CN113797955A - Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation method thereof - Google Patents

Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation method thereof Download PDF

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CN113797955A
CN113797955A CN202111242122.8A CN202111242122A CN113797955A CN 113797955 A CN113797955 A CN 113797955A CN 202111242122 A CN202111242122 A CN 202111242122A CN 113797955 A CN113797955 A CN 113797955A
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catalyst
mixed solution
carbon dioxide
carbon
organic amine
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CN113797955B (en
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王琪
肖平
徐越
吴桐
程阿超
秦晔
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Huaneng Clean Energy Research Institute
Huaneng Power International Inc
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Huaneng Power International Inc
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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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds
    • 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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Abstract

The invention belongs to the technical field of carbon dioxide recycling, and particularly relates to a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and a preparation method thereof. The raw materials of the catalyst comprise iron salt, magnesium salt, organic amine and ammonium bicarbonate, and the catalyst can adapt to a wider raw material carbon-hydrogen ratio and has higher catalytic activity and selectivity. The catalyst has high iron content, organic amine and ammonium bicarbonate are used as raw materials of the catalyst, controllability of a precipitation process is guaranteed, atomic-level dispersion of iron and magnesium is guaranteed, appropriate active sites are generated, appropriate interlayer ions and molecules are inserted, the size of the interlayer distance is adjusted, and other metal impurity ions cannot be introduced.

Description

Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation method thereof
Technical Field
The invention belongs to the technical field of carbon dioxide recycling, and particularly relates to a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and a preparation method thereof.
Background
Carbon dioxide has attracted more and more attention to climate change. Carbon dioxide is a greenhouse gas, but is also an important carbon source, and the utilization and the conversion of carbon dioxide into fuels and materials are important ways for realizing sustainable development. Hydrogen obtained by utilizing renewable energy sources and carbon dioxide are subjected to hydrogenation reaction, so that various valuable chemicals such as carbon monoxide, methane, low-carbon olefin, gasoline, aromatic hydrocarbon and the like can be obtained. Among them, low-carbon olefins are one of the most basic raw materials in the chemical industry.
The traditional synthesis process of the low-carbon olefin usually takes petroleum, coal or natural gas as raw materials, the carbon dioxide discharged in the process is more, if the carbon dioxide is taken as the raw material and hydrogen obtained by renewable energy is used for hydrogenation reaction, the carbon dioxide is not discharged, various chemical products can be produced, and the process is an important technical route for realizing the aim of carbon neutralization. The core of the successful technical route lies in developing a catalyst for preparing low-carbon olefin by directly hydrogenating high-performance carbon dioxide.
In the prior art, there are various methods for preparing low-carbon olefin catalysts, for example, chinese patent document CN106423263A discloses a catalyst for preparing low-carbon olefin by direct hydrogenation of carbon dioxide, which is formed by mixing two parts of metal oxide and molecular sieve, wherein the metal oxide is ZnO and ZrO2And a carrier, wherein the molecular sieve is SAPO-34, H-ZSM-5 or HY. For another example, chinese patent document CN108620089A discloses an iron-based catalyst with manganese modified surface for preparing low-carbon olefin by carbon dioxide hydrogenation, which comprises magnetic Fe hydrothermally synthesized3O4Nanospheres of Fe3O4Ultrasonic pretreatment of the surface of the nanosphere by adoptingImpregnation of pretreated Fe3O4Manganese additives with different contents are loaded on the surfaces of the nanospheres. For another example, chinese patent document CN104624194A discloses a catalyst for preparing low-carbon olefins by carbon dioxide hydrogenation, the constituent elements of the catalyst are iron, zirconium, potassium and oxygen, and the preparation method of the catalyst comprises the steps of preparing an iron source and a zirconium source aqueous solution, and then carrying out the processes of precipitation, microwave induction, washing, drying, roasting, potassium source impregnation, tabletting, granulation, hydrogen reduction and the like.
However, the prior art still has some technical problems to be solved, (1) the low carbon selectivity is low, and a large amount of alkane and long-chain olefin exist in the product; (2) the catalyst activity is not high, and a large amount of circulation is needed in the reaction, so that the energy consumption is high; (3) the renewable energy has the characteristic of fluctuation, the hydrogen production amount of the electrolytic hydrogen production is unstable, the hydrogen-carbon ratio in the raw material has a large variation range, and the problems of poor product selectivity, carbon deposition inactivation and the like are caused. In the prior art, a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, which can tolerate the fluctuation of a large range of hydrogen-carbon ratio and has high conversion rate and high selectivity, is still lacked.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the low-carbon olefin catalyst in the prior art is not resistant to the influence of the fluctuation range of the hydrogen-carbon ratio, the activity and the selectivity of the low-carbon olefin catalyst are poor and the like, thereby providing the catalyst for preparing the low-carbon olefin by carbon dioxide hydrogenation and the preparation method thereof.
Therefore, the invention provides the following technical scheme.
The invention provides a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, which comprises iron salt, magnesium salt, organic amine and ammonium bicarbonate.
The molar ratio of the organic amine to the ammonium bicarbonate is (1-100): (1-100);
the organic amine is diethylamine, triethylamine or tetraethylammonium hydroxide.
The iron salt comprises ferrous salt and ferric salt;
the ratio of the total molar amount of ferrous iron ions and magnesium ions to the molar amount of ferric iron ions is (1.5-5): 1;
the ratio of the total molar amount of ferrous ions and ferric ions to the molar amount of magnesium ions is (1-3): 1.
in the catalyst, 3Fe3+、2Fe2+And 2Mg2+The ratio of the total molar weight of the organic amine to the total molar weight of the organic amine is (0.1-1) to (0.1-10); wherein, 3Fe3+Means 3 times of molar weight of ferric ions, 2Fe2+2Mg which is 2 times of the molar weight of ferrous ions2+Means 2 times the molar amount of magnesium ions.
The invention also provides a preparation method of the catalyst for preparing the low-carbon olefin by carbon dioxide hydrogenation, which comprises the following steps,
(1) forming a mixed solution A by using iron salt and magnesium salt; organic amine and ammonium bicarbonate form a mixed solution B; mixing the mixed solution A and the mixed solution B to obtain a mixture C;
(2) crystallizing and roasting the mixture C to obtain a catalyst;
in the step (2), the roasting atmosphere comprises O2And H2O。
O in the atmosphere of the calcination2The volume fraction of (A) is 0.001-2%;
h in the roasting atmosphere2The volume fraction of O is 0.001-5%.
The firing atmosphere also includes inert atmospheres such as nitrogen, argon, and the like.
The mixed solution A and the mixed solution B are mixed at 60-90 ℃ under the atmosphere of carbon dioxide.
The specific steps of mixing the mixed solution A and the mixed solution B comprise the steps of firstly adding part of the mixed solution B into water, dropwise adding the mixed solution A and the rest of the mixed solution B into the water under the atmosphere of carbon dioxide, and obtaining a mixture C after the dropwise adding is finished; wherein, the amount of the part of the mixed solution B added in advance in water is not specifically limited, and when the mixture C is prepared, the 3Fe in the mixed solution A and the mixed solution B is only required3+、2Fe2+And 2Mg2+The ratio of the total molar quantity of the organic amine to the total molar quantity of the organic amine is (0.1-1) to (0.1-10).
The crystallization temperature is 80-180 ℃, and the crystallization time is 2-96 h.
The roasting temperature is 500-950 ℃, and the roasting time is 0.1-20 h.
The iron salt can be, but is not limited to, iron salt hydrochloride, iron nitrate, iron sulfate, and the like; the magnesium salt may be, but is not limited to, magnesium hydrochloride, magnesium nitrate, magnesium sulfate, and the like.
The low-carbon olefin refers to an olefin product with the carbon number of 2-4.
The technical scheme of the invention has the following advantages:
1. the catalyst for preparing the low-carbon olefin by the carbon dioxide hydrogenation comprises the raw materials of iron salt, magnesium salt, organic amine and ammonium bicarbonate, can adapt to a wider raw material carbon-hydrogen ratio, and simultaneously has higher catalytic activity and selectivity. The catalyst has high iron content, organic amine and ammonium bicarbonate are used as raw materials of the catalyst, controllability of a precipitation process is guaranteed, atomic-level dispersion of iron and magnesium is guaranteed, appropriate active sites are generated, appropriate interlayer ions and molecules are inserted, the size of the interlayer distance is adjusted, and other metal impurity ions cannot be introduced. Organic amine is used as a raw material of the catalyst, and the catalyst is carbonized and nitrided to generate active sites in the activation process, so that the adsorption of carbon dioxide and hydrogen is enhanced. Furthermore, water is generated in the catalytic reaction process, and reversible surface hydroxylation is generated in the ordered lamellar structure of the catalyst under the action of the water, so that the catalyst can adapt to a wider raw material hydrogen-carbon ratio, and the catalytic activity and selectivity of the catalyst are improved.
2. The catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation provided by the invention can utilize the buffering action of ion pairs to stabilize the microenvironment in the precipitation process by controlling the molar ratio of organic amine to ammonium bicarbonate, so that iron and magnesium in the catalyst can be dispersed at the atomic level, and a high-activity and high-selectivity catalytic crystal face structure surface can be controllably formed.
The diethylamine, triethylamine and tetraethyl ammonium hydroxide are common organic amines, the source is wide, the price is low, the unique space structure can effectively regulate and control the lamellar structure of the catalyst precursor, and the activity and the selectivity of the catalyst are improved.
By regulating and controlling the molar ratio of ferrous ions, ferric ions and magnesium ions, the iron content in the catalyst can be improved, so that the catalyst forms a catalyst precursor with an ordered lamellar structure, and the selectivity of the catalyst is improved.
3. The invention provides a preparation method of a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, which comprises the following steps of (1) forming a mixed solution A by iron salt and magnesium salt; organic amine and ammonium bicarbonate form a mixed solution B; mixing the mixed solution A and the mixed solution B to obtain a mixture C; (2) crystallizing and roasting the mixture C to obtain a catalyst; in the step (2), the roasting atmosphere comprises O2And H2And O. The precursor of the catalyst prepared by the method has an ordered lamellar structure, and the obtained catalyst can perform reversible surface hydroxylation reaction under the action of water, can adapt to a wider raw material hydrogen-carbon ratio, and simultaneously has higher catalytic activity and selectivity.
Organic amine and ammonium bicarbonate are added during preparation of the catalyst, so that controllability of a precipitation process can be guaranteed, atomic-level dispersion of iron and magnesium is guaranteed, a proper active site is generated, proper interlayer ions and molecules are inserted, the interlayer spacing of a hydrotalcite-like structure is adjusted, other metal impurity ions cannot be introduced, the organic amine is carbonized and nitrided in an activation process of the catalyst to generate the active site, adsorption of carbon dioxide and hydrogen is enhanced, and selectivity and activity of the catalyst are improved.
The activation process of the catalyst can be effectively controlled by controlling the atmosphere in the roasting process, high-efficiency active sites are generated by carbonization and nitridation, the electron transfer in the oxidation-reduction process of the catalyst is promoted, the generation of byproducts is inhibited, and the selectivity is improved;
in the mixing process of the mixed solution A and the mixed solution B, the atomic-level dispersion of iron and magnesium can be realized, and the crystal face orientation of the catalyst can be controlled.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
In some embodiments of the present invention, the raw material of the catalyst for preparing low carbon olefin by carbon dioxide hydrogenation comprises iron salt, magnesium salt, organic amine and ammonium bicarbonate, wherein the molar ratio of the organic amine to the ammonium bicarbonate is (1-100): (1-100), in other specific embodiments, the molar ratio of organic amine to ammonium bicarbonate can be any of the above ratios, or (20-80): (30-70), and can be (50-60): (40-60), for example, the molar ratio of organic amine to ammonium bicarbonate can be 5:95, 25:75, 45:65, 55:48, 86:23, etc., which is not limited by the present invention.
Example 1
This example provides a catalyst for preparing low carbon olefin by carbon dioxide hydrogenation, the raw material of which comprises Fe (NO)3)3、FeSO4、Mg(NO3)2Triethylamine and ammonium bicarbonate.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
(1) taking Fe (NO)3)3、FeSO4、Mg(NO3)2Adding water to prepare Fe3+、Fe2And Mg2+The mixed solution A with the molar concentrations of 0.08mol/L, 0.02mol/L and 0.1mol/L is reserved;
mixing triethylamine, ammonium bicarbonate and water to prepare a mixed solution B, wherein the molar concentrations of the triethylamine and the ammonium bicarbonate in the mixed solution B are respectively 0.1mol/L and 0.1mol/L for later use;
adding 50mL of mixed solution B into 200mL of deionized water, and dropwise adding the mixed solution A and the mixed solution B at the same time at the dropping speed of 1mL/min and 5.5mL/min in the atmosphere of carbon dioxide at 60 ℃ until 100mL of mixed solution A and 550mL of mixed solution B are added to obtain a mixture C;
(2) and transferring the mixture C into a hydrothermal kettle, crystallizing at 100 ℃ for 12h, filtering to obtain a solid-phase product, washing, filtering under a nitrogen protective gas, drying to obtain an intermediate product, placing the intermediate product in a mixed atmosphere of oxygen, water and nitrogen, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting for 20h, and cooling to obtain the catalyst. Wherein the volume fraction of oxygen in the mixed atmosphere formed by oxygen, water and nitrogen is 0.001%, and the volume fraction of water vapor is 5%.
Example 2
This example provides a catalyst for preparing low carbon olefin by carbon dioxide hydrogenation, the raw material of which comprises FeCl3、FeCl2、MgCl2Diethylamine, and ammonium bicarbonate.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
(1) taking FeCl3、FeCl2、MgCl2Adding water to prepare Fe3+、Fe2And Mg2+The mixed solution A with the molar concentrations of 0.1mol/L, 0.35mol/L and 0.15mol/L is reserved;
mixing diethylamine, ammonium bicarbonate and water to prepare a mixed solution B, wherein the molar concentrations of diethylamine and ammonium bicarbonate in the mixed solution B are respectively 1mol/L and 0.01mol/L for standby;
adding 20mL of mixed solution B into 200mL of deionized water, and dropwise adding the mixed solution A and the mixed solution B at the same time at the dropping speeds of 3mL/min and 4mL/min at 90 ℃ under the atmosphere of carbon dioxide until 150mL of mixed solution A and 200mL of mixed solution B are added to obtain a mixture C;
(2) and transferring the mixture C into a hydrothermal kettle, crystallizing at 180 ℃ for 12h, filtering to obtain a solid-phase product, washing, filtering under an argon protective gas, drying to obtain an intermediate product, placing the intermediate product in a mixed atmosphere of oxygen, water and nitrogen, heating to 900 ℃ at a heating rate of 0.5 ℃/min, roasting for 0.5h, and cooling to obtain the catalyst. Wherein the volume fraction of oxygen in the mixed atmosphere formed by oxygen, water and nitrogen is 2%, and the volume fraction of water vapor is 0.001%.
Example 3
This example provides a catalyst for preparing low carbon olefin by carbon dioxide hydrogenation, the raw material of which comprises Fe2(SO4)3、FeSO4、MgSO4Tetraethylammonium hydroxide and ammonium bicarbonate.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
(1) taking Fe2(SO4)3、FeSO4、MgSO4Adding water to prepare Fe3+、Fe2And Mg2+Mixed solution A with the molar concentrations of 0.003mol/L, 0.005mol/L and 0.004mol/L respectively for later use;
mixing tetraethyl ammonium hydroxide solution, ammonium bicarbonate and water to prepare mixed solution B, wherein the molar concentrations of the tetraethyl ammonium hydroxide solution and the ammonium bicarbonate in the mixed solution B are 0.01mol/L and 1mol/L respectively for later use;
adding 50mL of mixed solution B into 200mL of deionized water, and dropwise adding the mixed solution A and the mixed solution B at the same time at the temperature of 60 ℃ and in the atmosphere of carbon dioxide, wherein the dropwise adding speed is 0.5mL/min and 1.5mL/min respectively until 100mL of mixed solution A and 300mL of mixed solution B are added to obtain a mixture C;
(2) and transferring the mixture C into a hydrothermal kettle, crystallizing at 80 ℃ for 96h, filtering to obtain a solid-phase product, washing, filtering under a helium protective gas, drying to obtain an intermediate product, placing the intermediate product in a mixed atmosphere of oxygen, water and nitrogen, heating to 660 ℃ at a heating rate of 1 ℃/min, roasting for 24h, and cooling to obtain the catalyst. Wherein the volume fraction of oxygen in the mixed atmosphere formed by oxygen, water and nitrogen is 1%, and the volume fraction of water vapor is 2%.
Comparative example 1
Comparison of booksThe catalyst for preparing low carbon olefin by carbon dioxide hydrogenation is provided, and the raw material of the catalyst comprises Fe (NO)3)3、FeSO4、Mg(NO3)2Sodium hydroxide and ammonium bicarbonate.
The amount and preparation method of the raw materials in the catalyst are the same as those in example 1, and the amount of sodium hydroxide is the same as that of triethylamine.
Comparative example 2
The comparative example provides a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, and the raw material of the catalyst comprises Fe (NO)3)3、FeSO4、Mg(NO3)2Triethylamine and sodium carbonate.
The amount and preparation method of the raw materials in the catalyst are the same as those in example 1, and the amount of sodium carbonate is the same as that of ammonium bicarbonate.
Comparative example 3
The comparative example provides a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, and the raw material of the catalyst comprises Fe (NO)3)3、FeSO4、Mg(NO3)2Triethylamine and ammonium bicarbonate.
The preparation method of the catalyst comprises the following steps:
(1) taking Fe (NO)3)3、FeSO4、Mg(NO3)2Adding water to prepare Fe3+、Fe2And Mg2+The mixed solution A with the molar concentrations of 0.08mol/L, 0.02mol/L and 0.1mol/L is reserved;
mixing triethylamine, ammonium bicarbonate and water to prepare a mixed solution B, wherein the molar concentrations of the triethylamine and the ammonium bicarbonate in the mixed solution B are respectively 0.1mol/L and 0.1mol/L for later use;
adding 50mL of mixed solution B into 200mL of deionized water, and dropwise adding the mixed solution A and the mixed solution B at the same time at the dropping speed of 1mL/min and 5.5mL/min in the atmosphere of carbon dioxide at 60 ℃ until 100mL of mixed solution A and 550mL of mixed solution B are added to obtain a mixture C;
(2) and transferring the mixture C into a hydrothermal kettle, crystallizing at 100 ℃ for 12h, filtering to obtain a solid-phase product, washing, filtering under a nitrogen protective gas, drying to obtain an intermediate product, placing the intermediate product in a pure nitrogen atmosphere, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting for 20h, and cooling to obtain the catalyst.
Test examples
The test example provides performance tests and test results of the catalysts prepared in each example and comparative example.
1mL of each catalyst prepared in examples and comparative examples was charged into a fixed bed reactor, and the reaction was carried out at 350 ℃ and 5MPa in the presence of CO2The flow rate is 3000mL h-1The reaction evaluation was performed under the conditions of (1) to simulate a wide variation in hydrogen-carbon ratio, hydrogen gas was introduced at different flow rates at 1 hour, 2 hours, and 3 hours, the hydrogen-carbon ratio (molar ratio of hydrogen gas to carbon dioxide) was 3, 0.2, and 6, respectively, the product composition was detected by gas chromatography, and the space-time yield and the selectivity to low-carbon olefins (ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene, and isobutylene) were calculated.
TABLE 1 Performance test results of catalysts of examples and comparative examples
Figure BDA0003319886380000101
Through the test results of comparative example 1 and comparative example 2 described in table 1, it can be illustrated that the catalyst for preparing low carbon olefin by hydrogenation of carbon dioxide of the present invention uses organic amine and ammonium bicarbonate as raw materials, so that the catalyst can adapt to a wider raw material hydrogen-carbon ratio, and the selectivity and activity of the catalyst can be improved.
Through the test result of the comparative example 3, the invention can obviously improve the selectivity and the activity of the catalyst and adapt to a wider hydrogen-carbon ratio under a specific roasting atmosphere when preparing the catalyst.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. The catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation comprises raw materials of iron salt and magnesium salt, and is characterized by also comprising organic amine and ammonium bicarbonate.
2. The catalyst of claim 1, wherein the molar ratio of the organic amine to the ammonium bicarbonate is (1-100): (1-100);
the organic amine is diethylamine, triethylamine or tetraethylammonium hydroxide.
3. The catalyst of claim 1 or 2, wherein the iron salts comprise ferrous and ferric salts;
the ratio of the total molar amount of ferrous iron ions and magnesium ions to the molar amount of ferric iron ions is (1.5-5): 1;
the ratio of the total molar amount of ferrous ions and ferric ions to the molar amount of magnesium ions is (1-3): 1.
4. the catalyst of claim 3, wherein 3Fe3+、2Fe2+And 2Mg2+The ratio of the total molar quantity of the organic amine to the molar quantity of the organic amine is (0.1-1) to (0.1-10).
5. A preparation method of a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation is characterized by comprising the following steps,
(1) forming a mixed solution A by using iron salt and magnesium salt; organic amine and ammonium bicarbonate form a mixed solution B; mixing the mixed solution A and the mixed solution B to obtain a mixture C;
(2) crystallizing and roasting the mixture C to obtain a catalyst;
in the step (2), the roasting atmosphere comprises O2And H2O。
6. According to the claimsThe method according to claim 5, wherein O is present in the atmosphere of the calcination2The volume fraction of (A) is 0.001-2%;
h in the roasting atmosphere2The volume fraction of O is 0.001-5%.
7. The production method according to claim 5 or 6, wherein the mixed solution A and the mixed solution B are mixed at 60 to 90 ℃ under an atmosphere of carbon dioxide.
8. The method according to any one of claims 5 to 7, wherein the mixing of the mixed solution A and the mixed solution B comprises the steps of adding a part of the mixed solution B to water, and adding the mixed solution A and the rest of the mixed solution B dropwise to the water under the atmosphere of carbon dioxide to obtain a mixture C after the completion of the dropwise addition.
9. The method according to any one of claims 5 to 8, wherein the crystallization temperature is 80 to 180 ℃ and the crystallization time is 2 to 96 hours.
10. The method as claimed in any one of claims 5 to 9, wherein the calcination is carried out at a temperature of 500 ℃ and 950 ℃ for a time of 0.1 to 20 hours.
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