Catalyst for preparing olefin from synthesis gas as well as preparation method and application of catalyst

Abstract

The invention relates to a catalyst for preparing olefin from synthesis gas as well as a preparation method and application of the catalyst. The catalyst for preparing olefin from synthesis gas is prepared from a modified metal Fe component and nano-porous polyethylene benzene, on the basis of the mass of the catalyst, the molar ratio of the mass ratio of the modified metal Fe component to the nano-porous polyethylene benzene is 1: (0.1-1). The invention aims to solve the problem that the prepared catalyst shows extremely high CO conversion rate, olefin selectivity and space time yield and has the characteristics of low CO2 selectivity and low CH4 selectivity by selecting Fe, IIB or VIIB metal, IA metal and nano-porous polyethylene benzene in a specific proportion.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalytic material preparation and CO conversion, and particularly relates to a catalyst for preparing olefins from synthesis gas as well as a preparation method and application thereof. BACKGROUND

[0002] Olefins are an important class of chemicals containing carbon-carbon double bonds, which are widely used in the fields of chemical industry, energy, materials, etc. According to the number of carbon atoms, olefins can be divided into low-carbon olefins (C2-C4) and high-carbon olefins (C5 and above). C2-C4 low-carbon olefins are the basic raw materials for the synthesis of various chemical products such as plastics and fibers. The linear alpha olefins with double bonds at the end of C5 and above are mainly used in the synthesis of plasticizers, lubricating oils, detergents, etc. At present, olefins are mainly produced by processes such as steam cracking of naphtha to produce low-carbon olefins, ethylene oligomerization, or cracking of paraffin wax to produce alpha olefins.

[0003] Under the background of double carbon, the conversion of olefins from renewable / recyclable carbon resources such as biomass, CO2, and waste plastics through synthesis gas (CO / H2) is an ideal reaction route. The current research on the direct conversion of synthesis gas to olefins mainly focuses on the development of catalysts, with Fe or Co-based catalysts with high activity, high olefin selectivity, and low CH4 selectivity as the main catalysts, such as activated carbon-supported Fe catalysts, ultrafine particle Fe catalysts, and molecular sieve-supported catalysts. By modifying and regulating the Fe5C2 active phase formed on the Fe catalyst, such as adding ZnO, ZrO2 as a structural promoter, changing the catalyst size and activity, and using alkali metals as an electronic promoter to further adjust the catalyst structure and inhibit the hydrogenation ability, the activity and selectivity of Fe-based catalysts are adjusted. However, due to the complex reaction mechanism, the content of heavy hydrocarbons is high, the yield of low-carbon olefins is low, and the CH x The coupling of intermediate species and the effective inhibition of the secondary hydrogenation of product olefins to form byproduct alkanes. In addition, the selectivity of CO2 is high, especially for coal-based synthesis gas, the low H2 / CO ratio leads to a CO2 selectivity in the product often higher than 30%. There is prior art that discloses a Fe-based catalyst for the conversion of synthesis gas to olefins, using a biochar-clay-based composite carrier prepared by hydrothermal treatment coupled with metal ion pore expansion method, under the conditions of H2 / CO molar ratio of 1:1, temperature of 300℃, space velocity of 18000h-1, CO conversion rate of 81.2%, CO2 selectivity of 15.3%, CH4 selectivity of 14.2%, and olefin selectivity of 77.5%. -1 2+ ＝ Olefins are an important class of chemicals containing carbon-carbon double bonds, which are widely used in the fields of chemical industry, energy, materials, etc. According to the number of carbon atoms, olefins can be divided into low-carbon olefins (C2-C4) and high-carbon olefins (C5 and above). C2-C4 low-carbon olefins are the basic raw materials for the synthesis of various chemical products such as plastics and fibers. The linear alpha olefins with double bonds at the end of C5 and above are mainly used in the synthesis of plasticizers, lubricating oils, detergents, etc. At present, olefins are mainly produced by processes such as steam cracking of naphtha to produce low-carbon olefins, ethylene oligomerization, or cracking of paraffin wax to produce alpha olefins.​-1 Under the condition, the CO conversion rate is 65.8%, the CO2 selectivity is 11.8%, the C 2+ ＝ The olefin selectivity is 32.5%.

[0004] In summary, the selectivity of olefin hydrocarbon products is usually not higher than 80% in the Fischer-Tropsch synthesis reaction on the modified metal catalyst due to the side reactions of CO hydrogenation to alkanes and hydrogen transfer reaction to generate alkanes, in addition, the Fischer-Tropsch reaction generates a higher CO2. In addition, harsh conditions such as high pressure and low space velocity can lead to more carbon deposition and even catalyst deactivation. SUMMARY

[0005] Therefore, the main purpose of the present application is to provide a catalyst for preparing olefins from synthesis gas and a preparation method and application thereof, and the problem to be solved is that by selecting a specific ratio of a hot melting method, high-temperature liquid phase mixing and structure regulation, a high-dispersion modified metal Fe component PDVB can be prepared, and the preparation of the catalyst by polymerization reaction combined with pore regulator regulation of pore structure makes the prepared catalyst show extremely high CO conversion rate, olefin selectivity, space-time yield, and has the characteristics of low CO2 selectivity and low CH4 selectivity.

[0006] The purpose of the present application and the technical problems solved thereby are achieved by adopting the following technical solutions. The present application provides a catalyst for preparing olefins from synthesis gas, which is composed of a modified metal Fe component and a nano-porous polyvinylbenzene; the mass ratio of the modified metal Fe component and the nano-porous polyvinylbenzene is 1:0.1-1 based on the mass of the catalyst.

[0007] The purpose of the present application and the technical problems solved thereby can be further achieved by adopting the following technical measures.

[0008] Preferably, the aforementioned catalyst for preparing olefins from synthesis gas, wherein the particle size of the modified metal Fe component is 5-50 nm.

[0009] Preferably, the aforementioned catalyst for preparing olefins from synthesis gas, wherein the particle size of the nano-porous polyvinylbenzene is 10-400 nm.

[0010] Preferably, the aforementioned catalyst for preparing olefins from synthesis gas, wherein the modified metal Fe component is composed of Fe, IIB or VIIB metal and IA metal, wherein the IIB metal comprises at least one of Zn and Cd, the VIIB metal comprises at least one of Mn and Tc, and the IA metal comprises at least one of Li, Na, K and Rb; the molar ratio of the Fe, IIB or VIIB metal, IA metal is 1:0.2-0.8:0.01-0.05 based on the molar amount of metal.

[0011] The object and solution to the technical problem of the present application are realized by the following technical scheme. The present application provides a preparation method of a catalyst for preparing olefins from synthesis gas, comprising the following steps:

[0012] S1 first pretreat Fe oxide, IIB or VIIB oxide and IA carbonate, and calcine the oxide and the carbonate at high temperature;

[0013] S2 mix the raw materials pretreated in step S1 according to the molar ratio, grind to obtain a mixed powder; heat the obtained mixed powder to a melting temperature of 700-1100℃ under the protection of an inert atmosphere, and keep for 1-3h; grind the block body after slow cooling to pass a 100-120 mesh sieve to obtain a modified metal Fe component;

[0014] S3 mix styrene, divinylbenzene and a pore-expanding agent according to the ratio, wherein the pore-expanding agent is at least one of toluene and cyclohexane; add an initiator, and ultrasonic disperse for 10-30min; dissolve the ultrasonic-treated product in deionized water, stir uniformly, then add polyvinyl alcohol to obtain an aqueous solution, heat to 60-70℃, and stir for 1-3h; perform hydrothermal treatment on the obtained stirring solution, and perform suction filtration and washing for 1-3 times to obtain a filter cake; dry and crush the obtained filter cake to 100-120 mesh to obtain a nano-porous polyvinylbenzene powder;

[0015] S4 mix the modified metal Fe component obtained in step S1 and the nano-porous polyvinylbenzene powder obtained in step S2 according to the metering ratio, grind, tabletize, granulate and sieve to 30-60 mesh to obtain the catalyst for preparing olefins from synthesis gas.

[0016] The object and solution to the technical problem of the present application can also be further realized by the following technical measures.

[0017] Preferably, the preparation method of the catalyst for preparing olefins from synthesis gas, wherein in step S1, the temperature of the high-temperature calcination is 500-800℃, and the time is 2-4h.

[0018] Preferably, the preparation method of the catalyst for preparing olefins from synthesis gas, wherein in step S1, the oxide comprises Fe2O3, ZnO or CdO, or Mn3O4, TcO2, and the IA carbonate comprises at least one of Li2CO3, Na2CO3, K2CO3 and Rb2CO3.

[0019] Preferably, the preparation method of the catalyst for preparing olefins from synthesis gas, wherein in step S2, the grinding time is 1-5h; and the inert atmosphere is N2.

[0020] Preferably, the method for preparing the catalyst for preparing olefins from synthesis gas, wherein in step S3, the mass ratio of the styrene, divinylbenzene and pore-expanding agent is 7:3:5; the pore-expanding agent is at least one selected from toluene and cyclohexane.

[0021] Preferably, the method for preparing the catalyst for preparing olefins from synthesis gas, wherein in step S3, the initiator is benzoyl peroxide; the amount of the benzoyl peroxide added is 1% of the mass of the styrene; the amount of the deionized water added is 1-10 times of the mass of the styrene; the amount of the polyvinyl alcohol added in the aqueous solution is 5wt%-10wt%.

[0022] Preferably, the method for preparing the catalyst for preparing olefins from synthesis gas, wherein in step S3, the temperature of the hydrothermal treatment is 100-120℃, and the time is 10-20h; the drying temperature is 100-120℃.

[0023] Preferably, the method for preparing the catalyst for preparing olefins from synthesis gas, wherein in step S4, the grinding time is 10-30min.

[0024] The application discloses a catalyst for preparing olefins from synthesis gas and application thereof.

[0025] The application discloses a catalyst for preparing olefins from synthesis gas and application thereof.

[0026] Preferably, the application of the catalyst for preparing olefins from synthesis gas in the reaction of preparing olefins from CO catalytic hydrogenation comprises the following steps: reducing the catalyst in a normal-pressure H2 atmosphere, cooling to room temperature, then introducing H2 / CO raw material gas, and performing temperature-increasing pressurization reaction to obtain product olefins.

[0027] The temperature of the reduction is 350-500℃, the time is 2-12h, and the space velocity of the reduction gas is 1000-15000h-1. -1 ;

[0028] The volume ratio of H2 to CO in the H2 / CO raw material gas is 2-6, and the space velocity of the H2 / CO raw material gas is 1000-15000h-1. -1 ;

[0029] The temperature of the temperature-increasing pressurization reaction is 200-500℃, and the pressure is 2-8MPa.

[0030] The catalyst for preparing olefins from synthesis gas, the preparation method and the application thereof have at least the following advantages:

[0031] The application adopts a hot melting method to prepare the catalyst, and the hot melting method can prepare the modified metal Fe component with high dispersion through high-temperature liquid phase mixing and structure regulation.

[0032] In the application, the preparation of the PDVB is combined with a pore structure regulation by a porogen to balance the crosslinking degree, the type of the porogen and the reaction condition, so that the porous material with high specific surface area and controllable pore size is finally obtained; and after being ground and mixed with the modified metal Fe component, the PDVB forms a hydrophobic layer to reduce the selectivity of CO2.

[0033] The catalyst has excellent performance of synthesizing the olefin from the syngas, the CO conversion rate is higher than 90%, the CO2 selectivity is higher than 10%, the methane selectivity is lower than 15%, the total selectivity of the olefin is higher than 75%, and the space-time yield of the olefin reaches 1.0 g / gcat -1 h -1 The above.

[0034] The preparation method is simple, the chemical raw materials are easy to obtain and low in price, and is suitable for large-scale industrial production.

[0035] The above description is only a summary of the technical scheme of the application, in order to more clearly understand the technical means of the application, and the application can be implemented according to the content of the description, and the following will be described in detail with the preferred embodiments of the application. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 The XRD graph of the Fe-Zn-Na metal oxide prepared in example 1 before reaction;

[0037] Figure 2 The scanning electron microscope graph of the PDVB prepared in example 1;

[0038] Figure 3 The performance graph of the Fe-Zn-Na / PDVB catalyst prepared in example 1 after 100h reaction. DETAILED DESCRIPTION

[0039] In order to further illustrate the technical means and effects adopted by the application to achieve the predetermined application purpose, the following will be described in detail with the preferred embodiments, the specific implementation, structure, characteristics and effects of the catalyst for preparing the olefin from the syngas and the preparation method and application thereof according to the application, as follows. In the following description, different "an embodiment" or "embodiments" do not necessarily refer to the same embodiment. In addition, the specific features, structures or characteristics in one or more embodiments can be combined in any suitable form.

[0040] The following materials or reagents, unless otherwise specified, are commercially available.

[0041] Some embodiments of the present application provide a catalyst for preparing olefins from synthesis gas, which is composed of modified metal Fe component and nano-porous polydivinylbenzene (PDVB); the mass ratio of the modified metal Fe component and the nano-porous polydivinylbenzene is 1:0.1-1 based on the mass of the catalyst. The modified metal Fe component plays a major conversion role, and the nano-porous polydivinylbenzene (PDVB) plays a hydrophobic role. Too much PDV mass will affect the conversion rate and is not suitable.

[0042] In some alternative embodiments, the particle size of the modified metal Fe component is 5-50 nm. In the preparation of the Fe component by the hot melt method, the particle size of the prepared component is in this range.

[0043] In some alternative embodiments, the particle size of the nano-porous polydivinylbenzene is 10-400 nm. The pore size of the nano-porous polydivinylbenzene is optimal for hydrophobic performance.

[0044] In some alternative embodiments, the modified metal Fe component is composed of Fe, IIB or VIIB metal and IA metal, wherein the IIB metal includes at least one of Zn and Cd, the VIIB metal includes at least one of Mn and Tc, and the IA metal includes at least one of Li, Na, K and Rb; the pore size of the nano-porous polydivinylbenzene is optimal for hydrophobic performance; and the molar ratio of the Fe, IIB or VIIB metal, and IA metal is 1:0.2-0.8:0.01-0.05 based on the molar amount of the metal. Fe is the main catalyst, the IIB metal and the VIIB metal are optimal between 0.2 and 0.8, the IA metal is optimal between 0.01 and 0.05, the content of the metal additive should not be too high, and too high content will lead to excessive hydrogenation effect, resulting in increased selectivity of alkanes, and the content of the additive should not be too low, which will lead to reduced hydrogenation capacity of the catalyst.

[0045] Tests show that the CO conversion rate of the catalyst for preparing olefins from synthesis gas is higher than 90%, the CO2 selectivity is more than 10%, the methane selectivity is less than 15%, the total selectivity of olefins is higher than 75%, and the space-time yield of olefins reaches 1.0 g gcat -1 h -1 The above.

[0046] Some embodiments of the present application also provide a preparation method of a catalyst for preparing olefins from synthesis gas, which comprises the following steps:

[0047] S1 first pre-treats Fe oxide, IIB or VIIB oxide and IA carbonate, puts the oxide and carbonate into a tube furnace, calcines at high temperature of 500-800℃ for 2-4h, if the temperature is lower than 500℃ and the time is less than 2h, the impurities in the oxide and carbonate put in cannot be treated cleanly. If the temperature is lower than 800℃ and the time is less than 4h, the oxide and carbonate put in will be hot-melted, failing to achieve the pre-treatment effect; the oxide includes Fe2O3, ZnO or CdO, or Mn3O4, TcO2, Fe is the main catalyst, Fe2O3 is adopted considering the melting point, other types of Fe oxide have too high melting point and are not conducive to hot-melting; considering the performance and melting point, the oxide of the four types of IIB metal and VIIB metal is selected, other types of oxide have too high melting point and are not conducive to hot-melting; the IA carbonate includes at least one of Li2CO3, Na2CO3, K2CO3 and Rb2CO3, such carbonate mixed with the previous oxide can play a dissolution effect to reduce the overall melting point; 2) mix the pre-treated raw materials according to the molar ratio, put them in an agate mortar or a ball mill and grind for 1-5h to ensure uniform dispersion, if the time is less than 1h, the grinding is uneven; if the time is more than 5h, the grinding time is too long and the powder is too dispersed; 3) put the mixed powder into an alumina crucible, put it into a tube furnace, heat it to a melting temperature of 700-1100℃ at a heating rate of 2-5℃ / min under the protection of inert gas N2 and keep it for 1-3h, if the heating rate is too large, such as more than 5℃ / min, the temperature rises too fast, causing the tube furnace to fly, affecting the hot-melting effect; if the heating rate is too small, such as less than 2℃ / min, the time is wasted; grind the block body after natural cooling after hot-melting and sieve it to 100-120 meshes to facilitate tabletting and granulation, obtaining a modified metal Fe component; if the temperature is lower than 700℃ and the time is less than 1h, the oxide and carbonate cannot be completely hot-melted; if the temperature is higher than 1100℃ and the time is more than 3h, the oxide is too hot-melted, causing too much agglomeration and affecting the performance.

[0048] S2 1) mixing styrene (St), divinylbenzene DVB, pore-expanding agent in proportion (St: DVB: pore-expanding agent = 7-10: 3-5: 5-8, mass ratio, the crystal form and pore performance obtained by hydrothermal in this range are better), the pore-expanding agent is selected from at least one of toluene and cyclohexane; 2) adding initiator benzoyl peroxide BPO (BPO is 1-5% of the mass of St, so setting the initiator benzoyl peroxide at 1-5% has the best effect), ultrasonic dispersion for 10-30 min, ensuring uniformity, less than 10 min, ultrasonic dispersion cannot be uniform, and more than 30 min, energy waste is easily caused; 3) stirring uniformly after ultrasonic dispersion in deionized water, deionized water is 1-10 times the mass of St, too much deionized water leads to too dispersed feeding; then adding polyvinyl alcohol PVA (PVA accounts for 5wt%-10wt% in the aqueous solution), heating to 60-70 DEG C, and stirring for 1-3 h; 4) putting the stirring liquid into a reaction kettle for hydrothermal treatment, the temperature is 100-120 DEG C, and the treatment time is 10-20 h; the hydrothermal reaction temperature is lower than 100 DEG C, and the time is lower than 10 h, which is not conducive to lattice formation, and amorphous or low crystalline state is easily caused; the hydrothermal reaction temperature is higher than 120 DEG C, and the time is higher than 20 h, the reaction rate is too fast at high temperature, and excessive growth of the product (such as agglomeration of nanoparticles into micron-level blocks) is easily caused; 5) after hydrothermal treatment, the liquid in the kettle is filtered, washed with ethanol or water for 1-3 times, less than 1 time, the washing times are too low, and free ions cannot be cleaned; and more than 3 times, waste is easily caused; 6) drying and crushing the filter cake to 100-120 meshes for grinding to facilitate granulation, the drying temperature is 100-120 DEG C to sufficiently volatilize water, and the nano-porous polydivinylbenzene (PDVB) is obtained;

[0049] S3 mixing the modified metal Fe component obtained in step S1 and the nano-porous polydivinylbenzene (PDVB) powder obtained in step S2 in a metering ratio, then grinding for 10-30 min, less than 10 min, the grinding time is too low, and the mixing is not uniform; more than 30 min, waste is easily caused; then tabletting, sieving and granulating, and sieving 30-60 mesh particles to obtain the catalyst.

[0050] Some embodiments of the present application also provide application of the catalyst for preparing olefins from synthesis gas in a CO catalytic hydrogenation reaction.

[0051] In the above technical solution, the modified metal Fe component with high dispersion can be prepared by high-temperature liquid phase mixing and structure regulation through a hot melting method, and the preparation of the nano-porous polydivinylbenzene (PDVB) is realized by combining polymerization reaction and pore-expanding agent regulation of pore structure, so that the prepared catalyst shows extremely high CO conversion rate, olefin selectivity and space-time yield, and has the characteristics of low CO2 selectivity and low CH4 selectivity.

[0052] The specific embodiments of the present invention will be described in further detail below with reference to examples, but this should not be construed as a limitation on the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention still fall within the scope of protection of the present invention.

[0053] Unless otherwise specified, all materials and reagents mentioned below are commercially available products well known to those skilled in the art; unless otherwise specified, all methods described are methods known in the art. Unless otherwise defined, the technical or scientific terms used should have the ordinary meaning understood by those skilled in the art to which this invention pertains.

[0054] Example 1

[0055] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0056] First, the oxides and carbonates, including Fe2O3, ZnO, and Na2CO3, are pretreated. The pretreated raw materials are then placed in a tube furnace and calcined at 600℃ for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 4.08g ZnO, and 0.13g Na2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a rate of 5℃ / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Na metal oxide.

[0057] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to 0.07g of benzoyl peroxide (BPO) as an initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered and washed three times with anhydrous ethanol. The filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB).

[0058] Fe-Zn-Na and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The powders were then passed through a 30-60 mesh sieve. The powders were mixed in a volume ratio of 1:2 to obtain Fe-Zn-Na / PDVB.

[0059] Fe-Zn-Na / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g.-1 h -1 The volume ratio of H2 / CO was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0060] Example 2

[0061] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0062] First, the oxides and carbonates are pretreated, including Fe2O3, ZnO, and K2CO3. The above are placed in a tube furnace and calcined at 600℃ for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 4.08g ZnO, and 0.17g K2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a rate of 5℃ / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-K metal oxide.

[0063] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to 0.07g of benzoyl peroxide (BPO) as an initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered and washed three times with anhydrous ethanol. The filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB).

[0064] Fe-Zn-K and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The resulting powders were then passed through a 30-60 mesh sieve. The powders were then mixed at a volume ratio of 1:2 to obtain...

[0065] Fe-Zn-K / PDVB.

[0066] Fe-Zn-K / PDVB was used in the CO hydrogenation process under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1The volume ratio of H2 / CO was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0067] Example 3

[0068] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0069] First, the oxides and carbonates are pretreated, including Fe2O3, Mn3O4, and K2CO3. The above are placed in a tube furnace and calcined at 600℃ for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 11.46g Mn3O4, and 0.17g K2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a rate of 5℃ / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Mn-K metal oxide.

[0070] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to 0.07g of benzoyl peroxide (BPO) as an initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered and washed three times with anhydrous ethanol. The filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB).

[0071] Fe-Mn-K and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The resulting powders were then passed through a 30-60 mesh sieve. The powders were then mixed at a volume ratio of 1:2 to obtain...

[0072] Fe-Mn-K / PDVB.

[0073] Fe-Mn-K / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1The H2 / CO ratio was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0074] Example 4

[0075] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0076] First, the oxides and carbonates are pretreated, including Fe2O3, Mn3O4, and Na2CO3. The above are placed in a tube furnace and calcined at 600℃ for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 11.46g Mn3O4, and 0.13g Na2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a rate of 5℃ / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Mn-Na metal oxide.

[0077] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to an initiator of 0.07g of benzoyl peroxide (BPO) and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min, and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered, washed three times with anhydrous ethanol, and the filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB). Fe-Mn-Na and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The powders were then passed through a 30-60 mesh sieve and mixed at a volume ratio of 1:2 to obtain Fe-Mn-Na / PDVB.

[0078] Fe-Mn-Na / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The H2 / CO ratio was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0079] Example 5

[0080] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0081] First, the oxides and carbonates are pretreated, including Fe2O3, ZnO, and Li2CO3. The above are placed in a tube furnace and calcined at 600℃ for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 4.08g ZnO, and 0.09g Li2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a rate of 5℃ / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Li metal oxide.

[0082] 7g styrene (St), 3g divinylbenzene (DVB), and 5g toluene were mixed with 0.07g benzoyl peroxide (BPO) as initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml deionized water and stirred until homogeneous. Then, 1.05g polyvinyl alcohol (PVA) was added, and the mixture was heated to 60℃ at a rate of 5℃ / min and stirred for 3 hours. The stirred mixture was then transferred to a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered, washed three times with anhydrous ethanol, and the filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB). Fe-Zn-Li and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The powders were then passed through a 30-60 mesh sieve. The powders were mixed at a volume ratio of 1:2 to obtain Fe-Zn-Li / PDVB.

[0083] Fe-Zn-Li / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The H2 / CO ratio was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0084] Example 6

[0085] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0086] First, the oxides and carbonates, including Fe2O3, ZnO, and Na2CO3, are pretreated. The pretreated raw materials are then placed in a tube furnace and calcined at 600°C for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 2.03g ZnO, and 0.13g Na2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000°C at a rate of 5°C / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Na metal oxide.

[0087] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to 0.07g of benzoyl peroxide (BPO) as an initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered and washed three times with anhydrous ethanol. The filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB).

[0088] Fe-Zn-Na and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The powders were then passed through a 30-60 mesh sieve. The powders were mixed in a volume ratio of 1:2 to obtain Fe-Zn-Na / PDVB.

[0089] Fe-Zn-Na / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The volume ratio of H2 / CO was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0090] Example 7

[0091] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0092] First, the oxides and carbonates, including Fe2O3, ZnO, and Na2CO3, are pretreated. The pretreated raw materials are then placed in a tube furnace and calcined at 600°C for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 6.09g ZnO, and 0.13g Na2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000°C at a rate of 5°C / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Na metal oxides.

[0093] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to 0.07g of benzoyl peroxide (BPO) as an initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered and washed three times with anhydrous ethanol. The filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB).

[0094] Fe-Zn-Na and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The powders were then passed through a 30-60 mesh sieve. The powders were mixed in a volume ratio of 1:2 to obtain Fe-Zn-Na / PDVB.

[0095] Fe-Zn-Na / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The volume ratio of H2 / CO was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0096] Example 8

[0097] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0098] First, the oxides and carbonates, including Fe2O3, ZnO, and Na2CO3, are pretreated. The pretreated raw materials are then placed in a tube furnace and calcined at 600℃ for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 8.12g ZnO, and 0.13g Na2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a rate of 5℃ / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Na metal oxide.

[0099] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to 0.07g of benzoyl peroxide (BPO) as an initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered and washed three times with anhydrous ethanol. The filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB).

[0100] Fe-Zn-Na and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The powders were then passed through a 30-60 mesh sieve. The powders were mixed in a volume ratio of 1:2 to obtain Fe-Zn-Na / PDVB.

[0101] Fe-Zn-Na / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The volume ratio of H2 / CO was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0102] Example 9

[0103] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0104] First, the oxides and carbonates, including Fe2O3, ZnO, and Na2CO3, are pretreated. The pretreated raw materials are then placed in a tube furnace and calcined at 600°C for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour with 20.0g Fe2O3, 4.08g ZnO, and 0.26g Na2CO3 to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000°C at a rate of 5°C / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Na metal oxide.

[0105] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to 0.07g of benzoyl peroxide (BPO) as an initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered and washed three times with anhydrous ethanol. The filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB).

[0106] Fe-Zn-Na and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The powders were then passed through a 30-60 mesh sieve. The powders were mixed in a volume ratio of 1:2 to obtain Fe-Zn-Na / PDVB.

[0107] Fe-Zn-Na / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The volume ratio of H2 / CO was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0108] Example 10

[0109] This embodiment provides a method for preparing a catalyst for the synthesis of olefins from syngas, comprising the following steps:

[0110] First, the oxides and carbonates, including Fe2O3, ZnO, and Na2CO3, are pretreated. The pretreated raw materials are then calcined at 600℃ for 2 hours in a tube furnace. The pretreated raw materials are then ground in a ball mill for 1 hour to ensure uniform dispersion and to a mesh size of 120. The mixed powder is placed in an alumina crucible and then placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a rate of 5℃ / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Na metal oxide.

[0111] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to 0.07g of benzoyl peroxide (BPO) as an initiator and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered and washed three times with anhydrous ethanol. The filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB).

[0112] Fe-Zn-Na and PDVB powders were ground in an agate mortar and then pressed into cylindrical shapes using a tablet press. The powders were then passed through a 30-60 mesh sieve. The powders were mixed in a volume ratio of 1:2 to obtain Fe-Zn-Na / PDVB.

[0113] Fe-Zn-Na / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The volume ratio of H2 / CO was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0114] Comparative Example 1

[0115] This comparative example provides a method for preparing a catalyst, comprising the following steps:

[0116] First, the oxides and carbonates are pretreated, including Fe2O3, ZnO, and Na2CO3. The above are placed in a tube furnace and calcined at 600℃ for 2 hours. The pretreated raw materials are then ground in a ball mill for 1 hour, with 20.0g Fe2O3, 4.08g ZnO, and 0.13g Na2CO3 mixed to ensure uniform dispersion and to a mesh size of 120. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a rate of 5℃ / min and held for 3 hours. The melted and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Na metal oxide.

[0117] Fe-Zn-Na was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The H2 / CO ratio was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0118] Comparative Example 2

[0119] This comparative example provides a method for preparing a catalyst, comprising the following steps:

[0120] First, the oxides, including Fe2O3 and ZnO, are pretreated. The oxides are then calcined at 600℃ for 2 hours in a tube furnace. The pretreated raw materials are then ground in a ball mill for 1 hour, with 20.0g of Fe2O3 and 4.08g of ZnO mixed to ensure uniform dispersion. The mixed powder is then placed in an alumina crucible and ground in a ball mill for 1 hour to ensure uniform dispersion, and ground to 120 mesh. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a heating rate of 5℃ / min and held for 3 hours. The molten and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Zn metal oxide.

[0121] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to an initiator of 0.07g of benzoyl peroxide (BPO) and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min, and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered, washed three times with anhydrous ethanol, and the filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB). Fe-Zn and PDVB powders were ground, granulated, and sieved through a 30-60 mesh sieve. The powders were then mixed at a volume ratio of 1:2 to obtain Fe-Zn / PDVB.

[0122] Fe-Zn / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The H2 / CO ratio was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0123] Comparative Example 3

[0124] This comparative example provides a method for preparing a catalyst, comprising the following steps:

[0125] First, the oxides and carbonates are pretreated, including Fe2O3, ZnO, and Na2CO3. The above are placed in a tube furnace and calcined at 600℃ for 2 hours. The pretreated raw materials are then placed in a ball mill and ground for 1 hour to ensure uniform dispersion, and ground to 120 mesh. The mixed powder is placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a heating rate of 5℃ / min and held for 3 hours. The molten block is then ground and sieved through a 120-mesh sieve to obtain Fe-Zn-Na metal oxide.

[0126] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to an initiator of 0.07g of benzoyl peroxide (BPO) and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min, and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered, washed three times with anhydrous ethanol, and the filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB). The Fe-Zn-Na and PDVB powders were granulated separately, sieved through a 30-60 mesh sieve, and then mixed at a volume ratio of 1:2 to obtain Fe-Zn-Na+PDVB.

[0127] Fe-Zn-Na+PDVB was used in the CO hydrogenation process under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The H2 / CO ratio was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0128] Comparative Example 4

[0129] This comparative example provides a method for preparing a catalyst, comprising the following steps:

[0130] First, the oxides, including Fe2O3 and Mn3O4, are pretreated. The oxides are then calcined at 600℃ for 2 hours in a tube furnace. The pretreated raw materials are then ground in a ball mill for 1 hour, with 20.0g of Fe2O3 and 11.46g of Mn3O4 mixed to ensure uniform dispersion. The mixed powder is then placed in an alumina crucible and ground in a ball mill for 1 hour to ensure uniform dispersion, and ground to 120 mesh. The mixed powder is then placed in an alumina crucible and placed in a tube furnace. Under an inert atmosphere of N2, the temperature is raised to the melting temperature of 1000℃ at a heating rate of 5℃ / min and held for 3 hours. The molten and naturally cooled blocks are then ground and sieved through a 120-mesh sieve to obtain Fe-Mn metal oxide.

[0131] 7g of styrene (St), 3g of divinylbenzene (DVB), and 5g of toluene were added to an initiator of 0.07g of benzoyl peroxide (BPO) and ultrasonically dispersed for 30 minutes to ensure uniformity. The ultrasonically dispersed product was dissolved in 50ml of deionized water and stirred until homogeneous. Then, 1.05g of polyvinyl alcohol (PVA) was added, and the temperature was increased to 60℃ at 5℃ / min, and stirred for 3 hours. The stirred liquid was then placed in a reaction vessel and hydrothermally treated at 100℃ for 12 hours. After hydrothermal treatment, the liquid in the vessel was filtered, washed three times with anhydrous ethanol, and the filter cake was dried at 100℃, crushed, and ground to 120 mesh to obtain nanoporous polyvinylbenzene (PDVB). Fe-Zn and PDVB powders were ground, granulated, and sieved through a 30-60 mesh sieve. The powders were then mixed at a volume ratio of 1:2 to obtain Fe-Zn / PDVB.

[0132] Fe-Mn / PDVB was used for CO hydrogenation under the following conditions: reaction pressure 3.5 MPa, reaction temperature 300 °C, and space velocity 8000 mL g / g. -1 h -1 The H2 / CO ratio was 2, and the reaction was carried out under normal pressure H2 atmosphere at 400℃ for 2 hours before the reaction. The reactants (H2 / CO with a volume ratio of 2:1) and products (including CO2, various α-olefins, methane, straight-chain alkanes, and other byproducts) were introduced into the gas chromatograph for online analysis through an insulated pipeline. The specific catalytic performance is listed in Table 1.

[0133] 1g of the catalysts from Examples 1-10 and Comparative Examples 1-4 were respectively loaded into quartz reaction tubes with an inner diameter of 8mm. The quartz tubes were then placed into a fixed-bed reactor. The hydrogen injection valve was opened, and the flow rate was controlled at 250mL / min. The needle valve of the valve box and the reactor outlet were closed. The pressure was increased to a reaction pressure of 3.5MPa, and the reaction flow rate (CO: 133mL / min) was controlled. The mixture was heated to a reaction temperature of 300℃. When the temperature reached 300℃, the chromatographic needle valve was opened for analysis. The reaction was then complete. The analytical results are shown in […]. Figure 3 .

[0134] The CO conversion rate and the selectivity for CH4 and CO2 are mainly calculated from the TCD data in gas chromatography. Using Ar as the internal standard gas, since this gas does not change before and after the reaction, the CO conversion rate is calculated as follows:

[0135] CO conversion rate is calculated using Ar in the feed gas as an internal standard, and the formula is as follows:

[0136]

[0137] In the formula, Ao(CO) represents the peak area of ​​CO on the TCD before the reaction, and Ao(Cr) represents the peak area of ​​Ar gas on the TCD before the reaction; A(CO) represents the peak area of ​​CO on the TCD at the time of sampling, and A(Ar) represents the area of ​​Ar gas on the TCD at the time of sampling.

[0138] The formulas for calculating the flow rate and selectivity of each substance on the TCD are as follows:

[0139]

[0140] Where n represents the gas flow rate, and f represents the relative molar correction factor for each gas. The gas mixture used in this experiment consisted of 64% H2, 32% CO, and 4% Ar, and the gas flow rate was 133 mL / min. -1 The flow rates of CO and Ar were calculated. f was calculated after online colorimetric chromatography with calibrated gas.

[0141] The selectivity of each product of FID is given by the following formula:

[0142]

[0143] The space-time yield (STY) of olefins is calculated using the following formula:

[0144]

[0145] F (mL / min) is the flow rate, W is the mass of the catalyst, 32% is the CO content, and 14 (g·mol) -1 () represents the mass of the olefin. The selectivity of the target product.

[0146] The Fe-Zn-Na metal oxide of Example 1 of this invention was characterized by XRD. This XRD characterization was performed on a Rigaku Ultima IV X-ray powder diffractometer. The test results are shown below. Figure 1 The test conditions were: Cu(Kα) (λ=0.15418nm), tube voltage 40kV, tube current 30mA, scanning angle 5-90°, and scanning speed 10°·min. -1 or 1°·min -1 The phase composition of the catalyst was analyzed by comparing the obtained scanned spectra with the JCPDS database. Figure 1It can be seen that a characteristic peak appears at approximately 36.5° of the 2θ angle, which, according to standard calipers, can be classified as a monoclinic ZnO crystal structure; a small characteristic peak appears at approximately 41.5° of the 2θ angle, which, according to standard calipers, can be classified as a monoclinic FeO crystal; and a characteristic peak appears at approximately 45° of the 2θ angle, which, according to standard calipers, can be classified as a monoclinic Fe crystal. This indicates that Fe is the main active site after reduction.

[0147] The PDVB of Example 1 of this invention was characterized by field emission scanning electron microscopy (SEM) using a SUPRA55 field emission electron microscope. The test results are shown in [Figure 1]. Figure 2 The testing procedure was as follows: 10 mg of the catalyst to be tested was uniformly dispersed in 5 ml of anhydrous ethanol to form a solution. Then, 0.5 ml of the solution was dropped onto a silicon wafer using a burette and dried at 50°C for 2 min. Next, gold sputtering was performed to make the catalyst conductive. Finally, the catalyst was placed under a SEM, and a voltage of 20 kV was set for scanning and image capture. The gold sputtering procedure was as follows: The gold sputtering instrument (common models such as Quorum Q150R S) was turned on. The dried silicon wafer (containing the catalyst) was fixed on the sample stage, ensuring the sample surface was unobstructed and directly facing the gold sputtering source. The vacuum chamber door of the gold sputtering instrument was closed, and the vacuuming program was started. Vacuuming was stopped after the vacuum level reached 10⁻² Pa. The gold sputtering parameters were set: highly conductive gold (Au) was used as the metal target, the sputtering time was controlled at 30 seconds, and the coating thickness was 10 nm. The gold sputtering program was started, and after completion, the vacuum chamber was allowed to return to atmospheric pressure before the sample was removed. Figure 2 It can be seen that the PDVB in Example 1 has a particle size ranging from less than 0.15 μm to close to 0.35 μm, but it is mainly distributed around 0.25 μm.

[0148] Figure 3 This is a performance graph of the Fe-Zn-Na / PDVB catalyst prepared in Example 1 of this invention after 100 h of reaction; from Figure 3 It can be seen that the CO conversion rate in Example 1 is around 93%, the CO2 selectivity is around 10%, the methane selectivity is around 10%, and the C... 2+ ＝ The selectivity is around 80%, and the performance is stable after 100 hours of operation.

[0149] Table 1. Catalytic performance evaluation results of Examples 1-10 and Comparative Examples 1-4

[0150]

[0151]

[0152] As can be seen from the data in Table 1, the catalysts of Examples 1-10 of this invention exhibit a CO conversion rate of 90.5%-95.8%, a CO2 selectivity of 10.2%-16.3%, a methane selectivity of 9.4%-14.9%, a total olefin selectivity of 75.1%-83.2%, and an olefin space-time yield of 1.0-1.1 g. cat -1 h -1 Examples 1, 2, and 5 of this invention, using the method of hot-melting different Group IA metal elements, show that Example 1 exhibits higher olefin selectivity and lower CO2 selectivity. A comparison of Examples 1, 6, 7, and 8 shows that with increasing Zn content, CH4 selectivity increases, CO2 selectivity increases, and C5 selectivity increases. +＝ The selectivity of olefins was significantly improved. A comparison of Examples 1, 9, and 10 shows that as the Na content increases, the CO2 selectivity increases significantly, while the other selectivity changes little. Examples 1 and Comparative Example 1 show that the catalyst performance is significantly improved after grinding and mixing. Examples 1 and Comparative Examples 2 and 4 show that the performance of the three-component Fn-Zn-Na catalyst is significantly improved compared to the two-component Fe-Zn and Fe-Na catalysts. Examples 1 and Comparative Example 3 show that the performance of the ground and mixed Fe-Zn-Na / PDVB catalyst is significantly improved compared to the directly mixed Fe-Zn-Na+PDVB catalyst.

[0153] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0154] The numerical range described in this invention includes all values ​​within this range, and also includes any range value composed of any two values ​​within this range. Different values ​​of the same indicator appearing in all embodiments of this invention can be arbitrarily combined to form a range value.

[0155] The technical features in the claims and / or specification of this invention can be combined, and the combination is not limited to the combinations obtained through reference in the claims. Technical solutions obtained by combining the technical features in the claims and / or specification are also within the scope of protection of this invention.

[0156] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A catalyst for the production of olefins from synthesis gas, characterized in that, The catalyst for preparing olefins from synthesis gas is composed of modified metal Fe component and nano-porous polyvinyl benzene; the mass ratio of the modified metal Fe component and the nano-porous polyvinyl benzene is 1:0.1-1 based on the mass of the catalyst.

2. The catalyst for the production of olefins from synthesis gas according to claim 1, characterized in that, The particle size of the modified metal Fe component is 5-50 nm.

3. The catalyst for the production of olefins from synthesis gas according to claim 1, characterized in that, The particle size of the nano-porous polyvinyl benzene is 10-400 nm.

4. The catalyst for the production of olefins from synthesis gas according to claim 1, characterized in that, The modified metal Fe component is composed of Fe, IIB or VIIB metal and IA metal, wherein the IIB metal comprises at least one of Zn and Cd, the VIIB metal comprises at least one of Mn and Tc, and the IA metal comprises at least one of Li, Na, K and Rb; the molar ratio of the Fe, IIB or VIIB metal and IA metal is 1:0.2-0.8:0.01-0.05 based on the molar amount of the metal.

5. A method for producing a catalyst for the production of olefins from synthesis gas, characterized in that It comprises the following steps: S1: first, pretreat Fe oxide, IIB or VIIB oxide and IA carbonate, and calcine the oxide and carbonate at high temperature; S2: mix the raw materials pretreated in step S1 according to the molar ratio, grind to obtain a mixed powder; heat the obtained mixed powder to a melting temperature of 700-1100℃ under the protection of inert atmosphere for 1-3 h, grind the block body after slow cooling to 100-120 mesh, and obtain the modified metal Fe component; S3: mix styrene, divinylbenzene and pore-expanding agent according to the ratio, wherein the pore-expanding agent is at least one of toluene and cyclohexane; add an initiator, ultrasonic dispersion for 10-30 min; dissolve the ultrasonic product in deionized water, stir uniformly, then add polyvinyl alcohol to obtain an aqueous solution, heat to 60-70℃, and stir for 1-3 h; perform hydrothermal treatment on the obtained stirring liquid, perform suction filtration and washing for 1-3 times to obtain a filter cake; dry and crush the obtained filter cake to 100-120 mesh, and obtain nano-porous polyvinyl benzene powder; S4: mix the modified metal Fe component obtained in step S1 and the nano-porous polyvinyl benzene powder obtained in step S2 according to the metering ratio, then grind, tabletize, granulate and sieve through a 30-60 mesh sieve to obtain the catalyst for preparing olefins from synthesis gas.

6. The method for preparing the catalyst for syngas-to-olefins as described in claim 5, characterized in that, In step S1, the calcination temperature is 500-800℃ and the time is 2-4 h; the oxide comprises Fe2O3, ZnO or CdO, or Mn3O4, TcO2, and the IA carbonate comprises at least one of Li2CO3, Na2CO3, K2CO3 and Rb2CO3; in step S2, the grinding time is 1-5 h; and the inert atmosphere is N2.

7. The method for preparing the catalyst for syngas-to-olefins as described in claim 5, characterized in that, In step S3, the mass ratio of styrene, divinylbenzene and pore-expanding agent is 7:3:5; the pore-expanding agent is at least one selected from toluene and cyclohexane; the initiator is benzoyl peroxide; the addition amount of the benzoyl peroxide is 1% of the mass of styrene; the addition amount of deionized water is 1-10 times of the mass of styrene; and the addition amount of polyvinyl alcohol in the aqueous solution accounts for 5wt%-10wt%.

8. The method for preparing a catalyst for the production of olefins by the CO2 / CO hydrogenation according to claim 5, characterized by, In step S3, the temperature of the hydrothermal treatment is 100-120℃, and the time is 10-20h; the drying temperature is 100-120℃; in step S4, the grinding time is 10-30min.

9. Use of a catalyst for preparing olefins from synthesis gas in a reaction of catalytic hydrogenation of CO to olefins.

10. Use of the catalyst for the production of olefins from synthesis gas according to claim 9 in the reaction of catalytic hydrogenation of CO to olefins, characterized in that, The use comprises the following steps: reducing the above catalyst under normal pressure H2 atmosphere, cooling to room temperature, then passing in H2 / CO raw material gas, and performing a temperature rising and pressure increasing reaction to obtain product olefins. The temperature of the reduction is 350-500℃, the time is 2-12h, and the space velocity of the reducing gas is 1000-15000h -1 ; the volume ratio of H2 to CO in the H2 / CO raw gas is 2-6, and the space velocity of the H2 / CO raw gas is 1000-15000h -1 ; the temperature of the temperature-raising and pressurizing reaction is 200-500℃, and the pressure is 2-8MPa.

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