CN108862191B - Sodium borohydride hydrolysis hydrogen production unit - Google Patents

Sodium borohydride hydrolysis hydrogen production unit Download PDF

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CN108862191B
CN108862191B CN201810936186.XA CN201810936186A CN108862191B CN 108862191 B CN108862191 B CN 108862191B CN 201810936186 A CN201810936186 A CN 201810936186A CN 108862191 B CN108862191 B CN 108862191B
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catalyst
sodium borohydride
hydrogen production
production unit
aqueous solution
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CN108862191A (en
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李海龙
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Harbin Haiwei Zhixin Technology Co ltd
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Shenzhen Yahua Weiyi Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides a sodium borohydride hydrolysis hydrogen production unit. The hydrogen production unit comprises a first catalytic section and a second catalytic section, wherein Co-loaded active alumina is arranged in the first catalytic section for the first time as a first catalyst, and the incomplete coordination of aluminum atoms on the surface of the active alumina is utilized to ensure that the active alumina has certain acidity; then, the heated sodium borohydride enters a second catalytic section to contact with a second catalyst loaded with Co-B foamed nickel to produce hydrogen, and the hydrogen production speed is finally improved. Meanwhile, the first catalyst and the second catalyst are matched with each other, so that the durability of the sodium borohydride hydrolysis hydrogen production unit is improved, and the whole hydrogen production process is continuously and stably carried out.

Description

Sodium borohydride hydrolysis hydrogen production unit
Technical Field
The invention relates to the technical field of hydrogen production, in particular to a sodium borohydride hydrolysis hydrogen production unit
Background
Hydrogen energy has been receiving much attention as one of clean energy. The storage modes of hydrogen include: storage in molecular form in pressure vessels, storage in liquefied hydrogen tanks, storage in carbon materials, and storage in Metal Hydrides (MH), metal aluminum hydrides and metal borohydrides, etc.
The sodium borohydride hydrolysis hydrogen production has the advantages of high hydrogen storage capacity, mild hydrolysis condition, controllable reaction and the like, and is an ideal hydrogen source of the fuel cell. The chemical equation for the hydrolysis reaction of sodium borohydride is as follows: NaBH4+4H2O→NaBO2+4H2And ℃,. at 25 ℃ in the standard state, the enthalpy change of the reaction process is-217 kJ, and the reaction is exothermic.
The above reaction proceeds without a catalyst, but the reaction rate is slow. When different catalysts are used, the generation speed of hydrogen is different, and the influence of various metal catalysts on the hydrolysis speed of sodium borohydride is also different. Noble metal-based catalysts, particularly ruthenium (Ru) and platinum (Pt), have proven to be effective sodium borohydride hydrolysis catalysts. However, due to the low precious metal content and high cost, inexpensive transition metal based catalysts would be a desirable alternative. Most of the existing transition metal catalysts are metal catalysts composed of NixB, Ni powder and Co powder, but the catalysts have the disadvantages of too long start-up time, low hydrogen production speed and poor durability.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of overlong starting time, lower hydrogen production speed and poor durability of the sodium borohydride hydrolysis hydrogen production catalyst in the prior art, and further provide the sodium borohydride hydrolysis hydrogen production unit with short starting time, high hydrogen production speed and good durability.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a sodium borohydride hydrolysis hydrogen production unit comprises a first catalytic section and a second catalytic section, wherein a first catalyst is arranged in the first catalytic section, the first catalyst is active alumina loaded with Co, a second catalyst is arranged in the second catalytic section, and the second catalyst is foamed nickel loaded with Co-B.
Further, the mass ratio of Co to alumina in the Co-loaded activated alumina is (10-20): 100, respectively;
the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is (26-201): 100.
Further, still including being cylindric casing, along the axial of casing, first catalysis section and second catalysis section set gradually in on the casing.
Further, the shell is obtained by rolling a plurality of circles of sheet-shaped base materials to form a cylinder, a gap exists between every two adjacent circles, and the first catalyst and the second catalyst are both arranged on the surfaces of the base materials on the two sides of the gap.
Further, the preparation method of the first catalyst comprises the following steps:
dipping activated alumina into a cobalt-containing aqueous solution for the first dipping;
and sequentially carrying out primary drying and primary calcining on the first impregnated activated alumina to obtain the first catalyst.
Further, the mass fraction of the cobalt-containing aqueous solution is 20-30%, and the time for first impregnation is 20-28 h; preferably, the aqueous solution containing cobalt is an aqueous solution of cobalt chloride, and the first impregnation is performed under vacuum;
the temperature of the first drying is 140-160 ℃, and the time is 8-16 h; preferably, the first drying is performed under vacuum;
the first calcination is calcination under inert atmosphere, the temperature of the first calcination is 270-330 ℃, and the time is 2-3 h.
Further, before the first impregnation, the method also comprises the steps of placing the activated alumina in deionized water, carrying out ultrasonic oscillation for 5-10min, and then drying at 140-160 ℃ for 8-16 h;
and adding phosphoric acid into the cobalt-containing aqueous solution until the concentration of the phosphoric acid is 1-1.5 mol/L.
preferably, the activated alumina is α type activated alumina and/or gamma-type activated alumina.
Further, the preparation method of the second catalyst comprises the following steps:
soaking the foamed nickel in an aqueous solution containing a cobalt compound and hypophosphite for the second time;
reducing the foamed nickel after the second impregnation by using an aqueous solution of sodium borohydride and sodium hydroxide;
and sequentially carrying out secondary drying and secondary calcining on the reduced foam nickel to obtain the second catalyst.
Further, the concentration of the cobalt-containing compound in the aqueous solution of the cobalt-containing compound and hypophosphite is 0.4-0.5mol/L, and the concentration of the hypophosphite is 0.4-0.5 mol/L; preferably, the cobalt-containing compound is cobalt chloride and the hypophosphite is sodium hypophosphite.
The concentration of sodium borohydride in the aqueous solution of sodium borohydride and sodium hydroxide is 1.0-1.2mol/L, and the concentration of sodium hydroxide is 0.25-0.30 mol/L;
preferably, 5ml of aqueous solution of sodium borohydride and sodium hydroxide is slowly dropped above the foamed nickel after the reduction to the second impregnation, so that the aqueous solution of sodium borohydride and sodium hydroxide slowly covers the whole foamed nickel, then the foamed nickel is turned over, and 5ml of aqueous solution of sodium borohydride and sodium hydroxide is slowly dropped on the other side of the foamed nickel, so that the aqueous solution of sodium borohydride and sodium hydroxide slowly covers the whole foamed nickel;
the temperature of the secondary drying is 50-70 ℃;
the second calcination is calcination under inert atmosphere, the temperature of the second calcination is 230-270 ℃, and the time is 2-3 h.
Further, before the second impregnation, immersing the foamed nickel into a hydrochloric acid aqueous solution with the concentration of 0.1-0.3% by mass fraction, after ultrasonic oscillation for 5-10min, immersing the foamed nickel into ethanol again, performing ultrasonic oscillation for 5-10min, and finally drying;
after the reduction and before the second drying, the method also comprises the step of washing the reduced foam nickel in deionized water at 70-80 ℃.
Preferably, the porosity of the nickel foam is not less than 98%.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the sodium borohydride hydrolysis hydrogen production unit comprises a first catalytic section and a second catalytic section, wherein Co-loaded active alumina is arranged in the first catalytic section for the first time and is used as a first catalyst, aluminum atoms on the surface of the active alumina are not completely coordinated, so that the active alumina has certain acidity, and in the catalytic process, the pH value of a solution can be reduced to a certain extent due to the acidity, so that the hydrolysis reaction rate is accelerated, the reaction starting time is greatly shortened, and the effect of heating and warming sodium borohydride is achieved; then, the heated sodium borohydride enters a second catalytic section to contact with a second catalyst loaded with Co-B foamed nickel to produce hydrogen, and the hydrogen production speed is finally improved. Meanwhile, the first catalyst and the second catalyst are matched with each other, so that the durability of the sodium borohydride hydrolysis hydrogen production unit is improved, and the whole hydrogen production process is continuously and stably carried out.
(2) According to the sodium borohydride hydrogen production unit provided by the invention, the mass ratio of Co to alumina in the Co-loaded active alumina and the mass ratio of Co-B to nickel foam in the Co-B-loaded nickel foam are reasonably configured, so that the whole hydrogen production process is further optimized, the short starting time is ensured, and the durability of the sodium borohydride hydrogen production unit can be maintained. The first catalyst is doped with phosphorus for modification, so that the hydrolysis reaction rate can be further improved, and the reaction starting time is shorter.
(3) The sodium borohydride hydrolysis hydrogen production unit provided by the invention is provided with a cylindrical shell, and a first catalytic section and a second catalytic section are sequentially arranged on the inner part of the shell along the axial direction of the shell; more specifically, the shell is obtained by rolling a sheet-shaped substrate into a cylinder by a plurality of circles, a gap exists between every two adjacent circles, and the first catalyst and the second catalyst are both arranged on the surfaces of the substrates on the two sides of the gap, so that sodium borohydride solution can be conveniently and fully contacted with the corresponding catalysts through the first catalytic section and the second catalytic section in sequence.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a schematic diagram of the reaction start-up time of a sodium borohydride hydrolysis hydrogen production unit in examples 1-7 of the present invention;
FIG. 2 is a schematic diagram showing the reaction start-up time of a sodium borohydride hydrolysis hydrogen production unit in a comparative example of the present invention;
FIG. 3 is a graph showing the catalytic efficiency of 15% mass fraction sodium borohydride solution in examples 1-3 of the present invention;
FIG. 4 is a graph showing the catalytic efficiency of 25% by mass sodium borohydride solution in examples 1-3 of the present invention;
fig. 5 is a schematic view of the overall structure of a sodium borohydride hydrolysis hydrogen production unit in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "first", "second", "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The embodiment provides a sodium borohydride hydrolysis hydrogen production unit, as shown in fig. 5, which includes a first catalytic section and a second catalytic section, a first catalyst is disposed in the first catalytic section, the first catalyst is Co-loaded activated alumina, a second catalyst is disposed in the second catalytic section, the second catalyst is Co-B-loaded nickel foam, wherein a mass ratio of Co to alumina in the Co-loaded activated alumina is 15: 100, respectively; the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is 71: 100;
the preparation method of the first catalyst comprises the following steps:
1. and (3) cleaning and drying the carrier: taking 20g of gamma-type activated alumina, and putting the gamma-type activated alumina into deionized water for ultrasonic oscillation for 5min to remove surface impurities and loose powder; then taking out the activated alumina, putting the activated alumina into a vacuum oven at 140 ℃ for drying for 8 hours, and fully dehydrating;
2. solution preparation: CoCl with the mass fraction of 25 percent2100ml of the aqueous solution, fully stirring to completely dissolve;
3. catalyst loading: putting the fully dried activated alumina into the prepared CoCl2In the aqueous solution, putting a beaker filled with the mixture into a vacuum box, removing bubbles in the solution, and soaking for 20 hours to ensure that the solution is fully immersed into the carrier; then taking out the active alumina carrier in the solution, and putting the active alumina carrier in a drying oven at 140 ℃ for drying for 8 hours to complete the loading of the catalyst;
4. and (3) calcining: and (3) putting the dried catalyst into a tubular furnace, introducing argon protective gas, and calcining for 2 hours at 270 ℃ to ensure that the catalyst is supported more firmly.
The preparation method of the second catalyst comprises the following steps:
1. cutting: cutting off a large piece of foam nickel according to the required size by using a scalpel, wherein the size of the cut piece is 5cm x 13cm, the edge is required to be neat during cutting, and weighing after cutting;
2. solution preparation: two solutions are required: CoCl2With NaH2PO2For soaking a foamed nickel support, CoCl2Has a concentration of 0.4mol/L, NaH2PO2The concentration of (A) is 0.4 mol/L; NaBH4With an alkaline aqueous solution of NaOH for reduction on the surface of the support, in which NaBH is present4The concentration of 1.0mol/L, NaOH is 0.25 mol/L;
3. cleaning a foamed nickel carrier: immersing the prepared nickel foam into a dilute HCl solution with the mass fraction of 0.2%, and ultrasonically oscillating for 8min to remove oxides and other impurities on the surface; then putting the foamed nickel into absolute ethyl alcohol, and ultrasonically cleaning for 8min to remove impurities such as HCl, oil stains and the like; finally, putting the mixture into a thermostat for drying until the surface impurities are completely volatilized;
4. catalyst loading: 200ml of CoCl was taken2With NaH2PO2Putting the water solution into a beaker, putting clean and dry foam nickel into the solution for soaking, taking out after completely soaking, putting the arch upwards, and slowly dripping 5ml of NaBH in the middle of the arch4The mixed aqueous solution of NaOH is used for slowly covering the whole foam nickel sheet as much as possible; then reversing the foamed nickel, and slowly dripping 5ml of mixed solution from two sides respectively to ensure that the reduction reaction is uniformly carried out on the surface of the whole foamed nickel carrier; after dropwise adding, putting the foam nickel into deionized water at 70 ℃ for rinsing, and removing NaBO in pores2(ii) a And finally, putting the foamed nickel into a 60 ℃ oven for drying. This is a primary loading process, and the loading is repeated for a total of 30 times;
5. and (3) calcining: and (3) putting the supported catalyst into a calcining furnace, introducing argon as a protective gas, slowly raising the temperature to 250 ℃ for 2 hours, slowly cooling to room temperature, and taking out.
The starting time test is carried out on the sodium borohydride hydrolysis hydrogen production unit, and the test steps are as follows:
1. preparing a conical gas washing bottle which needs to be good in air tightness;
2. putting the hydrogen production unit into a conical gas washing bottle to ensure that the hydrogen production unit can be directly contacted with the catalyst after liquid is dropped;
3. the air inlet end of the bottle is connected with 1 syringe with the volume of 1ml, and the syringe is filled with 15 percent of NaBH by mass fraction4The air outlet end of the aqueous solution is connected into a beaker filled with water;
4. rapidly injecting liquid into the container, starting timing, stopping timing after the air outlet end starts to stably generate bubbles, and recording the time as starting duration;
5. measuring again after cooling, measuring for 5 times in total, and taking an average value;
the test results are shown in FIG. 1, with a start-up time of 3.0 s.
Example 2
The embodiment provides a sodium borohydride hydrolysis hydrogen production unit, which comprises a first catalytic section and a second catalytic section, wherein a first catalyst is arranged in the first catalytic section, the first catalyst is active alumina loaded with Co, a second catalyst is arranged in the second catalytic section, the second catalyst is foamed nickel loaded with Co-B, and the mass ratio of Co to alumina in the active alumina loaded with Co is 15: 100, respectively; the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is 48: 100;
the preparation method of the first catalyst comprises the following steps:
1. and (3) cleaning and drying the carrier: taking 20g of gamma-type activated alumina, and putting the gamma-type activated alumina into deionized water for ultrasonic oscillation for 5min to remove surface impurities and loose powder; then taking out the activated alumina, putting the activated alumina into a vacuum oven at 140 ℃ for drying for 8 hours, and fully dehydrating;
2. solution preparation: CoCl with the mass fraction of 25 percent2100ml of the aqueous solution, fully stirring to completely dissolve;
3. catalyst loading: putting the fully dried activated alumina into the prepared CoCl2In the aqueous solution, putting a beaker filled with the mixture into a vacuum box, removing bubbles in the solution, and soaking for 20 hours to ensure that the solution is fully immersed into the carrier; then taking out the active alumina carrier in the solution, and putting the active alumina carrier in a drying oven at 140 ℃ for drying for 8 hours to complete the loading of the catalyst;
4. and (3) calcining: and (3) putting the dried catalyst into a tubular furnace, introducing argon protective gas, and calcining for 2 hours at 270 ℃ to ensure that the catalyst is supported more firmly.
The preparation method of the second catalyst comprises the following steps:
1. cutting: cutting off a large piece of foam nickel according to the required size by using a scalpel, wherein the size of the cut piece is 5cm x 13cm, the edge is required to be neat during cutting, and weighing after cutting;
2. solution preparation: two solutions are required: CoCl2With NaH2PO2For soaking a foamed nickel support, CoCl2Has a concentration of 0.5mol/L, NaH2PO2The concentration of (A) is 0.5 mol/L; NaBH4With an alkaline aqueous solution of NaOH for reduction on the surface of the support, in which NaBH is present4The concentration of 1.2mol/L, NaOH is 0.30 mol/L;
3. cleaning a foamed nickel carrier: immersing the prepared nickel foam into a dilute HCl solution with the mass fraction of 0.1%, and ultrasonically oscillating for 5min to remove oxides and other impurities on the surface; then putting the foamed nickel into absolute ethyl alcohol, and ultrasonically cleaning for 5min to remove impurities such as HCl, oil stains and the like; finally, putting the mixture into a thermostat for drying until the surface impurities are completely volatilized;
4. catalyst loading: 200ml of CoCl was taken2With NaH2PO2Putting the water solution into a beaker, putting clean and dry foam nickel into the solution for soaking, taking out after completely soaking, putting the arch upwards, and slowly dripping 5ml of NaBH in the middle of the arch4The mixed aqueous solution of NaOH is used for slowly covering the whole foam nickel sheet as much as possible; then reversing the foamed nickel, and slowly dripping 5ml of mixed solution from two sides respectively to ensure that the reduction reaction is uniformly carried out on the surface of the whole foamed nickel carrier; after dropwise adding, putting the foam nickel into deionized water at 70 ℃ for rinsing, and removing NaBO in pores2(ii) a And finally, putting the foamed nickel into a 50 ℃ oven for drying. This is a primary loading process, and the loading is repeated for a total of 20 times;
5. and (3) calcining: and (3) putting the supported catalyst into a calcining furnace, introducing argon as a protective gas, slowly raising the temperature to 230 ℃ for 2 hours, slowly cooling to room temperature, and taking out.
The start-up time test was performed on the above-described sodium borohydride hydrolysis hydrogen production unit, the test procedure was as in example 1, the test result is shown in fig. 1, and the start-up time was 3.4 s.
Example 3
The embodiment provides a sodium borohydride hydrolysis hydrogen production unit, which comprises a first catalytic section and a second catalytic section, wherein a first catalyst is arranged in the first catalytic section, the first catalyst is active alumina loaded with Co, a second catalyst is arranged in the second catalytic section, the second catalyst is foamed nickel loaded with Co-B, and the mass ratio of Co to alumina in the active alumina loaded with Co is 15: 100, respectively; the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is 26: 100;
the preparation method of the first catalyst comprises the following steps:
1. and (3) cleaning and drying the carrier: taking 20g of gamma-type activated alumina, and putting the gamma-type activated alumina into deionized water for ultrasonic oscillation for 5min to remove surface impurities and loose powder; then taking out the activated alumina, putting the activated alumina into a vacuum oven at 140 ℃ for drying for 8 hours, and fully dehydrating;
2. solution preparation: CoCl with the mass fraction of 25 percent2100ml of the aqueous solution, fully stirring to completely dissolve;
3. catalyst loading: putting the fully dried activated alumina into the prepared CoCl2In the aqueous solution, putting a beaker filled with the mixture into a vacuum box, removing bubbles in the solution, and soaking for 20 hours to ensure that the solution is fully immersed into the carrier; then taking out the active alumina carrier in the solution, and putting the active alumina carrier in a drying oven at 140 ℃ for drying for 8 hours to complete the loading of the catalyst;
4. and (3) calcining: and (3) putting the dried catalyst into a tubular furnace, introducing argon protective gas, and calcining for 2 hours at 270 ℃ to ensure that the catalyst is supported more firmly.
The preparation method of the second catalyst comprises the following steps:
1. cutting: cutting off a large piece of foam nickel according to the required size by using a scalpel, wherein the size of the cut piece is 5cm x 13cm, the edge is required to be neat during cutting, and weighing after cutting;
2. solution preparation: two solutions are required: CoCl2With NaH2PO2For soaking a foamed nickel support, CoCl2Has a concentration of 0.5mol/L, NaH2PO2The concentration of (A) is 0.5 mol/L; NaBH4With NaAn alkaline mixed aqueous solution of OH for reduction on the surface of the support, wherein NaBH4The concentration of 1.2mol/L, NaOH is 0.30 mol/L;
3. cleaning a foamed nickel carrier: immersing the prepared nickel foam into a dilute HCl solution with the mass fraction of 0.1%, and ultrasonically oscillating for 5min to remove oxides and other impurities on the surface; then putting the foamed nickel into absolute ethyl alcohol, and ultrasonically cleaning for 5min to remove impurities such as HCl, oil stains and the like; finally, putting the mixture into a thermostat for drying until the surface impurities are completely volatilized;
4. catalyst loading: 200ml of CoCl was taken2With NaH2PO2Putting the water solution into a beaker, putting clean and dry foam nickel into the solution for soaking, taking out after completely soaking, putting the arch upwards, and slowly dripping 5ml of NaBH in the middle of the arch4The mixed aqueous solution of NaOH is used for slowly covering the whole foam nickel sheet as much as possible; then reversing the foamed nickel, and slowly dripping 5ml of mixed solution from two sides respectively to ensure that the reduction reaction is uniformly carried out on the surface of the whole foamed nickel carrier; after dropwise adding, putting the foam nickel into deionized water at 70 ℃ for rinsing, and removing NaBO in pores2(ii) a And finally, putting the foamed nickel into a 50 ℃ oven for drying. This is a primary loading process, and the loading is repeated for a total of 10 times;
5. and (3) calcining: and (3) putting the supported catalyst into a calcining furnace, introducing argon as a protective gas, slowly raising the temperature to 230 ℃ for 2 hours, slowly cooling to room temperature, and taking out.
The above-described sodium borohydride hydrolysis hydrogen production unit was tested for start-up time, as in example 1. The test results are shown in FIG. 1, with a start-up time of 3.8 s.
Example 4
The embodiment provides a sodium borohydride hydrolysis hydrogen production unit, which comprises a first catalytic section and a second catalytic section, wherein a first catalyst is arranged in the first catalytic section, the first catalyst is active alumina loaded with Co, a second catalyst is arranged in the second catalytic section, the second catalyst is foamed nickel loaded with Co-B, and the mass ratio of Co to alumina in the active alumina loaded with Co is 15: 100, respectively; the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is 201: 100;
the preparation method of the first catalyst comprises the following steps:
1. and (3) cleaning and drying the carrier: taking 20g of gamma-type activated alumina, and putting the gamma-type activated alumina into deionized water for ultrasonic oscillation for 5min to remove surface impurities and loose powder; then taking out the activated alumina, putting the activated alumina into a vacuum oven at 140 ℃ for drying for 8 hours, and fully dehydrating;
2. solution preparation: CoCl with the mass fraction of 25 percent2100ml of the aqueous solution, fully stirring to completely dissolve;
3. catalyst loading: putting the fully dried activated alumina into the prepared CoCl2In the aqueous solution, putting a beaker filled with the mixture into a vacuum box, removing bubbles in the solution, and soaking for 20 hours to ensure that the solution is fully immersed into the carrier; then taking out the active alumina carrier in the solution, and putting the active alumina carrier in a drying oven at 140 ℃ for drying for 8 hours to complete the loading of the catalyst;
4. and (3) calcining: and (3) putting the dried catalyst into a tubular furnace, introducing argon protective gas, and calcining for 2 hours at 270 ℃ to ensure that the catalyst is supported more firmly.
The preparation method of the second catalyst comprises the following steps:
1. cutting: cutting off a large piece of foam nickel according to the required size by using a scalpel, wherein the size of the cut piece is 5cm x 13cm, the edge is required to be neat during cutting, and weighing after cutting;
2. solution preparation: two solutions are required: CoCl2With NaH2PO2For soaking a foamed nickel support, CoCl2Has a concentration of 0.4mol/L, NaH2PO2The concentration of (A) is 0.4 mol/L; NaBH4With an alkaline aqueous solution of NaOH for reduction on the surface of the support, in which NaBH is present4The concentration of 1.0mol/L, NaOH is 0.25 mol/L;
3. cleaning a foamed nickel carrier: immersing the prepared nickel foam into a dilute HCl solution with the mass fraction of 0.3%, and ultrasonically oscillating for 10min to remove oxides and other impurities on the surface; then putting the foamed nickel into absolute ethyl alcohol, and ultrasonically cleaning for 10min to remove impurities such as HCl, oil stains and the like; finally, putting the mixture into a thermostat for drying until the surface impurities are completely volatilized;
4. catalyst loading: 200ml of CoCl was taken2With NaH2PO2Putting the water solution into a beaker, putting clean and dry foam nickel into the solution for soaking, taking out after completely soaking, putting the arch upwards, and slowly dripping 5ml of NaBH in the middle of the arch4The mixed aqueous solution of NaOH is used for slowly covering the whole foam nickel sheet as much as possible; then reversing the foamed nickel, and slowly dripping 5ml of mixed solution from two sides respectively to ensure that the reduction reaction is uniformly carried out on the surface of the whole foamed nickel carrier; after dropwise adding, putting the foamed nickel into deionized water at the temperature of 80 ℃ for rinsing, and removing NaBO in pores2(ii) a And finally, putting the foamed nickel into a 70 ℃ oven for drying. This is a primary loading process, and the loading is repeated for a total of 60 times;
5. and (3) calcining: and (3) putting the supported catalyst into a calcining furnace, introducing argon as a protective gas, slowly raising the temperature to 270 ℃, maintaining for 3 hours, and slowly cooling to room temperature and then taking out.
The above-described sodium borohydride hydrolysis hydrogen production unit was tested for start-up time, as in example 1. The test results are shown in FIG. 1, with a start-up time of 2.8 s.
Example 5
The embodiment provides a sodium borohydride hydrolysis hydrogen production unit, which comprises a first catalytic section and a second catalytic section, wherein a first catalyst is arranged in the first catalytic section, the first catalyst is active alumina loaded with Co, a second catalyst is arranged in the second catalytic section, the second catalyst is foamed nickel loaded with Co-B, and the mass ratio of Co to alumina in the active alumina loaded with Co is 20: 100, respectively; the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is 71: 100;
the preparation method of the first catalyst comprises the following steps:
1. and (3) cleaning and drying the carrier: taking 20g of gamma-type activated alumina, and putting the gamma-type activated alumina into deionized water for ultrasonic oscillation for 10min to remove surface impurities and loose powder; then taking out the activated alumina, putting the activated alumina into a vacuum oven at 160 ℃ for drying for 16h, and fully dehydrating;
2. solution preparation: CoCl with the mass fraction of 25 percent2100ml of aqueous solution is fully stirred to be completely dissolved, and phosphoric acid is added until the concentration of phosphoric acid is 1 mol/L;
3. catalyst loading: putting the fully dried activated alumina into the prepared CoCl2In the aqueous solution, putting a beaker filled with the mixture into a vacuum box, removing bubbles in the solution, and soaking for 28 hours to ensure that the solution is fully immersed in the carrier; then taking out the active alumina carrier in the solution, and drying the active alumina carrier in a drying oven at 160 ℃ for 16h to complete the loading of the catalyst;
4. and (3) calcining: and putting the dried catalyst into a tubular furnace, introducing argon protective gas, and calcining for 3 hours at 330 ℃ to ensure that the catalyst is supported more firmly.
The preparation method of the second catalyst comprises the following steps:
1. cutting: cutting off a large piece of foam nickel according to the required size by using a scalpel, wherein the size of the cut piece is 5cm x 13cm, the edge is required to be neat during cutting, and weighing after cutting;
2. solution preparation: two solutions are required: CoCl2With NaH2PO2For soaking a foamed nickel support, CoCl2Has a concentration of 0.4mol/L, NaH2PO2The concentration of (A) is 0.4 mol/L; NaBH4With an alkaline aqueous solution of NaOH for reduction on the surface of the support, in which NaBH is present4The concentration of 1.0mol/L, NaOH is 0.25 mol/L;
3. cleaning a foamed nickel carrier: immersing the prepared nickel foam into a dilute HCl solution with the mass fraction of 0.2%, and ultrasonically oscillating for 8min to remove oxides and other impurities on the surface; then putting the foamed nickel into absolute ethyl alcohol, and ultrasonically cleaning for 8min to remove impurities such as HCl, oil stains and the like; finally, putting the mixture into a thermostat for drying until the surface impurities are completely volatilized;
4. catalyst loading: 200ml of CoCl was taken2With NaH2PO2Putting the water solution into a beaker, soaking clean and dry foam nickel in the solution, taking out after complete soaking, placing the foam nickel with the arch facing upwards, placing the foam nickel in the beakerSlowly dripping 5ml NaBH in the middle of the arch4The mixed aqueous solution of NaOH is used for slowly covering the whole foam nickel sheet as much as possible; then reversing the foamed nickel, and slowly dripping 5ml of mixed solution from two sides respectively to ensure that the reduction reaction is uniformly carried out on the surface of the whole foamed nickel carrier; after dropwise adding, putting the foam nickel into deionized water at 70 ℃ for rinsing, and removing NaBO in pores2(ii) a And finally, putting the foamed nickel into a 60 ℃ oven for drying. This is a primary loading process, and the loading is repeated for a total of 30 times;
5. and (3) calcining: and (3) putting the supported catalyst into a calcining furnace, introducing argon as a protective gas, slowly raising the temperature to 250 ℃ for 2 hours, slowly cooling to room temperature, and taking out.
The above-described sodium borohydride hydrolysis hydrogen production unit was tested for start-up time, as in example 1. The test results are shown in fig. 1, with a start-up time of 2.4 s.
Example 6
The embodiment provides a sodium borohydride hydrolysis hydrogen production unit, which comprises a first catalytic section and a second catalytic section, wherein a first catalyst is arranged in the first catalytic section, the first catalyst is active alumina loaded with Co, a second catalyst is arranged in the second catalytic section, the second catalyst is foamed nickel loaded with Co-B, and the mass ratio of Co to alumina in the active alumina loaded with Co is 10: 100, respectively; the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is 71: 100;
the preparation method of the first catalyst comprises the following steps:
1. cleaning and drying the carrier, namely taking 20g of α type activated alumina, putting the α type activated alumina into deionized water, performing ultrasonic oscillation for 5min to remove surface impurities and loose powder, taking out the activated alumina, putting the activated alumina into a vacuum oven at 150 ℃ for drying for 12h, and fully dehydrating;
2. solution preparation: CoCl with 20% mass fraction2100ml of the aqueous solution, fully stirring to completely dissolve;
3. catalyst loading: putting the fully dried activated alumina into the prepared CoCl2In the aqueous solution, the mixture is put into a furnacePutting the cup into a vacuum box, removing bubbles in the solution, and soaking for 24h to ensure that the solution is fully immersed into the carrier; then taking out the active alumina carrier in the solution, and drying the active alumina carrier in a drying oven at 150 ℃ for 12 hours to complete the loading of the catalyst;
4. and (3) calcining: and putting the dried catalyst into a tubular furnace, introducing argon protective gas, and calcining for 2 hours at 300 ℃ to ensure that the catalyst is supported more firmly.
The preparation method of the second catalyst comprises the following steps:
1. cutting: cutting off a large piece of foam nickel according to the required size by using a scalpel, wherein the size of the cut piece is 5cm x 13cm, the edge is required to be neat during cutting, and weighing after cutting;
2. solution preparation: two solutions are required: CoCl2With NaH2PO2For soaking a foamed nickel support, CoCl2Has a concentration of 0.4mol/L, NaH2PO2The concentration of (A) is 0.4 mol/L; NaBH4With an alkaline aqueous solution of NaOH for reduction on the surface of the support, in which NaBH is present4The concentration of 1.0mol/L, NaOH is 0.25 mol/L;
3. cleaning a foamed nickel carrier: immersing the prepared nickel foam into a dilute HCl solution with the mass fraction of 0.2%, and ultrasonically oscillating for 8min to remove oxides and other impurities on the surface; then putting the foamed nickel into absolute ethyl alcohol, and ultrasonically cleaning for 8min to remove impurities such as HCl, oil stains and the like; finally, putting the mixture into a thermostat for drying until the surface impurities are completely volatilized;
4. catalyst loading: 200ml of CoCl was taken2With NaH2PO2Putting the water solution into a beaker, putting clean and dry foam nickel into the solution for soaking, taking out after completely soaking, putting the arch upwards, and slowly dripping 5ml of NaBH in the middle of the arch4The mixed aqueous solution of NaOH is used for slowly covering the whole foam nickel sheet as much as possible; then reversing the foamed nickel, and slowly dripping 5ml of mixed solution from two sides respectively to ensure that the reduction reaction is uniformly carried out on the surface of the whole foamed nickel carrier; after dropwise adding, putting the foam nickel into deionized water at 70 ℃ for rinsing, and removing NaBO in pores2(ii) a Finally, putting the foamed nickel into a 60 ℃ ovenAnd (5) drying. This is a primary loading process, and the loading is repeated for a total of 30 times;
5. and (3) calcining: and (3) putting the supported catalyst into a calcining furnace, introducing argon as a protective gas, slowly raising the temperature to 250 ℃ for 2 hours, slowly cooling to room temperature, and taking out.
The above-described sodium borohydride hydrolysis hydrogen production unit was tested for start-up time, as in example 1. The test results are shown in FIG. 1, with a start-up time of 3.1 s.
Example 7
The embodiment provides a sodium borohydride hydrolysis hydrogen production unit, which comprises a first catalytic section and a second catalytic section, wherein a first catalyst is arranged in the first catalytic section, the first catalyst is active alumina loaded with Co, a second catalyst is arranged in the second catalytic section, the second catalyst is foamed nickel loaded with Co-B, and the mass ratio of Co to alumina in the active alumina loaded with Co is 20: 100, respectively; the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is 71: 100;
the preparation method of the first catalyst comprises the following steps:
1. cleaning and drying the carrier, namely taking 20g of α type activated alumina, putting the α type activated alumina into deionized water, performing ultrasonic oscillation for 10min to remove surface impurities and loose powder, taking out the activated alumina, putting the activated alumina into a vacuum oven at 160 ℃ for drying for 16h, and fully dehydrating;
2. solution preparation: CoCl with the mass fraction of 30 percent2100ml of aqueous solution is fully stirred to be completely dissolved, and phosphoric acid is added until the concentration of phosphoric acid is 1 mol/L;
3. catalyst loading: putting the fully dried activated alumina into the prepared CoCl2In the aqueous solution, putting a beaker filled with the mixture into a vacuum box, removing bubbles in the solution, and soaking for 28 hours to ensure that the solution is fully immersed in the carrier; then taking out the active alumina carrier in the solution, and drying the active alumina carrier in a drying oven at 160 ℃ for 16h to complete the loading of the catalyst;
4. and (3) calcining: and putting the dried catalyst into a tubular furnace, introducing argon protective gas, and calcining for 3 hours at 330 ℃ to ensure that the catalyst is supported more firmly.
The preparation method of the second catalyst comprises the following steps:
1. cutting: cutting off a large piece of foam nickel according to the required size by using a scalpel, wherein the size of the cut piece is 5cm x 13cm, the edge is required to be neat during cutting, and weighing after cutting;
2. solution preparation: two solutions are required: CoCl2With NaH2PO2For soaking a foamed nickel support, CoCl2Has a concentration of 0.4mol/L, NaH2PO2The concentration of (A) is 0.4 mol/L; NaBH4With an alkaline aqueous solution of NaOH for reduction on the surface of the support, in which NaBH is present4The concentration of 1.0mol/L, NaOH is 0.25 mol/L;
3. cleaning a foamed nickel carrier: immersing the prepared nickel foam into a dilute HCl solution with the mass fraction of 0.2%, and ultrasonically oscillating for 8min to remove oxides and other impurities on the surface; then putting the foamed nickel into absolute ethyl alcohol, and ultrasonically cleaning for 8min to remove impurities such as HCl, oil stains and the like; finally, putting the mixture into a thermostat for drying until the surface impurities are completely volatilized;
4. catalyst loading: 200ml of CoCl was taken2With NaH2PO2Putting the water solution into a beaker, putting clean and dry foam nickel into the solution for soaking, taking out after completely soaking, putting the arch upwards, and slowly dripping 5ml of NaBH in the middle of the arch4The mixed aqueous solution of NaOH is used for slowly covering the whole foam nickel sheet as much as possible; then reversing the foamed nickel, and slowly dripping 5ml of mixed solution from two sides respectively to ensure that the reduction reaction is uniformly carried out on the surface of the whole foamed nickel carrier; after dropwise adding, putting the foam nickel into deionized water at 70 ℃ for rinsing, and removing NaBO in pores2(ii) a And finally, putting the foamed nickel into a 60 ℃ oven for drying. This is a primary loading process, and the loading is repeated for a total of 30 times;
5. and (3) calcining: and (3) putting the supported catalyst into a calcining furnace, introducing argon as a protective gas, slowly raising the temperature to 250 ℃ for 2 hours, slowly cooling to room temperature, and taking out.
The above-described sodium borohydride hydrolysis hydrogen production unit was tested for start-up time, as in example 1. The test results are shown in FIG. 1, with a start-up time of 2.6 s.
Comparative example
The comparative example provides a sodium borohydride hydrolysis hydrogen production unit, and the first section catalytic section and the second catalytic section both adopt second catalysts. The reaction start time was measured separately using different loadings in the same manner as in example 1, and the results are shown in FIG. 2.
As can be seen from the comparative example, as shown in FIG. 2, the reaction start time using Co-B/Ni alone was longer, with 5.5s in the case of 71% loading, the reaction start time was longer as the loading decreased, and with 6.7s in the case of 26% loading, the reaction start time was shorter as the loading increased. At 201% loading, the reaction start-up time was 4.6s, but at this time the loading was too high and the catalyst particles occupied a large amount of the pores of the nickel foam, making the support brittle and prone to clogging and breakage during actual use.
Test examples
The catalytic efficiency test of the sodium borohydride hydrolysis hydrogen production unit is that as shown in fig. 3 and 4, the first catalyst of the hydrogen production unit adopts Co/gamma-Al2O3The catalyst and the second catalyst respectively adopt catalysts with 71%, 48% and 26% of carrying capacity, namely the hydrogen production units of the corresponding examples 1, 2 and 3, and when the fuel liquid is 15 wt% sodium borohydride solution and 25 wt% sodium borohydride solution, the liquid inlet rates are different from the hydrogen generation rates.
The hydrogen generation rate is related to the catalyst loading, and generally, higher loading means a larger hydrogen production rate, but the influence is different when the feed liquid flow rate is different. Under the condition of lower feed liquid flow rate, the higher the loading capacity is, the higher the hydrogen generation rate is, and the hydrogen generation rate can reach about 90% of the theoretical hydrogen production rate when the second catalyst loading catalyst is more than 48%. At a higher feed flow rate, the hydrogen production efficiency decreases with increasing flow rate, and the influence of catalyst loading is also gradually reduced.
With the same catalyst, the hydrogen production performance is obviously improved by using 25 wt% of sodium borohydride solution compared with 15 wt%, but the hydrogen production rate is far from the theoretical ratio difference by using higher concentration of sodium borohydride solution. When the carrying capacity is large, the hydrogen production efficiency is high at the stage of low liquid inlet flow velocity, which can reach about 90% of the theoretical value, and the solution utilization rate of lower concentration is higher. The higher the concentration of the solution, the faster the fuel utilization decreases with increasing feed flow rate.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (9)

1. A sodium borohydride hydrolysis hydrogen production unit is characterized by comprising a first catalytic section and a second catalytic section, wherein a first catalyst is arranged in the first catalytic section, the first catalyst is active alumina loaded with Co, a second catalyst is arranged in the second catalytic section, the second catalyst is foamed nickel loaded with Co-B, and the mass ratio of Co to alumina in the active alumina loaded with Co is (10-20): 100, respectively;
the mass ratio of Co-B to foamed nickel in the Co-B-loaded foamed nickel is (26-201): 100.
2. The sodium borohydride hydrolysis hydrogen production unit according to claim 1, further comprising a cylindrical housing, wherein the first catalytic section and the second catalytic section are sequentially disposed on the inside of the housing along the axial direction of the housing.
3. The sodium borohydride hydrolysis hydrogen production unit according to claim 2, wherein the shell is obtained by rolling a sheet-like substrate into a plurality of circles to form a cylinder, a gap is formed between adjacent circles, and the first catalyst and the second catalyst are both disposed on the surfaces of the substrate on both sides of the gap.
4. The sodium borohydride hydrolysis hydrogen production unit according to claim 1, wherein the preparation method of the first catalyst comprises the following steps:
dipping activated alumina into a cobalt-containing aqueous solution for the first dipping;
and sequentially carrying out primary drying and primary calcining on the first impregnated activated alumina to obtain the first catalyst.
5. The sodium borohydride hydrolysis hydrogen production unit according to claim 4, wherein the mass fraction of the cobalt-containing aqueous solution is 20-30%, and the time of the first impregnation is 20-28 h;
the temperature of the first drying is 140-160 ℃, and the time is 8-16 h;
the first calcination is calcination under inert atmosphere, the temperature of the first calcination is 270-330 ℃, and the time is 2-3 h.
6. The sodium borohydride hydrolysis hydrogen production unit according to claim 5, further comprising placing the activated alumina in deionized water for ultrasonic oscillation for 5-10min before the first impregnation, and then drying at 140-160 ℃ for 8-16 h;
and adding phosphoric acid into the cobalt-containing aqueous solution until the concentration of the phosphoric acid is 1-1.5 mol/L.
7. The sodium borohydride hydrolysis hydrogen production unit according to claim 1, wherein the preparation method of the second catalyst comprises the following steps:
soaking the foamed nickel in an aqueous solution containing a cobalt compound and hypophosphite for the second time;
reducing the foamed nickel after the second impregnation by using an aqueous solution of sodium borohydride and sodium hydroxide;
and sequentially carrying out secondary drying and secondary calcining on the reduced foam nickel to obtain the second catalyst.
8. The unit for hydrogen production by hydrolysis of sodium borohydride according to claim 7, characterized in that the concentration of the cobalt-containing compound in the aqueous solution of the cobalt-containing compound and hypophosphite is 0.4-0.5mol/L, and the concentration of hypophosphite is 0.4-0.5 mol/L;
the concentration of sodium borohydride in the aqueous solution of sodium borohydride and sodium hydroxide is 1.0-1.2mol/L, and the concentration of sodium hydroxide is 0.25-0.30 mol/L;
the temperature of the secondary drying is 50-70 ℃;
the second calcination is calcination under inert atmosphere, the temperature of the second calcination is 230-270 ℃, and the time is 2-3 h.
9. The sodium borohydride hydrolysis hydrogen production unit according to claim 8, further comprising immersing the nickel foam into 0.1-0.3% hydrochloric acid aqueous solution before the second immersion, after ultrasonic oscillation for 5-10min, immersing into ethanol again, ultrasonic oscillation for 5-10min, and finally drying;
after the reduction and before the second drying, the method also comprises the step of washing the reduced foam nickel in deionized water at 70-80 ℃.
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