CN112387283A - Low-temperature carbon dioxide methanation catalyst and preparation method thereof - Google Patents
Low-temperature carbon dioxide methanation catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 21
- 230000032683 aging Effects 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 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 15
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- 239000012716 precipitator Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 4
- 230000018109 developmental process Effects 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000008021 deposition Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 239000002620 silicon nanotube Substances 0.000 description 1
- 229910021430 silicon nanotube Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- B01J23/755—Nickel
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/61—
-
- 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
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
Abstract
The invention discloses a low-temperature carbon dioxide methanation catalyst and a preparation method thereof. The catalyst comprises an active component and a carrier; the active component is Ni, and the carrier is alumina, zirconia or a composite carrier of the alumina and the zirconia; the active component Ni accounts for 5-25 wt%, and the balance is a carrier. Dissolving aluminum nitrate, zirconium nitrate or a compound of the aluminum nitrate and the zirconium nitrate and nickel nitrate in deionized water to obtain a mixed solution; dropwise adding a precipitator into the obtained mixed solution, and stirring to obtain a solid-liquid mixture; aging the obtained solid-liquid mixture, and washing the solid-liquid mixture to be neutral by using distilled water to obtain a solidA sample; and finally, drying and roasting the solid sample in sequence, and obtaining the Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst after treatment. The methanation catalyst prepared by the method has obviously better effect than the traditional Ni/Al catalyst2O3The catalyst has simple preparation method, stable performance and long service life; has excellent development prospect.
Description
The technical field is as follows:
the invention relates to the technical field of natural gas, in particular to a low-temperature carbon dioxide methanation catalyst and a preparation method thereof.
Secondly, background art:
the characteristics of rich coal, poor oil and less gas are obvious characteristics of energy in China, and the development of a clean and efficient utilization technology of coal has very important significance. The method has the advantages that the coal is used as the raw material, the natural gas is catalytically produced by the synthesis gas, the condition of natural gas shortage in China can be relieved, energy conservation, emission reduction and natural gas supply diversification are realized, the efficient clean utilization of coal resources can be realized, and the method conforms to the national clean utilization of coal and resource strategic safety strategy.
The methanation technology refers to the CO/CO under the action of a catalyst2And H2The reaction is carried out to generate methane as the main product. Methanation studies began in the last 40 th century, and as the world's energy structure changed, syngas methanation technology began to enter a period of rapid development.
At present, the catalyst for methanation is mainly a Ni-based catalyst which has the characteristics of high catalytic activity, good selectivity, relatively low price, wide material acquisition and the like; however, the Ni-based catalyst is liable to self-accumulation and surface carbon deposition during the reaction, and thus the stability of the catalyst is not high. Therefore, it is required to support the active component on the carrier, and to improve the activity and stability of the catalyst and reduce the carbon deposition on the surface of the catalyst by utilizing the high dispersibility of the active component. More recently, the more widely used support has been Al2O3、ZrO2、CeO2、TiO2Etc.; the support has a physical supporting and dispersing effect on the active component, which may have an effect on the activity, selectivity and lifetime of the catalyst. Aiming at the current situations of low-temperature activity, poor stability and poor anti-carbon deposition performance of the existing methanation catalyst, research on the methanation catalyst focuses on mild conditionsThe activity, stability and anti-carbon deposition performance of the catalyst are improved.
At present, there are many reports on related patent documents relating to methanation catalysts. For example: 1. the invention patent CN 111514897A discloses a carbon-doped mesoporous silicon nanotube nickel-based methanation catalyst, which is subjected to a chemical reaction at an airspeed GHSV of 20000h-1 and a temperature of 400 ℃, and CO is obtained2The conversion rate can reach 79 percent, but the gas space velocity in the reaction is lower, and the retention time is longer. 2. The invention patent CN 106944084A discloses a methanation catalyst which is Al2O3Mo is used as an active component of the catalyst, and an auxiliary agent is added to modify the performance of the catalyst. 3. The invention patent CN 111266130A discloses a method for preparing a methanation catalyst with a carrier of a composite structure, and the catalyst prepared by the method has the characteristics of low activation temperature, high activity and high stability. 4. The technical scheme disclosed by the invention patent CN 111514889A is to prepare the ruthenium-based catalyst by taking ionic liquid, ruthenium nitrate and ruthenium iodide solution as raw materials, but the noble metal Ru-based catalyst is expensive and cannot be widely applied to methanation reaction.
Thirdly, the invention content:
the technical problem to be solved by the invention is as follows: in order to overcome the defects of low-temperature activity, poor stability, poor carbon deposition resistance and the like of the existing methanation catalyst. The invention provides a low-temperature carbon dioxide methanation catalyst and a preparation method thereof2O3、ZrO2As a support, ZrO2The addition of the catalyst can inhibit the formation of a spinel structure, and simultaneously improve the dispersion degree of active components, thereby being beneficial to the methanation reaction. The catalyst prepared by the technical scheme of the invention has higher activity and stability at low temperature and good carbon deposition resistance.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a low-temperature carbon dioxide methanation catalyst, which comprises an active component and a carrier; the active component is Ni, and the carrier is alumina, zirconia or a composite carrier of the alumina and the zirconia; the catalyst comprises 5-25 wt% of active component Ni and the balance of a carrier, wherein the active component Ni accounts for the total mass of the catalyst.
According to the low-temperature carbon dioxide methanation catalyst, when the carrier is a composite carrier of alumina and zirconia, the molar ratio of Al to Zr is 1-5: 1 to 2.5.
In addition, a preparation method of the low-temperature carbon dioxide methanation catalyst is provided, and the preparation method comprises the following steps:
a. dissolving aluminum nitrate, zirconium nitrate or a compound of the aluminum nitrate and the zirconium nitrate and nickel nitrate in deionized water, and fully stirring at room temperature to obtain a mixed solution;
when the carrier is aluminum nitrate, the mass ratio of the aluminum nitrate to the nickel nitrate is 2-14: 1;
when the carrier is zirconium nitrate, the mass ratio of the zirconium nitrate to the nickel nitrate is 2-13: 1;
when the carrier is a complex of aluminum nitrate and zirconium nitrate, the mass ratio of the aluminum nitrate to the zirconium nitrate to the nickel nitrate is 1.8-10: 2-6: 1;
b. dropwise adding a precipitator into the mixed solution obtained in the step a under the condition of continuously stirring at 60-70 ℃, finishing dropwise adding when the pH value of the solution is 9-10, and continuously stirring for 1-4 hours at 60-70 ℃ to obtain a solid-liquid mixture;
c. b, aging the solid-liquid mixture obtained in the step b, and washing the aged solid-liquid mixture by using distilled water to obtain a solid sample;
d. and c, drying and roasting the solid sample obtained in the step c in sequence, and treating to obtain the Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst.
According to the preparation method of the low-temperature carbon dioxide methanation catalyst, the precipitator in the step b is 0.5-1.0 mol/L of Na2CO3Solution, 0.5-1.0 mol/L of K2CO3Solution or 1.0mol/L ammonia water.
According to the preparation method of the low-temperature carbon dioxide methanation catalyst, the aging time in the step c is 12-24 hours.
According to the preparation method of the low-temperature carbon dioxide methanation catalyst, in the washing process with distilled water in the step c, the distilled water is washed until the pH value of the solution is 7-8.
According to the preparation method of the low-temperature carbon dioxide methanation catalyst, in the step d, during drying, the drying temperature is 80-100 ℃, and the drying time is 12-24 hours.
According to the preparation method of the low-temperature carbon dioxide methanation catalyst, in the step d, the roasting temperature is 300-450 ℃ and the heat preservation time is 4-6 hours.
The invention has the following positive beneficial effects:
1. the raw materials adopted in the preparation process of the catalyst are green and environment-friendly, have wide sources, and are cheap and easy to obtain.
2. The catalyst of the invention has simple preparation method, short preparation flow, flexible operation conditions and easy repetition, and is suitable for large-scale industrial production.
3. The technical scheme of the invention for preparing the methanation catalyst has mild methanation reaction conditions, and CO reacts at normal pressure and 300 ℃ under the condition of reaction2Conversion of 72%, CH4The selectivity is 99%, and the stability can reach over 160 h; the applicable airspeed range is wide, and the airspeed is 12000-60000 mL-g-1h-1In-range of CO2The conversion rate can reach 69-79% (see the attached figures 1-3 for details).
4. The catalyst prepared by the technical scheme of the invention has good carbon deposit resistance, high specific surface area and good CO2Adsorption performance; the catalyst carrier has adjustable composition, and has excellent activity, selectivity and stability under mild reaction conditions (see the attached figures 4-6 for details).
Fourthly, explanation of the attached drawings:
FIG. 1 is a graph of the performance of the catalyst prepared in example 4 of the present invention;
from the performance plots of the catalysts prepared with the different precipitants it can be seen that: catalyst pair CO prepared by using sodium carbonate, potassium carbonate and ammonia water as precipitating agents2The methanation has good catalytic performance. Wherein sodium carbonate is used asThe catalyst prepared by the precipitator has the most excellent methanation performance, and CO2The conversion rate can reach 72 percent, and CH4The selectivity was 99%.
FIG. 2 is a graph of the performance of the catalyst prepared in example 4 of the present invention at different space velocities and different pressures;
the influence of space velocity and pressure on the performance is researched by figure 2, and the space velocity is 12000-60000 mL-g under normal pressure-1h-1In-range of CO2The conversion rate is 69 to 79 percent, and CH4The selectivity is 99%. CO increases from 0.1MPa to 0.5MPa with reaction pressure2The conversion increased rapidly to 91.5% and thereafter increased slowly. The result shows that the catalyst has excellent methanation performance in a high space velocity range, and the catalyst has mild reaction conditions and is easy to operate.
FIG. 3 is a graph of the stability of the catalyst prepared in example 4 of the present invention;
the stability test of the catalyst is carried out under the reaction conditions of normal pressure and 300 ℃, and the CO of the catalyst is found2Conversion rate was 72%, CH4The selectivity was 99% and remained stable for 160 h. The catalyst is shown to have excellent stability.
FIG. 4 is a drawing showing nitrogen adsorption-desorption of a catalyst prepared in example 4 of the present invention;
the adsorption type is IV type isothermal adsorption and desorption curve, and the BET specific surface area is 95m2(ii)/g; the pore diameter is 4.09 nm. Higher specific surface area and pore size are beneficial to improving the performance of the catalyst.
FIG. 5 in situ CO of catalyst prepared in example 4 of the present invention2Adsorbing an infrared spectrogram;
CO2adsorption on the catalyst of the invention will form carbonate and formate species and at low temperatures the adsorbed species will have formed indicating that the catalyst has good CO2And (4) adsorption performance. As the temperature increases, the adsorbed species are converted from carbonate to formate; the formation of formate species is beneficial to further hydrogenation to generate a target product CH4。
FIG. 6 is an in-situ Raman spectrum of the methanation reaction process of the catalyst prepared in example 4 of the present invention.
As can be seen from the Raman spectrogram, the depth of the reaction gas is 1200cm in the methanation process-1～1600cm-1No peak of carbon species was detected at the Raman shift while methane was switched on and H was switched off2No obvious carbon deposition phenomenon exists in the gas process, which shows that the catalyst has good carbon deposition resistance in the methanation process.
The fifth embodiment is as follows:
the invention is further illustrated by the following examples, which do not limit the scope of the invention.
Example 1:
the preparation method of the low-temperature carbon dioxide methanation catalyst comprises the following detailed steps:
a. 7.50g of Al (NO)3)3·9H2O and 0.56gNi (NO)3)2·6H2Dissolving O (all chemical purity) in 100mL of deionized water, and stirring for 1h under a magnetic stirrer to obtain a mixed solution;
b. under the condition of 65 ℃ and continuous stirring, 1.0mol/L of Na is added into a precipitator2CO3The solution is added dropwise to the mixed solution obtained in step a (Na)2CO3The solution is obtained by dissolving anhydrous sodium carbonate in deionized water), and the dropwise addition is completed when the pH value of the mixed solution is 9; then continuously stirring for 2 hours at 65 ℃ to obtain a solid-liquid mixture;
c. b, aging the solid-liquid mixture obtained in the step b for 24 hours, washing the solid-liquid mixture with distilled water after aging until the pH value of the solution is 7, and obtaining a solid sample;
d. and d, drying the solid sample obtained in the step c at 80 ℃ for 12h, heating to 450 ℃ after drying, roasting for 4h, and roasting to obtain the product Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst.
The mass percentage of the active component in the catalyst prepared by the embodiment is 10 wt%, and the rest is carrier alumina.
Example 2:
the preparation method of the low-temperature carbon dioxide methanation catalyst comprises the following detailed steps:
a. 6.26g of Al (NO)3)3·9H2O、1.42g Zr(NO3)4·5H2O and 0.69g Ni (NO)3)2·6H2Dissolving O (all chemical purity) in 100mL of deionized water, and stirring for 1h under a magnetic stirrer to obtain a mixed solution;
b. under the condition of 60 ℃ and continuous stirring, 0.8mol/L of Na as precipitator is added by a peristaltic pump2CO3The solution is added dropwise to the mixed solution obtained in step a (Na)2CO3The solution is obtained by dissolving anhydrous sodium carbonate in deionized water), and the dropwise addition is completed when the pH value of the mixed solution is 10; then continuously stirring for 2 hours at the temperature of 60 ℃ to obtain a solid-liquid mixture;
c. b, aging the solid-liquid mixture obtained in the step b for 24 hours, washing the solid-liquid mixture with distilled water after aging until the pH value of the solution is 8, and obtaining a solid sample;
d. and d, drying the solid sample obtained in the step c at 90 ℃ for 12h, heating to 450 ℃ after drying, roasting for 4h, and roasting to obtain the product Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst.
The mass percentage of the active component in the catalyst prepared in this example is 10 wt%, and the mass percentage of the alumina and the mass percentage of the zirconia in the carrier are 60.95% and 29.05%, respectively.
Example 3:
the preparation method of the low-temperature carbon dioxide methanation catalyst comprises the following detailed steps:
a. adding 5.36g of Al (NO)3)3·9H2O、2.44g Zr(NO3)4·5H2O and 0.78g Ni (NO)3)2·6H2Dissolving O (all chemical purity) in 100mL of deionized water, and stirring for 1h under a magnetic stirrer to obtain a mixed solution;
b. under the condition of continuously stirring at 70 ℃, 0.5mol/L of Na is added into a precipitator by a peristaltic pump2CO3The solution is added dropwise to the mixed solution obtained in step a (Na)2CO3The solution is obtained by dissolving anhydrous sodium carbonate in deionized waterDissolved in water), and the dripping is completed when the pH value of the mixed solution is 10; then continuously stirring for 2 hours at 70 ℃ to obtain a solid-liquid mixture;
c. b, aging the solid-liquid mixture obtained in the step b for 24 hours, washing the solid-liquid mixture with distilled water after aging until the pH value of the solution is 8, and obtaining a solid sample;
d. and d, drying the solid sample obtained in the step c at 80 ℃ for 12h, heating to 450 ℃ after drying, roasting for 4h, and roasting to obtain the product Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst.
The mass percentage of the active component in the catalyst prepared in this example is 10 wt%, and the mass percentage of the alumina and the mass percentage of the zirconia in the carrier are 45.89% and 44.11%, respectively.
Example 4:
the preparation method of the low-temperature carbon dioxide methanation catalyst comprises the following detailed steps:
a. 3.75g of Al (NO)3)3·9H2O、4.29g Zr(NO3)4·5H2O and 0.95g Ni (NO)3)2·6H2Dissolving O (all chemical purity) in 100mL of deionized water, and stirring for 1h under a magnetic stirrer to obtain a mixed solution;
b. under the condition of 65 ℃ and continuous stirring, 0.8mol/L of Na is added into a precipitator by a peristaltic pump2CO3The solution is added dropwise to the mixed solution obtained in step a (Na)2CO3The solution is obtained by dissolving anhydrous sodium carbonate in deionized water), and the dropwise addition is completed when the pH value of the mixed solution is 9; then continuously stirring for 2 hours at 65 ℃ to obtain a solid-liquid mixture;
c. b, aging the solid-liquid mixture obtained in the step b for 24 hours, washing the solid-liquid mixture with distilled water after aging until the pH value of the solution is 8, and obtaining a solid sample;
d. and d, drying the solid sample obtained in the step c at 100 ℃ for 16h, heating to 350 ℃ after drying, roasting for 6h, and roasting to obtain the Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst.
The mass percentage of the active component in the catalyst prepared in this example is 10 wt%, and the mass percentage of the alumina and the mass percentage of the zirconia in the carrier are 26.37% and 63.63%, respectively.
Example 5:
the preparation method of the low-temperature carbon dioxide methanation catalyst comprises the following detailed steps:
a. 2.14g of Al (NO)3)3·9H2O、6.14g Zr(NO3)4·5H2O and 1.12g Ni (NO)3)2·6H2Dissolving O (all chemical purity) in 100mL of deionized water, and stirring for 1h under a magnetic stirrer to obtain a mixed solution;
b. under the condition of continuously stirring at 70 ℃, a peristaltic pump is used for adding 1.0mol/L of Na into a precipitator2CO3The solution is added dropwise to the mixed solution obtained in step a (Na)2CO3The solution is obtained by dissolving anhydrous sodium carbonate in deionized water), and the dropwise addition is completed when the pH value of the mixed solution is 9; then continuously stirring for 2 hours at 70 ℃ to obtain a solid-liquid mixture;
c. b, aging the solid-liquid mixture obtained in the step b for 24 hours, washing the solid-liquid mixture with distilled water after aging until the pH value of the solution is 8, and obtaining a solid sample;
d. and d, drying the solid sample obtained in the step c at 80 ℃ for 12h, heating to 450 ℃ after drying, roasting for 4h, and roasting to obtain the product Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst.
The mass percentage of the active component in the catalyst prepared in this example is 10 wt%, and the mass percentage of the alumina and the mass percentage of the zirconia in the carrier are 12.76% and 77.24%, respectively.
Example 6:
the preparation method of the low-temperature carbon dioxide methanation catalyst comprises the following detailed steps:
a. adding 8.58g Zr (NO)3)4·5H2O and 1.35g Ni (NO)3)2·6H2Dissolving O (all chemical purity) in 100mL of deionized water, and stirring for 1h under a magnetic stirrer to obtain a mixed solution;
b. under the condition of 65 ℃ and continuous stirring, 0.8mol/L of Na is added into a precipitator by a peristaltic pump2CO3The solution is added dropwise to the mixed solution obtained in step a (Na)2CO3The solution is obtained by dissolving anhydrous sodium carbonate in deionized water), and the dropwise addition is completed when the pH value of the mixed solution is 10; then stirring for 2 hours at 65 ℃ to obtain a solid-liquid mixture;
c. b, aging the solid-liquid mixture obtained in the step b for 24 hours, washing the solid-liquid mixture with distilled water after aging until the pH value of the solution is 8, and obtaining a solid sample;
d. and d, drying the solid sample obtained in the step c at 80 ℃ for 12h, heating to 400 ℃ after drying, roasting for 5h, and roasting to obtain the product Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst.
The mass percentage of the active component in the catalyst prepared in this example is 10 wt%, and the rest is carrier zirconia.
Catalyst evaluation conditions:
(1) and (3) catalyst reduction conditions:
weighing 0.1-0.5 g (80-120 mesh) of catalyst, and reacting at 400 deg.C and 10% H2Reducing for 4 hours in an Ar atmosphere;
(2) the catalyst reaction conditions are as follows:
carrying out methanation reaction in a four-channel high-pressure tubular fixed bed reactor, wherein the reaction temperature is 200-400 ℃, the reaction pressure is normal pressure-1.5 MPa, and the raw material gas constitutes H2/CO2The volume ratio of/Ar is 4:1:3, and the space velocity is 12000-60000 mL-g-1h-1；
The product was detected on-line by gas chromatography (Agilent 6890N) thermal conductivity cell detector (TCD), and the reaction results are detailed in tables 1 and 2.
The results shown in Table 1 are experimental data of catalytic activity of the catalyst at 300 ℃ under normal pressure
| Examples | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| CO2Conversion rate | 16.6％ | 28.4％ | 38.8％ | 72.8％ | 32.9％ | 6.9％ |
| CH4Selectivity is | 80.8％ | 91.3％ | 94.7％ | 98.4％ | 90.5％ | 70.5％ |
Table 2 shows the reaction performance of the catalyst prepared in example 4 of the present invention at normal pressure and different temperatures
| Temperature of | 200℃ | 220℃ | 240℃ | 260℃ | 280 |
300℃ | 350℃ | 400℃ |
| CO2Conversion rate | 2.9％ | 6.4％ | 12.6％ | 25.8％ | 54.5％ | 72.8％ | 77.2％ | 70.9％ |
| CH4Selectivity is | 94.0％ | 94.9％ | 95.3％ | 95.7％ | 97.6％ | 98.4％ | 99.3％ | 97.9％ |
| CH4Yield of | 2.7％ | 6.1％ | 11.9％ | 24.7％ | 53.2％ | 71.8％ | 76.6％ | 69.4％ |
From the above results, it can be seen that: the catalyst prepared by the method can effectively improve the dispersion degree of NiO on the surface of the catalyst, thereby improving CO2The conversion of (a). When the ratio of Al to Zr is 1:1, the methanation catalyst is evaluated under the conditions of 300 ℃ and normal pressure, and CO2The conversion rate can reach 72.8%. The methanation catalyst has obviously better effect than the traditional Ni/Al catalyst2O3The catalyst has simple preparation method, stable performance and long service life; has excellent development prospect.
Claims (8)
1. A low-temperature carbon dioxide methanation catalyst is characterized in that: the catalyst comprises an active component and a carrier; the active component is Ni, and the carrier is alumina, zirconia or a composite carrier of the alumina and the zirconia; the catalyst comprises 5-25 wt% of active component Ni and the balance of a carrier, wherein the active component Ni accounts for the total mass of the catalyst.
2. The low temperature carbon dioxide methanation catalyst of claim 1, wherein: when the carrier is a composite carrier of alumina and zirconia, the molar ratio of Al to Zr is 1-5: 1 to 2.5.
3. A preparation method of a low-temperature carbon dioxide methanation catalyst is characterized by comprising the following steps:
a. dissolving aluminum nitrate, zirconium nitrate or a compound of the aluminum nitrate and the zirconium nitrate and nickel nitrate in deionized water, and fully stirring at room temperature to obtain a mixed solution;
when the carrier is aluminum nitrate, the mass ratio of the aluminum nitrate to the nickel nitrate is 2-14: 1;
when the carrier is zirconium nitrate, the mass ratio of the zirconium nitrate to the nickel nitrate is 2-13: 1;
when the carrier is a complex of aluminum nitrate and zirconium nitrate, the mass ratio of the aluminum nitrate to the zirconium nitrate to the nickel nitrate is 1.8-10: 2-6: 1;
b. dropwise adding a precipitator into the mixed solution obtained in the step a under the condition of continuously stirring at 60-70 ℃, finishing dropwise adding when the pH value of the solution is 9-10, and continuously stirring for 1-4 hours at 60-70 ℃ to obtain a solid-liquid mixture;
c. b, aging the solid-liquid mixture obtained in the step b, and washing the aged solid-liquid mixture by using distilled water to obtain a solid sample;
d. and c, drying and roasting the solid sample obtained in the step c in sequence, and treating to obtain the Ni-based catalyst, namely the low-temperature carbon dioxide methanation catalyst.
4. The preparation method of the low-temperature carbon dioxide methanation catalyst according to claim 3, characterized by comprising the following steps: in the step b, the precipitator is 0.5-1.0 mol/L of Na2CO3Solution, 0.5-1.0 mol/L of K2CO3Solution or 1.0mol/L ammonia water.
5. The preparation method of the low-temperature carbon dioxide methanation catalyst according to claim 3, characterized by comprising the following steps: and c, during the aging in the step c, the aging time is 12-24 h.
6. The preparation method of the low-temperature carbon dioxide methanation catalyst according to claim 3, characterized by comprising the following steps: and c, in the washing process by using distilled water in the step c, washing the solution by using the distilled water until the pH value of the solution is 7-8.
7. The preparation method of the low-temperature carbon dioxide methanation catalyst according to claim 3, characterized by comprising the following steps: and d, during drying in the step d, the drying temperature is 80-100 ℃, and the drying time is 12-24 hours.
8. The preparation method of the low-temperature carbon dioxide methanation catalyst according to claim 3, characterized by comprising the following steps: and d, during roasting in the step d, roasting temperature is 300-450 ℃, and heat preservation time is 4-6 h.
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