CN112246273B - Catalyst for preparing low-carbon alcohol through carbon dioxide conversion, preparation method and application - Google Patents

Catalyst for preparing low-carbon alcohol through carbon dioxide conversion, preparation method and application Download PDF

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CN112246273B
CN112246273B CN202011171103.6A CN202011171103A CN112246273B CN 112246273 B CN112246273 B CN 112246273B CN 202011171103 A CN202011171103 A CN 202011171103A CN 112246273 B CN112246273 B CN 112246273B
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catalyst
carbon
carbon dioxide
core
alcohol
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CN112246273A (en
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徐威
于洋
丁良辉
丁克强
吴功德
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Nanjing Institute of Technology
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/398—
    • B01J35/40—
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof

Abstract

The invention provides a catalyst for preparing low-carbon alcohol by converting carbon dioxide, which has a three-layer core-shell structure; in the core-shell structure, the core is metal and accounts for 40-80% of the weight of the catalyst; the middle layer is nitrogen doped porous carbon and accounts for 1-10% of the weight of the catalyst; the outermost layer is silicon dioxide, and accounts for 10-59% of the weight of the catalyst; wherein the core comprises one or more of Cu, co metal nanoparticles; the invention also provides a preparation method and application of the catalyst for preparing the low-carbon alcohol by converting carbon dioxide. The three-layer core-shell structure provided by the invention establishes a nano reactor for preparing low-carbon alcohol by hydrogenating carbon dioxide with adjustable structure and performance, can solve the problem of low selectivity of low-carbon alcohol in the prior art, and catalyzes CO 2 The hydrogenation can directly obtain alcohol fuels with high added value such as ethanol, propanol and the like, and has low price, simple preparation method and good industrial application prospect.

Description

Catalyst for preparing low-carbon alcohol through carbon dioxide conversion, preparation method and application
Technical Field
The invention belongs to the technical field of carbon dioxide conversion, and particularly relates to a catalyst for preparing low-carbon alcohol through carbon dioxide conversion, a preparation method and application thereof.
Background
With the increasing global energy demand, fossil fuel consumption and CO 2 The total discharge amount is rapidly increased, thereby bringing double pressure of environment and energy, and CO 2 Can be converted into chemical or fuel, on one hand can solve the problem of CO in the atmosphere 2 The environmental problem caused by the increase of the concentration can also reduce the dependence on fossil fuel, and has important significance on energy structures, ecological environment and people's life. Wherein CO 2 The reaction for hydrogenation to alcohols is CO 2 Transformation utilizes one of the most promising approaches, which is currently studied moreCO 2 The hydrogenation is used for preparing the methanol, however, the ethanol and the low-carbon alcohol have higher added value than the methanol, and compared with the methanol, the hydrogenation has the characteristics of high heat value, low toxicity, safe transportation, wide application and the like, and is prepared from CO 2 The hydrogenation to obtain ethanol and lower alcohols in one step is simpler and more economical.
CO 2 The key point of hydrogenation synthesis of low-carbon alcohol is the catalyst, and the main catalytic system comprises copper-based catalyst, noble metal catalyst, other types of catalysts and the like. At present, the screening of effective components of the catalyst and the perfection of a catalyst preparation method are main research directions for improving the catalytic performance. CN 201510388581.5 discloses a catalyst for synthesizing low-carbon alcohol by hydrogenation of carbon dioxide, a preparation method and application thereof, the catalyst is obtained by taking basic nickel carbonate as a template, introducing transition metal molybdenum, then impregnating alkali metal potassium, and finally vulcanizing, wherein the mole fraction of ethanol in the total alcohol in the catalyst catalytic carbon dioxide hydrogenation product is 43%. CN201911147327.0 discloses a preparation method of a catalyst for synthesizing low-carbon alcohol by hydrogenation of carbon dioxide, which takes a mixed solution of ethanol and butyl titanate as a solvent, copper nitrate, ferric nitrate and cobalt nitrate are directly added, and ethylene glycol is taken as a complexing agent to obtain the catalyst through hydrolysis, drying and roasting. In the current research, the supported catalyst is mainly used, the preparation method is mainly an impregnation method or a coprecipitation method, but the catalytic performance of the catalyst is not ideal, and CO exists 2 Low conversion rate, C 2+ Alcohol selectivity is not high. Based on the above, the invention provides a catalyst for preparing low-carbon alcohol by converting carbon dioxide, a preparation method and application thereof to solve the problems.
Disclosure of Invention
The first object of the present invention is to provide a catalyst for preparing low-carbon alcohol by carbon dioxide conversion, which aims at overcoming the defects of the prior art;
a second object of the present invention is to provide a method for preparing a catalyst for carbon dioxide conversion to lower alcohols;
a third object of the present invention is to provide the use of the above catalyst in the field of carbon dioxide conversion to produce lower alcohols.
The invention adopts the following technical scheme:
a catalyst for preparing low-carbon alcohol by converting carbon dioxide, which has a three-layer core-shell structure; in the core-shell structure, the core is metal and accounts for 40-80% of the weight of the catalyst; the middle layer is nitrogen doped porous carbon and accounts for 1-10% of the weight of the catalyst; the outermost layer is silicon dioxide, and the silicon dioxide accounts for 10-59% of the weight of the catalyst.
Further, in the catalyst, the core comprises one or more of Cu and Co metal nano particles.
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
s1, mixing soluble metal salt and an organic ligand, and dissolving the mixture in water, wherein the organic ligand is a nitrogen-containing heterocyclic compound; wherein, the molar ratio of the total metal ions to the organic ligand is: 1:0.5-3, carrying out hydro-thermal treatment on the mixed solution after regulating the pH value, and then carrying out suction filtration or evaporating the solution to dry the solvent to obtain solid powder;
s2, dispersing the solid powder prepared in the step S1 in ethanol, carrying out ultrasonic oscillation, adding a certain amount of template agent while stirring, then dropwise adding a certain amount of tetraethoxysilane, slowly adding a certain amount of alkali liquor, carrying out heating reaction, obtaining a precipitate after the reaction is finished, washing and drying the precipitate, and roasting in an inert gas atmosphere to obtain the catalyst.
Further, in S1, the soluble metal salt is one or more of nitrate, sulfate, acetate and chloride of Cu or Co.
In the step S2, the template agent is one or more of cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, polyvinyl alcohol, oleate or laurate.
In S2, the solid content in the reaction solution is 5-50%.
In S1, the pH is adjusted to 9-10, and the hydrothermal temperature is 100-180 ℃.
The invention also provides application of the catalyst in preparing low-carbon alcohol through carbon dioxide conversion
The invention has the beneficial effects that:
the invention provides a three-layer core-shell structure based on metal, nitrogen doped porous carbon and silicon dioxide, thereby establishing a nano reactor for preparing low-carbon alcohol by hydrogenating carbon dioxide with adjustable structure and performance. Compared with the prior art, the invention has the advantages that:
1) The catalyst has high catalytic activity, the conversion rate of carbon dioxide is improved to be approximately 30%, and the catalyst has excellent stability;
2) The catalyst of the invention has high C compared with the traditional supported catalyst 2 ~C 4 Alcohol selectivity;
3) The catalyst has the advantages of low raw material price, relatively simple preparation method, strong practicability and wide applicability.
The specific embodiment is as follows:
for the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a catalyst for preparing low-carbon alcohol by converting carbon dioxide, which has a three-layer core-shell structure; in the core-shell structure, the core is metal and accounts for 40-80% of the weight of the catalyst; the middle layer is nitrogen doped porous carbon and accounts for 1-10% of the weight of the catalyst; the outermost layer is silicon dioxide, and accounts for 10-59% of the weight of the catalyst; in the catalyst, the core comprises one or more of Cu and Co metal nano particles.
The invention also provides a preparation method of the catalyst for preparing the low-carbon alcohol by converting carbon dioxide, which comprises the following steps:
s1, mixing soluble metal salt and an organic ligand, and dissolving the mixture in water, wherein the organic ligand is a nitrogen-containing heterocyclic compound; wherein, the molar ratio of the total metal ions to the organic ligand is: 1:0.5-3, adjusting the pH of the mixed solution to 9-10, performing hydrothermal treatment (the hydrothermal temperature is 100-180 ℃), and then performing suction filtration or evaporating the solution to dry the solvent to obtain solid powder; the soluble metal salt is one or more of nitrate, sulfate, acetate and chloride of Cu or Co;
s2, dispersing the solid powder prepared in the step S1 in ethanol, carrying out ultrasonic oscillation, adding a certain amount of template agent while stirring, then dropwise adding a certain amount of tetraethoxysilane, slowly adding a certain amount of alkali liquor, carrying out heating reaction, obtaining a precipitate after the reaction is finished, washing and drying the precipitate, and roasting in an inert gas atmosphere to obtain the catalyst; the solid content in the reaction liquid is 5-50%; the template agent is one or more of cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, polyvinyl alcohol, oleate or laurate.
The invention also provides application of the catalyst based on the three-layer core-shell structure of metal, nitrogen doped porous carbon and silicon dioxide in preparing low-carbon alcohol through carbon dioxide conversion.
Example 1
S1, mixing copper nitrate trihydrate and 2-methylpyridine according to a molar ratio of 1:3, dissolving the mixture in water, adjusting the pH value to 10.0, performing hydrothermal treatment at 120 ℃, and performing suction filtration on the obtained mixture to obtain solid powder;
s2, dispersing 1g of the solid powder in 20mL of ethanol, carrying out ultrasonic oscillation, adding 0.1g of cetyltrimethylammonium bromide while stirring, then dropwise adding 5mL of tetraethoxysilane into the solution, dropwise adding 1mol/L ammonia water (pH=8.5) while vigorously stirring, heating to 90 ℃ for continuous reaction for 12 hours, obtaining a precipitate after the reaction, washing and drying the precipitate, and roasting in a nitrogen atmosphere to obtain the catalyst, namely Cu@CN@SiO 2 。
Example 2
S1, mixing copper sulfate pentahydrate, cobalt acetate tetrahydrate and phthalocyanine according to a molar ratio of 0.5:0.5:0.5, dissolving the mixture in water, adjusting the pH value to 9.5, performing hydrothermal treatment at 100 ℃, and evaporating the obtained mixture to dryness to obtain solid powder;
s2, dispersing 1g of the solid powder into 20mL of ethanol, ultrasonically oscillating, adding 0.1g of polyvinylpyrrolidone while stirring, then dropwise adding 10mL of tetraethoxysilane into the solution, dropwise adding 1mol/L ammonia water (pH=9) while vigorously stirring, heating to 80 ℃ for continuous reaction for 24 hours, obtaining a precipitate after the reaction is finished, washing and drying the precipitate, and roasting under helium atmosphere to obtain the catalyst, namely CuCo@CN@SiO 2 。
Example 3
S1, mixing cobalt chloride hexahydrate and phthalocyanine according to a molar ratio of 1:2, dissolving the mixture in water, adjusting the pH value to 9.5, performing hydrothermal treatment at 150 ℃, and evaporating the obtained mixture to dryness to obtain solid powder;
s2, dispersing 1g of the solid powder in 50mL of ethanol, ultrasonically oscillating, adding 0.2g of polyvinyl alcohol while stirring, then dropwise adding 20mL of tetraethoxysilane into the solution, dropwise adding 1mol/L ammonia water (pH=9) while vigorously stirring, heating to 80 ℃ for continuous reaction for 12 hours, obtaining a precipitate after the reaction is finished, washing and drying the precipitate, and roasting under nitrogen atmosphere to obtain a catalyst, namely Co@CN@SiO 2 。
Example 4
S1, mixing copper acetate monohydrate, cobalt nitrate hexahydrate and phenanthroline according to the molar ratio of 0.1:0.9:2, dissolving the mixture in water, adjusting the pH value to 9, performing hydrothermal treatment at 100 ℃, and evaporating the obtained mixture to dryness to obtain solid powder;
s2, dispersing 1g of the solid powder in 20mL of ethanol, ultrasonically oscillating, adding 0.1g of sodium oleate and 0.1g of cetyltrimethylammonium bromide while stirring, then dropwise adding 8mL of tetraethoxysilane into the solution, dropwise adding 1mol/L ammonia water (pH=10) while vigorously stirring, heating to 80 ℃ for continuous reaction for 12 hours, obtaining a precipitate after the reaction, washing and drying the precipitate, and roasting in a nitrogen atmosphere to obtain the catalyst, namely Cu 1 Co 9 @CN@SiO 2 。
Example 5
S1, mixing copper chloride dihydrate, cobalt nitrate hexahydrate and porphyrin according to the molar ratio of 0.8:0.2:1.5, dissolving in water, adjusting the pH value to 10, performing hydrothermal treatment at 180 ℃, and evaporating the obtained mixture to dryness to obtain solid powder;
s2, dispersing 1g of the solid powder in 20mL of ethanol, carrying out ultrasonic oscillation, adding 0.3g of potassium laurate while stirring, then dropwise adding 8mL of tetraethoxysilane into the solution, dropwise adding 1mol/L ammonia water (pH=10) while vigorously stirring, heating to 80 ℃ for continuous reaction for 12 hours, obtaining a precipitate after the reaction is finished, washing and drying the precipitate, and roasting the precipitate in a nitrogen atmosphere to obtain the catalyst, namely Cu 8 Co 2 @CN@SiO 2 。
Comparative example 1
The catalyst is prepared by adopting a traditional mixing and dipping method: dissolving 4.5g of copper nitrate trihydrate and 4g of 2-methylimidazole in 50mL of water, uniformly mixing, adding 3g of silicon dioxide powder, soaking for 12 hours, carrying out suction filtration, washing to obtain solid powder, and roasting in a nitrogen atmosphere to obtain a catalyst, namely Cu/CN/SiO 2 。
Comparative example 2
The catalyst is prepared by adopting a traditional mixing and dipping method: dissolving 2.4g of copper nitrate trihydrate, 2.9g of cobalt nitrate hexahydrate and 5g of phenanthroline in 100mL of water, uniformly mixing, adding 5g of silicon dioxide powder, soaking for 12 hours, carrying out suction filtration, washing to obtain solid powder, and roasting in a nitrogen atmosphere to obtain a catalyst, namely CuCo/CN/SiO 2 。
The catalysts prepared in examples 1-5 and comparative examples 1-2 were used to conduct experiments for preparing low-carbon alcohols by hydrogenation of carbon dioxide, and the specific method is as follows: CO in a molar ratio of 1:3 2 Feeding the catalyst and hydrogen into a fixed bed reactor through a mixer, filling the catalyst prepared in the examples and comparative examples in the reactor, controlling the reaction temperature to 260 ℃, the pressure to 3.0Mpa and the reaction space velocity to 10000h -1 The corresponding conversion and product distribution are shown in Table 1:
TABLE 1
Figure 735623DEST_PATH_IMAGE002
As can be seen from Table 1, the present invention was used as compared with the conventional catalyst prepared by the mixing and impregnating methodWhen the three-layer core-shell structure catalyst is prepared by the preparation method provided by Ming, the catalytic activity and the low-carbon alcohol (C 2 ~C 4 ) The selectivity is greatly improved, and the catalyst deactivation rate is greatly reduced. The catalyst prepared by the method of the invention catalyzes CO 2 The conversion rate of hydrogenation can reach approximately 30 percent, and meanwhile, C 2~ C 4 The selectivity of the alcohol is obviously improved and can reach 42.5% at most, and the catalyst composed of different metals and core-shell structures has a regulating and controlling effect on the distribution of low-carbon alcohol products.
The invention provides a three-layer core-shell structure based on metal, nitrogen doped porous carbon and silicon dioxide, thereby establishing a nano reactor for preparing low-carbon alcohol by hydrogenating carbon dioxide with adjustable structure and performance. The catalyst of the invention can solve the problem of low selectivity of low-carbon alcohol in the prior art, and catalyze CO 2 The hydrogenation can directly obtain alcohol fuels with high added value such as ethanol and propanol, the distribution of alcohol products can be adjusted through the regulation and control of catalyst composition, the catalyst is an effective catalyst for preparing methanol by hydrogenating carbon oxides such as carbon dioxide, the cost is low, the preparation method is relatively simple, and the catalyst has good industrial application prospect.
The foregoing is merely a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiments, but all technical solutions falling under the concept of the present invention fall within the scope of the present invention, and it should be noted that, for those skilled in the art, several modifications and adaptations without departing from the principles of the present invention should and are intended to be regarded as the scope of the present invention.

Claims (4)

1. The application of the catalyst in preparing low-carbon alcohol by converting carbon dioxide is characterized in that the catalyst has a three-layer core-shell structure; in the core-shell structure, the core is Cu and/or Co metal nano particles, and the weight of the core is 40-80% of that of the catalyst; the middle layer is nitrogen doped porous carbon and accounts for 1-10% of the weight of the catalyst; the outermost layer is silicon dioxide, and accounts for 10-59% of the weight of the catalyst; the preparation method comprises the following steps:
s1, mixing soluble metal salt and an organic ligand, and dissolving the mixture in water, wherein the organic ligand is a nitrogen-containing heterocyclic compound; wherein the molar ratio of the total metal ions to the organic ligand is 1 (0.5-3), the mixed solution is subjected to pH adjustment and then is subjected to hydro-thermal treatment, and then the solution is subjected to suction filtration or solvent evaporation to obtain solid powder; the soluble metal salt is Cu and/or Co salt;
s2, dispersing the solid powder prepared in the step S1 in ethanol, carrying out ultrasonic oscillation, adding a certain amount of template agent while stirring, then dropwise adding a certain amount of tetraethoxysilane, slowly adding a certain amount of alkali liquor, carrying out heating reaction, obtaining a precipitate after the reaction is finished, washing and drying the precipitate, and roasting in an inert gas atmosphere to obtain the catalyst.
2. Use of the catalyst according to claim 1 for the preparation of lower alcohols by carbon dioxide conversion, wherein in S1 the soluble metal salt is one or more of the nitrate, sulfate, acetate, chloride of Cu and/or Co.
3. The use of the catalyst according to claim 1 in preparing lower alcohols by carbon dioxide conversion, wherein in S2, the template agent is one or more of cetyltrimethylammonium bromide, polyvinylpyrrolidone, polyvinyl alcohol, oleate or laurate.
4. The use of the catalyst according to claim 1 for preparing low-carbon alcohol by carbon dioxide conversion, wherein in S1, the pH is adjusted to 9-10 and the hydrothermal temperature is 100-180 ℃.
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