CN105688919A - Slurry reactor nickel-based methanation catalyst prepared according to sediment burning method and application thereof - Google Patents
Slurry reactor nickel-based methanation catalyst prepared according to sediment burning method and application thereof Download PDFInfo
- Publication number
- CN105688919A CN105688919A CN201610062034.2A CN201610062034A CN105688919A CN 105688919 A CN105688919 A CN 105688919A CN 201610062034 A CN201610062034 A CN 201610062034A CN 105688919 A CN105688919 A CN 105688919A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- speed
- solution
- aqueous solution
- concentration
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002002 slurry Substances 0.000 title claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 title abstract description 5
- 239000013049 sediment Substances 0.000 title abstract 3
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 5
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims abstract description 5
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 5
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 86
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 66
- 239000007864 aqueous solution Substances 0.000 claims description 55
- 239000004202 carbamide Substances 0.000 claims description 33
- 235000013877 carbamide Nutrition 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 32
- 239000012018 catalyst precursor Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 16
- 238000002485 combustion reaction Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 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 claims description 10
- 230000002269 spontaneous effect Effects 0.000 claims description 10
- DVENVBCPDCQQGD-UHFFFAOYSA-N dysprosium(3+);trinitrate Chemical compound [Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DVENVBCPDCQQGD-UHFFFAOYSA-N 0.000 claims description 7
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- -1 alkyl biphenyl Chemical compound 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 36
- 230000001276 controlling effect Effects 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000012544 monitoring process Methods 0.000 description 9
- 238000004062 sedimentation Methods 0.000 description 9
- 239000003345 natural gas Substances 0.000 description 7
- 239000003245 coal Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/393—
-
- B01J35/615—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a slurry reactor nickel-based methanation catalyst prepared according to a sediment burning method and an application thereof. The invention relates to a methanation nickel-based catalyst prepared according to the sediment burning method and a preparation method thereof. The methanation catalyst comprises the following raw materials by mass percent: 15-50wt% of Ni, 47-80wt% of Al2O3 and 1-10wt% of auxiliaries, wherein the auxiliaries are selected from one or two of Dy2O3, La2O3, Eu2O3 and Gd2O3; the grain size of the catalyst is 60-220 meshes; the specific surface area is 150-250 m<2>/g; the Ni crystal grain size is 12-16nm. The methanation catalyst provided by the invention has the advantages that the preparation process is simple, the preparation period is short and the activity and selectivity in the slurry reactor methanation reaction are high.
Description
Technical field
The present invention relates to the preparation method of a kind of nickel-base catalyst and application, particularly relate to a kind of Ni-based methanation catalyst being applied to slurry bed system methanation reaction and preparation method thereof。
Background technology
Natural gas is a kind of cleaning, safely and conveniently high-grade energy。In recent years, along with the fast development of economic construction, the demand sustainable growth to natural gas, 2014, China's natural gas Apparent con-sumption was 1800 billion cubic meters, increases by 7.4% on a year-on-year basis, and wherein external dependence degree reaches 32.2%。Rich coal resources in China, the coal per year over 80% is directly used, and compares with developed country, and the deep exploitation level of coal is relatively low。Utilize coal gas technology that abundant coal resources are changed into natural gas, be not only effectively increased capacity usage ratio, it also greatly reduce the discharge of greenhouse gases。This has important strategic importance in protecting the sustainable development of Chinese energy safety, reduction energy-saving and emission-reduction, the promotion energy。
Development of Coal preparing natural gas can alleviate the problem that China's natural gas is under-supply, substitutes inlet natural gas, and Chinese energy safety and energy-saving and emission-reduction is significant。CO methanation reaction belongs to strong exothermal reaction, and reactor adiabatic temperature rise is big, very easily causes bed temperature runaway to cause sintering of catalyst and carbon distribution, affects catalyst methane voltinism energy。At present, industry methanation reaction process all adopts fixed bed reactors, it is generally adopted tubular heat exchanger and removes reaction heat, or adopt multiple fixed bed reactors to connect and reduce the conversion per pass control reaction temperature of unstripped gas in single reactor, control bed temperature by multistep gas circulation cooling step by step simultaneously, the technique of this multiple fixed bed reactors series connection temperature control causes that cost of investment increases, and energy expenditure increases。Compared with fixed bed reactors, paste state bed reactor introduces heat conductivity is big, thermal capacitance is big inertia liquid phase heat carrier, can form the airwater mist cooling system of high turbulence, and beds is close to isothermal, thus high temperature sintering and the carbon distribution of catalyst can be avoided, extend the service life of catalyst。Institutes Of Technology Of Taiyuan and SaiDing Engineering Co., Ltd have developed a kind of slurry bed system methanation process (patent CN101979475A and CN101979476A) cooperatively, this technique introduces the liquid phase component that heat conductivity is big, thermal capacitance is big in methanation reaction process, catalyst can be made to be dispersed in inert fluid, realize the isothermal of beds, and the conversion per pass of reaction mass can be improved。
Being stirred vigorously environment owing to slurry bed system beds is in, therefore catalyst should have good wearability, and active component should be stronger with the adhesion of carrier simultaneously, it is to avoid in whipping process, active component comes off from carrier, thus improving the stability of catalyst。The sedimentation method are as one of the conventional preparation method of nickel-base catalyst, and the catalyst of preparation has spherical or class spherical structure, and wearability is good, and active component and carrier concurrently form in precipitation process, and interaction force is strong, it is adaptable to slurry bed system system。But the Some features of the sedimentation method also limit its application: specific surface area of catalyst prepared by (1) sedimentation method is less, crystal grain is relatively big, causes that the active sites of catalyst surface is less, it is poor to disperse；(2) sedimentation method building-up process needs through aging, washing, dry and roasting, higher to controlling range request, improve production cost。
Summary of the invention
It is an object of the present invention to provide a kind of preparation flow simple, generated time is short, the method for making of the nickel-base catalyst being applicable to slurry bed system methanation process that catalysis activity is high and application thereof。
For reaching above-mentioned purpose, the present invention prepares nickel-base catalyst by first precipitating the method for after-combustion。
A kind of Ni-based methanation catalyst of slurry bed system, by mass percentage, it consists of: Ni15 ~ 50wt%；Al2O347 ~ 80wt%；Auxiliary agent is 1 ~ 10wt%；Described auxiliary agent is Dy2O3、La2O3、Eu2O3、Gd2O3In one or both；The granularity of described catalyst is 60 ~ 220 orders, and specific surface area is 150 ~ 250m2/ g, Ni crystal particle diameter is 12 ~ 16nm。
Described catalyst is prepared by precipitating combustion method, and concrete preparation method is as follows:
1) preparing the nitrate aqueous solution of the aluminum nitrate solution that solution concentration is 0.5 ~ 10.0mol/L and the auxiliary agent presoma that solution concentration is 0.5 ~ 2.0mol/L respectively, preparation solution concentration is the aqueous solution of urea of 5.0 ~ 20.0mol/L simultaneously。Above-mentioned nitrate aqueous solution and urea liquid are continuously added in reactor respectively to precipitation completely。The addition speed controlling aluminum nitrate solution in process respectively is 5.0 ~ 60mL/min, the addition speed of auxiliary agent precursor water solution is 0.1 ~ 3.0mL/min, regulating urea liquid addition speed is 20 ~ 60mL/min, so as to be under 70 ~ 90 DEG C of conditions in temperature, stir speed (S.S.) is precipitation in the reactor of 400 ~ 800 turns per minute, joining day is 1 ~ 3h, monitors solution ph with accurate pH test paper in this process, and controlling solution ph is 8 ~ 11。
2) being kept stirring for speed constant, be at 10 ~ 70 DEG C in temperature, adding solution concentration in above-mentioned mixed solution suspension is the nickel nitrate aqueous solution of 0.5 ~ 5.0mol/L, and addition speed is 5.0 ~ 30mL/min。Add solution concentration be the aqueous fuel of 1 ~ 5.0mol/L in order to provide fuel, addition speed is 10 ~ 60mL/min。Carry out spontaneous combustion after then suspension be placed under 300 ~ 600 DEG C of conditions heating evaporation concentration, the powder after burning is collected, grind, pelletize, obtain the catalyst precursor of certain order number。
3) gained catalyst precursor is used in fixed bed reactors reducing gases reductase 12 ~ 8h, namely obtain catalyst。
The presoma of catalyst as described above auxiliary agent is one or both in Dysprosium trinitrate, Lanthanum (III) nitrate, europium nitrate or Gadolinium trinitrate。
Precipitant as above is carbamide。
Fuel as above is at least one in carbamide, starch, glycine。
Reducing gases as above is made up of nitrogen and hydrogen, and volume consists of 5 ~ 85%H2With 15～95%N2, reduction temperature is 450～700 DEG C, and reduction pressure is 0.1～2.0MPa, and reducing gases air speed is 1000～12000mL/(g h)。
The catalyst of the present invention is applied to paste state bed reactor and carries out synthesis gas methanation, reaction condition is: using materials that heat conductivity is big, thermal capacitance is big, boiling point is high such as paraffin hydrocarbon, alkyl biphenyl type conduction oil or methyl-silicone oils as inert liquid phase component, reaction temperature 250 ~ 320 DEG C；Reaction pressure 0.5 ~ 4.0MPa；Air speed 500 ~ 5000mL/(g h)；Slurry bed system catalyst concn 0.013 ~ 0.050g/mL, unstripped gas H2/ CO volume ratio is 2.5 ~ 4.0。
The technical advantage of the present invention is as follows:
A kind of method adopting first precipitation after-combustion to prepare nickel-base catalyst of disclosure, compared with preparing nickel-base catalyst with the sedimentation method, the substantive distinguishing features that the present invention has and progress are in that:
(1) a large amount of gases that combustion process produces make catalytic inner produce abundant pore passage structure, and product specific surface area is big, reaches 150 ~ 250m2/ g, is conducive to the dispersion of active component Ni, and Ni crystal particle diameter is decreased to 12 ~ 16nm, it is provided that more catalytic active site, and then improves slurry bed system methanation activity。
(2) replace aging, the washing of the tradition sedimentation method, sucking filtration, drying and roasting process by combustion process, the preparation time of catalyst can be reduced to 4 ~ 8 hours from 2 ~ 6 days and reduce energy consumption。
Detailed description of the invention
Further describe the method for preparing catalyst disclosed in patent of the present invention below by specific embodiment, but the present invention is not by the restriction of following embodiment。The present invention reacts the catalytic performance probe reaction for catalyst with carbon monoxide and hydrogen synthesizing methane。
Embodiment 1
(1) preparation solution concentration is the aluminum nitrate solution of 1.0mol/L respectively, and solution concentration is the lanthanum nitrate aqueous solution of 1.0mol/L and solution concentration is the urea liquid of 5.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 58.6mL/min, it is 0.1mL/min that lanthanum nitrate aqueous solution adds speed, and it is 50.0mL/min that urea liquid adds speed, so as to be 75 DEG C in temperature, in the reactor that stir speed (S.S.) is 500 turns per minute, precipitation is completely, stops adding after 2h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 8.0。
(2) speed it is kept stirring for constant, it is at 60 DEG C in temperature, it is simultaneously introduced, to above-mentioned suspension, nickel nitrate aqueous solution that solution concentration is 1.0mol/L and solution concentration is the aqueous solution of urea of 5.0mol/L, stop adding after adding speed respectively 10mL/min and 50mL/min, 2h。Spontaneous combustion after then suspension be placed under 350 DEG C of conditions heating evaporation concentration, the powder after burning collected, grind, pelletize to 80 ~ 120 orders, obtain catalyst precursor。
(3) gained catalyst precursor is consisted of 25%H at gas volume2With 75%N2, air speed is 3000mL/(g h), pressure be 0.2MPa fixing bed in reduction 4h under 550 DEG C of conditions, namely obtain methanation nickel-base catalyst, this catalyst consists of: Ni19wt.%, Al2O380wt.%, La2O31wt.%。
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。The concrete steps that catalyst activity is evaluated: above-mentioned for certain mass catalyst and 120mL inert liquid medium are injected in 250mL slurry reactor still, at ambient temperature, uses N2It is pressurized to reaction pressure to system, is warming up to reaction temperature with 5 DEG C/min, in reactor, then pass into 25mL/minCO and a certain amount of H2, and under 750r/min stirs, start reaction, sample analysis after reaction a period of time。
Embodiment 2
(1) preparation solution concentration is the aluminum nitrate solution of 1.0mol/L respectively, and solution concentration is the Dysprosium trinitrate aqueous solution of 1.0mol/L and solution concentration is the urea liquid of 6.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 17.1mL/min, it is 0.2mL/min that Dysprosium trinitrate aqueous solution adds speed, and it is 50.0mL/min that urea liquid adds speed, so as to be 75 DEG C in temperature, in the reactor that stir speed (S.S.) is 400 turns per minute, precipitation is completely, stops adding after 1h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 8.0。
(2) speed it is kept stirring for constant, it is at 40 DEG C in temperature, it is simultaneously introduced, to above-mentioned suspension, nickel nitrate aqueous solution that solution concentration is 0.5mol/L and solution concentration is the aqueous solution of urea of 2.0mol/L, stop adding after adding speed respectively 13.0mL/min and 20mL/min, 1h。Spontaneous combustion after then suspension be placed under 400 DEG C of conditions heating evaporation concentration, the powder after burning collected, grind, pelletize to 160 ~ 200 orders, obtain catalyst precursor。
(3) gained catalyst precursor is consisted of 10%H at gas volume2With 90%N2, air speed is 5000mL/(g h), pressure be 1.0MPa fixing bed in reduction 7h under 650 DEG C of conditions, namely obtain methanation nickel-base catalyst, this catalyst consists of: Ni35wt.%, Al2O363wt.%, Dy2O32wt.%。
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。Concrete steps are as described in Example 1。
Embodiment 3
(1) preparation solution concentration is the aluminum nitrate solution of 2.0mol/L respectively, and solution concentration is the lanthanum nitrate aqueous solution of 0.5mol/L and solution concentration is the urea liquid of 5.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 21.2mL/min, it is 0.5mL/min that the aqueous solution of Lanthanum (III) nitrate adds speed, and it is 50.0mL/min that urea liquid adds speed, so as to be 80 DEG C in temperature, in the reactor that stir speed (S.S.) is 700 turns per minute, precipitation is completely, stops adding after 0.5h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 10.0。
(2) speed it is kept stirring for constant, it is at 30 DEG C in temperature, it is simultaneously introduced, to above-mentioned suspension, nickel nitrate aqueous solution that solution concentration is 2.0mol/L and solution concentration is the aqueous solution of urea of 5.0mol/L, stop adding after adding speed respectively 10mL/min and 50mL/min, 0.5h。Spontaneous combustion after then suspension be placed under 600 DEG C of conditions heating evaporation concentration, the powder after burning collected, grind, pelletize to 140 ~ 180 orders, obtain catalyst precursor。
(3) gained catalyst precursor is consisted of 35%H at gas volume2With 65%N2, air speed is 1000mL/(g h), pressure be 0.1MPa fixing bed in reduction 5h under 600 DEG C of conditions, namely obtain methanation nickel-base catalyst, this catalyst consists of: Ni40wt.%, Al2O358wt.%, La2O32wt.%。
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。Concrete steps are as described in Example 1。
Embodiment 4
(1) preparation solution concentration is the aluminum nitrate solution of 8.0mol/L respectively, and solution concentration is the Gadolinium trinitrate aqueous solution of 1.5mol/L and solution concentration is the urea liquid of 10.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 9.6mL/min, it is 1.6mL/min that the aqueous solution of Gadolinium trinitrate adds speed, and it is 50.0mL/min that urea liquid adds speed, so as to be 85 DEG C in temperature, in the reactor that stir speed (S.S.) is 800 turns per minute, precipitation is completely, stops adding after 1.5h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 9.0。
(2) speed it is kept stirring for constant, it is at 40 DEG C in temperature, it is simultaneously introduced, to above-mentioned suspension, nickel nitrate aqueous solution that solution concentration is 0.5mol/L and solution concentration is the aqueous solution of urea of 5.0mol/L, stop adding after adding speed respectively 25.5mL/min and 45.0mL/min, 1.5h。Spontaneous combustion after then suspension be placed under 300 DEG C of conditions heating evaporation concentration, the powder after burning collected, grind, pelletize to 100 ~ 140 orders, obtain catalyst precursor。
(3) gained catalyst precursor is consisted of 50%H at gas volume2With 50%N2, air speed is 7000mL/(g h), pressure be 1.5MPa fixing bed in reduction 5h under 500 DEG C of conditions, namely obtain methanation nickel-base catalyst, this catalyst consists of: Ni18wt.%, Al2O374wt.%, Gd2O35wt.%, La2O33wt.%。
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。Concrete steps are as described in Example 1。
Embodiment 5
(1) preparation solution concentration is the aluminum nitrate solution of 5.0mol/L respectively, and solution concentration is the Dysprosium trinitrate aqueous solution of 1.0mol/L, and solution concentration is the aqueous solution of the Lanthanum (III) nitrate of 1.0mol/L and solution concentration is the urea liquid of 18.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 25.6mL/min, it is 2.3mL/min that the aqueous solution of Dysprosium trinitrate adds speed, it is 2.7mL/min that the aqueous solution of Lanthanum (III) nitrate adds speed, it is 30.0mL/min that urea liquid adds speed, so as to be 80 DEG C in temperature, in the reactor that stir speed (S.S.) is 600 turns per minute, precipitation is completely, stops adding after 1h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 10.5。
(2) speed it is kept stirring for constant, it is at 15 DEG C in temperature, it is simultaneously introduced, to above-mentioned suspension, nickel nitrate aqueous solution that solution concentration is 3.5mol/L and solution concentration is the aqueous solution of urea of 3.0mol/L, stop adding after adding speed respectively 5mL/min and 50mL/min, 1h。Spontaneous combustion after then suspension be placed under 500 DEG C of conditions heating evaporation concentration, the powder after burning collected, grind, pelletize to 80 ~ 120 orders, obtain catalyst precursor。
(3) gained catalyst precursor is consisted of 80%H at gas volume2With 20%N2, air speed is 6000mL/(g h), pressure be 0.8MPa fixing bed in reduction 3h under 550 DEG C of conditions, namely obtain methanation nickel-base catalyst, this catalyst consists of: Ni15wt.%, Al2O375wt.%, Dy2O35wt.%, La2O35wt.%。
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。Concrete steps are as described in Example 1。
Embodiment 6
(1) preparation solution concentration is the aluminum nitrate solution of 9.0mol/L respectively, and solution concentration is the europium nitrate aqueous solution of 0.5mol/L and solution concentration is the urea liquid of 8.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 6.1mL/min, it is 2.0mL/min that the aqueous solution of europium nitrate adds speed, and it is 40.0mL/min that urea liquid adds speed, so as to be 85 DEG C in temperature, in the reactor that stir speed (S.S.) is 600 turns per minute, precipitation is completely, stops adding after 1.5h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 8.5。
(2) speed it is kept stirring for constant, it is at 60 DEG C in temperature, it is simultaneously introduced, to above-mentioned suspension, nickel nitrate aqueous solution that solution concentration is 4.0mol/L and solution concentration is the aqueous solution of urea of 5.0mol/L, stop adding after adding speed respectively 10mL/min and 70mL/min, 1.5h。Spontaneous combustion after then suspension be placed under 400 DEG C of conditions heating evaporation concentration, the powder after burning collected, grind, pelletize to 180 ~ 220 orders, obtain catalyst precursor。
(3) gained catalyst precursor is consisted of 60%H at gas volume2With 40%N2, air speed is 11000mL/(g h), pressure be 0.3MPa fixing bed in reduction 3h under 700 DEG C of conditions, namely obtain methanation nickel-base catalyst, this catalyst consists of: Ni50wt.%, Al2O347wt.%, Eu2O33wt.%。
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。Concrete steps are as described in Example 1。
Embodiment 7
(1) preparation solution concentration is the aluminum nitrate solution of 2.5mol/L respectively, and solution concentration is the Gadolinium trinitrate aqueous solution of 1.5mol/L and solution concentration is the urea liquid of 15.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 35.6mL/min, it is 1.9mL/min that the aqueous solution of Dysprosium trinitrate adds speed, and it is 35.0mL/min that urea liquid adds speed, so as to be 75 DEG C in temperature, in the reactor that stir speed (S.S.) is 800 turns per minute, precipitation is completely, stops adding after 3.0h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 10.0。
(2) speed it is kept stirring for constant, it is at 35 DEG C in temperature, it is simultaneously introduced, to above-mentioned suspension, nickel nitrate aqueous solution that solution concentration is 3.0mol/L and solution concentration is the aqueous solution of urea of 4.0mol/L, stop adding after adding speed respectively 15.0mL/min and 20mL/min, 3.0h。Spontaneous combustion after then suspension be placed under 450 DEG C of conditions heating evaporation concentration, the powder after burning collected, grind, pelletize to 120 ~ 160 orders, obtain catalyst precursor。
(3) gained catalyst precursor is consisted of 55%H at gas volume2With 45%N2, air speed is 2000mL/(g h), pressure be 1.2MPa fixing bed in reduction 4h under 450 DEG C of conditions, namely obtain this catalyst of methanation nickel-base catalyst and consist of: Ni40wt.%, Al2O354wt.%, Gd2O34wt.%, La2O32wt.%。
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。Concrete steps are as described in Example 1。
Embodiment 8
(1) preparation solution concentration is the aluminum nitrate solution of 2.0mol/L respectively, and solution concentration is the europium nitrate aqueous solution of 2.0mol/L and solution concentration is the urea liquid of 6.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 17.6mL/min, it is 0.5mL/min that the aqueous solution of europium nitrate adds speed, and it is 20.0mL/min that urea liquid adds speed, so as to be 80 DEG C in temperature, in the reactor that stir speed (S.S.) is 600 turns per minute, precipitation is completely, stops adding after 1.0h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 9.5。
(2) speed it is kept stirring for constant, it is at 20 DEG C in temperature, it is simultaneously introduced, to above-mentioned suspension, nickel nitrate aqueous solution that solution concentration is 1.0mol/L and solution concentration is the aqueous solution of urea of 3.5mol/L, stop adding after adding speed respectively 5.0mL/min and 35mL/min, 1.0h。Spontaneous combustion after then suspension be placed under 350 DEG C of conditions heating evaporation concentration, the powder after burning collected, grind, pelletize to 60 ~ 100 orders, obtain catalyst precursor。
(3) gained catalyst precursor is consisted of 70%H at gas volume2With 30%N2, air speed is 4000mL/(g h), pressure be 0.5MPa fixing bed in reduction 6h under 550 DEG C of conditions, namely obtain methanation nickel-base catalyst, this catalyst consists of: Ni16wt.%, Al2O377wt.%, Eu2O35wt.%, La2O32wt.%。
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。Concrete steps are as described in Example 1。
Comparative example
Methanation nickel-base catalyst prepared by the sedimentation method, specifically comprises the following steps that
(1) preparation solution concentration is the aluminum nitrate solution of 1.0mol/L respectively, and solution concentration is the nickel nitrate solution of 1.0mol/L, and solution concentration is the aqueous solution of the Lanthanum (III) nitrate of 1.0mol/L and solution concentration is the urea liquid of 5.0mol/L。Regulating aluminum nitrate aqueous solution addition speed is 58.6mL/min, it is 10.0mL/min that nickel nitrate aqueous solution adds speed, it is 0.1mL/min that lanthanum nitrate aqueous solution adds speed, it is 50.0mL/min that urea liquid adds speed, so as to be 75 DEG C in temperature, in the reactor that stir speed (S.S.) is 500 turns per minute, precipitation is completely, stops adding after 2h。Monitoring solution ph with accurate pH test paper in this process, controlling solution ph is 8.0。
(2) precipitate after completely, mother liquor of precipitation of ammonium 500 turns per minute in stir speed (S.S.), temperature is under 60 DEG C of conditions after aging 2.0h, precipitate with deionized water cyclic washing, dry 12h under 120 DEG C of conditions, be subsequently placed into Muffle furnace, 450 DEG C of roasting 4h, after roasting, remaining powder is collected, and after grinding, pelletize is to 80 ~ 120 orders, obtains catalyst precursor。
(3) gained catalyst precursor is consisted of 25%H at gas volume2With 75%N2, air speed is 3000mL/(g h), pressure be 0.2MPa fixing bed in reduction 4h under 550 DEG C of conditions, namely obtain methanation nickel-base catalyst should, catalyst precursor consists of: Ni20wt.%, Al2O380wt.%, La2O31wt.%。Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1。Concrete steps are as described in Example 1。
The nickel-base catalyst of the embodiment of the present invention 1 preparation having been carried out XRD and BET sign, and the catalyst prepared with the sedimentation method (comparative example) contrasts, its result sees subordinate list 2。By subordinate list 2, adopt catalyst prepared by precipitation solution combustion method, the catalyst that particle diameter is prepared less than the sedimentation method, there is bigger specific surface area simultaneously。
Subordinate list illustrates:
The catalyst that table 1 is each embodiment and prepared by comparative example is in the evaluation result of synthesis gas methanation reaction。
The specific surface area of the catalyst that table 2 is embodiment 1 and prepared by comparative example and particle size determination results contrast。
Table 1
Table 2
Claims (8)
1. the Ni-based methanation catalyst of slurry bed system, by mass percentage, it consists of: Ni15 ~ 50wt%；Al2O347 ~ 80wt%；Auxiliary agent is 1 ~ 10wt%；Described auxiliary agent is Dy2O3、La2O3、Eu2O3、Gd2O3In one or both；The granularity of described catalyst is 60 ~ 220 orders, and specific surface area is 150 ~ 250m2/ g, Ni crystal particle diameter is 12 ~ 16nm。
2. the Ni-based methanation catalyst of slurry bed system as claimed in claim 1, it is characterised in that the preparation method of described catalyst, comprises the steps:
1) compound concentration is the nitrate aqueous solution of the aluminum nitrate aqueous solution of 0.5 ~ 10.0mol/L and auxiliary agent presoma that concentration is 0.5 ~ 2.0mol/L respectively, by above-mentioned aluminum nitrate aqueous solution, auxiliary agent nitrate aqueous solution and precipitant respectively with 5.0 ~ 60mL/min, 0.1 ~ 3.0mL/min, 20 ~ 60mL/min speed be continuously added to precipitation completely, the pH value controlling solution in this process is 8 ~ 11；
2) speed it is kept stirring for constant, it is at 10 ~ 70 DEG C in temperature, add, with the speed of 5.0 ~ 30mL/min, the nickel nitrate aqueous solution that concentration is 0.5 ~ 5.0mol/L in above-mentioned mixed solution suspension, then add, with the speed of 10 ~ 60mL/min, the aqueous fuel that concentration is 1 ~ 5.0mol/L, spontaneous combustion is carried out after then gained suspension be placed under 300 ~ 600 DEG C of conditions heating evaporation concentration, by the powder collection after burning, grinding, pelletize, obtain the catalyst precursor of certain order number；
3) gained catalyst precursor is used in fixed bed reactors reducing gases reductase 12 ~ 8h, namely obtain catalyst。
3. the Ni-based methanation catalyst of slurry bed system as claimed in claim 2, it is characterised in that in the preparation process of catalyst, the presoma of described auxiliary agent is one or both in Dysprosium trinitrate, Lanthanum (III) nitrate, europium nitrate or Gadolinium trinitrate。
4. the Ni-based methanation catalyst of slurry bed system as claimed in claim 2, it is characterised in that in the preparation process of catalyst, described precipitant is solution concentration is the urea liquid of 5.0 ~ 20.0mol/L。
5. the Ni-based methanation catalyst of slurry bed system as claimed in claim 2, it is characterised in that in the preparation process of catalyst, described fuel is at least one in carbamide, starch, glycine。
6. the Ni-based methanation catalyst of slurry bed system as claimed in claim 2, it is characterised in that in step 1), control the temperature of mixed solution be 70 ~ 90 DEG C, stir speed (S.S.) be 400 ~ 800r/min。
7. the Ni-based methanation catalyst of slurry bed system as claimed in claim 2, it is characterised in that in step 1), described reducing gases is consisted of 5 ~ 85%H by volume2With 15～95%N2Being formed, reduction temperature is 450～700 DEG C, and reduction pressure is 0.1～2.0MPa, and reducing gases air speed is 1000～12000mL/(g h)。
8. the Ni-based methanation catalyst of slurry bed system described in any of the above-described claim is applied to paste state bed reactor and carries out synthesis gas methanation, reaction condition is: using materials that heat conductivity is big, thermal capacitance is big, boiling point is high such as paraffin hydrocarbon, alkyl biphenyl type conduction oil or methyl-silicone oils as inert liquid phase component, reaction temperature 250 ~ 320 DEG C；Reaction pressure 0.5 ~ 4.0MPa；Air speed 500 ~ 5000mL/(g h)；Slurry bed system catalyst concn 0.013 ~ 0.050g/mL, unstripped gas H2/ CO volume ratio is 2.5 ~ 4.0。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610062034.2A CN105688919B (en) | 2016-01-29 | 2016-01-29 | It is a kind of to precipitate the Ni-based methanation catalyst of slurry bed system and its application prepared by combustion method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610062034.2A CN105688919B (en) | 2016-01-29 | 2016-01-29 | It is a kind of to precipitate the Ni-based methanation catalyst of slurry bed system and its application prepared by combustion method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105688919A true CN105688919A (en) | 2016-06-22 |
| CN105688919B CN105688919B (en) | 2018-04-03 |
Family
ID=56229757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610062034.2A Active CN105688919B (en) | 2016-01-29 | 2016-01-29 | It is a kind of to precipitate the Ni-based methanation catalyst of slurry bed system and its application prepared by combustion method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105688919B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816238A (en) * | 2018-05-21 | 2018-11-16 | 北京石油化工学院 | A kind of Ni-based CO catalyst for hydrogenation and the preparation method and application thereof |
| CN109046364A (en) * | 2018-07-24 | 2018-12-21 | 南昌大学 | A kind of preparation method and applications of Fe2O3 doping lanthana supported nickel based catalysts |
| CN109833874A (en) * | 2017-11-29 | 2019-06-04 | 中国石油天然气股份有限公司 | A kind of Raney nickel and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012167351A1 (en) * | 2011-06-08 | 2012-12-13 | University Of Regina | Sulfur tolerant catalysts for hydrogen production by carbon dioxide reforming of methane-rich gas |
| CN102872874A (en) * | 2012-09-19 | 2013-01-16 | 太原理工大学 | Loaded type nickel-based catalyst used for slurry bed methanation, and preparation method and application thereof |
| EP2684856A1 (en) * | 2012-07-09 | 2014-01-15 | Paul Scherrer Institut | A method for methanation of gasification derived producer gas on metal catalysts in the presence of sulfur |
| CN103537288A (en) * | 2013-10-25 | 2014-01-29 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing methanation catalyst by adopting urea combustion method |
| CN104028270A (en) * | 2014-06-10 | 2014-09-10 | 中国华能集团清洁能源技术研究院有限公司 | Methanation catalyst and preparation method thereof |
-
2016
- 2016-01-29 CN CN201610062034.2A patent/CN105688919B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012167351A1 (en) * | 2011-06-08 | 2012-12-13 | University Of Regina | Sulfur tolerant catalysts for hydrogen production by carbon dioxide reforming of methane-rich gas |
| EP2684856A1 (en) * | 2012-07-09 | 2014-01-15 | Paul Scherrer Institut | A method for methanation of gasification derived producer gas on metal catalysts in the presence of sulfur |
| CN102872874A (en) * | 2012-09-19 | 2013-01-16 | 太原理工大学 | Loaded type nickel-based catalyst used for slurry bed methanation, and preparation method and application thereof |
| CN103537288A (en) * | 2013-10-25 | 2014-01-29 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing methanation catalyst by adopting urea combustion method |
| CN104028270A (en) * | 2014-06-10 | 2014-09-10 | 中国华能集团清洁能源技术研究院有限公司 | Methanation catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吉可明: ""燃烧法制备Ni基催化剂及其浆态床甲烷化性能的研究"", 《中国博士学位论文全文数据库工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833874A (en) * | 2017-11-29 | 2019-06-04 | 中国石油天然气股份有限公司 | A kind of Raney nickel and its preparation method and application |
| CN109833874B (en) * | 2017-11-29 | 2021-09-28 | 中国石油天然气股份有限公司 | Nickel catalyst and preparation method and application thereof |
| CN108816238A (en) * | 2018-05-21 | 2018-11-16 | 北京石油化工学院 | A kind of Ni-based CO catalyst for hydrogenation and the preparation method and application thereof |
| CN109046364A (en) * | 2018-07-24 | 2018-12-21 | 南昌大学 | A kind of preparation method and applications of Fe2O3 doping lanthana supported nickel based catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105688919B (en) | 2018-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102872874B (en) | Loaded type nickel-based catalyst used for slurry bed methanation, and preparation method and application thereof | |
| CN106031871B (en) | A kind of CO2Hydrogenation takes ferrum-based catalyst and its preparation and the application of low-carbon alkene | |
| CN106732647B (en) | A kind of perovskite type methyl hydride combustion catalyst and the preparation method and application thereof | |
| CN108187716A (en) | A kind of N doping Carbon Materials Multi-metal supported catalyst and its preparation method and application | |
| CN104399491B (en) | A kind of high temperature resistant methanation catalyst and preparation method thereof | |
| CN101879448A (en) | Ordered structure catalyst for hydrogenation of oxalic ester for preparing ethylene glycol and preparation method thereof | |
| CN103480375A (en) | Carbon monoxide methanating catalyst and preparation method thereof | |
| CN105381803A (en) | Fluidized bed catalyst for syngas methanation, preparation method thereof and applications thereof | |
| CN109908903A (en) | A kind of high-specific surface area Lignin-Based Activated Carbon is nickel-base catalyst and its preparation and application of carrier | |
| CN105562014A (en) | Nickel-based methanation catalyst prepared through gel combustion method and application of nickel-based methanation catalyst | |
| CN110773218A (en) | Nitrogen-doped biochar-loaded metal nickel catalyst and application thereof | |
| CN107233890A (en) | A kind of nickel-base catalyst of attapulgite load of zinc modification and its preparation method and application | |
| CN111841608A (en) | High-activity and anti-carbon composite catalyst, preparation method thereof and application thereof in methane dry gas reforming | |
| CN105688919A (en) | Slurry reactor nickel-based methanation catalyst prepared according to sediment burning method and application thereof | |
| CN107029726A (en) | A kind of preparation method and application of the Ni-based CO methanation catalysts of nanometer | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN112264029B (en) | Ni-based diesel reforming catalyst and preparation method and application thereof | |
| CN110215927A (en) | A kind of preparation method of the support type catalyst of phosphatizing nickel of high dispersive | |
| CN107790136A (en) | A kind of preparation method of high temperature resistant methanation catalyst | |
| CN101693203B (en) | Method for preparing Ni base catalyst for methane portion oxidation synthesis gas | |
| CN102259004B (en) | Catalyst used in coal natural gas methanation reactor and preparation method thereof | |
| CN105772107A (en) | Carrier, preparation method thereof, cobalt-based catalyst, and preparation method and application of cobalt-based catalyst | |
| CN113019410A (en) | Metal oxide-boron nitride composite catalyst for dry reforming of methane, and preparation method and application thereof | |
| CN113952970A (en) | Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof | |
| CN104815662A (en) | Low-temperature high-activity nano-composite catalyst for methanation of synthesis gas and preparation method 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 | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Cui Liping Inventor after: Li Zhong Inventor after: Gao Yuan Inventor after: Meng Fanhui Inventor before: Li Zhong Inventor before: Gao Yuan Inventor before: Meng Fanhui |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |