CN103933978B - A kind of carrier nanometer catalyst for catalysis transform of carbon dioxide and its preparation method and application - Google Patents

A kind of carrier nanometer catalyst for catalysis transform of carbon dioxide and its preparation method and application Download PDF

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CN103933978B
CN103933978B CN201410141351.4A CN201410141351A CN103933978B CN 103933978 B CN103933978 B CN 103933978B CN 201410141351 A CN201410141351 A CN 201410141351A CN 103933978 B CN103933978 B CN 103933978B
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catalyst
carbon dioxide
carrier
nanometer
auxiliary agent
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CN103933978A (en
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王志巧
郭国聪
徐忠宁
张明建
彭思艳
陈毓敏
陈青松
王明盛
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Fujian Institute of Research on the Structure of Matter of CAS
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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
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

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 optionally auxiliary agent.In the quality of carrier, the percentage composition of active component nanometer Cu particle is 1-40%, and the percentage composition of auxiliary agent is less than or equal to 20%.The average-size of active component nanometer Cu particle is 1-20nm, and specific surface area active is 100-400m 2g -1.The invention also discloses a kind of preparation method of the carrier nanometer catalyst for catalysis transform of carbon dioxide and a kind of application of carrier nanometer catalyst in synthesizing methanol by hydrogenating carbon dioxide and reaction of carbon monoxide for catalysis transform of carbon dioxide.

Description

A kind of carrier nanometer catalyst for catalysis transform of carbon dioxide and its preparation method and application
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, nearly decades, and it produces the global warming caused with continued emissions in a large number and has been subject to various circles of society's extensive concern.In air, carbon dioxide is mainly derived from the burning utilization of fossil fuel.International Energy Agency predict: until the year two thousand thirty fossil fuel be still the main energy.Therefore, Optimization of Energy Structure is with while reducing CO2 emission, and realizing the seizure of carbon dioxide, storage and catalyzed conversion has been the focus paid close attention to of the whole world and focus.Realize the catalyzed conversion of carbon dioxide, not only can alleviate the pressure that carbon dioxide brings to environment, the chemicals that also can provide and have economic worth is provided, as methyl alcohol, methane, formic acid, dimethyl ether, urea and dimethyl carbonate etc.But carbon dioxide is a kind of inertia Small molecular, be difficult to activation.Therefore, development of new catalyst activates carbon dioxide and realizes its Efficient Conversion is one of the crucial sciences problems in this field.
Catalytic hydrogenation of carbon dioxide synthesizing methanol and carbon monoxide are the technology paths of an Appropriate application carbon dioxide, and one of its product methyl alcohol is a kind of important industrial chemicals especially, world's annual requirement about 5 × 10 7ton, is widely used in the fields such as organic synthesis, medicine, fuel.Especially, along with the development of Chemical Engineering Technology, if it is that raw material is produced with carbon dioxide that methyl alcohol can realize complete, himself can be used as a kind of sustainable synthetic fuel, thus the circulation of " energy fuel-carbon dioxide-methyl alcohol-energy fuel " can be realized, alleviate the earth to burn the carbon dioxide greenhouse gas problem caused because of fossil energy, realize carbon cycle.Another kind of product carbon monoxide is one of composition of synthesis gas, in chemical industry synthesis, have 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 introduce in CuZnAl catalyst if the auxiliary agents such as Zr (201310227211.4), Ce (200910163236.6), La (201110124422.6), Mg (201010502152.3), Ti (201210066240.2) are to improve carbon dioxide conversion and methyl alcohol is selective.Be by improving copper-zinc-based catalyst preparation method to increase specific surface area of catalyst on the other hand, thus improve catalytic reaction activity and methyl alcohol selective (201210024149.9).But, the CuZnAl catalyst basis of industrial co hydrogenation synthesizing methanol is developed the progress that synthesizing methanol by hydrogenating carbon dioxide catalyst obtains still very limited.Carbon dioxide conversion and the methyl alcohol of the catalyst reported at present are selective still lower.Active lower common reason is that the size of active ingredient copper in catalyst is comparatively large, decentralization is lower, specific surface area active 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, and the specific area improving copper effectively can improve catalytic reaction activity (Science, 2012,336,893-897).At present, CuZnAl catalyst is because adopting the preparation of conventional coprecipitation method, and the size of active ingredient copper is comparatively large, and decentralization is lower, and specific surface area active is lower, and the specific surface area active of copper only reaches 40m at the most according to the literature 2g -1, have quite a few copper not play catalytic action, thus catalytic activity is lower.
Therefore, develop the new catalyst that a kind of size is little, decentralization is high, specific surface area active is high, realize efficient catalytic chemical recycling of carbon dioxide significant.
Summary of the invention
The problem that carbon dioxide conversion for synthesizing methanol by hydrogenating carbon dioxide in prior art and CO catalyst is on the low side and methyl alcohol is selective also on the low side, 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 adopting 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%, after adding auxiliary agent, methyl alcohol is selective is 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 optionally auxiliary agent.The average-size of active component nanometer Cu particle is 1-20nm, preferred 1-10nm, and specific surface area active is 100-400m 2g -1; Auxiliary agent is any one or two kinds of metals in iron, cobalt, nickel, manganese, zinc, palladium, barium, aluminium or oxide, preferred 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%, preferred 1-10%.
The invention also discloses a kind of preparation method of the carrier nanometer catalyst for catalysis transform of carbon dioxide, as mentioned above, preparation process is as follows for catalyst composition:
(1) by copper presoma with optionally auxiliary agent presoma is soluble in water successively, the mixed aqueous solution of cupric and auxiliary agent is obtained;
(2) be 9-12 by the pH value of mixed aqueous solution in ammoniacal liquor regulating step (1);
(3) add carrier silica gel, under 70-130 DEG C of condition, add thermal agitation until solution ph becomes 5-6;
(4) centrifugal, washing, 60-150 DEG C dry 2-15 hour, 300-800 DEG C roasting 1-8 hour, 200-400 DEG C 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 application of carrier nanometer catalyst in synthesizing methanol by hydrogenating carbon dioxide and reaction of carbon monoxide for catalysis transform of carbon dioxide, 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 DEG C, and pressure is under the condition of 1-10MPa, in catalyst surface reaction, obtains methyl alcohol and carbon monoxide.
The invention has the beneficial effects as follows: the size of the active component nanometer Cu particle of the carrier nanometer catalyst adopting preparation method disclosed by the invention to obtain is little, decentralization is high, specific surface area active is high, thus 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.
Detailed description of the invention:
Embodiment 1:
Take 0.5gCu (NO 3) 23H 2o is dissolved in 10mL deionized water, makes it dissolve completely, obtains copper nitrate solution concentration to be: 0.2mol/L; Dropwise drip 28% ammoniacal liquor in copper nitrate aqueous solution, regulate solution ph to be 10; Add 1g silica gel, 80 DEG C add thermal agitation until pH value becomes 6; Centrifugation, outwells supernatant liquor, spends deionized water solids three times, 120 DEG C of dryings 8 hours; 450 DEG C of roastings 3 hours; 300 DEG C of pure hydrogen reductions 5 hours, obtain the carrier nanometer catalyst 1 for synthesizing methanol by hydrogenating carbon dioxide and carbon monoxide, its transmission electron microscope picture is shown in Fig. 1, and the average grain diameter of nanometer Cu particle is 2.1nm, decentralization is 54%, specific surface area active is 367.9m 2g -1, carbon dioxide conversion is shown in Fig. 2 with reaction time variation diagram, and experience 120 hours, reactivity does not almost reduce, and gas-chromatography flame ionization ditector analysis of spectra is shown in Fig. 3.
Embodiment 2:
Take 0.7gCu (NO 3) 23H 2o is dissolved in 10mL deionized water, makes it dissolve completely, obtains salpeter solution concentration to be: 0.3mol/L; Dropwise drip 28% ammoniacal liquor in copper nitrate aqueous solution, regulate solution ph to be 11; Add 1g silica gel, 90 DEG C add thermal agitation until pH value becomes 5; Centrifugation, outwells supernatant liquor, spends deionized water solids three times, 100 DEG C of dryings 8 hours; 600 DEG C of roastings 3 hours; 300 DEG C of pure hydrogen reductions 5 hours, obtain the carrier nanometer catalyst 2 being applied to synthesizing methanol by hydrogenating carbon dioxide and carbon monoxide, gas-chromatography flame ionization ditector analysis of spectra is shown in Fig. 4.
Embodiment 3:
Take 0.4gCu (NO 3) 23H 2o and 0.1gCo (NO 3) 26H 2o is dissolved in 10mL deionized water, makes it dissolve completely; Dropwise drip 28% ammoniacal liquor in mixed solution, regulate solution ph to be 11; Add 1g silica gel, 80 DEG C add thermal agitation until pH value becomes 6; Centrifugation, outwells supernatant liquor, spends deionized water solids three times, 100 DEG C of dryings 8 hours; 450 DEG C of roastings 6 hours, 300 DEG C of pure hydrogen reductions 5 hours, obtain the carrier nanometer catalyst 3 being applied to synthesizing methanol by hydrogenating carbon dioxide and carbon monoxide, gas-chromatography flame ionization ditector analysis of spectra is shown in Fig. 5.
Embodiment 4:
Take 0.4gCu (NO 3) 23H 2o and 0.1gMn (NO 3) 24H 2o is dissolved in 10mL deionized water, makes it dissolve completely; Dropwise drip 28% ammoniacal liquor in mixed solution, regulate solution ph to be 12; Add 1g silica gel, 80 DEG C add thermal agitation until pH value becomes 6; Centrifugation, outwells supernatant liquor, spends deionized water solids three times, 100 DEG C of dryings 8 hours; 450 DEG C of roastings 6 hours, 300 DEG C of pure hydrogen reductions 5 hours, obtain the carrier nanometer catalyst 4 being applied to synthesizing methanol by hydrogenating carbon dioxide and carbon monoxide, gas-chromatography flame ionization ditector analysis of spectra is shown in Fig. 6.
Embodiment 5:
By the catalyst application of embodiment 1-4 in synthesizing methanol by hydrogenating carbon dioxide and reaction of carbon monoxide, the ratio of unstripped gas is: carbon dioxide: hydrogen: nitrogen=20:70:10, air speed 16000mLg -1h -1, reaction pressure 3MPa, reaction temperature 300 DEG C, product gas chromatograph carries out on-line checkingi analysis, and utilize inner mark method ration to analyze the content of each component in tail gas, 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, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within 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, in the quality of carrier, the percentage composition of active component nanometer Cu particle is 1-20%, the average-size of active component nanometer Cu particle is 1-10nm, and the specific surface area active of active component nanometer Cu particle is 100-400m 2g -1, the preparation method of catalyst is as follows:
(1) by soluble in water for copper presoma, the aqueous solution of cupric is obtained;
(2) be 9-12 by the pH value of copper solution in ammoniacal liquor regulating step (1);
(3) add carrier silica gel, under 70-130 DEG C of condition, add thermal agitation until solution ph becomes 5-6;
(4) centrifugal, washing, 60-150 DEG C dry 2-15 hour, 300-800 DEG C roasting 1-8 hour, 200-400 DEG C 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, in the quality of 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 in iron, cobalt, nickel, manganese, zinc, palladium, barium, aluminium or its oxide, and the preparation method of catalyst is as follows:
(1) by copper presoma with optionally auxiliary agent presoma is soluble in water successively, the mixed aqueous solution of cupric and auxiliary agent is obtained;
(2) be 9-12 by the pH value of mixed aqueous solution in ammoniacal liquor regulating step (1);
(3) add carrier silica gel, under 70-130 DEG C of condition, add thermal agitation until solution ph becomes 5-6;
(4) centrifugal, washing, 60-150 DEG C dry 2-15 hour, 300-800 DEG C roasting 1-8 hour, 200-400 DEG C of hydrogen reducing 2-10 hour, obtains carrier nanometer catalyst.
3. the carrier nanometer catalyst for catalysis transform of carbon dioxide according to claim 2, is characterized in that: 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. the carrier nanometer catalyst for catalysis transform of carbon dioxide according to claim 2, is characterized in that: auxiliary agent is cobalt or manganese.
5. the carrier nanometer catalyst for catalysis transform of carbon dioxide described in claim 1 or 2 is as the application of hydrogenation of carbon dioxide catalyst in order to synthesizing methanol and carbon monoxide, comprise the steps: in fixed bed reactors, raw material by volume content 10-50% carbon dioxide, 40-80% hydrogen, 5-10% nitrogen is 5000-20000mLg in air speed -1h -1, temperature is 200-500 DEG C, and pressure is under the condition of 1-10MPa, in catalyst surface reaction, obtains methyl alcohol and carbon monoxide.
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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
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
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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
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