CN117380217A - Catalyst for dehydrogenation reaction of organic liquid and preparation method thereof - Google Patents
Catalyst for dehydrogenation reaction of organic liquid and preparation method thereof Download PDFInfo
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- CN117380217A CN117380217A CN202311362511.3A CN202311362511A CN117380217A CN 117380217 A CN117380217 A CN 117380217A CN 202311362511 A CN202311362511 A CN 202311362511A CN 117380217 A CN117380217 A CN 117380217A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 42
- 239000012018 catalyst precursor Substances 0.000 claims description 29
- 229960003638 dopamine Drugs 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 15
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 aromatic organic compounds Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 1
- RQOCUPXJUOOIRL-UHFFFAOYSA-N 1,3-dicyclohexylpropan-2-ylbenzene Chemical compound C(C1CCCCC1)C(C1=CC=CC=C1)CC1CCCCC1 RQOCUPXJUOOIRL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention is applicable to the technical field of hydrogen energy storage and transportation, and provides a catalyst for dehydrogenation reaction of organic liquid, which comprises a carrier, a main active component and an auxiliary active component; wherein the carrier is one or more of metal oxide, carbon material or molecular sieve; the main active component is noble metal, and is one or two of platinum and palladium; the auxiliary active component is non-noble metal, and is one or more of Co, ni, cu, zn, mg, fe or La; the content of the main active component is 0.1-5wt.% and the content of the auxiliary active component is 0.01-0.3wt.% calculated by the composition of the catalyst. The catalyst reduces the consumption of noble metal by replacing part of noble metal with non-noble metal, and can maintain or even improve the dehydrogenation reaction rate and stability of the catalyst, thereby reducing the catalyst cost of an organic liquid dehydrogenation reaction system, and realizing high dehydrogenation rate and good stability when the catalyst is applied to the organic liquid dehydrogenation reaction.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy storage and transportation, and particularly relates to a catalyst for dehydrogenation reaction of organic liquid and a preparation method thereof.
Background
The organic liquid hydrogen storage technology has the unique advantages of higher hydrogen storage density, safe and controllable hydrogen storage and dehydrogenation process, easy realization of storage and transportation of hydrogen energy under normal temperature and normal pressure environment, and the like. The organic liquid hydrogen storage technology is to combine hydrogen and aromatic organic compounds through catalytic hydrogenation reaction to form saturated cyclic compounds with hydrogen combined in molecules, so that the hydrogen is stored and transported in liquid form at normal temperature and pressure, and the stored hydrogen is released through catalytic dehydrogenation reaction under the action of a catalyst. The process is reversible, the reactant products are recyclable, and the hydrogen reserves are relatively high (about 60-75kg H 2 /m 3 6-8 wt.%) and is transported for long distances in the form of an organic liquid. Therefore, the organic liquid hydrogen storage technology will take an important place in the field of safe storage and transportation of hydrogen energy.
At present, a mature organic liquid system in the organic liquid hydrogen storage technology is a dibenzyl toluene/perhydrodibenzyl system, and the organic liquid system has excellent physical and chemical properties, such as high boiling point at normal temperature and normal pressure, difficult volatilization, no toxicity, no flammability and other excellent characteristics, and is regarded as an excellent hydrogen energy storage medium. However, this system also has a problem that the catalyst efficiency and cost are difficult to be compatible. Currently, the dehydrogenation catalysts used in this system are mainly Pt catalysts. However, pure Pt catalysts have a problem of catalyst deactivation due to sintering or carbon deposition, and noble metal catalysts are rare in sources and expensive. Therefore, the development of a novel efficient, stable and low-cost dehydrogenation catalyst is a key for large-scale popularization and application of the technology.
Disclosure of Invention
The embodiment of the invention aims to provide a catalyst for dehydrogenation reaction of organic liquid and a preparation method thereof, and aims to solve the problems in the background art.
The embodiment of the invention is realized in such a way that the catalyst for the dehydrogenation reaction of the organic liquid comprises a carrier, a main active component and a co-active component; wherein the carrier is one or more of metal oxide, carbon material or molecular sieve; the main active component is noble metal, and is one or two of platinum and palladium; the auxiliary active component is non-noble metal, and is one or more of Co, ni, cu, zn, mg, fe or La; the content of the main active component is 0.1-5wt.% and the content of the auxiliary active component is 0.01-0.3wt.% calculated by the composition of the catalyst.
Further technical proposal, the specific surface of the carrier is 50-300m 2 And/g, the average pore diameter is 6-10nm.
Further technical proposal, the metal oxide is SiO 2 、MnO、La 2 O 3 、ZnO、Al 2 O 3 、TiO 2 And CeO 2 Etc.
According to a further technical scheme, the carbon material is activated carbon, graphite, carbon nanotubes, carbon nanofibers and the like.
According to a further technical scheme, the molecular sieve is SAPO-34, SBA-15 or ZSM-5.
Another object of the embodiment of the present invention is to provide a method for preparing a catalyst for dehydrogenation of an organic liquid, based on the catalyst for dehydrogenation of an organic liquid, comprising the steps of:
step 1, preparing a dopamine solution containing an active metal precursor according to a certain proportion, wherein the pH value of the solution is 8.5, and the solution preparation is carried out in an inert atmosphere;
step 2, preparing a catalyst carrier, fully drying the catalyst carrier before use, and measuring the saturated water absorption;
and 3, adding the dried catalyst carrier obtained in the step 2 into the dopamine solution prepared in the step 1, exposing the mixture to air and fully stirring, reacting for a period of time, drying the obtained solid at the drying temperature of 20-180 ℃ for 0.5-100h, and obtaining the catalyst precursor.
And 4, roasting the catalyst precursor obtained in the step 3, and then obtaining the target catalyst.
In a further technical scheme, in the step 1, the buffer used in the dopamine solution preparation process is Tris buffer, and the pH is 8.5.
According to a further technical scheme, in the step 1, the concentration of the dopamine in the dopamine solution is 0.5-1.0mol/L.
In a further embodiment, in the step 1, the active noble metal precursor in the dopamine solution is a water-soluble salt (e.g. Pt (NO 3 ) 2 ,PtCl 2 ) Or an acid (e.g. H) 2 PtCl 6 ，H 2 PdCl 4 ) The concentration thereof is in the range of 1-5 mM.
In a further technical scheme, in the step 1, the non-noble metal precursor in the dopamine solution is water-soluble nitrate or hydrochloride, and the concentration of the non-noble metal precursor is in the range of 0.1-2 mM.
In a further technical scheme, in the step 3, the volume of the dopamine solution is 1.2-2 times of the saturated water absorption capacity of the catalyst carrier.
According to a further technical scheme, in the step 3, the calcination of the catalyst precursor is performed in air or inert atmosphere, the temperature is 200-800 ℃, and the calcination time is 0.5-100 hours.
The catalyst for the dehydrogenation reaction of the organic liquid has the following beneficial effects:
(1) The catalyst reduces the consumption of noble metal by replacing part of noble metal with non-noble metal, and can maintain or even improve the dehydrogenation efficiency and stability of the catalyst, thereby reducing the catalyst cost of an organic liquid dehydrogenation reaction system;
(2) The preparation method of the catalyst can effectively control the dispersibility and uniformity of the active components of the catalyst, thereby ensuring the controllability of the catalyst in the preparation process.
(3) The catalyst realizes high dehydrogenation rate and good stability in the dehydrogenation reaction of organic liquid.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
The catalyst for the dehydrogenation reaction of the organic liquid comprises a carrier, a main active component and a co-active component; wherein the carrier is one or more of metal oxide, carbon material or molecular sieve; the main active component is noble metal, and is one or two of platinum and palladium; the auxiliary active component is non-noble metal, and is one or more of Co, ni, cu, zn, mg, fe or La; the content of the main active component is 0.1-5wt.% and the content of the auxiliary active component is 0.01-0.3wt.% calculated by the composition of the catalyst.
As a preferred embodiment of the present invention, the specific surface area of the carrier is 50-300m 2 And/g, the average pore diameter is 6-10nm.
As a preferred embodiment of the present invention, the metal oxide is SiO 2 、MnO、La 2 O 3 、ZnO、Al 2 O 3 、TiO 2 And CeO 2 Etc.
As a preferred embodiment of the present invention, the carbon material is activated carbon, graphite, carbon nanotubes, carbon nanofibers, or the like.
As a preferred embodiment of the present invention, the molecular sieve is SAPO-34, SBA-15, ZSM-5, or the like.
The preparation method of the catalyst for the dehydrogenation reaction of the organic liquid provided by one embodiment of the invention is based on the catalyst for the dehydrogenation reaction of the organic liquid, and comprises the following steps of:
step 1, preparing a dopamine solution containing an active metal precursor according to a certain proportion, wherein the pH value of the solution is 8.5, and the solution preparation is carried out in an inert atmosphere;
step 2, preparing a catalyst carrier, fully drying the catalyst carrier before use, and measuring the saturated water absorption;
and 3, adding the dried catalyst carrier obtained in the step 2 into the dopamine solution prepared in the step 1, exposing the mixture to air and fully stirring, reacting for a period of time, drying the obtained solid at the drying temperature of 20-180 ℃ for 0.5-100h, and obtaining the catalyst precursor.
And 4, roasting the catalyst precursor obtained in the step 3, and then obtaining the target catalyst.
As a preferred embodiment of the present invention, in the step 1, the buffer used in the dopamine solution preparing process is Tris buffer, and the pH is 8.5.
As a preferred embodiment of the present invention, in the step 1, the concentration of dopamine in the dopamine solution is 0.5-1.0mol/L.
As a preferred embodiment of the present invention, in the step 1, the active noble metal precursor in the dopamine solution is a water-soluble salt (e.g., pt (NO 3 ) 2 ,PtCl 2 ) Or an acid (e.g. H) 2 PtCl 6 ，H 2 PdCl 4 ) The concentration thereof is in the range of 1-5 mM.
As a preferred embodiment of the present invention, in the step 1, the non-noble metal precursor in the dopamine solution is water-soluble nitrate or hydrochloride, and the concentration thereof is in the range of 0.1-2 mM.
As a preferred embodiment of the present invention, in said step 3, the volume of the dopamine solution used is 1.2-2 times the saturated water absorption capacity of the catalyst carrier.
As a preferred embodiment of the present invention, in the step 3, the calcination of the catalyst precursor is performed in air or an inert atmosphere at a temperature of 200 to 800 ℃ for a calcination period of 0.5 to 100 hours.
The following list of some specific examples serves as a specific verification of the effect of catalyst use:
example 1:
step one, 40mL of 0.5mol/L Tris buffer (pH=8.5) was measured and placed in a sealIn a closed container, continuously introducing nitrogen gas for 2 hours, adding 4.74g of dopamine hydrochloride, stirring thoroughly, and adding 5mL of PtCl with concentration of 73.5mmol/L after the dopamine hydrochloride is completely dissolved 2 Solution and 5mL of Co (NO) with concentration of 7.35mmol/L 3 ) 2 And (3) preparing a catalyst precursor solution.
And step two, selecting spherical aluminum oxide as the catalyst carrier, putting 30g of aluminum oxide carrier into a vacuum drying oven, and fully drying until the moisture is completely removed, wherein the saturated water absorption capacity is 35g.
And thirdly, mixing the dried aluminum oxide carrier obtained in the second step with the catalyst precursor solution prepared in the first step, exposing the mixed system in air and fully stirring, and drying the mixed system to remove excessive moisture after reacting for 2 hours to finally obtain the target catalyst precursor.
Step four, the catalyst precursor obtained in the step three is put into a condition of 500 ℃ to be roasted for 6 hours, and the target catalyst of 0.5 percent Pt0.05 percent Co/Al is obtained 2 O 3 。
Example 2:
step one, 40mL of 0.5mol/L Tris buffer (pH=8.5) was measured and placed in a closed vessel, then nitrogen was continuously introduced thereinto for 2 hours, 4.74g of dopamine hydrochloride was further added thereto and sufficiently stirred, and after the dopamine hydrochloride was completely dissolved, 5mL of PtCl having a concentration of 147mmol/L was further added thereto 2 Solution and 5mL of Co (NO) with concentration of 7.35mmol/L 3 ) 2 And (3) preparing a catalyst precursor solution.
And step two, selecting spherical aluminum oxide as the catalyst carrier, putting 30g of aluminum oxide carrier into a vacuum drying oven, and fully drying until the moisture is completely removed, wherein the saturated water absorption capacity is 35g.
And thirdly, mixing the dried aluminum oxide carrier obtained in the second step with the catalyst precursor solution prepared in the first step, exposing the mixed system in air and fully stirring, and drying the mixed system to remove excessive moisture after reacting for 2 hours to finally obtain the target catalyst precursor.
Step four, the catalyst precursor obtained in the step three is put into a condition of 500 ℃ to be roasted for 6 hours, and the target catalyst 1% Pt0.05% Co/Al is obtained 2 O 3 。
Example 3
Step one, 40mL of 0.5mol/L Tris buffer (pH=8.5) was measured and placed in a closed vessel, then nitrogen was continuously introduced thereinto for 2 hours, 4.74g of dopamine hydrochloride was further added thereto and sufficiently stirred, and after the dopamine hydrochloride was completely dissolved, 5mL of PtCl having a concentration of 117.6mmol/L was further added thereto 2 Solution and 5mL of Co (NO) at a concentration of 29.4mmol/L 3 ) 2 And (3) preparing a catalyst precursor solution.
And step two, selecting spherical aluminum oxide as the catalyst carrier, putting 30g of aluminum oxide carrier into a vacuum drying oven, and fully drying until the moisture is completely removed, wherein the saturated water absorption capacity is 35g.
And thirdly, mixing the dried aluminum oxide carrier obtained in the second step with the catalyst precursor solution prepared in the first step, exposing the mixed system in air and fully stirring, and drying the mixed system to remove excessive moisture after reacting for 2 hours to finally obtain the target catalyst precursor.
Step four, the catalyst precursor obtained in the step three is put into a condition of 500 ℃ to be roasted for 6 hours, and the target catalyst of 0.8 percent Pt0.2 percent Co/Al is obtained 2 O 3 。
Example 4:
step one, 40mL of 0.5mol/L Tris buffer (pH=8.5) was measured and placed in a closed vessel, then nitrogen was continuously introduced thereinto for 2 hours, 4.74g of dopamine hydrochloride was further added thereto and sufficiently stirred, and after the dopamine hydrochloride was completely dissolved, 5mL of PtCl having a concentration of 117.6mmol/L was further added thereto 2 Solution and 5mL of Ni (NO) with concentration of 29.4mmol/L 3 ) 2 And (3) preparing a catalyst precursor solution.
And step two, selecting spherical aluminum oxide as the catalyst carrier, putting 30g of aluminum oxide carrier into a vacuum drying oven, and fully drying until the moisture is completely removed, wherein the saturated water absorption capacity is 35g.
And thirdly, mixing the dried aluminum oxide carrier obtained in the second step with the catalyst precursor solution prepared in the first step, exposing the mixed system in air and fully stirring, and drying the mixed system to remove excessive moisture after reacting for 2 hours to finally obtain the target catalyst precursor.
Step four, the catalyst precursor obtained in the step three is put into a condition of 500 ℃ to be roasted for 6 hours, and the target catalyst of 0.8 percent Pt0.2 percent Ni/Al is obtained 2 O 3 。
Comparative example:
step one, 45mL of 0.5mol/L Tris buffer (pH=8.5) was measured and placed in a closed vessel, then nitrogen was continuously introduced thereinto for 2 hours, 4.74g of dopamine hydrochloride was further added thereto and sufficiently stirred, and after the dopamine hydrochloride was completely dissolved, 5mL of PtCl having a concentration of 147mmol/L was further added thereto 2 And (3) preparing a catalyst precursor solution.
And step two, selecting spherical aluminum oxide as the catalyst carrier, putting 30g of aluminum oxide carrier into a vacuum drying oven, and fully drying until the moisture is completely removed, wherein the saturated water absorption capacity is 35g.
And thirdly, mixing the dried aluminum oxide carrier obtained in the second step with the catalyst precursor solution prepared in the first step, exposing the mixed system in air and fully stirring, and drying the mixed system to remove excessive moisture after reacting for 2 hours to finally obtain the target catalyst precursor.
Step four, the catalyst precursor obtained in the step three is put into a condition of 500 ℃ to be roasted for 6 hours, and the target catalyst 1 percent Pt/Al is obtained 2 O 3 。
The conversion and selectivity of the catalysts prepared in examples 1-4 and comparative examples are shown in the following table:
experimental results
| Catalyst | Conversion (%) | Selectivity (%) | |
| Example 1 | 0.5％Pt0.05％Co/Al 2 O 3 | 90 | 92 |
| Example 2 | 1％Pt0.05％Co/Al 2 O 3 | 95 | 96 |
| Example 3 | 0.8％Pt0.2％Co/Al 2 O 3 | 92 | 98 |
| Example 4 | 0.8％Pt0.2％Ni/Al 2 O 3 | 90 | 95 |
| Comparative example | 1％Pt/Al 2 O 3 | 70 | 85 |
Based on the above table, the invention provides the supported bimetallic catalyst with better catalyst performance than pure Pt/Al in the dehydrogenation reaction of the perhydrodibenzyl toluene 2 O 3 A catalyst.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (12)
1. A catalyst for dehydrogenation reaction of organic liquid, which is characterized by comprising a carrier, a main active component and a co-active component; wherein the carrier is one or more of metal oxide, carbon material or molecular sieve; the main active component is one or two of platinum or palladium; the auxiliary active component is one or more of Co, ni, cu, zn, mg, fe or La; the content of the main active component is 0.1-5wt.% and the content of the auxiliary active component is 0.01-0.3wt.% calculated by the composition of the catalyst.
2. The catalyst for dehydrogenation of organic liquids according to claim 1, wherein the specific surface area of the carrier is 50-300m 2 And/g, the average pore diameter is 6-10nm.
3. The catalyst for dehydrogenation of organic liquids according to claim 1, wherein said metal oxide is SiO 2 、MnO、La 2 O 3 、ZnO、Al 2 O 3 、TiO 2 Or CeO 2 。
4. The catalyst for dehydrogenation reactions of organic liquids according to claim 1, characterized in that the carbon material is activated carbon, graphite, carbon nanotubes or carbon nanofibers.
5. The catalyst for dehydrogenation of organic liquids according to claim 1, characterized in that the molecular sieve is SAPO-34, SBA-15 or ZSM-5.
6. A method for preparing a catalyst for dehydrogenation of organic liquids, based on the catalyst for dehydrogenation of organic liquids according to any one of the previous claims 1 to 5, characterized in that it comprises the following steps:
step 1, preparing a dopamine solution containing an active metal precursor according to a proportion, wherein the pH value of the solution is 8.5, and the solution preparation is carried out in an inert atmosphere;
step 2, preparing a catalyst carrier, fully drying the catalyst carrier before use, and measuring the saturated water absorption;
step 3, adding the dried catalyst carrier obtained in the step 2 into the dopamine solution prepared in the step 1, simultaneously exposing the obtained mixture to air and fully stirring, drying the obtained solid after reaction at the drying temperature of 20-180 ℃ for 0.5-100h, and then obtaining a catalyst precursor;
and 4, roasting the catalyst precursor obtained in the step 3, and then obtaining the target catalyst.
7. The method for preparing a catalyst for dehydrogenation reaction of organic liquid according to claim 6, wherein the buffer used in the preparation of the dopamine solution in the step 1 is Tris buffer, and the pH is 8.5.
8. The method for preparing a catalyst for dehydrogenation reaction of organic liquids according to claim 7, wherein the concentration of dopamine in the dopamine solution is 0.5-1.0mol/L in the step 1.
9. The method for preparing a catalyst for dehydrogenation reaction of organic liquids according to claim 8, wherein in the step 1, the active noble metal precursor in the dopamine solution is a water-soluble salt or an acid, and the concentration thereof is in the range of 1 to 5 mM; wherein the water soluble salt is Pt (NO) 3 ) 2 Or PtCl 2 The acid is H 2 PtCl 6 Or H 2 PdCl 4 。
10. The method for preparing a catalyst for dehydrogenation reaction of organic liquid according to claim 9, wherein in the step 1, the non-noble metal precursor in the dopamine solution is water-soluble nitrate or hydrochloride in a concentration ranging from 0.1 to 2 mM.
11. The method for preparing a catalyst for dehydrogenation of organic liquids according to claim 10, wherein in the step 3, the volume of the dopamine solution used is 1.2 to 2 times the saturated water absorption of the catalyst carrier.
12. The method for preparing a catalyst for dehydrogenation reactions of organic liquids according to claim 11, characterized in that in said step 3, the calcination of the catalyst precursor is performed in air, hydrogen or inert atmosphere at a temperature of 200-800 ℃ for a calcination period of 0.5-100 hours.
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