CN103933978A - Supported nanocatalyst for catalytic conversion of carbon dioxide as well as preparation method and application thereof - Google Patents
Supported nanocatalyst for catalytic conversion of carbon dioxide as well as preparation method and application thereof Download PDFInfo
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- CN103933978A CN103933978A CN201410141351.4A CN201410141351A CN103933978A CN 103933978 A CN103933978 A CN 103933978A CN 201410141351 A CN201410141351 A CN 201410141351A CN 103933978 A CN103933978 A CN 103933978A
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Abstract
The invention discloses a supported nanocatalyst for catalytic conversion of carbon dioxide. The supported nanocatalyst comprises active component Cu particles, carrier silica gel and an optional auxiliary agent, wherein based on the weight of a carrier, the percentage content of the active component Cu particles is 1-40%, and the percentage content of the auxiliary agent is less than or equal to 20%; the average size of the active component Cu particles is 1-20nm, and the active specific surface areas of the active component Cu particles are 100-400m<2>.g<-1>. The invention further discloses a preparation method of the supported nanocatalyst and application of the supported nanocatalyst for catalytic conversion of carbon dioxide in the synthesis of methanol by virtue of a carbon dioxide hydrogenation reaction and the carbon monoxide reaction.
Description
Technical field:
The invention belongs to carbon dioxide activation and utilize technical field, be specifically related to a kind of carrier nanometer catalyst for catalysis transform of carbon dioxide and its preparation method and application.
Background technology:
Carbon dioxide is a kind of greenhouse gases, and nearly decades, its a large amount of global warmings that cause with lasting discharge that produce have been subject to various circles of society's extensive concern.In atmosphere, carbon dioxide is mainly derived from the burning utilization of fossil fuel.International Energy Agency prediction: until the year two thousand thirty fossil fuel be still the main energy.Therefore, Optimization of Energy Structure is when reducing CO2 emission, and seizure, storage and the catalyzed conversion of realizing carbon dioxide has been focus and the focus that the whole world is paid close attention to.Realize the catalyzed conversion of carbon dioxide, not only can alleviate the pressure that carbon dioxide brings to environment, also the more important thing is the chemicals with economic worth can be provided, as methyl alcohol, methane, formic acid, dimethyl ether, urea and dimethyl carbonate etc.But carbon dioxide is the little molecule of a kind of inertia, be difficult to activation.Therefore, to activate carbon dioxide and realize its Efficient Conversion be one of the crucial science difficult problem in this field to development of new catalyst.
Catalytic hydrogenation of carbon dioxide synthesizing methanol and carbon monoxide are technology paths that rationally utilizes carbon dioxide, and one of its product methyl alcohol is a kind of important industrial chemicals especially, world's annual requirement approximately 5 * 10
7ton, is widely used in the fields such as organic synthesis, medicine, fuel.Especially, development along with Chemical Engineering Technology, if methyl alcohol can be realized and take carbon dioxide completely and produce as raw material, himself can be used as a kind of sustainable synthetic fuel, thereby can realize the circulation of " energy fuel-carbon dioxide-methyl alcohol-energy fuel ", alleviate the earth because of the carbon dioxide greenhouse gas problem that fossil energy burning causes, realize carbon cycle.Another kind of product carbon monoxide is one of composition of synthesis gas, in chemical industry is synthetic, has purposes extremely widely.At present, the catalyst of synthesizing methanol by hydrogenating carbon dioxide is mainly at co hydrogenation catalst for synthesis of methanol (Cu/ZnO/Al
2o
3) basis on develop.On the one hand in CuZnAl catalyst, to introduce to improve carbon dioxide conversion and methyl alcohol is selective as auxiliary agents such as Zr (201310227211.4), Ce (200910163236.6), La (201110124422.6), Mg (201010502152.3), Ti (201210066240.2).Be by improving copper zinc-base method for preparing catalyst to increase specific surface area of catalyst on the other hand, thereby improve catalytic reaction activity and methyl alcohol selective (201210024149.9).But, on the CuZnAl catalyst basis of industrial co hydrogenation synthesizing methanol, develop the progress that synthesizing methanol by hydrogenating carbon dioxide catalyst obtains still very limited.Carbon dioxide conversion and the methyl alcohol of the catalyst of having reported are at present selectively still lower.Active lower common reason is that the size of active ingredient copper in catalyst is large, decentralization is lower, specific activity surface area is lower.According to the literature, for copper-based catalysts of the same type, the specific area of active ingredient copper and catalyst activity have good correlation, the specific area that improves copper can effectively improve catalytic reaction activity (Science, 2012,336,893-897).At present, CuZnAl catalyst is because adopting traditional coprecipitation method preparation, and the size of active ingredient copper is larger, and decentralization is lower, and specific activity surface area is lower, and the specific activity surface area of copper only reaches 40m at the most according to the literature
2g
-1, have quite a few copper not bring into play catalytic action, thereby catalytic activity is lower.
Therefore, develop the new catalyst that a kind of size is little, decentralization is high, specific activity surface area is high, realize efficient catalytic chemical recycling of carbon dioxide significant.
Summary of the invention
The problem that carbon dioxide conversion is on the low side and methyl alcohol is selective also on the low side for synthesizing methanol by hydrogenating carbon dioxide in prior art and CO catalyst, the invention provides a kind of carrier nanometer catalyst for catalysis transform of carbon dioxide and its preparation method and application, the carrier nanometer catalyst that adopts preparation method disclosed by the invention to obtain is applied in synthesizing methanol by hydrogenating carbon dioxide and reaction of carbon monoxide, carbon dioxide conversion per pass reaches 23%, add after auxiliary agent, methyl alcohol is selectively greater than 95%.
The invention discloses a kind of carrier nanometer catalyst for catalysis transform of carbon dioxide, comprise active component nanometer Cu particle, carrier silica gel and auxiliary agent optionally.The average-size of active component nanometer Cu particle is 1-20nm, preferred 1-10nm, and specific activity surface area is 100-400m
2g
-1; Auxiliary agent is any one or two kinds of metals or the oxide in iron, cobalt, nickel, manganese, zinc, palladium, barium, aluminium, preferably cobalt or manganese; In the quality of carrier, the percentage composition of active component nanometer Cu particle is 1-40%, preferred 5-20%, and the percentage composition of auxiliary agent is less than or equal to 20%, preferably 1-10%.
The invention also discloses a kind of preparation method of the carrier nanometer catalyst for catalysis transform of carbon dioxide, catalyst forms as mentioned above, and preparation process is as follows:
(1), by copper presoma with optionally auxiliary agent presoma is soluble in water successively, obtain the mixed aqueous solution of cupric and auxiliary agent;
(2) by the pH value of mixed aqueous solution in ammoniacal liquor regulating step (1), be 9-12;
(3) add carrier silica gel, under 70-130 ℃ of condition, add thermal agitation until pH becomes 5-6;
(4) centrifugal, washing, 60-150 ℃ of dry 2-15 hour, 300-800 ℃ of roasting 1-8 hour, 200-400 ℃ of hydrogen reducing 2-10 hour, obtains carrier nanometer catalyst.
Described copper presoma comprises the combination of any one or more materials in copper halide, nitric acid copper and copper sulfate.
Described auxiliary agent presoma comprises the combination of any one or more materials in halide and nitrate.
In described hydrogen reducing, the content of hydrogen is: 5-100%.
The invention also discloses a kind of carrier nanometer catalyst for catalysis transform of carbon dioxide in the application of synthesizing methanol by hydrogenating carbon dioxide and reaction of carbon monoxide, comprise the steps:
In fixed bed reactors, raw material by volume content carbon dioxide (10-50%), hydrogen (40-80%), nitrogen (5-10%) is 5000-20000mLg in air speed
-1h
-1, temperature is 200-500 ℃, under the condition that pressure is 1-10MPa, in catalyst surface reaction, obtains methyl alcohol and carbon monoxide.
The invention has the beneficial effects as follows: adopt the size of active component nanometer Cu particle of the carrier nanometer catalyst that preparation method disclosed by the invention obtains little, decentralization is high, specific activity surface area is high, thereby can efficient catalytic chemical recycling of carbon dioxide, possess industrial application value.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of embodiment 1 catalyst.
Fig. 2 is that embodiment 1 catalyst carbon dioxide conversion is with reaction time variation diagram.
Fig. 3 is the gas-chromatography flame ionization ditector analysis of spectra of embodiment 1 catalyst.
Fig. 4 is the gas-chromatography flame ionization ditector analysis of spectra of embodiment 2 catalyst.
Fig. 5 is the gas-chromatography flame ionization ditector analysis of spectra of embodiment 3 catalyst.
Fig. 6 is the gas-chromatography flame ionization ditector analysis of spectra of embodiment 4 catalyst.
The specific embodiment:
Embodiment 1:
Take 0.5g Cu (NO
3)
23H
2o is dissolved in 10mL deionized water, and it is dissolved completely, obtains copper nitrate solution concentration to be: 0.2mol/L; Dropwise drip 28% ammoniacal liquor to copper nitrate aqueous solution, regulator solution pH value is 10; Add 1g silica gel, 80 ℃ add thermal agitation until pH value becomes 6; Centrifugation, outwells supernatant liquor, by deionized water, washs solids three times, and 120 ℃ are dried 8 hours; 450 ℃ of roastings 3 hours; 300 ℃ of pure hydrogen reductions 5 hours, obtain the carrier nanometer catalyst 1 for synthesizing methanol by hydrogenating carbon dioxide and carbon monoxide, and its transmission electron microscope picture is shown in Fig. 1, and the average grain diameter of nanometer Cu particle is that 2.1nm, decentralization are 54%, specific activity surface area is 367.9m
2g
-1, carbon dioxide conversion is shown in Fig. 2 with reaction time variation diagram, experiences 120 hours, and reactivity does not almost reduce, and gas-chromatography flame ionization ditector analysis of spectra is shown in Fig. 3.
Embodiment 2:
Take 0.7g Cu (NO
3)
23H
2o is dissolved in 10mL deionized water, and it is dissolved completely, obtains salpeter solution concentration to be: 0.3mol/L; Dropwise drip 28% ammoniacal liquor to copper nitrate aqueous solution, regulator solution pH value is 11; Add 1g silica gel, 90 ℃ add thermal agitation until pH value becomes 5; Centrifugation, outwells supernatant liquor, by deionized water, washs solids three times, and 100 ℃ are dried 8 hours; 600 ℃ of roastings 3 hours; 300 ℃ of pure hydrogen reductions 5 hours, obtain being applied to the carrier nanometer catalyst 2 of synthesizing methanol by hydrogenating carbon dioxide and carbon monoxide, and gas-chromatography flame ionization ditector analysis of spectra is shown in Fig. 4.
Embodiment 3:
Take 0.4g Cu (NO
3)
23H
2o and 0.1gCo (NO
3)
26H
2o is dissolved in 10mL deionized water, and it is dissolved completely; Dropwise drip 28% ammoniacal liquor to mixed solution, regulator solution pH value is 11; Add 1g silica gel, 80 ℃ add thermal agitation until pH value becomes 6; Centrifugation, outwells supernatant liquor, by deionized water, washs solids three times, and 100 ℃ are dried 8 hours; 450 ℃ of roastings 6 hours, 300 ℃ of pure hydrogen reductions 5 hours, obtain being applied to the carrier nanometer catalyst 3 of synthesizing methanol by hydrogenating carbon dioxide and carbon monoxide, and gas-chromatography flame ionization ditector analysis of spectra is shown in Fig. 5.
Embodiment 4:
Take 0.4g Cu (NO
3)
23H
2o and 0.1gMn (NO
3)
24H
2o is dissolved in 10mL deionized water, and it is dissolved completely; Dropwise drip 28% ammoniacal liquor to mixed solution, regulator solution pH value is 12; Add 1g silica gel, 80 ℃ add thermal agitation until pH value becomes 6; Centrifugation, outwells supernatant liquor, by deionized water, washs solids three times, and 100 ℃ are dried 8 hours; 450 ℃ of roastings 6 hours, 300 ℃ of pure hydrogen reductions 5 hours, obtain being applied to the carrier nanometer catalyst 4 of synthesizing methanol by hydrogenating carbon dioxide and carbon monoxide, and gas-chromatography flame ionization ditector analysis of spectra is shown in Fig. 6.
Embodiment 5:
The catalyst of embodiment 1-4 is applied in synthesizing methanol by hydrogenating carbon dioxide and reaction of carbon monoxide, and the ratio of unstripped gas is: carbon dioxide: hydrogen: nitrogen=20:70:10, air speed 16000mLg
-1h
-1, reaction pressure 3MPa, 300 ℃ of reaction temperatures, product carries out online detection with gas chromatograph to be analyzed, and utilizes inner mark method ration to analyze the content of each component in tail gas, and reaction result is in Table 1.
The performance of table 1 embodiment catalyst in synthesizing methanol by hydrogenating carbon dioxide and reaction of carbon monoxide
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of making, be equal to replacement, improvement etc., within all should being included in the scope of protection of the invention.
Claims (5)
1. the carrier nanometer catalyst for catalysis transform of carbon dioxide, it is characterized in that: catalyst comprises active component nanometer Cu particle and carrier silica gel, quality in carrier, the percentage composition of active component nanometer Cu particle is 1-40%, the average-size of active component nanometer Cu particle is 1-20nm, and the specific activity surface area of active component nanometer Cu particle is 100-400m
2g
-1, the preparation method of catalyst is as follows:
(1) copper presoma is soluble in water, obtain the aqueous solution of cupric;
(2) by the pH value of copper solution in ammoniacal liquor regulating step (1), be 9-12;
(3) add carrier silica gel, under 70-130 ℃ of condition, add thermal agitation until pH becomes 5-6;
(4) centrifugal, washing, 60-150 ℃ of dry 2-15 hour, 300-800 ℃ of roasting 1-8 hour, 200-400 ℃ of hydrogen reducing 2-10 hour, obtains carrier nanometer catalyst.
2. the carrier nanometer catalyst for catalysis transform of carbon dioxide according to claim 1, described catalyst also comprises auxiliary agent, quality in carrier, the percentage composition of auxiliary agent is less than or equal to 20%, described auxiliary agent is any one or two kinds of metals or its oxide in iron, cobalt, nickel, manganese, zinc, palladium, barium, aluminium, and the preparation method of catalyst is as follows:
(1), by copper presoma with optionally auxiliary agent presoma is soluble in water successively, obtain the mixed aqueous solution of cupric and auxiliary agent;
(2) by the pH value of mixed aqueous solution in ammoniacal liquor regulating step (1), be 9-12;
(3) add carrier silica gel, under 70-130 ℃ of condition, add thermal agitation until pH becomes 5-6;
(4) centrifugal, washing, 60-150 ℃ of dry 2-15 hour, 300-800 ℃ of roasting 1-8 hour, 200-400 ℃ of hydrogen reducing 2-10 hour, obtains carrier nanometer catalyst.
3. method for preparing catalyst according to claim 1 and 2, is characterized in that: preferred copper presoma comprises the combination of any one or more materials in copper halide, nitric acid copper and copper sulfate; Auxiliary agent presoma comprises the combination of any one or two kinds of materials in halide and nitrate; In hydrogen reducing, the content of hydrogen is: 5-100%.
4. carrier nanometer catalyst according to claim 2, is characterized in that: the preferred cobalt of auxiliary agent or manganese.
5. the application in order to synthesizing methanol and carbon monoxide as hydrogenation of carbon dioxide catalyst of the carrier nanometer catalyst for catalysis transform of carbon dioxide described in claim 1 or 2, comprise the steps: in fixed bed reactors, raw material by volume content carbon dioxide (10-50%), hydrogen (40-80%), nitrogen (5-10%) is 5000-20000mLg in air speed
-1h
-1, temperature is 200-500 ℃, under the condition that pressure is 1-10MPa, in catalyst surface reaction, obtains methyl alcohol and carbon monoxide.
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Cited By (8)
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|---|---|---|---|---|
| CN105170151A (en) * | 2015-10-23 | 2015-12-23 | 中国科学院上海高等研究院 | Core-shell structure type copper-based catalyst as well as preparation method and application thereof |
| CN106040237A (en) * | 2016-05-31 | 2016-10-26 | 大连理工大学 | Method for preparing nanogold catalyst for producing CO by catalyzing CO2 hydrogenation reduction and application of nanogold catalyst |
| CN106076396A (en) * | 2016-06-06 | 2016-11-09 | 昆明理工大学 | A kind of preparation method and applications of the Cu support type mesoporous catalyst of Au doping |
| CN108435184A (en) * | 2018-04-08 | 2018-08-24 | 太原理工大学 | The catalyst and preparation and application of carbon dioxide and water methanol |
| CN110368974A (en) * | 2018-04-13 | 2019-10-25 | 本田技研工业株式会社 | The copper nanocatalyst of novel N doping for carbon dioxide reduction reaction |
| CN113842914A (en) * | 2021-10-29 | 2021-12-28 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
| CN114602476A (en) * | 2022-03-04 | 2022-06-10 | 太原理工大学 | CO (carbon monoxide)2Hydrogenation to C2+Preparation method and application of copper-iron-zinc-based catalyst of alcohol |
| CN114618500A (en) * | 2022-04-22 | 2022-06-14 | 武汉公合隆电力工程有限公司 | Method for preparing catalyst for synthesizing methanol from carbon dioxide and hydrogen |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170151A (en) * | 2015-10-23 | 2015-12-23 | 中国科学院上海高等研究院 | Core-shell structure type copper-based catalyst as well as preparation method and application thereof |
| CN106040237A (en) * | 2016-05-31 | 2016-10-26 | 大连理工大学 | Method for preparing nanogold catalyst for producing CO by catalyzing CO2 hydrogenation reduction and application of nanogold catalyst |
| CN106076396A (en) * | 2016-06-06 | 2016-11-09 | 昆明理工大学 | A kind of preparation method and applications of the Cu support type mesoporous catalyst of Au doping |
| CN106076396B (en) * | 2016-06-06 | 2018-06-15 | 昆明理工大学 | A kind of preparation method and applications of the Cu support type mesoporous catalysts of Au doping |
| CN108435184A (en) * | 2018-04-08 | 2018-08-24 | 太原理工大学 | The catalyst and preparation and application of carbon dioxide and water methanol |
| CN108435184B (en) * | 2018-04-08 | 2021-01-01 | 太原理工大学 | Catalyst for preparing methanol from carbon dioxide and water, preparation method and use method thereof |
| CN110368974A (en) * | 2018-04-13 | 2019-10-25 | 本田技研工业株式会社 | The copper nanocatalyst of novel N doping for carbon dioxide reduction reaction |
| CN113842914A (en) * | 2021-10-29 | 2021-12-28 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
| WO2023071244A1 (en) * | 2021-10-29 | 2023-05-04 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for synthesizing carbon dioxide into methanol, preparation method therefor, and use thereof |
| CN114602476A (en) * | 2022-03-04 | 2022-06-10 | 太原理工大学 | CO (carbon monoxide)2Hydrogenation to C2+Preparation method and application of copper-iron-zinc-based catalyst of alcohol |
| CN114602476B (en) * | 2022-03-04 | 2024-02-06 | 太原理工大学 | CO (carbon monoxide) 2 Hydrogenation for preparing C 2+ Preparation method and application of copper-iron-zinc-based catalyst of alcohol |
| CN114618500A (en) * | 2022-04-22 | 2022-06-14 | 武汉公合隆电力工程有限公司 | Method for preparing catalyst for synthesizing methanol from carbon dioxide and hydrogen |
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