CN109534939B - Method for directly preparing alpha-olefin in high selectivity at one step by catalyzing synthesis gas with Co-based catalyst - Google Patents

Method for directly preparing alpha-olefin in high selectivity at one step by catalyzing synthesis gas with Co-based catalyst Download PDF

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CN109534939B
CN109534939B CN201811336937.0A CN201811336937A CN109534939B CN 109534939 B CN109534939 B CN 109534939B CN 201811336937 A CN201811336937 A CN 201811336937A CN 109534939 B CN109534939 B CN 109534939B
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olefin
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oxide
synthesis gas
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CN109534939A (en
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刘忠文
朱敏莉
宋永红
刘昭铁
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Shaanxi Normal University
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Abstract

The invention discloses a method for preparing alpha-olefin directly in one step with high selectivity by catalyzing synthesis gas with a Co-based catalyst, wherein the Co-based catalyst takes Co metal or oxide thereof as an active component, at least one of C, N, P elements as a first auxiliary agent, at least one of Mn, Mg, Zn, Ce, La, Zr, Fe, Cr, Cu, Mo, Ti, Ln and Ga or oxide thereof as a second auxiliary agent, and at least one of silicon oxide, aluminum oxide, titanium oxide and zirconium oxide as a carrier; the catalyst is used in a lower reaction temperature range of 200-230 ℃, the CO single-pass conversion rate can reach 76% to the maximum, and CH4Selectivity is less than or equal to 8.0 percent, and CO2The selectivity is less than or equal to 1.0 percent, the olefin selectivity can reach 60 percent at most, wherein the long-chain alpha-olefin (C is more than or equal to 4) accounts for 70 percent. The catalyst has the characteristics of high activity, good long-period stability, high yield of long-carbon-chain alpha-olefin and the like, and has the advantages of simple preparation process, wide sources of auxiliary agents and carrier raw materials and small scale preparation amplification effect.

Description

Method for directly preparing alpha-olefin in high selectivity at one step by catalyzing synthesis gas with Co-based catalyst
Technical Field
The invention belongs to the technical field of carbon monoxide hydrogenation, and particularly relates to a method for preparing alpha-olefin by catalyzing synthesis gas with a Co-based catalyst in a one-step method at high selectivity.
Background
Coal, biomass and the like are subjected to synthesis gas (CO + H)2) The Fischer-Tropsch (F-T) synthesis process for converting the Fischer-Tropsch (F-T) into the clean liquid fuel or the high-value-added chemicals plays an important role in the aspect of clean and efficient utilization of coal resources. The alpha-olefin is an important chemical raw material, and has wide application range and high added value of products. The technology for preparing high-quality alpha-olefin by one-step high selectivity synthesis of synthesis gas through F-T is developed, and has important theoretical significance and practical application value.
The F-T synthesis is essentially a surface polymerization reaction, and due to the limitation of Anderson-Schulz-Flory (ASF) polymerization kinetics, the product selectivity depends on the carbon chain growth probability, the selectivity to specific target products such as gasoline, diesel oil and the like is poor, and particularly the selectivity of high value-added alpha-olefin is lower. Therefore, the ASF distribution limitation is effectively broken through by catalyst design, the one-step high-selectivity synthesis of alpha-olefin from synthesis gas is realized, and the method has important theoretical significance and industrial application value, but is also a challenging subject in F-T synthesis related research.
The olefin products prepared from the synthesis gas reported at present mainly comprise low-carbon olefins (C)2-C4 ＝) Mainly comprises the following steps: k.p.de Jong reported that S and Na modified Fe-based catalysts catalyzed the conversion of syngas to lower olefins with a selectivity of 60% of hydrocarbon products (Science 2012,335, 835-; the Fe/activated carbon catalyst added with Mn and K auxiliaries reported by Zhang Jingchang, Beijing chemical university (CN 101219384A) has the CO conversion rate of more than 95 percent and the content of low-carbon olefin in hydrocarbon of more than 68 percent; the catalyst which is reported by Panxilian, Panxilian and the like (CN106311317A) of the institute of chemical and physical of the university of Chinese academy of sciences and consists of a multi-component metal compound and an inorganic solid acid with a hierarchical pore structure has the low-carbon olefin selectivity of 50-85 percent; the Co-based catalyst with Mn as an auxiliary agent, which is prepared by Fei et al (CN105107523A) of Shanghai high research institute of Chinese academy of sciences, is used for the reaction of directly preparing low-carbon olefin from synthesis gas, wherein the low-carbon olefin accounts for more than 50% of the total hydrocarbon product content.
In comparison, there are very limited reports on the one-step synthesis gas production of long chain alpha olefins. The Zn-Fe-Na coprecipitation catalyst reported by Martin project group of Beijing university has CO conversion rate of about 70% and long-chain olefin accounting for 50% of hydrocarbon products under the reaction conditions of 2.0MPa and 340 ℃ (Angew. chem. int. Ed.2016,55, 9902-. However, Fe-based catalysts inevitably have a high water-gas reaction activity, resulting in CO2The selectivity is higher, and the utilization efficiency of CO is reduced. The Co-based catalyst has better carbon chain extending capability and low water-gas reaction activity, but the product is mainly long straight-chain alkane. The Lihao et al (CN 107020154A) of Jiangnan university adopts multiple reduction-carbonization-reduction treatments, and can improve Co-based catalysis to a certain extentStability of the agent and overall olefin selectivity.
The technology makes good progress in the aspect of preparing olefin by using synthesis gas, and has the main problems that: the product is mainly low-carbon olefin, and the selectivity of long-carbon-chain alpha-olefin (C is more than or equal to 4) is low; product CH4And CO2The selectivity is too high; the preparation process of part of the catalyst is complex, the cost of raw materials is high, the stability of the catalyst is poor, and the catalyst is not suitable for industrial application.
Disclosure of Invention
The invention aims to provide a simple and efficient method for preparing long carbon chain alpha-olefin by directly using synthesis gas in a one-step method at high selectivity aiming at the problem of poor selectivity of the existing synthesis gas for preparing the alpha-olefin, especially the long carbon chain alpha-olefin.
Aiming at the purposes, the technical scheme adopted by the invention is as follows: to contain H2And the synthetic gas of the CO is used as raw material gas, conversion reaction is carried out in a hydrocarbon synthesis reactor, the adopted catalyst is a Co-based catalyst, and the Fischer-Tropsch synthesis reaction conditions are as follows: the reaction temperature is 200-230 ℃, the reaction pressure is 0.3-3.0 MPa, and H2The volume ratio of/CO is 1.0-4.0, and the volume space velocity is 1-15L-g-1·h-1。
The Co-based catalyst comprises an active component metal Co or an oxide thereof, at least one of C, N, P elements of a first auxiliary agent, at least one of Mn, Mg, Zn, Ce, La, Zr, Fe, Cr, Cu, Mo, Ti, Ln and Ga or an oxide thereof of a second auxiliary agent, and a carrier is at least one of silicon oxide, aluminum oxide, titanium oxide and zirconium oxide, wherein the loading amount of the active component is 5-30 wt.%, the loading amount of the first auxiliary agent is 0.01-10 wt.%, and the loading amount of the second auxiliary agent is 0.05-30 wt.%; the carrier has a particle diameter of 0.5 to 500 μm and a specific surface area of 50 to 900m2The pore volume is 0.1-10 mL/g, and the pore diameter is 5 nm-1 μm.
In the Co-based catalyst, the loading amount of the active component is preferably 10-20 wt.%, the loading amount of the first auxiliary agent is 0.05-1 wt.%, the loading amount of the second auxiliary agent is 0.5-5 wt.%, the particle size of the carrier is 10-100 μm, and the specific surface area is 200-600 m2The pore volume is 0.5-5 mL/g, the pore diameter is 5 nm-100nm。
In the above Co-based catalyst, the first promoter is preferably C or N, the second promoter is one or two of Mn, Mg, Ce, and Zr, and further preferably includes at least one of the third promoters K, Na, and the loading amount of the third promoters is 0.01 wt.% to 1 wt.%.
The average particle size of metal Co or oxide thereof on the Co-based catalyst is 5-30 nm, and the Co-based catalyst is prepared by a step-by-step impregnation method, and the method comprises the following specific steps: dissolving a first auxiliary agent precursor in a solvent, adding a carrier under the stirring condition, uniformly stirring, and carrying out vacuum impregnation, filtration, washing, drying and roasting on the mixture to obtain a carrier loaded with a first auxiliary agent; dissolving an active component precursor, a second auxiliary agent precursor and a third auxiliary agent precursor in a solvent, then adding a carrier loaded with a first auxiliary agent under the condition of stirring, uniformly stirring, carrying out vacuum impregnation, filtering, washing, drying and roasting on the mixture, and grinding, tabletting and screening the obtained powder to obtain the Co-based catalyst particles with the particle size of 40-60 meshes.
The active component precursor is any one of cobalt nitrate, cobalt acetate, cobalt carbonyl, cobalt oxalate and ZIF-67.
The precursor of the first auxiliary agent C element is at least one of fructose, sucrose, chitosan, maltose, lactose, sodium alginate, oxalic acid and citric acid, and preferably one or two of fructose, sucrose, maltose, sodium alginate, oxalic acid and citric acid.
The precursor of the first auxiliary agent N element is at least one of ethylenediamine, ethylenediamine tetraacetic acid, diethanolamine, amino acid, ammonium triacetate, hexadecyl trimethyl ammonium, imidazole and dimethyl imidazole, and preferably one or two of ethylenediamine, ethylenediamine tetraacetic acid, diethanolamine and dimethyl imidazole.
The precursor of the first auxiliary agent P element is at least one of phosphoric acid, trialkyl phosphine and triphenyl phosphine.
The second auxiliary agent precursor is soluble inorganic salt and metal organic compound of the second auxiliary agent component.
Compared with the existing Fischer-Tropsch synthesis technology for preparing alpha-olefin by using synthesis gas, the Fischer-Tropsch synthesis technology has the following beneficial effects:
the Co-based catalyst has stronger carbon chain growth capacity, and the introduction of the first auxiliary agent as a structural auxiliary agent is beneficial to obtaining uniform metal Co or oxide particles thereof, is beneficial to adjusting the interaction between the metal Co or oxide thereof and a carrier, and is beneficial to promoting the formation of high-activity hcp phase metal Co; the second auxiliary agent is introduced as an electron auxiliary agent and interacts with the metal Co or the oxide thereof to adjust the surface electron performance of the metal Co or the oxide thereof particles, promote CO adsorption and dissociation and inhibit H at the same time2The competitive adsorption is beneficial to the generation and desorption of olefin, and the one-step method for preparing the alpha-olefin by the synthesis gas with high selectivity is realized. The test result shows that the catalyst is used in a lower reaction temperature range of 200-230 ℃, the highest CO single-pass conversion rate can reach 76%, and CH4Selectivity is less than or equal to 8.0 percent, and CO2The selectivity is less than or equal to 1.0 percent, the olefin selectivity is as high as 60 percent, wherein the long carbon chain alpha-olefin accounts for 70 percent. The catalyst used in the method has good stability, mild reaction conditions, simple process flow, less equipment investment and good economic benefit and industrial application prospect.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
10mL 10 wt.% H3PO42.0g of SiO were added to the aqueous solution2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain P/SiO2(ii) a 2.47g of Co (NO)3)2·6H2O、0.25g Zn(NO3)3·6H2O was dissolved in 20mL of water and then 2.2g P/SiO was added with stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 20% Co-2% Zn-0.1% P/SiO2A catalyst.
0.5g of 20% Co-2% Zn-0.1% P/SiO2The catalyst is placed in a fixed bed reactor, and pure H is introduced2Gas (H)299.9%), and the temperature was increased to 400 ℃ at a rate of 5 ℃/min for 5 hours. After the reduction is finished, the temperature is reduced to 180 ℃, and the volume ratio of H is introduced22.0 of volume ratio of CO, at 220 deg.C, 1.0MPa of pressure and 4.8L-g of volume space velocitycat -1·h-1The synthesis of olefins was carried out under the conditions shown in Table 1.
Example 2
Dissolving 0.2g of sucrose in 10mL of water, stirring uniformly, adding 2.0g of SiO2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain C/SiO2(ii) a 1.75g of Co (NO)3)2·6H2O、0.05g Mn(CH3COO)2Dissolved in 20mL of water and then added with 2.2g C/SiO under stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co-0.5% Mn-0.1% C/SiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Example 3
Dissolving 0.03g of sodium alginate in 10mL of water, stirring uniformly, adding 2.0g of Al2O3Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain Na-C/Al2O3(ii) a 1.75g of Co (NO)3)2·6H2O、0.22g Ce(NO3)2·6H2O was dissolved in 20mL of water, and then 2.2g of Na-C/Al was added with stirring2O3Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co-3% Ce-0.21% Na-0.05% C/Al2O3A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Example 4
0.3g of ethylene glycolDissolving amine in 10mL of methanol, stirring uniformly, adding 2.0g of TiO2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain N-C/TiO2(ii) a 1.16g of Co (NO)3)2·6H2O、0.36g Zr(NO3)2·5H2O is dissolved in 20mL of water, and then 2.2g N-C/TiO is added with stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 10% Co-2% Zr-0.5% N-0.2% C/TiO2A catalyst. The catalyst thus obtained was subjected to olefin synthesis reaction in accordance with the procedure of example 1, and the reaction results are shown in Table 1.
Example 5
0.4g of citric acid was dissolved in 10mL of water, stirred well, and 2.0g of ZrO was added2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain C/ZrO2(ii) a 1.75g of Co (NO)3)2·6H2O、0.125g Mg(NO3)2Dissolved in 20mL of water and then added with 2.2g C/ZrO under stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co-2% Mg-0.5% C/ZrO2A catalyst.
Example 6
Dissolving 0.2g of ethylenediamine tetraacetic acid in 10mL of water, stirring uniformly, adding 2.0g of TiO2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain N-C/TiO2(ii) a 2.47g of Co (NO)3)2·6H2O、0.364g Zr(NO3)2·5H2O is dissolved in 20mL of water, and then 2.2g N-C/TiO is added with stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 20% Co-2% Zr-0.02% -0.5% N-0.2% C/TiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Example 7
Dissolving 0.36g oxalic acid in 10mL water, stirring well, adding 2.0g SiO2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain C/SiO2(ii) a 1.16g of Co (NO)3)2·6H2O、0.110g Mn(CH3COO)2、0.005g NaNO3Dissolved in 20mL of water and then added with 2.2g C/SiO under stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 10% Co-1% Mn-0.02% Na-0.2% C/SiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Example 8
Dissolving 0.36g of dimethylimidazole in 10mL of water, stirring uniformly, adding 2.0g of SiO2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain N-C/SiO2(ii) a 1.75g of Co (NO)3)2·6H2O、0.30g Mn(CH3COO)2Dissolved in 50mL of water and then added with 2.2g N-C/SiO under stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co-3% Mn-0.2% N-0.5% C/SiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Example 9
Dissolving 0.2 fructose in 10mL water, stirring well, adding 2.0g SiO2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain C/SiO2(ii) a 2.82g of Co (NO)3)2·6H2O、0.45g La(NO3)2·6H2O was dissolved in 20mL of water and then 2.2g C/SiO was added with stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 20% Co-5% La-0.5% C/SiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Example 10
Dissolving 0.2 maltose in 10mL water, stirring well, adding 2.0g SiO2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain C/SiO2(ii) a 1.97g of Co (NO)3)2·6H2O、1.62g Mg(NO3)2、0.01g La(NO3)2·6H2O was dissolved in 20mL of water and then 2.2g C/SiO was added with stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co-10% Mg-0.1% La-0.5% C/SiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Example 11
Dissolving 0.36g of diethanolamine in 10mL of water, stirring uniformly, adding 2.0g of Al2O3Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain N-C/Al2O3(ii) a 2.63g of Co (NO)3)2·6H2O、0.60g Mn(CH3COO)2、0.04g Ce(NO3)2·6H2O was dissolved in 20mL of water and then 2.2g N-C/Al was added with stirring2O3Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 20% Co-5% Mn-0.5% Ce-0.5% N-0.3% C/Al2O3A catalyst. The catalyst thus obtained was subjected to ene condensation in accordance with the procedure of example 1The results of the hydrocarbon synthesis reaction are shown in Table 1.
Comparative example 1
1.74g of Co (NO)3)2·6H2O was dissolved in 20mL of deionized water, and 2.0g of SiO was added with stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co/SiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Comparative example 2
1.74g of Co (NO)3)2·6H2O was dissolved in 20mL of deionized water, and 2.0g of Al was added with stirring2O3Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co/Al2O3A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Comparative example 3
1.74g of Co (NO)3)2·6H2O、0.05g Mn(CH3COO)2、0.03g Na2CO3Dissolved in 20mL of water and then added with 2.0g of SiO under stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co-0.5% Mn-0.05% Na/SiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Comparative example 4
1.75g of Co (NO)3)2·6H2O、0.22g Ce(NO3)2·6H2O was dissolved in 20mL of water, and 2.0g of Al was added with stirring2O3Stirring, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 400 deg.C for 5 hr to obtain the final productGrinding, tabletting and screening the obtained powder to obtain 40-60 meshes of 15% Co-3% Ce/Al2O3A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
Comparative example 5
Dissolving 0.2g citric acid in 10mL water, stirring well, adding 2.0g SiO2Mixing, vacuum soaking the mixture for 5 hr, filtering, washing, drying at 100 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain C/SiO2(ii) a 1.74g of Co (NO)3)2·6H2O is dissolved in 20mL of deionized water, and then 2.2g C/SiO is added with stirring2Uniformly stirring, vacuum-soaking the mixture for 5h, filtering, washing, drying at 100 ℃ for 12h, roasting at 400 ℃ for 5h, grinding, tabletting and screening the obtained powder to obtain 40-60-mesh 15% Co-0.5% C/SiO2A catalyst. The catalyst thus obtained was subjected to the olefin synthesis reaction in the same manner as in example 1, and the reaction results are shown in Table 1.
TABLE 1 reactivity and product distribution of syngas catalyzed by different catalysts
Figure BDA0001861429070000081
As can be seen from Table 1, in comparative examples 1 and 2, no auxiliary agent was added, and the reactivity and olefin selectivity of the catalyst were relatively low; when only the second auxiliary agent and the third auxiliary agent are added (comparative examples 3 and 4), the catalyst activity is not obviously changed, and the olefin selectivity is slightly improved; when only the first promoter was added (comparative example 5), the catalyst activity was significantly improved, but the selectivity to olefin was still relatively low. From examples 1 to 11, it can be seen that the catalyst prepared by the method has the characteristics of high activity, high yield of long carbon chain alpha-olefin and the like, the CO conversion rate is over 55%, the selectivity of the product olefin is over 30%, and more than 60% of the product olefin is long chain alpha-olefin (C is more than or equal to 4). The catalyst adopted by the invention has the advantages of simple preparation process, wide sources of the auxiliary agent and the carrier raw material, small large-scale preparation amplification effect and good industrial application prospect.

Claims (8)

1. A method for directly preparing alpha-olefin in one step with high selectivity by catalyzing synthesis gas with a Co-based catalyst is characterized by comprising the following steps: to contain H2And the synthetic gas of the CO is used as raw material gas, conversion reaction is carried out in a hydrocarbon synthesis reactor, the adopted catalyst is a Co-based catalyst, and the Fischer-Tropsch synthesis reaction conditions are as follows: the reaction temperature is 200-230 ℃, the reaction pressure is 0.3-3.0 MPa, and H2The volume ratio of/CO = 1.0-4.0, and the volume space velocity = 1-15L-g-1·h-1；
The Co-based catalyst comprises an active component metal Co or an oxide thereof, at least one of C, N, P elements as a first auxiliary agent, at least one of Mn, Mg, Zn, Ce, La, Zr, Fe, Cr, Cu, Mo, Ti, Ln and Ga as a second auxiliary agent or an oxide thereof, and at least one of silicon oxide, aluminum oxide, titanium oxide and zirconium oxide as a carrier; the loading capacity of the active component is 5-30 wt.%, the loading capacity of the first auxiliary agent is 0.01-10 wt.%, and the loading capacity of the second auxiliary agent is 0.05-30 wt.%; the particle size of the carrier is 0.5-500 mu m, and the specific surface area is 50-900 m2The pore volume is 0.1-10 mL/g, and the pore diameter is 5 nm-1 mu m;
the catalyst is prepared by a step-by-step impregnation method, wherein a precursor of a first auxiliary agent C element used in the preparation process is at least one of fructose, sucrose, chitosan, maltose, lactose, sodium alginate, oxalic acid and citric acid, a precursor of a first auxiliary agent N element used in the preparation process is at least one of ethylenediamine, diethanolamine, amino acid, hexadecyl trimethyl ammonium, imidazole and dimethyl imidazole, and a precursor of a first auxiliary agent P element used in the preparation process is at least one of phosphoric acid, trialkyl phosphine and triphenyl phosphine.
2. The method for preparing alpha-olefin directly in one step with high selectivity by catalyzing synthesis gas by using the Co-based catalyst according to claim 1, is characterized in that: the load capacity of the active component in the Co-based catalyst is 10-20 wt.%, the load capacity of the first auxiliary agent is 0.05-1 wt.%, and the load capacity of the second auxiliary agent is 0.5-5 wt.%; the particle size of the carrier is 10-100 mu m, and the specific surface area is 200-600 m2The pore volume is 0.5-5 mL/g, the pore diameter is 5 nm-100 nm。
3. The method for directly preparing alpha-olefin with high selectivity by catalyzing synthesis gas by using the Co-based catalyst according to claim 2, is characterized in that: the first auxiliary agent of the Co-based catalyst is C or N.
4. The method for directly preparing alpha-olefin with high selectivity by catalyzing synthesis gas by using the Co-based catalyst according to claim 3, is characterized in that: the precursor of the first auxiliary agent C element is one or two of fructose, sucrose, maltose, sodium alginate, oxalic acid and citric acid.
5. The method for directly preparing alpha-olefin with high selectivity by catalyzing synthesis gas by using the Co-based catalyst according to claim 3, is characterized in that: precursors of the first auxiliary agent N element are one or two of ethylenediamine, diethanolamine and dimethylimidazole.
6. The method for directly preparing alpha-olefin with high selectivity by catalyzing synthesis gas by using the Co-based catalyst according to claim 2, is characterized in that: the second assistant of the Co-based catalyst is one to two metals of Mn, Mg, Ce and Zr.
7. The method for preparing alpha-olefin directly in one step with high selectivity by catalyzing synthesis gas by using the Co-based catalyst according to claim 1, is characterized in that: the average particle size of the metal Co or the oxide thereof on the Co-based catalyst is 5-30 nm.
8. The method for directly preparing alpha-olefin in one step with high selectivity by catalyzing synthesis gas with the Co-based catalyst according to any one of claims 1 to 7, is characterized in that: the Co-based catalyst also comprises at least one third auxiliary agent K, Na, and the loading amount of the third auxiliary agent is 0.01-1 wt.%.
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