CN114870846B - Carbon dioxide methanation catalyst and preparation method and application thereof - Google Patents
Carbon dioxide methanation catalyst and preparation method and application thereof Download PDFInfo
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- CN114870846B CN114870846B CN202210631626.7A CN202210631626A CN114870846B CN 114870846 B CN114870846 B CN 114870846B CN 202210631626 A CN202210631626 A CN 202210631626A CN 114870846 B CN114870846 B CN 114870846B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 10
- 239000001569 carbon dioxide Substances 0.000 title description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 5
- 239000002028 Biomass Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 239000012670 alkaline solution Substances 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 9
- ZSJFLDUTBDIFLJ-UHFFFAOYSA-N nickel zirconium Chemical compound [Ni].[Zr] ZSJFLDUTBDIFLJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 22
- 150000002815 nickel Chemical class 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 150000003754 zirconium Chemical class 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical group [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002612 dispersion medium Substances 0.000 abstract description 7
- 239000012266 salt solution Substances 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 60
- 239000000243 solution Substances 0.000 description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 238000001035 drying Methods 0.000 description 23
- 238000003756 stirring Methods 0.000 description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 6
- 235000010344 sodium nitrate Nutrition 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 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 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to CO 2 The technical field of methanation catalysts, in particular to a catalyst for preparing CO 2 Methanation catalyst, and a preparation method and application thereof. The invention takes alkaline solution dissolved with biomass tar as precipitant, ni and Zr mixed salt solution is added into alkaline solution containing biomass tar to obtain nickel-zirconium catalyst precursor taking biomass tar as dispersion medium, and then CO is obtained by calcination 2 Methanation catalyst. The method uses phenolic organic matters in biomass tar as a dispersion medium to obtain CO with a porous structure 2 Methanation catalyst, which has good performance, shows excellent catalytic activity at low temperature, and is resistant to CO 2 The conversion rate of (2) is high. Meanwhile, in the preparation process of the catalyst, no extra reduction step is needed, and the preparation method is simple and suitable for large-scale production.
Description
Technical Field
The invention belongs to CO 2 Methanation catalyst technical field. And more particularly to a CO 2 Methanation catalyst, and a preparation method and application thereof.
Background
After the industrial revolution, the use of traditional energy has greatly promoted the development of economy, society and technology, but also caused CO 2 Is so large that CO in the atmosphere 2 The concentration is increased rapidly, and the ecological balance of the earth is affected. CO is processed by 2 Synthesis of methane (CH) by hydrogenation techniques 4 ) Not only can relieve CO in the atmosphere 2 The problem of concentration surge can fully utilize renewable resource hydrogen, and reduce the waste of the existing renewable energy sources.
The carbon dioxide methanation technology is to catalyze CO with a specific catalyst 2 Technology for preparing methane by hydrogenation and theoretical CO 2 Can be completely converted into methane, so that CO can be effectively utilized 2 And realize CO 2 Conversion to methane. As disclosed in Chinese patent application, a highly dispersed nanocomposite catalyst is disclosed which has a high CO content 2 Conversion rate butThe catalyst needs to be catalyzed at 700-800 ℃, the temperature is extremely high, and the energy consumption is relatively high. And in the prior art catalyze CO 2 Methanation catalysts generally require temperatures of 350 ℃ or even above to be catalytic. Thus, there is a strong need to provide a catalyst that is effective at catalyzing CO at relatively low temperatures 2 A catalyst for conversion to methane.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the prior catalytic CO 2 The defect and deficiency of high catalytic temperature required by methanation catalyst provide a catalyst capable of converting CO efficiently under low temperature (250 ℃), and the catalyst is suitable for the production of high-performance catalyst 2 CO of gas 2 A preparation method of methanation catalyst.
The invention aims to provide a CO 2 Methanation catalyst.
It is another object of the present invention to provide the CO 2 Methanation catalyst is used for catalyzing CO 2 Conversion to CH 4 Is used in the field of applications.
The above object of the present invention is achieved by the following technical solutions:
CO (carbon monoxide) 2 The preparation method of the methanation catalyst comprises the steps of uniformly mixing biomass tar with an alkaline solution, adding a mixed solution containing nickel salt and zirconium salt, completely reacting, filtering to obtain a nickel-zirconium catalyst precursor, and calcining the nickel-zirconium catalyst precursor at 500-800 ℃ for 1-3 h to obtain the catalyst;
the main component of the biomass tar is phenolic organic matters, and the content of the phenolic organic matters is 40% -60%;
the filtration was rinsed with deionized water.
The invention takes sodium hydroxide solution dissolved with biomass tar as a precipitator, and adds Ni and Zr mixed salt solution into alkaline solution containing biomass tar to obtain nickel-zirconium catalyst precursor taking biomass tar as dispersion medium, and then calcining to obtain CO 2 Methanation catalyst.
According to the method, phenolic organic matters in biomass tar are creatively used as a dispersion medium, the phenolic organic matters are easy to dissolve in an alkaline solution, the alkaline environment of the phenolic organic matters can be destroyed by adding metal salt into the alkaline solution, so that the phenolic organic matters are separated out, the metal salt is precipitated, a catalyst precursor with excellent dispersibility and taking the phenolic organic matters as the dispersion medium is formed through spontaneous crosslinking in the process of separating out the metal salt precipitation and the phenolic organic matters, a carbon fiber network is gradually carbonized in the process of calcining the catalyst precursor, and meanwhile, the metal salt is dehydrated and carbon reduced to obtain stable metal particles.
The network structure formed by the phenolic organic matters can rapidly wrap metal salt precipitation so as to limit the size and the size of the metal active components, and meanwhile, the carbon fiber network formed after carbonization can efficiently disperse the metal active components, so that the multi-site catalytic characteristic is realized. The carbon fiber network formed in situ can effectively protect active metals such as Ni and the like from being oxidized by carbon dioxide, so that the catalytic stability of the catalyst is ensured.
Preferably, the preparation method of the biomass tar comprises the following steps:
pyrolyzing pine nut shell powder (passing through a 80-mesh sieve) at 600-800 ℃, controlling the residence time to be about 8-10 min through a spiral sample injector, collecting pyrolyzed volatile matters obtained by pyrolysis through a condensing tube (-15-25 ℃), standing the collected condensate for 20-30 h, and removing supernatant liquid to obtain biomass tar.
Preferably, the mass ratio of the biomass tar to the solute in the alkaline solution is 1:0.5-1.5.
More preferably, the mass ratio of biomass tar to solute in alkaline solution is 1:2.5.
Preferably, the solute of the alkaline solution is sodium hydroxide or potassium hydroxide.
Preferably, water is also added after the biomass tar is mixed with the alkaline solution uniformly.
Preferably, the mass ratio of the added water to the sodium hydroxide is 20-40:1.
Preferably, the nickel salt is nickel nitrate, nickel sulfate, nickel chloride or a hydrate of any of the above nickel salts.
Preferably, the zirconium salt is zirconium nitrate, zirconium sulfate, zirconium chloride or a hydrate of any of the above zirconium salts. Preferably, the molar amount of the nickel salt is calculated as Ni, the molar amount of the zirconium salt is calculated as Zr, and the molar ratio of the nickel salt to the zirconium salt is 4-6:1.
The molar quantity of the nickel salt is calculated according to Ni, namely the molar quantity of corresponding Ni is obtained by conversion according to the molar quantity of Ni element in the nickel salt, and the mass of the nickel salt is calculated according to the molar quantity of converted Ni; that is, the molar amount of the Ni element in elemental Ni is the same as that in nickel salt. For example, the nickel salt is nickel nitrate, the nickel nitrate is 0.025mol, the molar amount of the Ni element is kept unchanged, the nickel nitrate is converted into Ni, the molar amount of the Ni is 0.025mol, the relative molecular weight of the nickel nitrate is 290.79, and the mass of the nickel salt calculated as the Ni is 7.26g.
Preferably, the mass ratio of the nickel salt to the biomass tar is 1-3: 1.
preferably, the mass ratio of the zirconium salt to the biomass tar is 0.5-2: 1.
preferably, the mixed solution of the nickel salt and the zirconium salt is added dropwise.
Preferably, the reaction time is 30 to 60 minutes.
Preferably, the temperature of the reaction is 20 to 40 ℃.
Preferably, the reaction is carried out while stirring, and the stirring speed is 600-1000 r/min.
Preferably, the calcination temperature is 550 to 700 ℃.
Preferably, the concentration of the alkaline solution is 3-6 g/100ml.
Preferably, water is also added in portions during the filtration.
Preferably, the filtering is preceded by drying in a forced air drying oven at 65-105 ℃ for 6 hours.
More preferably, the drying method is drying in a forced air drying oven at 105 ℃ for 6 hours.
Preferably, the calcination is preceded by a pre-calcination, the pre-calcination temperature is 400-600 ℃, and the time is 30 min-2 h.
The invention further protects a CO 2 Methanation catalyst, which is prepared by the preparation method.
The invention further protects a CO 2 Methanation catalyst is used for catalyzing CO 2 Conversion to CH 4 Is used in the field of applications.
Preferably, the method for converting carbon dioxide into methane comprises the steps of 2 With CO 2 (H 2 ：CO 2 =4: 1) Is introduced into the mixed gas containing CO 2 And heating the catalyst bed layer of the methanation catalyst to react to generate methane gas.
More preferably, the temperature of the heating reaction is 200 to 400 ℃.
More preferably, the space velocity of the heating reaction is 15000-150000 mL.g -1 ·h -1 。
The invention has the following beneficial effects:
the invention takes alkaline solution dissolved with biomass tar as precipitant, ni and Zr mixed salt solution is added into alkaline solution containing biomass tar to obtain nickel-zirconium catalyst precursor taking biomass tar as dispersion medium, and then CO is obtained by calcination 2 Methanation catalyst. The method uses phenolic organic matters in biomass tar as a dispersion medium to obtain CO with a porous structure 2 Methanation catalyst, which has good performance, shows excellent catalytic activity at low temperature, and is resistant to CO 2 The conversion rate of (2) is high. Meanwhile, in the preparation process of the catalyst, no extra reduction step is needed, and the preparation method is simple and suitable for large-scale production.
Drawings
FIG. 1 is a CO obtained in example 1 2 Transmission electron microscopy of methanation catalyst.
FIG. 2 is a CO obtained in example 1 2 SEM image of methanation catalyst.
FIG. 3 is a transmission electron microscope image of the catalyst prepared in comparative example 1.
Fig. 4 is an SEM image of the catalyst prepared in comparative example 1.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
The preparation method of the biomass tar comprises the following steps:
pyrolyzing pine nut shell powder (passing through 80 mesh sieve) at 700deg.C, controlling residence time at about 10min by spiral sample injector, collecting pyrolyzed volatile matters obtained by pyrolysis by condenser tube (-20deg.C), standing the condensate obtained by collection for 24 hr, and removing supernatant to obtain biomass tar.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
EXAMPLE 1CO 2 Preparation of methanation catalyst
Mixing 5g of filtered biomass tar with 0.12mol of sodium hydroxide solution (the mass ratio of the filtered biomass tar to the sodium hydroxide is 1:1.04), adding 100ml of water, stirring for 30min to obtain solution A, mixing 0.04mol of nickel nitrate hexahydrate (11.63 g) with 0.01mol of zirconium nitrate pentahydrate (4.29 g), adding 50ml of deionized water, stirring for 30min to obtain solution B (the mole ratio of Ni to Zr is 1:4.00), then dropwise adding the solution B into the solution A, stirring for 30min again, suction filtering, adding 600ml of deionized water for flushing three times during suction filtering to remove sodium nitrate generated in the solution, drying the precipitate in a 105 ℃ blast drying oven for 12h, heating to 600 ℃ at a speed of 10 ℃/min in an atmosphere furnace after drying, and calcining for 1h at 600 ℃ to obtain the biomass tar.
EXAMPLE 2CO 2 Preparation of methanation catalyst
Mixing 5g of filtered biomass tar with 0.12mol of sodium hydroxide solution (the mass ratio of the filtered biomass tar to the sodium hydroxide is 1:1.04), adding 100ml of water, stirring for 30min to obtain solution A, mixing 0.04mol of nickel nitrate hexahydrate (11.63 g) with 0.01mol of zirconium nitrate pentahydrate (4.29 g), adding 50ml of deionized water, stirring for 30min to obtain solution B (the mole ratio of Ni to Zr is 1:4.00), then dropwise adding the solution B into the solution A, stirring for 30min again, suction filtering, adding 600ml of deionized water for three times during suction filtering to remove sodium nitrate generated in the solution, drying the precipitate in a 105 ℃ blast drying oven for 12h, heating to 500 ℃ at a speed of 10 ℃/min in an atmosphere furnace after drying, and calcining for 1h at 500 ℃ to obtain the biomass tar.
In comparison with example 1, the calcination temperature was 500℃and the other raw materials were used in the same amounts and in the same manner as in example 1.
EXAMPLE 3CO 2 Preparation of methanation catalyst
Mixing 3.6g of filtered biomass tar with 0.12mol of sodium hydroxide solution (the mass ratio of the filtered biomass tar to the sodium hydroxide is 1:0.75), adding 100ml of water, stirring for 30min to obtain solution A, mixing 0.04mol of nickel nitrate hexahydrate (11.63 g) with 0.01mol of zirconium nitrate pentahydrate (4.29 g), adding 50ml of deionized water, stirring for 30min to obtain solution B (the mole ratio of Ni to Zr is 1:4.00), dropwise adding the solution B into the solution A, stirring for 30min again, suction filtering, adding 600ml of deionized water for three times during suction filtering to remove sodium nitrate generated in the solution, drying the precipitate in a 105 ℃ blast drying oven for 12h, heating to 600 ℃ at a speed of 10 ℃/min in an atmosphere furnace after drying, and calcining for 1h at 600 ℃.
The difference from example 1 is that the mass ratio of biomass tar to sodium hydroxide after filtration is 1:0.75, and other raw materials are used in the same amount and operation steps as in example 1.
EXAMPLE 4CO 2 Preparation of methanation catalyst
Mixing 6.0g of filtered biomass tar with 0.12mol of sodium hydroxide solution (the mass ratio of the filtered biomass tar to the sodium hydroxide is 1:1.25), adding 100ml of water, stirring for 30min to obtain solution A, mixing 0.04mol of nickel nitrate hexahydrate (11.63 g) with 0.01mol of zirconium nitrate pentahydrate (4.29 g), adding 50ml of deionized water, stirring for 30min to obtain solution B (the mole ratio of Ni to Zr is 1:4.00), dropwise adding the solution B into the solution A, stirring for 30min again, suction filtering, adding 600ml of deionized water for three times during suction filtering to remove sodium nitrate generated in the solution, drying the precipitate in a 105 ℃ blast drying oven for 12h, heating to 600 ℃ at a speed of 10 ℃/min in an atmosphere furnace after drying, and calcining for 1h at 600 ℃.
The difference from example 1 is that the mass ratio of biomass tar to sodium hydroxide after filtration is 1:1.25, and other raw materials are used in the same amount and operation steps as in example 1.
Comparative example 1 preparation of Ni-based catalyst
Conventional Ni-based catalysts;
0.04mol of nickel nitrate and 0.01mol of zirconium nitrate pentahydrate were dissolved in 50ml of water, 4.8g of sodium hydroxide was dissolved in 100ml of water, stirred for 30 minutes, then the two solutions were mixed, the mixed solution was dried in a forced air drying oven at 105℃for 12 hours, then heated to 600℃at a heating rate of 10℃per minute in an atmosphere furnace, and then calcined at 600℃for 1 hour.
Comparative example 2CO 2 Preparation of methanation catalyst
Mixing 5g of filtered biomass tar with 0.12mol of sodium hydroxide solution (the mass ratio of the filtered biomass tar to the sodium hydroxide is 1:1.04), adding 100ml of water, stirring for 30min to obtain solution A, mixing 0.04mol of nickel nitrate hexahydrate (11.63 g) with 0.01mol of zirconium nitrate pentahydrate (4.29 g), adding 50ml of deionized water, stirring for 30min to obtain solution B (the mole ratio of Ni to Zr is 1:4.00), then dropwise adding the solution B into the solution A, stirring for 30min again, suction filtering, adding 600ml of deionized water for three times during suction filtering to remove sodium nitrate generated in the solution, drying the precipitate in a 105 ℃ blast drying oven for 12h, heating to 600 ℃ at a speed of 10 ℃/min after drying, and calcining at 600 ℃ for 30min to obtain the biomass tar.
The difference between this example and example 1 is that the temperature rise rate of 10deg.C/min is increased to 600deg.C and calcination is performed for 30min, i.e. calcination time is changed to 30min, and other raw materials are used in the same amount and operation steps as in example 1.
Comparative example 3CO 2 Preparation of methanation catalyst
Mixing 5g of filtered biomass tar with 0.12mol of sodium hydroxide solution (the mass ratio of the filtered biomass tar to the sodium hydroxide is 1:1.04), adding 100ml of water, stirring for 30min to obtain solution A, mixing 0.03mol of nickel nitrate hexahydrate with 0.01mol of zirconium nitrate pentahydrate (4.29 g), adding 50ml of deionized water, stirring for 30min to obtain solution B (the mole ratio of Ni to Zr is 1:3.00), then dropwise adding the solution B into the solution A, stirring for 30min again, suction filtering, adding 600ml of deionized water for flushing three times during suction filtering to remove sodium nitrate generated in the solution, drying the precipitate in a 105 ℃ blast drying oven for 12h, heating to 600 ℃ at a speed of 10 ℃/min after drying, and calcining for 1h at 600 ℃ to obtain the biomass tar.
The difference from example 1 is that the molar ratio of Ni to Zr was changed to 3.00, and the other raw materials were used in the same amounts and the same procedures as in example 1.
Comparative example 4CO 2 Preparation of methanation catalyst
Mixing 5g of filtered biomass tar with 0.12mol of sodium hydroxide solution (the mass ratio of the filtered biomass tar to the sodium hydroxide is 1:1.04), adding 100ml of water, stirring for 30min to obtain solution A, mixing 0.04mol of nickel nitrate hexahydrate (11.63 g) with 0.01mol of zirconium nitrate pentahydrate (4.29 g), adding 50ml of deionized water, stirring for 30min to obtain solution B (the mole ratio of Ni to Zr is 1:4.00), then dropwise adding the solution B into the solution A, stirring again for 30min, suction filtering, placing the precipitate into a 105 ℃ blast drying oven for drying for 12h after suction filtering, heating to 600 ℃ at a speed of 10 ℃/min in an atmosphere furnace, and calcining for 1h at 600 ℃.
This example differs from example 1 in that deionized water is not used for the suction filtration, and other raw materials are used in the same amounts and the same operation steps as in example 1.
Structural characterization
CO prepared in example 1 2 And performing transmission electron microscopy and SEM (scanning electron microscope) test on the methanation catalyst and the Ni-based catalyst prepared in the comparative example 1.
Example 1CO produced 2 The transmission electron microscope diagram of the methanation catalyst is shown in fig. 1: the metal active component is dispersed in the form of particles on a carbon framework derived from the platy phenolic organic material.
The SEM image is shown in fig. 2: the microscopic morphology of the catalyst is represented by a petal-shaped lamellar structure.
The transmission electron microscope of the catalyst prepared in comparative example 1 is shown in fig. 3: the catalyst showed significant agglomeration.
The SEM image is shown in fig. 4: the catalyst exhibits an aggregated state.
It is demonstrated that: CO prepared by the invention 2 The methanation catalyst has good dispersibility.
Experimental example 1
The experimental method comprises the following steps:
0.1g of CO prepared in example 1 was reacted with 2 The methanation catalyst and the Ni-based catalyst prepared in comparative example 1 were packed in a fixed bed reactor, one end of the fixed bed was connected to an air inlet, and a vent pipe was connected to H 2 /CO 2 The mixture gas with the proportion of 4 has the reaction temperature of 250 ℃ and the reaction space velocity of 15000 mL.g -1 ·h -1 . Testing the reacted gas product with Agilent 6820 as CO in gas 2 The higher the conversion is, the better the catalytic performance is.
Example 1CO produced 2 Methanation catalyst shows good catalytic activity and stability in the 16h reaction process, and CO thereof 2 The conversion rate can reach 83%, while the CO of the Ni-based catalyst prepared in comparative example 1 2 The conversion rate can only reach about 45%, and the performance of the catalyst gradually declines after 10 hours of reaction.
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| CO 2 Conversion rate | 83％ | 45％ | 30％ | 57％ | 37％ |
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. CO (carbon monoxide) 2 The preparation method of the methanation catalyst is characterized by comprising the following steps of: uniformly mixing biomass tar with an alkaline solution, adding a mixed solution containing nickel salt and zirconium salt, filtering after the reaction is completed to obtain a nickel-zirconium catalyst precursor, and calcining the nickel-zirconium catalyst precursor at 500-800 ℃ for 1-3 hours to obtain the catalyst;
the main component of the biomass tar is phenolic organic matters, and the content of the phenolic organic matters is 40% -60%;
washing with deionized water during the filtration;
the nickel salt is nickel nitrate, nickel sulfate, nickel chloride or hydrate of any one of the nickel salts;
the zirconium salt is zirconium nitrate, zirconium sulfate, zirconium chloride or a hydrate of any one of the zirconium salts.
2. The preparation method according to claim 1, wherein the mass ratio of the nickel salt to the biomass tar is 1-3: 1.
3. the method according to claim 1, wherein the mass ratio of the biomass tar to the solute in the alkaline solution is 1:0.5-1.5.
4. The method according to claim 1, wherein the reaction time is 30 to 60 minutes.
5. The process according to claim 1, wherein the temperature of the reaction is 20 to 40 ℃.
6. The method according to claim 1, wherein the calcination temperature is 550 to 700 ℃.
7. CO (carbon monoxide) 2 Methanation catalyst, characterized in that it is prepared by the preparation method according to any one of claims 1 to 6.
8. The CO of claim 7 2 Methanation catalyst is used for catalyzing CO 2 Conversion to CH 4 Is used in the field of applications.
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