CN112691657B - Sepiolite carrier, preparation method thereof, methane combustion catalyst and application thereof - Google Patents
Sepiolite carrier, preparation method thereof, methane combustion catalyst and application thereof Download PDFInfo
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- CN112691657B CN112691657B CN201911012018.2A CN201911012018A CN112691657B CN 112691657 B CN112691657 B CN 112691657B CN 201911012018 A CN201911012018 A CN 201911012018A CN 112691657 B CN112691657 B CN 112691657B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 239000004113 Sepiolite Substances 0.000 title claims abstract description 92
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 92
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 92
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011343 solid material Substances 0.000 claims abstract description 5
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000004537 pulping Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002736 metal compounds Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000007084 catalytic combustion reaction Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 230000002269 spontaneous effect Effects 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 159000000008 strontium salts Chemical class 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 titanium ions Chemical group 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 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 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J23/83—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 rare earths or actinides
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
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Abstract
The invention provides a sepiolite carrier and a preparation method thereof, a methane combustion catalyst and application thereof, wherein the preparation method of the sepiolite carrier comprises the following steps: adding sepiolite into the modified solution, heating to not less than 50 ℃ for reaction, and then roasting the reacted solid material to obtain modified sepiolite, namely the sepiolite carrier; wherein the modified solution is titanic acid and inorganic acid, and the inorganic acid is one or more of nitric acid, hydrochloric acid and sulfuric acid. The invention obtains the carrier for loading the active component of the methane combustion catalyst by modifying the sepiolite, and the methane combustion catalyst adopting the sepiolite carrier has excellent thermal stability and low-temperature activity.
Description
Technical Field
The invention belongs to the technical field of energy utilization and environmental protection, and relates to a sepiolite carrier, a preparation method thereof, a methane combustion catalyst and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
With the increasing problems of environmental pollution and energy shortage, the development of clean energy has received much attention. Methane is a clean energy source and is the main component of natural gas. However, because the combustion temperature of natural gas is very high (generally, more than 1500 ℃), the combustion of natural gas in air can generate harmful gases such as nitrogen oxides, CO and the like, thereby causing environmental pollution. The catalytic combustion is flameless combustion, realizes combustion under the catalytic action of active particles, and has high combustion efficiency and energy utilization rate; and nitrogen oxides are generally formed at a high temperature of more than 1300 ℃, nitrogen and oxygen are generated through a free radical reaction, and the working temperature of catalytic combustion is below 1300 ℃, so that the generation of the nitrogen oxides can be greatly inhibited, and meanwhile, the catalytic combustion process is easier to carry out and more thorough in methane combustion by virtue of the action of catalytic particles, so that CO generated by incomplete methane combustion is obviously reduced. Catalytic combustion is therefore considered to be an effective way to solve the problem of high temperature combustion of natural gas.
For the purpose, noble metal catalysts and metal oxide catalysts have been studied more for methane combustion catalysts. Although the noble metal (such as Pd, pt, rh, au, etc.) catalyst has excellent catalytic activity, the noble metal catalyst has high price and poor thermal stability, which brings high cost to industrial production, so that the defects greatly affect the industrial application of the noble metal catalyst. The raw materials of the metal oxide catalyst are cheap and easy to obtain, the catalytic combustion activity of the metal oxide catalyst is close to that of a noble metal catalyst, and the metal oxide catalyst has higher thermal stability, so that part of the noble metal catalyst can be replaced.
Perovskite type metal oxide catalyst with general formula ABO 3 Generally, A is a system metal and B is a transition metal, and the combustion activity of the catalyst on methane mainly depends on the oxide of the B site component. It has been found that when the A and B sites are partially substituted, the catalytic performance of the catalyst can be significantly changed, such as the substitution of the A site (A) 1-x A' x BO 3 ) B site substitution (AB) 1-y B' y O 3 ) Or both A and B sites are substituted（A 1-x A' x B 1-y B' y O 3 ). However, the inventors of the present invention have found through experiments that even if a partially substituted perovskite-type metal oxide catalyst is used, the problems of low specific surface area and easy sintering at high temperature still exist, which affect the popularization and application of the catalyst.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a sepiolite carrier and a preparation method thereof, a methane combustion catalyst and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the invention provides a preparation method of a sepiolite carrier, which comprises the steps of adding sepiolite into a modified solution, heating to the temperature of not lower than 50 ℃ for reaction, and then roasting the reacted solid material to obtain the modified sepiolite, namely the sepiolite carrier; wherein the modified solution is titanic acid and inorganic acid, and the inorganic acid is one or more of nitric acid, hydrochloric acid and sulfuric acid.
Sepiolite is a magnesium-rich silicate clay mineral. Its theoretical chemical formula is Mg 8 [Si 2 O 30 ](OH) 4 ·12H 2 O, 4 of the water molecules are crystal water: the balance being zeolite water. Sepiolite belongs to S monoclinic system or orthorhombic system chain layered hydrous magnesium aluminum silicate or magnesium silicate mineral, and has huge specific surface area capable of adsorbing active components of various reactants and catalysts. The sepiolite modified by acid-titanium utilizes titanium ions and acid proton H + Magnesium ions in the sepiolite framework are partially replaced, so that the magnesia octahedral sheets sandwiched by the silica tetrahedral sheets are partially deconstructed, internal channels are communicated and expanded, the specific surface area of the sepiolite carrier is obviously increased, and the obtained sepiolite carrier has good performances such as good activity, high heat resistance and the like.
At the same time, the present inventionModifying sepiolite to obtain TiO 2 The sepiolite carrier is propped into the sepiolite layers with the layered structure, the interlayer spacing is changed, the specific surface area and the specific pore volume of the sepiolite carrier are further obviously increased, the adsorption and the dispersion of active components are facilitated, and the saturated adsorption quantity of the sepiolite can be increased.
In another aspect, the invention provides a sepiolite carrier obtained by the above preparation method.
Titanium content in TiO 2 5 to 10 percent by weight.
In a third aspect, the invention provides a methane combustion catalyst, which comprises an active component and a carrier, wherein the carrier loads the active component, the active component is a perovskite type metal oxide catalyst, and the carrier is the sepiolite carrier.
The methane combustion catalyst provided by the invention has excellent thermal stability and low-temperature activity, and can be used for reporting the stability of methane catalytic combustion within a long running time.
Active component is La x Sr 1-x Co y Ni 1-y O 3 Wherein x =0 to 0.9, y =0.4 to 0.7.
In a fourth aspect, the invention provides a method for preparing a methane combustion catalyst, comprising the steps of loading metal salt to the sepiolite carrier by a sol-gel method, then combusting gel on the sepiolite carrier, and then calcining to obtain the methane combustion catalyst, wherein the metal salt is a metal compound of metal elements required by the perovskite type metal oxide catalyst.
The preparation steps are as follows: adding citric acid and ammonia water into a metal salt aqueous solution, heating to generate gel, adding an ethylene glycol solution, uniformly mixing, adding a sepiolite carrier, stirring and pulping, evaporating water in the slurry to dryness, heating to enable the gel to be self-ignited, adding a binder and an extrusion aid into the burnt ash, extruding and molding, and calcining to obtain the methane combustion catalyst.
Dissolving citric acid in ammonia water, adjusting the pH value to 6-8, and then adding the solution into a metal salt aqueous solution.
Heating to 200 to 250 ℃ to ensure that the gel is self-ignited, and introducing air with the oxygen content of 15 to 18 percent after self-ignition to control the combustion speed.
The methane catalytic combustion can provide more stable heat, the catalytic activity of the methane combustion catalyst is required for the methane catalytic combustion, and the catalytic combustor and the gas heat exchanger can both adopt the methane catalytic combustion to provide a heat source, so that the fifth aspect of the invention provides the application of the methane combustion catalyst in the catalytic combustor and/or the gas heat exchanger.
The invention has the beneficial effects that:
the methane combustion catalyst provided by the invention adopts acid-titanium to modify sepiolite as a carrier, a beating method is adopted to load active component gel onto the modified sepiolite, the active component gel is roasted after self-combustion to generate a perovskite structure, so that the active component is uniformly dispersed on the sepiolite carrier, and the perovskite type methane combustion catalyst is prepared. The preparation method of the catalyst is simple to operate, the perovskite component has high purity and small particle size, the defect of poor dispersion of the perovskite powder prepared by the self-combustion method is overcome, the high-temperature sintering resistance of the catalyst is improved, and the catalyst has good low-temperature activity.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is a schematic flow chart of an atmospheric pressure evaluation apparatus for detecting a catalyst used in each example of the present invention.
FIG. 2 is an activity curve of catalyst A prepared in example 1 of the present invention in continuous operation for 200 hours at 620 ℃ for catalytic combustion of methane.
The system comprises a pressure reducer 1, a pressure reducer 2, a stop valve 3, a mass flow meter 4, a preheater 5, a reactor 6, a gas-liquid separator 7, a dryer 8 and a chromatograph.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the problems of low specific surface area, easy sintering at high temperature and the like of the perovskite type metal oxide catalyst, the invention provides a sepiolite carrier and a preparation method thereof, a methane combustion catalyst and application thereof.
The invention provides a typical implementation mode of a sepiolite carrier, which comprises the steps of adding sepiolite into a modified solution, heating to a temperature of not lower than 50 ℃ for reaction, roasting the reacted solid material, and obtaining the modified sepiolite, namely the sepiolite carrier; wherein the modified solution is titanic acid and inorganic acid, and the inorganic acid is one or more of nitric acid, hydrochloric acid and sulfuric acid.
The sepiolite modified by acid-titanium utilizes titanium ions and acid proton H + Magnesium ions in the sepiolite framework are partially replaced, so that the magnesia octahedral sheets sandwiched by the silica tetrahedral sheets are partially deconstructed, internal channels are communicated and expanded, the specific surface area of the sepiolite carrier is obviously increased, and the obtained sepiolite carrier has good performances such as good activity, high heat resistance and the like.
Meanwhile, after the sepiolite is modified, the TiO is enabled to be 2 The sepiolite carrier is propped into the sepiolite layers with the layered structure, the interlayer spacing is changed, the specific surface area and the specific pore volume of the sepiolite carrier are further obviously increased, the adsorption and the dispersion of active components are facilitated, and the saturated adsorption quantity of the sepiolite can be increased.
In one or more embodiments of this embodiment, the concentration of the inorganic acid is 0.2 to 0.4 mol/L.
In one or more embodiments of this embodiment, the mineral acid is nitric acid.
In one or more embodiments of this embodiment, the concentration of titanic acid is 0.01 to 0.1 mol/L.
In one or more embodiments of this embodiment, the sepiolite is an alpha-type sepiolite, and is white or light gray in color, avoiding light red, light yellow or brown, etc. When the sepiolite is white sepiolite or gray sepiolite, the white sepiolite comprises the following components in percentage by mass: siO 2 2 66%~68%，MgO 30%~32%，Fe x O y Less than 0.2 percent and the balance of Al 2 O 3 CaO; the grey white sepiolite comprises the following components in percentage by mass: siO 2 2 65%~67%，MgO 30%~32%，Fe x O y Less than 1.0 percent and the balance of Al 2 O 3 And CaO. The loading effect is better by adopting the sepiolite of the type.
In one or more embodiments of the embodiment, the solid-liquid mass ratio of the sepiolite to the modification solution is 1.
In one or more embodiments of the embodiment, the reaction temperature is 50 to 100 ℃, and the reaction time is 8 to 12h.
In one or more embodiments of this embodiment, the reacted material is filtered, washed, and dried to obtain a solid material.
In one or more embodiments of the embodiment, the baking temperature is 350 to 400 ℃, and the baking time is 4 to 8h.
In another embodiment of the invention, a sepiolite carrier is provided, which is obtained by the preparation method.
In one or more examples of this embodiment, the titanium content is in the form of TiO 2 5 to 10 percent by weight.
In a third embodiment of the present invention, there is provided a methane combustion catalyst, comprising an active component and a carrier, wherein the carrier carries the active component, the active component is a perovskite type metal oxide catalyst, and the carrier is the sepiolite carrier.
The methane combustion catalyst provided by the invention has excellent thermal stability and low-temperature activity, and can compensate the stability of methane catalytic combustion within a long running time.
In one or more embodiments of this embodiment, the active ingredient is 25 to 35% by weight, with the balance being a carrier.
In one or more embodiments of this embodiment, the active component is La x Sr 1-x Co y Ni 1-y O 3 Wherein x =0 to 0.9, y =0.4 to 0.7. When x =0.5 to 0.6 and y =0.6 to 0.7, the catalytic effect of the catalyst is better. When x =0.6, y =0.7, or x =0.5, y =0.6, the catalytic effect of the catalyst is more excellent.
In one or more embodiments of this embodiment, the pore volume is 0.30 to 0.55 mL/g.
In one or more embodiments of this embodiment, 90% of the pores are 20 to 45 nm in diameter.
In one or more embodiments of the present disclosure, the specific surface area is 100 to 120 m 2 /g。
In one or more embodiments of the embodiment, the bulk density of the catalyst is 0.75 to 0.85Kg/L, and the side pressure strength of the catalyst is 100 to 120N/cm.
In a fourth embodiment of the present invention, a method for preparing a methane combustion catalyst is provided, in which a metal salt is loaded on the sepiolite carrier by a sol-gel method, and then the gel on the sepiolite carrier is combusted, followed by calcination to obtain the methane combustion catalyst, wherein the metal salt is a metal compound of a metal element required by the perovskite-type metal oxide catalyst.
The metal salt of the invention is a soluble compound.
In one or more embodiments of this embodiment, the preparing step is: adding citric acid and ammonia water into a metal salt aqueous solution, heating to generate gel, adding an ethylene glycol solution, uniformly mixing, adding a sepiolite carrier, stirring and pulping, evaporating water in the slurry to dryness, heating to enable the gel to be self-ignited, adding a binder and an extrusion aid into the burnt ash, extruding and molding, and calcining to obtain the methane combustion catalyst.
In the series of embodiments, the total concentration of metal ions of the metal salt is 0.1 to 3 mol/L.
In the series of embodiments, the metal salt is lanthanum salt, strontium salt, cobalt salt or nickel salt. The lanthanum salt in the invention refers to a compound containing lanthanum element, such as lanthanum chloride, lanthanum nitrate, lanthanum sulfate, etc. The strontium salt according to the present invention refers to a compound containing strontium element, such as cobalt strontiate, strontium nitrate, strontium sulfate, etc. The cobalt salt according to the present invention refers to a compound containing cobalt element, such as cobalt chloride, cobalt nitrate, cobalt sulfate, and the like. The nickel salt according to the present invention refers to a compound containing nickel element, such as nickel chloride, nickel nitrate, nickel sulfate, and the like. When the metal salt is a nitrate, the catalyst performance is better.
In the series of embodiments, citric acid is dissolved in ammonia water, the pH value is adjusted to 6 to 8, and then a metal salt aqueous solution is slowly added. This pH aids gel formation. When the pH is 6.5 to 7, the gel formation effect is more excellent.
The ethylene glycol plays a role of a combustion improver in the preparation process, and in the series of embodiments, the ethylene glycol accounts for 10 to 15 percent of the total mass of the metal salt. The mass concentration of the ethylene glycol solution is not less than 60 percent.
In the series of embodiments, the gel is heated to 200 to 250 ℃ to be self-ignited, and air with the oxygen content of 15 to 18 percent is introduced after the gel is self-ignited to control the combustion speed.
The binder is a reagent capable of binding materials together, such as water glass, citric acid, oxalic acid, nitric acid and the like, and in the series of embodiments, the binder is the water glass and the citric acid. The catalytic effect can be better prevented from being influenced by the binder. The addition amount of the binder is generally 1 to 6 percent of the mass of the raw materials, and the effect is better when the addition amount of the binder is 2 to 4 percent.
The extrusion aid disclosed by the invention can be used for assisting in better extrusion forming of materials, such as sesbania powder, starch and the like. In the series of embodiments, the extrusion aid is sesbania powder. The addition amount of the extrusion aid is generally 1 to 6 percent of the mass of the raw materials, and when the addition amount of the extrusion aid is 2 to 4 percent, the effect is better.
In this series of examples, drying was performed prior to calcination. The drying mode is airing.
In this series of examples, the calcination temperature was 600 to 800 ℃. The formation of the perovskite serving as the active component is influenced by the temperature. When the calcination temperature is 720 to 750 ℃, the effect is better. The calcination time is 4 to 8 hours, and when the calcination time is 5 hours, the calcination effect is better.
In a fifth embodiment of the invention, there is provided a use of the above methane combustion catalyst in a catalytic combustor and/or a gas fired heat exchanger.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
The preparation method of the perovskite type methane combustion catalyst provided by the embodiment comprises the following steps:
1) Dissolving 97g of alpha-titanic acid in 16000 mL of dilute nitric acid solution with the concentration of 0.2mol/L to prepare modified solution; adding 585 g of sepiolite and the modified solution into a reactor, heating to 85 ℃, stirring for 12 hours, after stirring, carrying out suction filtration, washing with distilled water, placing to be neutral, drying, and roasting at 400 ℃ for 6 hours to obtain the required modified sepiolite;
2) Weighing 403.6g La (NO) 3 ) 3 ·6H 2 O、131.1g Sr(NO 3 ) 2 、316.5g Co(NO 3 ) 2 ·6H 2 O、135.5g Ni(NO 3 ) 2 ·6H 2 Preparing water solution from O, slowly adding ammonia water with the concentration of 5 percent (mass percent) and 650g of citric acid dissolved in the ammonia water, stirring, heating the mixed solution to 90 ℃, adding 35g of glycol water solution with the concentration of 65 percent (mass percent) after gel is generated, and uniformly stirring.
3) Adding the modified sepiolite into the gel, stirring strongly and pulping, evaporating the water in the slurry to dryness, and moving the slurry into an electric furnace to heat to 250 ℃ at constant temperature to initiate spontaneous combustion. Crushing the combustion ash, adding 20g of citric acid and 40g of sesbania powder, extruding, forming, airing, roasting at 780 ℃ for 5 hours to obtain the catalyst A, wherein the molecular general formula of the active component is La 0.6 Sr 0.4 Co 0.7 Ni 0.3 O 3 The active component loading was 35%.
Example 2
The preparation method of the perovskite type methane combustion catalyst provided by the embodiment comprises the following steps:
1) Dissolving 90.5g of alpha-titanic acid in 15000mL of dilute nitric acid solution with the concentration of 0.3mol/L to prepare modified solution; adding 610g of sepiolite and the modified solution into a reactor, heating to 85 ℃, stirring for 8 hours, performing suction filtration after stirring, washing with distilled water, placing to be neutral, drying, and roasting at 390 ℃ for 6 hours to obtain the required modified sepiolite;
2) 324.5g La (NO) are weighed out 3 ) 3 ·6H 2 O、158.1g Sr(NO 3 ) 2 、261.8g Co(NO 3 ) 2 ·6H 2 O、174.4g Ni(NO 3 ) 2 ·6H 2 Preparing water solution from O, slowly adding into 10% (mass percent) ammonia water containing 600g of citric acid, stirring, heating the mixed solution to 90 ℃, adding 50g of glycol water solution with the concentration of 60% (mass percent) after generating gel, and uniformly stirring.
3) Adding the modified sepiolite into the gel, stirring and pulping, evaporating the water in the slurry to dryness, and transferring the slurry into an electric furnace to heat to 240 ℃ at constant temperature to initiate spontaneous combustion. Crushing the combustion ash, adding 30g of water glass and 30g of sesbania powder, extruding, forming, airing, and roasting at 760 ℃ for 5 hours to obtain a catalyst B, wherein the general molecular formula of an active component of the catalyst B is La 0.5 Sr 0.5 Co 0.6 Ni 0.4 O 3 The active component loading was 33%.
Example 3
The preparation method of the perovskite type methane combustion catalyst provided by the embodiment comprises the following steps:
1) Dissolving 81.6g of alpha-titanic acid in 12000mL of dilute nitric acid solution with the concentration of 0.3mol/L to prepare modified solution; adding 625g of sepiolite and the modified solution into a reactor, heating to 90 ℃, stirring for 10 hours, after stirring, carrying out suction filtration, washing with distilled water, placing to be neutral, drying, and roasting at 380 ℃ for 6 hours to obtain the required modified sepiolite;
2) Weighing 257.8g La (NO) 3 ) 3 ·6H 2 O、188.4g Sr(NO 3 ) 2 、216.6g Co(NO 3 ) 2 ·6H 2 O、216.4g Ni(NO 3 ) 2 ·6H 2 Preparing water solution from O, slowly adding 600g of ammonia water with citric acid concentration of 10% (mass percentage), stirring, heating the mixed solution to 90 ℃, adding 38g of ethylene glycol water solution with concentration of 70% (mass percentage) after gel is generated, and uniformly stirring.
3) Adding the modified sepiolite into the gel, stirring and pulping, evaporating the water in the slurry to dryness, and transferring the slurry into an electric furnace to heat at constant temperature of 230 ℃ to initiate spontaneous combustion. Crushing the combustion ash, adding 35g of water glass and 30g of sesbania powder, extruding, forming, airing, roasting at 770 ℃ for 8 hours to obtain a catalyst C, wherein the general molecular formula of an active component of the catalyst C is La 0.4 Sr 0.6 Co 0.5 Ni 0.5 O 3 The active component loading was 32%.
Example 4
The preparation method of the perovskite type methane combustion catalyst provided by the embodiment comprises the following steps:
1) Dissolving 73.6g of alpha-titanic acid in 9000mL of dilute nitric acid solution with the concentration of 0.4mol/L to prepare modified solution; adding 651g of sepiolite and the modified solution into a reactor, heating to 80 ℃, stirring for 12 hours, performing suction filtration after stirring, washing with distilled water, placing to be neutral, drying, and roasting at 350 ℃ for 8 hours to obtain the required modified sepiolite;
2) 185.7g La (NO) are weighed out 3 ) 3 ·6H 2 O、211.2g Sr(NO 3 ) 2 、166.5g Co(NO 3 ) 2 ·6H 2 O、249.5g Ni(NO 3 ) 2 ·6H 2 Preparing aqueous solution from O, slowly adding 580g of ammonia water dissolved with citric acid concentration of 12% (mass percentage), stirring, heating the mixed solution to 85 ℃, adding 39g of glycol aqueous solution with concentration of 60% (mass percentage) after generating gel, and uniformly stirring.
3) Adding the modified sepiolite into the gel, stirring and pulping, evaporating the water in the slurry to dryness, and transferring the slurry into an electric furnace to heat to 200 ℃ at constant temperature to initiate spontaneous combustion. Crushing the combustion ash, adding 20g of water glass and 45g of sesbania powder, extruding, forming, airing, and roasting at 720 ℃ for 8 hours to obtain a catalyst D, wherein the general molecular formula of an active component of the catalyst D is La 0.3 Sr 0.7 Co 0.4 Ni 0.6 O 3 The active component loading was 30%.
Example 5
The preparation method of the perovskite type methane combustion catalyst provided by the embodiment comprises the following steps:
1) Dissolving 58.5g of alpha-titanic acid in 10000mL of dilute nitric acid solution with the concentration of 0.3mol/L to prepare modified solution; adding 611g of sepiolite and the modified solution into a reactor, heating to 75 ℃, stirring for 12 hours, performing suction filtration after stirring, washing with distilled water, placing to be neutral, drying, and roasting at 380 ℃ for 6 hours to obtain the required modified sepiolite;
2) Weighing 148g La (NO) 3 ) 3 ·6H 2 O、288.5g Sr(NO 3 ) 2 、348.3g Co(NO 3 ) 2 ·6H 2 O、149.1gNi(NO 3 ) 2 ·6H 2 Preparing water solution from O, slowly adding ammonia water dissolved with 700g of citric acid with the concentration of 5 percent (mass percent), stirring, heating the mixed solution to 90 ℃, adding 49g of glycol water solution with the concentration of 65 percent (mass percent) after gel is generated, and uniformly stirring.
3) Adding the modified sepiolite into the gel, stirring and pulping, evaporating the water in the slurry to dryness, transferring to an electric furnace, heating to 220 ℃ at constant temperature, and initiating spontaneous combustion. Crushing the combustion ash, adding 40g of water glass and 45g of starch, extruding, forming, airing, roasting at 740 ℃ for 6 hours to obtain a catalyst E, wherein the molecular general formula of an active component of the catalyst E is La 0.2 Sr 0.8 Co 0.7 Ni 0.3 O 3 The active component loading was 35%.
Example 6
The preparation method of the perovskite type methane combustion catalyst provided by the embodiment comprises the following steps:
1) Dissolving 112.6g of alpha-titanic acid in 18000mL of dilute nitric acid solution with the concentration of 0.3mol/L to prepare modified solution; adding 675g of sepiolite and the modified solution into a reactor, heating to 90 ℃, stirring for 12 hours, after stirring, carrying out suction filtration, washing with distilled water, placing to be neutral, drying, and roasting at 380 ℃ for 4 hours to obtain the required modified sepiolite;
2) 404.7g La (NO) was weighed out 3 ) 3 ·6H 2 O、21.2g Sr(NO 3 ) 2 、211.6g Co(NO 3 ) 2 ·6H 2 O、90.6g Ni(NO 3 ) 2 ·6H 2 Preparing an aqueous solution from O, slowly adding the aqueous solution into ammonia water dissolved with 450g of citric acid and 8 percent (mass percentage), stirring, heating the mixed solution to 85 ℃, adding 39g of ethylene glycol aqueous solution with 65 percent (mass percentage) of concentration after generating gel, and uniformly stirring.
3) Adding the modified sepiolite into the gel, stirring and pulping, evaporating the water in the slurry to dryness, and transferring the slurry into an electric furnace to heat to 240 ℃ at constant temperature to initiate spontaneous combustion. Crushing the combustion ash, adding 20g of citric acid and 40g of sesbania powder, extruding, forming, airing, roasting at 770 ℃ for 6 hours to obtain a catalyst F, wherein the general molecular formula of an active component of the catalyst F is La 0.9 Sr 0.1 Co 0.7 Ni 0.3 O 3 The active component loading was 25%.
Comparative example 1
Comparative example the modified sepiolite carrier in experimental example 1 was replaced with unmodified sepiolite, and the preparation method of the perovskite-type methane combustion catalyst provided comprises the following steps:
1) Weighing 403.6g La (NO) 3 ) 3 ·6H 2 O、131.1g Sr(NO 3 ) 2 、316.5g Co(NO 3 ) 2 ·6H 2 O、135.5g Ni(NO 3 ) 2 ·6H 2 Preparing water solution from O, slowly adding ammonia water with the concentration of 5 percent (mass percent) and 650g of citric acid dissolved in the ammonia water, stirring, heating the mixed solution to 90 ℃, adding 35g of glycol water solution with the concentration of 65 percent (mass percent) after gel is generated, and uniformly stirring.
2) Adding sepiolite raw ore into the gel, stirring and pulping, evaporating water in the slurry to dryness, transferring to an electric furnace, heating to 250 ℃ at constant temperature, and initiating spontaneous combustion. Crushing the combustion ash, adding 20G of citric acid and 40G of sesbania powder, extruding, forming, airing, roasting at 780 ℃ for 5 hours to obtain a catalyst G, wherein the general molecular formula of an active component of the catalyst G is La 0.6 Sr 0.4 Co 0.7 Ni 0.3 O 3 The active component loading was 35%.
Examples of the experiments
The perovskite catalysts A to F prepared in examples 1 to 6 of the present invention were subjected to activity evaluation using an atmospheric pressure activity evaluation apparatus (shown in FIG. 1) as a methane catalytic combustion evaluation apparatus. The methane catalytic combustion evaluation device comprises a methane raw material device, an oxygen raw material device, a nitrogen raw material device, a preheater 4, a reactor 5, a gas-liquid separator 6, a dryer 7 and a chromatograph 8. Methane feed device, oxygen feed device, nitrogen gas feed device are connected with pre-heater 4 respectively, and pre-heater 4 is connected with reactor 5, and reactor 5 is connected with desicator 6, and desicator 6 is connected with chromatograph 8. The pipeline that the raw materials device is connected with preheater 4 sets up pressure reducer 1, stop valve 2, mass flow meter 3 respectively. The gas generated after the reaction enters a chromatograph 8 for detection, the carrier gas enters the chromatograph 8, and the gas passing through the chromatograph 8 is discharged. According to the evaluation conditions of the catalytic activity, the conversion rate of methane under different catalytic conditions of the catalyst is measured.
The specific catalyst activity evaluation conditions were:
the particle size of the catalyst is as follows: 40 to 60 meshes;
loading of the catalyst: 10mL;
the raw material gas composition is as follows: CH (CH) 4 3.0%（v/v），O 2 18% (v/v) and the balance N 2 ；
Space velocity: 25000h -1 。
The specific catalyst stability evaluation conditions were:
the particle size of the catalyst is as follows: 40-60 meshes;
the raw material gas composition is as follows: CH (CH) 4 3.0%（v/v），O 2 18% (v/v) with the remainder being N 2 ；
Space velocity: 25000h -1 ；
Evaluation temperature: 650 ℃.
Table 1 lists the conversion rate of methane combustion under the catalysis conditions of the catalysts A-G prepared in the examples, and it can be seen that the series of catalysts can convert 10% of methane to reach the ignition temperature when the temperature is lower than 460 ℃, and the final conversion temperature for converting 90% of methane is lower than 620 ℃, so that excellent low-temperature activity is shown.
TABLE 1 conversion of the catalyst to catalyze the combustion of methane at various temperatures
FIG. 2 shows the results of activity stability tests of catalyst A prepared in example 1 and comparative catalyst G in continuous operation at 620 ℃ for 200 h. It can be seen that the activity of the catalyst A is basically unchanged in the whole reaction, which indicates that the catalyst can keep the stability of the reaction in a longer running time, which is very important for industrial production, while the activity of the comparative catalyst G is rapidly reduced after running for 100 hours, which indicates that the sepiolite carrier is not modified, the dispersion of active components is poor, and the high-temperature activity stability is poor due to the high-temperature sintering phenomenon.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The methane combustion catalyst is characterized by comprising an active component and a carrier, wherein the carrier is used for loading the active component, and the active component is a perovskite type metal oxide catalyst; the carrier is sepiolite carrier, the preparation method is that the sepiolite is added into the modified solution, the modified solution is heated to not lower than 50 ℃ for reaction, then the reacted solid material is roasted, and the obtained modified sepiolite is sepiolite carrier; wherein the modified solution is titanic acid and inorganic acid, and the inorganic acid is one or more of nitric acid, hydrochloric acid and sulfuric acid.
2. The methane combustion catalyst according to claim 1 wherein said sepiolite support has a titanium content of TiO 2 5 to 10 percent by weight.
3. The methane combustion catalyst according to claim 1,characterized in that the active component is La x Sr 1-x Co y Ni 1-y O 3 Wherein x =0 to 0.9, y =0.4 to 0.7.
4. A process for preparing a methane combustion catalyst, characterized in that a metal salt is loaded on the sepiolite carrier of claim 1 by a sol-gel method, the gel on the sepiolite carrier is burned, and then the catalyst is calcined to obtain the methane combustion catalyst, wherein the metal salt is a metal compound of a metal element required for the perovskite-type metal oxide catalyst.
5. The process for producing a methane combustion catalyst according to claim 4, characterized by comprising the steps of: adding citric acid and ammonia water into a metal salt aqueous solution, heating to generate gel, adding an ethylene glycol solution, uniformly mixing, adding a sepiolite carrier, stirring and pulping, evaporating water in the slurry to dryness, heating to enable the gel to be self-ignited, adding a binder and an extrusion aid into the burnt ash, extruding and molding, and calcining to obtain the methane combustion catalyst.
6. The method for producing a methane combustion catalyst according to claim 5, wherein the citric acid is dissolved in aqueous ammonia, the pH is adjusted to 6 to 8, and then the solution is added to the aqueous solution of a metal salt.
7. The method for preparing a methane combustion catalyst according to claim 5, wherein the gel is heated to 200 to 250 ℃ to self-ignite, and air with an oxygen content of 15 to 18% is introduced after self-ignition to control the combustion speed.
8. Use of the methane combustion catalyst according to any one of claims 1 to 3 or the methane combustion catalyst obtained by the preparation method according to any one of claims 4 to 7 in a catalytic burner and/or a gas heat exchanger.
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