CN115805079A - CO methanation purifying agent based on titanium oxide modified mesoporous alumina and preparation and application thereof - Google Patents
CO methanation purifying agent based on titanium oxide modified mesoporous alumina and preparation and application thereof Download PDFInfo
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- CN115805079A CN115805079A CN202211574490.7A CN202211574490A CN115805079A CN 115805079 A CN115805079 A CN 115805079A CN 202211574490 A CN202211574490 A CN 202211574490A CN 115805079 A CN115805079 A CN 115805079A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 99
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 95
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000012629 purifying agent Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 114
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010926 purge Methods 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000011259 mixed solution Substances 0.000 claims description 57
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 230000032683 aging Effects 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 26
- 238000002791 soaking Methods 0.000 claims description 26
- 239000010936 titanium Substances 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 24
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 15
- 229910052734 helium Inorganic materials 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 6
- 238000000231 atomic layer deposition Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical group 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- 229910004349 Ti-Al Inorganic materials 0.000 description 98
- 229910004692 Ti—Al Inorganic materials 0.000 description 98
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 96
- 229910052757 nitrogen Inorganic materials 0.000 description 48
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- 230000000052 comparative effect Effects 0.000 description 34
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 32
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000001307 helium Substances 0.000 description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 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 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000943 NiAl Inorganic materials 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
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- 229910021529 ammonia Inorganic materials 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 239000011240 wet gel Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
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- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention relates to a CO methanation purifying agent based on titanium oxide modified mesoporous alumina, and preparation and application thereof. Compared with the prior art, the low-load Ni-based purifying agent can remove the 2vol% CO in the crude hydrogen to 0.2ppm at the reaction temperature of less than or equal to 200 ℃.
Description
Technical Field
The invention belongs to the technical field of CO methanation purificant, and relates to a CO methanation purificant based on titanium oxide modified mesoporous alumina, and preparation and application thereof.
Background
Hydrogen is an important industrial raw material and clean energy, and is widely applied to the industries of ammonia synthesis, oil refining industry, petrochemical industry, fuel cells and the like. The petroleum industry is the largest hydrogen user, and the hydrogen consumption accounts for about 35 percent of the total consumption of hydrogen. The hydrogen-rich fraction (also called crude hydrogen) produced in the ethylene process usually contains 1000-20000ppm impurities like carbon monoxide. In many industrial processes such as ammonia synthesis, petroleum processing, fuel cells, etc., CO removal of hydrogen to 10ppm or less is required to prevent catalyst poisoning.
Recent years have purified H with respect to hydrogen-rich systems for CO removal 2 The method of (3) includes a metal alloy membrane separation method, a water gas shift reaction method, a selective oxidation method and a methanation method. The more common chemical method for removing CO from hydrogen in the chemical industry is methanation.
Methanation is the reaction of reducing CO with hydrogen in the presence of a catalyst to form methane and water. The main reaction equation is:
the methanation and CO removal of hydrogen-rich gas in China is divided into two processes of high temperature and low temperature. Compared with the two processes, the high-temperature process has the advantages that the reaction starting temperature is high, generally higher than 280 ℃, the temperature control requirement is strict, the outlet temperature reduction procedure is complex, and the overall energy consumption is higher. And too high a temperature easily deposits carbon on the active components, further affecting the activity. The reaction of the low-temperature CO removal process is generally less than 200 ℃, so that the energy consumption is reduced, and meanwhile, the long-period operation of the purifying agent is facilitated. The low-temperature process can ensure the purity of the clean energy hydrogen, reduce energy consumption and achieve the effects of energy conservation and emission reduction. Therefore, low temperature methanation CO removal processes have gradually replaced high temperature processes in recent years.
The Ru catalyst can obtain higher activity and selectivity under the condition of low temperature, but the unit mass price of Ru is 120 times of that of Ni; although the Ni-based catalyst has a slightly lower activity than Ru, ni is industrially more selected as a main active component because Ni has a high selectivity. The Ni series purifying agents removed by methanation of the hydrogen-rich system CO have respective pertinence and limitation, for example, certain nickel series catalysts are simple in preparation process and low in cost, but the methanation rate of the CO is low, so that the higher removal requirement cannot be met; or the methanation rate of CO is high, but the preparation process is complex and the reaction temperature is high; some methyl alkylating agents have excellent activity at the low temperature of 200 ℃, but the loading of active components is high (> 30 wt%), and the preparation cost is high.
CN113318743A discloses a method for preparing a catalyst by reacting Ni ZrO (zirconium oxide) 2 The methanation catalyst prepared by mixing the metal salt and the chelating agent to form wet gel and drying and roasting the wet gel has simple preparation method and process and convenient operation, but the CO conversion rate can only reach 68 percent at 260 ℃;
CN107626314A discloses a methanation catalyst prepared by a sol-gel method, wherein nickel acetate is used as a nickel source, butyl phthalate and aluminum isopropoxide are used as raw materials of a composite carrier, block polyether F-127 and polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer P123 are used as composite template agents, and the conversion rate of CO of the methanation agent prepared by the method can reach 99%, but the whole preparation process is complex, and the required reaction temperature is high (260-280 ℃);
CN113499780A discloses a methanation agent with nickel as a main active component, wherein the mass content of the nickel is 4.5% -6.5%, the preparation method is simple in process, the CO conversion rate is more than 95%, but the activation temperature of a methyl alkylation agent needs to reach 280 ℃.
CN108816238B describes a nickel-based CO hydrogenation catalyst, a preparation method and an application thereof, the preparation method is simple, excellent activity and stability can be kept below 200 ℃, the CO removal depth can reach 1ppm in the range of 5000ppm, however, the content of the active component NiO of the methanation agent prepared by the method reaches 55-90%, and the production cost is high.
The carrier of the industrial methanation catalyst is mostly Al 2 O 3 。γ-Al 2 O 3 Al on the surface 3+ And O 2- The ions have strong residual bonding capability, and are beneficial to the dispersion of NiO on the surface of the NiO. But at the same time, niO and Al 2 O 3 The reaction force between the catalyst and the catalyst can cause difficult reduction of the catalyst and is easy to produce and inert in the preparation processSexual NiAl 2 O 4 Spinel.
The mesoporous alumina is a material with the aperture of 2-50 nm and a larger specific surface, and has high adsorption performance and stronger sieving capability. Meanwhile, under the influence of the pore diameter, the active components loaded on the mesoporous alumina easily enter into the larger pore channels of the carrier and agglomerate, thereby weakening the surface activity of the catalyst. Therefore, the pore diameter of the catalyst carrier is optimized, and simultaneously, the large specific surface area is maintained, so that the utilization rate of the active component can be effectively improved, and the reaction activity of the catalyst is promoted.
The traditional preparation process, such as a precipitation method, a sol-gel method, an impregnation method, a dry mixing method and the like, has the disadvantages of multiple influencing factors, complex process, difficult accurate control of specific surface, pore volume and pore diameter, and high-content active components need to be loaded to realize low-temperature activity, so that the production cost is increased.
Disclosure of Invention
The invention aims to provide a CO methanation purifying agent based on titanium oxide modified mesoporous alumina, and preparation and application thereof, wherein the low-load Ni series purifying agent can remove 2vol% CO in crude hydrogen to 0.2ppm at the reaction temperature of less than or equal to 200 ℃.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a CO methanation purifying agent based on titanium oxide modified mesoporous alumina, which comprises a titanium oxide modified mesoporous alumina carrier, and an active component and an auxiliary agent loaded on the titanium oxide modified mesoporous alumina carrier, wherein the active component is a metal oxide NiO, and the auxiliary agent is at least one oxide of Zr, ce and La.
Furthermore, in the CO methanation purifying agent, the content of NiO is 15-20 wt%, the content of the auxiliary agent is 0.5-5 wt%, and the balance is a titanium oxide modified mesoporous alumina carrier, wherein the content of titanium oxide used for modification in the titanium oxide modified mesoporous alumina carrier is 3-10 wt%.
Further, in the CO methanation purifying agent, the content of NiO is 17wt%, the content of the auxiliary agent is 2wt%, and the balance is a titanium oxide modified mesoporous alumina carrier, wherein the content of titanium oxide for modification in the titanium oxide modified mesoporous alumina carrier is 5wt%.
Furthermore, the specific surface area of the titanium oxide modified porous alumina carrier is about 235 to 245m 2 Per g, pore volume of about 1.00-1.05 cm 3 (ii)/g, the average pore diameter is about 16 to 18nm.
Furthermore, the specific surface area of the CO methanation purifying agent of the titanium oxide modified mesoporous alumina is 198-206 m 2 Per gram, pore volume of about 0.74-0.80 cm 3 (ii)/g, the average pore diameter is about 14-169m, and the average size of NiO particles is 12nm.
The second technical scheme of the invention provides a preparation method of a CO methanation purifying agent based on titanium oxide modified mesoporous alumina, which comprises the following steps:
(1) By atomic layer deposition of TiO 2 Deposition to gamma-Al 2 O 3 The method comprises the following steps: will be coated with gamma-Al 2 O 3 The glass slide is placed in a vacuum reaction chamber and is swept by high-purity inert gas, titanium precursor vapor is firstly introduced into the vacuum reaction chamber, then the high-purity inert gas is swept, then water vapor is introduced into the vacuum reaction chamber for oxidation, and the high-purity inert gas is swept again to complete a period (namely TiCl is introduced after the inert gas replacement 4 The operation steps of steam → inert gas purging → water steam → inert gas purging are a period), the above period is circulated for a plurality of times to form a film, and then the film is calcined to obtain the titanium oxide modified mesoporous alumina carrier with high specific surface;
(2) Dissolving soluble precursors of Ni and an auxiliary agent in deionized water to form a mixed solution;
(3) And (3) soaking the titanium oxide modified mesoporous alumina carrier in the mixed solution obtained in the step (2) to form a suspension, standing, aging, rotary evaporating, drying and roasting to obtain the target product catalyst.
Further, in the step (1), the temperature of the vacuum reaction chamber is 200-300 ℃, and preferably 250 ℃; the pressure is 10 to 100Pa, preferably 50Pa.
Further, in the step (1), the titanium precursor is TiCl 4 。
Further, in the step (1), the high-purity inert gas is N 2 One of He and Ar.
Further, in the step (1), the introduction time of the titanium precursor vapor is 0.5 to 2 seconds, preferably 1 second; the purging time of the high-purity inert gas is 5 to 10 seconds, preferably 6 seconds; the time for introducing the water vapor is 1 to 4 seconds, preferably 2 seconds; finally, purging with a high purity inert gas for 5 to 10 seconds, preferably 8 seconds.
Further, in the step (1), the number of the cycles is 200 to 1000, preferably 500.
Further, in the step (1), the calcining temperature is 300-550 ℃, preferably 400-500 ℃; the calcination time is 3 to 5 hours, preferably 4 hours.
Further, in the step (2), the soluble precursor of Ni is selected from one of nickel nitrate, nickel oxalate and basic nickel carbonate, and preferably nickel nitrate.
Further, in the step (2), the soluble precursor of the auxiliary agent is selected from one of soluble nitrate and soluble oxalate.
Further, in the step (2), the concentration of Ni in the mixed solution is 0.10 to 0.25mol/L, preferably 0.2mol/L, and the concentration of the auxiliary agent is 0.01 to 0.05mol/L, preferably 0.02mol/L.
Further, in the step (3), the ratio of the titania-modified mesoporous alumina support to the mixed solution is 0.4 to 0.6g/10mL, preferably 0.5g/10mL.
Further, in the step (3), the temperature for standing and aging is 20-40 ℃, preferably 30 ℃, and the time is 12-24 hours, preferably 12 hours.
Further, in the step (3), the temperature of the rotary evaporation is 70 to 90 ℃, preferably 80 ℃.
Further, in the step (3), the drying temperature is 100-120 ℃, preferably 120 ℃, and the drying time is 2-4 h, preferably 4h.
Further, in the step (3), the roasting temperature is 300-550 ℃, preferably 400-500 ℃ and the time is 4-6 h, preferably 5h.
The third technical scheme of the invention provides application of the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina, the CO methanation purifying agent is used for deeply removing CO in a hydrogen-rich system, and the removal effect can reach less than 0.2ppm.
Furthermore, the CO methanation purifying agent is suitable for a hydrogen-rich system with the CO concentration range of 0.5-2 vol%.
Compared with the prior art, the invention has the following advantages:
(1) By adding titanium oxide to modify mesoporous alumina, al is relieved 3+ And Ni 2+ Strong bonding capability between the two, shows good nickel carbonyl resistance under low temperature, and inhibits NiAl 2 O 4 And (4) generating. The titanium oxide modified alumina structure is introduced by adopting an atomic layer deposition method, so that the control and cutting of the composite carrier can be realized more accurately, the specific surface and the pore diameter of the carrier are effectively optimized, the surface dispersion performance of NiO is improved, the formation of large crystal grain NiO is avoided, and the reduction performance is improved.
(2) The invention can solve the problem of gamma-Al 2 O 3 The defects also keep the characteristic of high specific surface area of the alumina, realize low-activity components and high reactivity under low temperature conditions, and simplify the overall preparation process of the purifying agent.
(3) The catalyst provided by the invention has high specific surface, low NiO load content and high activity, can remove the CO of 2vol% in a hydrogen-rich system to be less than 0.2ppm at a lower temperature (less than or equal to 200 ℃), and can be used for removing the CO of crude hydrogen in the olefin industry.
Drawings
FIG. 1 is an XRD pattern of a CO methanation purifying agent prepared in comparative examples 1 to 4 and example 5;
FIG. 2 shows H of the CO methanation purificant prepared in example 1 and comparative examples 2 to 4 2 -a TPR map.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the conventional commercially available raw materials or conventional processing techniques in the art are indicated.
Example 1
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 2
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature of the vacuum reaction chamber to be 275 ℃ and the pressure to be 50Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 0.5 second, purging with high-purity helium for 8 seconds, introducing water vapor into the vacuum reaction chamber for 1.5 seconds, purging with high-purity helium for 8 seconds, completing a period, circulating for 600 times to form a film, and calcining for 4 hours at the temperature of 400 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.14mol/L nickel nitrate and 0.02mol/L zirconium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 18 hours at the room temperature of 35 ℃; setting the temperature of a rotary evaporator to be 75 ℃ and slowly evaporating to remove water; drying at 100 ℃ for 4h, and then placing in a muffle furnace to roast at 400 ℃ for 2.5h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 3
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 200 ℃ and 90Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity helium for 6 seconds, introducing water vapor into the vacuum reaction chamber for 2.5 seconds, purging with high-purity helium for 10 seconds, completing a period, circulating 900 times to form a film, and calcining for 4 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.14mol/L nickel oxalate and 0.03mol/L lanthanum nitrate.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 24 hours at the room temperature of 25 ℃; setting the temperature of a rotary evaporator to 90 ℃ and slowly evaporating to remove water; drying at 110 ℃ for 3h, and then placing in a muffle furnace to roast at 375 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 4
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 90Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity argon for 8 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity argon for 8 seconds, completing a period, circulating for 800 times to form a film, and calcining for 3 hours at the temperature of 450 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.16mol/L nickel nitrate and 0.015mol/L lanthanum nitrate.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 20 ℃; setting the temperature of a rotary evaporator to 85 ℃ and slowly evaporating to remove water; drying at 100 ℃ for 4h, and then placing in a muffle furnace to roast at 375 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 5
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing in a vacuum reaction chamber, and purifying with high purityPurging with nitrogen, setting the temperature of the vacuum reaction chamber at 280 ℃ and the pressure at 50Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 3 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 600 times to form a film, and calcining for 4 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.14mol/L nickel nitrate and 0.01mol/L cerium nitrate.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 24 hours at the room temperature of 25 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 425 ℃ for 2h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 6
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction kettle in a vacuum reaction chamber, purging the reaction kettle by high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 210 ℃ and 40Pa; and (3) introducing titanium precursor steam into the vacuum reaction chamber for 1.5 seconds, purging with high-purity nitrogen for 8 seconds, introducing water vapor into the vacuum reaction chamber for 2.5 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating 900 times to form a film, and calcining for 4 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel oxalate and 0.015mol/L lanthanum nitrate.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 18 hours at the room temperature of 25 ℃; setting the temperature of a rotary evaporator to 85 ℃ and slowly evaporating to remove water; drying at 100 ℃ for 3h, and then placing in a muffle furnace at 475 ℃ for roasting for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 7
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction kettle in a vacuum reaction chamber, purging the reaction kettle by high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 210 ℃ and 80Pa; introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, and introducing high-purity nitrogenAnd (3) purging with gas for 5 seconds, introducing water vapor into the vacuum reaction chamber for 3 seconds, purging with high-purity nitrogen for 10 seconds to complete one period, circulating 1000 times to form a film, and calcining at 400 ℃ for 3 hours to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.18mol/L nickel oxalate and 0.035mol/L zirconium nitrate.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 85 ℃ and slowly evaporating to remove water; drying at 100 ℃ for 4h, and then placing in a muffle furnace to roast at 500 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 8
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 210 ℃ and 40Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity helium for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2.5 seconds, purging with high-purity helium for 10 seconds, completing one period, circulating for 400 times to form a film, and calcining for 4 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.16mol/L nickel oxalate and 0.04mol/L zirconium nitrate.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 24 hours at the room temperature of 25 ℃; setting the temperature of a rotary evaporator to 90 ℃ and slowly evaporating to remove water; and drying at 120 ℃ for 3h, and then placing in a muffle furnace at 475 ℃ for roasting for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 9
Step 1, taking 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; introducing titanium precursor vapor into the vacuum reaction chamber for 1.5 seconds, purging with high-purity nitrogen for 10 seconds, introducing water vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, completing a period, and circulating for 700 times to form the filmAnd calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.015mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 10
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature of the vacuum reaction chamber to be 275 ℃ and the pressure to be 50Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity argon for 10 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity argon for 10 seconds, completing a period, circulating for 500 times to form a film, and calcining for 4 hours at 400 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.17mol/L nickel nitrate and 0.01mol/L lanthanum nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 18 hours at the room temperature of 35 ℃; setting the temperature of a rotary evaporator to be 75 ℃ and slowly evaporating to remove water; drying at 100 ℃ for 4h, and then placing in a muffle furnace to roast at 400 ℃ for 2.5h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 11:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature of the vacuum reaction chamber to be 200 ℃ and the pressure to be 10Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 12:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 300 ℃ and 90Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃, and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 13:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; and drying at 120 ℃ for 4h, and then placing in a muffle furnace for roasting at 300 ℃ for 5h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 14:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 550 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 15:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerous oxalate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃, and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 16:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.1mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; and drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 330 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 17:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.18mol/L nickel nitrate and 0.02mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 18:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 24 hours at the room temperature of 20 ℃; setting the temperature of a rotary evaporator to 70 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to roast at 300 ℃ for 6h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Example 19:
step 1, weighing 0.7g of gamma-Al 2 O 3 Placing the reaction product in a vacuum reaction chamber, purging the reaction product by using high-purity nitrogen, and setting the temperature and the pressure of the vacuum reaction chamber to be 220 ℃ and 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity nitrogen for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity nitrogen for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 15 hours at the room temperature of 40 ℃; setting the temperature of a rotary evaporator to 90 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 550 ℃ for 4h to obtain the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina.
Comparative example 1 gamma-Al 2 O 3 Raw powder
Step 1, weighing 5.0g of gamma-Al 2 O 3 The raw powder is roasted in a muffle furnace for 4h at 550 ℃. Obtaining the mesoporous alumina.
Comparative example 2 impregnation method
Step 1, weighing 5.0g of gamma-Al 2 O 3 The raw powder is roasted in a muffle furnace for 4h at 550 ℃. Obtaining the mesoporous alumina.
And 2, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 3, weighing 3g of the mesoporous alumina in the step 1, soaking the mesoporous alumina in the 60mL of mixed solution, and standing and aging the mesoporous alumina at the room temperature of 30 ℃ for 12 hours; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to roast at 330 ℃ for 3h to obtain the CO methanation purifying agent Ni-Ce/Al.
Comparative example 3 Sol-gel method and dipping method
Step 1, weighing 1.1g of tetrabutyl titanate, dissolving in an ethanol solution, wherein the volume ratio of tetrabutyl titanate to ethanol is 1:3, and adding dilute nitric acid to adjust the pH value to be =3 to obtain a mixed solution.
Step 2, weighing 5.0g of gamma-Al 2 O 3 Adding 50mL of deionized water into the alumina powder, and quickly stirring to obtain slurry gamma-Al 2 O 3 ，
Step 3, slowly adding the mixed solution in the step 1 into the slurry-state gamma-Al in the step 2 2 O 3 And stirred for 3h to form a gel.
And 4, drying the gel obtained in the step 3 at 120 ℃ for 12 hours, and then roasting the gel in a muffle furnace at 550 ℃ for 5 hours to obtain the Ti-Al composite carrier.
And 5, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 6, weighing 3g of the Ti-Al composite carrier in the step 4, soaking the Ti-Al composite carrier in the 60mL of mixed solution, and standing and aging the Ti-Al composite carrier for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent Ni-Ce/Ti-Al.
Comparative example 4 precipitation method and impregnation method
Step 1, 0.8g of titanium sulfate is dissolved in deionized water, and 5.0g of gamma-Al is added 2 O 3 Mixing and stirring, slowly dripping ammonia water at the speed of 1ml/min to adjust the pH value to 8, stirring for 6 hours, standing and aging for 18 hours to obtain a Ti-Al slurry mixture.
And 2, carrying out suction filtration on the Ti-Al slurry mixture obtained in the step 1, washing with deionized water until the pH is =7, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ in a muffle furnace for 4 hours to obtain the Ti-Al composite carrier.
And 3, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate.
Step 4, weighing 3g of the Ti-Al composite carrier in the step 2, soaking the Ti-Al composite carrier in the 60mL of mixed solution, and standing and aging the Ti-Al composite carrier for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent Ni-Ce/Ti-Al.
Comparative example 5 mixing and milling method and dipping method
Step 1, 0.25g of TiO is taken 2 、5.0gγ-Al 2 O 3 Mixing with 0.15g sesbania powder, adding 40ml of water, and uniformly stirring to obtain a Ti-Al adhesive mixture.
And 2, drying the Ti-Al sticky mixture obtained in the step 1 at 120 ℃ for 4 hours, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the Ti-Al composite carrier.
And 3, preparing a mixed solution of 0.15mol/L nickel nitrate and 0.01mol/L cerium nitrate solution.
Step 4, weighing 3g of the Ti-Al composite carrier in the step 2, soaking the Ti-Al composite carrier in the 60mL of mixed solution, and standing and aging the Ti-Al composite carrier for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃ and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purifying agent Ni-Ce/Ti-Al.
Comparative example 6
The same is true as in example 1, except that the addition of cerium nitrate is omitted.
Step 1, weighing 0.7g of gamma-Al 2 O 3 Placing in a vacuum reaction chamber, purging with high-purity nitrogen, and settingThe temperature of the vacuum reaction chamber is 220 ℃, and the pressure is 100Pa; and (3) introducing titanium precursor vapor into the vacuum reaction chamber for 1 second, purging with high-purity helium for 5 seconds, introducing water vapor into the vacuum reaction chamber for 2 seconds, purging with high-purity helium for 10 seconds, completing a period, circulating for 400 times to form a film, and calcining for 3 hours at 500 ℃ to obtain the titanium oxide modified mesoporous alumina carrier Ti-Al.
And 2, preparing 0.15mol/L nickel nitrate solution.
Step 3, weighing 0.5g of carrier Ti-Al, soaking the carrier Ti-Al into the 10mL of mixed solution, and standing and aging the carrier Ti-Al for 12 hours at the room temperature of 30 ℃; setting the temperature of a rotary evaporator to 80 ℃, and slowly evaporating to remove water; drying at 120 ℃ for 4h, and then placing in a muffle furnace to bake at 330 ℃ for 3h to obtain the CO methanation purificant Ni/Ti-Al based on the titanium oxide modified mesoporous alumina.
The characterization conditions are as follows:
the characterization data of the supports prepared in the examples and comparative examples are shown in table 1, wherein the specific surface area, pore volume, and average pore diameter are obtained from BET test; the characterization data of the CO methanation purifiers prepared in the examples and comparative examples are shown in Table 2. Wherein, the specific surface area, the pore volume and the average pore diameter are obtained by a BET test; the reduction temperature of alpha-NiO, beta-NiO and gamma-NiO is controlled by H 2 TPR test, wherein the alpha peak is NiO in free state, the beta peak is NiO in dispersed state, and the gamma peak is NiO strongly attached to the carrier; the Ni particle size is calculated by XRD according to the Sherle formula.
The forms of the components of the CO methanation purifiers prepared in comparative examples 1 to 4 and example 1 are shown in figure 1, and the analysis result is obtained by XRD.
And (3) performance testing:
the removal effects of the CO methanation purifiers prepared in the examples and the comparative examples are shown in Table 3, and the reaction stabilities of the purifiers prepared in the examples and the comparative examples are shown in Table 4. Wherein the CO removal effect is evaluated by the following conditions: 0.75mL of each of the CO methanation purificant of the titanium oxide modified mesoporous alumina prepared in the embodiment 1-19 of the invention and the CO methanation purificant prepared in the comparative example 1-6 of the invention is respectively weighed and respectively filled in a fixed bed reactor for reaction and on-line analysis. Firstly, reducing for 2 hours at 400 ℃ by using nitrogen-hydrogen mixed gas; wherein the volume ratio of the nitrogen-hydrogen mixed gas is 95; after reduction, purging with nitrogen, cooling to 190 ℃, and introducing feed gas for reaction; wherein the feed gas components are 2% (v/v) CO and 98% (v/v) hydrogen, the flow rate is 62.5ml/min, namely the gas space velocity is 5000h-1.
The removal reaction stability of the CO methanation purificant prepared in the examples and the comparative example is shown in table 4, wherein the reaction conditions are the same as the evaluation conditions of the CO removal effect of the purificant, which are measured by GC-FID on-line analysis by a purificant evaluation apparatus.
The reducibility of the CO methanation purifiers prepared in example 1 and comparative examples 3 to 5 is shown in FIG. 2, from H 2 -TPR measurement.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
As shown in table 1, it can be known that: (1) TiO 2 2 By adding a reduced average pore diameter of the support (2) by introducing TiO 2 The preparation methods are different, and the characterization effects presented by the carriers are also different; atomic layer deposition method for introducing TiO 2 The modified alumina carrier has optimal effect. Specifically, the carriers prepared in examples 1 to 19 and comparative examples 2 to 6 were compared with γ -Al of comparative example 1 2 O 3 Comparing the raw powder, which shows that the introduction of the titanium oxide effectively reduces the average pore diameter of the carrier; the average pore diameter of the carrier prepared in examples 1 to 19 and comparative example 6 is smaller than that of the carrier prepared in comparative examples 1 to 5, and the specific surface is obviously improved compared with that of the original powder, which shows that TiO introduced by the atomic layer deposition method 2 Does not occupy gamma-Al 2 O 3 The active sites on the surface increase the overall specific surface area of the carrier, which is more favorable for the loading and dispersion of active components and additives on the surface of the carrier and avoids the agglomeration in the carrier pore canal.
As shown in Table 2, compared with comparative examples 2 to 6, the specific surface of the CO methanation purificant of the titanium oxide modified mesoporous alumina prepared in the examples 1 to 19 of the invention is larger, which shows that the active sites are still more after loading; compared with comparative examples 2 to 6, the CO methanation purificant prepared from the titanium oxide modified mesoporous alumina in the examples 1 to 19 of the invention has smaller change of the average pore diameter relative to the average pore diameter of the carrier shown in the table 1, which shows that the active component and the auxiliary agent have better dispersibility on the surface rather than agglomeration in the inner pore channel; compared with comparative examples 2 to 6, niO particles on the surface of the CO methanation purifying agent of the titanium oxide modified mesoporous alumina prepared in the embodiments 1 to 19 of the invention have smaller particle size, and are more favorable for avoiding agglomeration to generate nickel spinel; compared with comparative examples 2 to 6, the reduction temperatures of the alpha peak and the beta peak of the CO methanation purificant of the titanium oxide modified mesoporous alumina prepared in the examples 1 to 19 of the invention are lower.
As shown in FIG. 1, the diffraction peaks at 37.2 °, 43.2 ° and 75.4 ° 2 θ areNiO characteristic peak; diffraction peak at 2 theta of 28.6 DEG is TiO 2 One of the characteristic peaks of (a); diffraction peaks at 28.6 ° and 56.3 ° 2 θ were CeO 2 Characteristic peak of (a); a diffraction peak at 2 theta of 66.9 DEG is Al 2 O 3 One of the characteristic peaks of (a); a diffraction peak at 2 theta of 45.7 DEG is Al 2 O 3 With NiAl 2 O 4 Overlapping characteristic peaks of (a); a diffraction peak at 2 theta of 62.8 DEG is Al 2 O 3 With TiO 2 Overlapping characteristic peaks.
Compared with the CO methanation purifying agent of titanium oxide modified mesoporous alumina prepared in the embodiment 1 of the invention, niO diffraction peaks in the CO methanation purifying agents prepared in the comparative examples 2-4 are sharper, which shows that NiO particles in the purifying agent prepared in the embodiment 1 are smaller and are dispersed more uniformly; and a diffraction peak of 45.7 DEG is Al 2 O 3 With NiAl 2 O 4 Compared with the comparative example 1, the purifying agents prepared in the comparative examples 2 to 4 have nickel spinel which is difficult to reduce, and the purifying agent prepared in the example 1 has no nickel spinel which is difficult to reduce on the surface; example 1 TiO in scavenger in comparison with comparative examples 2 to 4 2 The diffraction peak signal is weaker, indicating that TiO 2 Dispersedly enter Al 2 O 3 The channels of (2) do not occupy surface active sites.
As shown in Table 3, compared with comparative examples 1 to 6, the CO methanation purificant prepared by the titanium oxide modified mesoporous alumina in the embodiments 1 to 19 of the invention has higher reaction activity under low temperature (190 ℃) and better CO removal depth.
As shown in Table 4, compared with comparative examples 1 to 6, the CO methanation purificant of the titanium oxide modified mesoporous alumina prepared in the examples 1 to 19 of the invention has better reaction stability, and the CO removal effect is still less than 0.2ppm (v) after continuous reaction for 100 hours.
As shown in FIG. 2, the reduction temperature of comparative example 5 is 450 to 490 ℃, the reduction temperature is high, and the reduction peak area is small; the reduction temperature of the comparative example 3 is between 395 ℃ and 540 ℃, the reduction temperature is lower, the reduction temperature range is large, and the reduction peak area is lower; the reduction temperature of the comparative example 4 is between 385 ℃ and 490 ℃, the reduction temperature is lower, and the reduction peak area is lower; example 1 the reduction temperature was between 380 ℃ and 480 ℃ andthe original temperature is low, and the reduction peak area is large; in comparison with comparative examples 3 to 5, H 2 The TPR results show that example 1 has a lower activation temperature and a higher activity in the low temperature range, which is consistent with the characterization results.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The CO methanation purifying agent based on the titanium oxide modified mesoporous alumina is characterized by comprising a titanium oxide modified mesoporous alumina carrier, and an active component and an auxiliary agent which are loaded on the titanium oxide modified mesoporous alumina carrier, wherein the active component is a metal oxide NiO, and the auxiliary agent is at least one oxide of Zr, ce and La.
2. The CO methanation purifying agent based on the titanium oxide modified mesoporous alumina as claimed in claim 1, wherein the content of NiO in the CO methanation purifying agent is 15-20 wt%, the content of the auxiliary agent is 0.5-5 wt%, the balance is a titanium oxide modified mesoporous alumina carrier, and the content of titanium oxide for modification in the titanium oxide modified mesoporous alumina carrier is 3-10 wt%.
3. The CO methanation purifying agent based on titanium oxide modified mesoporous alumina as claimed in claim 1, wherein the content of NiO in the CO methanation purifying agent is 17wt%, the content of the auxiliary agent is 2wt%, the balance is a titanium oxide modified mesoporous alumina carrier, and the content of titanium oxide for modification in the titanium oxide modified mesoporous alumina carrier is 5wt%.
4. The CO methanation purifying agent based on titanium oxide modified mesoporous alumina as claimed in claim 1, wherein the specific surface area of the titanium oxide modified porous alumina carrier is about 235-245 m 2 Per g, pore volume of about 1.00-1.05 cm 3 Per gram, the average pore diameter is about 16 to 18nm.
5. The preparation method of the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
(1) By atomic layer deposition of TiO 2 Deposition to gamma-Al 2 O 3 The method comprises the following steps: will be coated with gamma-Al 2 O 3 Placing the glass slide in a vacuum reaction chamber, purging with high-purity inert gas, firstly introducing titanium precursor steam into the vacuum reaction chamber, then purging with the high-purity inert gas, then introducing water vapor into the vacuum reaction chamber for oxidation, then purging with the high-purity inert gas again to complete a period, circulating the period for a plurality of times to form a film, and then calcining to obtain the titanium oxide modified mesoporous alumina carrier with the high specific surface;
(2) Dissolving soluble precursors of Ni and an auxiliary agent in deionized water to form a mixed solution;
(3) And (3) soaking the titanium oxide modified mesoporous alumina carrier in the mixed solution obtained in the step (2) to form a suspension, standing for aging, performing rotary evaporation, drying, and roasting to obtain the target product catalyst.
6. The preparation method of the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina as claimed in claim 5, wherein in the step (1), the temperature in the vacuum reaction formula is 200-300 ℃, and the pressure is 10-100 Pa;
the vapor of the titanium precursor is TiCl 4 Steam;
the high-purity inert gas is N 2 One of He or Ar;
the introduction time of the titanium precursor vapor is 0.5-2 seconds, the purging time of the high-purity inert gas is 5-10 seconds, the introduction time of the water vapor is 1-4 seconds, and the purging time of the high-purity inert gas after the water vapor is introduced for oxidation is 5-10 seconds;
the cycle number is 200-1000;
the calcining temperature is 300-550 ℃ and the time is 3-5 h.
7. The preparation method of the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina as claimed in claim 5, wherein in the step (2), the soluble precursor of Ni is selected from one of nickel nitrate, nickel oxalate and basic nickel carbonate;
the soluble precursor of the auxiliary agent is selected from one of soluble nitrate and soluble oxalate;
in the mixed solution, the concentration of Ni is 0.10-0.25 mol/L, and the concentration of the auxiliary agent is 0.01-0.05 mol/L.
8. The preparation method of the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina as claimed in claim 5, wherein in the step (3), the ratio of the titanium oxide modified mesoporous alumina carrier to the mixed solution is 0.4-0.6 g/10mL;
standing and aging at 20-40 deg.c for 12-24 hr;
the temperature of rotary evaporation is 70-90 ℃;
the drying temperature is 100-120 ℃, and the drying time is 2-4 h;
the roasting temperature is 300-550 ℃ and the roasting time is 4-6 h.
9. Use of a CO methanation scavenger based on titania modified mesoporous alumina as claimed in any of claims 1 to 4 for the deep removal of CO in a hydrogen rich system.
10. The application of the CO methanation purifying agent based on the titanium oxide modified mesoporous alumina as claimed in claim 9, wherein the CO methanation purifying agent is suitable for a hydrogen-rich system with a CO concentration ranging from 0.5% to 2% (vol).
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| CN104815662A (en) * | 2015-04-17 | 2015-08-05 | 东南大学 | Low-temperature high-activity nano-composite catalyst for methanation of synthesis gas and preparation method thereof |
| CN108057445A (en) * | 2017-12-21 | 2018-05-22 | 厦门大学 | A kind of methanation catalyst of titaniferous aluminium complex carrier and preparation method thereof |
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| CN104815662A (en) * | 2015-04-17 | 2015-08-05 | 东南大学 | Low-temperature high-activity nano-composite catalyst for methanation of synthesis gas and preparation method thereof |
| CN109833891A (en) * | 2017-11-29 | 2019-06-04 | 中国石油天然气股份有限公司 | A kind of catalyst for hydro-processing heavy distillate and its application |
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