CN112940771B - Application of metal organic framework material in Fischer-Tropsch synthesis reaction and Fischer-Tropsch synthesis method - Google Patents
Application of metal organic framework material in Fischer-Tropsch synthesis reaction and Fischer-Tropsch synthesis method Download PDFInfo
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- CN112940771B CN112940771B CN202110138904.0A CN202110138904A CN112940771B CN 112940771 B CN112940771 B CN 112940771B CN 202110138904 A CN202110138904 A CN 202110138904A CN 112940771 B CN112940771 B CN 112940771B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
Abstract
The invention relates to the technical field of Fischer-Tropsch synthesis, and discloses application of a metal organic framework material in Fischer-Tropsch synthesis reaction and a Fischer-Tropsch synthesis method, wherein the metal organic framework material is selected from at least one of MIL-101 (Fe), MIL-53 (Fe), ZIF-100 (Co) and ZIF-67 (Co). The invention takes the metal organic framework material as the catalyst for the Fischer-Tropsch synthesis reaction, and can obviously improve the conversion rate of CO and C 5 + Selectivity, lowering of CH 4 And (4) selectivity.
Description
Technical Field
The invention relates to the technical field of Fischer-Tropsch synthesis, and discloses application of a metal organic framework material in Fischer-Tropsch synthesis reaction and a Fischer-Tropsch synthesis method.
Background
Fischer-Tropsch (F-T) synthesis is a catalytic process for the synthesis of liquid fuels. The reaction is an exothermic reaction in which hydrogen and carbon monoxide in the synthesis gas react to form valuable hydrocarbon products under the action of a catalyst. Generally, fischer-tropsch synthesis can be classified into 3 types, i.e., a Coal-to-liquids (CTL) line in which Coal is a raw material, a Gas-to-liquids (GTL) line in which natural Gas is a raw material, and a Biomass-to-liquids (BTL) line in which Biomass is a raw material, depending on the raw material. The Fischer-Tropsch synthesis technology has important strategic significance for China rich in coal and little in oil, and the research and development of high-efficiency catalysts are the primary conditions for realizing industrialization of Fischer-Tropsch synthesis.
The specific surface area, thermal stability, mechanical strength and the like of the Fischer-Tropsch synthesis catalyst have important influences on the improvement of catalytic activity and the improvement of product selectivity. The active components of the existing Fischer-Tropsch synthesis catalyst are ideal transition metals such as Fe, co, ni and Ru, and the activity is high. However, the noble metal Ru is expensive, so that the wide use of the noble metal Ru is limited and the noble metal Ru is only used for basic research; the Ni-based catalyst is easy to generate methane due to too strong hydrogenation capacity, and the application is limited; the Fe-based and Co-based catalysts are applied in industrial production, but the preparation process of the Fe-based and Co-based catalysts is complex.
Therefore, the exploration of the catalyst with high activity and high stability as the Fischer-Tropsch synthesis catalyst has important significance.
Disclosure of Invention
The invention aims to solve the problems of high cost, limited application, complex preparation process and the like of the existing Fischer-Tropsch synthesis catalyst, and provides application of a metal organic framework material in Fischer-Tropsch synthesis reaction and a Fischer-Tropsch synthesis method 5 + And (4) selectivity.
In order to achieve the above object, the present invention provides, in a first aspect, a use of a metal-organic framework material selected from at least one of MIL-101 (Fe), MIL-53 (Fe), ZIF-100 (Co), and ZIF-67 (Co) in a fischer-tropsch synthesis reaction.
In a second aspect the invention provides a process for fischer-tropsch synthesis, the process comprising: in the presence of a catalyst, the catalyst contains CO and H 2 The raw material gas is subjected to Fischer-Tropsch synthesis reaction, and the catalyst is a metal organic framework material.
By adopting the technical scheme, the metal organic framework material is used as the catalyst for the Fischer-Tropsch synthesis reaction, so that the conversion rate of CO and C can be obviously improved 5 + Selectivity, decrease of CH 4 And (4) selectivity. For example, in the embodiment 1 of the present invention, a mass ratio of 1:1.2 ZIF-100 (Co) and ZIF-67 (Co) as catalysts, giving a CO conversion of 92%, CH 4 Selectivity of 8% and C 5 + The selectivity is 86%; while comparative example 1 was prepared by using conventional Co-Al 2 O 3 As a catalyst, the conversion of CO is only 80%, CH 4 Selectivity of only 12%, C 5 + The selectivity was only 73%.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As mentioned above, the first aspect of the present invention provides a use of a metal organic framework material selected from at least one of MIL-101 (Fe), MIL-53 (Fe), ZIF-100 (Co) and ZIF-67 (Co) in a Fischer-Tropsch synthesis reaction.
In some embodiments of the present invention, preferably, the metal organic framework material is ZIF-100 (Co) and/or ZIF-67 (Co), which is more favorable for improving the selectivity of the target product.
According to the present invention, preferably, when the metal organic framework material is ZIF-100 (Co) and ZIF-67 (Co), the mass ratio of ZIF-100 (Co) to ZIF-67 (Co) is 1:1-1.5, more preferably 1:1.1-1.4. In this preferable case, the selectivity of the target product can be further improved.
In a second aspect, the present invention provides a fischer-tropsch synthesis process, the process comprising: in the presence of a catalyst, the catalyst will contain CO and H 2 The raw material gas is subjected to Fischer-Tropsch synthesis reaction, and the catalyst is a metal organic framework material. According to the invention, the metal organic framework material is used as the catalyst in the Fischer-Tropsch synthesis reaction, so that the Fischer-Tropsch synthesis reaction can be promoted to be carried out efficiently.
The invention has wide selection range of the metal organic framework material, and preferably, the metal organic framework material is selected from at least one of MIL-101 (Fe), MIL-53 (Fe), ZIF-100 (Co) and ZIF-67 (Co); further preferably, the metal organic framework material is ZIF-100 (Co) and/or ZIF-67 (Co). When the metal organic framework material is ZIF-100 (Co) and ZIF-67 (Co), the quality between the two materials is as described above, and details are not repeated here.
The preparation method of the metal organic framework material is not particularly limited, and the metal organic framework material can be prepared by the existing preparation method in the field, preferably by a hydrothermal synthesis method, and then is subjected to tabletting, grinding and sieving treatment.
In some embodiments of the present invention, preferably, the feed gas comprises CO and H 2 In a molar ratio of1-2:1, preferably 1.5 to 1.8:1.
in some embodiments of the present invention, it is more advantageous to improve the catalytic effect and increase the selectivity of the target product by mixing the raw material gas and the catalyst in a suitable ratio, and preferably, the volume space velocity of the raw material gas is 1.5 to 2.5NL/h/g, and more preferably, 1.8 to 2.1NL/h/g. In the present invention, "NL/h/g" represents the volume of feed gas passing per gram of catalyst per hour, and NL is normal liter and represents the volume at the standard condition of 1 atmosphere at 20 degrees Celsius.
In some embodiments of the invention, preferably, the conditions of the fischer-tropsch synthesis reaction comprise: the temperature is 170-240 ℃, the pressure is 1-4MPa, and the time is 60-100h; preferably, the conditions of the Fischer-Tropsch synthesis reaction include: the temperature is 180-225 deg.C, and the pressure is 2-3MPa.
The inventor of the invention finds that the application of the metal organic framework material as the catalyst in the Fischer-Tropsch synthesis reaction meeting the specific conditions can obtain higher CO conversion rate and C 5 + Selectivity, lower CH 4 And (4) selectivity.
The apparatus for carrying out the Fischer-Tropsch synthesis reaction according to the present invention is not particularly limited, and may be an apparatus commonly used in the art, including, but not limited to, a slurry bed reactor, for example.
In order to clearly describe the Fischer-Tropsch synthesis process of the present invention, a preferred embodiment is provided below for illustration:
placing ZIF-100 (Co) and/or ZIF-67 (Co) in a slurry bed reactor, and introducing CO and H 2 In a molar ratio of 1.5 to 1.8:1, performing Fischer-Tropsch synthesis reaction for 60-100h under the conditions that the temperature is 180-225 ℃, the pressure is 2-3MPa and the volume space velocity of the raw material gas is 1.8-2.1NL/h/g.
The pressures described herein are all expressed as gauge pressures unless otherwise specified.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
Example 1
ZIF-100 (Co) and ZIF-67 (Co) were mixed in the following ratio of 1:1.2 mass ratio, placing in a slurry bed reactor, and introducing CO and H 2 In a molar ratio of 1.5:1, carrying out Fischer-Tropsch synthesis reaction for 75h under the conditions that the temperature is 190 ℃, the pressure is 2MPa and the volume space velocity of the raw material gas is 2 NL/h/g.
Example 2
ZIF-100 (Co) is placed in a slurry bed reactor, and CO and H are introduced 2 In a molar ratio of 1.5:1, carrying out Fischer-Tropsch synthesis reaction for 100 hours under the conditions that the temperature is 200 ℃, the pressure is 2.5MPa and the volume space velocity of the raw material gas is 1.8 NL/h/g.
Example 3
ZIF-67 (Co) is placed in a slurry bed reactor, and CO and H are introduced 2 In a molar ratio of 1.5:1, carrying out the Fischer-Tropsch synthesis reaction for 87h under the conditions that the temperature is 195 ℃, the pressure is 3MPa and the volume space velocity of the raw material gas is 2.1NL/h/g.
Example 4
MIL-101 (Fe) is placed in a slurry bed reactor, and CO and H are introduced 2 In a molar ratio of 1.5:1, carrying out the Fischer-Tropsch synthesis reaction for 90 hours under the conditions that the temperature is 210 ℃, the pressure is 3MPa and the volume space velocity of the raw material gas is 1.8 NL/h/g.
Example 5
MIL-53 (Fe) is placed in a slurry bed reactor, and CO and H are introduced 2 In a molar ratio of 1.5:1, carrying out the Fischer-Tropsch synthesis reaction for 100 hours under the conditions that the temperature is 225 ℃, the pressure is 2.5MPa and the volume space velocity of the raw material gas is 1.9 NL/h/g.
Example 6
The method of example 1 was followed, except that the mass ratio of ZIF-100 (Co) to ZIF-67 (Co) was changed to 1:1, carrying out Fischer-Tropsch synthesis reaction.
Example 7
The method of example 1 was followed, except that the mass ratio of ZIF-100 (Co) to ZIF-67 (Co) was changed to 1:2, carrying out Fischer-Tropsch synthesis reaction.
Example 8
The process of example 2 is followed except that the feed gas isIn CO and H 2 Was changed to 1:1, carrying out Fischer-Tropsch synthesis reaction.
Example 9
The process of example 2 was followed except that CO and H were added to the feed gas 2 Was changed to 3:1, carrying out Fischer-Tropsch synthesis reaction.
Example 10
The Fischer-Tropsch synthesis reaction was carried out as in example 2, except that the volume space velocity of the feed gas was changed to 1.5 NL/h/g.
Example 11
The Fischer-Tropsch synthesis reaction was carried out according to the procedure of example 2, except that the volume space velocity of the feed gas was changed to 1NL/h/g.
Example 12
The procedure of example 2 was followed except that the temperature was changed to 230 ℃ to carry out the Fischer-Tropsch synthesis reaction.
Example 13
The procedure of example 2 was followed except that the temperature was changed to 250 ℃ to carry out the Fischer-Tropsch synthesis reaction.
Example 14
The Fischer-Tropsch synthesis reaction was carried out as in example 2, except that the pressure was changed to 1 MPa.
Example 15
The Fischer-Tropsch synthesis reaction was carried out as in example 2, except that the pressure was changed to 4.5 MPa.
Comparative example 1
The procedure is as in example 2, except that conventional Co-Al is used 2 O 3 Catalyst (relative to Al) 2 O 3 And the supported amount of Co is 15 wt%) instead of ZIF-100 (Co), and carrying out Fischer-Tropsch synthesis reaction.
The CO conversion and CH in the above examples and comparative examples were calculated 4 Selectivity and C 5 + The selectivity, calculated as shown in table 1, wherein,
TABLE 1
As can be seen from the results in Table 1, compared with the conventional Fischer-Tropsch synthesis catalyst, the Fischer-Tropsch synthesis reaction using the metal organic framework material as the catalyst can significantly improve the CO conversion rate and the C content 5 + Selectivity, lowering of CH 4 And (4) selectivity. Furthermore, when the ZIF-100 (Co) and/or ZIF-67 (Co) is/are used as a catalyst to carry out Fischer-Tropsch synthesis reaction under the preferable Fischer-Tropsch synthesis conditions, the CO conversion rate can reach more than 85%, and CH 4 Selectivity of less than 10 percent, C 5 + The selectivity reaches more than 82 percent, namely, the reaction is carried out by matching the preferable metal organic framework material with the preferable Fischer-Tropsch synthesis condition, so that the effect can be further highlighted; but does not satisfy the above-mentioned synergistic conditions and the obtained effect is not good.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A fischer-tropsch synthesis process, comprising: in the presence of a catalyst, the catalyst contains CO and H 2 The raw material gas is subjected to Fischer-Tropsch synthesis reaction, and the catalyst is a metal organic framework material;
the metal organic framework material is selected from at least one of MIL-101 (Fe), MIL-53 (Fe), ZIF-100 (Co) and ZIF-67 (Co).
2. The method of claim 1, wherein the metal organic framework material is ZIF-100 (Co) and/or ZIF-67 (Co).
3. The method of claim 2, wherein when the metal organic framework material is ZIF-100 (Co) and ZIF-67 (Co), a mass ratio of ZIF-100 (Co) to ZIF-67 (Co) is 1:1-1.5.
4. The method of claim 3, wherein when the metal organic framework material is ZIF-100 (Co) and ZIF-67 (Co), the mass ratio of ZIF-100 (Co) to ZIF-67 (Co) is 1:1.1-1.4.
5. The method according to any of claims 1-4, wherein the feed gas is CO and H 2 In a molar ratio of 1-2:1;
and/or the volume space velocity of the feed gas is 1.5-2.5 NL/h/g.
6. The method of claim 5, wherein the feed gas comprises CO and H 2 In a molar ratio of 1.5 to 1.8:1;
and/or the volume space velocity of the feed gas is 1.8-2.1NL/h/g.
7. The process of any one of claims 1 to 4 and 6, wherein the Fischer-Tropsch synthesis reaction conditions comprise: the temperature is 170-240 ℃; the pressure is 1-4MPa; the time is 60-100h.
8. The process of claim 7, wherein the Fischer-Tropsch synthesis reaction conditions comprise: the temperature is 180-225 ℃; the pressure is 2-3MPa.
9. The process of claim 5, wherein the Fischer-Tropsch synthesis reaction conditions comprise: the temperature is 170-240 ℃; the pressure is 1-4MPa; the time is 60-100h.
10. The process of claim 9, wherein the fischer-tropsch synthesis reaction conditions comprise: the temperature is 180-225 ℃; the pressure is 2-3MPa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106488803A (en) * | 2014-05-16 | 2017-03-08 | 陶氏环球技术有限责任公司 | The method of synthesis cementite fischer-tropsch catalysts |
| WO2019175717A1 (en) * | 2018-03-14 | 2019-09-19 | Desiccant Rotors International Private Limited | Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof |
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| CN106488803A (en) * | 2014-05-16 | 2017-03-08 | 陶氏环球技术有限责任公司 | The method of synthesis cementite fischer-tropsch catalysts |
| WO2019175717A1 (en) * | 2018-03-14 | 2019-09-19 | Desiccant Rotors International Private Limited | Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof |
Non-Patent Citations (2)
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| 一步热解可控制备多孔炭限域Co纳米颗粒及其费-托反应研究;郭立鹏;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》;20180615;第1.3.2、1.4、2.3节 * |
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