CN113620784B - Alkane dehydrogenation and lignin-based ether hydrogenation reaction coupling process - Google Patents
Alkane dehydrogenation and lignin-based ether hydrogenation reaction coupling process Download PDFInfo
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Abstract
The invention discloses a coupling alkane dehydrogenation and lignin-based ether hydrogenation reaction process. The method comprises the following steps: mixing a supported metal catalyst and a lignin-based ether compound/alkane mixture, stirring at 200-300 ℃ in an inert gas atmosphere to enable alkane and ether lignin-based ether compound to perform dehydrogenation hydrogenation coupling reaction, wherein the molar ratio of alkane to ether compound is 40-200: 1, wherein the supported metal catalyst is a supported PtM bimetallic catalyst or a mixed catalyst of a supported Pt catalyst and a supported M metal catalyst. The reaction process provided by the invention has coupling effect in both energy and substance aspects, the energy consumption required in the reaction process is low, hydrogenation or hydrogen recovery is not required, the alkane and lignin-based ether can be jointly converted into high value-added chemicals, an additional hydrogen source is not required, and the reaction process has the characteristics of simple process, low cost, high energy utilization rate and the like.
Description
Technical Field
The invention belongs to the field of coupled catalytic reaction, and relates to a process for alkane dehydrogenation and lignin-based oxygen-containing compound hydrogenation coupled reaction.
Background
Energy is the foundation of social development, and with the continuous consumption of traditional petrochemical resources, the development of clean fuels is continuously concerned worldwide. The biomass has wide sources and is the only sustainable carbonaceous resource which can be directly converted into liquid hydrocarbon fuel. The method for efficiently converting lignin into high-added-value chemicals through hydrogenation is an important component of the strategic development of renewable energy resources in various countries, and provides a feasible route for reducing carbon emission and producing replaceable fuel oil. However, hydrogen from fossil sources is mostly used as a hydrogen source in the lignin hydrotreating process, and the defects of high economic cost, inconvenience in storage and transportation, flammability, explosiveness and the like exist.
The other technical approach of hydrogenation is hydrogen transfer reduction, which is safer and more environment-friendly compared with the hydrogen reduction process using hydrogen as a reducing agent. Different kinds of hydrogen sources (e.g. HCOOH, HCOONH) 4 、PhSiH 3 、isopropanol/KOH、H 2 NNH 2 ) Have been used for the catalytic transfer hydrogenation of nitro compounds. As an ideal organic liquid hydrogen storage system, Cyclohexane (CYH) has a mass hydrogen storage density of 7.19 wt% and a volume hydrogen storage density of 56kg/m 3 (ii) a Methylcyclohexane also has a relatively high hydrogen storage density of 6.1 wt% in terms of mass and 47kg/m in terms of volume 3 And thus gradually draws a wide attention. Chinese patent CN 105037066A discloses a method for dehydrogenation of methylcyclohexane by Pt/C catalysis, wherein the reaction temperature is 280-300 ℃, the dehydrogenation conversion rate of the methylcyclohexane is 80-95%, and the dehydrogenation amount is 300-550 mmol/g/min. Chinese patent CN 110882703A discloses an alkaline earth metal-containing naphthene dehydrogenation catalyst Mg-Ti-S doped PtSnAl 2 O 3 The catalyst comprises 0.4 wt% of Pt, 0.5 wt% of Sn, 0.6 wt% of S, 0.45 wt% of Mg and 2.0 wt% of Ti, the reaction temperature is 430 ℃, the reaction pressure is 1MPa, the conversion rate of the naphthenic hydrocarbon can reach 90%, and the yield of the benzene is 84%. Also, cyclohexane and methylcyclohexane are industrially mass-produced chemicals that can realize safe mass storage and long-distance transport [ research progress of organic liquid hydrogen storage material [ J ]]Chemical evolution, 2016, 35(9):2869-2874]. Thus dehydrogenating non-aromatic compounds, e.g. cyclohexane, to aromatic compounds(e.g., benzene) and direct in situ hydrogen transfer to effect hydrogenation reactions, reducing the reaction process. Wherein the aromatic compound produced by dehydrogenation of cycloalkane can be widely used as the raw material for the subsequent process. The dehydrogenation and hydrogenation reactions are coupled, so that a plurality of reaction processes of dehydrogenation-hydrogen transfer-hydrogenation can be synchronously carried out, and the high value-added chemicals can be prepared in one step under mild and non-hydrogenation reaction conditions.
Chinese patent CN 1789255A discloses a production process for coupling maleic anhydride hydrogenation and cyclohexanol dehydrogenation, which uses a supported Cu-based catalyst, H 2 The mol ratio of the mixture of maleic anhydride and cyclohexanol is 5-50, the mol ratio of cyclohexanol to maleic anhydride is 4-7, and dehydrogenation and hydrogenation integrated reaction is carried out at 250-300 ℃ under normal pressure to generate gamma-butyrolactone and cyclohexanone, however, hydrogen still exists in the process. In addition, chinese patent CN 1789256a discloses a process for producing 2-methylfuran and cyclohexanone by coupling furfural hydrogenation and cyclohexanol dehydrogenation, wherein the cyclohexanol dehydrogenation endotherm is 63.4 kJ/mol. Whereas the dehydrogenation reaction of cyclohexane is a strongly endothermic process (e.g. C) 6 H 12 (g)→C 6 H 6 (g)+3H 2 +206.07kJ/mol), which generally needs to be carried out under catalytic and high temperature conditions. The reaction process is limited by heat transfer and thermodynamic equilibrium, so that the dehydrogenation conversion efficiency is low, in addition, hydrogen generated by the reaction is discharged to cause huge waste, and if the hydrogen is recycled through a series of unit operations, the production cost is obviously increased.
Disclosure of Invention
The invention aims to provide a coupling alkane dehydrogenation and lignin-based ether hydrogenation reaction process, the related reaction process has coupling effect in the aspects of energy and substances, the energy consumption required by the reaction process is low, hydrogenation or hydrogen recovery is not required, the alkane and lignin-based ether can be converted into high value-added chemicals together, and the coupling alkane dehydrogenation and lignin-based ether hydrogenation reaction process has the characteristics of simple process, low cost, high energy utilization rate and the like.
In order to solve the technical problems, the invention provides the following technical scheme:
the provided coupling alkane dehydrogenation and lignin-based ether hydrogenation reaction process comprises the following steps:
mixing a supported metal catalyst and a lignin-based ether compound/alkane mixture, stirring at 200-300 ℃ in an inert gas atmosphere to enable alkane and ether lignin-based ether compound to perform dehydrogenation hydrogenation coupling reaction, wherein the molar ratio of alkane to ether compound is 40-200: 1, wherein the supported metal catalyst is a supported PtM bimetallic catalyst or a mixed catalyst of a supported Pt catalyst and a supported M metal catalyst.
According to the scheme, the stirring speed is 500-1200 rpm.
According to the scheme, the dehydrogenation and hydrogenation coupling time is 2-5 h.
According to the scheme, the lignin-based ether compound is at least one of phenoxyethylbenzene, benzyl phenyl ether, anisole and methyl anisole; the alkane is at least one of linear alkane or cycloalkane, and the linear alkane is at least one of pentane, hexane, heptane and dodecane; the cycloalkane is at least one of cyclohexane, methylcyclohexane and decalin.
According to the scheme, the mass ratio of the lignin-based ether compound to the supported metal catalyst is 0.5-5: 1.
according to the scheme, when the supported metal catalyst is a supported PtM bimetallic catalyst, the carrier is Al 2 O 3 、SiO 2 At least one of HY or ZSM-5 molecular sieve; the first active metal is Pt, and the second active metal M is at least one selected from Sn, Ni or Co; when the supported metal catalyst is a mixed catalyst of a supported Pt catalyst and a supported metal M catalyst, the carrier is Al 2 O 3 、SiO 2 HY or ZSM-5 molecular sieve, and metal M selected from at least one of Sn, Ni or Co.
According to the scheme, the supported metal catalyst contains 0.3-2 wt% of metal Pt and 0.1-10 wt% of metal M by mass percent.
According to the scheme, the supported PtM bimetallic catalyst is prepared by at least one method of ion exchange, mechanical mixing, co-impregnation or step impregnation.
Compared with other technologies, the coupling alkane dehydrogenation and lignin-based ether hydrogenation reaction process provided by the invention couples two reactions which are respectively carried out, and has the following advantages:
1. the coupling process provided by the invention is a material matching and energy matching process, alkane dehydrogenation is a strong endothermic reaction, lignin-based ether hydrogenation is an exothermic reaction, the two energy matches, the energy consumption required by the reaction process is low, the reaction temperature is reduced by utilizing the coupling process, the reaction time is shortened, and hydrogenation or hydrogen recovery is not needed, so that the coupling process is an efficient coupling process.
2. The invention breaks through the traditional two-step process, avoids the hydrogen obtained by dehydrogenation from being compressed and transported to be hydrogenated in another reactor, has safer and more efficient reaction process, improves the comprehensive utilization rate from two aspects of energy and substances, and has the advantages of simplicity and centralized process.
3. Besides the hydrogenation product, the dehydrogenation product is also a high value-added chemical product, and the bilateral high-value one-step synthesis is realized.
4. The alkane source is wide, and when the alkane is cycloparaffin, the dehydrogenation product and the lignin ether hydrogenation product of the coupling reaction are aromatic hydrocarbons, so that the difficulty in separating the products is reduced, and a new way is provided for the generation of high-efficiency and green chemicals.
Drawings
Fig. 1 is an XRD spectrum of the catalysts of example 1, example 5, example 15 and comparative example 3 and comparative example 5.
Fig. 2 is TEM images of catalysts of examples 1, 5 and 15.
Detailed Description
The following examples are intended to illustrate the coupled alkane dehydrogenation and lignin-based ether hydrogenation processes and catalysts of the present invention in further detail, and are not intended to limit the scope of the invention.
In the following examples, when cyclohexane is used as the alkane and phenoxyethylbenzene is used as the lignin-based ether compound, benzene, ethylbenzene, phenol, etc. are obtained by the reaction. The reaction products were analyzed by gas chromatography, and the conversion and selectivity were calculated as follows:
phenoxyethylbenzene conversion (PEB Conv.) (moles of phenol product)/initial phenoxyethylbenzene mole x 100% yield of product i (Y i ) (number of moles of product i)/initial phenoxyethylbenzene mole x 100%.
Example 1
The PtSn/HY catalyst is prepared by a step-by-step impregnation method, and the specific steps are as follows: soaking certain mass of HY in a uniform chloroplatinic acid solution, standing and aging for 12h, and drying at 80 ℃ to obtain Pt/HY. Re-immersing Pt/HY in SnCl 2 After stirring and drying, PtSn/HY is obtained by reduction at 550 ℃, wherein the Pt loading is 0.6 wt% and the Sn loading is 0.3 wt%.
Coupling catalytic reaction: the catalyst activity evaluation was carried out in a reaction vessel. Before evaluation, 0.198g of Phenoxyethylbenzene (PEB) was dissolved in 10mL of Cyclohexane (CYH), 0.15g of PtSn/HY catalyst was added thereto, and the mixture was purged with nitrogen several times and then purged with nitrogen under normal pressure. Subsequently, the reaction kettle was heated to 250 ℃ with a stirring rate of 1200rpm, and after 2 hours of reaction, the product was detected and analyzed by GC-MS. The analysis result showed that the PtSn/HY catalyst had a PEB conversion of 100.0%, a benzene yield of 10.0%, a phenol yield of 72.0% and an isomerate yield of 4.8%.
Example 2
The catalyst was prepared as in example 1.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: the reaction temperature was 230 ℃. The final PtSn/HY catalyst had a PEB conversion of 100.0%, a benzene yield of 6.8%, a phenol yield of 62.2%, and an isomerate yield of 25.0%.
Example 3
The catalyst was prepared as in example 1.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: the reaction temperature was 280 ℃. The final PtSn/HY catalyst had a PEB conversion of 98.2%, a benzene yield of 15.3%, a phenol yield of 62.8%, and an isomerate yield of 5.1%.
Example 4
The catalyst was prepared as in example 1.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: the reaction temperature was 300 ℃. The final PtSn/HY catalyst had a PEB conversion of 100.0%, a benzene yield of 31.9%, a phenol yield of 49.1%, and an isomerate yield of 4.0%.
Example 5
The catalyst was prepared as in example 1, except that: using Al 2 O 3 As a carrier, PtSn/Al is prepared 2 O 3 The catalyst had a Pt loading of 0.6 wt% and a Sn loading of 0.3 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 4, except that: using PtSn/Al 2 O 3 A catalyst. Final PtSn/Al 2 O 3 The catalyst had a PEB conversion of 98.8%, a benzene yield of 0.9%, a phenol yield of 45.6%, and an isomerate yield of 2.2%.
Example 6
The catalyst was prepared as in example 5.
Coupling catalytic reaction: the reaction conditions were the same as in example 5, except that: the amount of hydrogen donor cyclohexane used was 5 mL. Final PtSn/Al 2 O 3 The catalyst had a PEB conversion of 98.5%, a benzene yield of 0.6%, a phenol yield of 49.1%, and an isomerate yield of 12.6%.
Example 7
The catalyst was prepared as in example 5.
Coupling catalytic reaction: the reaction conditions were the same as in example 5, except that: the amount of hydrogen-donating cyclohexane used was 20 m. Final PtSn/Al 2 O 3 The catalyst had a PEB conversion of 100%, a benzene yield of 1.8%, a phenol yield of 51.6%, and an isomerate yield of 4.2%.
Example 8
The catalyst was prepared as in example 1, except that: a PtSn/ZSM-5 catalyst was prepared using ZSM-5(Si/Al ═ 38) as a support, with a Pt loading of 0.6 wt% and a Sn loading of 0.3 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 4, except that: a PtSn/ZSM-5 catalyst was used. The final PtSn/ZSM-5 catalyst had a PEB conversion of 57.1%, a benzene yield of 4.9%, a phenol yield of 16.1%, and an isomerate yield of 49.3%.
Example 9
The catalyst was prepared as in example 1, except that: using Ni (NO) 3 ) 2 And (3) taking the aqueous solution as an impregnation liquid of a second metal M to carry out second impregnation to prepare the PtNi/HY catalyst, wherein the Pt loading is 0.6 wt%, and the Ni loading is 5 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: PtNi/HY catalyst was used. The final PtNi/HY catalyst had a PEB conversion of 90.8%, a benzene yield of 5.9%, a phenol yield of 42.6%, and an isomerate yield of 40.3%.
Example 10
The PtNi/HY-co catalyst is prepared by adopting a co-impregnation method, and the specific steps are as follows: soaking certain mass of HY molecular sieve in chloroplatinic acid and Ni (NO) 3 ) 2 ·6H 2 And (3) standing and aging in an O aqueous solution for 12h, drying at 80 ℃ and reducing at 550 ℃ to obtain PtNi/HY-co, wherein the Pt loading is 0.6 wt% and the Ni loading is 5 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, and the final PtNi/HY-co catalyst had a PEB conversion of 93.5%, a benzene yield of 4.4%, a phenol yield of 28.1%, and an isomeric product yield of 61.0%.
Example 11
The Pt/HY + Ni/HY catalyst is prepared by a mechanical mixing method and comprises the following specific steps: soaking HY molecular sieve in chloroplatinic acid and Ni (NO) 3 )·6H 2 And (2) standing and aging in an O aqueous solution for 12h, drying at 80 ℃ to respectively obtain Pt/HY and Ni/HY, mechanically mixing the Pt/HY and the Ni/HY, and reducing at 550 ℃ to obtain Pt/HY + Ni/HY, wherein the Pt loading capacity is 0.6 wt% and the Ni loading capacity is 5 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: the amount of Pt/HY + Ni/HY catalyst used was 0.3 g. The final PEB conversion of the Pt/HY + Ni/HY catalyst was 100.0%, the benzene yield was 6.1%, the phenol yield was 53.8%, and the yield of the isomerate was 35.5%.
Example 12
Example 12 the catalyst was prepared as in example 1.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: n-hexane (n-hexane) was used as a hydrogen donor. The final PtSn/HY catalyst had a PEB conversion of 100.0%, a benzene yield of 13.6%, a phenol yield of 68.1%, and an isomerate yield of 9.7%.
Example 13
The catalyst was prepared as in example 1.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: dodecane (dodecane) was used as a hydrogen donor. The final PtSn/HY catalyst had a PEB conversion of 44.9%, a benzene yield of 1.8%, a phenol yield of 28.8%, and an isomerate yield of 29.3%.
Example 14
The catalyst was prepared as in example 5.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: decahydronaphthalene (decalin) was used as the hydrogen donor. Final PtSn/Al 2 O 3 The catalyst had a PEB conversion of 61.4%, a benzene yield of 0.3%, a phenol yield of 28.4%, and an isomerate yield of 41.2%.
Example 15
The catalyst was prepared as in example 1, except that: using SiO 2 As a carrier, preparing PtSn/SiO 2 The catalyst had a Pt loading of 0.6 wt% and a Sn loading of 0.3 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, except that: 1mmol of Benzyl Phenyl Ether (BPE) was used
As a reactant, the reaction temperature was 300 ℃. Final PtSn/SiO 2 The catalyst had a BPE conversion of 96.0%, a benzene yield of 0.3%, a phenol yield of 25.6%, and an isomerate yield of 58.0%.
Example 16
The catalyst was prepared as in example 1.
Coupling catalytic reaction: the reaction conditions differ from example 1 only in that: 1mmol of Anisole (ANI)
As a reactant. The final PtSn/HY catalyst had ANI conversion of 83.6%, benzene yield of 5.8%, phenol yield of 56.9% and isomerate yield of 0.0%.
Comparative example 1
The catalyst was prepared as in example 5.
Coupling catalytic reaction: the reaction conditions differ from example 1 only in that: methylnaphthalene was used as solvent. Because methylnaphthalene is a non-hydrogen donor (contains no hydrogen available for transfer). Final PtSn/Al 2 O 3 The catalyst had a PEB conversion of only 1.1%, a benzene yield of 0.0%, a phenol yield of 1.1%, and an isomerate yield of 0.0%.
Comparative example 2
The catalyst was prepared as in example 1.
Coupling catalytic reaction: the reaction conditions differ from example 1 only in that: the reaction temperature was 300 ℃ without adding the reactant PEB, and the final PtSn/HY catalyst had a cyclohexane conversion of 0.2%, a benzene yield of 0.2%, a phenol yield of 0.0%, and an isomerate yield of 0.0%.
Comparative example 3
Preparation of Pt/Al by dipping method 2 O 3 The catalyst comprises the following specific steps: a certain mass of Al 2 O 3 Soaking in uniform chloroplatinic acid solution, standing and aging for 12h, and drying at 80 deg.C to obtain Pt/Al 2 O 3 . Reducing at 550 ℃ to obtain Pt/Al 2 O 3 The Pt loading was 0.6 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, final Pt/Al 2 O 3 The catalyst had a PEB conversion of 9.9%, a benzene yield of 0.0%, a phenol yield of 7.0%, and an isomerate yield of 21.5%.
Comparative example 4
The Pt/HY catalyst is prepared by an impregnation method and comprises the following specific steps: soaking certain mass of HY in a uniform chloroplatinic acid solution, standing and aging for 12h, drying at 80 ℃, and reducing at 550 ℃ to obtain Pt/HY with the Pt loading amount of 0.6 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, and the final Pt/HY catalyst had a PEB conversion of 7.6%, a benzene yield of 0.5%, a phenol yield of 5.6%, and an isomerate yield of 25.3%.
Comparative example 5
Preparation of Sn/Al by dipping method 2 O 3 The catalyst comprises the following specific steps: a certain mass of Al 2 O 3 Impregnating in SnCl 2 Stirring and drying the obtained product in acetone solution, and reducing the obtained product at 550 ℃ to obtain Sn/Al 2 O 3 And Sn loading was 0.3 wt%.
Coupling catalytic reaction: the reaction conditions were the same as in example 1, and the final Sn/Al 2 O 3 The catalyst had a PEB conversion of 29.7%, a benzene yield of 0.0%, a phenol yield of 21.7%, and an isomerate yield of 6.4%.
Comparative example 6
The Ni/HY catalyst is prepared by an impregnation method, and the specific steps are as follows: impregnating certain mass of HY in Ni (NO) 3 ) 2 ·6H 2 In the O aqueous solution, after stirring and drying, Ni/HY is obtained by reduction at 450 ℃, and the Ni load is 5 wt%. Coupling catalytic reaction: the reaction conditions were the same as in example 1, and the final Ni/HY catalyst had a PEB conversion of 21.7%, a benzene yield of 1.0%, a phenol yield of 10.4%, and an isomerate yield of 12.6%.
Claims (5)
1. A coupling alkane dehydrogenation and lignin-based ether hydrogenation reaction process is characterized by comprising the following steps:
mixing a supported metal catalyst and a lignin-based ether compound/alkane mixture, and then, in an inert gas atmosphere, 200-300 g o Stirring at the temperature of C to ensure that alkane and lignin-based ether compounds are subjected to dehydrogenation hydrogenation coupling reaction, wherein:
the molar ratio of the alkane to the ether compound is 40-200: 1;
the lignin-based ether compound is at least one of phenoxyethylbenzene, benzyl phenyl ether, anisole and methyl anisole; the alkane is at least one of linear alkane or cycloalkane, and the linear alkane is at least one of pentane, hexane, heptane and dodecane; the cycloalkane is at least one of cyclohexane, methylcyclohexane and decahydronaphthalene;
the supported metal catalyst is a supported PtM bimetallic catalyst or a mixed catalyst of a supported Pt catalyst and a supported M metal catalyst; when the supported metal catalyst is a supported PtM bimetallic catalyst, the carrier is Al 2 O 3 、SiO 2 At least one of HY or ZSM-5 molecular sieve; the first active metal is Pt, and the second active metal M is at least one selected from Sn, Ni or Co; when the supported metal catalyst is a mixed catalyst of a supported Pt catalyst and a supported metal M catalyst, the carrier is Al 2 O 3 、SiO 2 At least one of HY or ZSM-5 molecular sieve, and metal M selected from at least one of Sn, Ni or Co.
2. The process of claim 1, wherein the dehydrogenation-hydrogenation coupling time is 2-5 hours.
3. The process according to claim 1, wherein the mass ratio of the lignin-based ether compound to the supported metal catalyst is 0.5-5: 1.
4. the process of claim 1, wherein the supported metal catalyst comprises 0.3 to 2 wt% of metal Pt and 0.1 to 10 wt% of metal M, based on the mass percentage.
5. The process of claim 1, wherein the supported PtM bimetallic catalyst is prepared by at least one of ion exchange, mechanical mixing, co-impregnation, or step impregnation.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789255A (en) * | 2005-12-14 | 2006-06-21 | 中国科学院山西煤炭化学研究所 | Method for preparing gamma-butyrolactone and cyclohexanone by couple process |
| CN103694202A (en) * | 2013-11-28 | 2014-04-02 | 江苏大学 | Coupling reaction method for preparing tetrahydrofuran and methyl formate |
| CN104388110A (en) * | 2014-10-29 | 2015-03-04 | 华东师范大学 | Method for preparing chain alkane from lignin |
| US10519081B1 (en) * | 2018-07-24 | 2019-12-31 | Tianjin University | Process for the preparation of a bicyclic fused-ring alkane |
| WO2020224584A1 (en) * | 2019-05-06 | 2020-11-12 | 中国石油化工股份有限公司 | Catalyst for dehydrogenating organic hydrogen storage raw material, carrier for catalyst, hydrogen storage alloy, and method for providing high purity hydrogen |
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| FI119588B (en) * | 2003-11-27 | 2009-01-15 | Neste Oil Oyj | Precious metal catalyst for hydrocarbon conversion, process of production thereof and process for production of diesel fuel |
| SG11201506293QA (en) * | 2013-03-14 | 2015-09-29 | Exxonmobil Chem Patents Inc | Methyl-substituted biphenyl compounds, their production and their use in the manufacture of plasticizers |
| JP6770824B2 (en) * | 2016-04-15 | 2020-10-21 | Ｅｎｅｏｓ株式会社 | A method for producing a dehydrogenation catalyst, a method for producing an unsaturated hydrocarbon, and a method for producing a conjugated diene. |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789255A (en) * | 2005-12-14 | 2006-06-21 | 中国科学院山西煤炭化学研究所 | Method for preparing gamma-butyrolactone and cyclohexanone by couple process |
| CN103694202A (en) * | 2013-11-28 | 2014-04-02 | 江苏大学 | Coupling reaction method for preparing tetrahydrofuran and methyl formate |
| CN104388110A (en) * | 2014-10-29 | 2015-03-04 | 华东师范大学 | Method for preparing chain alkane from lignin |
| US10519081B1 (en) * | 2018-07-24 | 2019-12-31 | Tianjin University | Process for the preparation of a bicyclic fused-ring alkane |
| WO2020224584A1 (en) * | 2019-05-06 | 2020-11-12 | 中国石油化工股份有限公司 | Catalyst for dehydrogenating organic hydrogen storage raw material, carrier for catalyst, hydrogen storage alloy, and method for providing high purity hydrogen |
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