CN105597768A - Preparation method of superfine nano Ni catalyst applied to alkane pre-reforming in low steam-to-carbon ratio - Google Patents
Preparation method of superfine nano Ni catalyst applied to alkane pre-reforming in low steam-to-carbon ratio Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 238000002407 reforming Methods 0.000 title claims abstract description 36
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 20
- -1 nickel-lanthanum (cerium)-aluminum Chemical compound 0.000 claims abstract description 19
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 64
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 238000004448 titration Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 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
- 239000002243 precursor Substances 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 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
- 238000000034 method Methods 0.000 abstract description 30
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 11
- 239000003915 liquefied petroleum gas Substances 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 230000007423 decrease Effects 0.000 abstract description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- NJQQARGXPXDEQX-UHFFFAOYSA-N [Ni].[La].[Ce] Chemical compound [Ni].[La].[Ce] NJQQARGXPXDEQX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003303 NiAl2O4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/76—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a preparation method of a superfine nano Ni catalyst applied to alkane pre-reforming in a low steam-to-carbon ratio. According to the preparation method, a sol of a nickel-lanthanum (cerium)-aluminum composite oxide is prepared with a method for partially hydrolyzing a soluble nonorganic aluminum salt, an inorganic nickel salt and rare earth element (La/Ce) nitrate by the aid of ammonium carbonate; free water is removed after drying, dried gel of the nickel-lanthanum (cerium)-aluminum composite oxide is formed, the nickel-lanthanum (cerium)-aluminum composite oxide is formed after roasting decomposition of ammonium nitrate and loss of water in molecules, and the superfine Ni nano-particle catalyst is prepared after the composite oxide is reduced in H2 atmosphere. The prepared catalyst is used for alkane steam pre-reforming with LPG (liquefied petroleum gas) serving as a model, does not generate phenomena of activity decline and carbon deposition after reaction is performed for 200 h under the conditions that the reaction temperature is 350 DEG C, S/C is equal to 0.6 and SV is equal to 8,750 mLg<-1>h<-1>, and has high activity and super-high stability.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, particularly relate to a kind of preparation method of Ni catalyst, be applied to Industrial Catalysis field of material preparation.
Background technology
With H2For the Proton Exchange Membrane Fuel Cells (PEMFC) of fuel has high energy conversion efficiency, it is vehicle-mounted and the optimization power supply of fixing electricity consumption. To have become development clean because having high hydrogen gas production rate for alkane vapor reforming hydrogen production, the key technology of efficient hydrogen fuel cell. The reaction of alkane steam has strong suction thermal property, and therefore, for improving the productivity ratio of hydrogen, reaction is all at higher temperature (> 800oC) under carry out, but under high temperature, High-carbon alkane cracking process can cause catalyst because of carbon distribution and active component sintering inactivation and cause the obstruction of reaction bed. For effectively addressing this problem, can just adopt water at low temperature steam reforming is pre-reforming reaction, first High-carbon alkane is converted to methane and hydrocarbon (CO2, CO) etc. micro-molecular gas, and then through high temperature, methane reforming is produced to hydrogen and hydrocarbon (CO2, CO). In general, alkane pre-reforming is conventionally at 300 – 500oC, carries out (SV < 3000h under higher steam/hydrocarbons ratio (S/C >=2.5) and lower air speed-1). But, in order to improve efficiency and to reduce the weight and volume of reactor, develop a kind of pre-reforming catalyst can under low steam carbon ratio condition with high activity and high stability, the hydrogen fuel cell technology to development taking High-carbon alkane as hydrogen carrier has great importance.
Also few about the report of efficient low steam carbon ratio alkane pre-reforming catalyst at present. SuzukiT, IwanamiHI, IwamotoO, KitaharaT.IntJHydrogenEnergy2001; 26:935 – 940 and ChenFZ, ZhaSW, DongJ, LiuML.SolidStateIonics2004; In 166:269 – 273., point out, Ru base and Pt are catalyst based has higher active and stronger anti-carbon performance in low steam carbon ratio alkane pre-reforming, but its application has been limited in the high price of noble metal and rare source thereof. The Ni catalyst of the catalyst based especially alumina load of Ni is widely used in alkane compared with high activity and cheap price and reforms because having, but its in course of reaction easily because of carbon distribution inactivation. Research shows the size of the Ni of catalyst active center particle and the activity of catalyst, and stability is closely related with anti-carbon performance, and the size that reduces Ni particle can significantly improve Ni/Al2O3The anti-carbon performance of catalyst in alkane is reformed, even, when the size of Ni particle reduces to a certain extreme value, just can there is not carbon distribution phenomenon in catalyst. Therefore, finding a kind of suitable method and suitable preparation condition, to prepare the catalyst of superfine nano Ni nano particle significant for low steam carbon ratio alkane pre-reforming.
Summary of the invention
In order to solve prior art problem, the object of the invention is to overcome the deficiency that prior art exists, a kind of preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst is provided, successfully prepare the ultra-fine Ni nanoparticle catalyst of 2～3nm, for the alkane water vapour pre-reforming taking LPG as model, be 350 DEG C, S/C=0.6, SV=8750mLg in reaction temperature-1h-1Condition under after 200h reaction, there is not active decline and the phenomenon of carbon distribution, show high activity and superpower stability.
Create object for reaching foregoing invention, adopt following technical proposals:
A preparation method for low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst, step is as follows:
A. a certain amount of nickel salt, rare earth element nitrate, aluminium salt are dissolved in a certain amount of deionized water, preparation mixed solution, making aluminium ion concentration in mixed solution is 1～4mol/L, and makes the nickel ion in mixed solution: rare earth element ion: the ratio of aluminum ions amount of substance is (210～240): (15～56): 1000; Aluminium salt preferably adopts aluminum nitrate or aluminum sulfate; Nickel salt preferably adopts nickel nitrate or nickelous sulfate; Rare earth element nitrate preferably adopts the mixture of any one nitrate in La nitrate and Ce nitrate or two kinds of nitrate;
B. under the constant temperature of 30～70 DEG C, the mixed solution of preparing in step a is stirred, dropwise in mixed solution, splash into the sal volatile that concentration is 1～4mol/L while stirring, the rate of titration of controlling ammonium carbonate is 1mL/min, the moment that question response obtains clear gel stops, to titration sal volatile in mixed solution, in mixed solution, obtaining gel; Splash into sal volatile in mixed solution time, preferably control ammonium carbonate and aluminum ions mol ratio for (1.0～1.3): 1; Splash into sal volatile in mixed solution time, the pH value of preferably controlling mixed solution is 5.0～5.8;
C. by the gel forming after titration in step b constant temperature ageing 24 hours at 20～30 DEG C, proceed to subsequently baking oven, at 80～100 DEG C dry 12～24 hours, obtain dry gel;
D. dried gel in step c is heated up with the heating rate of 10 DEG C/min, 300～800 DEG C of roasting temperatures 10 hours, prepare composite oxides xerogel, obtain composite oxide catalysts precursor;
E. by the composite oxides xerogel of preparing in step c at 600 DEG C and at H2Reductase 12 h under atmosphere, finally makes the composite oxide catalysts of alumina load superfine nano Ni particle.
As the preferred technical scheme of the present invention, in step a, prepare the nickel ion in mixed solution: rare earth element ion: the ratio of aluminum ions amount of substance is (230～240): (37～56): 1000; In step b, splash into sal volatile in mixed solution time, controlling ammonium carbonate and aluminum ions mol ratio is (1.25～1.3): 1.
The present invention, by the method for ammonium carbonate partial hydrolysis solubility inorganic aluminate, inorganic nickel, rare earth element (La/Ce) nitrate, prepares the colloidal sol of nickel lanthanum (cerium) aluminium composite oxide. After dry, deviate from free water, form nickel lanthanum (cerium) aluminium composite oxide xerogel, then through Roasting Decomposition ammonium nitrate with lose in molecule after water, formed nickel lanthanum (cerium) aluminium composite oxide. Afterwards by prepared sample through H2Under atmosphere, after reduction, successfully prepare ultra-fine Ni nanoparticle catalyst. Prepared catalyst, for the alkane water vapour pre-reforming taking LPG as model, is 350 in reaction temperatureoC,S/C=0.6,SV=8750mLg-1h-1Condition under after 200h reaction, there is not active decline and the phenomenon of carbon distribution, show high activity and superpower stability.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the inventive method adopts saline hydrolysis sol-gal process, the repeatability of preparing product is high, and prepared Ni and Ni-La/Ce oxide high degree of dispersion are on aluminium oxide, solve the easy carbon distribution problem of catalyst in low steam carbon ratio alkane reforming process, for good basis has been established in the research and development of functional material;
2. the selected system of the inventive method, taking the industrial nitrate being easy to get and ammonium carbonate as raw material, greatly reduces production cost;
3. the inventive method only needs a few reactive material, and in reaction, solvent used is deionized water, therefore have easy and simple to handle, process equipment is simple, with low cost, preparation catalyst purity high, be easy to control, free of contamination advantage, be beneficial to suitability for industrialized production;
4. the inventive method can synthesize the ultra-fine Ni nanoparticle catalyst with 2 to 3nm by easy reaction, it is catalyst excellent in low steam carbon ratio alkane reforming process, prepared catalyst, for ultralow steam/hydrocarbons ratio (S/C=0.6) alkane pre-reforming, has high activity (SV=8750mLg-1h-1) and superpower anti-carbon performance and stability, for low steam carbon ratio alkane pre-reforming provides efficient catalyst.
Brief description of the drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of the intermediate product composite oxide jel product in the embodiment of the present invention one preparation process.
Fig. 2 is the TEM figure of the composite oxide catalysts prepared of the embodiment of the present invention one.
Fig. 3 adopts the composite oxide catalysts prepared of the embodiment of the present invention one to be applied to catalytic performance in LPG water vapour pre-reforming to scheme over time.
Fig. 4 is the TEM figure of the composite oxide catalysts prepared of the embodiment of the present invention two.
Fig. 5 is the TEM figure of the composite oxide catalysts prepared of the embodiment of the present invention three.
Fig. 6 is the TEM figure of the composite oxide catalysts prepared of the embodiment of the present invention four.
Fig. 7 is the TEM figure of the composite oxide catalysts prepared of the embodiment of the present invention five.
Detailed description of the invention
Details are as follows for the preferred embodiments of the present invention:
Embodiment mono-:
In the present embodiment, a kind of preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst, step is as follows:
A. by 0.024mol nickel nitrate, 0.0056mol lanthanum nitrate and 0.1mol aluminum nitrate are dissolved in 50ml deionized water and mix, constantly stir the uniform mixed solution of preparation, making aluminium ion concentration in mixed solution is 2mol/L, in mixed solution, Ni mass fraction is 18%, and in mixed solution, the mass fraction of lanthanum is 10%;
B. under 70 DEG C of constant temperature, the mixed solution of preparing in step a is stirred, dropwise in mixed solution, splash into the sal volatile that concentration is 1mol/L while stirring, the rate of titration of controlling ammonium carbonate is 1mL/min, and the ratio of controlling ammonium carbonate and aluminum ions amount of substance is 1.30:1, the moment that question response obtains gel stops, to titration sal volatile in mixed solution, in mixed solution, obtaining gel;
C. by the gel forming after titration in step b constant temperature ageing 24 hours at 30 DEG C, proceed to subsequently baking oven, at 100 DEG C dry 24 hours, obtain dry gel;
D. dried gel in step c is heated up with the heating rate of 10 DEG C/min, 400 DEG C of roasting temperatures 10 hours, grind and obtain nickel lanthanum aluminium composite oxide catalyst, obtain composite oxides xerogel, obtain composite oxide catalysts precursor, referring to Fig. 1;
E. by the composite oxides xerogel of preparing in step c at 600 DEG C and at H2Reductase 12 h under atmosphere, finally makes the composite oxide catalysts of alumina load superfine nano Ni particle, referring to Fig. 2.
In the present embodiment, intermediate product composite oxides xerogel in preparation process is carried out to XRD collection of illustrative plates mensuration, it is to carry out at RigakuD/max-2550X x ray diffractometer x that the XRD that intermediate product composite oxides xerogel is carried out detects, condition determination is CuKa(l=1.5406), 40KV, 100mA, Scanspeed:8 °/min, Fig. 1 is X-ray powder diffraction (XRD) figure of the intermediate product composite oxides xerogel in preparation process. From the XRD spectra of Fig. 1, remove 2θ=37o，45o，66oCorresponding NiAl2O4Diffraction maximum outside, the NiO and the La that not do not occur2O3Corresponding diffraction maximum, shows that in composite oxide catalysts prepared by the present embodiment method, nickel and lanthanum are dispersed in the lattice of aluminium oxide. In the present embodiment, composite oxide catalysts prepared by the present embodiment method carries out tem analysis, it is to complete on JEOLJEM-2010F field transmitting HR-TEM that composite oxide catalysts prepared by the present embodiment method carries out TEM detection, and its accelerating potential is 200KV. After the composite oxide catalysts of the present embodiment alumina load superfine nano Ni particle, H takes a morsel2After reduction, composite oxide catalysts sample is dissolved in absolute ethyl alcohol, after be put in agate mortar and grind, ultrasonic afterwards, then get a supernatant and splash into the copper mesh that is loaded with carbon film, detect immediately after drying, wherein Ni nanoparticle size is to measure at random 200 Ni particles in TEM picture. Fig. 2 is the TEM figure of the composite oxide catalysts prepared of the present embodiment method, as shown in Figure 2, composite oxide catalysts prepared by the present embodiment method is keeping uniform worm meso-porous structure, and this structure has proved to have high stability and good mass transfer and heat-transfer effect. The metallic nickel nano granule forming is dispersed on alumina support, known by the size statistics to nickel particle, and its size, between 2～3.0nm, has no at present and reported so little Ni nano particle. In Fig. 2, do not occur the particle of obvious lanthana, known its high degree of dispersion is in catalyst, and this is consistent with XRD result. The reaction of LPG water vapour pre-reforming completes in homemade device, and reaction temperature is by the thermocouple control of beds central authorities, and LPG and water are respectively by mass flowmenter and HPLC micro-sampling pump control flow. Product is used respectively with the GC-9800 chromatogram of the GC-9800 type chromatogram of flame ionization ditector (FID) and thermal conductivity detector (TCD) (TCD) and is detected online. Fig. 3 is that to adopt the composite oxide catalysts prepared of the present embodiment to be applied to reaction temperature be 350 DEG C, S/C=0.6, SV=8750mLg-1h-1In LPG water vapour pre-reforming under condition, catalytic activity is schemed over time, known after long-time reaction, and the phenomenon declining does not appear in catalyst activity, has shown superpower stability.
The present embodiment, by the method for ammonium carbonate partial hydrolysis solubility inorganic aluminate, inorganic nickel, rare-earth elements La nitrate, is prepared the colloidal sol of nickel lanthanum aluminium composite oxide. After dry, deviate from free water, form nickel lanthanum aluminium composite oxide xerogel. At 400 DEG C of degree Roasting Decomposition ammonium nitrate with lose in molecule after water, form nickel lanthanum aluminium composite oxide. The H through 600 DEG C by prepared sample afterwards2Under atmosphere, after reduction, successfully prepare the ultra-fine Ni nanoparticle catalyst of 2～3nm. Prepared catalyst, for the alkane water vapour pre-reforming taking LPG as model, is 350 in reaction temperatureoC,S/C=0.6,SV=8750mLg-1h-1Condition under after 200h reaction, there is not active decline and the phenomenon of carbon distribution, show high activity and superpower stability.
Embodiment bis-:
The present embodiment and embodiment mono-are basic identical, and special feature is:
In the present embodiment, a kind of preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst, step is as follows:
A. by 0.023mol nickel nitrate, 0.0037mol lanthanum nitrate and 0.1mol aluminum nitrate are dissolved in 50mL deionized water and mix, constantly stir the uniform mixed solution of preparation, making aluminium ion concentration in mixed solution is 2mol/L, in mixed solution, Ni mass fraction is 18%, and in mixed solution, the mass fraction of lanthanum is 7%;
B. under 70 DEG C of constant temperature, the mixed solution of preparing in step a is stirred, dropwise in mixed solution, splash into the sal volatile that concentration is 1mol/L while stirring, the rate of titration of controlling ammonium carbonate is 1mL/min, and the ratio of controlling ammonium carbonate and aluminum ions amount of substance is 1.25:1, the moment that question response obtains gel stops, to titration sal volatile in mixed solution, in mixed solution, obtaining gel;
C. by the gel forming after titration in step b constant temperature ageing 24 hours at 30 DEG C, proceed to subsequently baking oven, at 100 DEG C dry 12 hours, obtain dry gel;
D. dried gel in step c is heated up with the heating rate of 10 DEG C/min, 400 DEG C of roasting temperatures 10 hours, grind and obtain nickel lanthanum aluminium composite oxide catalyst, obtain composite oxide catalysts precursor;
E. by the composite oxides xerogel of preparing in step c at 600 DEG C and at H2Reductase 12 h under atmosphere, finally makes the composite oxide catalysts of alumina load superfine nano Ni particle, referring to Fig. 4.
In the present embodiment, composite oxide catalysts prepared by the present embodiment method carries out tem analysis, and Fig. 4 is the TEM figure of the composite oxide catalysts prepared of the present embodiment method. As shown in Figure 4, composite oxide catalysts prepared by the present embodiment method is keeping uniformly and is having the worm meso-porous structure in narrow aperture, and metallic nickel nano granule is dispersed on alumina support, and Ni granular size is between 2.5～3.5nm. Do not occur as shown in Figure 4 the particle of obvious lanthana, known its high degree of dispersion is in catalyst.
Embodiment tri-:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, a kind of preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst, step is as follows:
A. by 0.021mol nickel nitrate, 0.0015mol lanthanum nitrate and 0.1mol aluminum nitrate are dissolved in 50mL deionized water and mix, constantly stir the uniform mixed solution of preparation, making aluminium ion concentration in mixed solution is 2mol/L, in mixed solution, Ni mass fraction is 18%, and in mixed solution, the mass fraction of lanthanum is 3%;
B. under 70 DEG C of constant temperature, the mixed solution of preparing in step a is stirred, dropwise in mixed solution, splash into the sal volatile that concentration is 1mol/L while stirring, the rate of titration of controlling ammonium carbonate is 1mL/min, and the ratio of controlling ammonium carbonate and aluminum ions amount of substance is 1.2:1, the moment that question response obtains gel stops, to titration sal volatile in mixed solution, in mixed solution, obtaining gel;
C. by the gel forming after titration in step b constant temperature ageing 24 hours at 30 DEG C, proceed to subsequently baking oven, at 100 DEG C dry 24 hours, obtain dry gel;
D. dried gel in step c is heated up with the heating rate of 10 DEG C/min, 400 DEG C of roasting temperatures 10 hours, grind and obtain nickel lanthanum aluminium composite oxide catalyst, obtain composite oxide catalysts precursor;
E. by the composite oxides xerogel of preparing in step c at 600 DEG C and at H2Reductase 12 h under atmosphere, finally makes the composite oxide catalysts of alumina load superfine nano Ni particle, referring to Fig. 5.
In the present embodiment, composite oxide catalysts prepared by the present embodiment method carries out tem analysis, and Fig. 5 is the TEM figure of the composite oxide catalysts prepared of the present embodiment method. As shown in Figure 5, composite oxide catalysts prepared by the present embodiment method is keeping uniformly and is having the worm meso-porous structure in narrow aperture, and metallic nickel nano granule is dispersed on alumina support, and Ni granular size is between 5～7nm. Do not occur as shown in Figure 5 the particle of obvious lanthana, known its high degree of dispersion is in catalyst.
Embodiment tetra-:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, a kind of preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst, step is as follows:
A. by 0.023mol nickel nitrate, 0.0037mol cerous nitrate and 0.1mol aluminum nitrate are dissolved in 50mL deionized water and mix, constantly stir the uniform mixed solution of preparation, making aluminium ion concentration in mixed solution is 2mol/L, in mixed solution, Ni mass fraction is 18%, and in mixed solution, the mass fraction of cerium is 7%;
B. under 30 DEG C of constant temperature, the mixed solution of preparing in step a is stirred, dropwise in mixed solution, splash into the sal volatile that concentration is 1mol/L while stirring, the rate of titration of controlling ammonium carbonate is 1mL/min, and the ratio of controlling ammonium carbonate and aluminum ions amount of substance is 1.25:1, the moment that question response obtains gel stops, to titration sal volatile in mixed solution, in mixed solution, obtaining gel;
C. by the gel forming after titration in step b constant temperature ageing 24 hours at 30 DEG C, proceed to subsequently baking oven, at 100 DEG C dry 12 hours, obtain dry gel;
D. dried gel in step c is heated up with the heating rate of 10 DEG C/min, 400 DEG C of roasting temperatures 10 hours, grind and obtain nickel cerium-aluminium composite oxide catalyst, obtain composite oxide catalysts precursor;
E. by the composite oxides xerogel of preparing in step c at 600 DEG C and at H2Reductase 12 h under atmosphere, finally makes the composite oxide catalysts of alumina load superfine nano Ni particle, referring to Fig. 6.
In the present embodiment, composite oxide catalysts prepared by the present embodiment method carries out tem analysis, and Fig. 6 is the TEM figure of the composite oxide catalysts prepared of the present embodiment method. As shown in Figure 6, composite oxide catalysts prepared by the present embodiment method is keeping uniformly and is having the worm meso-porous structure in narrow aperture, and metallic nickel nano granule is dispersed on alumina support, and Ni granular size is between 2.5～3.5nm. Do not occur as shown in Figure 6 the particle of obvious cerium oxide, known its high degree of dispersion is in catalyst.
Embodiment five:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, a kind of preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst, step is as follows:
A. by 0.021mol nickel nitrate, 0.0015mol cerous nitrate and 0.1mol aluminum nitrate are dissolved in 50mL deionized water and mix, constantly stir the uniform mixed solution of preparation, making aluminium ion concentration in mixed solution is 2mol/L, in mixed solution, Ni mass fraction is 18%, and in mixed solution, the mass fraction of cerium is 3%;
B. under 70 DEG C of constant temperature, the mixed solution of preparing in step a is stirred, dropwise in mixed solution, splash into the sal volatile that concentration is 1mol/L while stirring, the rate of titration of controlling ammonium carbonate is 1mL/min, and the ratio of controlling ammonium carbonate and aluminum ions amount of substance is 1.2:1, the moment that question response obtains gel stops, to titration sal volatile in mixed solution, in mixed solution, obtaining gel;
C. by the gel forming after titration in step b constant temperature ageing 24 hours at 30 DEG C, proceed to subsequently baking oven, at 100 DEG C dry 12 hours, obtain dry gel;
D. dried gel in step c is heated up with the heating rate of 10 DEG C/min, 400 DEG C of roasting temperatures 10 hours, grind and obtain nickel cerium-aluminium composite oxide catalyst, obtain composite oxide catalysts precursor;
E. by the composite oxides xerogel of preparing in step c at 600 DEG C and at H2Reductase 12 h under atmosphere, finally makes the composite oxide catalysts of alumina load superfine nano Ni particle, referring to Fig. 7.
In the present embodiment, composite oxide catalysts prepared by the present embodiment method carries out tem analysis, and Fig. 7 is the TEM figure of the composite oxide catalysts prepared of the present embodiment method. As shown in Figure 7, composite oxide catalysts prepared by the present embodiment method is keeping uniformly and is having the worm meso-porous structure in narrow aperture, and metallic nickel nano granule is dispersed on alumina support, and Ni granular size is between 5～7nm. Do not occur as shown in Figure 7 the particle of obvious cerium oxide, known its high degree of dispersion is in catalyst.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; can also make multiple variation according to the object of innovation and creation of the present invention; the change made under all Spirit Essences according to technical solution of the present invention and principle, modification, substitute, combination or simplify; all should be equivalent substitute mode; as long as goal of the invention according to the invention; only otherwise deviate from the preparation method's of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst of the present invention know-why and inventive concept, all belong to protection scope of the present invention.
Claims (7)
1. a preparation method for low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst, is characterized in that, step is as follows:
A. a certain amount of nickel salt, rare earth element nitrate, aluminium salt are dissolved in a certain amount of deionized water, preparation mixed solution, making aluminium ion concentration in mixed solution is 1～4mol/L, and makes the nickel ion in mixed solution: rare earth element ion: the ratio of aluminum ions amount of substance is (210～240): (15～56): 1000;
B. under the constant temperature of 30～70 DEG C, the mixed solution of preparing in described step a is stirred, dropwise in mixed solution, splash into the sal volatile that concentration is 1～4mol/L while stirring, the rate of titration of controlling ammonium carbonate is 1mL/min, the moment that question response obtains clear gel stops, to titration sal volatile in mixed solution, in mixed solution, obtaining gel;
C. by the gel forming after titration in described step b constant temperature ageing 24 hours at 20～30 DEG C, proceed to subsequently baking oven, at 80～100 DEG C dry 12～24 hours, obtain dry gel;
D. dried gel in described step c is heated up with the heating rate of 10 DEG C/min, 300～800 DEG C of roasting temperatures 10 hours, prepare composite oxides xerogel, obtain composite oxide catalysts precursor;
E. by the composite oxides xerogel of preparing in described step c at 600 DEG C and at H2Reductase 12 h under atmosphere, finally makes the composite oxide catalysts of alumina load superfine nano Ni particle.
2. the preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst according to claim 1, it is characterized in that: in described step b, splash into sal volatile in mixed solution time, controlling ammonium carbonate and aluminum ions mol ratio is (1.0～1.3): 1.
3. the preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst according to claim 1, is characterized in that: in described step b, splash into sal volatile in mixed solution time, the pH value of controlling mixed solution is 5.0～5.8.
4. according to the preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst described in any one in claim 1～3, it is characterized in that: in described step a, prepare the nickel ion in mixed solution: rare earth element ion: the ratio of aluminum ions amount of substance is (230～240): (37～56): 1000; In described step b, splash into sal volatile in mixed solution time, controlling ammonium carbonate and aluminum ions mol ratio is (1.25～1.3): 1.
5. according to the preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst described in any one in claim 1～3, it is characterized in that: in described step a, described aluminium salt is aluminum nitrate or aluminum sulfate.
6. according to the preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst described in any one in claim 1～3, it is characterized in that: in described step a, described nickel salt is nickel nitrate or nickelous sulfate.
7. according to the preparation method of low steam carbon ratio alkane pre-reforming superfine nano Ni catalyst described in any one in claim 1～3, it is characterized in that: in described step a, rare earth element nitrate is the mixture of any one nitrate or two kinds of nitrate in La nitrate and Ce nitrate.
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| CN102133533A (en) * | 2011-02-23 | 2011-07-27 | 上海大学 | LPG water vapor pre-reforming catalyst and application method thereof |
| CN104028271A (en) * | 2014-01-02 | 2014-09-10 | 上海大学 | Preparation method of mesoporous nickel-magnesium-aluminum oxide with high specific surface area |
| CN104549289A (en) * | 2014-11-26 | 2015-04-29 | 上海大学 | Mesoporous alumina nickel-based catalyst with high activity and high stability for CO2 reforming CH4 reaction and preparation method of mesoporous alumina nickel-based catalyst |
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| JPS5331590A (en) * | 1976-09-06 | 1978-03-24 | Tokyo Gas Co Ltd | Catalysts for manufacturing methaneecontaining gas |
| CN102133533A (en) * | 2011-02-23 | 2011-07-27 | 上海大学 | LPG water vapor pre-reforming catalyst and application method thereof |
| CN104028271A (en) * | 2014-01-02 | 2014-09-10 | 上海大学 | Preparation method of mesoporous nickel-magnesium-aluminum oxide with high specific surface area |
| CN104549289A (en) * | 2014-11-26 | 2015-04-29 | 上海大学 | Mesoporous alumina nickel-based catalyst with high activity and high stability for CO2 reforming CH4 reaction and preparation method of mesoporous alumina nickel-based catalyst |
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