CN102350356A - Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method - Google Patents
Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method Download PDFInfo
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Abstract
The invention discloses a hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method, belonging to the technical field of hydrogen production and energy sources. The chemical composition of the catalyst is represented as MxB, wherein, M represents one or more of Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or Mg, x is no less than 1 and no larger than 4 and can be a non-integer. The catalyst comprises a monodispersed boride material, and the catalyst has high specific surface area, uniform particle size distribution, and high catalytic activity, and the dehydrogenation rate can reach more than 95 %. The invention also discloses a preparation method of the catalyst, characterized by carrying out solution chemical reaction and vacuum freeze treatment at low temperature to obtain a predecessor, then carrying out heat treatment to obtain the catalyst. The preparation method has the advantages of rapid early-stage reaction, simple and convenient post-treatment and strong operability.
Description
Technical field
The present invention relates to a kind of borohydride hydrolytic hydrogen production Catalysts and its preparation method, belong to Preparation of Hydrogen and energy technology field.
Background technology
In recent years, the exploitation and the application problem of relevant hydrogen energy source receive the great attention of China and countries in the world, and hydrogen energy source is considered to a kind of clear energy sources that is expected to replace fossil energy, and " hydrogen economy " notion is rooted in the hearts of the people.In the existing hydrogen producing technology, the borohydride hydrolytic hydrogen production technology is a kind of safe, technology of novel generation hydrogen easily, also is the Study on Technology focus of present catalysis generation hydrogen.Environmentally friendly, advantages such as hydrogen storage content is high, the easy control of hydrogen-producing speed that the boron hydride solution system has; For high capacity hydrogen storage and hydrogen producing technology provide a new way (Zhao J Z; Ma H; Chen J; International Journal of Hydrogen Engergy; 2007, (32): 4711-4716).
Boron hydride can be according to the dehydrogenation that is hydrolyzed of reactions formula:
NaBH
4+2H
2O→NaBO
2+4H
2
One of key technology of hydrogen energy source application technology is how to improve hydrogen production efficiency.Can know that from existing bibliographical information the character of catalyst for preparing hydrogen all has very significant effects to the hydrogen output and the hydrogen-producing speed of boron hydride solution hydrolysis.In the catalyst for preparing hydrogen of research, the catalytic performance of noble metal catalyst for preparing hydrogen is (Brown H C, Brown C A, Journal of the American Chemical Society, 1962, (84): 1493-1944 well at present; Hsueh C L; Chen C U; Ku J R, Journal of Power Sources, 2008; (177): 485-492); For example Ru base catalyst for preparing hydrogen dehydrogenation efficient when catalysis sodium borohydride solution hydrolytic hydrogen production of Steven C.Amendola research can reach (Steven C.Amendola, Stefanie L.Sharp-Goldman, M.Saleem Janjua more than 93%; International Journal of Hydrogen Energy, 2000 (25): 969-975).But the cost of considering the noble metal catalyst for preparing hydrogen is high, in practical application, is difficult to large-scale production, therefore the catalyst for preparing hydrogen that a kind of cost is low and catalytic efficiency is high need be provided.
At present, cheap transition metal catalyst for preparing hydrogen causes people's attention gradually, and human traditional chemical reducing process such as Bai Ying are synthetic, and under treatment of different temperature, obtain the Co-B alloy, and the table of discovery area is at 2.8～32m
2/ g, the Co-B that obtains under 500 ℃ of processing has the highest catalytic activity, and dehydrogenation efficient is 80～85%.(Bai Ying, Wu Feng, Wuchuan .Co
2The B alloy is at NaBH
4Application study in the on-the-spot hydrogen manufacturing. modern chemical industry, 2006,26 (4): 282-311) Wuchuan etc. through the solution chemistry reaction with two levels of thermal processing to obtain chemical composition be M
xThe metal boride catalyst of B except that containing metallic element and boron element, also is combined with H or O impurity through chemical bond or physical action in this catalyst, and dehydrogenation efficient is 86～96%.(Wuchuan; Wu Feng; Old reality; Dan Zhongqiang; Earlier firm. a kind of have highly active metal boride and preparation method thereof to hydrogen. Chinese patent. patent No. ZL200410088869.2) but the synthetic metal boride catalyst catalytic efficiency of said method is lower, and have that distribution of particles is inhomogeneous, the distribution of particles size is wide, contain problem such as dephasign.Therefore the borohydride hydrolytic hydrogen production catalyst of a kind of catalytic efficiency height, particle good dispersion, specific area height and size distribution homogeneous need be provided.
Summary of the invention
There is the high problem of cost to noble metal catalyst in the prior art; There is the problem that catalytic efficiency is lower, distribution of particles is inhomogeneous, the distribution of particles size is wide, contain dephasign in metal boride catalyst; One of the object of the invention is to provide a kind of borohydride hydrolytic hydrogen production catalyst; Said catalyst for preparing hydrogen; Cheap; Raw material obtain easily, and are active high, do not contain other impurity except that metallic element with the boron element.
Two of the object of the invention is to provide a kind of borohydride hydrolytic hydrogen production Preparation of catalysts method.The catalyst of said method preparation has the characteristics of good dispersion, specific area height and size distribution homogeneous.
For realizing above-mentioned purpose, technical scheme of the present invention is following:
A kind of borohydride hydrolytic hydrogen production catalyst: the chemical formula of said catalyst for preparing hydrogen is M
xB, wherein M is one or more metallic elements among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or the Mg, 1≤x≤4; Said catalyst for preparing hydrogen is for all disperseing boride material; Structural form is crystalline state or amorphous state.
The particle diameter of said catalyst for preparing hydrogen is 2nm～50 μ m; Specific area is 5m
2/ g～200m
2/ g.
A kind of borohydride hydrolytic hydrogen production Preparation of catalysts method, said method step is following:
Step 1, the solution that will contain soluble metallic salt add in the reactor, add that to use alkali or cushioning liquid to regulate the pH value be 7～14 the BH that contains again
4 -Solution, hybrid reaction obtains sediment 1;
Step 2, with behind sediment 1 usefulness detergent washing>=2 time, Separation of Solid and Liquid obtains sediment 2; Then sediment 2 is cooled to below-10 ℃, under vacuum≤10.0Pa, carries out application of vacuum then, obtain predecessor;
Step 3, predecessor is heat-treated under the starvation condition, obtain a kind of borohydride hydrolytic hydrogen production catalyst provided by the present invention, chemical formula is M
xB;
Wherein, the metallic element in the soluble metallic salt described in the step 1 is one or more among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or the Mg; Contain BH
4 -Solution in solute be one or more the mixture in potassium borohydride, sodium borohydride or the aluminium borohydride; Alkali is one or more the mixture in NaOH, NaOH, lithium hydroxide, ammoniacal liquor, sodium carbonate, sodium acid carbonate, potash, saleratus, calcium hydroxide, barium hydroxide, potassium dihydrogen phosphate or the sodium hydrogen phosphate; Cushioning liquid is a kind of in ammoniacal liquor-chloride buffer solution, borax-calcium chloride cushioning liquid or the borax-sodium carbonate cushioning liquid;
Washing agent in the step 2 is distilled water, deionized water, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol, acetone or MEK; Can use identical or different washing agent to wash respectively during washing; Solid-liquid separating method is the conventional means of chemical field; Vacuum processing time is 1h～48h;
Heat treatment temperature is 50 ℃～850 ℃ in the step 3, and heat treatment time is 1～48h.
Wherein, drip to add using alkali or cushioning liquid to regulate the pH value in the preferred steps one is 7～14 the BH that contains
4 -Solution, drop rate is 1mL/min～20mL/min; Mix and finish continued stirring 0.5h～1h; Mixing condition is that supersonic oscillations, glass bar stir, a kind of in electronic stirring or the magnetic agitation.
Wherein, in the preferred steps one reactor is placed-20 ℃～4 ℃ environment.
Wherein, the process of in the preferred steps two sediment 2 being reduced to below-10 ℃ is: sediment 2 is put into cold-trap, reduce to-10 ℃～-200 ℃ with cold-trap, rate of temperature fall is 5～90 ℃/min; Cooling time is 1h～12h.
Wherein, The process of in the preferred steps two sediment 2 being reduced to below-10 ℃ is: condenser temperature is reduced to-10 ℃～-200 ℃; Sediment 2 placed >=1 hour in the liquid nitrogen of 0 ℃～-20 ℃ refrigerator or-196 ℃～-209 ℃ after, put into the freezing 1h～12h of cold-trap.
Wherein, in the step 3 starvation condition for charging into inert gas or vacuum≤10.0Pa; Inert gas is Ar gas or N
2Gas.
Beneficial effect
1. borohydride hydrolytic hydrogen production catalyst M of the present invention
xB is the base metal catalyst for preparing hydrogen, and cost is low, can in reality, carry out large-scale production; Structure and functional has high catalytic activity, and the dehydrogenation rate can reach more than 95%; Form in order to divide equally, shape is identical by loose powder body particle for said catalyst for preparing hydrogen, and particle size distribution is narrow, does not have the particle of reuniting between the particle;
2. a kind of borohydride hydrolytic hydrogen production Preparation of catalysts method of the present invention, have the early stage be swift in response, subsequent processes is simple and convenient, workable advantage;
3. preparation method according to the invention contains BH through dropping in the step 1
4 -Solution with drip to finish continued and stir, reaction is carried out fully;
4. preparation method according to the invention; Hybrid reaction obtains sediment 1 and is exothermic reaction in the step 1, reactor is placed-20 ℃～4 ℃ environment, can reduce the temperature of reaction system; Make reaction temperature and carry out, prevent that the particle of sediment 1 from reuniting the growth change greatly because of heat;
5. preparation method according to the invention; Make sediment 2 at first be in frozen state through refrigerating process in the step 2; Pass through application of vacuum then; Make that liquid is removed through sublimation process in the sediment 2; Avoided the hole collapse phenomenon that caused because of the capillary effect of solid liquid interface; The institutional framework and the pore size distribution of dry postprecipitation thing 2 are preserved to greatest extent, can suppress the generation of particle hard aggregation effectively, obtain the catalyst for preparing hydrogen particle of specific area height, size distribution homogeneous;
6. preparation method according to the invention, the predecessor in the step 3 is heat-treated under the starvation condition, has effectively avoided the generation of oxidation reaction.
Description of drawings
The X-ray spectrum diffraction pattern of a kind of borohydride hydrolytic hydrogen production catalyst that Fig. 1 prepares for embodiment 1.
The X-ray spectrum diffraction pattern of a kind of borohydride hydrolytic hydrogen production catalyst that Fig. 2 prepares for embodiment 2.
The sem photograph of a kind of borohydride hydrolytic hydrogen production catalyst that Fig. 3 prepares for embodiment 2.
The specific embodiment
Describe the present invention in detail through specific embodiment below:
Detect through following instrument and method end product embodiment of the invention 1-9:
Form through Inductive Coupled Plasma Emission Spectrometer (IRIS/AP, Thermo Jarrell Ash) analytical element, obtain the chemical composition of end product; On NOVA 1200e nitrogen absorption specific surface analyzer, measure the specific area of end product; Carry out pattern with JEOL JSM-6301F ESEM and characterize, can obtain the particle size values of end product; Adopt Rigaku DMAX2400 type X-ray diffractometer to characterize the structural form of end product.
Detect the dehydrogenation activity of the end product of embodiment of the invention 1-9 through following method:
With NaBH
4Solution places reactor, then end product is added in the reactor; The hydrogen that produces is via the gas flowmeter recording volume.The hydrogen volume of gas flowmeter physical record is a dehydrogenation efficient with the ratio of the hydrogen volume that should produce in theory.
Embodiment 1
Reactor is placed 4 ℃ of environment, under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 1mL/min, dropwise drip excessive NaBH again with NaOH adjust pH to 12
4(0.5mol/L 100mL), drip to finish continued and stirs 0.5h solution, reacts completely guaranteeing, obtains sediment 1.The sediment 1 of gained is spent suction filtration after the deionised water three times, obtain sediment 2.Sediment 2 is put into cold-trap, reduce to-90 ℃ with cold-trap, rate of temperature fall is 15 ℃/min, freezing 3h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 24h under-90 ℃ the condition, obtains presoma.Presoma in Ar atmosphere, with 400 ℃ of calcining 4h, is obtained end product in the tube furnace.Through detecting said end product chemical composition is Co
2.01B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.Fig. 1 is the X-ray spectrum diffraction pattern of embodiment 1 end product, contains a plurality of very narrow " spike " independent of each other among the figure, and characteristic peak wherein is Co
3The diffraction maximum of B, CoB and Co shows that end product is a crystalline state.From sem photograph, can obtain said end product for dividing equally the loose powder body, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that the specific area of said end product is 36.04m
2/ g, particle diameter are 300nm, and dehydrogenation efficient is 97.5%.
Embodiment 2
Reactor is placed 4 ℃ of environment, under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 5mL/min, dropwise drip excessive NaBH again with NaOH adjust pH to 12
4(0.1mol/L 100mL), drip to finish continued and stirs 0.5h solution, reacts completely guaranteeing, drives bubble hydrogen away, obtains sediment 1.The sediment 1 of gained is spent suction filtration after the deionised water three times, obtain sediment 2.Sediment 2 is put into cold-trap, reduce to-90 ℃ with cold-trap, rate of temperature fall is 15 ℃/min, freezing 3h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 6h under-90 ℃ the condition, obtains presoma.With presoma 50 ℃ of heat treatment 48h under vacuum≤10.0Pa condition, obtain end product.Through detecting said end product chemical composition is Co
2.05B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.Fig. 2 is the X-ray spectrum diffraction pattern of embodiment 2 end products, in whole scanning angle scope, only observes the mild variation of the X ray intensity that is scattered, and no obvious characteristics peak shows that end product is an amorphous state.Detect to such an extent that the specific area of said end product is 23.39m
2/ g; Fig. 3 be embodiment 2 end products sem photograph, can obtain particle diameter is 1 μ m, for dividing equally the loose powder body, promptly particle is formed, shape is identical, particle size distribution is narrow, not have the particle of reunion between the particle.The dehydrogenation efficient that records said end product is 96.4%.
Embodiment 3
Reactor is placed-8 ℃ of environment, under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 5mL/min, dropwise drip excessive NaBH again with ammoniacal liquor adjust pH to 12
4(0.5mol/L 100mL), drip to finish continued and stirs 0.5h solution, reacts completely guaranteeing, drives bubble hydrogen away, obtains sediment 1.With the sediment 1 usefulness absolute ethanol washing of gained 3 times, suction filtration after the deionized water washing 1 time obtains sediment 2, in-4 ℃ refrigerator, places 1 hour.Condenser temperature is reduced to-90 ℃, again the sediment of placing 1 hour in-4 ℃ of refrigerators 2 is put into cold-trap, freezing 6h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 48h under-90 ℃ the condition, obtains presoma.Presoma is calcined 1h with 500 ℃ in Ar atmosphere tube type stove, obtain end product.Through detecting said end product chemical composition is Co
2B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that said end product is a crystalline state.From sem photograph, can obtain said end product for dividing equally the loose powder body, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that said end product specific area is 71.4m
2/ g, particle diameter are 100nm, and dehydrogenation efficient is 98.6%.
Embodiment 4
Reactor is placed-8 ℃ of environment, under the magnetic stirrer condition, with 0.2mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 10mL/min, dropwise drip excessive NaBH again with KOH adjust pH to 12
4(1.0mol/L 100mL), drip to finish continued and stirs 1h solution, reacts completely guaranteeing, drives bubble hydrogen away, obtains sediment 1.The sediment 1 of gained is spent suction filtration after the deionised water three times, obtain sediment 2, in-196 ℃ liquid nitrogen, placed 2 hours.Condenser temperature is reduced to-200 ℃, the sediment 2 that will in-196 ℃ liquid nitrogen, place 2 hours is put into cold-trap freezing 1h under-200 ℃ again.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 3, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 24h under-200 ℃ the condition, obtains presoma.Presoma is calcined 12h with 300 ℃ under the argon gas atmosphere in tube furnace, obtain end product.Through detecting said end product chemical composition is Co
1.85B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that said end product is a crystalline state.From sem photograph, can obtain said end product for dividing equally the loose powder body, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that said end product specific area is 198.2m
2/ g, particle diameter are 2nm, and dehydrogenation efficient is 99.3%.
Embodiment 5
Under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 10mL/min, dropwise drip NaBH again with NaOH adjust pH to 14
4(0.5mol/L 100mL), drip to finish continued and stirs 0.5h solution, reacts completely guaranteeing, drives bubble hydrogen away, obtains sediment 1.Sediment 1 is spent suction filtration after the deionised water 5 times, obtain sediment 2.Condenser temperature is reduced to-90 ℃, again sediment 2 is put into cold-trap, freezing 12h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 12h under-90 ℃ the condition, obtains presoma.Presoma is calcined 36h with 700 ℃ under the argon gas in tube furnace, obtain end product.Through detecting said end product chemical composition is Co
1.23B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that said end product is a crystalline state.From sem photograph, can obtain said end product for dividing equally the loose powder body, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that said end product specific area is 10.59m
2/ g, particle diameter are 20 μ m, and dehydrogenation efficient is 95.6%.
Embodiment 6
Under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 20mL/min, dropwise drip the NaBH of the 0.5mol/L that contains ammoniacal liquor-chloride buffer solution again
4Solution, to the pH value of solution value be 8.Drip to finish continued and stir 0.5h, react completely guaranteeing, drive bubble hydrogen away, obtain sediment 1.Sediment 1 is spent suction filtration after the deionised water 3 times, obtain sediment 2.Condenser temperature is reduced to-10 ℃, again sediment 2 is put into cold-trap freezing 12h under-10 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 1h under-10 ℃ the condition, obtains presoma.With presoma in tube furnace under the argon gas atmosphere 850 ℃ the calcining 24h, obtain end product.Through detecting said end product chemical composition is Co
2.79B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that said end product is a crystalline state.From sem photograph, can obtain said end product for dividing equally the loose powder body, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that said end product specific area is 5.23m
2/ g, particle diameter are 50 μ m, and dehydrogenation efficient is 95.2%.
Embodiment 7
There-necked flask is placed-20 ℃ of environment, under electronics agitator stirring condition, with 100mLCoCl
2And NiCl
2Mixed solution (Co is 1: 1 with the ratio of the amount of substance of Ni) places in the there-necked flask, is 10 5wt%NaBH again with the pH value
4+ 1wt%NaOH solution 100mL dropwise adds in the there-necked flask with 5mL/min speed under the effect of peristaltic pump, fully carries out NaBH in order to ensure reduction reaction
4With the amount of substance ratio of metallic atom be 5: 1.Drip and finish continued stirring 0.5h, obtain sediment 1.The sediment 1 of gained is spent suction filtration after the deionised water 4 times, obtain sediment 2.Condenser temperature is reduced to-80 ℃, again sediment 2 is put into cold-trap freezing 3h under-80 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 24h under-80 ℃ the condition, obtains presoma.With presoma in tube furnace under the argon gas atmosphere 400 ℃ the calcining 4h, obtain end product.Through detecting said end product chemical composition is Co
1.05Ni
1.01B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that said end product is a crystalline state.From sem photograph, can obtain said end product for dividing equally the loose powder body, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that said end product specific area is 41.06m
2/ g, particle diameter are 200nm, and dehydrogenation efficient is 98.2%.
Embodiment 8
There-necked flask is placed 0 ℃ of ice bath environment, under the glass bar stirring condition, with 100 milliliters of CoCl
2And MgCl
2Mixed solution (Co is 5: 1 with the ratio of the amount of substance of Mg) places in the there-necked flask, and will use 100mL sodium carbonate and NaOH to transfer pH again is 12 NaBH
4Solution 100mL is as reducing agent, dropwise adds in the there-necked flask in order to 7.5mL/min speed at the work of peristaltic pump, drips to finish continued and stir 45min and obtain sediment 1.With the sediment 1 usefulness distilled water of gained washing 3 times, suction filtration behind the absolute ethanol washing 1 time obtains sediment 2.Condenser temperature is reduced to-90 ℃, again sediment 2 is put into cold-trap freezing 3h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 24h under-90 ℃ the condition, obtains presoma.With presoma N in tube furnace
2With 400 ℃ of calcining 4h, obtain end product under the atmosphere.Through detecting said end product chemical composition is Co
2.07Mg
1.89B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that said end product is a crystalline state.From sem photograph, can obtain said end product for dividing equally the loose powder body, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that said end product specific area is 47.51m
2/ g, particle diameter are 200nm, and dehydrogenation efficient is 98.2%.
Embodiment 9
Reactor is placed 4 ℃ of environment, under the supersonic oscillations condition, with 0.1mol/L, the FeCl of 100mL
3Solution adds in the reactor.With the speed of 1mL/min, dropwise drip excessive KBH again with saleratus and potassium hydroxide adjust pH to 12
4(0.5mol/L 100mL), drip to finish continued vibration 0.5h to solution, reacts completely guaranteeing, obtains sediment 1.Sediment 1 is spent deionised water 2 times, and suction filtration behind the washing with acetone 1 time obtains sediment 2.Sediment 2 is put into cold-trap, reduce to-90 ℃ with cold-trap, rate of temperature fall is 15 ℃/min.Be incubated 3h down at-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum≤10.0Pa (under this experimental technique condition vacuum remain on≤10.0Pa gets final product, vacuum is constantly to change in the actual experiment process), temperature carries out application of vacuum 24h under-90 ℃ the condition, obtains presoma.With presoma N in tube furnace
2With 500 ℃ of calcining 1h, obtain end product under the atmosphere.Through detecting said end product chemical composition is Fe
2B is a kind of borohydride hydrolytic hydrogen production catalyst of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that said end product is a crystalline state.From sem photograph, can obtain said end product for dividing equally the loose powder body, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that said end product specific area is 30.24m
2/ g, particle diameter are 600nm, and dehydrogenation efficient is 96.9%.
In sum, more than be preferred embodiment of the present invention only, be not to be used to limit protection scope of the present invention.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. borohydride hydrolytic hydrogen production catalyst, it is characterized in that: the chemical formula of said catalyst for preparing hydrogen is M
xB, wherein M is one or more metallic elements among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or the Mg, 1≤x≤4; Said catalyst for preparing hydrogen is for all disperseing boride material; Structural form is crystalline state or amorphous state.
2. a kind of borohydride hydrolytic hydrogen production catalyst according to claim 1 is characterized in that: the particle diameter of said catalyst for preparing hydrogen is 2nm～50 μ m; Specific area is 5m
2/ g～200m
2/ g.
3. borohydride hydrolytic hydrogen production Preparation of catalysts method as claimed in claim 1 is characterized in that: concrete preparation process is following:
Step 1, the solution that will contain soluble metallic salt add in the reactor, and adding excessive use alkali or cushioning liquid again, to regulate the pH value be 7～14 the BH that contains
4 -Solution, hybrid reaction obtains sediment 1;
Step 2, with behind sediment 1 usefulness detergent washing>=2 time, Separation of Solid and Liquid obtains sediment 2; Then sediment 2 is cooled to below-10 ℃, under vacuum≤10.0Pa, carries out application of vacuum then, obtain predecessor;
Step 3, predecessor is heat-treated under the starvation condition, obtaining chemical formula is M
xA kind of borohydride hydrolytic hydrogen production catalyst of B;
Wherein, the metallic element in the soluble metallic salt described in the step 1 is one or more among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or the Mg; Contain BH
4 -Solution in solute be one or more the mixture in potassium borohydride, sodium borohydride or the aluminium borohydride; Alkali is one or more the mixture in NaOH, NaOH, lithium hydroxide, ammoniacal liquor, sodium carbonate, sodium acid carbonate, potash, carbon calcium, barium hydroxide, potassium dihydrogen phosphate or the sodium hydrogen phosphate; Cushioning liquid is a kind of in ammoniacal liquor-chloride buffer solution, borax-calcium chloride cushioning liquid or the borax-sodium carbonate cushioning liquid;
Washing agent in the step 2 is distilled water, deionized water, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol, acetone or MEK; Can use identical or different washing agent to wash respectively during washing; Vacuum processing time is 1h～48h;
Heat treatment temperature is 50 ℃～850 ℃ in the step 3, and heat treatment time is 1～48h.
4. a kind of borohydride hydrolytic hydrogen production Preparation of catalysts method according to claim 3 is characterized in that: adding use alkali or cushioning liquid adjusting pH value are 7～14 the BH that contains in the step 1
4 -Solution, be to drip with the speed of 1mL/min～20mL/min; Drip and finish continued mixing 0.5h～1h; Mixing condition is that supersonic oscillations, glass bar stir, a kind of in electronic stirring or the magnetic agitation.
5. a kind of borohydride hydrolytic hydrogen production Preparation of catalysts method according to claim 3 is characterized in that: in the step 1 reactor is placed-20 ℃～4 ℃ environment.
6. a kind of borohydride hydrolytic hydrogen production Preparation of catalysts method according to claim 3; It is characterized in that: the process of in the step 2 sediment 2 being reduced to below-10 ℃ is: sediment 2 is put into cold-trap; Be cooled to-10 ℃～-200 ℃ with cold-trap, rate of temperature fall is 5～90 ℃/min; Cooling time is 1h～12h.
7. a kind of borohydride hydrolytic hydrogen production Preparation of catalysts method according to claim 3; It is characterized in that: the process of in the step 2 sediment 2 being reduced to below-10 ℃ is: condenser temperature is reduced to-10 ℃～-200 ℃; Sediment 2 placed >=1 hour in the liquid nitrogen of 0 ℃～-20 ℃ refrigerator or-196 ℃～-209 ℃ after, put into the freezing 1h～12h of cold-trap.
8. a kind of borohydride hydrolytic hydrogen production method for preparing catalyst according to claim 3 is characterized in that: the starvation condition is for charging into inert gas or vacuum≤10.0Pa in the step 3; Inert gas is Ar gas or N
2Gas.
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| CN102824913A (en) * | 2012-09-11 | 2012-12-19 | 中国计量学院 | Preparation method of catalyst for hydrolyzing sodium borohydride to prepare hydrogen |
| CN102950009A (en) * | 2012-10-12 | 2013-03-06 | 南京大学 | Load type CoB catalyst for process of preparing hydrogen through hydrolysis of sodium borohydride and preparation method of load type CoB catalyst |
| CN103145098A (en) * | 2013-03-04 | 2013-06-12 | 长安大学 | Solid hydrogen storage material and preparation method thereof |
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