CN112808295A - Preparation method and application of single-site Co (II) catalyst - Google Patents
Preparation method and application of single-site Co (II) catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 16
- 238000005470 impregnation Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 2
- 238000001354 calcination Methods 0.000 abstract description 21
- 238000007598 dipping method Methods 0.000 abstract description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 41
- 239000001294 propane Substances 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000003421 catalytic decomposition reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a preparation method of a single-site Co (II) catalyst, which comprises the steps of dipping a pure silicon carrier into a cobalt salt solution by an isometric dipping method, uniformly mixing, dipping for 10-15H, drying, tabletting, crushing and sieving to obtain 40-60-mesh particles, putting the particles into a fixed bed reactor, introducing H containing 8-12 percent2Heating the mixture to 550-650 ℃ for reaction for 1.5-2.5h to obtain a single-site Co (II) catalyst, wherein the content of Co is 2% -6%; the method of the invention is implemented byThe problem of low alkane dehydrogenation efficiency caused by easy generation of cobalt oxide in the roasting of the traditional muffle furnace is solved by the reduction; compared with the traditional strong electrostatic adsorption method, the preparation method has the advantages of simple preparation process, less time consumption and low cost, and the catalyst prepared by the method has higher conversion rate under the same reaction condition compared with the catalyst prepared by the common impregnation and calcination method; the method opens up a new way for obtaining the single-site metal catalyst.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of a single-site Co (II) catalyst and application of the single-site Co (II) catalyst in preparation of propylene by alkane dehydrogenation.
Background
Ethylene and propylene are raw materials of petrochemical industry and are used for producing various chemicals such as polymers, oxygen-containing compounds and important chemical intermediates. In recent years, with the development of market economy, the demand of downstream products of ethylene and propylene is rapidly increased, and the global demand of olefins is greatly promoted. The traditional methods for obtaining olefins by steam cracking and naphtha catalytic cracking have been far from meeting the demand of our country for olefins, and thus, the production of olefins from other sources, mainly including the dehydrogenation of alkanes, is becoming increasingly important. The olefin preparation by alkane dehydrogenation not only can reduce the cost and reduce the dependence degree on naphtha cracking and catalytic cracking processes, but also can obtain high-value hydrogen so as to improve the added value of products. The shale gas resource reserves are the first place in the world in China, and sufficient raw material sources are provided for the development of the olefin dehydrogenation industry.
Co is an important non-noble metal, and is emerging in the field of alkane dehydrogenation research because of its low cost, non-toxicity, and superior activation capability for C — H bonds. However, the existing form of cobalt is greatly different from that of olefin prepared by alkane dehydrogenation, the cobalt oxide mainly cracks alkane into methane and coke, the single-site Co (II) has excellent dehydrogenation performance, the single-site Co (II) is mainly obtained by a strong electrostatic adsorption method at present, the cost is high, the process is complex, and the large-scale application of the single-site Co (II) is hindered to a certain extent.
Disclosure of Invention
Aiming at the problems of complex process and high preparation cost of obtaining single-site divalent cobalt, the invention provides a simple preparation method of a single-site Co (II) catalyst, wherein the single-site Co (II) is obtained in a direct reduction mode after drying and is used for preparing olefin by alkane dehydrogenation, higher conversion rate is obtained under the same reaction condition compared with the catalyst prepared by a common impregnation calcining method, and the single-site Co (II) catalyst is obtained by the method through characterization.
The method comprises the steps of dipping a pure silicon carrier with high specific surface area into a cobalt salt solution by an isometric dipping method, uniformly mixing, dipping for 10-15H, drying, tabletting, crushing and sieving to obtain 40-60-mesh particles, putting the particles into a fixed bed reactor, introducing H containing 8-12%2The temperature of the argon is raised to 550 ℃ and 650 ℃ at the heating rate of 8-12 ℃/min for reaction for 1.5-2.5h, and then the single-site Co (II) catalyst is prepared, wherein the content of Co is 2-6%.
The cobalt salt is cobalt nitrate or cobalt acetate.
The pure silicon carrier with high specific surface area is SBA15 or MCM 41.
The drying is carried out at 110 ℃ for 10-15 h.
The invention also aims to apply the catalyst obtained by the method in the preparation of olefin by alkane dehydrogenation, and specifically, the single-site Co (II) catalyst is filled in a fixed bed reactor, inert gas is used for purging, and raw material gas with the alkane concentration of 130000-150000ppm is introduced into the reactor to carry out alkane dehydrogenation reaction to prepare olefin; the reaction temperature is 550-600 ℃, and the flow rate of the raw material gas is 30-40 mL/min.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional strong electrostatic adsorption method, the method has the advantages of simple preparation process, less time consumption and cost saving, and obtains higher conversion rate under the same reaction condition compared with the catalyst prepared by the common dipping and calcining method, the cobalt oxide is an active center for cracking alkane into methane, and the method well avoids the generation of cobalt oxide in the preparation process, so that the alkane at the early stage can not be over dehydrogenated.
Drawings
FIG. 1 shows the propane conversion for the catalytic decomposition of propane to propylene using 2% Co-SBA15 prepared by the hydrogen direct reduction process and 2% Co-SBA15 prepared by the conventional impregnated air calcination process;
FIG. 2 shows the selectivity of 2% Co-SBA15 prepared by direct reduction of hydrogen and 2% Co-SBA15 prepared by conventional impregnation air calcination to catalytically decompose propane to propylene;
FIG. 3 is a graph of 2% Co-SBA15 prepared by hydrogen direct reduction and 2% Co-SBA15 UV-vis prepared by conventional impregnation air calcination;
FIG. 4 shows H for 2% Co-SBA15 prepared by hydrogen direct reduction and 2% Co-SBA15 prepared by conventional impregnation air calcination2-TPR；
FIG. 5 shows the propane conversion for the catalytic decomposition of propane to propylene using 4% Co-SBA15 prepared by the hydrogen direct reduction process and 2% Co-SBA15 prepared by the conventional impregnated air calcination process;
FIG. 6 shows the selectivity of propylene from the catalytic decomposition of propane with 4% Co-SBA15 prepared by hydrogen direct reduction and 2% Co-SBA15 prepared by conventional impregnation air calcination;
FIG. 7 shows the propane conversion for the catalytic decomposition of propane to propylene using 6% Co-SBA15 prepared by the hydrogen direct reduction process and 2% Co-SBA15 prepared by the conventional impregnated air calcination process;
FIG. 8 shows the propylene selectivity for the catalytic decomposition of propane to propylene using 6% Co-SBA15 prepared by the direct reduction of hydrogen and 2% Co-SBA15 prepared by the conventional impregnated air calcination method;
FIG. 9 is an ethane conversion for the catalytic decomposition of ethane to ethylene with 2% Co-SBA15 prepared by the hydrogen direct reduction process;
FIG. 10 shows the ethylene selectivity of 2% Co-SBA15 catalytically decomposed ethane to ethylene prepared by hydrogen direct reduction.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto.
Example 1: preparation of 2g of 2% Co-SBA15 catalyst
(1) Weighing 0.2016g of cobalt nitrate in a 100mL crucible, adding 8mL of deionized water, stirring and mixing uniformly, adding 2g of SBA15, stirring vigorously for 10min, carrying out ultrasonic treatment for 10min, dipping for 12h, and drying at 110 ℃ for 10 h; tabletting, pulverizing, sieving to obtain 40-60 mesh material, loading into fixed bed reactor, and introducing H containing 10 vol% of H230mL of argon (C)Heating to 600 ℃ at a speed of 10 ℃/min for 2h to prepare a single-site Co (II) catalyst;
meanwhile, preparing a catalyst by adopting a common impregnation air calcination method as a reference, specifically weighing 0.2016g of cobalt nitrate into a 100mL crucible, adding 8mL of deionized water, stirring and mixing uniformly, adding 2g of SBA15, stirring vigorously for 10min, carrying out ultrasonic treatment for 10min, impregnating for 12h, and drying at 110 ℃ for 10 h; calcining in a muffle furnace at 600 ℃ for 300 min;
(2) catalytic propane dehydrogenation using single site Co (II) catalyst
The prepared catalyst is purged by nitrogen, the filling mass of the catalyst is 0.4g, gas with the propane concentration of 140000ppm is introduced, and the total space velocity of feeding is 6990 h-1Propane dehydrogenation is carried out at the normal pressure and the reaction temperature of 600 ℃ to prepare propylene;
as can be seen from fig. 1 and 2, the maximum conversion rate of propane in the catalyst obtained by the hydrogen direct reduction method is about 55%, the gas phase selectivity is 96%, and the catalytic activity is obviously improved compared with that of the catalyst obtained by the ordinary impregnation air calcination method; after 10h of reaction, the conversion rate of propane is reduced to 40%, and the selectivity is almost unchanged. From FIG. 3, it can be seen that Co (II) is obtained by the hydrogen direct reduction method, whereas ordinary air calcination mainly yields cobaltosic oxide; as can be seen from fig. 4, the catalyst obtained by the hydrogen direct reduction method also has a high-temperature reduction peak at about 800 ℃, which represents that Co (ii) having a strong force with the carrier is formed and a low-temperature reduction peak does not occur, indicating that it does not have cobalt oxide but has single-site Co (ii); the reduction peak of the catalyst calcined by common impregnation air is between 250 ℃ and 600 ℃, which represents the process of gradually reducing cobaltosic oxide into cobalt oxide and simple substance cobalt, and single-site Co (II) does not appear.
Example 2: preparation of 2g of 4% Co-SBA15 catalyst
(1) Weighing 0.4117g of cobalt nitrate into a 100mL crucible, adding 8mL of deionized water, stirring and mixing uniformly, adding 2g of SBA-15, stirring vigorously for 10min, performing ultrasonic treatment for 10min, soaking for 12h, and drying at 110 ℃ for 12 h; tabletting, pulverizing, sieving to obtain 40-60 mesh material, loading into fixed bed reactor, and introducing H containing 9 vol% of H2The temperature of the argon gas is increased to 600 ℃ at the speed of 12 ℃/min, wherein the argon gas is 35mL/minKeeping for 2 hours to prepare a single-site Co (II) catalyst;
meanwhile, preparing the catalyst by adopting a common impregnation air calcination method as a reference, specifically weighing 0.4117g of cobalt nitrate into a 100mL crucible, adding 8mL of deionized water, stirring and mixing uniformly, adding 2g of SBA15, stirring vigorously for 10min, performing ultrasonic treatment for 10min, impregnating for 12h, and drying at 110 ℃ for 12 h; calcining in a muffle furnace at 600 ℃ for 300 min;
(2) catalytic propane dehydrogenation using single site Co (II) catalyst
The prepared catalyst is purged by nitrogen, the filling mass of the catalyst is 0.4g, gas with the propane concentration of 140000ppm is introduced, and the total space velocity of feeding is 6990 h-1Propane dehydrogenation is carried out at the normal pressure and the reaction temperature of 600 ℃ to prepare propylene;
from fig. 5 and 6, it can be seen that the maximum conversion of 4% Co-SBA15 catalyst to propane is about 56%, and the gas phase selectivity is 96%, which is higher than that of the catalyst prepared by the conventional impregnation calcination method.
Example 3: preparation of 2g of 6% -SBA15 catalyst
(1) Weighing 0.6307g of cobalt nitrate in a 100mL crucible, adding 8mL of deionized water, stirring and mixing uniformly, adding 2g of SBA-15, stirring vigorously for 10min, performing ultrasonic treatment for 10min, dipping for 12h, and drying at 110 ℃ for 15 h; tabletting, pulverizing, sieving to obtain 40-60 mesh material, loading into fixed bed reactor, and introducing H with volume percentage of 12%230mL/min of argon, heating to 600 ℃ at the speed of 9 ℃/min, and keeping for 2 hours to prepare a single-site Co (II) catalyst;
meanwhile, preparing a catalyst by adopting a common impregnation air calcination method as a reference, specifically weighing 0.6307g of cobalt nitrate into a 100mL crucible, adding 8mL of deionized water, stirring and mixing uniformly, adding 2g of SBA15, stirring vigorously for 10min, carrying out ultrasonic treatment for 10min, impregnating for 12h, and drying at 110 ℃ for 15 h; calcining in a muffle furnace at 600 ℃ for 300 min;
(2) catalytic propane dehydrogenation using single site Co (II) catalyst
The prepared catalyst is purged by nitrogen, the filling mass of the catalyst is 0.4g, gas with the propane concentration of 140000ppm is introduced, and the total space velocity of feeding is 6990 h-1Propane removal is carried out at normal pressure and reaction temperature of 600 DEG CPreparing propylene by hydrogen;
from fig. 7 and 8, it can be seen that the maximum conversion rate of the catalyst obtained by the method of this example with 6% Co-SBA15 is about 50% for propane, and the gas phase selectivity is 96%, which is higher than that obtained by the conventional calcination method.
Example 4: preparation of 2g of 2% -SBA15 catalyst
(1) Weighing 0.2016g of cobalt nitrate in a 100mL crucible, adding 8mL of deionized water, stirring and mixing uniformly, adding 2g of SBA-15, stirring vigorously for 10min, performing ultrasonic treatment for 10min, dipping for 12h, and drying at 110 ℃ for 13 h; tabletting, pulverizing, sieving to obtain 40-60 mesh material, loading into fixed bed reactor, and introducing H containing 10 vol% of H2Heating to 600 ℃ at the speed of 10 ℃/min with 30mL/min of argon, and keeping for 2h to prepare a single-site Co (II) catalyst;
(2) catalytic dehydrogenation of ethane using single site Co (II) catalyst
The prepared catalyst is purged by nitrogen, the filling mass of the catalyst is 0.4g, gas with ethane concentration of 140000ppm is introduced, and the total space velocity of feeding is 6990 h-1Dehydrogenating ethane at normal pressure and reaction temperature of 600 deg.c to prepare ethylene;
from FIGS. 9 and 10, it is clear that the maximum conversion of 2% Co-SBA15 to ethane is about 18%, and the propylene gas phase selectivity is 98%.
Claims (6)
1. A preparation method of a single-site Co (II) catalyst is characterized by comprising the following steps: soaking pure silicon carrier in cobalt salt solution by equal volume impregnation method, mixing, soaking for 10-15 hr, drying, tabletting, pulverizing, sieving to obtain 40-60 mesh granule, placing the granule in fixed bed reactor, introducing H containing 8-12%2Heating the mixture to 550-650 ℃ for reaction for 1.5-2.5h to obtain the single-site Co (II) catalyst, wherein the content of Co is 2% -6%.
2. The method of preparing a single-site Co (ii) catalyst of claim 1, wherein: the cobalt salt is cobalt nitrate or cobalt acetate.
3. The method of preparing a single-site Co (ii) catalyst of claim 1, wherein: the pure silicon carrier is SBA15 or MCM 41.
4. The method of preparing a single-site Co (ii) catalyst of claim 1, wherein: the temperature is raised to 550-650 ℃ at a temperature raising rate of 8-12 ℃/min.
5. Use of a single site Co (II) catalyst prepared by the method of any one of claims 1 to 4 in the dehydrogenation of an alkane to produce an alkene.
6. Use according to claim 5, characterized in that: filling a single-site Co (II) catalyst in a fixed bed reactor, purging by inert gas, and introducing raw material gas with alkane concentration of 130000-150000ppm into the reactor for alkane dehydrogenation reaction to prepare olefin; the reaction temperature is 550-600 ℃, and the flow rate of the raw material gas is 30-40 mL/min.
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Cited By (2)
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| CN114588911A (en) * | 2022-03-23 | 2022-06-07 | 昆明理工大学 | Method for preparing synthesis gas by catalyzing propane carbon dioxide with cobalt-based catalyst |
| CN115007200A (en) * | 2022-06-17 | 2022-09-06 | 昆明理工大学 | Preparation method and application of sub-nanocluster Co-based catalyst |
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| CN114588911A (en) * | 2022-03-23 | 2022-06-07 | 昆明理工大学 | Method for preparing synthesis gas by catalyzing propane carbon dioxide with cobalt-based catalyst |
| CN115007200A (en) * | 2022-06-17 | 2022-09-06 | 昆明理工大学 | Preparation method and application of sub-nanocluster Co-based catalyst |
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