CN111282573A - Iron-based catalyst and preparation method and application thereof - Google Patents
Iron-based catalyst and preparation method and application thereof Download PDFInfo
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- CN111282573A CN111282573A CN201811501739.5A CN201811501739A CN111282573A CN 111282573 A CN111282573 A CN 111282573A CN 201811501739 A CN201811501739 A CN 201811501739A CN 111282573 A CN111282573 A CN 111282573A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 163
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 239000002912 waste gas Substances 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005977 Ethylene Substances 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 238000005859 coupling reaction Methods 0.000 abstract description 9
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000012495 reaction gas Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100182729 Homo sapiens LY6K gene Proteins 0.000 description 1
- 102100032129 Lymphocyte antigen 6K Human genes 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to an iron-based catalyst in the field of methane catalytic oxidation, which comprises a carrier and Fe loaded on the carrier2O3(ii) a Wherein the carrier is selected from at least one of alumina, silica and titania; preferably, the Fe is based on the total weight of the catalyst2O3The content of (A) is 1.0-15.0 wt%; preferably 4.0 to 10.0 wt%. The catalyst can simply and conveniently separate methane from the waste gas generated in the preparation of ethylene by catalytic oxidation coupling of methane, so that the obtained methane can be recycled to a methane catalytic oxidation reaction kettle for continuous reaction, the utilization rate of raw material methane is improved, the defect that the waste gas can only be treated as waste gas at present is overcome, and the catalyst has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of methane catalytic oxidation, and particularly relates to an iron-based catalyst, and a preparation method and application thereof.
Background
The oxidative coupling of methane to produce ethylene is the most direct and efficient process in methane chemical applications. The reaction involved comprises the following steps: under the action of catalyst, methane and oxygen produce coupling reaction to produce ethylene and ethane, methane (and ethane and ethylene) produce oxidation reaction to produce carbon monoxide and carbon dioxide, and ethane high-temperature dehydrogenation and methane steam conversion reaction to produce hydrogen, etc. After a single pass of the feed through the catalyst bed, about 50 wt% of the methane is converted to ethylene, ethane, and the off-gases hydrogen, carbon monoxide, carbon dioxide, etc. After the material output from the reactor is subjected to carbon dioxide removal and ethylene and ethane separation, the main waste gas comprises unreacted methane, carbon monoxide and hydrogen. In this case, if the exhaust gas is recycled without being treated, the activity of the catalyst for the oxidative coupling of methane may be lowered, thereby greatly affecting the efficiency and yield of the reaction. Therefore, in the current reaction for preparing ethylene by methane oxidation coupling, the waste gas contains more carbon monoxide and hydrogen, the treatment is complex and the cost is high, and the waste gas is usually treated as the waste gas, such as being used as fuel gas for a reaction kettle or being sold, so that the utilization efficiency of carbon in a reaction system is reduced. If the carbon monoxide and hydrogen in the waste gas can be removed, and little or no methane is consumed, methane purification is realized, so that the methane can be circulated back to the methane oxidation coupling reaction kettle to react with fresh methane, and the utilization efficiency of the methane is improved. The prior art has not been studied in this respect because of the high technical difficulty of removing both high concentrations of carbon monoxide and hydrogen without consuming methane, and there are few mention about the catalyst and the reaction conditions.
Carbon monoxide is typically removed by catalytic oxidation. The research on catalysts and catalytic systems involved in this reaction has mainly focused on two areas: automobile exhaust gas treatment (three-wa)y catalyst) and Proton Exchange Membrane Fuel Cells (PEMFCs), preferentially and selectively remove CO in a hydrogen-rich atmosphere. Under normal working conditions, the concentration of CO in the automobile exhaust is lower than 2%. In PEMFCs, natural gas, gasoline, or methanol is first converted into a hydrogen-rich gas (typically having a gas composition of H) through a steam reforming reaction or an autothermal reaction by an on-board fuel processor2: 45-75 vol%, CO: 0.5-2 vol%), then reducing the content of CO as much as possible by a steam conversion device, and removing CO preferentially by catalytic oxidation by a catalyst. From this, it is found that the CO concentration is low in the above two fields, and is usually 2 vol% or less.
However, in the oxidative coupling reaction of methane, the conversion rate of methane is about 50%, the selectivity of CO in the product is 15-25%, and after carbon dioxide is removed and ethylene and ethane are separated out, the CO concentration in the waste gas is about 13-20 vol%. Besides CO, the exhaust gas also contains a small amount of H2. Higher concentration of CO and small amount of H2The activity and stability of the catalyst are adversely affected. It is therefore highly desirable to provide a process for the preferential simultaneous removal of high concentrations of CO and small amounts of H under methane-rich conditions2The method of (1).
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the iron-based catalyst, when the catalyst is used in the method for recovering methane from the waste gas generated in the preparation of ethylene by oxidative coupling of methane, under the condition of methane enrichment, the method preferentially and simultaneously removes high-concentration carbon monoxide and a small amount of hydrogen, consumes little methane, recycles the obtained methane to a methane catalytic oxidation reaction kettle for continuous reaction, and improves the utilization rate of the raw material methane.
To this end, the first aspect of the present invention provides an iron-based catalyst comprising a carrier and Fe supported on the carrier2O3(ii) a Wherein the carrier is selected from at least one of alumina, silica and titania.
In some preferred embodiments of the present invention, the Fe is based on the total weight of the catalyst2O3The content of (A) is 1.0-15.0 wt%; preferably, the Fe2O3The content of (B) is 4.0-10.0 wt%. Within the range, the synergistic effect of the active component (Fe) and the oxide carrier can be exerted, the stability, the activity and the selectivity of the catalyst are improved, and the improvement of the selectivity of carbon monoxide and hydrogen and the reduction of the selectivity of methane are facilitated.
In a second aspect, the present invention provides a method for preparing a catalyst according to the first aspect of the present invention, comprising the steps of:
s1, soaking the carrier in the ferric salt solution, and then filtering, washing, drying and roasting to obtain the catalyst.
In some embodiments of the invention, the iron salt is a water-soluble iron salt; preferably, the iron salt is selected from at least one of ferric chloride, ferric nitrate and ferric sulfate; more preferably, the iron salt is ferric nitrate.
In some embodiments of the invention, the temperature of the drying is 60 to 160 ℃, preferably 80 to 120 ℃; the drying time is 2 to 10 hours, preferably 6 to 8 hours.
In other embodiments of the present invention, the temperature of the roasting is 200-; the roasting time is 2-10 hours, preferably 4-8 hours.
In some embodiments of the invention, firing is carried out after raising the temperature to the firing temperature at a rate of (3-15) deg.C/min, preferably at a rate of (4-12) deg.C/min. Within the range, the distribution of the active component on the carrier is more uniform, and the obtained catalyst has higher activity and stability.
In a third aspect, the present invention provides a process for recovering methane from an offgas from the oxidative coupling of methane to ethylene using a catalyst as described in the first aspect of the present invention or a catalyst prepared by a process as described in the second aspect of the present invention.
In some embodiments of the present invention, methane is obtained after contacting and reacting the exhaust gas from the oxidative coupling of methane to produce ethylene and an oxygen source with the catalyst.
In some preferred embodiments of the present invention, the exhaust gas is contacted with the catalyst after the nitrogen and oxygen are contacted with the catalyst to activate the catalyst.
In some embodiments of the present invention, the oxygen source is oxygen gas or a mixed gas containing oxygen gas; preferably, the oxygen source is oxygen gas and/or air.
In some embodiments of the invention, the total space velocity of the reaction is from 10 to 150L h-1g-1(catalyst), preferably 12 to 130L h-1g-1(catalyst). In the present invention, the total space velocity refers to the sum of the volume space velocity of the exhaust gas and the volume space velocity of the oxygen in the oxygen source.
In some preferred embodiments of the present invention, the volumetric air-to-air ratio of the exhaust gas to the oxygen in the oxygen source is (2-20):1, preferably (5-15): 1.
In some embodiments of the invention, the temperature of the reaction is 200-700 deg.C, preferably 250-600 deg.C.
In other embodiments of the invention, the pressure of the reaction is between 0.08 and 1.0MPa, preferably between 0.1 and 0.4 MPa.
In some preferred embodiments of the invention, the temperature is raised to the reaction temperature at a rate of 2.0-20 deg.C/min, preferably at a rate of 5.0-15 deg.C/min.
In some embodiments of the invention, the off-gas comprises methane, carbon monoxide and hydrogen; preferably, the volume ratio of methane, carbon monoxide and hydrogen is (15-90): 1-25):1, more preferably (15-90): 3-20): 1.
According to the invention, after the waste gas is subjected to a single contact reaction with the catalyst, the effects of carbon monoxide conversion rate of more than 90%, hydrogen conversion rate of more than 85% and methane conversion rate of less than 2% can be achieved, and the obtained methane can be circularly conveyed to the methane catalytic oxidation reaction kettle for continuous reaction.
In addition, the heat generated by the oxidation reaction in the method can be used for directly heating the methane catalytic oxidation material (namely the raw material of the methane oxidative coupling reaction, such as methane, oxygen and the like). It features internal heating to raise temp, and almost 100% of heat can be used. Especially, when the heat is used for heating materials at a high temperature stage, the energy-saving effect is more remarkable.
Fourth inventionAspects provide the use of a catalyst according to the first aspect of the invention, a catalyst prepared according to the process of the second aspect of the invention or a process according to the third aspect of the invention in the field of catalytic oxidation of methane. The tail gas of the methane catalytic oxidation coupling reaction is treated, and finally the waste gas mainly comprises methane, CO and hydrogen. If the waste gas is directly recycled, CO and/or hydrogen in the waste gas can influence the methane catalytic oxidation coupling reaction. The method for recovering methane in the waste gas generated in the preparation of ethylene by oxidative coupling of methane by using the catalyst provided by the invention converts most of CO and hydrogen into CO harmless to the catalytic oxidative coupling reaction of methane2And water can be directly mixed with fresh methane to enter a methane catalytic oxidation coupling device without separation, so that the utilization rate of methane is improved.
The invention has the beneficial effects that: the catalyst can simply and conveniently separate methane from the waste gas generated in the preparation of ethylene by oxidative coupling of methane, so that the obtained methane can be recycled to a methane catalytic oxidation reaction kettle for continuous reaction, the utilization rate of raw material methane is improved, the defect that the waste gas can only be treated as waste gas at present is overcome, and the catalyst has wide application prospect.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
0.68g Fe (NO)3)3·9H2O is dissolved in 30ml of water, 3g of titanium dioxide carrier is added, and the mixture is stirred for 5 hours at room temperature. Drying by evaporation in a water bath at 80 ℃ for 6h at 120 ℃. Then heating to 300 ℃ at the speed of 5 ℃/min in the air and roasting for 5 hours. Cooling to room temperature, tabletting, crushing, sieving, and taking the part of 20-40 meshes to obtain the catalyst: fe2O3/TiO2In which Fe2O3The content of (B) was 4.3 wt%.
0.2g of catalyst Fe was charged into a quartz glass tube reactor (inner diameter: 8mm)2O3/TiO2The catalyst is filled with quartz sand (20-40 meshes) from top to bottom. Nitrogen (40ml/min) and oxygen (4.0ml/min) were passed through the reactor and the temperature was raised to 250 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to an offgas reaction gas (which contains CO15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4.0 ml/min). After 300min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 2
1.87g Fe (NO)3)3·9H2O is dissolved in 50ml of water, 5g of alumina carrier is added, and the mixture is stirred for 5 hours at room temperature. Drying by evaporation in 80 deg.C water bath, and drying at 80 deg.C for 8 hr. Then heating to 600 ℃ at the speed of 10 ℃/min in the air and roasting for 8 hours. Cooling to room temperature, tabletting, crushing, sieving, and taking the part of 20-40 meshes to obtain the catalyst: fe2O3/Al2O3In which Fe2O3The content of (B) was 6.9 wt%.
0.2g of catalyst Fe was charged into a quartz glass tube reactor (inner diameter: 8mm)2O3/Al2O3The catalyst is filled with quartz sand (20-40 meshes) from top to bottom. Nitrogen (100ml/min) and oxygen (10.5ml/min) were passed through the reactor and the temperature was raised to 470 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to an offgas reaction gas (which contains CO20 vol%, H)21 vol%, the balance methane, 100ml/min) and oxygen (10.5 ml/min). After 656min of reaction, CO conversion, CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 3
2.12g Fe (NO)3)3·9H2O was dissolved in 40ml of water, 4g of silica carrier was added, and the mixture was stirred at room temperature for 5 hours. The mixture was evaporated to dryness in a 80 ℃ water bath and dried at 105 ℃ for 7 hours. Then heating to 500 ℃ at the speed of 8 ℃/min in the air and roasting for 6 hours. Cooling to room temperature, tabletting, pulverizing, sieving, and collecting 20-40 mesh fractionAgent: fe2O3/SiO2In which Fe2O3The content of (B) was 9.5 wt%.
0.091g of catalyst Fe is charged into a quartz glass tube reactor (internal diameter 8mm)2O3/SiO2The catalyst is filled with quartz sand (20-40 meshes) from top to bottom. Nitrogen (180ml/min) and oxygen (18ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to an offgas reaction gas (which contains CO16 vol%, H)22 vol%, the balance methane, 180ml/min) and oxygen (18 ml/min). After 300min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Example 4
The difference from example 2 is that 5g of titanium dioxide was added as the carrier. The catalyst obtained was Fe2O3/TiO2In which Fe2O3The content of (B) was 6.9 wt%. The test results are shown in Table 1.
Example 5
The difference from example 2 is that 5g of silica is added as support. The catalyst obtained was Fe2O3/SiO2In which Fe2O3The content of (B) was 6.9 wt%. The test results are shown in Table 1.
Example 6
The difference from example 2 is that 0.68g Fe (NO)3)3·9H2O was dissolved in 30ml of water, and 3g of an alumina carrier was added. The catalyst obtained was Fe2O3/Al2O3In which Fe2O3The content of (B) was 4.3 wt%. The test results are shown in Table 1.
Example 7
The difference from example 2 is that 2.12g Fe (NO)3)3·9H2O was dissolved in 40ml of water, and 4g of an alumina carrier was added. The catalyst obtained was Fe2O3/Al2O3In which Fe2O3The content of (B) was 9.5 wt%. The test results are shown in Table 1.
Example 8
The difference from example 2 is that the temperature was raised to 600 ℃ at a rate of 10 ℃/min and maintained for 30 min. The test results are shown in Table 1.
Example 9
The difference from example 2 is that the temperature was raised to 250 ℃ at a rate of 10 ℃/min and maintained for 30 min. The test results are shown in Table 1.
Example 10
The difference from example 2 was that nitrogen (40ml/min) and oxygen (4.2ml/min) were introduced, and the temperature was raised to 470 ℃ at a rate of 10 ℃/min and maintained for 30 min. Switching to an offgas reaction gas (which contains CO20 vol%, H)21 vol%, the balance methane, 40ml/min) and oxygen (4.2 ml/min). The test results are shown in Table 1.
Example 11
The difference from example 2 was that 0.091g of catalyst was charged, nitrogen (180ml/min) and oxygen (18.9ml/min) were passed through, and the temperature was raised to 470 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to an offgas reaction gas (which contains CO20 vol%, H)21 vol%, the balance methane, 180ml/min) and oxygen (18.9 ml/min). The test results are shown in Table 1.
Example 12
In a quartz glass tube reactor (inner diameter of 8mm), 0.2g of the catalyst prepared in example 2 was charged, and the catalyst was packed with quartz sand (20 to 40 mesh) on the upper and lower sides. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to an offgas reaction gas (which contains CO15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 300min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
TABLE 1
Comparative example 1
Into a quartz glass tube reactor (inner diameter: 8mm), 0.2g of Fe as a catalyst prepared in example 2 was charged2O3/TiO2The catalyst is filled with quartz sand (20-40 meshes) from top to bottom. Nitrogen (20ml/min) and oxygen (2ml/min) were passed through the reactor and the temperature was raised to 800 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to an offgas reaction gas (which contains CO15 vol%, H)25 vol%, the remainder being methane, 20ml/min) and oxygen (2 ml/min). After 300min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 2.
Comparative example 2
0.2g of Au/TiO catalyst was charged into a quartz glass tube reactor (inner diameter: 8mm)2The catalyst is filled with quartz sand (20-40 meshes) from top to bottom. Nitrogen (40ml/min) and oxygen (4ml/min) were passed through the reactor and the temperature was raised to 600 ℃ at a rate of 10 ℃/min and held for 30 min. Switching to an offgas reaction gas (which contains CO15 vol%, H)25 vol%, the remainder being methane, 40ml/min) and oxygen (4 ml/min). After 300min of reaction, the CO conversion and CH were determined by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 2.
TABLE 2
From the above examples, it can be seen that the present invention can rapidly and simply purify the waste gas from the preparation of ethylene by methane catalytic oxidation coupling under the action of the iron-based catalyst, obtain high-purity methane, return the methane to the reaction kettle for preparing ethylene by methane catalytic oxidation coupling to continue the reaction, and maintain the high activity and selectivity of the methane catalytic oxidation catalyst in the long-term reaction.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. An iron-based catalyst comprising a carrier and Fe supported on the carrier2O3(ii) a Wherein the carrier is selected from at least one of alumina, silica and titania;
preferably, the Fe is based on the total weight of the catalyst2O3The content of (A) is 1.0-15.0 wt%; preferably 4.0 to 10.0 wt%.
2. A method of preparing the catalyst of claim 1, comprising the steps of:
s1, soaking the carrier in the ferric salt solution, and then filtering, washing, drying and roasting to obtain the catalyst.
3. The method of claim 2, wherein the iron salt is a water-soluble iron salt; preferably, the iron salt is selected from at least one of ferric chloride, ferric nitrate and ferric sulfate; more preferably, the iron salt is ferric nitrate.
4. A method according to claim 2 or 3, characterized in that the temperature of the drying is 60-160 ℃, preferably 80-120 ℃; the drying time is 2-10 hours, preferably 6-8 hours; and/or the presence of a gas in the gas,
the roasting temperature is 200-1000 ℃, and preferably 300-700 ℃; the roasting time is 2-10 hours, preferably 4-8 hours.
5. A method according to any one of claims 2 to 4, characterized in that the calcination is carried out after the temperature has been raised to the calcination temperature at a rate of (3-15) C/min, preferably at a rate of (4-12) C/min.
6. A process for recovering methane from an offgas from the oxidative coupling of methane to ethylene, using a catalyst as claimed in claim 1 or a catalyst prepared by a process as claimed in any of claims 2 to 5.
7. The method according to claim 6, wherein methane is obtained after the contact reaction of the waste gas from the oxidative coupling of methane to produce ethylene and an oxygen source with the catalyst; preferably, after the catalyst is activated by nitrogen and oxygen, the exhaust gas is contacted with the catalyst for reaction; further preferably, the oxygen source is oxygen or a mixed gas containing oxygen; still further preferably, the oxygen source is oxygen gas and/or air.
8. The process of claim 7, wherein the total space velocity of the reaction is from 10 to 150L h-1g-1(catalyst), preferably 12 to 130L h-1g-1(catalyst); and/or the presence of a gas in the gas,
the volume-air ratio of the waste gas to the oxygen in the oxygen source is (2-20) to 1, preferably (5-15) to 1; and/or the presence of a gas in the gas,
the reaction temperature is 200-700 ℃, preferably 250-600 ℃; and/or the presence of a gas in the gas,
the pressure of the reaction is 0.08-1.0MPa, preferably 0.1-0.4 MPa; and/or the presence of a gas in the gas,
the temperature is raised to the reaction temperature at a rate of 2.0-20 deg.C/min, preferably at a rate of 5.0-15 deg.C/min.
9. The method of claim 7 or 8, wherein the off-gas comprises methane, carbon monoxide and hydrogen; preferably, the volume ratio of methane, carbon monoxide and hydrogen is (15-90): 1-25):1, more preferably (15-90): 3-20): 1.
10. Use of a catalyst according to claim 1, a catalyst prepared by a process according to any one of claims 2 to 5 or a process according to any one of claims 6 to 9 in the catalytic oxidation of methane.
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