Mo: 37.4 percent
Synthesis of bisphenol A diallyl ether
2282.9g (10mol) of bisphenol A and 2320.0g (40mol) of allyl alcohol were added to a 10L reactor, then 228.3.0g of a bimetallic catalyst was added, the reactor was sealed after 3 times of nitrogen substitution, the reactor was heated to 150 ℃ to react for 3 hours, cooled to room temperature, the reaction mass was poured out, the catalyst was filtered off, washed with pure water and dried to obtain 2973.94g of a product with a yield of 96.5%.
Elemental analysis: c: 78.92%, H: 7.55%, O: 13.53 percent.
Example 3
Preparation of the catalyst
80.0g (1.0mol) of TiO 2 Adding into Na-containing solution 2 MoO 4 (10.3g, 0.05mol) in 20% dilute aqueous solution, drying the impregnated mixture at 150 deg.C for 2 hr after 10 hr, and then at 10 deg.C for 10 min in air -1 The temperature rise rate is increased from 150 ℃ to 450 ℃ for calcination, the calcination is continued at the temperature after the temperature is increased to 450 ℃ for 3 hours, and finally 84.8g of the bimetallic catalyst is obtained, wherein the chemical formula obtained according to the element analysis is TiMo 0.2 O 2 。
Elemental analysis: ti: 48.4%, O: 32.3%, Mo: 19.3 percent of
Synthesis of allyl butyl ether
741.2g (10mol) of butanol and 871.2g (15mol) of allyl alcohol were added to a 3L reactor, 80.65g of a bimetallic catalyst was then added, the reactor was sealed after 3 times of nitrogen substitution, the reactor was heated to 150 ℃ for 3 hours, cooled to room temperature, the reaction mass was poured off, the catalyst was filtered off, washed with pure water and dried to give 1116.7g of a product with a yield of 97.8%.
Elemental analysis: c: 72.01%, H: 12.08%, O: 15.91 percent.
Example 4
Preparation of the catalyst
The catalyst preparation was carried out in the same manner as in example 1 to obtain 86.84g of a bimetallic catalyst.
Synthesis of trihydroxymethyl triallyl ether
1341.7g (10mol) of trimethylolpropane and 17.42kg (300mol) of allyl alcohol are added into a 20L reaction kettle, 402.51g of bimetallic supported catalyst is added, the reaction kettle is sealed after being replaced by nitrogen for 3 times, the reaction kettle is heated to 150 ℃, the reaction kettle is reacted for 3 hours, the reaction kettle is cooled to room temperature, the reactant is poured out, the catalyst is filtered out, the catalyst is washed by pure water and dried, and 2497.91g of a product with the yield of 99.8 percent is finally obtained.
Elemental analysis: c: 69.55%, H: 10.11%, O: 20.34 percent.
Example 5
Preparation of the catalyst
The catalyst is the catalyst recovered after the reaction of the example 1; batches 1-15 refer to the recovered catalyst of example 1 recycled 1-15 times.
Synthesis of allyl butyl ether
741.2g (10mol) of butanol and 871.2g (15mol) of allyl alcohol were added to a 3L reactor, 80.65g of a bimetallic catalyst was then added, the reactor was sealed after 3 times of nitrogen substitution, the reactor was heated to 160 ℃ for 3 hours, cooled to room temperature, the reaction mass was poured off, the catalyst was filtered off, washed with pure water and dried to give 1109.9g of a product with a yield of 97.2%.
Elemental analysis: c: 72.03%, H: 12.12%, O: 15.85 percent.
TABLE 1 catalyst recycle 15 times data
| Batches of | Yield% |
| 1 | 97.2 |
| 3 | 96.95 |
| 6 | 96.87 |
| 9 | 96.74 |
| 12 | 96.67 |
| 15 | 96.61 |
Example 6
Preparation of the catalyst
The catalyst preparation was the same as in example 2, and 91.68g of a bimetallic catalyst was finally obtained.
Synthesis of trihydroxymethyl triallyl ether
1341.7g (10mol) of trimethylolpropane and 8.7kg (150mol) of allyl alcohol were charged into a 10L reactor, then 670.85g of a bimetallic supported catalyst was added, the reactor was sealed after 3 times of nitrogen substitution, the reactor was heated to 150 ℃ to react for 3 hours, cooled to room temperature, the reaction mass was poured out, the catalyst was filtered off, washed with pure water and dried to obtain 2497.91g of a product with a yield of 99.7%.
Elemental analysis: c: 69.55%, H: 10.11%, O: 20.34 percent.
Comparative example 1
Synthesis of 1, 3-propanediol diallyl ether
760.0g (10mol) of 1, 3-propanediol and 1740.0g (30mol) of allyl alcohol are charged into a 5L reactor, followed by 68.4g of TiO 2 With 7.6g of MoO 3 After 3 times of replacement with nitrogen, the reaction was carried outThe vessel was sealed, the reactor was heated to 145 ℃ for 3 hours, and cooled to room temperature to give 14.84g of product with a yield of 0.95%.
Elemental analysis: c: 65.72%, H: 10.32%, O: 23.96 percent.
Comparative example 2
Synthesis of trihydroxymethyl triallyl ether
1341.7g (10mol) of trimethylolpropane and 2613.6.2g (45mol) of allyl alcohol were charged into a 5L reactor, followed by 139.65g of TiO 2 The catalyst is replaced by nitrogen for 3 times, then the reactor is sealed, the reaction kettle is heated to 150 ℃, the reaction lasts for 3 hours, the reaction kettle is cooled to room temperature, and the reactants are poured out, and no product is generated after analysis.
Comparative example 3
Synthesis of allyl butyl ether
741.2g (10mol) of butanol and 871.2g (15mol) of allyl alcohol were added to a 3L reactor, followed by 80.65g of MoO 3 The catalyst is replaced by nitrogen for 3 times, then the reactor is sealed, the reaction kettle is heated to 160 ℃, the reaction lasts for 3 hours, the reaction kettle is cooled to room temperature, and the reactants are poured out, and no product is generated after analysis.
Compared with the comparative example, the allyl ether compound synthesized by the bimetallic catalyst has the advantages of simple process route, reusable and easily-recycled catalyst, 15 times of maximum application of the catalyst, and capability of meeting the long-period production requirement. In addition, no solvent is required to be added in the synthesis process, no corrosive by-product is generated, and the product yield is more than 96%.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes or modifications of the technical solution of the present invention are within the spirit of the present invention.
Claims (12)
1. Use of a bimetallic catalyst, characterized in that: the preparation method of the bimetallic catalyst used for synthesizing the allyl ether compound comprises the following steps: adding titanium-containing compound into dilute aqueous solution of molybdenum salt, soaking, and drying at 50-150 deg.C for 2-5 hr; then heating to 450-;
the molecular formula of the bimetallic catalyst is TiMo x O y Wherein, the value of x is 0.2 to 1.0; the value of y is 2-4.
2. Use of a bimetallic catalyst according to claim 1, characterized in that: the titanium-containing compound is Ti (NO) 3 ) 4 、TiO 2 、Ti(OH) 4 、Ti(Cl) 4 、TiOSO 4 One or more of the above, and/or;
the molybdenum salt is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、Na 2 MoO 4 、MgMoO 4 、Al 2 (MoO 4 ) 3 One or more of them.
3. Use of a bimetallic catalyst according to claim 2, characterized in that: the titanium-containing compound is TiO 2 The molybdenum salt is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O。
4. Use of a bimetallic catalyst according to claim 1, characterized in that: the ratio of the molar amount of molybdenum to the molar amount of titanium added is 1 (1-20).
5. Use of a bimetallic catalyst according to claim 4, characterized in that: the ratio of the molar amount of molybdenum to the molar amount of titanium added is 1 (3-10).
6. Use of a bimetallic catalyst according to claim 1, characterized in that: the dipping time is 0.5-10 h; and/or the drying temperature is 110-120 ℃, and the heating rate is 5-7 ℃/min.
7. Use of a bimetallic catalyst according to claim 6, characterized in that: the dipping time is 3-4 h.
8. Use of a bimetallic catalyst according to any one of claims 1-7, characterized in that: the molecular formula of the bimetallic catalyst is TiMo x O y Wherein, the value of x is 0.5 to 1.0; the value of y is 2-3.
9. A method for synthesizing an allyl ether compound, which is characterized by comprising the following steps: the method comprises the following steps:
allyl alcohol is used as a first raw material, one or more of monohydric alcohol, polyhydric alcohol and bisphenol A are used as a second raw material, and the allyl ether compound is prepared by a Wilson synthesis method in the presence of a bimetallic catalyst, wherein the preparation method of the bimetallic catalyst comprises the following steps: adding titanium-containing compound into dilute aqueous solution of molybdenum salt, soaking, and drying at 50-150 deg.C for 2-5 hr; then heating to 450-; the molecular formula of the bimetallic catalyst is TiMo x O y Wherein, the value of x is 0.2 to 1.0; the value of y is 2-4;
wherein the monohydric alcohol is selected from one or more of ethanol, propanol, butanol, pentanol, isopentanol, hexanol, heptanol, or octanol; and/or the polyol is selected from one or more of trimethylolpropane, pentaerythritol, glycerol, diethylene glycol and ethylene glycol, 1, 2-propanediol, 1, 3-propanediol or butanediol.
10. The method for synthesizing an allyl ether compound according to claim 9, wherein: the amount of allyl alcohol added is 1.5 to 10.0 times the molar amount of hydroxyl groups contained in the second raw material added, and/or;
the mass of the added bimetallic catalyst is 10-50% of the mass of the added second raw material.
11. The method for synthesizing an allyl ether compound according to claim 10, comprising: the amount of allyl alcohol added is 1.5 to 5.0 times the molar amount of hydroxyl groups contained in the second raw material added, and/or; the mass of the added bimetallic catalyst is 10-30% of the mass of the added second raw material.
12. The process for synthesizing an allyl ether compound according to any one of claims 9 to 11, wherein: the synthesis method of the allyl ether compound comprises the following steps:
adding the bimetallic catalyst into allyl alcohol and one or more raw materials selected from monohydric alcohol, polyhydric alcohol and bisphenol A to obtain reactants; under the protection of inert gas, heating the reactant to 140-160 ℃, reacting for 2-5 hours, cooling to room temperature, pouring out the reactant, filtering out the catalyst, washing and drying to obtain the allyl ether compound.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3355502A (en) * | 1964-09-02 | 1967-11-28 | Reichhold Chemicals Inc | Process for the production of monohydroxy diethers of trihydric alcohols |
| US5650544A (en) * | 1994-09-19 | 1997-07-22 | Nippon Shokubai Co., Ltd. | Process for production of unsaturated ether and catalyst used for production of unsaturated ether |
| CN102300838A (en) * | 2009-01-28 | 2011-12-28 | 迈图专业化学股份有限公司 | Process for the preparation of an ally alkyl ehter by catalytic allyation |
| CN103252229A (en) * | 2013-05-12 | 2013-08-21 | 大连理工大学 | Molybdenum-dioxide-based oxidative desulfurization catalyst |
| CN108002986A (en) * | 2016-10-27 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method that propylene glycol monomethyl ether is prepared by propylene |
| CN109867589A (en) * | 2017-12-01 | 2019-06-11 | 万华化学集团股份有限公司 | A kind of preparation method of propylene-glycol monoalky lether |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9718046B2 (en) * | 2011-05-24 | 2017-08-01 | Saudi Arabian Oil Company | Bimetallic titania-based electrocatalysts deposited on ionic conductors for hydrodesulfurization reactions |
-
2020
- 2020-10-20 CN CN202011125281.5A patent/CN112206765B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3355502A (en) * | 1964-09-02 | 1967-11-28 | Reichhold Chemicals Inc | Process for the production of monohydroxy diethers of trihydric alcohols |
| US5650544A (en) * | 1994-09-19 | 1997-07-22 | Nippon Shokubai Co., Ltd. | Process for production of unsaturated ether and catalyst used for production of unsaturated ether |
| CN102300838A (en) * | 2009-01-28 | 2011-12-28 | 迈图专业化学股份有限公司 | Process for the preparation of an ally alkyl ehter by catalytic allyation |
| CN103252229A (en) * | 2013-05-12 | 2013-08-21 | 大连理工大学 | Molybdenum-dioxide-based oxidative desulfurization catalyst |
| CN108002986A (en) * | 2016-10-27 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method that propylene glycol monomethyl ether is prepared by propylene |
| CN109867589A (en) * | 2017-12-01 | 2019-06-11 | 万华化学集团股份有限公司 | A kind of preparation method of propylene-glycol monoalky lether |
Non-Patent Citations (1)
| Title |
|---|
| "Effect of oxomolybdate species dispersion on direct methanol oxidation to dimethoxymethane over MoOx/TiO2 catalysts";Jeremy Faye等;《Energy Science & Engineering》;20141229;第3卷(第2期);115-125 * |
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