CN114433101B - Complete methanation catalyst, preparation method and application thereof and method for preparing synthetic natural gas by methanation reaction - Google Patents
Complete methanation catalyst, preparation method and application thereof and method for preparing synthetic natural gas by methanation reaction Download PDFInfo
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- CN114433101B CN114433101B CN202011197521.2A CN202011197521A CN114433101B CN 114433101 B CN114433101 B CN 114433101B CN 202011197521 A CN202011197521 A CN 202011197521A CN 114433101 B CN114433101 B CN 114433101B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 56
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000012065 filter cake Substances 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 45
- 239000003960 organic solvent Substances 0.000 claims abstract description 40
- 238000001556 precipitation Methods 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 238000000975 co-precipitation Methods 0.000 claims abstract description 22
- 238000010992 reflux Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000032683 aging Effects 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000000470 constituent Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 150000002910 rare earth metals Chemical class 0.000 claims description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- -1 alkali metal salt Chemical class 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 3
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 238000011021 bench scale process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 239000003245 coal Substances 0.000 description 11
- 239000003345 natural gas Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 4
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100149737 Caenorhabditis elegans sng-1 gene Proteins 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910002852 Sm(NO3)3·6H2O Inorganic materials 0.000 description 1
- 101100276531 Streptomyces halstedii sch4 gene Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a complete methanation catalyst, a preparation method and application thereof and a method for preparing synthetic natural gas by methanation reaction, wherein the method comprises the following steps: (1) Weighing the soluble salts of the specified amounts of the constituent elements to prepare mixed salt solution; (2) preparing a precipitant solution; (4) Dripping the mixed salt solution and the precipitant solution into a precipitation tank respectively by adopting a parallel flow coprecipitation method for coprecipitation; (5) ending the precipitation, standing and aging; (6) Filtering and washing, and refluxing the washed filter cake by adopting an organic solvent, and then drying and roasting. The catalyst provided by the invention has excellent activity and stability, and completely meets the performances of good low-temperature activity, good high-temperature heat stability, good high-temperature water resistance and the like required by the complete methanation of the synthetic gas. The catalyst was evaluated in a laboratory bench-scale apparatus at an ultra-high space velocity (40000 ml.g) ‑1 ·h ‑1 ) The reaction is carried out continuously for about 200 hours, the CO conversion rate is always more than or equal to 99 percent, CH 4 The selectivity is always more than or equal to 97 percent.
Description
Technical Field
The invention belongs to the fields of coal chemical industry and natural gasification industry, and in particular relates to a complete methanation catalyst, a preparation method of the complete methanation catalyst and a catalyst prepared by the method; and the application of the complete methanation catalyst in the complete methanation reaction of the synthesis gas and a method for complete methanation of the synthesis gas.
Background
The energy resource of our country is characterized by rich coal, lean oil (petroleum) and less gas (natural gas). The proportion of coal consumption accounting for one-time consumption of energy is about 70 percent. Natural gas is a clean, convenient and fast transportation and safe high-quality energy source. Along with the acceleration of industrialization and town process in China and the implementation of energy conservation and emission reduction policies, the consumption proportion of clean energy sources such as natural gas and the like is larger and larger. The synthesis gas is obtained by gasifying coal or biomass, and then the synthesis natural gas is prepared by methanation, so that the synthesis natural gas becomes an effective way for making up the deficiency of the gas source. The energy conversion rate of the natural gas produced by the coal is high, the water consumption is low, the waste treatment is relatively simple, and the method becomes one of the most effective utilization modes of the coal.
The technological process of producing natural gas by coal mainly comprises four parts of coal gasification, shift conversion, synthesis gas purification and synthesis gas methanation. The key of the technical route of the natural gas from coal is the synthetic gas methanation technology, and the core of the synthetic gas methanation technology is a methanation catalyst and a methanation reactor. Methanation of synthesis gas is the methanation of about 20% CO and small amounts of CO in the synthesis gas 2 And H is 2 Methanation reaction is carried out. Methanation is a strongly exothermic process, and every 1% CO conversion in the reaction system will result in an adiabatic temperature rise of the reactor of 72 ℃. Thus, in existing synthesis gas methanation processes, at least two reactors are typically employed in series. The first reactor must be operated at high temperature and high pressure in order to increase the utilization rate of the equipment and the production efficiency. Therefore, the catalyst must have good low temperature activity and high temperature stability.
Currently, high temperature and high pressure methanation catalysts (technologies) are mainly provided by foreign companies such as david company in the united kingdom and topira company in denmark. Since the methanation reaction of the synthesis gas is a strongly exothermic reaction, the methanation reaction at high temperature is affected by chemical equilibrium and cannot be completed. Thus, the second reactor is operated at a medium and low temperature (250-450 ℃) to achieve complete conversion of unconverted synthesis gas in the first reactor.
At present, only normal pressure partial methanation technology for producing urban gas and trace CO/CO in China 2 The methanation catalyst for purifying the gas has no mature catalyst and matched process in the process of preparing natural gas from coal. In recent years, the coal-to-natural gas project of domestic construction mainly adopts foreign methanation technology, so that huge patent use fees are paid. Therefore, it is highly desirable to develop a syngas methanation catalyst with independent intellectual property rights and corresponding support processes and reactors.
Disclosure of Invention
The invention aims to provide a catalyst for complete methanation of synthesis gas and a preparation method thereof, and the catalyst prepared by the method has high activity (CO conversion rate is close to 100 percent) and high methane selectivity (CH) when being applied to complete methanation of synthesis gas 4 The selectivity is close to 98 percent), the raw material processing capability is high, and the catalyst has the characteristics of good high-temperature heat stability, strong carbon deposit resistance, good high-temperature heat stability and the like, and completely meets the requirements of preparing the natural gas complete methanation catalyst from coke oven gas or coal-based synthesis gas.
According to a first aspect of the present invention, there is provided a complete methanation catalyst, the catalyst comprising: ni element, alkaline earth metal element, rare earth metal element, alkali metal element and Al 2 O 3 。
Preferably, the Ni content is 5-20wt%, alkaline earth metal content is 5-20wt%, rare earth metal content is 2-10wt%, alkali metal content is 0.5-5wt%, al 2 O 3 The content is 45-87.5wt%.
Preferably, the specific surface area of the catalyst is 158-240m 2 Preferably 200-231m 2 /g; and/or NiO crystal grain size of 6-20nm, preferably 7-9nm.
Preferably, the catalyst adopts co-current co-precipitation of a coprecipitation agent solution and a mixed salt solution of each component element to obtain a filter cake, and the filter cake is obtained by drying, roasting and forming, and is preferably subjected to reflux treatment by an organic solvent before drying.
Preferably, the organic solvent is one or more of C1-C4 alcohol, C3-C5 ketone, C2-C4 ether; preferably, the organic solvent is one or more of methanol, ethanol, diethyl ether and acetone; and/or the volume ratio of the organic solvent to the filter cake is 3-10:1; and/or conditions of the reflow process include: the temperature is 60-100deg.C, and the time is 2-30h.
Preferably, the alkaline earth metal element is one or more of Be, mg, ca, sr and Ba, preferably one or more of Mg, ca and Ba, further preferably Mg and/or Ca; and/or the rare earth metal element is one or more of Y, la, ce, pr and Sm, preferably one or more of Y, la and Ce, further preferably La and/or Ce; and/or the alkali metal element is one or more of K and Cs, preferably K.
Preferably, the catalyst contains graphite, preferably in an amount of 1 to 5 wt%, preferably 2 to 4 wt%, based on the total weight of the catalyst.
According to a second aspect of the present invention, there is provided a process for preparing a complete methanation catalyst according to one of the present invention, the process comprising: (1) Weighing the soluble salts of the specified amounts of the constituent elements to prepare mixed salt solution; (2) preparing a precipitant solution; (4) Dripping the mixed salt solution and the precipitant solution into a precipitation tank respectively by adopting a parallel flow coprecipitation method for coprecipitation; (5) ending the precipitation, standing and aging; (6) Filtering and washing, and refluxing the washed filter cake by adopting an organic solvent, and then drying and roasting.
Preferably, when the alkali metal is K, the mixed salt of step (1) does not include an alkali metal salt, and the method further comprises: drying the filter cake subjected to reflux treatment, mixing with kalioplast, ball milling, roasting, mixing with graphite, and forming; preferably, the kaliophlomis is natural kaliophlomis.
Preferably, the mixing ball milling time is 5 to 48 hours, preferably 8 to 24 hours; and/or the amount of graphite added is 1 to 5wt%, preferably 2 to 4wt%.
Preferably, the precipitant is NaOH and/or Na 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the soluble nickel salt is one or more of nickel nitrate, basic nickel carbonate, nickel chloride and nickel-containing hydrate, preferably Ni (NO 3 ) 2 ·6H 2 O; and/or the soluble alkaline earth metal salt is one or more of alkaline earth metal nitrate, alkaline earth metal chloride and alkaline earth metal hydrate; and/or the soluble rare earth metal salt is one or more of rare earth metal nitrate, rare earth metal chloride and rare earth metal hydrate; and/or the aluminum salt is one or more of an aluminum-containing nitrate, an aluminum-containing sulfate, an aluminum-containing chloride salt and an aluminum-containing hydrate.
Preferably, the total metal ion concentration in the mixed salt solution in the step (1) is 0.1-1 mol/L; and/or the concentration of the coprecipitate solution is 0.2 to 5mol/L, preferably 0.5 to 2mol/L; and/or the dropping speed of the mixed salt solution and the precipitant solution is such that the pH value of the solution in the precipitation tank is stabilized at 7-13, preferably 8-12; meanwhile, the temperature of the precipitation tank is controlled at 25-90 ℃, preferably 40-80 ℃; and/or the time of standing and aging is 1 to 10 hours, preferably 1.5 to 5 hours; filtering after standing and aging, taking out a filter cake, washing with deionized water, wherein the ratio of the volume of deionized water to the volume of the filter cake is preferably 2-20:1, more preferably 5-15:1, and the washing times are 1-10, more preferably 2-6, wherein the conductivity of the final filtrate is less than 2 mu S/cm.
Preferably, the organic solvent is one or more of C1-C4 alcohol, C3-C5 ketone, C2-C4 ether; preferably the organic solvent is one or more of methanol, ethanol, diethyl ether and acetone, preferably ethanol and/or acetone; and/or the volume ratio of the organic solvent to the filter cake is 3-10:1, preferably 3-6:1; and/or conditions of the reflow process include: the temperature is 60-100 ℃; the time is 3 to 24 hours, preferably 5 to 12 hours.
Preferably, the drying conditions include: the temperature is 80-150 ℃, preferably 100-130 ℃; and/or for a time of 1 to 24 hours, preferably 2 to 10 hours; and/or firing conditions include: the temperature is 500-1000 ℃, preferably 600-800 ℃; and/or for a time of 1 to 10 hours, preferably 2 to 5 hours.
According to a third aspect of the invention, the invention provides a catalyst prepared by the preparation method of the invention.
According to a fourth aspect of the invention, the invention provides the use of the catalyst according to the invention in the preparation of synthetic natural gas by methanation.
According to a fifth aspect of the present invention, there is provided a process for the production of synthetic natural gas by methanation, wherein the process comprises: filling a catalyst into a fixed bed reactor, and under the condition of preparing synthetic natural gas by methanation reaction, making H 2 Contact with CO; the catalyst is the catalyst disclosed by the invention.
Preferably, the conditions of the contacting include: h by volume 2 The molar ratio of the catalyst to CO is 2-4:1, preferably 3-4:1, and the reaction temperature is 250-750 ℃, preferably 280-650 ℃; the pressure is 0-6 MPa, preferably 1-4 MPa; the space velocity of the raw material gas is 1000-100000 ml.g -1 ·h -1 Preferably 5000 to 40000 ml.g -1 ·h -1 。
According to a second aspect of the present invention, there is provided a process for preparing the complete methanation catalyst according to the present invention, the process comprising:
(1) Weighing the soluble salts of the specified amounts of the constituent elements to prepare mixed salt solution;
(2) Preparing a precipitant solution;
(4) Dripping the mixed salt solution and the precipitant solution into a precipitation tank respectively by adopting a parallel flow coprecipitation method for coprecipitation;
(5) Standing and aging after precipitation is finished;
(6) Filtering and washing, and refluxing the washed filter cake by adopting an organic solvent, and then drying and roasting.
According to a third aspect of the present invention there is provided a catalyst prepared according to the method of the present invention.
According to a fourth aspect of the invention, the invention provides the use of the catalyst according to the invention in the preparation of synthetic natural gas by methanation.
According to a fifth aspect of the present invention, there is provided a process for the production of synthetic natural gas by methanation, wherein the process comprises: filling a catalyst into a fixed bed reactor, and under the condition of preparing synthetic natural gas by methanation reaction, making H 2 Contact with CO; the catalyst is the catalyst disclosed by the invention.
Compared with the prior similar catalysts, the catalyst provided by the invention has excellent activity and stability when the catalyst prepared by the method is used for complete methanation of the synthetic gas, and completely meets the performances of good low-temperature activity, good high-temperature thermal stability, good high-temperature hydration resistance and the like required by the complete methanation of the synthetic gas. The catalyst was evaluated in a laboratory bench-scale apparatus at an ultra-high space velocity (40000 ml.g) -1 ·h -1 ) The reaction is carried out continuously for about 200 hours, the CO conversion rate is always more than or equal to 99 percent, CH 4 The selectivity is always more than or equal to 97 percent.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a catalyst H obtained in example 1 2 -a TPR profile;
FIG. 2 is a graph of evaluation data of methanation reaction catalyzed by the catalyst obtained in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The present invention provides a complete methanation catalyst comprising: ni element, alkaline earth metal element, rare earth metal element, alkali metal element and Al 2 O 3 。
According to a preferred embodiment of the present invention, ni is 5 to 20wt%, alkaline earth is 5 to 20wt%, rare earth is 2 to 10wt%, alkali is 0.5 to 5wt%, and carrier is 45 to 87.5wt% in terms of oxide. The catalyst with the composition and the parameters disclosed by the invention has excellent activity and stability compared with the conventional similar catalyst when being used for complete methanation reaction of the synthesis gas, and completely meets the performances of good low-temperature activity, good high-temperature heat stability, good high-temperature water resistance and the like required by the complete methanation of the synthesis gas. For example, the catalyst was evaluated in a laboratory bench scale at an ultra-high space velocity (40000 ml.g -1 ·h -1 ) The reaction is carried out continuously for about 200 hours, the CO conversion rate is always more than or equal to 99 percent, CH 4 The selectivity is always more than or equal to 97 percent.
According to a preferred embodiment of the invention, the active metal NiO is present in an amount of from 5 to 20% by weight, preferably from 8 to 18% by weight, based on the total weight of the final catalyst obtained, calculated as oxide.
According to a preferred embodiment of the present invention, the alkaline earth metal oxide is added in an amount of 5 to 20wt%, preferably 6 to 16wt%, in terms of oxide.
According to a preferred embodiment of the present invention, the rare earth metal oxide is added in an amount of 2 to 10wt%, preferably 3 to 8wt%, in terms of oxide.
According to a preferred embodiment of the invention, the alkali metal content is 0.5 to 5 wt.%, calculated as oxide.
According to a preferred embodiment of the invention, al, calculated as oxide 2 O 3 The content is 45-87.5wt%.
According to a preferred embodiment of the invention, the specific surface area of the catalyst is 158-240m 2 Preferably 200-231m 2 /g。
According to a preferred embodiment of the present invention, preferably, the NiO crystal grain size of the catalyst is from 6 to 20nm, preferably from 7 to 9nm.
According to a preferred embodiment of the invention, the catalyst adopts co-current co-precipitation of a coprecipitation agent solution and a mixed salt solution of each constituent element to obtain a filter cake, and the filter cake is obtained by drying, roasting and forming, and is preferably subjected to reflux treatment by an organic solvent before drying. The catalyst prepared by the preparation method can obviously improve the specific surface area of the catalyst, and simultaneously has better high-temperature thermal stability.
In the present invention, the organic solvent is selected from one or more of C1-C4 alcohol, C3-C5 ketone and C2-C4 ether, and the organic solvent can be selected from a wide range of organic solvents; preferably, the organic solvent is one or more of methanol, ethanol, diethyl ether and acetone. The adoption of the preferable organic solvent reflux treatment can obviously improve the high-temperature thermal stability of the catalyst.
According to a preferred embodiment of the invention, the volume ratio of the organic solvent to the filter cake is 3-10:1.
According to a preferred embodiment of the present invention, the conditions of the reflow process include: the temperature is 60-100deg.C and/or the time is 2-30h, preferably 3-24h. Wherein, the reflux time can be adjusted according to the temperature.
According to the present invention, the alkaline earth metal element may be used in the present invention, and for the present invention, it is preferably one or more of Be, mg, ca, sr and Ba, preferably one or more of Mg, ca and Ba, and further preferably Mg and/or Ca.
According to the present invention, the rare earth metal elements may be used in the present invention, and for the present invention, one or more of Y, la, ce, pr and Sm are preferable; preferably one or more of Y, la and Ce, more preferably La and/or Ce.
According to the present invention, the optional range of the kind of the alkali metal element is wide, and for the present invention, one or both of Cs and K is preferable, and K is more preferable.
According to a preferred embodiment of the invention, the catalyst contains graphite, preferably in an amount of 1 to 5% by weight, preferably 2 to 4% by weight, based on the total weight of the catalyst.
The aim of the invention can be achieved by adopting the catalyst with the composition and parameters, and the preparation method of the catalyst has no special requirement, and the preparation method of the complete methanation catalyst is preferably provided for the invention, and comprises the following steps:
(1) Weighing the soluble salts of the specified amounts of the constituent elements to prepare mixed salt solution;
(2) Preparing a precipitant solution;
(4) Dripping the mixed salt solution and the precipitant solution into a precipitation tank respectively by adopting a parallel flow coprecipitation method for coprecipitation;
(5) Standing and aging after precipitation is finished;
(6) Filtering and washing, and refluxing the washed filter cake by adopting an organic solvent, and then drying and roasting. The catalyst of the invention is prepared by adopting the preferable preparation method, so that the performance of the catalyst can be improved.
According to a preferred embodiment of the present invention, when the alkali metal element is K, the mixed salt of step (1) does not include an alkali metal salt, and the method further comprises: and (3) drying the filter cake subjected to the reflux treatment, mixing with kalioplast, ball-milling, roasting, mixing with graphite, and forming. With such preferred embodiments, various properties of the catalyst can be significantly improved.
According to the present invention, preferably the kaliophlomis is natural kaliophlomis.
According to a preferred embodiment of the invention, the time of mixing ball milling is 5 to 48 hours, preferably 8 to 24 hours.
According to a preferred embodiment of the present invention, the amount of graphite added is 1 to 5wt%, preferably 2 to 4wt%.
In the invention, the types of the coprecipitation agent and the soluble salt have wide optional range, and the invention has no special requirement on the types.
The following are illustrative but not limiting of the scope of the invention:
in the present invention, the coprecipitate is, for example, naOH and/or Na 2 CO 3 More preferably Na 2 CO 3 。
In the present invention, the type of the soluble nickel salt may be selected from a wide range, and commonly used types may be used, and for the present invention, one or more of nickel nitrate, basic nickel carbonate, nickel chloride and nickel-containing hydrate are preferable.
According to the invention, the soluble nickel salt is preferably Ni (NO 3 ) 2 ·6H 2 O, basic nickel carbonate or NiCl 2 ·6H 2 O, more preferably Ni (NO) 3 ) 2 ·6H 2 O。
In the present invention, the soluble alkaline earth metal salt may be selected from a wide range of types, and commonly used types may be used, and for the present invention, one or more of alkaline earth metal nitrate, alkaline earth metal chloride and alkaline earth metal hydrate are preferable.
In the invention, the soluble rare earth metal salt has a wide optional range, and can be used in the invention in common use, and for the invention, one or more of rare earth metal nitrate, rare earth metal chloride and rare earth metal hydrate are preferable.
In the present invention, the types of the aluminum salts may be widely selected, and common ones may be used in the present invention, and for the present invention, one or more of aluminum-containing nitrate, aluminum-containing sulfate, aluminum-containing chloride and aluminum-containing hydrate are preferable.
In the present invention, it is preferable that the total metal ion concentration in the mixed salt solution in the step (1) is 0.1 to 1mol/L.
In the present invention, the concentration of the coprecipitate solution is preferably 0.2 to 5mol/L, and more preferably 0.5 to 2mol/L.
According to a preferred embodiment of the present invention, the dropping speed of the mixed salt solution and the precipitant solution is such that the pH of the solution in the precipitation tank is stabilized at 7 to 13, preferably 8 to 12; at the same time, the temperature of the precipitation tank is controlled between 25 and 90 ℃, preferably between 40 and 80 ℃.
According to a preferred embodiment of the invention, the time of the rest ageing is from 1 to 10 hours, preferably from 1.5 to 5 hours.
According to a preferred embodiment of the invention, the filter cake is removed by filtration after ageing by standing and washing with deionized water, preferably with a ratio of the volume of deionized water per wash to the volume of filter cake of 2-20:1, preferably 5-15:1, for a number of times of 1-10, preferably 2-6, based on a final filtrate conductivity of less than 2. Mu.S/cm.
In the present invention, the organic solvent is selected from one or more of C1-C4 alcohol, C3-C5 ketone and C2-C4 ether, and the organic solvent can be selected from a wide range of organic solvents; preferably, the organic solvent is one or more of methanol, ethanol, diethyl ether and acetone, more preferably ethanol and/or acetone. The adoption of the preferable organic solvent reflux treatment can obviously improve the high-temperature thermal stability of the catalyst.
According to a preferred embodiment of the invention, the volume ratio of organic solvent to filter cake is 3-10:1, preferably 3-6:1.
According to a preferred embodiment of the present invention, the conditions of the reflow process include: the temperature is 60-100℃and/or the time is 2-30, preferably 3-24 hours, preferably 5-12 hours.
According to the present invention, the optional range of conditions for drying and firing is wide, and for the present invention, preferable conditions for drying include: the temperature is 80 to 150 ℃, preferably 100 to 130 ℃, and/or the time is 1 to 24 hours, preferably 2 to 10 hours.
According to the invention, the conditions for calcination preferably include: the temperature is 500 to 1000 ℃, preferably 600 to 800 ℃, and/or the time is 1 to 10 hours, preferably 2 to 5 hours.
According to a preferred embodiment of the invention, the preparation of the catalyst comprises the following steps:
(1) Weighing the soluble salts of the specified amounts of the constituent elements to prepare mixed salt solution;
(2) At a certain concentration of NaOH and/or Na 2 CO 3 The solution is a precipitator;
(3) Dripping the salt solution and the precipitant into a precipitation tank respectively at a certain flow rate by adopting a parallel flow coprecipitation method;
(4) Standing and aging for a certain time after the precipitation is finished;
(5) Filtering and washing, and pouring the washed filter cake into an organic solvent for reflux treatment for a certain time;
(6) Filtering and drying the filter cake, and mixing and ball-milling the filter cake with natural kalioplast of a certain mass;
(7) After being uniformly mixed, the solid mixture is placed in a muffle furnace for roasting;
(8) And after the roasting is finished, adding a certain proportion of graphite, mixing, and tabletting and forming to prepare the complete methanation catalyst.
In the preferred embodiment of the invention, the catalyst preparation method provided by the invention comprises the steps of firstly preparing a precipitate of mixed salt by adopting a parallel flow coprecipitation method, then placing the precipitate into an organic solvent for reflux treatment, and drying after a certain time of treatment; after the drying is finished, mixing and ball-milling the precipitate and kalioplast, and roasting after ball-milling for a certain time; adding a certain amount of graphite into the solid powder obtained after roasting, fully and uniformly mixing, and finally, tabletting and forming to obtain the required complete methanation catalyst. The catalyst prepared by adopting the preferable method has high mechanical strength and high-temperature sintering resistance; meanwhile, as the active metal components are uniformly dispersed in the system space, smaller metal grain size can be obtained, and the catalyst has excellent low-temperature activity, high-temperature sintering resistance and high-temperature water resistance in the complete methanation reaction of the synthesis gas.
According to a preferred embodiment of the invention, the precipitant is NaOH and/or Na 2 CO 3 The concentration of the precipitant solution is 0.2 to 5mol/L, preferably 0.5 to 2mol/L, based on the molar concentration of the alkali metal ions.
According to the invention, when the cocurrent coprecipitation operation is carried out, the salt solution and the precipitant are respectively dripped into the precipitation tank at a certain flow rate so as to control the pH value of the solution in the precipitation tank to be stabilized at 7-13, preferably 8-12; at the same time, the temperature of the precipitation tank is controlled between 25 and 90 ℃, preferably between 40 and 80 ℃.
According to the invention, the aging time is 1 to 10 hours, preferably 1.5 to 5 hours;
according to the invention, the filter cake is washed with deionized water, the ratio of the volume of deionized water to the volume of the filter cake per washing is 2-20:1, preferably 5-15:1, and the number of times of washing is 1-10, preferably 2-6, based on the final filtrate conductivity of less than 2 [ mu ] S/cm.
According to the invention, after washing, placing the filter cake in an organic solvent again for reflux treatment, wherein the organic solvent can be methanol, ethanol, diethyl ether or acetone, and the like, preferably ethanol and/or acetone, and the volume ratio of the organic solvent to the filter cake is 3-10:1, preferably 3-6:1; the time of the reflow treatment is 3 to 24 hours, preferably 5 to 12 hours.
According to the invention, the drying temperature of the filter cake after the treatment with the organic solvent is 80-150 ℃, preferably 100-130 ℃, and the drying time is 1-24 hours, preferably 2-10 hours.
According to the invention, the dried sample is ball milled with a mass of natural kalioplast for 5-48 hours, preferably 8-24 hours, the kalioplast being added in an amount by mass of the final catalyst such that K 2 The content of O is 0.5 to 5wt%, preferably 1 to 4wt%.
According to the invention, the solid powder after ball milling is placed in a muffle furnace and baked at 500-1000 ℃, preferably 600-800 ℃, and the baking time is 1-10 hours, preferably 2-5 hours.
According to the invention, a certain mass of graphite is added into the baked solid powder, and the mixture is uniformly mixed, wherein the addition amount of the graphite is 1-5 wt%, preferably 2-4 wt%; and then the catalyst is subjected to sheeting and molding, and the particle size can be 4 multiplied by 4 or 5 multiplied by 5, so that the required complete methanation catalyst is obtained.
The invention provides a catalyst prepared by the preparation method.
The invention provides application of the catalyst in preparation of synthetic natural gas through methanation reaction.
The catalyst prepared by the method provided by the invention needs to carry out reduction activation on active metals in the presence of hydrogen before being used for complete methanation of synthesis gas, and the reduction conditions are as follows: the reduction temperature is 300 to 800 ℃, preferably 400 to 600 ℃, and further preferably 400 to 550 ℃; the reduction time is 0.5 to 10 hours, preferably 1 to 5 hours, more preferably 2 to 4 hours, and the reduction may be performed in pure hydrogen or in a mixture of hydrogen and an inert gas, for example, in a mixture of hydrogen and nitrogen and/or argon, and the hydrogen pressure is 0 to 2MPa, preferably 0 to 1MPa, more preferably 0 to 0.5MPa.
The invention provides a method for preparing synthetic natural gas by methanation reaction, which comprises the following steps: filling a catalyst into a fixed bed reactor, and under the condition of preparing synthetic natural gas by methanation reaction, making H 2 Contact with CO; the catalyst is the catalyst disclosed by the invention.
According to a preferred embodiment of the present invention, the conditions of the contacting include: h by volume 2 The molar ratio of the catalyst to CO is 2-4:1, preferably 3-4:1, and the reaction temperature is 250-750 ℃, preferably 280-650 ℃; the pressure is 0-6 MPa, preferably 1-4 MPa; the space velocity of the raw material gas is 1000-100000 ml.g -1 ·h -1 Preferably 5000 to 40000 ml.g -1 ·h -1 。
The following examples are provided to further illustrate the invention and should not be construed as limiting the invention.
Example 1
(1) Preparation of the catalyst
116.8g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、190.9g Mg(NO 3 )·6H 2 O、42.5g La(NO 3 ) 3 ·6H 2 O and 853.2g Al (NO) 3 ) 3 ·6H 2 Pouring O into 3500mL deionized water, stirring and dissolving; 420g NaOH was weighed into 10500mL deionized water and dissolved with stirring. The salt solution and the precipitant are respectively and co-current at a certain flow ratePrecipitating in a precipitation tank, controlling the pH value of the solution in the precipitation tank to be 9, and controlling the temperature of the precipitation tank to be 65 ℃. And after the precipitation is finished, standing and aging for 2.5 hours. And then filtering and washing, wherein the volume ratio of deionized water to filter cake is 10:1, and washing for 3 times. The filter cake obtained was heated under reflux in absolute ethanol (volume ratio of ethanol to filter cake 5:1) at 80℃for 12 hours, and then filtered. Drying the filter cake in an oven at 120 ℃ for 8 hours, taking out, adding 13.3g of natural kalioplast, mixing and ball milling for 12 hours; and after ball milling, taking out the ball mill, and putting the ball mill into a muffle furnace to be roasted for 2 hours at 700 ℃. The resulting solid powder was then thoroughly mixed by adding 4g of graphite. Then, the mixture was subjected to sheeting and molding to obtain a desired complete methanation catalyst, designated as SNG-1, having a particle size of 4X 4. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
The catalyst obtained in example 1, although calcined at 700℃had a specific surface area of 214m 2 And/g, which is significantly larger than the specific surface area of catalysts prepared by conventional methods. XRD analysis shows that the crystal grain size of NiO in the catalyst is 7.6nm and is also obviously smaller than that of NiO in the catalyst prepared by the traditional method; h of the catalyst 2 The TPR spectrum is shown in FIG. 1, and it can be seen from FIG. 1 that the main reduction temperature zone of the methanation catalyst prepared by the method is between 350 and 700 ℃, which shows that the interaction between the metal Ni and the auxiliary agent is weaker, thus being beneficial to the reduction and activation of the catalyst, and greatly simplifying the process of starting up the catalyst for the application of the catalyst industry.
(2) Activity evaluation
0.5g of SNG-1 catalyst was weighed and packed in a microchannel reactor, and the catalyst was reduced at 500℃for 3 hours under normal pressure in a pure hydrogen atmosphere to activate the catalyst. After the completion of the reduction, the temperature was lowered to 350℃under a hydrogen atmosphere, and the feed gas (H) was switched 2 /co=3/1) with a space velocity of 10000ml g -1 ·h -1 The reaction pressure was 2MPa. Gas chromatography on-line sampling analysis tail gas composition, and calculation to obtain: x is X CO ＝99％，S CH4 ＝97％。
The stability evaluation data of the catalyst obtained in example 1 are shown in fig. 2, specifically, methanation reaction performance catalyzed by the catalyst with a reaction time of 0 to 200 hours. As can be seen from fig. 2, the reaction performance of the catalyst is very stable.
Example 2
(1) Preparation of the catalyst
140.2g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、135.2g Mg(NO 3 )·6H 2 O、26.6g La(NO 3 ) 3 ·6H 2 O and 897.4g Al (NO) 3 ) 3 ·6H 2 Pouring O into 2250mL deionized water, stirring and dissolving; 405.6g NaOH was weighed out and poured into 14480mL deionized water and dissolved with stirring. And co-current co-precipitating the salt solution and the precipitant into a precipitation tank respectively at a certain flow rate, controlling the pH value of the solution in the precipitation tank to be 8, and controlling the temperature of the precipitation tank to be 55 ℃. And (5) standing and aging for 5 hours after the precipitation is finished. And then filtering and washing, wherein the volume ratio of deionized water to filter cake is 8:1, and washing for 5 times. The resulting filter cake was heated to 75 ℃ in absolute ethanol (6:1 volume ratio of ethanol to filter cake) for 8 hours at reflux, and then filtered. Drying the filter cake in an oven at 110 ℃ for 10 hours, taking out, adding 26.7g of natural kalioplast, mixing and ball milling for 20 hours; and after ball milling, taking out the ball mill, and putting the ball mill into a muffle furnace to be roasted for 4 hours at 600 ℃. The resulting solid powder was then thoroughly mixed by adding 6g of graphite. Then, the mixture was subjected to sheeting and molding to obtain a desired complete methanation catalyst, designated as SNG-2, having a particle size of 5X 5. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation reaction was carried out under the same conditions as in example 1. The tail gas composition is analyzed by gas chromatography on-line sampling, and the calculation is obtained: x is X CO ＝100％，S CH4 ＝98.2％。
Example 3
(1) Preparation of the catalyst
93.4g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、152.7g Mg(NO 3 )·6H 2 O、15.9g La(NO 3 ) 3 ·6H 2 O and 1000g Al (NO) 3 ) 3 ·6H 2 O is poured into 9050mL of deionized waterStirring and dissolving; 434.2g NaOH was weighed out and poured into 5430mL deionized water and dissolved with stirring. And co-current co-precipitating the salt solution and the precipitant into a precipitation tank respectively at a certain flow rate, controlling the pH value of the solution in the precipitation tank to be 10, and controlling the temperature of the precipitation tank to be 75 ℃. And after the precipitation is finished, standing and aging for 1.5 hours. And then filtering and washing, wherein the volume ratio of deionized water to filter cake is 12:1, and washing for 2 times. The filter cake obtained was heated to 70℃in absolute ethanol (volume ratio of ethanol to filter cake 8:1) for 16 hours under reflux and then filtered. Drying the filter cake in a baking oven at 100 ℃ for 16 hours, taking out, adding 6.7g of natural kalioplast, mixing and ball milling for 16 hours; after ball milling, the mixture is taken out and put into a muffle furnace to be roasted for 1 hour at 800 ℃. The solid powder obtained was further mixed with 8g of graphite. Then, the mixture was subjected to sheeting and molding to obtain a desired complete methanation catalyst, designated as SNG-3, having a particle size of 4X 4. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation reaction was carried out under the same conditions as in example 1. The tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: x is X CO ＝93.2％，S CH4 ＝96.7％。
Example 4
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1, except that Na was used 2 CO 3 NaOH was replaced and the amount was 556.5g. The desired complete methanation catalyst, designated SNG-4, was obtained. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: x is X CO ＝99.5％，S CH4 ＝97.6％。
Example 5
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1, except that the solvent for washing was an equivalent amount of acetone, to obtain the desired complete methanation catalyst, designated as SNG-5. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: x is X CO ＝96.8％，S CH4 ＝95.9％。
Example 6
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1, except that 10ml of a solution containing 8.5g of potassium nitrate was used instead of natural kalioplast and the obtained dried cake was subjected to thorough mixing and ball milling for 12 hours, and then taken out and put into a muffle furnace to be calcined at 700℃for 2 hours, maintaining the same K as in example 1 2 O mass. The resulting solid powder was then thoroughly mixed by adding 4g of graphite. Then the mixture is subjected to sheeting and molding, and the particle size is 4 multiplied by 4, so that the required complete methanation catalyst is obtained. The resulting catalyst was designated SNG-6. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: x is X CO ＝91.3％，S CH4 ＝93.6％。
Example 7
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1 except that n-propanol was used instead of ethanol to reflux the precipitated cake. The resulting catalyst was designated SNG-7. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. Meter with a meter bodyThe calculation results are: x is X CO ＝93.5％，S CH4 ＝96.1％。
Example 8
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1, except that 51.1g of Ba (NO 3 ) 2 Instead of Mg (NO) 3 ) 2 ·6H 2 O. The resulting catalyst was designated SNG-8. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: x is X CO ＝89.9％，S CH4 ＝93.6％。
Example 9
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1, except that 40.8g of Sm (NO 3 ) 3 ·6H 2 O replaces La (NO) 3 ) 3 ·6H 2 O. The resulting catalyst was designated SNG-9. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: x is X CO ＝93.9％，S CH4 ＝95.6％。
Example 10
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1, except that 10ml of a solution containing 10.8g of sodium nitrate (concentration: 12.7 mol/l) was used instead of natural kaliophene, and after ball milling was performed with sufficient mixing with the obtained dried cake for 12 hours, it was taken out and put into a muffle furnace to be baked at 700℃for 2 hours. The resulting solid powder was then thoroughly mixed by adding 4g of graphite. Then the mixture is subjected to sheeting and molding, and the particle size is 4 multiplied by 4, so that the required complete methanation catalyst is obtained. The resulting catalyst was designated SNG-10. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: x is X CO ＝83.3％，S CH4 ＝91.6％。
Comparative example 1
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1 except that the cake obtained by precipitation was not subjected to reflux treatment with an organic solvent, and the obtained catalyst was designated DB-1. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: xco=78.6%, sch4=91.7%.
Comparative example 2
(1) Preparation of the catalyst
A catalyst was prepared in the same manner as in example 1 except that no alkaline earth metal and rare earth metal auxiliary were added, and the resultant catalyst was designated DB-2. The specific surface area of the catalyst obtained and the crystal grain size of NiO in the catalyst are shown in table 1.
(2) Activity evaluation
The catalyst was activated and methanation was carried out under the same conditions as in example 1, and the tail gas composition was analyzed by gas chromatography on-line sampling. And (3) calculating to obtain: x is X CO ＝54.5％，S CH4 ＝89.4％。
TABLE 1
The reaction results of the embodiment show that the catalyst prepared by the method has excellent reaction activity and methane selectivity, has good high-temperature stability and anti-carbon performance, can realize continuous and stable operation of a plant period without inactivation, and completely meets the performance requirements of the complete methanation of the synthesis gas on the catalyst.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (26)
1. A complete methanation catalyst, characterized in that it comprises: ni element, alkaline earth metal element, rare earth metal element, alkali metal element and Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Calculated by oxide, the Ni content is 5-20wt%, the alkaline earth metal content is 5-20wt%, the rare earth metal content is 2-10wt%, the alkali metal content is 0.5-5wt%, and the Al 2 O 3 The content is 45-87.5wt%; the specific surface area of the catalyst is 158-240 m 2 /g; the size of NiO crystal grains is 6-20nm;
the catalyst adopts co-current co-precipitation of a coprecipitation agent solution and a mixed salt solution of each constituent element to obtain a filter cake, and the filter cake is obtained by drying, roasting and forming, and the filter cake is subjected to reflux treatment by using an organic solvent before drying;
the volume ratio of the organic solvent to the filter cake is 3-10:1;
the conditions of the reflow treatment include: the temperature is 60-100 ℃ and the time is 2-30h;
the organic solvent is one or more of methanol, ethanol, diethyl ether and acetone.
2. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 200-231 m 2 /g; and/or NiO crystal grain size of 7-9nm.
3. The catalyst according to claim 1, wherein,
the alkaline earth metal element is one or more of Be, mg, ca, sr and Ba; and/or
The rare earth metal element is one or more of Y, la, ce, pr and Sm; and/or
The alkali metal element is one or more of K and Cs.
4. The catalyst according to claim 3, wherein,
the alkaline earth metal element is one or more of Mg, ca and Ba; and/or
The rare earth metal element is one or more of Y, la and Ce.
5. The catalyst according to claim 4, wherein,
the alkaline earth metal element is Mg and/or Ca; and/or
The rare earth metal element is La and/or Ce; and/or
The alkali metal element is K.
6. The catalyst of claim 1, wherein the catalyst comprises graphite in an amount of 1 to 5 wt%, based on the total weight of the catalyst.
7. The catalyst of claim 6, wherein the graphite is present in an amount of 2 to 4 wt.%, based on the total weight of the catalyst.
8. A process for preparing the complete methanation catalyst according to any one of claims 1-7, characterised in that it comprises:
(1) Weighing the soluble salts of the specified amounts of the constituent elements to prepare mixed salt solution;
(2) Preparing a precipitant solution;
(4) Dripping the mixed salt solution and the precipitant solution into a precipitation tank respectively by adopting a parallel flow coprecipitation method for coprecipitation;
(5) Standing and aging after precipitation is finished;
(6) Filtering and washing, and refluxing the washed filter cake by adopting an organic solvent, and then drying and roasting;
the organic solvent is one or more of methanol, ethanol, diethyl ether and acetone;
the volume ratio of the organic solvent to the filter cake is 3-10:1;
the conditions of the reflow treatment include: the temperature is 60-100deg.C, and the time is 2-30h.
9. The production method according to claim 8, wherein when the alkali metal is K, the mixed salt of step (1) does not include an alkali metal salt, the method further comprising:
and (3) drying the filter cake subjected to the reflux treatment, mixing with kalioplast, ball-milling, roasting, mixing with graphite, and forming.
10. The method of manufacturing of claim 9, wherein the kaliophlomis is natural kaliophlomis.
11. The preparation method according to claim 9, wherein,
the time of mixing and ball milling is 5-48 hours; and/or
The addition amount of graphite is 1-5wt%.
12. The preparation method according to claim 11, wherein,
the time of mixing and ball milling is 8-24 hours; and/or
The addition amount of graphite is 2-4wt%.
13. The preparation method according to claim 8, wherein,
the precipitant is NaOH and/or Na 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The soluble nickel salt is one or more of nickel nitrate, basic nickel carbonate, nickel chloride and nickel-containing hydrate; and/or
The soluble alkaline earth metal salt is one or more of alkaline earth metal nitrate, alkaline earth metal chloride and alkaline earth metal hydrate; and/or
The soluble rare earth metal salt is one or more of rare earth metal nitrate, rare earth metal chloride and rare earth metal hydrate; and/or
The aluminum salt is one or more of aluminum-containing nitrate, aluminum-containing sulfate, aluminum-containing chloride and aluminum-containing hydrate.
14. The process according to claim 13, wherein,
the precipitant is Na 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The soluble nickel salt is Ni (NO) 3 ) 2 •6H 2 O。
15. The preparation method according to claim 8, wherein,
the concentration of total metal ions in the mixed salt solution in the step (1) is 0.1-1 mol/L; and/or
The concentration of the coprecipitation agent solution is 0.2-5 mol/L; and/or
The dropping speed of the mixed salt solution and the precipitator solution enables the pH value of the solution in the precipitation tank to be stabilized at 7-13; simultaneously, the temperature of the precipitation tank is controlled to be 25-90 DEG o C, performing operation; and/or
Standing and aging for 1-10 hours;
and taking out a filter cake after standing and ageing through filtering, and washing with deionized water for 1-10 times, wherein the final filtrate conductivity is smaller than 2 [ mu ] S/cm.
16. The process according to claim 15, wherein,
the concentration of the coprecipitation agent solution is 0.5-2 mol/L; and/or
The dropping speed of the mixed salt solution and the precipitator solution enables the pH value of the solution in the precipitation tank to be stabilized at 8-12; meanwhile, the temperature of the precipitation tank is controlled to be 40-80 ℃; and/or
Standing and aging for 1.5-5 hours;
and taking out the filter cake after standing and ageing, and washing with deionized water, wherein the ratio of the volume of deionized water to the volume of the filter cake is 2-20:1, and the washing times are 2-6 times, and the electric conductivity of the final filtrate is smaller than 2 [ mu ] S/cm.
17. The method according to claim 16, wherein,
the ratio of the volume of deionized water to the volume of filter cake is 5-15:1.
18. The preparation method according to claim 8, wherein,
the organic solvent is one or more of methanol, ethanol, diethyl ether and acetone; and/or
The volume ratio of the organic solvent to the filter cake is 3-6:1; and/or
The time of the reflow treatment is 5-12 hours.
19. The process according to claim 18, wherein,
the organic solvent is ethanol and/or acetone.
20. The preparation method according to claim 8, wherein,
The drying conditions included: the temperature is 80-150 DEG C o C, performing operation; and/or the time is 1-24 hours; and/or
The roasting conditions include: the temperature is 500-1000 DEG C o C, performing operation; and/or for 1-10 hours.
21. The process according to claim 20, wherein,
the drying conditions included: the temperature is 100-130 ℃; and/or the time is 2-10 hours; and/or
The roasting conditions include: the temperature is 600-800 ℃; and/or the time is 2-5 hours.
22. A catalyst prepared by the preparation method of any one of claims 8-21.
23. Use of the catalyst of any one of claims 1-7 and claim 22 in methanation reactions to produce synthetic natural gas.
24. A method for producing synthetic natural gas by methanation, wherein the method comprises: filling a catalyst into a fixed bed reactor, and under the condition of preparing synthetic natural gas by methanation reaction, making H 2 Contact with CO; the catalyst is as claimed in any one of claims 1 to 7 and claim 22.
25. The process according to claim 24, wherein,
the conditions of contact include: h by volume 2 The molar ratio of CO to CO is 2-4:1, and the reaction temperature is 250-750 ℃; the pressure is 0-6 MPa; the space velocity of the raw material gas is 1000-100000 ml.g -1 •h -1 。
26. The process according to claim 25, wherein,
the conditions of contact include: h by volume 2 The molar ratio of the catalyst to CO is 3-4:1, and the reaction temperature is 280-650 ℃; the pressure is 1-4 MPa; the airspeed of the raw material gas is 5000-40000 ml g -1 •h -1 。
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