CN114345357B - Preparation method of isothermal methanation catalyst - Google Patents
Preparation method of isothermal methanation catalyst Download PDFInfo
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- CN114345357B CN114345357B CN202011090683.6A CN202011090683A CN114345357B CN 114345357 B CN114345357 B CN 114345357B CN 202011090683 A CN202011090683 A CN 202011090683A CN 114345357 B CN114345357 B CN 114345357B
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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 18
- 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
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 238000004537 pulping Methods 0.000 claims description 14
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 5
- 238000002156 mixing 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 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
- 238000010304 firing Methods 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 5
- 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
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000571 coke Substances 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
- 239000004480 active ingredient Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 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
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 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
- 239000003245 coal Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 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
- 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 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
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 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
- 230000007246 mechanism Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 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
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling 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 adopting a hydrothermal treatment process under the synergistic effect of Cu, zn, ce, zr, mo, mn, la and other multi-metal components, and obtaining a precursor with good specific surface area, pore diameter, heat and mass transfer performance by means of drying, roasting, tabletting and the like; the bimetallic Ni-Ce is used as an active ingredient 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 one-stage isothermal non-circulating reaction process, when the composition of the coke oven gas is 6-10% of CO, 2 2~5%,C2H6 1~4%,H2 -60% of CO, the balance is N 2, the airspeed is 5000-10000 h ‑1, the pressure is 1.5-3.0 MPa, and the conversion rate of CO and CO 2 reaches more than 99.0% under the condition of 250-400 ℃.
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 increasingly improved, and the consumption of natural gas in China reaches 3300 hundred million cubic meters according to the prediction of related mechanisms at the end of 2020, so that a supply and demand gap is serious. Because of the energy characteristics of rich coal, lean oil and less gas in China, the preparation of the synthetic natural gas not only can produce high-grade clean 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 used as a core technology for preparing the synthetic natural gas, and a circulating multistage adiabatic fixed bed methanation technology is mainly adopted in the industry at present, and has the advantages of high reaction temperature, low heat transfer rate, complex process flow, extremely easy temperature runaway caused by the failure of a circulating compressor and severe requirements on the high temperature resistance of a reactor and a catalyst. 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 as a refrigerant in the reactors to take away the 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. However, since methanation reaction is a strong exothermic reaction, although the isothermal fixed bed reactor is adopted to effectively remove the heat of reaction, the heat released in the reaction process has higher requirements on the conduction and heat transfer performance of the catalyst, so that it is very necessary to develop an isothermal methanation catalyst which is suitable for an isothermal fixed bed and has good activity, high stability and excellent heat and mass transfer performance.
Chinese patent CN105195160a describes an isothermal methanation catalyst and a process for its preparation, which uses a composite oxide of magnesium, aluminum and silicon as monolithic catalyst support, nickel as active component, at a space velocity of 4000h -1, a pressure of 2.0Mpa, a temperature of 400 ℃, an inlet gas CO:3.63%, CO 2: 1.3% of isothermal fixed bed shows good low-temperature activity, but the patent adopts a strip extrusion molding mode to obtain a carrier, and the carrier has good external surface area and rich pore channels, but the strength of the strip extrusion molded catalyst is low, the activity and 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, isothermal methanation is more and more paid attention to domestic and foreign scientific research institutions due to the short process flow and low energy consumption. The development of a low-temperature and high-efficiency methanation catalyst as one of key technologies of isothermal methanation is an important subject to be solved by current scientific researchers.
Disclosure of Invention
The purpose of the invention is that: a method for preparing isothermal methane synthesis catalyst is provided. 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.
The invention has the main characteristics that:
(1) Preparing a modified mesoporous alumina precursor by adopting a hydrothermal treatment process under the synergistic effect of Cu, zn, ce, zr, mo, mn, la and other multi-metal components, and obtaining a carrier with good specific surface area, pore diameter, heat and mass transfer performance by means of drying, roasting, tabletting and the like;
(2) The bimetallic Ni-Ce is adopted as an active component, the modulation effect of the phosphotungstic heteropoly acid is achieved, the surface and the pore canal of the catalyst are free from carbon deposition after long-time use, the catalyst is not sintered, and the stability is good;
(3) Under the condition of one-stage isothermal non-circulating reaction process, when the composition of the coke oven gas is 6-10% of CO, 2 2~5%,C2H61~4%,H2 -60% of CO, the balance is N 2, the airspeed is 5000-10000 h -1, the pressure is 1.5-3.0 MPa, and the conversion rate of CO and CO 2 respectively reaches more than 99.0% at the temperature of 250-400 ℃.
The invention provides a preparation method of an isothermal methanation catalyst, which is characterized in that the catalyst is prepared by the following steps:
(1) Preparation of the carrier: roasting pseudo-boehmite in an air atmosphere to obtain gamma-Al 2O3; placing gamma-Al 2O3 into an autoclave lined with polytetrafluoroethylene, adding deionized water, uniformly stirring, adding nitric acid to adjust the pH value of the solution, heating and boosting, and performing hydrothermal treatment; placing the material after the hydro-thermal treatment into an autoclave lined with polytetrafluoroethylene, then placing one or a mixture of water solutions of Cu, zn, ce, zr, mo, mn, la nitrate into the autoclave, and fully mixing and pulping by controlling the temperature and the pressure to carry out modification treatment; and drying, roasting and tabletting the modified material to obtain the modified mesoporous alumina carrier.
(2) Preparation of active component: dissolving Ni and Ce nitrate in water, and adding 0.02-0.1 mol/L phosphotungstic acid until the pH value is 5.5-6.5 to obtain an impregnating solution rich in active components;
(3) Preparation of the catalyst:
Controlling the temperature to be 70-90 ℃, and immersing the mesoporous alumina carrier in the impregnating solution for 1.0-3.0 h in an equal volume; and taking out the impregnated catalyst precursor, and drying and roasting to obtain a catalyst finished product.
In the above steps, the molar ratio of Al to Cu, zn, ce, zr, mo, mn, la is 1:0.1-0.5.
The loading of the active component Ni and Ce in the steps is 5-10% and 1-3% of the weight of the catalyst respectively.
The roasting temperature in the steps is 500-550 ℃, and the roasting time is 3-4 hours.
The PH value of the hydrothermal treatment solution in the steps is 5.5-6.5.
The hydrothermal treatment temperature in the steps is 150-200 ℃ and the pressure is 1.0-2.0 MPa.
The hydrothermal treatment time in the steps is 3-4 hours.
The temperature of the carrier modification treatment in the steps is 150-200 ℃, and the pressure is 1.0-2.0 MPa.
The pulping time of the carrier modification treatment in the steps is 20-30 min.
The roasting temperature of the carrier in the steps is 400-550 ℃ and the roasting time is 4-5 h.
The roasting temperature of the catalyst precursor in the steps is 300-450 ℃, and the roasting time is 2-3 h.
A typical laboratory preparation process of the invention is as follows:
1) Placing pseudo-boehmite into a muffle furnace, and roasting for 3-4 hours at the temperature of 500-550 ℃ in an air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 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 of oxides of zinc, copper, molybdenum, manganese, lanthanum and cerium into the above materials, pulping for 20-30 min under the conditions of the temperature of 150-200 ℃ and the pressure of 1.0-2.0 MPa, and carrying out modification treatment; 4) Roasting the modified material for 4-5 hours at the temperature of 400-550 ℃; 5) Dissolving Ni (NO 3)2•6H2O、Ce(NO3)2•6H2 O in water, adding 0.02-0.1 mol/L phosphotungstic acid to pH value of 5.5-6.5, obtaining impregnation liquid rich in active components; 6) Immersing the mesoporous alumina carrier in the impregnating solution for 1.0-3.0 h at the temperature of 70-90 ℃; 7) And (3) drying the impregnated catalyst precursor, and roasting for 2-3 hours at 300-450 ℃ to obtain a catalyst finished product.
The isothermal bed methane synthesis catalyst prepared by the invention has simple preparation method, is beneficial to industrial production, and has good activity and stability.
Detailed Description
The process of the present invention is described in detail by the following examples, which are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention.
Example 1
1) Placing 200g of pseudo-boehmite into a muffle furnace, and roasting for 4 hours at the temperature of 500 ℃ in an air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 4 hours 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, 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•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 5.5, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 75 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 2.0h in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting for 2 hours at 350 ℃ to obtain a catalyst finished product Y-1.
Example 2
1) Placing 200g of pseudo-boehmite into a muffle furnace, and roasting for 3 hours at the temperature of 550 ℃ in an air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 3 hours 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 10g of zinc and 5g of cerium oxide into the materials, 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•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 6.0, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 80 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 1.0h in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting at 400 ℃ for 2 hours to obtain a catalyst finished product Y-2.
Example 3
1) 200G of pseudo-boehmite is put into a muffle furnace, and the temperature of the muffle furnace is 520 ℃ and roasted for 3.5 hours in the air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 3 hours 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 10g of zinc, 8g of copper and 3g of manganese oxide into the materials, pulping for 30min at 180 ℃ under the pressure of 1.5MPa for modification treatment; 4) Roasting the modified material for 4 hours at 550 ℃; 5) 30g of Ni (NO 3)2•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 5.5, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 90 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 1.0h in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting for 2 hours at 450 ℃ to obtain a catalyst finished product Y-3.
Example 4
1) Placing 200g of pseudo-boehmite into a muffle furnace, and roasting for 4 hours at the temperature of 500 ℃ in an air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 3 hours 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 materials, pulping for 20min at 180 ℃ under the pressure of 1.5MPa for modification treatment; 4) Roasting the modified material for 4 hours at 550 ℃; 5) 30g of Ni (NO 3)2•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 5.5, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 85 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 1.0h in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting for 3 hours at 350 ℃ to obtain a catalyst finished product Y-4.
Example 5
1) Placing 200g of pseudo-boehmite into a muffle furnace, and roasting for 4 hours at the temperature of 500 ℃ in an air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 3 hours 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, 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•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 6.5, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 75 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 3.0h in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting at 450 ℃ for 3 hours to obtain a catalyst finished product Y-5.
Example 6
1) 200G of pseudo-boehmite is put into a muffle furnace, and the temperature of the muffle furnace is 500 ℃ and baked for 3 hours in an air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 3 hours 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 10g of zinc, 5g of copper and 3g of lanthanum oxide into the materials, 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•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 6.0, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 85 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 1.5h in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting at 400 ℃ for 2 hours to obtain a catalyst finished product Y-6.
Example 7
1) 200G of pseudo-boehmite is put into a muffle furnace, and the temperature of the muffle furnace is 550 ℃ and roasted for 3.5 hours in the air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 3 hours 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, 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•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 6.0, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 80 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 2.5h in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting at 430 ℃ for 3 hours to obtain a catalyst finished product Y-7.
Example 8
1) Placing 200g of pseudo-boehmite into a muffle furnace, and roasting for 4 hours at the temperature of 500 ℃ in an air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 3 hours 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, 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•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 6.5, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 80 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 2.5h in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting at 400 ℃ for 2.5 hours to obtain a catalyst finished product Y-8.
Example 9
1) Placing 200g of pseudo-boehmite into a muffle furnace, and roasting for 3 hours at the temperature of 530 ℃ in an air atmosphere to obtain gamma-Al 2O3; 2) Carrying out hydrothermal treatment on 100g of gamma-Al 2O3 in an autoclave for 3 hours 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, 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•6H2 O and 10gCe (NO 3)2•6H2 O are dissolved in water, 0.02-0.1 mol/L phosphotungstic acid is added to the pH value of 6.0, so as to obtain an impregnating solution rich in active components; 6) at the temperature of 85 ℃, the mesoporous alumina carrier is immersed in the impregnating solution for 2 hours in equal volume; 7) And (3) drying the impregnated catalyst precursor, and roasting at 430 ℃ for 2 hours to obtain a catalyst finished product Y-9.
Comparative example 1
1) Performing heat treatment on 100g of pseudo-boehmite at 500 ℃, and tabletting to obtain an alumina carrier; 2) Immersing the carrier in Ni (NO 3)2 and Ce (NO 3)2•6H2 O) for 2h at 75 ℃, taking out the immersed 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 a suspension; 2) Adding a certain amount of Ni (NO 3)2、Ce(NO3)2•6H2 O into the above solution at 70deg.C, and mixing thoroughly; 3) And evaporating the mixed solution, roasting at 550 ℃ and extruding strips to obtain a comparative catalyst D-2 with N, ce loading of 7% and 3% respectively.
Comparative example 3
1) 100G of pseudo-boehmite was dissolved in water to prepare a suspension, and 1:1 preparing aluminum sol by dilute nitric acid; 2) Adding a certain amount of Ni (NO 3)2、Ce(NO3)2•6H2 O into the sol at 80deg.C, and mixing thoroughly; 3) And evaporating the mixed solution, roasting at 600 ℃ and tabletting to obtain the comparative catalyst D-3 with Ni and Ce loading amounts of 5% and 5% respectively.
Evaluation of catalyst Performance
Example Y-1~Y-9 and comparative example D-1~D-3 were packed in an isothermal bed reactor at 300 ℃, at 3.0. 3.0 MPa, and at 10000h -1,H2/co=3 space velocity for sampling analysis at 72h and 200 h.
Specific data are shown in Table 1 below.
Table 1 comparison of catalyst performance for examples and comparative examples
As can be seen from the reaction data in the table, the catalyst Y-1~Y-9 prepared by the method shows good CO conversion rate and CO 2 conversion rate performance after 72 hours and 300 hours, and the stability is ensured; while comparative examples D-1, D-2 and D-3 showed good conversion performance at 72 hours, the reaction conversion and selectivity were greatly reduced after 300 hours, and the catalyst was proved to have poor running stability under isothermal bed conditions for a long time.
Meanwhile, after the catalyst Y-1~Y-9 prepared by the method is removed after running for 300 hours, the phenomenon of blocking or carbon deposition on the surface and the inside is not found by SEM scanning electron microscope detection, and the comparative examples D-1, D-2 and D-3 all have carbon deposition with different degrees, which is probably the reason that the activity and the selectivity of the comparative examples in the later stage are reduced with different degrees.
In addition, the comparative example had a chalking phenomenon at 300 hours of operation, and a decrease in mechanical strength was remarkable.
Claims (8)
1. The preparation method of the isothermal methanation catalyst is characterized in that the catalyst is prepared by the following steps:
(1) Preparation of the carrier:
a. Roasting pseudo-boehmite in an air atmosphere to obtain gamma-Al 2O3;
b. Placing gamma-Al 2O3 in the step a in an autoclave lined with polytetrafluoroethylene, adding deionized water, uniformly stirring, adding nitric acid to adjust the pH value of the solution to 5.5-6.5, heating and boosting, and performing hydrothermal treatment;
c. B, placing the material subjected to the hydro-thermal treatment in an autoclave lined with polytetrafluoroethylene, then placing an aqueous solution of one or a mixture of Cu, zn, zr, mo, mn, la nitrate in the autoclave, controlling the temperature to be 150-200 ℃ and the pressure to be 1.0-2.0 MPa for modification treatment, and fully mixing and pulping;
d. C, drying, roasting and tabletting the material obtained in the step c to obtain a modified mesoporous alumina carrier;
(2) Preparation of active component:
dissolving Ni and Ce nitrate in water, and adding 0.02-0.1 mol/L phosphotungstic acid until the pH value is 5.5-6.5 to obtain an impregnating solution rich in active components;
(3) Preparation of the catalyst:
Controlling the temperature to be 70-90 ℃, and immersing the mesoporous alumina carrier in the impregnating solution for 1.0-3.0 h in an equal volume; and taking out the impregnated catalyst precursor, and drying and roasting to obtain a catalyst finished product.
2. The 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 of the nitrates of Cu, zn, ce, zr, mo, mn, la in 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 firing temperature in step a is 500 to 550 ℃ and the firing time is 3 to 4 hours.
5. The method according to claim 1, wherein the temperature in the step b is 150 to 200 ℃ and the pressure is 1.0 to 2.0MPa.
6. The method of claim 1, wherein the hydrothermal treatment time in step b is 3-4 hours.
7. The method of claim 1, wherein the pulping time in step c is 20 to 30 minutes.
8. The preparation method of claim 1, wherein the roasting temperature of the carrier in the step d is 400-550 ℃ and the roasting time is 4-5 h; the roasting temperature of the catalyst precursor is 300-450 ℃, and the roasting time is 2-3 h.
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