CN107913718B - Iron-based catalyst for directly synthesizing low-carbon olefin by synthesis gas - Google Patents
Iron-based catalyst for directly synthesizing low-carbon olefin by synthesis gas Download PDFInfo
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Abstract
The invention relates to an iron-based catalyst for directly synthesizing low-carbon olefin by synthesis gas, which mainly solves the problems of low CO conversion rate and low-carbon olefin selectivity in the reaction of directly synthesizing low-carbon olefin by synthesis gas in the prior art. The invention relates to an iron-based catalyst for directly synthesizing low-carbon olefin by using synthesis gas, which comprises the following components in parts by weight: a) 18-50 parts of iron element or oxide thereof; b) 10-25 parts of at least one element selected from manganese and zinc or an oxide thereof; c) 10-25 parts of at least one element selected from magnesium and strontium or an oxide thereof; d) 20-60 parts of aluminum element or oxide thereof; e) 1-5 parts of niobium or an oxide thereof; f) the technical scheme of 1-5 parts of tantalum element or the oxide thereof well solves the problem and can be used for industrial production of directly synthesizing low-carbon olefin from synthesis gas.
Description
Technical Field
The invention relates to an iron-based catalyst for directly synthesizing low-carbon olefin by synthesis gas.
Background
The lower olefin is an olefin having 4 or less carbon atoms. The low-carbon olefin represented by ethylene and propylene is a very important basic organic chemical raw material, and the market of the low-carbon olefin is short in supply and demand for a long time along with the rapid growth of the economy of China. At present, the production of low-carbon olefin mainly adopts a petrochemical route of light hydrocarbon (ethane, naphtha and light diesel oil) cracking, and due to the gradual shortage of global petroleum resources and the long-term high-order running of the price of crude oil, the development of the tubular cracking furnace process which only depends on the light hydrocarbon as the raw material in the low-carbon olefin industry encounters larger and larger raw material problems, and the production process and the raw material of the low-carbon olefin need to be diversified. The one-step method for directly preparing the low-carbon olefin from the synthesis gas is a process for directly preparing the low-carbon olefin with the carbon atom number less than or equal to 4 by the Fischer-Tropsch synthesis reaction of carbon monoxide and hydrogen under the action of the catalyst, and the process does not need to further prepare the olefin from the synthesis gas through methanol or dimethyl ether like an indirect process, thereby simplifying the process flow and greatly reducing the investment. At present, the shortage of petroleum resources in China, higher and higher external dependence and the soaring international oil price, the process for preparing olefin by selecting synthesis gas can broaden the raw material sources, and the synthesis gas can be produced by taking crude oil, natural gas, coal and renewable materials as raw materials, so that a substitute scheme can be provided for the technical aspect of steam cracking based on high-cost raw materials such as naphtha. The abundant coal resources and the relatively low coal price in China provide good market opportunities for developing processes for refining coal and preparing low-carbon olefins by using synthesis gas. In the vicinity of the rich oil-gas field of natural gas in China, if the natural gas is low in price, the method is also an excellent opportunity for preparing low-carbon olefin by using the synthesis gas. If the abundant coal and natural gas resources in China can be utilized, the synthesis gas (the mixed gas of carbon monoxide and hydrogen) is prepared by gas making, and the development of the petroleum alternative energy technology for preparing low-carbon olefin from the synthesis gas is bound to have great significance for solving the energy problem in China.
The technology for directly synthesizing the low-carbon olefin from the synthesis gas originates from the traditional Fischer-Tropsch synthesis reaction, the carbon number distribution of the traditional Fischer-Tropsch synthesis product conforms to ASF distribution, and each hydrocarbon has the maximum theoretical selectivity, such as C2-C4The maximum selectivity of the fraction is 57%, the gasoline fraction (C)5-C11) The selectivity of (a) is at most 48%. The greater the value of the chain growth probability α, the greater the selectivity of the product heavy hydrocarbons. Once the alpha value is determined, the selectivity of the overall synthesis product is determined, and the chain growth probability alpha value depends on the catalyst composition, particle size, reaction conditions, and the like. In recent years, it has been found that the product distribution deviates from the ideal ASF distribution due to secondary reactions of olefins caused by re-adsorption of olefins on the catalyst. The Fischer-Tropsch synthesis is a strong exothermic reaction, and a large amount of reaction heat promotes the carbon deposition reaction of the catalyst to generate methane and low-carbon alkane more easily, so that the selectivity of the low-carbon alkene is greatly reduced; secondly, the complex kinetic factors also cause disadvantages for selectively synthesizing the low-carbon olefin; the ASF distribution of the Fischer-Tropsch synthesis product limits the selectivity of synthesizing low-carbon olefin. The catalyst for preparing low-carbon olefin from Fischer-Tropsch synthesis gas is mainly iron series catalyst, and is used for improving the selectivity of directly preparing low-carbon olefin from synthesis gasThe Fischer-Tropsch synthesis catalyst can be subjected to physical and chemical modification, for example, a proper pore channel structure of a molecular sieve is utilized, so that the low-carbon olefin can be conveniently diffused away from a metal active center in time, and the secondary reaction of the low-carbon olefin is inhibited; the metal ion dispersibility is improved, and the olefin selectivity is better; the selectivity of the low-carbon olefin can also be improved by changing the interaction between the metal and the carrier; proper transition metal is added, so that the bond energy of the active component and carbon can be enhanced, the generation of methane is inhibited, and the selectivity of low-carbon olefin is improved; the electron promoting assistant is added to promote the increase of CO chemical adsorption heat, the increase of adsorption quantity and the decrease of hydrogen adsorption quantity, so that the selectivity of the low-carbon olefin is increased; eliminating the acid center of the catalyst can inhibit the secondary reaction of the low-carbon olefin and improve the selectivity of the low-carbon olefin. The performance of the catalyst can be obviously improved by the carrier effect of the catalyst carrier and the addition of certain transition metal additives and alkali metal additives, and a novel Fischer-Tropsch synthesis catalyst with non-ASF distribution of products and high activity and high selectivity for preparing low-carbon olefin is developed.
The synthesis of low-carbon olefin directly from synthesis gas has become one of the research hotspots for developing Fischer-Tropsch synthesis catalysts. In patent CN1083415A published by institute of chemical and physical sciences in the chinese academy of sciences, an iron-manganese catalyst system supported by an alkali metal oxide of group IIA such as MgO or a high-silicon zeolite molecular sieve (or a phospho-aluminum zeolite) is used, and strong base K or Cs ions are used as an auxiliary agent, so that high activity (90% of CO conversion) and high selectivity (66% of low-carbon olefin selectivity) can be obtained at a reaction temperature of 300-400 ℃ under a reaction pressure of 1.0-5.0 MPa for preparing low-carbon olefin from synthesis gas. However, the preparation process of the catalyst is complex, and particularly, the preparation and forming process of the carrier zeolite molecular sieve has high cost and is not beneficial to industrial production. In the patent application No. 01144691.9 filed by Beijing university of chemical industry, the Fe is prepared by combining laser pyrolysis with solid phase reaction combined technology3The Fe-based nano catalyst mainly containing C is applied to preparing low-carbon olefin from synthesis gas, and obtains good catalytic effect, the preparation process is relatively complicated due to the need of using a laser pyrolysis technology, and the raw material adopts Fe (CO)5The catalyst cost is high, and industrialization is difficult. In patent ZL03109585.2 filed by Beijing university of chemical industry, manganese, copper, zinc, silicon, potassium and the like are prepared by adopting a vacuum impregnation methodThe Fe/activated carbon catalyst of the auxiliary agent is used for the reaction of preparing low-carbon olefin from synthesis gas, and under the condition of no circulation of raw material gas, the conversion rate of CO is 96 percent, and the selectivity of the low-carbon olefin in hydrocarbon is 68 percent. The iron salt and the auxiliary agent manganese salt used for preparing the catalyst are relatively expensive and relatively difficult to dissolve, and simultaneously, the ethanol is used as a solvent, so that the raw material cost and the operation cost in the catalyst preparation process are inevitably increased. In order to further reduce the cost of the catalyst, in the patent application No. 200710063301.9, the catalyst is prepared by using common medicines and reagents, iron salt is used as ferric nitrate, manganese salt is used as manganese nitrate, potassium salt is used as potassium carbonate, activated carbon is coconut shell carbon, the catalyst needs to be roasted at high temperature and passivated under the protection of flowing nitrogen, special equipment is needed, the preparation process is complex, and the cost is high. And the catalyst has lower CO conversion rate and lower selectivity of the low-carbon olefin in the fixed bed reaction.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of low CO conversion rate and low selectivity of low carbon olefin in the product in the technology of directly synthesizing low carbon olefin by synthesis gas in the prior art, and provides a novel iron-based catalyst for directly synthesizing low carbon olefin by synthesis gas, and the catalyst has the advantages of high CO conversion rate and high selectivity of low carbon olefin in the product.
The second technical problem to be solved by the present invention is a method for preparing a catalyst corresponding to the catalyst described in one of the above technical problems.
The invention also provides a method for directly synthesizing low-carbon olefin by using the synthesis gas of the catalyst.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
the iron-based catalyst for directly synthesizing the low-carbon olefin by the synthesis gas comprises the following components in parts by weight:
a) 18-50 parts of iron element or oxide thereof;
b) 10-25 parts of at least one element selected from manganese and zinc or an oxide thereof;
c) 10-25 parts of at least one element selected from magnesium and strontium or an oxide thereof;
d) 20-60 parts of aluminum element or oxide thereof;
e) 1-5 parts of niobium or an oxide thereof;
f) 1-5 parts of tantalum element or its oxide.
In the above technical solution, the preferable scheme of the iron oxide is ferric oxide (Fe)2O3) The preferable range of the content is 25 to 45 parts.
In the above technical solutions, the preferable solutions of manganese and zinc oxides are manganese dioxide (MnO) respectively2) And zinc oxide (ZnO), the preferable range of the content is 10-20 parts.
In the technical scheme, the preferable schemes of the oxides of magnesium and strontium are respectively magnesium oxide (MgO) and strontium oxide (SrO), and the preferable range of the content is 10-20 parts.
In the above technical solution, the preferred embodiment of the aluminum oxide is α -alumina (α -Al)2O3) The preferable range of the content is 30 to 50 parts.
In the above-mentioned technical means, the preferable means of the oxide of niobium is niobium pentoxide (Nb)2O5) The preferable range of the content is 2 to 4 parts.
In the above technical solutions, a preferable example of the tantalum oxide is tantalum pentoxide (Ta)2O5) The preferable range of the content is 2 to 4 parts.
To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the iron-based catalyst for directly synthesizing the low-carbon olefin by the synthesis gas, which is described in any one of the technical schemes of the technical problems, comprises the following steps:
(1) mixing iron oxide, manganese or zinc containing oxide, magnesium or strontium containing oxide, aluminum containing oxide, niobium containing oxide, tantalum containing oxide and hydroxypropyl methyl cellulose powder, and grinding and mixing in a ball mill to obtain a material A;
(2) adding deionized water into the material A, and kneading to obtain a material B;
(3) extruding the material B into strips, forming and drying to obtain a material C;
(4) and sintering the material C at a high temperature, cooling, crushing and screening to obtain the required iron-based catalyst.
In the above technical scheme, in the preparation method of the iron-based catalyst for directly synthesizing low-carbon olefins from synthesis gas, the dosage of hydroxypropyl methylcellulose in the step (1) is preferably 2-6% of the total weight of all raw materials.
In the technical scheme, the usage amount of the deionized water in the step (2) is preferably 5-10% of the total weight of all the raw materials.
The total weight of all raw materials of the invention is the sum of the weight of iron oxide, manganese or zinc containing oxide, magnesium or strontium containing oxide, aluminum containing oxide, niobium containing oxide and tantalum containing oxide.
In the technical scheme, the preferable range of the milling and mixing time is 2-6 hours.
In the technical scheme, the preferable range of the high-temperature sintering temperature is 1500-1700 ℃.
To solve the third technical problem, the technical scheme of the invention is as follows: the method for directly synthesizing the low-carbon olefin by using the synthesis gas comprises the step of taking the synthesis gas as a raw material, and carrying out contact reaction on the raw material gas and the iron-based catalyst to generate C-containing2～C4The olefin of (1).
In the above technical scheme, H in the synthesis gas2The molar ratio of CO to CO is preferably 1 to 3.
In the technical scheme, the reaction temperature is preferably 250-400 ℃.
In the technical scheme, the reaction pressure is preferably 1.0-3.0 MPa.
In the technical scheme, the volume space velocity of the raw material gas is preferably 500-5000 h-1。
The method of the invention adopts transition metal Mn or Zn, alkaline earth metal Mg or Sr, and transition metal Nb and Ta as catalyst auxiliary agents to modulate the electronic valence state of the active component Fe, thereby being beneficial to improving the CO conversion rate of the catalyst and the selectivity of low-carbon olefin.
The method of the invention adopts the steps of uniformly mixing the active component, the cocatalyst component and the carrier component, and sintering at high temperature to obtain the catalyst with high strength and good thermal stability, and the catalyst can be broken but not crushed in the using process, thereby keeping the stability of the activity of the catalyst.
The method of the invention adds the bonding pore-forming agent hydroxypropyl methyl cellulose in the preparation of the catalyst, and the hydroxypropyl methyl cellulose has large specific surface and rich pore structure, so that the hydroxypropyl methyl cellulose is easy to react with oxygen at high temperature to generate carbon dioxide to be removed, a gap is left on the catalyst, the pore structure of the catalyst is enlarged, and the internal diffusion resistance is reduced.
The reaction conditions for preparing the low-carbon olefin from the synthesis gas are as follows: with H2And CO as a raw material, H2The molar ratio of the CO to the CO is 1-3, the reaction temperature is 250-400 ℃, the reaction pressure is 1.0-3.0 Mpa, and the volume space velocity of the raw material gas is 500-5000 h-1Under the condition, the raw material gas contacts with the iron-based catalyst, and the better technical effect is achieved: the CO conversion rate can reach 99.7 percent, which is improved by 3.7 percent compared with the prior art; the selectivity of the low-carbon olefin in hydrocarbon can reach 76.7 percent, which is improved by 8.7 percent compared with the prior art, and more detailed results are shown in the attached table.
The invention will be further illustrated by the following examples, without limiting the scope of the invention thereto.
Detailed Description
[ example 1 ]
30.0 g of iron (Fe) trioxide are weighed out2O3) 15.0 g manganese dioxide (MnO)2) 15.0 grams of magnesium oxide (MgO), 34.0 grams of alpha-alumina (alpha-Al)2O3) 3.0 g of niobium pentoxide (Nb)2O5) And 3.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing the six raw materials and 4 g of hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; kneading the mixtureFeeding the good material into a strip extruding machine, making into strips with the diameter of 5mm, cutting into columns with the length of 20mm, naturally drying, feeding into a drying device, and drying at 120 ℃ for 8 hours for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1600 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 30% Fe2O3，15％MnO2，15％MgO，34％α-Al2O3，3％Nb2O5，3％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 2 ]
50.0 g of iron (Fe) trioxide are weighed out2O3) 10.0 g manganese dioxide (MnO)2) 10.0 grams of magnesium oxide (MgO), 28.0 grams of alpha-alumina (alpha-Al)2O3) 1.0 g of niobium pentoxide (Nb)2O5) And 1.0 gram of tantalum pentoxide (Ta)2O5) Grinding and mixing six raw materials and 2 g of hydroxypropyl methyl cellulose powder accounting for 2 percent of the total weight of the raw materials in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1600 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 50% Fe2O3，10％MnO2，10％MgO，28％α-Al2O3，1％Nb2O5，1％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 3 ]
20.0 g of iron (Fe) trioxide are weighed out2O3) 25.0 g manganese dioxide (MnO)2) 25.0 grams of magnesium oxide (MgO), 20.0 grams of alpha-alumina (alpha-Al)2O3) 5.0 g of niobium pentoxide (Nb)2O5) And 5.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing six raw materials and 6 g of hydroxypropyl methyl cellulose powder with the weight percentage of 6 percent according to the total weight of the raw materials in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1600 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 20% Fe2O3，25％MnO2，25％MgO，20％α-Al2O3，5％Nb2O5，5％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 4 ]
18.0 g of iron (Fe) trioxide are weighed out2O3) 10.0 g manganese dioxide (MnO)2) 10.0 grams of magnesium oxide (MgO), 60.0 grams of alpha-alumina (alpha-Al)2O3) 1.0 g of niobium pentoxide (Nb)2O5) And 1.0 gram of tantalum pentoxide (Ta)2O5) Grinding and mixing the six raw materials and 4 g of hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials in a ball mill for 4 hours; adding 5 g of deionized water accounting for 5 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruder, making into strips with diameter of 5mm, and cutting into 20mm columnNaturally drying, and then sending into drying equipment, and drying for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1600 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 18% Fe2O3，10％MnO2，10％MgO，60％α-Al2O3，1％Nb2O5，1％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 5 ]
25.0 grams of iron (Fe) trioxide was weighed out2O3) 20.0 g manganese dioxide (MnO)2) 20.0 grams of magnesium oxide (MgO), 31.0 grams of alpha-alumina (alpha-Al)2O3) 2.0 g of niobium pentoxide (Nb)2O5) And 2.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing the six raw materials and 4 g of hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials in a ball mill for 4 hours; adding 10 g of deionized water accounting for 10 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 7.0 hours at 1400 ℃, cooling, crushing and screening into 60-80 meshes to obtain the needed iron-based catalyst for directly synthesizing the low-carbon olefin by using the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 25% Fe2O3，20％MnO2，20％MgO，31％α-Al2O3，2％Nb2O5，2％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 6 ]
Weighing 45.0 gIron (Fe) oxide2O3) 10.0 g manganese dioxide (MnO)2) 10.0 grams of magnesium oxide (MgO), 27.0 grams of alpha-alumina (alpha-Al)2O3) 4.0 g of niobium pentoxide (Nb)2O5) And 4.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing the six raw materials and 4 g of hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining at 1800 ℃ for 3.0 hours, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 45% Fe2O3，10％MnO2，10％MgO，27％α-Al2O3，4％Nb2O5，4％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 7 ]
26.0 grams of iron (Fe) trioxide was weighed out2O3) 10.0 g manganese dioxide (MnO)2) 10.0 grams of magnesium oxide (MgO), 50.0 grams of alpha-alumina (alpha-Al)2O3) 2.0 g of niobium pentoxide (Nb)2O5) And 2.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing the six raw materials and 4 g of hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials in a ball mill for 6 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; drying the precursorAnd feeding the mixture into a high-temperature furnace, calcining the mixture for 5.0 hours at 1500 ℃, cooling the mixture, crushing and screening the mixture into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 26% Fe2O3，10％MnO2，10％MgO，50％α-Al2O3，2％Nb2O5，2％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 8 ]
29.0 g of iron (Fe) trioxide are weighed out2O3) 10.0 g manganese dioxide (MnO)2) 25.0 grams of magnesium oxide (MgO), 30.0 grams of alpha-alumina (alpha-Al)2O3) 1.0 g of niobium pentoxide (Nb)2O5) And 5.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing the six raw materials and 4 g of hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials in a ball mill for 2 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1700 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 29% Fe2O3，10％MnO2，25％MgO，30％α-Al2O3，1％Nb2O5，5％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 9 ]
30.0 g of iron (Fe) trioxide are weighed out2O3) 15.0 g manganese dioxide (MnO)2) 15.0 g of oxideStrontium (SrO), 34.0 g alpha-alumina (alpha-Al)2O3) 3.0 g of niobium pentoxide (Nb)2O5) And 3.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing six raw materials and 6 g of hydroxypropyl methyl cellulose powder with the weight percentage of 6 percent according to the total weight of the raw materials in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1500 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 30% Fe2O3，15％MnO2，15％SrO，34％α-Al2O3，3％Nb2O5，3％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 10 ]
30.0 g of iron (Fe) trioxide are weighed out2O3) 15.0 grams of zinc oxide (ZnO), 15.0 grams of magnesium oxide (MgO), 34.0 grams of alpha-alumina (alpha-Al)2O3) 3.0 g of niobium pentoxide (Nb)2O5) And 3.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing six raw materials and 2 g of hydroxypropyl methyl cellulose powder accounting for 2 percent of the total weight of the raw materials in a ball mill for 2 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; feeding the dried precursor into a high-temperature furnace, calcining at 1700 ℃ for 5.0 hours, cooling, crushing and screening into 60-80 meshes to obtain the required synthesisThe gas is directly synthesized into the low-carbon olefin iron-based catalyst. The prepared iron-based catalyst comprises the following components in percentage by weight: 30% Fe2O3，15％ZnO，15％MgO，34％α-Al2O3，3％Nb2O5，3％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 11 ]
30.0 g of iron (Fe) trioxide are weighed out2O3) 15.0 g zinc oxide (ZnO), 15.0 g strontium oxide (SrO), 34.0 g alpha-alumina (alpha-Al)2O3) 3.0 g of niobium pentoxide (Nb)2O5) And 3.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing the six raw materials and 4 g of hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials in a ball mill for 6 hours; adding 10 g of deionized water accounting for 10 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 3.0 hours at 1600 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 30% Fe2O3，15％ZnO，15％SrO，34％α-Al2O3，3％Nb2O5，3％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ example 12 ]
The catalyst prepared in example 1 was used, and the reaction conditions were changed to prepare low-carbon olefins from synthesis gas, with the experimental results shown in table 2.
[ COMPARATIVE EXAMPLE 1 ]
30.0 g of iron (Fe) trioxide are weighed out2O3) 15.0 g manganese dioxide (MnO)2) 15.0 grams of magnesium oxide (MgO), 37.0 grams of alpha-alumina (alpha-Al)2O3) And 3.0 grams of tantalum pentoxide (Ta)2O5) Five raw materials and 4 g of hydroxypropyl methyl cellulose powder with the weight percentage of 4 percent according to the total weight of the raw materials are milled and mixed in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1600 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 30% Fe2O3，15％MnO2，15％MgO，37％α-Al2O3，3％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
30.0 g of iron (Fe) trioxide are weighed out2O3) 15.0 g manganese dioxide (MnO)2) 15.0 g of magnesium oxide (MgO), 31.0 g of alpha-alumina (alpha-Al)2O3) 6.0 g of niobium pentoxide (Nb)2O5) And 3.0 grams of tantalum pentoxide (Ta)2O5) Grinding and mixing the six raw materials and 4 g of hydroxypropyl methyl cellulose powder accounting for 4 percent of the total weight of the raw materials in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; the dried precursor is sent into a high-temperature furnace, calcined for 5.0 hours at 1600 ℃, cooled and then crushed and sieved into 60-80 meshes, and the required synthesis is obtainedThe gas is directly synthesized into the low-carbon olefin iron-based catalyst. The prepared iron-based catalyst comprises the following components in percentage by weight: 30% Fe2O3，15％MnO2，15％MgO，31％α-Al2O3，6％Nb2O5，3％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
30.0 g of iron (Fe) trioxide are weighed out2O3) 15.0 g manganese dioxide (MnO)2) 15.0 grams of magnesium oxide (MgO), 37.0 grams of alpha-alumina (alpha-Al)2O3) And 3.0 grams of niobium pentoxide (Nb)2O5) Five raw materials and 4 g of hydroxypropyl methyl cellulose powder with the weight percentage of 4 percent according to the total weight of the raw materials are milled and mixed in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1600 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 30% Fe2O3，15％MnO2，15％MgO，37％α-Al2O3，3％Nb2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
[ COMPARATIVE EXAMPLE 4 ]
30.0 g of iron (Fe) trioxide are weighed out2O3) 15.0 g manganese dioxide (MnO)2) 15.0 g of magnesium oxide (MgO), 31.0 g of alpha-alumina (alpha-Al)2O3) 3.0 g of niobium pentoxide (Nb)2O5) And 6.0 grams of tantalum pentoxide (Ta)2O5) Six raw materials and raw material-based total4 g of hydroxypropyl methyl cellulose powder with the weight percentage of 4 percent is milled and mixed in a ball mill for 4 hours; adding 7 g of deionized water accounting for 7 percent of the total weight of the raw materials into the milled and mixed materials, and kneading the materials to be soft; feeding the kneaded material into a strip extruding machine to prepare a strip with the diameter of 5mm, cutting the strip into a column shape with the length of 20mm, naturally drying the strip, feeding the dried strip into drying equipment, and drying the dried strip for 8 hours at 120 ℃ for later use; and (3) feeding the dried precursor into a high-temperature furnace, calcining for 5.0 hours at 1600 ℃, cooling, crushing and screening into 60-80 meshes to obtain the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas. The prepared iron-based catalyst comprises the following components in percentage by weight: 30% Fe2O3，15％MnO2，15％MgO，31％α-Al2O3，3％Nb2O5，6％Ta2O5(ii) a The prepared iron-based catalyst is used for directly synthesizing low-carbon olefin by using synthesis gas under certain reaction conditions, and the experimental results are listed in Table 1.
The reduction conditions of the above examples and comparative examples were:
the temperature is 450 DEG C
Pressure and atmosphere
Catalyst loading 3ml
Catalyst loading 2000 hours-1
Reducing gas H2
Reduction time 8 hours
The reaction conditions are as follows:
phi 8 mm fixed bed reactor
The reaction temperature is 325 DEG C
The reaction pressure is 1.5MPa
Catalyst loading 3ml
Catalyst loading 2000 hours-1
Raw material ratio (mol) H2/CO＝2.5/1
TABLE 1
TABLE 2
Evaluation conditions varied compared to the conditions described in table 1.
Claims (10)
1. The iron-based catalyst for directly synthesizing the low-carbon olefin by the synthesis gas comprises the following components in parts by weight:
a) 18-50 parts of iron oxide;
b) 10-25 parts of at least one selected from oxides of manganese and zinc;
c) 10-25 parts of at least one of oxides of magnesium and strontium;
d) 20-60 parts of an aluminum oxide;
e) 1-5 parts of niobium oxide;
f) 1-5 parts of tantalum oxide.
2. The iron-based catalyst for directly synthesizing low-carbon olefin by using synthesis gas as claimed in claim 1, wherein the iron oxide is ferric oxide, and the content of the iron oxide is 25-45 parts.
3. The iron-based catalyst for directly synthesizing the low-carbon olefin by the synthesis gas as claimed in claim 1, wherein the oxides of manganese and zinc are respectively manganese dioxide and zinc oxide, and the content of the oxides of manganese and zinc is 10-20 parts.
4. The iron-based catalyst for directly synthesizing the low-carbon olefin by using the synthesis gas as claimed in claim 1, wherein the oxides of magnesium and strontium are respectively magnesium oxide and strontium oxide, and the content of the oxides is 10-20 parts.
5. The iron-based catalyst for directly synthesizing the low-carbon olefin by the synthesis gas according to claim 1, wherein the aluminum oxide is alpha-alumina and the content of the aluminum oxide is 30-50 parts.
6. The iron-based catalyst for directly synthesizing low-carbon olefin by using synthesis gas as claimed in claim 1, wherein the oxide of niobium is niobium pentoxide, and the content of the niobium oxide is 2-4 parts.
7. The iron-based catalyst for directly synthesizing low-carbon olefin by using synthesis gas as claimed in claim 1, wherein the tantalum oxide is tantalum pentoxide, and the content of the tantalum oxide is 2-4 parts.
8. The preparation method of the iron-based catalyst for directly synthesizing the low-carbon olefin by the synthesis gas as claimed in any one of claims 1 to 7, which comprises the following steps:
(1) mixing iron oxide, manganese or zinc containing oxide, magnesium or strontium containing oxide, aluminum containing oxide, niobium containing oxide, tantalum containing oxide and hydroxypropyl methyl cellulose powder, and grinding and mixing in a ball mill to obtain a material A;
(2) adding deionized water into the material A, and kneading to obtain a material B;
(3) extruding the material B into strips, forming and drying to obtain a material C;
(4) and sintering the material C at a high temperature, cooling, crushing and screening to obtain the required iron-based catalyst.
9. The method for preparing the iron-based catalyst for directly synthesizing the low-carbon olefin from the synthesis gas according to claim 8, wherein the dosage of the hydroxypropyl methyl cellulose is 2-6% of the total weight of all raw materials, and the high-temperature sintering temperature is 1400-1800 ℃.
10. A method for directly synthesizing low-carbon olefin by using synthesis gas, which comprises the step of contacting and reacting the synthesis gas serving as a raw material with the iron-based catalyst for directly synthesizing the low-carbon olefin by using the synthesis gas according to any one of claims 1 to 7 to generate C-containing catalyst2～C4The olefin of (1).
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| US4861802A (en) * | 1988-02-17 | 1989-08-29 | E. I. Du Pont De Nemours And Company | Preparation of low molecular weight olefinic hydrocarbons using a perovskite catalyst |
| CN103773409A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for directly preparing light alkene by using synthetic gas as raw material |
| CN104437524A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Iron-based catalyst for preparing low-carbon alkane as well as preparation method and using method of iron-based catalyst for preparing low-carbon alkane |
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| US4861802A (en) * | 1988-02-17 | 1989-08-29 | E. I. Du Pont De Nemours And Company | Preparation of low molecular weight olefinic hydrocarbons using a perovskite catalyst |
| CN103773409A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for directly preparing light alkene by using synthetic gas as raw material |
| CN104437524A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Iron-based catalyst for preparing low-carbon alkane as well as preparation method and using method of iron-based catalyst for preparing low-carbon alkane |
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