CN102247861A - Coal gas high-temperature methanation catalyst and preparation method thereof - Google Patents
Coal gas high-temperature methanation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN102247861A CN102247861A CN2011101218611A CN201110121861A CN102247861A CN 102247861 A CN102247861 A CN 102247861A CN 2011101218611 A CN2011101218611 A CN 2011101218611A CN 201110121861 A CN201110121861 A CN 201110121861A CN 102247861 A CN102247861 A CN 102247861A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acid
- auxiliary agent
- temperature
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000003034 coal gas Substances 0.000 title abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 230000000694 effects Effects 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910002555 FeNi Inorganic materials 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000003345 natural gas Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 29
- 239000003245 coal Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 230000001376 precipitating effect Effects 0.000 claims description 23
- 238000007493 shaping process Methods 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 6
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- 239000000969 carrier Substances 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 238000005516 engineering process Methods 0.000 description 15
- 239000008187 granular material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000007605 air drying Methods 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- -1 acyl alcohol Chemical compound 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- IUFBBBDTDAHZOQ-UHFFFAOYSA-N carbonic acid;zirconium Chemical compound [Zr].OC(O)=O IUFBBBDTDAHZOQ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron 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
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- ILEXKRKTVIXABY-UHFFFAOYSA-J zirconium(4+);dicarbonate;hydrate Chemical group O.[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O ILEXKRKTVIXABY-UHFFFAOYSA-J 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a coal gas high-temperature methanation catalyst and a preparation method thereof. The coal gas high-temperature methanation catalyst is prepared from a Ni or FeNi alloy as an active component, Al2O3 and ZrO2 as carriers, and one or more of metals of Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce and La and/or oxides thereof, wherein the one or more of the metals and/or the oxides are utilized as auxiliary agent. The coal gas high-temperature methanation catalyst comprises: by weight, 1 to 50% of Ni or 1 to 55% of FeNi as an active component, 0.01 to 25% of one or more metals and/or oxides thereof as an auxiliary agent, and the balance Al2O3 and ZrO2 as carriers, wherein a weight ratio of Al2O3 to ZrO2 is in a range of 50 to 0.1. The coal gas high-temperature methanation catalyst has good high-temperature hydrothermal stability and high activity, and can reduce production cost and satisfy requirements of application of an adiabatic fixed bed high-temperature methanation process and other high-temperature methanation processes.
Description
Technical field
The present invention relates to coal preparing natural gas technology, more specifically, relate to a kind of high-temperature methanation catalyst that is suitable for this technology and preparation method thereof.
Background technology
Twice world energy sources crisis taken place in the 70-80 age in last century, and the energy supply of Western industrialized economy is cut off, and economy sinks into to stagnate.To the worry of gas reserves with guarantee the needs of the stable supply of following natural gas, the coal preparing natural gas that makes European and American countries just begin to carry out in more than 30 year before having strengthened is studied., develop a lot of coal preparing natural gas technology therebetween, also planned a lot of projects.But crude oil price one road drops after the energy crisis, and the coal preparing natural gas no longer has the economy advantage.Worldwide, have only the U.S. to set up the coal preparing natural gas factory of a commercial operation, i.e. llanura synthetic fuel factory in 1984.Enter 21 century, along with the attention of people to environmental protection, as a kind of important low-carbon (LC) clean energy technology, the coal preparing natural gas has shone life again.The U.S. plans at present, have more than the dozens of in the coal preparing natural gas project of building and runing.And, also reached 5 in the project of building through National Development and Reform Committee's approval by the end of the year 2010, among more coal preparing natural gas project is being fermented.
Insulation fix bed methanation in the operation of big plain in u.s.a synthetic fuel factory for many years, has been the coal preparing natural gas methanation process of current main flow in the world.This arts demand uses high-temperature methanation catalyst, to save equipment investment and to improve efficiency of energy utilization.Therefore, exploitation can be high temperature resistant, and the high-temperature methanation catalyst that has the good low temperature activity simultaneously again is the core of modern coal preparing natural gas methanation.The methanation catalyst that uses in traditional synthetic ammonia and the process for making hydrogen, serviceability temperature are lower usually, and rapid deactivation at high temperature can not satisfy the needs of coal preparing natural gas methanation process.China carried out small-sized gas project methanation technology research in the eighties in last century, and main effect is that the portion C O in the coal gas is converted to CH
4, improve calorific value of gas and reduce CO content in the coal gas, satisfy the requirement of national standard to artificial town gas.Employed methanation catalyst condition of work mostly is normal pressure and below 500 ℃, does not match with the coal pressure gasification process of modern main, and resistance to elevated temperatures is also obviously not enough.
Exploitation coal preparing natural gas high-temperature methanation catalyst need be produced employed methanation catalyst on maintenance low temperature active and selectivity basis to gas purification and gas, improves high-temperature hydrothermal stability (more than 700 ℃) and resistance to pressure (more than the 3MPa).The open CN101380581A of patent application has prepared the methanation catalyst that can use under 1.0-6.0MPa pressure, but serviceability temperature is still below 500 ℃.Though the methanation catalyst of the open CN101468311A preparation of patent application is claimed the many occasions that can be used for comprising the coal preparing natural gas, the catalyst in this patent application does not have the required high temperature resistant and withstand voltage properties of high-temperature methanation technology.The coke-oven gas methanation catalyst that the open CN101391218A of patent application proposes still has big gap with coal preparing natural gas technology on high temperature resistant and withstand voltage properties.
Summary of the invention
The producing coal preparing natural gas that the objective of the invention is to make a living provides a kind of coal preparing natural gas high-temperature methanation catalyst and preparation method thereof.
Therefore, in one embodiment, the invention provides a kind of coal preparing natural gas high-temperature methanation catalyst, comprising: as the Ni of active component; Al as carrier
2O
3And ZrO
2One or more metals and/or its oxide in the group of forming by Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce, La (or be mainly La rare earth metal) of being selected from as auxiliary agent; Wherein, this catalyst consisting of by weight percentage: the active component of 1-50%, the auxiliary agent of 0.01-25%, and the Al of surplus
2O
3/ ZrO
2The carrier of weight ratio in the 50-0.1 scope.
In an optimal way, this catalyst consists of in weight ratio: the described active component of 5-40%, the described auxiliary agent of 0.1-15%, and the Al of surplus
2O
3/ ZrO
2Weight ratio is described carrier in the 10-0.3 scope.
In another embodiment, the invention provides a kind of coal preparing natural gas high-temperature methanation catalyst, comprising: as the FeNi alloy of active component; Al as carrier
2O
3And ZrO
2One or more metals and/or its oxide in the group of forming by Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce, La (or be mainly La rare earth metal) of being selected from as auxiliary agent; Wherein, the Fe/Ni weight ratio of this active component is in the 0.02-50 scope, and this catalyst consisting of by weight percentage: the active component of 1-55%, the auxiliary agent of 0.01-25%, and the Al of surplus
2O
3/ ZrO
2The carrier of weight ratio in the 50-0.1 scope.
In an optimal way, the Fe/Ni weight ratio of active component is in the 0.05-20 scope, and this catalyst consisting of by weight percentage: the active component of 5-45%, the auxiliary agent of 0.1-15%, and the Al of surplus
2O
3/ ZrO
2The carrier of weight ratio in the 10-0.3 scope.
On the other hand, in one embodiment, the invention provides a kind of method for preparing above-mentioned catalyst, may further comprise the steps: the soluble compounds that comprises the metallic element in described catalyst activity component, carrier and the auxiliary agent that (a) aqueous solution itself is acidity is water-soluble, solvable or the insoluble compound of part that maybe will comprise the metallic element in described catalytic component, carrier and the auxiliary agent is handled with acid solution, so that the corresponding metal ion to be provided; (b) add alkaline precipitating agent,, and sediment is filtered and drying in aging back so that described metal ion precipitates; (c) this sediment of roasting is so that it is decomposed into corresponding oxide; (d) add shaping assistant so that shaping of catalyst; (e) preformed catalyst being carried out high temperature burns till and obtains oxidized catalyst; (f) obtain described activity of such catalysts component Ni or FeNi alloy by reducing described oxidized catalyst.
In a preferred implementation, in step (b) afterwards, first implementation step (d), and then implementation step (c), completing steps (e) and (f) again.
In a preferred implementation, comprise activity of such catalysts component, carrier and auxiliary agent metallic element solvable, part is solvable and insoluble compound is nitrate, sulfate, hydrochloride, carbonate, hydroxide, oxide and/or their hydrate that comprises described metallic element.
In a preferred implementation, comprise metallic element in the auxiliary agent solvable, part is solvable and insoluble compound is polyacid or the multi-acid salt that is selected from one or more metals among Mo, V and the W.
In a preferred implementation, acid solution is the aqueous solution that itself is the described soluble compounds of acidity, or is selected from the group of being made up of nitric acid, sulfuric acid and hydrochloric acid solution one or more, and described alkaline precipitating agent is for being selected from by (NH
4)
2CO
3, NH
4HCO
3, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, in the group formed of NaOH, KOH, ammoniacal liquor and urea one or more.
In a further preferred implementation, add described alkaline precipitating agent and under agitation drench described acid solution by the described acid solution of direct adding, after water-soluble, described acid solution under agitation drenched to mix into described alkaline precipitating agent or with described acid solution and stream implement.
In a further preferred implementation, in the solution that the water-soluble back of alkaline precipitating agent forms, also comprise the soluble compounds in the alkaline solution of metallic element of described activity of such catalysts component, carrier and auxiliary agent.
In a further preferred implementation, in the solution that the water-soluble back of described alkaline precipitating agent forms, also comprise aluminium salt.
In a further preferred implementation, in the solution that the water-soluble back of described alkaline precipitating agent forms, also comprise the polyacid or the multi-acid salt that are selected from one or more metals among Mo, V and the W.
In a preferred implementation, the soluble compounds of the metallic element in the auxiliary agent that comprises described catalyst in the step (a) can be by impregnation steps (c) or the preformed catalyst that obtains (d) add; Solvable or the insoluble compound of part that perhaps comprises the metallic element in the auxiliary agent of described catalyst in the step (a) can mix and add with the sediment that obtains in the step (b).
In a preferred implementation, carry out dry temperature in the step (b) between 100-200 ℃, the temperature of carrying out roasting in the step (c) and is carried out temperature that high temperature burns till between 800-1200 ℃ in the step (e) between 300-600 ℃.
In a preferred implementation, the reduction of catalyst activity composition is implemented to the temperature of the pressure of 10.0MPa and 200-1000 ℃ at normal pressure by hydrogen or synthesis gas in the step (f).
In a preferred implementation, shaping of catalyst in the step (d) is compression moulding, and the shaping assistant that wherein adds is to be selected from the group of being made up of cellulose, active carbon, graphite, talcum powder, paraffin, water, stearic acid, odium stearate, dolomol, 18 acyls alcohol one or more.
In a preferred implementation, extrusion molding during shaping of catalyst in the step (d), and the shaping assistant that wherein adds is to be selected from the group of being made up of cellulose, starch, active carbon, sesbania powder, water, nitric acid, hydrochloric acid, formic acid, trichloroacetic acid, oxalic acid, tartaric acid, citric acid, malonic acid one or more.
By using Ni or FeNi alloy as active component, and the Al of the good high strength refractory material of serviceability
2O
3/ ZrO
2As carrier, add and to be selected from by Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce, to be mainly one or more metals in the group that the rare earth metal of La forms and/or its oxide as auxiliary agent, the intensity and the thermal shock resistance of carrier are significantly improved, thereby improve intensity, activity and the high-temperature hydrothermal stability of catalyst.
And, as active component, use FeNi alloy ratio Ni to have higher methanation catalytic activity.Simultaneously, can also reduce the Ni consumption reduces production costs.
Coal preparing natural gas high-temperature methanation catalyst provided by the present invention, compare with existing methanation catalyst, to significantly improve high-temperature hydrothermal stability and long-life, have higher activity, and can reduce production costs, with insulation fix bed high-temperature methanation technology and other high-temperature methanation technologies that satisfy current main-stream.
Description of drawings
Fig. 1 shows according to a kind of indicative flowchart that is used to prepare the method for high-temperature methanation catalyst of the present invention;
Fig. 2 shows the indicative flowchart that another kind according to the present invention is used to prepare the method for high-temperature methanation catalyst.
The specific embodiment
The invention provides and be applicable to the coal preparing natural gas technology of producing natural gas by insulation fix bed methanation, for example with high CO content synthesis gas, and a kind of of other high-temperature methanation technology is the high-temperature methanation catalyst of active component with Ni or FeNi alloy.
As the preferred embodiment of the invention, described catalyst can prepare by following steps: the soluble compounds that comprises the metallic element in described catalyst activity component, carrier and the auxiliary agent that (a) aqueous solution itself is acidity is water-soluble, solvable or the insoluble compound of part that maybe will comprise the metallic element in described catalytic component, carrier and the auxiliary agent is handled with acid solution, so that the corresponding metal ion to be provided; (b) add alkaline precipitating agent,, and sediment is filtered and drying in aging back so that metal ion precipitates; (c) this sediment of roasting is so that it is decomposed into corresponding oxide; (d) add shaping assistant so that shaping of catalyst; (e) preformed catalyst is carried out that high temperature burns till and the catalyst that obtains oxidation state; (f) use hydrogen or synthesis gas, under certain pressure and temperature, with all or part of metal Ni (and Fe) that is reduced to of the Ni in the catalyst (and Fe) oxide.Fig. 1 shows the indicative flowchart of this method of preparation coal preparing natural gas high-temperature methanation catalyst of the present invention.
In the different phase of preparation process, also can select suitable catalyst aid addition manner according to the type of the compound that comprises the promoter metal ion.For example, in the present invention, comprise the soluble compounds of various metallic elements in the catalyst promoter, can enter catalyst inside by dipping; Comprise the solvable or insoluble compound of part of the various metallic elements in the catalyst promoter, can mix with precipitation.Afterwards, by drying, roasting, burn till, step such as reduction becomes the part that catalyst is formed.
In addition, in said method, the order of step (c) and step (d) can be changed, and promptly carries out (c) and add shaping assistant so that shaping of catalyst after step (b), and this sediment of (d) roasting is so that it is decomposed into corresponding oxide then; And through step (e) and (f) obtain catalyst of the present invention.Fig. 2 shows the indicative flowchart of this method of preparation coal preparing natural gas high-temperature methanation catalyst of the present invention.
In preparation method of the present invention, the various metallic elements that comprise activity of such catalysts component, carrier, soluble compounds as Ni, Fe, Al, Zr etc. is nitrate, sulfate, hydrochloride, and it is acid that the aqueous solution of these strong acid salts is itself, and the metal ion of free state can be provided; Solvable or the insoluble compound of part is carbonate, oxide, hydroxide, and the hydrate of oxide and mineral thereof, concrete as monohydrate alumina, hibbsite, alkaline carbonic acid zirconium etc., can pass through the aqueous solution such as nitric acid, sulfuric acid, hydrochloric acid, or the above aqueous solution that is acid soluble compounds itself carries out acidification, makes all or part of metallic element that wherein comprises soluble in water with the metal ion form.For avoiding the residual of hetero atom such as sulphur, chlorine etc., soluble salt is preferably selected nitrate for use, preferably selects for use nitric acid to carry out acidification, and the solvable or insoluble compound of part is preferentially selected the hydrate of carbonate, oxide, oxide for use.Need in the preparation process active component content and composition are controlled: by weight percentage, Ni accounts for 1-50% or FeNi alloy (wherein wt is than Fe/Ni=0.02-50) accounts for 1-55%.Preferably, the compositing range of active component is: by weight percentage, Ni accounts for 5-40% or FeNi alloy (wherein wt is than Fe/Ni=0.05-20) accounts for 5-45%.Al
2O
3And ZrO
2Weight ratio Al
2O
3/ ZrO
2High-temperature stability to catalysis has considerable influence.Therefore, be necessary in preparation process, to control Al
2O
3/ ZrO
2=50-0.1 is preferably Al
2O
3/ ZrO
2=10-0.3.
In preparation method of the present invention, alkaline precipitating agent can be (NH
4)
2CO
3, NH
4HCO
3, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, in NaOH, KOH, ammoniacal liquor, the urea etc. one or more, addition manner can be: alkaline precipitating agent directly adds to stir behind the above acid solution, the water-soluble formation solution of alkaline precipitating agent to drench to add to stir to drench to the solution of the water-soluble formation of alkaline precipitating agent or the water-soluble formation solution of alkaline precipitating agent to the above acid solution, the above acid solution and mixes with the above acid solution and stream.When using urea as precipitating reagent, reaction temperature need be controlled at 20-99 ℃, decomposes gradually making it.The compound or the mineral that dissolve in the alkaline precipitating reagent aqueous solution and comprise the metal ion that catalyst of the present invention forms also can add in the precipitant solution, for example Al (NO
3)
39H
2O is dissolved in Na
2CO
3Can form sodium aluminate solution behind the solution, stir to drench go into then to carry out in the solution or with solution and flow and mix.The gained sediment need wash removes Na
+, K
+Deng alkali metal ion, ageing time is generally 0-24 hour, and baking temperature is preferably 100-200 ℃.For avoiding Na
+, K
+Residual Deng alkali metal ion preferably used urea, ammoniacal liquor, (NH
4)
2CO
3, NH
4HCO
3As alkaline precipitating agent, post precipitation need not washing, NH in roasting and high temperature sintering process
4 +Can remove fully.
In preparation method of the present invention, sintering temperature is preferably between 300-600 ℃, so that dried sediment is decomposed into corresponding oxide.Preferably between 800-1200 ℃, this temperature range is temperature required higher than the high-temperature methanation reaction for shaping catalyst particle high temperature firing temperature.In sintering process, some high-temperature adaptabilities can take place and change in catalyst carrier, thereby improve the high-temperature hydrothermal stability of catalyst.In the present invention, can use pure hydrogen, and the common technology synthesis gas with different hydrogen and carbon monoxide content reduces to catalyst, the optional normal pressure of pressure is to 10.0MPa, and temperature is 200-1000 ℃.Preferably, the reduction pressure be normal pressure to 3.0MPa, temperature 500-900 ℃.In reduction process, the metal oxide auxiliary agent that burns till generation through roasting and high temperature in the catalyst may be reduced wholly or in part, so the form of auxiliary agent also can be to exist with metal and/or its hopcalite.
In the present invention, catalyst promoter can be solvable, part is solvable or insoluble compound.Soluble compounds, as Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce, the nitrate of rare earth metal (based on La), sulfate and hydrochloride, for Mo, V, W, especially, also comprise Mo, V, the polyacid of W or multi-acid salt, according to its solvability in acid-base solution, and effects of ion interaction relationship (can form precipitation) as molybdenum acid ion and nickel ion and aluminium ion, can add in acid solution or the alkaline sedimentation agent solution, in preparation with Ni (and Fe), the ion co-precipitation of metallic element such as Al and Zr, drying, roasting, burn till, steps such as reduction become corresponding metal and/or oxide; Also can be made into the aqueous solution, be impregnated into shaping catalyst particle inside, drying, roasting, burn till, step such as reduction becomes corresponding metal and/or oxide.The object that the catalyst promoter dipping adds can be: the shaping catalyst particle after catalyst granules, the shaping catalyst particle after the roasting and the high temperature after the first moulding burns till.Part is solvable, insoluble compound is carbonate, hydroxide, and the hydrate of oxide is as MgCO
3, Mg (OH)
2, CaCO
3, La
2O
3Deng, can be in preparation process mix with the sediment that forms of the contained metal ion of catalyst in the solution, drying, roasting, burn till, step such as reduction becomes corresponding metal and/or oxide.For avoiding the residual of hetero atom such as sulphur, chlorine etc., soluble salt is preferably selected nitrate for use, and the solvable or insoluble compound of part is preferentially selected the hydrate of carbonate, hydroxide, oxide, oxide for use.
In the catalyst of the present invention, catalyst promoter has considerable influence to catalyst strength, activity and high-temperature stability, needs its content is controlled: by weight percentage, catalyst promoter metal and oxide thereof account for 0.01-25%.Preferably, be 0.1-15%.
Catalyst of the present invention can be prepared by compressing tablet or the method for extruding, and selects corresponding shaping assistant for use according to the characteristics and the needs of technology.According to current Catalyst Production equipment and process condition, compression moulding technology is relatively simple, is particularly suitable for producing the catalyst granules greater than the 3mm particle diameter, and extrusion molding can be used for producing the catalyst granules less than the 3mm particle diameter.According to technological requirement, the shaping assistant of compression moulding can be to be selected from the group of being made up of cellulose, active carbon, graphite, talcum powder, paraffin, water, stearic acid, odium stearate, dolomol, 18 acyl alcohol etc. one or more; And in the group that the optional free-fiber element of the shaping assistant of extrusion molding, starch, active carbon, sesbania powder, water, nitric acid, hydrochloric acid, formic acid, trichloroacetic acid, oxalic acid, tartaric acid, citric acid, malonic acid etc. are formed one or more.
To illustrate the present invention by specific embodiment and comparative example below, should be appreciated that these embodiment only are used to describe the present invention, and the scope that does not limit the present invention in any way.
Embodiment
Comparative example 1
Get 37.7 gram Ni (NO
3)
26H
2O, 112.5 gram Al (NO
3)
39H
2O and 26.8 gram Zr (NO
3)
45H
2O is dissolved in the 1000ml deionized water.In 20 minutes, slowly add 103.2 gram carbonic hydroammonium, stirred again afterwards 2 hours.Suspension is filtered, get the washing of 2000ml deionized water, obtain the light green color precipitation.120 ℃ of following heated-air dryings 20 hours, 400 ℃ of following roastings after 16 hours, obtain 32.5 gram roasting samples.Crushing and by behind the 100 order sample sifters obtains cylindrical (Φ 3) catalyst granules with graphite and cellulose mixed pressuring plate.At last, the catalyst granules after the moulding was burnt till under 1100 ℃ 3 hours, obtain the catalyst A of oxidation state.
Embodiment 1
Get 37.7 gram Ni (NO
3)
26H
2O, 112.5 gram Al (NO
3)
39H
2O, 26.8 gram Zr (NO
3)
45H
2O, 0.3 gram Ir (NO
3)
4, be dissolved in the 1000ml deionized water.In 20 minutes, slowly add 103.2 gram carbonic hydroammonium, stirred again afterwards 2 hours.Suspension is filtered, get the washing of 2000ml deionized water, obtain the light green color precipitation.Filter cake obtains 32.6 gram roasting samples 120 ℃ of following heated-air dryings 20 hours, 400 ℃ of following roastings 16 hours.Crushing is also passed through 100 order sample sifters, obtains cylindrical (Φ 3) catalyst granules with graphite and cellulose mixed pressuring plate.After burning till 3 hours under 1100 ℃, obtain the catalyst B of oxidation state, wherein, IrO
2Content is 0.5%.
Embodiment 2
Get 37.7 gram Ni (NO
3)
26H
2O, 112.5 gram Al (NO
3)
39H
2O and 26.8 gram Zr (NO
3)
45H
2O, 20.8 gram Mg (NO
3)
26H
2O is dissolved in the 1000ml water, obtains green settled solution.MoO
3Content is the 250ml aqueous solution that the ammonium molybdate of 1.0 grams is dissolved in 103.2 gram carbonic hydroammonium preparations, with the aforementioned nitrate solution parallel-flow precipitation as acid solution.Aging after 3 hours, precipitation is filtered, and get the 2000ml water washing.After 20 hours, 100 order sample sifters are also passed through in crushing to filter cake 120 ℃ of following heated-air dryings, behind interpolation sesbania powder, oxalic acid, the water, extrude and obtain strip (Φ 3) catalyst granules.Burnt till 3 hours under 16 hours, 1100 ℃ 400 ℃ of following roastings, obtain the catalyst C of oxidation state, wherein, MgO and MoO
3Content be respectively 8.8% and 2.7%.
Embodiment 3
Get 0.5M lanthanum nitrate dilute aqueous solution, the catalyst C that gets among the part embodiment 2 preparation floods, and obtains the catalyst D of oxidation state, MgO, MoO after burning till under 120 ℃ of following heated-air dryings, 450 ℃ of following roastings, 1100 ℃
3, La
2O
3Content be respectively 8.6%, 2.6%, 2.6%.
Embodiment 4
Get 37.7 gram Ni (NO
3)
26H
2O, 112.5 gram Al (NO
3)
39H
2O, ZrO
2Content is zirconium carbonate hydrate, the 16.5 gram Fe (NO of 7.7 grams
3)
39H
2O and 20.8 gram Mg (NO
3)
26H
2O adds in the 1000ml water, adds an amount of nitric acid and heating and makes the solution clarification.After the cooling, in 30 minutes, slowly add 120.5 gram carbonic hydroammonium, stirred again afterwards 2 hours.To suspension filtered, get 2000ml water washing precipitation.Filter cake obtains 39.2 gram roasting samples 120 ℃ of following heated-air dryings 20 hours, 400 ℃ of following roastings after 16 hours.Crushing is also passed through 100 order stainless steel sifts, mixes the back compressing tablet with graphite and cellulose and obtains cylindrical (Φ 3) catalyst granules.Then, burnt till under 1100 ℃ 3 hours, obtain the catalyst E of oxidation state, wherein, the Fe/Ni weight ratio is 1: 3, MgO content 7.7%.
Embodiment 5
Get the 0.5M lanthanum nitrate hexahydrate, the catalyst E that gets among the part embodiment 4 preparation floods, and obtains the catalyst F of oxidation state after burning till under 120 ℃ of following heated-air dryings, 450 ℃ of following roastings, 1100 ℃, and wherein, the content of MgO is respectively 7.5%, La
2O
3Content is 2.3%.
Evaluating catalyst
Get the catalyst A-F for preparing in embodiment 1-5 and the comparative example respectively,, carry out side pressure strength and detect according to national standard HG-T2782-1996.
Get the oxidized catalyst for preparing among comparative example and the embodiment 1-5 respectively, sample sifter is crossed in crushing back, gets the catalyst granules of 1.0 gram particles footpath between 0.30-0.50mm, with the microreactor of packing into after the quartz sand of 6 volume same particle size mixes.Subsequently, under 800 ℃ and normal pressure, feed hydrogen catalyst is carried out reduction in 24 hours.After reduction is finished, feed synthesis gas (H
2/ CO=100-20), carry out methanation reaction at 250 ℃.Detect CH in the product by chromatogram
4Content, represent catalyst activity, unit with Unit Weight catalyst methane speed: mark rises CH
4/ hour/the gram catalyst.Then, be warming up to 700 ℃, under 3.0MPa pressure, feed the gaseous mixture (H of steam and hydrogen
2O accounts for 75%), hydrothermal treatment consists 100 hours.At last, under same condition the catalyst after the hydrothermal treatment consists being carried out activity detects.Catalytic activity accounts for the percentage (%) of handling preceding catalytic activity after the hydrothermal treatment consists, can be used to represent the hydrothermal stability of catalyst.The evaluation result that obtains is shown in the table 1.
Table 1: high-temperature methanation catalyst evaluation result
Evaluating catalyst result according to table 1, as can be seen, high-temperature methanation catalyst by the present invention's preparation, after reduction, no matter be that Ni or FeNi alloy are as active component, add such as Ir, Mg, Mo, La metal and/or its oxides additive, catalyst is improved at side pressure strength, catalytic activity and high-temperature hydrothermal stability.And, as active component, further improved catalytic activity with the FeNi alloy effectively.It is worthy of note that unshowned other kinds analog assistant and combination thereof in example can improve the performance of high-temperature methanation catalyst too.
This shows: using Ni or FeNi as active component, Al
2O
3/ ZrO
2In the catalyst as carrier, because Al
2O
3/ ZrO
2It is a kind of high strength refractory material of function admirable, by one or more metals and/or its oxide in the group of adding Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce, rare earth metal (based on La) composition, the intensity and the thermal shock resistance of carrier are significantly improved, improve intensity, activity and the high-temperature hydrothermal stability of catalyst.And FeNi alloy ratio Ni has higher catalytic activity, simultaneously, can also reduce the Ni consumption and reduces production costs.
It should be appreciated by those skilled in the art that and to make different modifications, combination, sub-portfolio and distortion according to designing requirement with other factors, as long as they are equal in the replacement restricted portion in claims or its.
Claims (19)
1. coal preparing natural gas high-temperature methanation catalyst comprises:
Ni as active component;
Al as carrier
2O
3And ZrO
2
As auxiliary agent be selected from by Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce,
One or more metals and/or its oxide in the group that La forms;
Wherein, described catalyst consisting of by weight percentage: the described active component of 1-50%, the described auxiliary agent of 0.01-25%, and the Al of surplus
2O
3/ ZrO
2The described carrier of weight ratio in the 50-0.1 scope.
2. coal preparing natural gas high-temperature methanation catalyst according to claim 1, wherein, described catalyst consists of in weight ratio: the described active component of 5-40%, the described auxiliary agent of 0.1-15%, and the Al of surplus
2O
3/ ZrO
2Weight ratio is described carrier in the 10-0.3 scope.
3. coal preparing natural gas high-temperature methanation catalyst comprises:
FeNi alloy as active component;
Al as carrier
2O
3And ZrO
2
As auxiliary agent be selected from by Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce,
One or more metals and/or its oxide in the group that La forms;
Wherein, the Fe/Ni weight ratio of described active component is in the 0.02-50 scope, and described catalyst consisting of by weight percentage: the described active component of 1-55%, the described auxiliary agent of 0.01-25%, and the Al of surplus
2O
3/ ZrO
2The described carrier of weight ratio in the 50-0.1 scope.
4. coal preparing natural gas high-temperature methanation catalyst according to claim 3, wherein, the Fe/Ni weight ratio of described active component is in the 0.05-20 scope, and described catalyst consisting of by weight percentage: the described active component of 5-45%, the described auxiliary agent of 0.1-15%, and the Al of surplus
2O
3/ ZrO
2The described carrier of weight ratio in the 10-0.3 scope.
5. method for preparing according to each described catalyst coal preparing natural gas high-temperature methanation catalyst among the claim 1-4 may further comprise the steps:
(a) it is water-soluble the aqueous solution itself to be the acid soluble compounds that comprises the metallic element in described catalyst activity component, carrier and the auxiliary agent, and/or the solvable or insoluble compound of the part that will comprise the metallic element in described catalytic component, carrier and the auxiliary agent handles with acid solution, so that the corresponding metal ion to be provided;
(b) add alkaline precipitating agent,, and sediment is filtered and drying in aging back so that described metal ion precipitates;
(c) this sediment of roasting is so that it is decomposed into corresponding oxide;
(d) add shaping assistant so that shaping of catalyst;
(e) preformed catalyst being carried out high temperature burns till and obtains oxidized catalyst;
(f) obtain described activity of such catalysts component Ni or FeNi alloy by reducing described oxidized catalyst.
6. method according to claim 5, wherein, in step (b) afterwards, first implementation step (d), and then implementation step (c), completing steps (e) and (f) again.
7. method according to claim 5, wherein, the described metallic element that comprises activity of such catalysts component, carrier and auxiliary agent solvable, part is solvable and insoluble compound is nitrate, sulfate, hydrochloride, carbonate, hydroxide, oxide and/or their hydrate that comprises described metallic element.
8. method according to claim 5, wherein, described comprise metallic element in the auxiliary agent solvable, part is solvable and insoluble compound is polyacid or the multi-acid salt that is selected from one or more metals among Mo, V and the W.
9. method according to claim 5, wherein, described acid solution is the aqueous solution that itself is the described soluble compounds of acidity, or is selected from the group of being made up of nitric acid, sulfuric acid and hydrochloric acid solution one or more, and described alkaline precipitating agent is for being selected from by (NH
4)
2CO
3, NH
4HCO
3, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, in the group formed of NaOH, KOH, ammoniacal liquor and urea one or more.
10. method according to claim 5, wherein, add described alkaline precipitating agent by it is directly added the acid solution of dissolved metal ions it is under agitation drenched described acid solution after water-soluble or with described acid solution under agitation drench into described alkaline sedimentation agent solution or with the alkaline precipitating agent aqueous solution with described acid solution and flow to mix and implement.
11. method according to claim 10 wherein, in the solution that the water-soluble back of described alkaline precipitating agent forms, also comprises the soluble compounds in the alkaline solution of metallic element of described activity of such catalysts component, carrier and auxiliary agent.
12. method according to claim 10 wherein, in the solution that the water-soluble back of described alkaline precipitating agent forms, also comprises aluminium salt.
13. method according to claim 10 wherein, in the solution that the water-soluble back of described alkaline precipitating agent forms, also comprises the polyacid or the multi-acid salt that are selected from one or more metals among Mo, V and the W.
14. method according to claim 5, wherein, the soluble compounds of the metallic element in the auxiliary agent that comprises described catalyst in the step (a) can add by the preformed catalyst that obtains in the impregnation steps (d); Solvable or the insoluble compound of part that perhaps comprises the metallic element in the auxiliary agent of described catalyst in the step (a) can mix and add with the sediment that obtains in the step (b).
15. method according to claim 6, wherein, the soluble compounds of the metallic element in the auxiliary agent that comprises described catalyst in the step (a) can be by impregnation steps (c) or the preformed catalyst that obtains (d) add; Solvable or the insoluble compound of part that perhaps comprises the metallic element in the auxiliary agent of described catalyst in the step (a) can mix and add with the sediment that obtains in the step (b).
16. method according to claim 5, wherein, carry out dry temperature in the step (b) between 100-200 ℃, the temperature of carrying out roasting in the step (c) and is carried out temperature that high temperature burns till between 800-1200 ℃ in the step (e) between 300-600 ℃.
17. method according to claim 5, wherein, the reduction of catalyst activity composition is implemented to the temperature of the pressure of 10.0MPa and 200-1000 ℃ at normal pressure by hydrogen or synthesis gas in the step (f).
18. according to the described method of claim 5, wherein, shaping of catalyst in the step (d) is compression moulding, and the shaping assistant that wherein adds is to be selected from the group of being made up of cellulose, active carbon, graphite, talcum powder, paraffin, water, stearic acid, odium stearate, dolomol, 18 acyls alcohol one or more.
19. according to the described method of claim 5, wherein, shaping of catalyst in the step (d) is extrusion molding, and the shaping assistant that wherein adds is to be selected from the group of being made up of cellulose, starch, active carbon, sesbania powder, water, nitric acid, hydrochloric acid, formic acid, trichloroacetic acid, oxalic acid, tartaric acid, citric acid, malonic acid one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101218611A CN102247861A (en) | 2011-05-11 | 2011-05-11 | Coal gas high-temperature methanation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101218611A CN102247861A (en) | 2011-05-11 | 2011-05-11 | Coal gas high-temperature methanation catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102247861A true CN102247861A (en) | 2011-11-23 |
Family
ID=44975640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101218611A Pending CN102247861A (en) | 2011-05-11 | 2011-05-11 | Coal gas high-temperature methanation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102247861A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513119A (en) * | 2011-12-15 | 2012-06-27 | 西南化工研究设计院 | Catalyst for natural gas from coal and preparation method thereof |
| CN102950006A (en) * | 2012-10-16 | 2013-03-06 | 大连瑞克科技有限公司 | High-temperature-resistant synthetic natural gas methanation catalyst and preparation method thereof |
| CN103157485A (en) * | 2011-12-15 | 2013-06-19 | 北京低碳清洁能源研究所 | Load-type sulfur-tolerant methanation catalyst |
| CN103191720A (en) * | 2013-04-26 | 2013-07-10 | 神华集团有限责任公司 | Magnesium aluminate spinel-supported sulphur-tolerant methanation catalyst |
| CN103203237A (en) * | 2013-05-02 | 2013-07-17 | 神华集团有限责任公司 | Aluminum oxide loaded methanation catalyst |
| WO2013166653A1 (en) * | 2012-05-08 | 2013-11-14 | 中国科学院过程工程研究所 | Method for preparing ni-mg/al2o3 catalyst |
| CN103433026A (en) * | 2013-08-26 | 2013-12-11 | 神华集团有限责任公司 | ZrO 2Of a loadHigh-stability sulfur-tolerant methanation catalyst |
| CN103480362A (en) * | 2013-10-14 | 2014-01-01 | 神华集团有限责任公司 | Preparation method of supported sulfur-tolerant methanation catalyst |
| CN103801287A (en) * | 2012-11-05 | 2014-05-21 | 北京低碳清洁能源研究所 | Supported sulfur tolerant methanation catalyst preparation method |
| CN103962123A (en) * | 2013-01-28 | 2014-08-06 | 神华集团有限责任公司 | ZrO2-loaded sulfur-tolerant methanation catalyst and preparation method thereof |
| CN104209127A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Ferronickel bimetallic methanation catalyst and preparation and application thereof |
| CN104475111A (en) * | 2014-11-24 | 2015-04-01 | 太原理工大学 | Catalyst for preparing methane by reaction of coal and carbon oxide and preparation method of catalyst |
| CN104857964A (en) * | 2014-02-26 | 2015-08-26 | 天津大学 | Synthetic gas methanation catalyst and preparation method thereof |
| CN105126856A (en) * | 2015-07-29 | 2015-12-09 | 中国华能集团清洁能源技术研究院有限公司 | High temperature-resistant methanation catalyst preparation method |
| CN105642306A (en) * | 2014-12-06 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of catalyst for syngas complete methanation to prepare natural gas |
| CN105709749A (en) * | 2014-12-03 | 2016-06-29 | 中国科学院大连化学物理研究所 | High-strength integrally-extruded nickel-based methanation catalyst and preparation method thereof |
| CN105797785A (en) * | 2016-04-15 | 2016-07-27 | 西安向阳航天材料股份有限公司 | Pre-reduction type high-temperature methanation catalyst and preparation method thereof |
| CN105854889A (en) * | 2016-04-15 | 2016-08-17 | 西安向阳航天材料股份有限公司 | High-temperature-resistant methanation catalyst and preparation method thereof |
| CN106475106A (en) * | 2016-01-07 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas preparing natural gas by methanation catalyst |
| CN106622321A (en) * | 2016-09-06 | 2017-05-10 | 中国海洋石油总公司 | Methanation catalyst and preparation method and application thereof |
| CN106944062A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas preparing natural gas catalyst |
| CN107790136A (en) * | 2017-11-08 | 2018-03-13 | 西安向阳航天材料股份有限公司 | A kind of preparation method of high temperature resistant methanation catalyst |
| CN110248728A (en) * | 2017-02-01 | 2019-09-17 | 日立造船株式会社 | The preparation method of methanation reaction catalyst, the preparation method of methanation reaction catalyst and methane |
| CN112705204A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Methanation catalyst for methanation reaction and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58101740A (en) * | 1981-12-14 | 1983-06-17 | Agency Of Ind Science & Technol | Methane synthesis catalyst |
| CN101300706A (en) * | 2005-09-02 | 2008-11-05 | 赫多特普索化工设备公司 | Process and catalyst for hydrogenation of carbon oxides |
| CN101890353A (en) * | 2010-07-01 | 2010-11-24 | 神华集团有限责任公司 | High-temperature methanation catalyst, preparation method and application thereof |
| CN102029161A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for preparing complete methanation catalyst for hydrothermal chemical process |
-
2011
- 2011-05-11 CN CN2011101218611A patent/CN102247861A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58101740A (en) * | 1981-12-14 | 1983-06-17 | Agency Of Ind Science & Technol | Methane synthesis catalyst |
| CN101300706A (en) * | 2005-09-02 | 2008-11-05 | 赫多特普索化工设备公司 | Process and catalyst for hydrogenation of carbon oxides |
| CN102029161A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for preparing complete methanation catalyst for hydrothermal chemical process |
| CN101890353A (en) * | 2010-07-01 | 2010-11-24 | 神华集团有限责任公司 | High-temperature methanation catalyst, preparation method and application thereof |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157485A (en) * | 2011-12-15 | 2013-06-19 | 北京低碳清洁能源研究所 | Load-type sulfur-tolerant methanation catalyst |
| CN102513119A (en) * | 2011-12-15 | 2012-06-27 | 西南化工研究设计院 | Catalyst for natural gas from coal and preparation method thereof |
| WO2013166653A1 (en) * | 2012-05-08 | 2013-11-14 | 中国科学院过程工程研究所 | Method for preparing ni-mg/al2o3 catalyst |
| CN102950006B (en) * | 2012-10-16 | 2014-04-02 | 大连瑞克科技有限公司 | High-temperature-resistant synthetic natural gas methanation catalyst and preparation method thereof |
| CN102950006A (en) * | 2012-10-16 | 2013-03-06 | 大连瑞克科技有限公司 | High-temperature-resistant synthetic natural gas methanation catalyst and preparation method thereof |
| CN103801287B (en) * | 2012-11-05 | 2016-05-11 | 神华集团有限责任公司 | A kind of preparation method of load type sulfur-tolerant methanation catalyst |
| CN103801287A (en) * | 2012-11-05 | 2014-05-21 | 北京低碳清洁能源研究所 | Supported sulfur tolerant methanation catalyst preparation method |
| CN103962123A (en) * | 2013-01-28 | 2014-08-06 | 神华集团有限责任公司 | ZrO2-loaded sulfur-tolerant methanation catalyst and preparation method thereof |
| CN103191720A (en) * | 2013-04-26 | 2013-07-10 | 神华集团有限责任公司 | Magnesium aluminate spinel-supported sulphur-tolerant methanation catalyst |
| CN103191720B (en) * | 2013-04-26 | 2015-10-21 | 神华集团有限责任公司 | A kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load |
| CN103203237B (en) * | 2013-05-02 | 2015-07-01 | 神华集团有限责任公司 | Aluminum oxide loaded methanation catalyst |
| CN103203237A (en) * | 2013-05-02 | 2013-07-17 | 神华集团有限责任公司 | Aluminum oxide loaded methanation catalyst |
| CN104209127A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Ferronickel bimetallic methanation catalyst and preparation and application thereof |
| CN103433026A (en) * | 2013-08-26 | 2013-12-11 | 神华集团有限责任公司 | ZrO 2Of a loadHigh-stability sulfur-tolerant methanation catalyst |
| CN103480362A (en) * | 2013-10-14 | 2014-01-01 | 神华集团有限责任公司 | Preparation method of supported sulfur-tolerant methanation catalyst |
| CN103480362B (en) * | 2013-10-14 | 2016-06-01 | 神华集团有限责任公司 | Preparation method of supported sulfur-tolerant methanation catalyst |
| CN104857964A (en) * | 2014-02-26 | 2015-08-26 | 天津大学 | Synthetic gas methanation catalyst and preparation method thereof |
| CN104475111A (en) * | 2014-11-24 | 2015-04-01 | 太原理工大学 | Catalyst for preparing methane by reaction of coal and carbon oxide and preparation method of catalyst |
| CN105709749B (en) * | 2014-12-03 | 2019-02-05 | 中国科学院大连化学物理研究所 | Ni-based methanation catalyst of a kind of high intensity integral extruding type and preparation method thereof |
| CN105709749A (en) * | 2014-12-03 | 2016-06-29 | 中国科学院大连化学物理研究所 | High-strength integrally-extruded nickel-based methanation catalyst and preparation method thereof |
| CN105642306A (en) * | 2014-12-06 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of catalyst for syngas complete methanation to prepare natural gas |
| CN105126856A (en) * | 2015-07-29 | 2015-12-09 | 中国华能集团清洁能源技术研究院有限公司 | High temperature-resistant methanation catalyst preparation method |
| CN106944062B (en) * | 2016-01-07 | 2018-12-18 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas preparing natural gas catalyst |
| CN106475106A (en) * | 2016-01-07 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas preparing natural gas by methanation catalyst |
| CN106944062A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas preparing natural gas catalyst |
| CN106475106B (en) * | 2016-01-07 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas preparing natural gas by methanation catalyst |
| CN105854889A (en) * | 2016-04-15 | 2016-08-17 | 西安向阳航天材料股份有限公司 | High-temperature-resistant methanation catalyst and preparation method thereof |
| CN105854889B (en) * | 2016-04-15 | 2019-01-15 | 西安向阳航天材料股份有限公司 | A kind of high temperature resistant methanation catalyst and preparation method thereof |
| CN105797785A (en) * | 2016-04-15 | 2016-07-27 | 西安向阳航天材料股份有限公司 | Pre-reduction type high-temperature methanation catalyst and preparation method thereof |
| CN106622321A (en) * | 2016-09-06 | 2017-05-10 | 中国海洋石油总公司 | Methanation catalyst and preparation method and application thereof |
| CN106622321B (en) * | 2016-09-06 | 2019-07-12 | 中国海洋石油集团有限公司 | A kind of methanation catalyst and the preparation method and application thereof |
| CN110248728A (en) * | 2017-02-01 | 2019-09-17 | 日立造船株式会社 | The preparation method of methanation reaction catalyst, the preparation method of methanation reaction catalyst and methane |
| CN107790136A (en) * | 2017-11-08 | 2018-03-13 | 西安向阳航天材料股份有限公司 | A kind of preparation method of high temperature resistant methanation catalyst |
| CN107790136B (en) * | 2017-11-08 | 2020-01-21 | 西安向阳航天材料股份有限公司 | Preparation method of high-temperature-resistant methanation catalyst |
| CN112705204A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Methanation catalyst for methanation reaction and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102247861A (en) | Coal gas high-temperature methanation catalyst and preparation method thereof | |
| CN101199933B (en) | Multi-element composite metal oxide catalyst and preparation method thereof | |
| CN103480375A (en) | Carbon monoxide methanating catalyst and preparation method thereof | |
| CN103071507B (en) | Completely-methanated catalyst as well as preparation method and application thereof | |
| CN103551153B (en) | A kind of copper-based catalysts for carbon dioxide methanation and preparation method thereof | |
| CN104028270A (en) | Methanation catalyst and preparation method thereof | |
| CN106268852B (en) | A kind of catalyst and the preparation method and application thereof for one-step method from syngas coproduction mixed alcohol and alpha-olefin | |
| US4153580A (en) | CO conversion catalyst | |
| CN101181686A (en) | Hydrotalcite type hydrocracking catalyst and method for preparing same | |
| WO2012040977A1 (en) | Catalyst for catalytically hydrogenating co2 to methanol and preparation thereof | |
| CN108043413A (en) | Catalyst for being combined to natural gas for coal methylmethane and preparation method thereof | |
| CA2838544A1 (en) | Cobalt- and molybdenum-containing mixed oxide catalyst, and production and use thereof as water gas shift catalyst | |
| CN102350355A (en) | Iron-based water gas transformation catalyst and preparation method thereof | |
| CN104525181A (en) | Catalyst for catalytic combustion of soot particulates and preparation method and application of catalyst | |
| CN104741131A (en) | Preparation method of Ni-Mn-Mg-O/MgAl2O4 reformed composite oxide catalyst | |
| CN102350375B (en) | Preparation method of methane synthetic catalyst carrier | |
| Fan et al. | Tuning lattice defects to facilitate the catalytic performance of Ni–Cu–O hybrid nanoparticles towards methane oxidation | |
| WO2012065326A1 (en) | Auxiliary-modified catalyst for producing methanol by catalytic hydrogenation of carbon dioxide and preparation thereof | |
| CN104815662A (en) | Low-temperature high-activity nano-composite catalyst for methanation of synthesis gas and preparation method thereof | |
| CN109718865B (en) | Catalyst carrier, supported catalyst, preparation method and application of supported catalyst, and method for preparing hydrogen by reforming methane steam | |
| CN106890650A (en) | Catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN104815660A (en) | Fischer-Tropsch synthesis cobalt-based catalyst and preparation method and application thereof | |
| CN101318137B (en) | High voltage sulphur resistant translation catalyst of CO and preparation method thereof | |
| CN102744080A (en) | Composite Fe3O4 type structured catalyst used for hydrogen production from methane, and preparation method thereof | |
| CN103464169A (en) | Fischer-Tropsch synthesis catalyst, preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111123 |