CN112808295B - 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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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 avoids the problem of low alkane dehydrogenation efficiency caused by easy generation of cobalt oxide in the roasting of the traditional muffle furnace through direct 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 is obtained under the same reaction conditions compared with the catalyst prepared by the common dipping and calcining methodA high conversion rate; 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 introducingAt a rate of 10% 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;
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 H2Heating the mixture to 600 ℃ at the speed of 12 ℃/min by using 35mL/min of argon, and keeping the temperature 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 was purged with nitrogen, the catalyst packing mass was 0.4g, and the propane concentration was 140000ppm gas, 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. 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 (2)
1. The application of a single-site Co (II) catalyst in the preparation of olefin by alkane dehydrogenation;
the single-site Co (II) catalyst is prepared by soaking pure silicon carrier in cobalt salt solution by an isometric soaking method, uniformly mixing, soaking for 10-15H, drying, tabletting, pulverizing, sieving to obtain 40-60 mesh granules, placing the granules in a fixed bed reactor, introducing H containing 8-12%2Heating the argon to 550-650 ℃ for reaction for 1.5-2.5h to obtain the catalyst, wherein the content of Co is 2% -6%;
the cobalt salt is cobalt nitrate or cobalt acetate, the pure silicon carrier is SBA15 or MCM41, and the temperature is raised to 550-650 ℃ at the temperature raising rate of 8-12 ℃/min.
2. Use according to claim 1, 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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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5036032A (en) * | 1988-03-25 | 1991-07-30 | Exxon Research And Engineering Company | Selective catalysts and their preparation for catalytic hydrocarbon synthesis |
CN107020154A (en) * | 2017-05-02 | 2017-08-08 | 江南大学 | A kind of preprocess method of the cobalt-base catalyst activity of raising CO Hydrogenation alkene |
CN110560145A (en) * | 2019-09-18 | 2019-12-13 | 昆明理工大学 | Preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan |
CN111085241A (en) * | 2019-12-24 | 2020-05-01 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and preparation method of catalyst thereof |
CN111925271A (en) * | 2020-08-17 | 2020-11-13 | 湘潭大学 | Catalytic decomposition method for preparing propylene by direct dehydrogenation of propane |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US9192919B2 (en) * | 2013-03-14 | 2015-11-24 | Uchicago Argonne, Llc | Selective alkane activation with single-site atoms on amorphous support |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5036032A (en) * | 1988-03-25 | 1991-07-30 | Exxon Research And Engineering Company | Selective catalysts and their preparation for catalytic hydrocarbon synthesis |
CN107020154A (en) * | 2017-05-02 | 2017-08-08 | 江南大学 | A kind of preprocess method of the cobalt-base catalyst activity of raising CO Hydrogenation alkene |
CN110560145A (en) * | 2019-09-18 | 2019-12-13 | 昆明理工大学 | Preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan |
CN111085241A (en) * | 2019-12-24 | 2020-05-01 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and preparation method of catalyst thereof |
CN111925271A (en) * | 2020-08-17 | 2020-11-13 | 湘潭大学 | Catalytic decomposition method for preparing propylene by direct dehydrogenation of propane |
Non-Patent Citations (6)
Title |
---|
Guo-Zhu Bian et al..Investigations on the structural changes of two Co/SiO.《Applied Catalysis A: General》.2003,第252卷(第2期),第251-260页. * |
Influence of Coordination Environment of Anchored Single-Site Cobalt Catalyst on CO2 Hydrogenation;Juan D. Jimenez et al.;《ChemCatChem》;20191022;第12卷(第3期);第846-854页 * |
Investigations on the structural changes of two Co/SiO;Guo-Zhu Bian et al.;《Applied Catalysis A: General》;20030731;第252卷(第2期);第252页2.1章节实验部分 * |
Propylene Hydrogenation and Propane Dehydrogenation by a Single-Site Zn2+ on Silica Catalyst;Neil M. Schweitzer et al.;《ACS Catalysis》;20140221;第4卷(第4期);第1091-1098页 * |
Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism;Bo Hu et al.;《Journal of Catalysis》;20141209;第322卷;第24页摘要 * |
费托合成Co基催化剂预处理研究进展;燕来等;《石油化工》;20200615(第06期);第605-610页 * |
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