CN117225403A - Dehydrogenation catalyst and preparation method and application thereof - Google Patents
Dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN117225403A CN117225403A CN202311509797.3A CN202311509797A CN117225403A CN 117225403 A CN117225403 A CN 117225403A CN 202311509797 A CN202311509797 A CN 202311509797A CN 117225403 A CN117225403 A CN 117225403A
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 101150003085 Pdcl gene Proteins 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 4
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- 238000009776 industrial production Methods 0.000 abstract description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 18H-dibenzyl toluene Chemical compound 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- SBVSDAFTZIVQEI-UHFFFAOYSA-N 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro-1h-carbazole Chemical compound C1CCCC2C3CCCCC3NC21 SBVSDAFTZIVQEI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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Abstract
The invention relates to the technical field of dehydrogenation catalysts, and discloses a dehydrogenation catalyst, a preparation method and application thereof. The dehydrogenation catalyst comprises: a modified silica support and an active component supported on the modified silica support; wherein the hydroxyl number on the modified silica carrier is 0.77-0.85mol/g. Impurities on the surface of the silica carrier can be removed and the number of hydroxyl groups on the surface of the silica carrier can be increased through the acid modified silica carrier, so that the dehydrogenation catalyst has low active component loading capacity, high dispersity and good stability; the preparation method of the dehydrogenation catalyst provided by the invention is simple and convenient for industrial production; when the dehydrogenation catalyst provided by the invention is used for dehydrogenation, the dehydrogenation efficiency can be effectively improved, and the raw material decomposition rate can be reduced.
Description
Technical Field
The invention relates to the technical field of dehydrogenation catalysts, in particular to a dehydrogenation catalyst and a preparation method and application thereof.
Background
Currently, hydrogen storage technologies mainly include physical hydrogen storage, adsorption hydrogen storage, and chemical hydrogen storage. Physical hydrogen storage technology has met the requirements of vehicles, but its high demands on equipment and demanding operating conditions make the contradiction between this technical performance and efficiency increasingly prominent. Adsorption hydrogen storage and chemical hydrogen storage are important points of current researches, and certain research results are obtained, but a certain gap is left from the technical requirements of vehicle-mounted hydrogen storage. The technology for storing hydrogen energy by organic liquid in chemical hydrogen storage (mainly including methylcyclohexane, cyclohexane, tetrahydronaphthalene, decalin, perhydroazoethylcarbazole, perhydrocarbazole and the like) realizes the storage of hydrogen energy by catalytic addition and dehydrogenation reversible reaction, the reaction is reversible, reactant products can be recycled, and the hydrogen storage amount is relatively high (about 60-75kg H) 2 /m 3 The mass fraction is 6-8%), meets the index stipulated by the International energy agency and the United states department of energy (DOE), carries out long-distance transportation in an organic liquid form or can solve the problem of uneven regional distribution of the energy, truly meets the requirements of green chemistry, and has stronger application prospect.
In the organic liquid hydrogen storage technology, hydrogenation and dehydrogenation processes coexist, the hydrogenation process is relatively simple, the technology is mature, the dehydrogenation process is a strong endothermic and highly reversible reaction, so that the dehydrogenation reaction is carried out at high temperature in terms of dynamics and thermodynamics, but side reactions such as raw material decomposition and cracking, carbon deposition and the like are easy to occur at high temperature, the activity of the catalyst is reduced or even deactivated, and the dehydrogenation reaction is not carried out easily. And the carrier such as titanium oxide, graphene and the like has higher cost, and if high-loading noble metals are used simultaneously, the catalyst cost is further increased.
Therefore, there is a need to develop a new modified support active component supported dehydrogenation catalyst.
Disclosure of Invention
The invention aims to solve the problems of high active component load, low dispersity and poor stability of a dehydrogenation catalyst in the prior art, low dehydrogenation efficiency and high raw material decomposition rate when the catalyst is used for dehydrogenation, and provides a dehydrogenation catalyst and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a dehydrogenation catalyst comprising: a modified silica support and an active component supported on the modified silica support;
wherein the hydroxyl number on the modified silica carrier is 0.77-0.85mol/g.
In a second aspect, the present invention provides a method for preparing a dehydrogenation catalyst, wherein the method comprises the steps of:
1) Mixing a silica carrier with acid liquor and performing first drying to obtain a modified silica carrier;
2) And mixing the modified silica carrier with a mixed solution containing an active component precursor and a complexing agent, and performing pH adjustment, washing, roasting and reduction on the obtained mixture to obtain the dehydrogenation catalyst.
In a third aspect, the present invention provides a dehydrogenation catalyst prepared by the above-described preparation method.
In a fourth aspect, the present invention provides the use of the dehydrogenation catalyst described above in the dehydrogenation of a liquid hydrogen storage medium, wherein the liquid hydrogen storage medium is at least one of dodecylhydrogen ethylcarbazole, 18H-dibenzyl toluene, methylcyclohexane, naphthalene and methylcyclohexane.
Through the technical scheme, the dehydrogenation catalyst provided by the invention, and the preparation method and application thereof have the following beneficial effects:
(1) The dehydrogenation catalyst provided by the invention comprises a modified silica carrier and an active component loaded on the modified silica carrier; the modified silica carrier is prepared by modifying a silica carrier by acid, impurities on the surface of the silica carrier can be removed by the acid modified silica carrier, and the hydroxyl number (0.77-0.85 mol/g) on the surface of the silica carrier is increased, so that the dehydrogenation catalyst has low active component loading, high dispersity and good stability;
(2) The preparation method of the dehydrogenation catalyst provided by the invention is simple and convenient for industrial production;
(3) When the dehydrogenation catalyst provided by the invention is used for dehydrogenation, the dehydrogenation efficiency (the conversion rate of the catalyst is 75-99% in 8h of reaction) can be effectively improved, and the raw material decomposition rate (the methane content is 38-125ppm and the ethane content is 25-68 ppm) can be reduced.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a dehydrogenation catalyst, wherein the dehydrogenation catalyst comprises: a modified silica support and an active component supported on the modified silica support;
wherein the hydroxyl number on the modified silica carrier is 0.77-0.85mol/g.
According to the invention, the acid modified silica carrier can remove impurities on the surface of the carrier and increase hydroxyl on the surface of the silica carrier, so that the dehydrogenation catalyst has low active component loading, high dispersity and good stability.
According to the invention, the dehydrogenation catalyst has a specific surface area of from 200 to 300m 2 /g。
In the present invention, when the specific surface area of the catalyst is less than 200m 2 G, its micro-pores are small, its active dehydrogenation activity is reduced; the specific surface area of the catalyst is more than 300m 2 And/g, the binding force of the active component and the modified carrier is too weak, and the dehydrogenation activity is reduced due to the fact that the active component is easy to fall off.
According to the invention, the dehydrogenation catalyst has an average particle size of from 10 to 35nm.
In the invention, the average grain diameter of the dehydrogenation catalyst is smaller than 10nm, the surface energy of the catalyst is large, the raw materials and pollutants in the environment are easy to be adsorbed, and the stability is reduced; the average grain diameter of the catalyst is larger than 35nm, the contact area of the material and the catalyst is small, the reaction speed is slow, and the reaction speed is low.
According to the invention, the active component is selected from palladium and/or platinum, preferably palladium.
According to the invention, the dehydrogenation catalyst contains 95-99.9 wt.% of the modified silica support and 0.1-5 wt.% of the active component, based on the total weight of the dehydrogenation catalyst.
In the present invention, when the contents of the modified silica carrier and the active component do not satisfy the above-defined ranges, the catalytic effect of the catalyst is unstable.
In a second aspect, the present invention provides a method for preparing a dehydrogenation catalyst, wherein the method comprises the steps of:
1) Mixing a silica carrier with acid liquor and performing first drying to obtain a modified silica carrier;
2) And mixing the modified silica carrier with a mixed solution containing an active component precursor and a complexing agent, and performing pH adjustment, washing, roasting and reduction on the obtained mixture to obtain the dehydrogenation catalyst.
According to the invention, in step 1), the acid liquid is selected from at least one of sulfuric acid, hydrochloric acid and nitric acid.
According to the invention, in step 1), the concentration of the acid solution is 40-60wt%.
According to the invention, in step 1), the mixing conditions include: the mixing rate is not particularly limited, and the time is 3 to 6 hours.
According to the present invention, in step 1), the first drying conditions include: the temperature is 80-120 ℃ and the time is 3-6h.
According to the invention, in the step 1), the mass volume ratio of the silicon dioxide carrier to the acid liquor is 1g (5-10) mL.
In the invention, the concentration of the acid solution is less than 40wt%, so that the amount of introduced hydrogen ions is small, the number of hydroxyl groups on the surface of the silica carrier is reduced, and the dehydrogenation activity is reduced.
According to the invention, in the step 2), the mass ratio of the modified carrier, the active component precursor and the complexing agent is 1 (0.001-0.05) to 0.05-0.1.
According to the invention, the complexing agent is selected from at least one of ammonia, ethylenediamine tetraacetic acid and diethylenetriamine pentacarboxylic acid, preferably ammonia.
In the invention, the complexing agent is adopted, which can carry out complexing reaction with the ions of the active component and carry out ion exchange with the ions on the surface of the modified silica carrier, so that the dispersity of the active component can be improved, the active component and the modified silica carrier are promoted to be combined more tightly, and the stability of the catalyst is improved.
According to the invention, the active ingredient precursor is selected from PdCl 2 、Pd(NO 3 ) 2 、H 2 PtCl 6 And Pd (acac) 2 At least one of them, preferably PdCl 2 。
According to the invention, the pH is 9-12.
According to the invention, the conditions of the calcination include: the temperature is 300-500 ℃ and the time is 2-4h.
According to the invention, the conditions for the reduction include: the temperature is 300-450 ℃ and the time is 2-4h.
In a third aspect, the present invention provides a dehydrogenation catalyst prepared by the above-described preparation method.
In a fourth aspect, the present invention provides the use of the dehydrogenation catalyst described above in the dehydrogenation of a liquid hydrogen storage medium, wherein the liquid hydrogen storage medium is at least one of dodecylhydrogen ethylcarbazole, 18H-dibenzyl toluene, methylcyclohexane, naphthalene and methylcyclohexane.
In the present invention, the raw material decomposition rate means loss of a substance as a hydrogen storage carrier during the cyclic dehydrogenation.
The present invention will be described in detail by examples. In the following examples of the present invention,
the specific surface area of the dehydrogenation catalyst is measured using BET;
the active component load of the dehydrogenation catalyst is measured by an inductively coupled plasma mass spectrometer;
the formula for calculating dehydrogenation efficiency:
x is the selectivity of each substance measured by chromatography;
the decomposition rate of the raw materials is measured by an Shimadzu gas chromatograph;
the raw materials used in the examples and comparative examples are all commercially available.
Example 1
Adding 45wt% hydrochloric acid into the silica carrier, stirring for 4 hours, and drying at 90 ℃ for 4 hours to obtain a modified silica carrier, wherein the mass-volume ratio of the silica carrier to sulfuric acid is 1 g/6 mL;
adding ammonia water into Pd (NO) 3 ) 2 Subsequently adding a modified silica carrier and deionized water, adjusting the pH to be 11, stirring for 5 hours, washing, roasting at 350 ℃ for 2.5 hours, and reducing at 400 ℃ for 3.5 hours to obtain a dehydrogenation catalyst A1, wherein the modified silica carrier and PdCl 2 The mass ratio of the catalyst to the ammonia water is 1:0.005:0.06.
Example 2
Adding nitric acid with the concentration of 55wt% into the silica carrier, stirring for 5 hours, and drying at 110 ℃ for 5 hours to obtain a modified silica carrier, wherein the mass-volume ratio of the silica carrier to sulfuric acid is 1 g/9 mL;
adding ammonia water into H 2 PtCl 6 Subsequently adding the modified silica carrier and deionized water, adjusting the pH to be 10, stirring for 4 hours, washing, and roasting at 450 ℃ for 3.5 hoursReducing at 350deg.C for 2.5 hr to obtain dehydrogenation catalyst A2, wherein modified silica carrier and PdCl 2 The mass ratio of the catalyst to the ammonia water is 1:0.005:0.9.
Example 3
Adding sulfuric acid with the concentration of 40wt% into the silica carrier, stirring for 3 hours, and drying at 80 ℃ for 3 hours to obtain a modified silica carrier, wherein the mass-volume ratio of the silica carrier to the sulfuric acid is 1g to 5mL;
adding ammonia into Pd (acac) 2 Then adding the modified silicon dioxide carrier and deionized water, adjusting the pH to be=9, stirring for 6 hours, washing, roasting at 300 ℃ for 2 hours, and reducing at 450 ℃ for 2 hours to obtain the dehydrogenation catalyst A3, wherein the modified silicon dioxide carrier and PdCl 2 The mass ratio of the catalyst to the ammonia water is 1:0.005:0.05.
Example 4
Adding the silica carrier into sulfuric acid with the concentration of 60wt% and stirring for 6 hours, and drying at 120 ℃ for 6 hours to obtain a modified silica carrier, wherein the mass-volume ratio of the silica carrier to the sulfuric acid is 1 g/10 mL;
adding ammonia water into PdCl 2 Then adding the modified silicon dioxide carrier and deionized water, adjusting the pH to be=12, stirring for 3 hours, washing, roasting at 500 ℃ for 4 hours, and reducing at 300 ℃ for 4 hours to obtain the dehydrogenation catalyst A4, wherein the modified silicon dioxide carrier and PdCl 2 The mass ratio of the catalyst to the ammonia water is 1:0.005:0.1.
Example 5
A dehydrogenation catalyst was prepared as in example 1, except that: the ammonia water is changed into ethylenediamine to prepare the dehydrogenation catalyst A5.
Example 6
A dehydrogenation catalyst was prepared as in example 1, except that: the ammonia water is changed into ethylenediamine tetraacetic acid to prepare the dehydrogenation catalyst A6.
Example 7
A dehydrogenation catalyst was prepared as in example 1, except that: the ammonia was replaced with diethylenetriamine pentacarboxylic acid to prepare dehydrogenation catalyst A7.
Example 8
A dehydrogenation catalyst was prepared as in example 1, except that: modified silica support, pdCl 2 The mass ratio of the catalyst to the ammonia water is changed to 1:0.017:0.06, and the dehydrogenation catalyst A8 is prepared.
Example 9
A dehydrogenation catalyst was prepared as in example 1, except that: modified silica support, pdCl 2 The mass ratio of the catalyst to the ammonia water is changed to 1:0.05:0.06, and the dehydrogenation catalyst A9 is prepared.
Example 10
A dehydrogenation catalyst was prepared as in example 1, except that: modified silica support, pdCl 2 The mass ratio of the catalyst to the ammonia water is changed to 1:0.085:0.06, and the dehydrogenation catalyst A10 is prepared.
Comparative example 1
A dehydrogenation catalyst was prepared as in example 1, except that: the modification of the silica support with sulfuric acid was not performed to prepare a dehydrogenation catalyst D1.
Comparative example 2
A dehydrogenation catalyst was prepared as in example 1, except that: the dehydrogenation catalyst D2 was prepared without using ammonia.
Test example 1
Specific surface area, average pore diameter and hydroxyl number were measured for the dehydrogenation catalysts in the above examples and comparative examples.
The specific surface area and the average pore size were measured using BET.
The hydroxyl number on the surface of the silicon dioxide carrier is determined by adopting an acid-base titration method, and the specific testing method is as follows:
2g of silica particles are weighed and put into a 500mL three-necked flask, 80mL of 0.05mol/L sodium hydroxide solution is added, the mixture is centrifuged after stirring for 24 hours at normal temperature, 10mL of supernatant is taken, three drops of phenolphthalein reagent are added as an indicator, 0.05g/L dilute hydrochloric acid is used for titration until neutralization (color becomes transparent), and the amount of the used dilute hydrochloric acid is AmL.
The above titration procedure was repeated in 0.05mol/L of blank sodium hydroxide, using a quantity of dilute hydrochloric acid of BmL,
the number of hydroxyl groups on the surface of the support (mol/g) = ((B-ase:Sub>A) ×0.05× 8)/(amount of silicase:Sub>A (g)).
The results are detailed in Table 1.
TABLE 1
Test example 2
The dehydrogenation catalysts prepared in examples and comparative examples were subjected to a catalytic performance test.
The evaluation conditions were as follows: 1g of the catalyst was charged into the three-necked flask reactor, the reaction pressure was normal pressure and the temperature was 200℃and dodecylhydrogen ethylcarbazole was used as a representative raw material for hydrogen storage in an organic liquid.
To examine the stability of the catalyst, X8 was defined as the conversion of the catalyst at 8h of reaction. The results are shown in Table 2.
TABLE 2
As is clear from Table 2, when the dehydrogenation catalyst prepared in the examples of the present invention was used in the dehydrogenation reaction, the reaction was conducted for 8 hours
The conversion rate of the catalyst is 75-99%, the methane content is 38-125ppm, the ethane content is 25-68ppm, the dehydrogenation efficiency is high and the raw material decomposition rate is low.
Examples the dehydrogenation catalyst prepared in the examples was acid-modified to have high dehydrogenation efficiency as compared to comparative example 1.
Compared with comparative example 2, the dehydrogenation catalyst prepared in the example is complexed by the complexing agent, and has high dehydrogenation efficiency and low raw material decomposition rate.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. A dehydrogenation catalyst, characterized in that the dehydrogenation catalyst comprises: a modified silica support and an active component supported on the modified silica support;
wherein the hydroxyl number on the modified silica carrier is 0.77-0.85mol/g.
2. The dehydrogenation catalyst of claim 1, wherein the dehydrogenation catalyst has a specific surface area of from 200 to 300m 2 /g。
3. The dehydrogenation catalyst of claim 1, wherein the dehydrogenation catalyst has an average particle size of from 20 to 60nm.
4. The dehydrogenation catalyst of claim 1, wherein the active component is selected from palladium and/or platinum.
5. The dehydrogenation catalyst of claim 1, wherein the dehydrogenation catalyst comprises 95-99.9wt% of the modified silica support and 0.1-5wt% of the active component based on the total weight of the dehydrogenation catalyst.
6. A process for preparing a dehydrogenation catalyst, comprising the steps of:
1) Mixing a silica carrier with acid liquor and performing first drying to obtain a modified silica carrier;
2) And mixing the modified silica carrier with a mixed solution containing an active component precursor and a complexing agent, and performing pH adjustment, washing, roasting and reduction on the obtained mixture to obtain the dehydrogenation catalyst.
7. The process according to claim 6, wherein in step 1), the silica carrier has an average particle diameter of 10 to 30nm.
8. The production method according to claim 6, wherein in step 1), the acid liquid is at least one selected from sulfuric acid, hydrochloric acid and nitric acid.
9. The production method according to claim 8, wherein the acid solution has a concentration of 40 to 60wt%.
10. The preparation method according to claim 6, wherein in the step 1), the mass-volume ratio of the silica carrier to the acid solution is 1g (5-10) mL.
11. The process according to claim 6, wherein in step 2), the mass ratio of the modified silica carrier, the active component precursor and the complexing agent is 1 (0.001-0.05): 0.05-0.1.
12. The production method according to claim 11, wherein the complexing agent is at least one selected from the group consisting of aqueous ammonia, ethylenediamine tetraacetic acid and diethylenetriamine pentacarboxylic acid.
13. The method of claim 11, wherein the active component precursor is selected from PdCl 2 、Pd(NO 3 ) 2 、H 2 PtCl 6 And Pd (acac) 2 At least one of the aqueous solutions of (a).
14. A dehydrogenation catalyst prepared by the preparation method of any one of claims 6-13.
15. Use of the dehydrogenation catalyst according to any one of claims 1-5 and 14 in the dehydrogenation of a liquid hydrogen storage medium wherein the liquid hydrogen storage medium is at least one of dodecylhydrogen ethylcarbazole, 18H-dibenzylmethyltoluene, methylcyclohexane, naphthalene and methylcyclohexane.
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