CN105665027A - Preparation method of high-dispersing supported metal nano catalyst - Google Patents
Preparation method of high-dispersing supported metal nano catalyst Download PDFInfo
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- CN105665027A CN105665027A CN201511020351.XA CN201511020351A CN105665027A CN 105665027 A CN105665027 A CN 105665027A CN 201511020351 A CN201511020351 A CN 201511020351A CN 105665027 A CN105665027 A CN 105665027A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 70
- 239000002184 metal Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 28
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 44
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 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 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 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
- 238000001354 calcination Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims 1
- 150000005309 metal halides Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000007598 dipping method Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 7
- 238000005554 pickling Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明涉及高分散负载型金属纳米催化剂的制备方法，属于催化剂技术领域。本发明解决的技术问题是提供负载型金属纳米催化剂的制备方法。该方法先采用过量浸渍法将活化后的多孔载体加入聚丙烯酸溶液中，过滤，固体干燥，得到聚丙烯酸改性载体；再采用等体积浸渍法将聚丙烯酸改性载体浸渍到金属前驱体溶液中，干燥，焙烧，即得负载型金属纳米催化剂。本发明用聚丙烯酸分散活性金属制备高分散催化剂，将链状的聚丙烯酸吸附到活性载体的表面及孔道中，用其络合金属离子的作用定向分散金属颗粒，制备得到高分散性的纳米催化剂，解决了目前工业中用浸渍法制备催化剂导致的活性金属团聚、分散不均匀，以至于催化活性不高的问题。
The invention relates to a preparation method of a highly dispersed and supported metal nano catalyst, belonging to the technical field of catalysts. The technical problem solved by the invention is to provide a preparation method of the supported metal nano catalyst. In this method, the activated porous carrier is firstly added to the polyacrylic acid solution by excessive impregnation, filtered, and dried to obtain a polyacrylic acid modified carrier; then the polyacrylic acid modified carrier is impregnated into the metal precursor solution by equal volume impregnation. , dried and calcined to obtain the supported metal nano catalyst. The invention uses polyacrylic acid to disperse active metals to prepare high-dispersion catalysts, absorbs chain-like polyacrylic acid to the surface and pores of the active carrier, uses its complexing metal ion to directional disperse metal particles, and prepares highly dispersed nano-catalysts , which solves the problem of agglomeration and uneven dispersion of active metals caused by the impregnation method in the industry to prepare catalysts, so that the catalytic activity is not high.
Description
Technical field
The present invention relates to the preparation method of high-dispersion loading type metal nano catalyzer, belong to catalyst technical field.
Background technology
Large-scale industrial production, as: hydrogenation reaction, catalytic cracking, petroleum cracking, oxidation of ethylene and synthetic ammonia etc., heterogeneous catalyst is all its integral part. And day by day fierce market competition makes people start to explore the better catalyzer of catalytic performance, metal nanoparticle is loaded to and the oxide compound of bigger serface prepares load type metal catalyst becomes an important research topic.
The preparation method of load type metal catalyst has a lot, such as pickling process, deposition-precipitation method, ion exchange method etc. Pickling process is impregnated on porous support based on active ingredient with salts solution form and penetrates into internal surface, and forms the principle of effective catalyst. Carrier is put into liquid containing active substance usually flood, when after dipping balance, isolate carrier, then be dried the postprocessing working procedures such as calcination activation and obtain catalyzer. Deposition-precipitation method is first immersed in the solution containing active ingredient after for some time by carrier, then adds the highly basic such as sodium hydroxide as precipitation agent, is slowly adding the catalyzer obtaining active particles under precipitation agent and vigorous stirring and being evenly distributed. Ion exchange method utilizes to there is exchangable ion on carrier surface, loads on carrier by active ingredient by ion-exchange, then the obtained catalyzer of the process such as washing, drying and roasting.
Pickling process because of its preparation method simple, cheap, pickling process becomes the method preparing load type metal nanocatalyst of widespread use in industry, but the active metal particles of the obtained catalyzer of this kind of method is easily reunited at carrier surface, crystallization, cause the uneven of its grain size and distribution, active ingredient high dispersing can not be made, thus can not show very high catalytic performance.
Summary of the invention
The technical problem that the present invention solves is to provide the preparation method of load type metal nanocatalyst, and the method polyacrylic acid dispersed active metal, prepares polymolecularity metal nano catalyzer.
The preparation method of load type metal nanocatalyst of the present invention, comprises the steps:
The preparation of a, polyacrylic acid modified carrier: adopting excessive pickling process to be impregnated in polyacrylic acid solution by the porous support after activation, filter, solid drying, obtains polyacrylic acid modified carrier;
The preparation of b, load type metal nanocatalyst: adopt equi-volume impregnating by polyacrylic acid modified carrier impregnation to, in metal precursor solution, dry, roasting, obtains load type metal nanocatalyst.
Wherein, in a step, described porous support is aluminum oxide, silicon oxide or molecular sieve.
In a step, the solvent of described polyacrylic acid solution is at least one in water, ethanol, methyl alcohol.
In a step, the concentration of described polyacrylic acid solution is 1～10mmol/L, and pH value is 5～9, it is preferable that the pH value of polyacrylic acid solution is 5～7.
In a step, the method for described activation is high-temperature roasting, and described high-temperature roasting is preferably 500 DEG C of roasting 3h.
Further, the metal in described load-type nanometer metal catalyst is nickel, palladium, platinum, copper, gold and silver or cobalt.
Wherein, in b step, described metal precursor is at least one in the halogenide of metal, nitrate, acetate; The solvent of described metallic precursor solution is water.
B step adopts repeatedly equi-volume impregnating, described repeatedly be preferably 3 times.
Roasting described in b step is 350～450 DEG C of roasting 5h.
Preferably, described porous support is aluminum oxide, and described metal precursor solution is nickel nitrate aqueous solution, and the charge capacity of metallic nickel is 5～15%.
The present invention's polyacrylic acid dispersed active metal prepares dispersed catalysts, in the surface that the PAA of chain shape is adsorbed onto active carrier and duct, with the directed dispersed metal particle of the effect of its complexation of metal ions, prepare the nanocatalyst of polymolecularity, solve at present industry the active metal caused with preparation catalyst reunite, disperse uneven, to such an extent as to the problem that catalytic activity is not high.
The present invention has the following advantages:
1) method for preparing catalyst of the present invention, can not only improve the dispersion of active metal at carrier surface, simultaneously it can be made to disperse more even in carrier duct, the catalyzer dispersity height for preparing, good stability, catalytic activity height.
2) the present invention is in the preparation of catalyzer, only needs to use active metal or active metal presoma, it is not necessary to the precious metal adding other is as auxiliary agent, reduce the cost of catalyzer, the catalyzer prepared is cheap, and toxin immunity is good, is applicable to suitability for industrialized production.
3) method for preparing catalyst in the present invention is the developing of a kind of methodology, has generality and universality, is applicable to the preparation of all load-type nanometer metal catalysts.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 and 2 load type metal nanocatalyst prepare schematic diagram.
Embodiment
The preparation method of load type metal nanocatalyst of the present invention, comprises the steps:
The preparation of a, polyacrylic acid modified carrier: adopting excessive pickling process to add in polyacrylic acid solution by the porous support after activation, filter, solid drying, obtains polyacrylic acid modified carrier;
The preparation of b, load type metal nanocatalyst: adopt equi-volume impregnating by polyacrylic acid modified carrier impregnation to, in metal precursor solution, dry, roasting, obtains load type metal nanocatalyst.
Wherein, porous support conventional in catalyzer is all applicable to the present invention, such as aluminum oxide, silicon oxide, titanium oxide, zinc oxide, magnesium oxide, cerium oxide, zirconium white, molecular sieve or mixed type metal oxide etc., it is preferable that, described porous support is aluminum oxide, silicon oxide or molecular sieve.
Further, in a step, the solvent of described polyacrylic acid solution should be polar solvent, it is preferable at least one in water, ethanol, methyl alcohol.
The concentration of polyacrylic acid solution will affect dipping effect, and concentration is too low, and impregnation rate is not high, and excessive concentration, soltion viscosity increases, and also will affect dipping effect. Therefore, polyacrylic acid solution concentration is preferably 1～10mmol/L.
In order to make PAA molecular chain better enter into the duct of porous support, it is preferable that the molecular weight of PAA is for being not more than 3000.
In an acidic solution, PAA molecular chain is in rolls up shape, and when the pH value of solution reaches 4.5, PAA starts to ionize out H+Ion, self becomes polyanion, and self repelling of polyanion makes the chain-unfolding of PAA open, and becomes chain-like structure. Therefore, the polyacrylic acid solution pH value in a step is preferably 5～9, it is more preferable to pH value is 5～7. In the pH value of reality regulates, NaOH can be adopted to regulate the pH value of PAA solution.
In the preparation method of load type metal nanocatalyst of the present invention, the porous support after activation is the porous support adopting conventional method to activate such as high-temperature roasting, it is preferable at 500 DEG C of roasting 3h.
Excessive pickling process of the present invention refers to steeps in excessive dipping solution by carrier, and namely dipping solution volume exceedes carrier and can absorb volume. Equi-volume impregnating refers to that the dipping solution by carrier and it can absorb volume mixes, and namely the volume of dipping solution is suitable with the micro pore volume of carrier.
The preparation method of the present invention is applicable to all load-type nanometer metal catalysts, is particularly useful for preparing the catalyzer such as load-type nanometer metal nickel, palladium, platinum, copper, gold and silver, cobalt. The catalyzer of the present invention is made up of active metal and carrier, and PAA, only for the preparation of dispersed active metal during catalyzer, can be burnt in the roasting process of b step, not participate in catalyzed reaction. The active ingredient of catalyzer is active metal, and the metal in described load-type nanometer metal catalyst is preferably nickel, palladium, platinum, copper, gold and silver or cobalt.
Described metal precursor is any one in the halogenide of metal, nitrate, acetate or its two or more arbitrary combination. It is an object of the invention to obtain the metal of catalyzer from these compounds, it is not these compounds, as long as therefore obtaining nano level metal by follow-up calcination steps.
The effect of described metallic precursor solution solvent is dissolution of metals precursor, and metallic precursor is adsorbed onto on carrier better, as long as so the solvent selected can dissolution of metals precursor, it is possible to be single solvent, it is possible to be mixed solvent. For cost-saving, the solvent of metallic precursor solution of the present invention is preferably water.
In order to improve dispersity, b step can adopt repeatedly equi-volume impregnating. Described repeatedly be preferably 3 times. Every time dry after dipping, and then flood, after last impregnation drying, then roasting.
Roasting described in b step is 350～450 DEG C of roasting 5h.
Preferably, described porous support is aluminum oxide, and described metal precursor solution is nickel nitrate aqueous solution, and the charge capacity of metallic nickel is 5～15%. Such as, it is carrier taking aluminum oxide, after polyacrylic acid modified, it be impregnated into and be respectively in the nickel nitrate solution of 5%, 15% by elemental nickel calculated load amount, prepare load type metal nickel catalyzator 5Ni/AP and 15Ni/AP. It is prepared schematic diagram and sees Fig. 1. This catalyzer has good katalysis, particularly 15Ni/AP for carbon dioxide methanation reaction, and reaction can be made to reach thermodynamic(al)equilibrium when 380 DEG C.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
Embodiment 1
Compound concentration is the PAA aqueous solution 100ml of 1mmol/L, adjust its pH value to 5.5 with the NaOH of 0.1mol/L, taking the activated alumina after 3.015g activation joins in solution, normal temperature (25 DEG C), magnetic stirrer 12h, stops, taking out and filter excessive solution, dried overnight in 110 DEG C of thermostat containers, obtains mixture. Taking the Nickelous nitrate hexahydrate of 0.779g, be mixed with the aqueous solution of 10ml, divide with equi-volume impregnating and be impregnated on complexes carrier 3 times, each dipping time is 30min, and time of drying is 3h. After last dipping, dried overnight in 110 DEG C of thermostat containers. Again at 450 DEG C of roasting 5h, obtain catalyzer 5Ni/AP5.5. It is prepared schematic diagram and sees Fig. 1. Not add contrasting as blank of PAA, numbering 5Ni/A.
Embodiment 2
Compound concentration is the PAA aqueous solution 100ml of 1mmol/L, adjust its pH value to 7 with the NaOH of 0.1mol/L, taking the activated alumina after 2.998g activation joins in solution, normal temperature (25 DEG C), magnetic stirrer 12h, stops, taking out and filter excessive solution, dried overnight in 110 DEG C of thermostat containers, obtains mixture. Taking the Nickelous nitrate hexahydrate of 0.771g, be mixed with the aqueous solution of 10ml, divide with equi-volume impregnating and be impregnated on complexes carrier 3 times, each dipping time is 30min, and time of drying is 3h. After last dipping, dried overnight in 110 DEG C of thermostat containers. Again at 450 DEG C of roasting 5h, obtain catalyzer 5Ni/AP7。
Embodiment 3
Compound concentration is the PAA ethanolic soln 100ml of 10mmol/L, adjust its pH value to 5.5 with the NaOH of 0.1mol/L, taking the activated alumina after 3.008g activation joins in solution, normal temperature (25 DEG C), magnetic stirrer 12h, stops, taking out and filter excessive solution, dried overnight in 110 DEG C of thermostat containers, obtains mixture. Taking the Nickelous nitrate hexahydrate of 2.623g, be mixed with the aqueous solution of 10ml, divide with equi-volume impregnating and be impregnated on complexes carrier 3 times, each dipping time is 30min, and time of drying is 3h. After last dipping, dried overnight in 110 DEG C of thermostat containers. Again at 350 DEG C of roasting 5h, obtain catalyzer 15Ni/AP5.5, it is prepared schematic diagram and sees Fig. 1. Not add contrasting as blank of PAA, numbering 15Ni/A.
Activity rating of catalyst in test example 1 embodiment
Taking 0.2g catalyzer, be placed in the middle of steel pipe that internal diameter is 3.5mm, quartz sand is filled up in both sides. First, reducing 1h in the hydrogen stream of 40ml/min, reduction temperature is 600 DEG C, and temperature rise rate is 10 DEG C/min, then cools to 100 DEG C, under normal pressure, leads to the mixed gas into hydrogen and carbonic acid gas, and ratio is H2: CO2=4:1 (40:10ml), air speed is 15000mlh-1gcat -1, temperature reaction, reacts half an hour respectively at 300,320,340,360,380 DEG C of places, carries out sampling analysis by chromatogram. During reaction, temperature rise rate is 5 DEG C/min. The product rate that embodiment 1 and embodiment 2 product catalysis obtain is in table 1.
Table 1 methanation product rate
A: thermodynamic equilibria, the result obtained by AspenPlus flowsheeting.
It can be seen that with the addition of the sample of PAA from table 1 result, its catalytic activity is significantly improved, particularly in low-temperature zone, this is owing to active metal obtains more even at its Dispersion on surface, has more avtive spot, it is to increase its activity. Sample 15Ni/AP, when 380 DEG C, reaches thermodynamic(al)equilibrium.
Claims (10)
Priority Applications (1)
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| CN111097462A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
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| CN116060087A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Grading method of hydrogenation catalyst and application of grading method in refining microcrystalline wax |
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| CN117205909A (en) * | 2023-09-05 | 2023-12-12 | 中国科学院过程工程研究所 | Preparation method and application of a polymer-modified aldol condensation catalyst |
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| CN111097489A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and its preparation |
| CN111097488A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
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| CN116726923A (en) * | 2023-08-09 | 2023-09-12 | 山东久元新材料有限公司 | High-load equal-volume uniform load process and application |
| CN116726923B (en) * | 2023-08-09 | 2023-10-27 | 山东久元新材料有限公司 | High-load equal-volume uniform load process and application |
| CN117205909A (en) * | 2023-09-05 | 2023-12-12 | 中国科学院过程工程研究所 | Preparation method and application of a polymer-modified aldol condensation catalyst |
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