CN114345357A - Preparation method of isothermal methanation catalyst - Google Patents
Preparation method of isothermal methanation catalyst Download PDFInfo
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- CN114345357A CN114345357A CN202011090683.6A CN202011090683A CN114345357A CN 114345357 A CN114345357 A CN 114345357A CN 202011090683 A CN202011090683 A CN 202011090683A CN 114345357 A CN114345357 A CN 114345357A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 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 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 24
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 15
- 239000012018 catalyst precursor Substances 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- 239000011964 heteropoly acid Substances 0.000 claims description 13
- 238000004537 pulping Methods 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 150000002823 nitrates Chemical class 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000012546 transfer Methods 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000571 coke Substances 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000011701 zinc Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
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- 230000001568 sexual effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of catalysis, and relates to an isothermal methanation catalyst and a preparation method thereof. Preparing a modified mesoporous alumina carrier by the synergistic effect of multi-metal components such as Cu, Zn, Ce, Zr, Mo, Mn, La and the like and adopting a hydrothermal treatment process, and then obtaining a precursor with good specific surface area and pore diameter and excellent heat and mass transfer performance by means of drying, roasting, tabletting and the like; bimetallic Ni-Ce is used as an active component to prepare the catalyst. The catalyst prepared by the method has good activity and stability, and solves the problems of poor heat and mass transfer performance, poor stability, poor mechanical strength and the like of the traditional methane synthesis catalyst under the condition of an isothermal fixed bed reactor. Under the condition of a one-stage isothermal non-cyclic reaction process, when the composition of the coke oven gas is 6-10% of CO, the CO is2 2~5%，C2H6 1~4%，H255-60% and the balance of N2Airspeed of 5000-10000 h‑1Under the conditions of pressure of 1.5-3.0 MPa and temperature of 250-400 ℃, CO and CO2The conversion rate reaches more than 99.0 percent.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to an isothermal methanation catalyst and a preparation method thereof.
Background
In recent years, the consumption proportion of natural gas in China is increasing day by day, the consumption of natural gas in China reaches 3300 billion cubic meters according to the forecast of relevant institutions at the end of 2020, and the supply and demand gaps are serious. Due to the energy characteristics of rich coal, poor oil and less gas in China, the prepared synthetic natural gas not only can produce high-grade clean fuel gas resources, but also can reduce the pollution of coal combustion to the environment, and has great social and economic benefits.
The methanation technology is taken as a core technology for preparing the synthetic natural gas, the circulation multi-section adiabatic fixed bed methanation technology is mainly adopted in the industry at present, the reaction temperature of the technology is high, the heat transfer rate is low, the process flow is complex, the temperature runaway is easily caused by the fault of a circulation compressor, and the requirement on the high temperature resistance of a reactor and a catalyst is strict. Compared with the isothermal fixed bed methanation process, the isothermal fixed bed methanation process has the advantages of high heat exchange efficiency, simple process flow, small number of reactors and the like because water or other liquid is adopted in the reactor as a refrigerant to take away reaction heat. The isothermal bed reactor can effectively avoid the problems of high-temperature sintering or carbon deposition of the catalyst in the fixed bed reactor and the like. However, because the methanation reaction is a strong exothermic reaction, although the isothermal fixed bed reactor can effectively remove the reaction heat, the heat released in the reaction process has higher requirements on the self heat transfer performance of the catalyst, so that the development of the isothermal methanation catalyst which is suitable for the isothermal fixed bed and has good activity, high stability and excellent heat transfer performance is necessary.
Chinese patent CN105195160A describes an isothermal methanation catalyst and a preparation method thereof, the isothermal methanation catalyst takes a composite oxide formed by magnesium, aluminum and silicon as a shaping catalyst carrier, nickel as an active component, and the space velocity is 4000h-1Pressure 2.0Mpa, temperature 400 ℃, inlet gas CO: 3.63% of CO2: the 1.3 percent isothermal fixed bed shows good low-temperature activity, but the patent adopts a strip extrusion molding mode to obtain a carrier, although the carrier has better external surface area and rich pore channels, the strength of the strip extrusion molded catalyst is lower, the activity and the stability of the catalyst are difficult to ensure after long-term use, and the stability of the catalyst is not mentioned in the patent.
At present, the isothermal methanation is more and more emphasized by domestic and foreign scientific research institutes due to short process flow and low energy consumption. One of the key technologies for developing a low-temperature and high-efficiency methanation catalyst as isothermal methanation is an important subject to be solved by researchers at present.
Disclosure of Invention
The purpose of the invention is as follows: provides a preparation method of isothermal methane synthesis catalyst. The problems of poor heat and mass transfer performance, poor stability, poor mechanical strength and the like of the traditional methane synthesis catalyst under the condition of an isothermal fixed bed reactor are solved.
The invention has the main characteristics that:
(1) preparing a modified mesoporous alumina precursor by a hydrothermal treatment process through the synergistic effect of multi-metal components such as Cu, Zn, Ce, Zr, Mo, Mn, La and the like, and then obtaining a carrier with good specific surface area, pore diameter and heat transfer and mass transfer performance through means such as drying, roasting, tabletting and the like;
(2) the bimetallic Ni-Ce is used as an active component, the catalyst has no carbon deposition on the surface and in a pore channel after being used for a long time under the modulation action of phosphotungstic heteropoly acid, and is not sintered and has good stability;
(3) under the condition of a one-stage isothermal non-cyclic reaction process, when the composition of the coke oven gas is 6-10% of CO, the CO is2 2~5%，C2H6 1~4%，H255-60% and the balance of N2Airspeed of 5000-10000 h-1Under the conditions of pressure of 1.5-3.0 MPa and temperature of 250-400 ℃, CO and CO2The conversion rates respectively reach more than 99.0 percent.
The invention provides a preparation method of an isothermal methanation catalyst, which is characterized in that the catalyst is obtained by the following steps:
(1) preparation of the carrier: calcining pseudo-boehmite in air atmosphere to obtain gamma-Al2O3(ii) a Mixing gamma-Al2O3Adding deionized water into the autoclave lined with polytetrafluoroethylene, uniformly stirring, adding nitric acid to adjust the pH value of the solution, heating and boosting the temperature, and then carrying out hydrothermal treatment; putting the material after the hydrothermal treatment into a high-pressure kettle lined with polytetrafluoroethylene, putting an aqueous solution of one or a mixture of nitrates of Cu, Zn, Ce, Zr, Mo, Mn and La into the high-pressure kettle, controlling the temperature and the pressure, fully mixing and pulping for modification treatment; and drying, roasting and tabletting the modified material to obtain the modified mesoporous alumina carrier.
(2) Preparation of active ingredients: dissolving nitrates of Ni and Ce in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 5.5-6.5 to obtain an impregnation liquid rich in active components;
(3) preparation of the catalyst:
controlling the temperature to be 70-90 ℃, and soaking the mesoporous alumina carrier in the impregnating solution for 1.0-3.0 h in the same volume; and taking out the impregnated catalyst precursor, drying and roasting to obtain the catalyst finished product.
In the step, the molar ratio of Al to Cu to Zn to Ce to Zr to Mo to Mn to La is 1: 0.1-0.5.
In the step, the loading amounts of the active components Ni and Ce are 5-10% and 1-3% of the weight of the catalyst respectively.
In the steps, the roasting temperature is 500-550 ℃, and the roasting time is 3-4 h.
The PH value of the hydrothermal treatment solution in the step is 5.5-6.5.
The hydrothermal treatment temperature in the above steps is 150-200 ℃, and the pressure is 1.0-2.0 MPa.
The hydrothermal treatment time in the above steps is 3-4 h.
In the above steps, the temperature of the carrier modification treatment is 150-200 ℃, and the pressure is 1.0-2.0 MPa.
In the steps, the pulping time of the carrier modification treatment is 20-30 min.
In the above step, the roasting temperature of the carrier is 400-550 ℃, and the roasting time is 4-5 h.
In the above step, the roasting temperature of the catalyst precursor is 300-450 ℃, and the roasting time is 2-3 h.
A typical laboratory preparation procedure of the present invention is as follows:
1) placing pseudo-boehmite into a muffle furnace, roasting for 3-4 h at the temperature of 500-550 ℃ in the air atmosphere to obtain gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment in an autoclave for 3-4 h under the conditions that the pH value of the solution is 5.5-6.5, the temperature is 150-200 ℃, and the pressure is 1.0-2.0 MPa; 3) adding 7-55 g of one or more oxides of zinc, copper, molybdenum, manganese, lanthanum and cerium into the materials, and pulping for 20-30 min for modification treatment under the conditions that the temperature is 150-200 ℃ and the pressure is 1.0-2.0 MPa; 4) roasting the modified material for 4-5 hours at the temperature of 400-550 ℃; 5) mixing Ni (NO)3)2•6H2O、Ce(NO3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 5.5-6.5 to obtain an impregnation liquid rich in active components; 6) soaking the mesoporous alumina carrier in the impregnating solution for 1.0-3.0 h in the same volume at the temperature of 70-90 ℃; 7) and drying the impregnated catalyst precursor, and roasting at 300-450 ℃ for 2-3 h to obtain a catalyst finished product.
The isothermal bed methane synthesis catalyst prepared by the method is simple in preparation method, beneficial to industrial production and good in activity and stability.
Detailed Description
The process of the present invention is described in detail below with reference to examples, but the examples are only illustrative and are not intended to limit the scope of the present invention.
Example 1
1) 200g of pseudo-boehmite is put into a muffle furnace and is roasted for 4 hours at the temperature of 500 ℃ in the air atmosphere to obtain gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment for 4h in an autoclave under the conditions that the pH value of the solution is 5.5, the temperature is 200 ℃ and the pressure is 1.0 MPa; 3) adding 10g of zinc, 5g of copper and 3g of cerium oxide into the materials, and pulping for 20min at the temperature of 150 ℃ and the pressure of 1.0MPa for modification treatment; 4) roasting the modified material for 4 hours at the temperature of 450 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 5.5 to obtain an impregnation solution rich in active components; 6) soaking a mesoporous alumina carrier in the impregnating solution for 2.0 hours at the temperature of 75 ℃ in the same volume; 7) and drying the impregnated catalyst precursor, and roasting at 350 ℃ for 2h to obtain a finished catalyst Y-1.
Example 2
1) 200g of pseudo-boehmite is put into a muffle furnace and roasted for 3h under the air atmosphere and the temperature of the muffle furnace is 550 ℃, so that gamma-Al is obtained2O3(ii) a 2) 100g of gamma-Al2O3In an autoclave, under the conditions of pH 6.0, temperature 150 ℃ and pressure 2.0MPaCarrying out hydrothermal treatment for 3 h; 3) adding 10g of zinc and 5g of cerium oxide into the materials, and pulping for 25min at the temperature of 200 ℃ and the pressure of 2.0MPa for modification treatment; 4) roasting the modified material for 4 hours at the temperature of 500 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 6.0 to obtain an impregnation liquid rich in active components; 6) soaking a mesoporous alumina carrier in the impregnating solution for 1.0h at the temperature of 80 ℃ in the same volume; 7) and drying the impregnated catalyst precursor, and roasting at 400 ℃ for 2h to obtain a finished catalyst Y-2.
Example 3
1) 200g of pseudo-boehmite is put into a muffle furnace and roasted for 3.5h under the air atmosphere and the temperature of the muffle furnace is 520 ℃, thus obtaining gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment for 3h in a high-pressure kettle under the conditions that the pH value of the solution is 6.5, the temperature is 180 ℃ and the pressure is 1.5 MPa; 3) adding oxides of 10g of zinc, 8g of copper and 3g of manganese into the materials, and pulping for 30min at the temperature of 180 ℃ and the pressure of 1.5MPa for modification treatment; 4) roasting the modified material for 4 hours at the temperature of 550 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 5.5 to obtain an impregnation solution rich in active components; 6) soaking a mesoporous alumina carrier in the impregnating solution for 1.0h at the temperature of 90 ℃ in the same volume; 7) and drying the impregnated catalyst precursor, and roasting at 450 ℃ for 2h to obtain a finished catalyst Y-3.
Example 4
1) 200g of pseudo-boehmite is put into a muffle furnace and is roasted for 4 hours at the temperature of 500 ℃ in the air atmosphere to obtain gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment for 3h in a high-pressure kettle under the conditions that the pH value of the solution is 6.0, the temperature is 180 ℃ and the pressure is 1.5 MPa; 3) adding 10g of zinc, 8g of copper and 3g of molybdenum oxide into the above materials, and pulping at 180 ℃ and 1.5MPaPerforming modification treatment for 20 min; 4) roasting the modified material for 4 hours at the temperature of 550 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 5.5 to obtain an impregnation solution rich in active components; 6) soaking a mesoporous alumina carrier in the impregnating solution for 1.0h at the temperature of 85 ℃ in the same volume; 7) and drying the impregnated catalyst precursor, and roasting at 350 ℃ for 3h to obtain a finished catalyst Y-4.
Example 5
1) 200g of pseudo-boehmite is put into a muffle furnace and is roasted for 4 hours at the temperature of 500 ℃ in the air atmosphere to obtain gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment for 3h in an autoclave under the conditions that the pH value of the solution is 6.5, the temperature is 200 ℃ and the pressure is 1.5 MPa; 3) adding 10g of zinc, 8g of copper and 3g of cerium oxide into the materials, and pulping for 20min at the temperature of 200 ℃ and the pressure of 1.5MPa for modification treatment; 4) roasting the modified material for 4.5 hours at the temperature of 500 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 6.5 to obtain an impregnation solution rich in active components; 6) soaking a mesoporous alumina carrier in the impregnating solution for 3.0 hours at the temperature of 75 ℃ in the same volume; 7) and drying the impregnated catalyst precursor, and roasting at 450 ℃ for 3h to obtain a finished catalyst Y-5.
Example 6
1) 200g of pseudo-boehmite is put into a muffle furnace and is roasted for 3 hours at the temperature of 500 ℃ in the air atmosphere to obtain gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment for 3h in a high-pressure kettle under the conditions that the pH value of the solution is 6.0, the temperature is 150 ℃ and the pressure is 2.0 MPa; 3) adding oxides of 10g of zinc, 5g of copper and 3g of lanthanum into the materials, and pulping for 30min at the temperature of 150 ℃ and the pressure of 2.0MPa for modification treatment; 4) roasting the modified material for 5 hours at the temperature of 450 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 6.0 to obtain an impregnation liquid rich in active components; 6) soaking a mesoporous alumina carrier in the impregnating solution for 1.5h at the temperature of 85 ℃ in the same volume; 7) and drying the impregnated catalyst precursor, and roasting at 400 ℃ for 2h to obtain a finished catalyst Y-6.
Example 7
1) 200g of pseudo-boehmite is put into a muffle furnace and roasted for 3.5h under the air atmosphere and the temperature of the muffle furnace is 550 ℃, thus obtaining gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment for 3h in a high-pressure kettle under the conditions that the pH value of the solution is 6.5, the temperature is 150 ℃ and the pressure is 2.0 MPa; 3) adding 10g of zinc and 5g of copper oxide into the materials, and pulping for 25min at the temperature of 150 ℃ and the pressure of 2.0MPa for modification treatment; 4) roasting the modified material for 5 hours at the temperature of 450 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 6.0 to obtain an impregnation liquid rich in active components; 6) soaking a mesoporous alumina carrier in the impregnating solution for 2.5 hours at the temperature of 80 ℃ in the same volume; 7) and drying the impregnated catalyst precursor, and roasting at 430 ℃ for 3h to obtain a finished catalyst Y-7.
Example 8
1) 200g of pseudo-boehmite is put into a muffle furnace and is roasted for 4 hours at the temperature of 500 ℃ in the air atmosphere to obtain gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment for 3h in a high-pressure kettle under the conditions that the pH value of the solution is 5.5, the temperature is 190 ℃ and the pressure is 1.8 MPa; 3) adding 10g of zinc and 5g of copper oxide into the materials, and pulping for 25min at the temperature of 150 ℃ and the pressure of 2.0MPa for modification treatment; 4) roasting the modified material for 5 hours at the temperature of 450 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to the pH value of 6.5 to obtain the product rich in phosphorusAn impregnation fluid of the sexual component; 6) soaking a mesoporous alumina carrier in the impregnating solution for 2.5 hours at the temperature of 80 ℃ in the same volume; 7) and drying the impregnated catalyst precursor, and roasting at 400 ℃ for 2.5 hours to obtain a finished catalyst Y-8.
Example 9
1) 200g of pseudo-boehmite is put into a muffle furnace, and is roasted for 3h at the temperature of 530 ℃ in the air atmosphere to obtain gamma-Al2O3(ii) a 2) 100g of gamma-Al2O3Carrying out hydrothermal treatment for 3h in a high-pressure kettle under the conditions that the pH value of the solution is 6.0, the temperature is 190 ℃ and the pressure is 1.8 MPa; 3) adding 15g of zinc oxide into the materials, and pulping for 25min at the temperature of 150 ℃ and the pressure of 2.0MPa for modification treatment; 4) roasting the modified material for 5 hours at the temperature of 450 ℃; 5) 30g of Ni (NO)3)2•6H2O and 10gCe (NO)3)2•6H2Dissolving O in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 6.0 to obtain an impregnation liquid rich in active components; 6) soaking a mesoporous alumina carrier in the impregnating solution for 2 hours at the temperature of 85 ℃ in equal volume; 7) and drying the impregnated catalyst precursor, and roasting at 430 ℃ for 2h to obtain a finished catalyst Y-9.
Comparative example 1
1) Carrying out heat treatment on 100g of pseudo-boehmite at 500 ℃, and tabletting to obtain an alumina carrier; 2) immersing the carrier in Ni (NO) at 75 deg.C3)2And Ce (NO)3)2•6H2O solution for 2 h; 3) and taking out the impregnated catalyst precursor, drying, and roasting at 450 ℃ for 2h to obtain a catalyst finished product D-1 with Ni and Ce loading amounts of 8% and 2% respectively.
Comparative example 2
1) Dissolving 100g of pseudo-boehmite in water to prepare suspension; 2) at 70 deg.C, adding a certain amount of Ni (NO)3)2、Ce(NO3)2•6H2Adding O into the solution, and fully mixing; 3) then the mixed solution is evaporated to dryness, roasted at 550 ℃ and extruded to obtain N, Ce comparative catalyst D-2 with the load of 7% and 3% respectively.
Comparative example 3
1）Dissolving 100g of pseudo-boehmite in water to prepare a suspension, and adding 1: 1, preparing aluminum sol from dilute nitric acid; 2) at 80 deg.C, adding a certain amount of Ni (NO)3)2、Ce(NO3)2•6H2Adding O into the sol, and fully mixing; 3) then evaporating the mixed solution to dryness, roasting at 600 ℃ and tabletting to obtain a comparative catalyst D-3 with Ni and Ce loading amounts of 5% and 5% respectively.
Evaluation of catalyst Performance
The examples Y-1 to Y-9 and the comparative examples D-1 to D-3 were packed in an isothermal bed reactor at a temperature of 300 ℃, a pressure of 3.0MPa and a space velocity of 10000h-1，H2Samples were taken at 72h and 200h for analysis at/CO = 3.
Specific data are shown in table 1 below.
TABLE 1 comparison of catalyst Performance between examples and comparative examples
As can be seen from the reaction data in the table, the catalysts Y-1-Y-9 prepared by the method show good CO conversion rate and CO conversion rate after 72 hours and 300 hours2The conversion rate performance and the stability are ensured; while the comparative examples D-1, D-2 and D-3 show good conversion rate performance in 72h, the conversion rate and the selectivity are greatly reduced after 300h reaction, which proves that the catalyst has poor stability in long-time operation under the condition of an isothermal bed.
Meanwhile, after the catalysts Y-1-Y-9 prepared by the method are removed after running for 300 hours, the phenomena of surface and internal blockage or carbon deposition are not found through SEM (scanning electron microscope) detection, and carbon deposition of different degrees appears in comparative examples D-1, D-2 and D-3, which may be the reason that the activity and selectivity of the later comparative examples are reduced in different degrees.
In addition, the comparative example had a powdering phenomenon at 300h of operation, and the reduction in mechanical strength was significant.
Claims (10)
1. The preparation method of the isothermal methanation catalyst is characterized in that the catalyst is obtained by the following steps:
(1) preparation of the carrier:
b. Subjecting the gamma-Al in the step a2O3Placing the mixture in an autoclave lined with polytetrafluoroethylene, adding deionized water, stirring uniformly, adding nitric acid to adjust the pH value of the solution, heating and boosting the pressure, and then carrying out hydrothermal treatment;
d. drying, roasting and tabletting the material obtained in the step c to obtain a modified mesoporous alumina carrier;
(2) preparation of active ingredients:
dissolving nitrates of Ni and Ce in water, and adding 0.02-0.1 mol/L phosphotungstic heteropoly acid to a pH value of 5.5-6.5 to obtain an impregnation liquid rich in active components;
(3) preparation of the catalyst:
controlling the temperature to be 70-90 ℃, and soaking the mesoporous alumina carrier in the impregnating solution for 1.0-3.0 h in the same volume; and taking out the impregnated catalyst precursor, drying and roasting to obtain the catalyst finished product.
2. The preparation method according to claim 1, wherein the molar ratio of Al to X is 1: 0.1-0.5, wherein X is one or more nitrates of Cu, Zn, Ce, Zr, Mo, Mn and La in the step c.
3. The preparation method of claim 1, wherein the loading amounts of the active components Ni and Ce are 5-10% and 1-3% of the weight of the catalyst respectively.
4. The method of claim 1, wherein the calcination temperature in step a is 500-550 ℃ and the calcination time is 3-4 hours.
5. The method according to claim 1, wherein the pH of the solution in step b is 5.5 to 6.5.
6. The method according to claim 1, wherein the temperature in step b is 150 to 200 ℃ and the pressure is 1.0 to 2.0 MPa.
7. The method according to claim 1, wherein the hydrothermal treatment time in step b is 3 to 4 hours.
8. The method according to claim 1, wherein the temperature in step c is 150 to 200 ℃ and the pressure in step c is 1.0 to 2.0 MPa.
9. The method according to claim 1, wherein the beating time in step c is 20 to 30 min.
10. The process according to claim 1, wherein the baking temperature of the carrier in step d is 400 to 400 ℃
Roasting for 4-5 h at 550 ℃; the roasting temperature of the catalyst precursor is 300-450 ℃, and the roasting time is 2-3 h.
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