CN112973698A - CO (carbon monoxide)2Method for preparing high-carbon linear alpha-olefin by hydrogenation and application thereof - Google Patents

CO (carbon monoxide)2Method for preparing high-carbon linear alpha-olefin by hydrogenation and application thereof Download PDF

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CN112973698A
CN112973698A CN201911283694.3A CN201911283694A CN112973698A CN 112973698 A CN112973698 A CN 112973698A CN 201911283694 A CN201911283694 A CN 201911283694A CN 112973698 A CN112973698 A CN 112973698A
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potassium
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孙剑
方传艳
葛庆杰
韩誉
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Dalian Institute of Chemical Physics of CAS
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    • 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

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Abstract

The invention designs a CO2The invention relates to a method for preparing catalyst of high carbon linear alpha-olefin by hydrogenation and application thereof, wherein a hydrothermal synthesis method is adopted to prepare carbon-doped Fe catalyst, the main active component is Fe, one or more of alkali metal elements K, Mg, Ca and the like are used as electron auxiliary agent of Fe catalyst, and CO can be used as electron auxiliary agent of Fe catalyst2The linear alpha-olefin is produced by high-efficiency conversion, the introduction of the auxiliary agent enhances the carbon chain growth capacity, and the selectivity of the high-carbon linear alpha-olefin product is greatly improved. Provides a new idea for the high-efficiency conversion process of preparing high value-added chemicals by selective hydrogenation of carbon dioxide, and has good industrial application prospect.

Description

CO (carbon monoxide)2Method for preparing high-carbon linear alpha-olefin by hydrogenation and application thereof
Technical Field
The invention relates to the technical field of carbon dioxide conversion, in particular to the application field of preparing high-carbon linear alpha-olefin by carbon dioxide hydrogenation.
Background
The low-carbon olefin mainly refers to ethylene and propylene, and is a basic organic raw material for synthesizing various chemical products such as plastics, fibers and the like. The high-carbon olefins generally refer to olefins having a carbon number of 4 or more, and particularly alpha-olefins (alpha-olefins) which are most important for producing high value-added fine chemicals. alpha-olefins mean double bonds at the ends of the molecular chainMono-olefin of (R-CH ═ CH)2) Wherein R is alkyl. If R is a straight chain alkyl group, it is referred to as a straight chain linear a-olefin (LAO). A-olefins of industrial products, having a wide distribution of carbon number (C)4-C40). Has wide application range and is C4-C18The linear alpha-olefin can be widely used for producing lubricating oil, plasticizer and detergent. At present, both low carbon olefins and high carbon alpha-olefins are mainly prepared by petroleum routes. The major global production route for high-carbon alpha-olefins is currently the Shell (Shell) high-carbon olefin process route (SHOP process), which is obtained by oligomerizing ethylene using a Ni-based catalyst. The shortage of petroleum resources is becoming an important factor restricting the economic society, and the search for an economic alternative process route to solve the problem of olefin short supply and short demand caused by the rising demand of petroleum has become a problem of great concern in all countries of the world.
In addition, over the last one hundred years, the widespread use of petroleum, coal and natural gas has led to the rapid development of human society, with the consequent rise in atmospheric carbon dioxide concentration, which has led to a series of ecological environmental problems, such as ocean acidification and greenhouse effect, that are increasingly attracting widespread attention of the whole human society. CO22The catalytic hydrogenation for preparing the hydrocarbons such as methane, methanol, formic acid, olefin and the like has important significance for reducing the emission of carbon dioxide, and simultaneously realizes the CO2Conversion processes to high value added liquid fuels and chemicals.
In the carbon dioxide hydrogenation process, because the raw material molecules are stable and the adsorption and desorption rate on the surface of the catalyst is slow, the generation of long-chain hydrocarbon is very difficult, and common products are concentrated in low-molecular methane, methanol or C2-C4The lower hydrocarbon of (2). The production of hydrocarbons generally employs iron, cobalt, etc. as reaction catalysts. In contrast to Fe-based catalysts, Co-based catalysts are generally considered methanation catalysts. Generally, the activity, stability and selectivity of a pure iron-based catalyst are not ideal, and the requirement of large-scale industrial production is not met. Therefore, in the preparation process of the iron-based catalyst, corresponding auxiliary agents are generally required to be added to reasonably and selectively modulate each item of the catalystPerformance index. According to the existing literature reports, the electron type auxiliary agent such as K can provide electrons to the d orbital of iron to increase the electron density of the iron, and is beneficial to increasing CO2Adsorption of (2) reduces H2The adsorption of the catalyst can increase the selectivity of olefin, and basic metals such as Ca, Mg and the like can also increase CO2Is widely added to the catalytic preparation process; therefore, a small amount of electronic or structural auxiliary agents such as K, Mg, Ca and the like are added, the reaction activity of the iron-based catalyst can be obviously improved, the selectivity of products can be changed, and the low CH content can be achieved4Under the selective condition, high olefin selectivity is realized and the activity of the catalyst is improved. Iron-based catalysts reported in the prior literature are used for preparing alpha-olefin by CO2 hydrogenation, and the alpha-C4 + olefin selectivity is low, so that industrialization is difficult to realize. Therefore, how to obtain high-carbon linear alpha-olefin with high activity and high selectivity is a great challenge in the application field of preparing high-carbon alpha-olefin by using the iron-based catalyst at present.
Disclosure of Invention
The invention aims to provide a simple auxiliary agent introduction mode and a green synthetic route of an iron-based catalyst with various modification auxiliary agents coexisting, and meanwhile, the catalyst can realize high-selectivity catalytic hydrogenation of carbon dioxide to produce olefin, wherein alpha-olefin is used as a main product in olefin products above C4+, and the preparation method is simple, low in cost and easy for industrial application.
In order to solve the technical problems, the invention is realized by the following technical scheme:
CO (carbon monoxide)2The method for preparing the catalyst for preparing the high-carbon linear alpha-olefin by hydrogenation and the application thereof are characterized in that: the catalyst adopted by the method is formed by mixing carbon-supported ferrous oxalate and a K-containing substance, and the mass ratio of the carbon-supported ferrous oxalate to the K-containing substance is controlled to be 10: 0.1-10: 5 (preferably 10: 0.4-10: 0.8); the K-containing substance is a K-containing compound, or the K-containing compound is mixed with a Ca-containing compound, or the K-containing compound is mixed with the Ca-containing compound and a Mg-containing compound; the catalyst is prepared by mixing carbon-supported ferrous oxalate and a potassium-containing substance, wherein the mass ratio of the carbon-supported ferrous oxalate to the potassium-containing substance is controlled to be 10: 0.1-10: 5; the potassium-containing substance is potassium-containing compound, or potassium-containing compound and Ca-containing compound or Mg-containing compound or Ca and Mg compoundMixing to form;
further, the preparation process of the ferrous oxalate comprises the steps of dissolving sugar and ferric salt in deionized water by a one-step hydrothermal synthesis method, and stirring; transferring the obtained mixed solution into a reaction kettle; sealing the reaction kettle and transferring the reaction kettle to hydrothermal synthesis equipment; the mass ratio of the iron to the carbon element in the glucose is controlled to be 1: 0.5-1: 10, and the conditions of the hydrothermal synthesis process are 80-180 ℃ and 12-48 hours; and washing the obtained product with deionized water and absolute ethyl alcohol respectively, and drying to obtain the carbon-supported ferrous oxalate.
Further, the iron salt is ferric nitrate (Fe (NO3)3) Iron (Fe) sulfate2(SO4)3) Iron chloride (FeCl)3) One or more than two of them.
Further, the sugar may be one or more of glucose, sucrose, cellulose, and xylose.
Further, the potassium-containing compound is one or two of potassium carbonate, potassium chloride or potassium acetate; the Ca-containing compound is calcium carbonate, the Mg-containing compound is magnesium oxide or basic magnesium carbonate, and the mass ratio of the potassium-containing compound to the Ca-containing compound or the Mg-containing compound or the Ca-containing compound to the Mg-containing compound is (K: Ca is 2.5: 1-1: 1) and (Ca: Mg is 3: 1-1: 1).
Further, the mixing is mechanical mixing. The powders of potassium carbonate (or potassium chloride), calcium oxide (or calcium carbonate) and magnesium oxide (or basic magnesium carbonate) are mechanically mixed in proportion.
The catalyst is in CO2The application of the hydrogenation reaction for preparing high-carbon linear alpha-olefin comprises the following steps:
and (3) an activation process: the catalyst is loaded into a fixed bed reactor, and H2/Ar mixed gas with the molar ratio of 1-50% or H2/N with the molar ratio of 1-50% is adopted2Pretreating the mixed gas or pure hydrogen, wherein the pretreatment temperature is 350-.
The reaction process is as follows: after the activation process is finished, the temperature in the fixed bed reactor is reduced to 350 ℃, and the mixture of the two components in the molar ratio of 5: 1-2: 1H2：CO2The raw material gas is reacted under the reaction pressure of 0.5-3.0MPaThe required feeding space velocity is 1000h-1-20000h-1。
Further, the activation process: filling the catalyst into a fixed bed reactor, wherein the pretreatment temperature is 350-;
further, the reaction process is as follows: after the activation process is finished, the temperature in the fixed bed reactor is reduced to 320 ℃, and H2: CO2 with the molar ratio of 3:1 is introduced into the fixed bed reactor for reaction, wherein the reaction pressure is 1.0-1.5MPa, and the feeding space velocity of the reaction is 2000-4000H-1。
The composite oxide is prepared by mechanically mixing potassium carbonate (or potassium chloride), calcium oxide (or calcium carbonate) and magnesium oxide (or basic magnesium carbonate) in proportion to make K not less than 75% by weight of K, Ca and Mg.
Compared with the prior art, the invention has the following advantages:
1) high content of active iron carbide species is easily generated. The ferrous oxalate component can form a large amount of iron carbide in the reduction process of the catalyst under the synergistic action of one or more alkali metal assistants mainly comprising potassium, thereby greatly improving CO2The carbon chain coupling capacity in the hydrogenation process promotes the high-selectivity generation of high-carbon alpha-olefin;
2) the preparation process is simple and easy to operate. Preparing an iron-based carbon microsphere catalyst with uniform distribution and excellent performance in a mild one-step hydrothermal synthesis system;
3) the catalyst has various synergistic electronic assistants. One or more of electronic additives such as K, Ca, Mg and the like can coexist in the iron-based catalyst and play a role of a synergistic catalytic additive, so that the reaction activity is optimized, and the selectivity of a product is regulated.
Detailed Description
The invention will now be further described with reference to specific embodiments, without limiting the scope of the invention to the following examples.
Example 1
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.2g of Fe/C, 0.11g of potassium carbonate powder, 0.018g of magnesium oxide powder and 0.06g of calcium carbonate powder were mechanically mixed by grinding, the Fe content in the catalyst was 14%, and the catalyst obtained was designated as Fe/C-K-Ca-Mg.
Applying the prepared catalyst to CO2In the catalytic reaction of preparing olefin by hydrogenation conversion. The catalyst was first activated in situ for 10 hours at 400 ℃ under hydrogen. After reduction, the temperature was lowered to 320 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction results are shown in table 1.
Example 2
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.2g of Fe/C, 0.144g of potassium carbonate powder, 0.048g of magnesium oxide powder were mechanically mixed by milling, and the catalyst obtained was designated as Fe/C-K-Mg. The Fe content in the catalyst is 14%, and the prepared catalyst is marked as Fe/C-K-Mg.
Applying the prepared catalyst to CO2In the catalytic reaction of preparing olefin by hydrogenation conversion. The catalyst was first activated in situ for 5 hours at 450 ℃ under hydrogen. After reduction, the temperature was lowered to 320 ℃ for the catalytic reaction. Immobilization of catalytic reactions in flowIn a bed reactor, the raw material synthesis gas is prepared from CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction results show.
Example 3
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.2g of Fe/C, 0.144g of potassium carbonate powder, and 0.204g of calcium carbonate powder were mechanically mixed by grinding, and the catalyst obtained was designated as Fe/C-K-Ca-I. The Fe content in the catalyst is 14%, and the prepared catalyst is marked as Fe/C-K-Ca-I.
Applying the prepared catalyst to CO2In the catalytic reaction of preparing olefin by hydrogenation conversion. The catalyst was first activated in situ for 20 hours at 350 ℃ under hydrogen. After reduction, the temperature was lowered to 300 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction is shown in table 1.
Example 4
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.2g of Fe/C, 0.144g of potassium carbonate powder, 0.082The calcium carbonate powder was mechanically mixed by grinding and the catalyst obtained was noted as Fe/C-K-Ca-II. The Fe content in the catalyst is 14%, and the prepared catalyst is marked as Fe/C-K-Ca-II. Applying the prepared catalyst to CO2In the catalytic reaction of preparing olefin by hydrogenation conversion. The catalyst was first activated in situ for 20 hours at 350 ℃ under hydrogen. After reduction, the temperature was lowered to 300 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction is shown in table 1.
Example 5
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.2g of Fe/C, 0.144g of potassium carbonate powder, 0.11g of calcium carbonate powder were mechanically mixed by grinding, and the catalyst obtained was designated as Fe/C-K-Ca-III. The Fe content in the catalyst is 14%, and the prepared catalyst is marked as Fe/C-K-Ca-III. Applying the prepared catalyst to CO2In the catalytic reaction of preparing olefin by hydrogenation conversion. The catalyst was first activated in situ for 20 hours at 350 ℃ under hydrogen. After reduction, the temperature was lowered to 300 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction is shown in table 1.
Example 6
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.0g of Fe/C was mechanically mixed with 0.12g of potassium carbonate powder by grinding, the Fe content in the catalyst was 14%, and the catalyst obtained was designated as Fe/C-K-I.
The catalyst was first activated in situ for 15 hours at 450 ℃ under hydrogen. After reduction, the temperature was lowered to 350 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction results are shown in table 1.
Example 7
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.0g of Fe/C was mechanically mixed with 0.07g of potassium carbonate powder by grinding, the Fe content in the catalyst was 14%, and the catalyst obtained was designated as Fe/C-K-II.
The catalyst was first activated in situ for 15 hours at 450 ℃ under hydrogen. After reduction, the temperature was lowered to 350 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction results are shown in table 1.
Example 8
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.0g of Fe/C was mechanically mixed with 0.14g of potassium carbonate powder by grinding, the Fe content in the catalyst was 14%, and the catalyst obtained was designated as Fe/C-K-III.
The catalyst was first activated in situ for 15 hours at 450 ℃ under hydrogen. After reduction, the temperature was lowered to 350 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction results are shown in table 1.
Comparative example 1
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.0g of Fe/C was mechanically mixed with 0.03g of potassium carbonate powder by grinding, the Fe content in the catalyst was 14%, and the catalyst obtained was designated as Fe/C-K-IV.
The catalyst was first activated in situ for 15 hours at 450 ℃ under hydrogen. After reduction, the temperature was lowered to 350 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction results are shown in table 1.
Comparative example 2
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C. 1.0g of Fe/C was mechanically mixed with 0.18g of potassium carbonate powder by grinding, the Fe content in the catalyst was 14%, and the catalyst obtained was designated as Fe/C-K-V.
The catalyst was first activated in situ for 15 hours at 450 ℃ under hydrogen. After reduction, the temperature was lowered to 350 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. The W/F value is defined as the ratio of the weight of the catalyst to the flow rate and is controlled to 10 during the experiment. The catalytic reaction results are shown in table 1.
Comparative example 3
The preparation process of the iron catalyst is as follows:
10g of glucose and 12g of ferric nitrate nonahydrate were dissolved in 150mL of deionized water and vigorously stirred. The obtained mixed solution is transferred to a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining. The reaction kettle is sealed and transferred to hydrothermal synthesis equipment. The conditions of the hydrothermal synthesis process are controlled at 120 ℃ for 20 hours. The product distribution obtained was washed several times with deionized water and absolute ethanol. And finally, drying the product for more than 12 hours, and taking out the product to obtain the Fe/C.
Applying the prepared catalyst to CO2In the catalytic reaction of preparing olefin by hydrogenation conversion. The catalyst was first activated in situ for 10 hours at 400 ℃ under hydrogen. After reduction, the temperature was lowered to 320 ℃ for the catalytic reaction. The catalytic reaction is carried out in a flowing fixed bed reactor, and the proportion of the raw material synthetic gas is CO2/H23: 1. W/F value is defined as the ratio of catalyst weight to flow rate, experimentIs controlled at 10. The catalytic reaction results are shown in table 1.
TABLE 1
Figure BDA0002317441940000071
Figure BDA0002317441940000081
The above embodiments are merely exemplary embodiments of the present invention, which are not intended to limit the scope of the present invention, and various modifications and applications made by the above embodiments are within the scope of the present invention.

Claims (8)

1. A method for preparing high-carbon linear alpha-olefin by CO2 hydrogenation is characterized by comprising the following steps: the catalyst adopted by the method is formed by mixing carbon-supported ferrous oxalate and a K-containing substance, and the mass ratio of the carbon-supported ferrous oxalate to the K-containing substance is controlled to be 10: 0.1-10: 5(10: 0.4-10: 0.8); the K-containing substance is formed by mixing a K-containing compound, or mixing the K-containing compound and a Ca-containing compound, or mixing a potassium-containing compound and a Mg-containing compound, or mixing the K-containing compound, the Ca-containing compound and the Mg-containing compound.
2. The method of claim 1, wherein:
the preparation process of the ferrous oxalate comprises the steps of dissolving sugar and soluble ferric salt in deionized water by adopting a one-step hydrothermal synthesis method, and stirring; transferring the obtained mixed solution into a reaction kettle; sealing the reaction kettle and transferring the reaction kettle to hydrothermal synthesis equipment; the mass ratio of iron in the ferric salt to carbon in the sugar is controlled to be 1: 0.5-1: 10, and the conditions of the hydrothermal synthesis process are 80-180 ℃ and 12-48 hours; and washing the obtained product with deionized water and absolute ethyl alcohol respectively, and drying to obtain the carbon-supported ferrous oxalate.
3. The catalyst of claim 2, wherein:
the iron salt is one or more of ferric nitrate (Fe (NO3)3), ferric sulfate (Fe2(SO4)3) and ferric chloride (FeCl 3).
4. The catalyst of claim 2, wherein:
the sugar may be one or more of glucose, sucrose, cellulose and xylose.
5. The catalyst of claim 1, wherein:
the potassium-containing compound is one or two of potassium carbonate, potassium chloride or potassium acetate;
the Ca-containing compound is calcium carbonate, the Mg-containing compound is magnesium oxide or basic magnesium carbonate, and the mass ratio of the potassium-containing compound to the Ca-containing compound is (K: Ca is 2.5: 1-1: 1);
or the mass ratio of the potassium-containing compound to the Mg-containing compound is (K: Mg is 3:1 to 1: 1);
or the mass ratio of the potassium-containing compound to the Ca-containing and Mg-containing compounds is (K: Ca is 2.5:1 to 1:1) and (Ca: Mg is 3:1 to 1: 1).
6. The catalyst of claim 1, wherein: the mixing is mechanical mixing.
7. Use of a catalyst according to any one of claims 1 to 6 in the hydrogenation of CO2 to produce higher linear alpha olefins, comprising the steps of:
and (3) an activation process: loading a catalyst into a fixed bed reactor, and pretreating by adopting H2/Ar mixed gas with the molar ratio of 1-50% or H2/N2 mixed gas with the molar ratio of 1-50% or pure hydrogen, wherein the pretreatment temperature is 350-450 ℃, the pressure is 0-2MPa, and the activation time is 1-50H;
the reaction process is as follows: after the activation process is finished, the temperature in the fixed bed reactor is reduced to 350 ℃, and the mixture of the two components in the molar ratio of 5: 1-2: h2 of 1: the raw material gas of CO2 is reacted under the pressure of 0.5-3.0MPa and the space velocity of the reaction is 1000h-1-20000 h-1.
8. Use according to claim 7, characterized in that it comprises the following steps:
and (3) an activation process: filling the catalyst into a fixed bed reactor, wherein the pretreatment temperature is 350-;
the reaction process is as follows: after the activation process is finished, the temperature in the fixed bed reactor is reduced to 320 ℃, and H2: CO2 with the molar ratio of 3:1 is introduced into the fixed bed reactor for reaction, wherein the reaction pressure is 1.0-1.5MPa, and the feeding space velocity of the reaction is 2000-4000H-1.
CN201911283694.3A 2019-12-13 2019-12-13 CO (carbon monoxide)2Method for preparing high-carbon linear alpha-olefin by hydrogenation and application thereof Pending CN112973698A (en)

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