CN113171776A - Supported catalyst for hydrogen production by hydrolysis of sodium borohydride solution, preparation method and application - Google Patents
Supported catalyst for hydrogen production by hydrolysis of sodium borohydride solution, preparation method and application Download PDFInfo
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- CN113171776A CN113171776A CN202110473252.6A CN202110473252A CN113171776A CN 113171776 A CN113171776 A CN 113171776A CN 202110473252 A CN202110473252 A CN 202110473252A CN 113171776 A CN113171776 A CN 113171776A
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- hydrogen production
- sodium borohydride
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 107
- 239000001257 hydrogen Substances 0.000 title claims abstract description 107
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 85
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 84
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 84
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 57
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007787 solid Substances 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 229910019236 CoFeB Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000001354 calcination Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000002525 ultrasonication Methods 0.000 abstract 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 12
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- -1 iron ions Chemical class 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 229910020674 Co—B Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C01B3/065—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 from a hydride
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明提供一种用于硼氢化钠溶液水解制氢的负载型催化剂、制备方法及应用，制备方法包括如下步骤：(1)取固态镍作为载体；(2)将钴源和铁源混合物溶于水，形成混合溶液，其中，钴源为钴的氯化物、硫酸盐或硝酸盐中的一种或多种，铁源为铁的氯化物、硫酸盐或硝酸盐的一种或多种；(3)将中固态镍载体浸入混合溶液中进行超声，形成催化剂前驱体；(4)用NaBH4溶液还原催化剂前驱体，得到活性组分为Co、Fe和B的负载型催化剂；(5)对负载型催化剂进行洗涤、过滤、烘干、煅烧处理，得到镍负载CoFeB硼氢化钠水解制氢催化剂。本发明制备的催化剂为颗粒状，产氢速率高，催化性能稳定，耐久性好，可重复利用，降低原料成本。The invention provides a supported catalyst for hydrogen production by hydrolysis of sodium borohydride solution, a preparation method and application. The preparation method includes the following steps: (1) taking solid nickel as a carrier; (2) dissolving a mixture of cobalt source and iron source into solution In water, a mixed solution is formed, wherein the cobalt source is one or more of cobalt chloride, sulfate or nitrate, and the iron source is one or more of iron chloride, sulfate or nitrate; (3) immersing the medium-solid nickel carrier in the mixed solution for ultrasonication to form a catalyst precursor; ( 4 ) reducing the catalyst precursor with a NaBH solution to obtain a supported catalyst with active components of Co, Fe and B; (5) The supported catalyst is washed, filtered, dried and calcined to obtain a nickel-supported CoFeB sodium borohydride hydrolysis catalyst for hydrogen production. The catalyst prepared by the invention is granular, has high hydrogen production rate, stable catalytic performance, good durability, can be reused, and reduces the cost of raw materials.
Description
Technical Field
The invention belongs to the field of catalyst synthesis, and particularly relates to a supported catalyst for hydrogen production by hydrolysis of a sodium borohydride solution, a preparation method and application.
Background
In order to cope with the climate crisis and reduce the emission of carbon, new energy technology is being improved to a new level. The hydrogen energy is used as one of new energy sources, the combustion product is water, greenhouse gases are not generated, a large amount of layout of energy industries of various countries is attracted, and the popularization and application pace of the hydrogen energy is accelerated.
Sodium borohydride (NaBH)4) The hydrogen storage density is high, the mass fraction of hydrogen storage is as high as 10.6 wt%, and the hydrogen storage can exist in a solid state or stably exist in an alkaline solution state. When contacting with a specific catalyst, the sodium borohydride solution will rapidly undergo hydrolysis reaction, releasing high purity hydrogen. The hydrogen can react with water to release hydrogen, has high purity, and is suitable for supplying hydrogen for proton exchange membrane fuel cells; the hydrolysis reaction does not need pressurization and heating, and the hydrolysis condition is easy to control. The hydrolysis reaction equation is as follows:
NaBH4+2H2O→4H2+NaBO2ΔH＝-217kJ/mol
in order to efficiently and stably use sodium borohydride for hydrolysis to obtain hydrogen, a specific hydrolysis hydrogen production catalyst is generally needed to be matched and carried out in a specific hydrogen production reactor.
Early researches show that VIII group metals such as Pt, Ru, Rh and the like and metal salts have good catalytic hydrolysis hydrogen production performance, the catalytic effect of the noble metals is optimal, but the natural reserves of the noble metals are limited, and the noble metals are expensive, so that the cost of a hydrogen production system is increased. Therefore, a hydrogen production catalyst with a lower noble metal loading or non-noble metal material is sought and becomes a new research target.
Chinese patent with publication number CN107413360B discloses a carbon fiber cloth-loaded CoMoP sodium borohydride hydrolysis hydrogen production catalyst and a preparation method thereof. The carbon fiber cloth is characterized by being prepared by loading cobalt, molybdenum and phosphorus on the surface of a carrier carbon fiber cloth; the cobalt, molybdenum and phosphorus are electroplated on the surface of the carbon fiber cloth by a mixed solution of cobalt chloride, sodium molybdate and sodium hypophosphite through a single pulse electroplating method, the electroplating step involves multiple parameter adjustment, the process is complex, the catalyst cannot be recycled, and the service life of the catalyst needs to be improved.
Chinese patent publication No. CN102350356A discloses a method for preparing a catalyst for hydrogen production by hydrolysis of borohydride, in which a precursor is obtained by a solution chemical reaction and freezing-vacuum treatment at a low temperature, and the catalyst for hydrogen production is obtained by heat treatment, which has the disadvantages of high requirement on preparation conditions and high cost.
Chinese patent publication No. CN109205555A provides a catalyst for hydrogen production by hydrolysis of sodium borohydride, which comprises borohydride, acid and water, wherein borohydride and acid are solid powders and are easily dispersed.
The existing hydrogen production catalyst has the following defects: the existing hydrogen production catalyst is powdery, is easy to disperse and is not beneficial to recycling; the existing catalyst is limited by factors such as complex preparation process, complex auxiliary system or carrier durability, the production and manufacturing cost of the catalyst is quite high, and the popularization of hydrogen production is influenced.
Disclosure of Invention
The invention aims to provide a supported catalyst for hydrogen production by hydrolysis of a sodium borohydride solution, a preparation method and application, which are simple in preparation process, overcomes the defect that a powdery catalyst is easy to disperse and cannot be recycled, improves the durability of the catalyst, realizes the recycling of the catalyst and reduces the cost of raw materials.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a supported catalyst for hydrogen production by hydrolysis of a sodium borohydride solution, which comprises the following steps:
(1) taking solid nickel as a carrier;
(2) dissolving a mixture of a cobalt source and an iron source in water to form a mixed solution, wherein the cobalt source is one or more of chloride, sulfate or nitrate of cobalt, and the iron source is one or more of chloride, sulfate or nitrate of iron;
(3) immersing the solid nickel carrier in the step 1 into the mixed solution in the step 2 for ultrasonic treatment to form a catalyst precursor;
(4) with NaBH4Reducing the catalyst precursor in the step 3 by using a solution to obtain a supported catalyst with active components of Co, Fe and B;
(5) and (4) washing, filtering, drying and calcining the supported catalyst in the step (4) to obtain the catalyst for hydrogen production through hydrolysis of the nickel-supported CoFeB sodium borohydride.
Further, in the step 2, in the mixed solution, the cobalt source is CoCl2The iron source is FeCl3。
Further, in step 2, in the mixed solution, CoCl2And FeCl3The molar percentage of the solution was 90: 10-99: 1.
Further, in the step 1, the solid nickel is foamed nickel, and the particle size of the foamed nickel ranges from 5 mm to 20 mm.
Further, in the step 3, ultrasonic soaking is carried out for 1-3 hours under the condition of 40-50 kHz.
Further, in step 5, the washing and drying steps are as follows: washing excess residual NaBH with deionized water4After the solution is obtained, the supported catalyst is placed in a vacuum drying oven at the temperature of 100-150 ℃ for drying for 20-28 h; the calcination steps are as follows: calcining for 1-3h in a nitrogen atmosphere, wherein the calcining temperature range is 350-550 ℃.
The invention also provides a supported catalyst for hydrogen production by hydrolysis of the sodium borohydride solution, which is prepared by the preparation method, wherein the catalyst takes solid nickel as a carrier, and Co, Fe and B are supported on the surface of the catalyst.
The invention further provides an application of the supported catalyst for hydrogen production by hydrolysis of the sodium borohydride solution, and the catalyst is used for catalyzing the alkaline sodium borohydride solution to produce hydrogen.
Further, the application of the supported catalyst for hydrogen production by hydrolysis of sodium borohydride solution comprises the following steps: selecting NaBH4And NaOH waterThe solution is used as a raw material, the catalyst for hydrogen production by hydrolysis of nickel-loaded CoFeB sodium borohydride and the raw material are placed in a hydrogen reactor, and hydrogen is collected.
Further, in the starting material, NaBH4The mass content of the sodium hydroxide is 5-15%, and the mass content of NaOH is 5-10%.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride, solid nickel is used as a carrier, and Co, Fe and B enter holes of the solid nickel through chemical force and are uniformly dispersed, so that the stable catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride is formed.
The nickel-loaded CoFeB sodium borohydride hydrolysis hydrogen production catalyst prepared by the method is granular, has high hydrogen production rate, stable catalytic performance and good durability, can be recycled, reduces the raw material consumption of preparing the powder catalyst by simply using metal raw materials, reduces the raw material cost, does not pollute the environment, and overcomes the defects that the powder catalyst is easy to disperse and cannot be recycled.
The preparation method of the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride has the advantages of short preparation time, simple preparation process and low requirements on preparation conditions, and is suitable for large-scale popularization and production.
Detailed Description
The invention will be further described with reference to the examples shown below.
The invention provides a preparation method of a supported catalyst for hydrogen production by hydrolysis of a sodium borohydride solution, which comprises the following steps:
(1) taking solid nickel as a carrier, wherein the solid nickel is preferably spherical foam nickel, the particle size range of the foam nickel is 5-20mm, the solid nickel has the advantages of porosity, large specific surface area and low cost, and the large specific surface area of the solid nickel is beneficial to loading more active ingredients on the solid nickel and improving the dispersibility of the active ingredients; the solid nickel is granular, different from powdery substances, the powdery substances are dissolved in the solution, and the granular substances are not dissolved in the solution;
(2) mixing cobalt source and iron sourceDissolving in water to form a mixed solution, wherein the cobalt source is one or more of cobalt chloride, sulfate or nitrate, such as cobalt chloride, cobalt sulfate, cobalt nitrate, and cobalt acetate; the iron source is one or more of chloride, sulfate or nitrate of iron, such as ferric chloride, ferric sulfate, ferric nitrate, preferably, the cobalt source is CoCl2The iron source is FeCl3，CoCl2And FeCl3The molar percentage range of the solution was 90: 10-99: 1.
(3) Immersing the solid nickel carrier in the step 1 into the mixed solution in the step 2 for ultrasonic treatment to form a catalyst precursor, wherein the ultrasonic treatment is ultrasonic immersion for 1-3h, preferably 2h, under the condition of 40-50 kHz, the ultrasonic treatment is a physical reaction, the dispersion is carried out by ultrasonic treatment, active components are favorably loaded on the surface of the carrier, and the spherical foamed nickel catalyst precursor with uniformly wetted inner and outer surfaces can be obtained through the ultrasonic treatment;
(4) with NaBH4The catalyst precursor in the step 3 is reduced by a solution to obtain a supported catalyst with active components of Co, Fe and B, and the step can be operated at normal temperature without special complex conditions;
specifically, CoCl2、FeCl3、NaBH4The reaction equation of the nickel carrier is as follows:
NaBH4+CoCl2+NaOH→CoxBy+NaCl (1)
NaBH4+FeCl3+NaOH→FexBy+NaCl (2)
the Co-B, Fe-B load is deposited on the nickel carrier, and chemical force acts between the Co-B, Fe-B load and the nickel carrier.
Preference is given to using an excess of NaBH4The solution is used to reduce the catalyst precursor in step 3 in an excess of more than 1.1 times the amount required for the reaction, i.e. until no gas is released.
(5) And (4) washing, filtering, drying and calcining the supported catalyst in the step (4) to obtain the catalyst for hydrogen production by hydrolysis of the nickel-supported CoFeB sodium borohydride, wherein the active surface is combined compactly.
In step 5, the washing and drying steps are as follows: washing the excess residue with deionized waterNaBH of4After the solution is obtained, the supported catalyst is placed in a vacuum drying oven at the temperature of 100-150 ℃ for drying for 20-28h, preferably in the vacuum drying oven at the temperature of 110 ℃ for drying for 24h, and the moisture is removed; the calcination steps are as follows: calcining for 1-3h (preferably placing in a muffle furnace for 2h) in the nitrogen atmosphere, wherein the calcining temperature range is 350-550 ℃, and obtaining the catalyst for hydrogen production through hydrolysis of the nickel-loaded CoFeB sodium borohydride.
The invention also provides a supported catalyst for hydrogen production by hydrolysis of the sodium borohydride solution, which is prepared by the preparation method, wherein the catalyst takes solid nickel as a carrier, and Co, Fe and B are supported on the surface of the catalyst.
The invention also provides an application of the supported catalyst for hydrogen production by hydrolysis of sodium borohydride solution, and the catalyst is used for catalyzing alkaline sodium borohydride solution to produce hydrogen. Which comprises the following steps: selecting NaBH4And NaOH aqueous solution is taken as a raw material, the granular nickel-loaded CoFeB sodium borohydride hydrolysis hydrogen production catalyst and the raw material are placed in a hydrogen reactor, hydrogen is collected, and NaBH is added into the raw material4The mass content of the sodium hydroxide is 5-15%, the mass content of NaOH is 5-10%, and the alkaline environment is ensured.
The catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride, which is prepared by the invention, takes solid nickel as a carrier, uniformly mixes a cobalt source, an iron source and the solid nickel by ultrasound to obtain a catalyst precursor, and uses NaBH4The catalyst precursor is reduced by the solution, and active components of iron ions, cobalt ions and boron ions or the three components enter pores in the solid nickel through chemical force and are well distributed and fixed in the solid nickel to form stable solid nickel-iron ions, solid nickel-cobalt ions, solid nickel-boron ions and solid nickel-iron ions/cobalt ions/boron ions compounds.
According to the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride, the granular carrier solid nickel is mixed with the liquid raw material to produce hydrogen easily, and after hydrogen production is finished, the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride can be taken out to be used for next hydrogen production, while in the traditional hydrogen production method, the powdery catalyst is mixed with NaBH4After the hydrogen is produced by mixing, the separation is difficult, and the hydrogen is only used once.
Example 1
Preparation method: (1) taking spherical foam nickel as a carrier, wherein the particle size range of the spherical foam nickel is 5-20 mm; (2) taking 9mol of CoCl2And 1mol of FeCl3Preparing a mixed impregnation liquid; (3) soaking the spherical foamed nickel carrier into the mixed soaking liquid obtained in the step (2) for ultrasonic treatment for 2 hours under the ultrasonic condition to form a catalyst precursor; (4) with an excess of NaBH4Reducing the catalyst precursor in the step 3 by using a solution to obtain a supported catalyst with active components of Co, Fe and B; (5) and (4) washing, filtering, drying and calcining the supported catalyst in the step (4) to obtain the catalyst for hydrogen production through hydrolysis of the nickel-supported CoFeB sodium borohydride.
The hydrogen production method comprises the following steps: taking alkaline sodium borohydride solution as 15 wt% NaBH4And (3) taking a 10% NaOH aqueous solution as a raw material, placing the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride and the raw material in a hydrogen reactor, testing the catalyst, and keeping the hydrogen production rate to be 14.8L/min g in the sodium borohydride aqueous solution at 50 ℃.
Example 2
The preparation method comprises the following steps: (1) taking spherical foam nickel as a carrier, wherein the particle size range of the spherical foam nickel is 5-20 mm; (2) 9.5mol of CoCl are taken2And 0.5mol of FeCl3Preparing a mixed impregnation liquid; (3) soaking the spherical foamed nickel carrier into the mixed soaking liquid obtained in the step (2) for ultrasonic treatment for 2 hours under the ultrasonic condition to form a catalyst precursor; (4) with an excess of NaBH4Reducing the catalyst precursor in the step 3 by using a solution to obtain a supported catalyst with active components of Co, Fe and B; (5) and (4) washing, filtering, drying and calcining the supported catalyst in the step (4) to obtain the catalyst for hydrogen production through hydrolysis of the nickel-supported CoFeB sodium borohydride.
The hydrogen production method comprises the following steps: taking alkaline sodium borohydride solution as 15 wt% NaBH4And (3) taking a 10% NaOH aqueous solution as a raw material, placing the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride and the raw material in a hydrogen reactor, testing the catalyst, and obtaining the hydrogen production rate as high as 12.7L/min g in the sodium borohydride aqueous solution under the condition that the temperature is 50 ℃.
Example 3
The preparation method comprises the following steps: (1) taking spherical foam nickel as a carrier, wherein the particle size range of the spherical foam nickel is 5-20 mm; (2) 9.9mol of CoCl are taken2And 0.1mol of FeCl3Preparing a mixed impregnation liquid; (3) soaking the spherical foamed nickel carrier into the mixed soaking liquid obtained in the step (2) for ultrasonic treatment for 2 hours under the ultrasonic condition to form a catalyst precursor; (4) with an excess of NaBH4Reducing the catalyst precursor in the step 3 by using a solution to obtain a supported catalyst with active components of Co, Fe and B; (5) and (4) washing, filtering, drying and calcining the supported catalyst in the step (4) to obtain the catalyst for hydrogen production through hydrolysis of the nickel-supported CoFeB sodium borohydride.
The hydrogen production method comprises the following steps: taking alkaline sodium borohydride solution as 15 wt% NaBH4And (3) taking a 10% NaOH aqueous solution as a raw material, placing the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride and the raw material in a hydrogen reactor, testing the catalyst, and obtaining the hydrogen production rate as high as 11.3L/min g in the sodium borohydride aqueous solution under the condition that the temperature is 50 ℃.
Comparative example 1
Comparative example 1 differs from example 1 in that: selecting nickel powder;
the preparation method comprises the following steps: (1) taking nickel powder; (2) taking 9mol of CoCl2And 1mol of FeCl3Preparing a mixed impregnation liquid; (3) soaking nickel powder into the mixed soaking solution obtained in the step (2) for ultrasound, and soaking for 2 hours under the ultrasound condition to form a catalyst precursor; (4) with an excess of NaBH4Reducing the catalyst precursor in the step 3 by using a solution to obtain a catalyst; (5) and (4) washing, filtering, drying and calcining the catalyst in the step (4) to obtain a catalyst product.
The hydrogen production method comprises the following steps: taking alkaline sodium borohydride solution as 15 wt% NaBH4And the catalyst and the raw material are placed in a hydrogen reactor, the catalyst is tested, the temperature in the sodium borohydride aqueous solution is 50 ℃, and the hydrogen production rate is 2L/min-g.
The catalyst prepared by using the nickel powder has low hydrogen production rate, and after hydrogen production, the catalyst is difficult to separate and cannot be recycled for the second time, so that the cost is increased.
Further, the catalyst of example 1 is recycled after primary hydrogen production, and tests show that: after the catalyst is repeatedly used for 10 times, the hydrogen production rate is reduced by about 5 percent, which shows thatThe catalyst has good durability in use, and the principle is that the CoFeB-loaded sodium borohydride hydrolysis hydrogen production catalyst has good activity and can be repeatedly used in multiple hydrogen production processes. Compared with a powdery catalyst, the supported catalyst is granular, can support active ingredients, is convenient to recycle, and reduces the raw material consumption of preparing the powdery catalyst by simply using metal raw materials (the powdery catalyst and NaBH)4And is difficult to separate after hydrogen is produced by mixing). In addition, because the cobalt and the iron have the advantage of low price, the cobalt and the iron are easier to popularize and apply than common noble metal elements, and the production cost is greatly reduced.
In examples 1, 2 and 3, the particle sizes of the spherical foamed nickel carriers in step 1 were the same, and the hydrogen production conditions were the same. Examples 1, 2 and 3 differ from each other in CoCl2And FeCl3In different molar percentages.
According to the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride, solid nickel is used as a carrier, and Co, Fe and B enter holes of the solid nickel through chemical force and are uniformly dispersed, so that the stable catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride is formed. The nickel-loaded CoFeB sodium borohydride hydrolysis hydrogen production catalyst prepared by the method is granular, has high hydrogen production rate, stable catalytic performance and good durability, can be recycled, reduces the raw material consumption of preparing the powder catalyst by simply using metal raw materials, reduces the raw material cost, does not pollute the environment, and overcomes the defect that the powder catalyst is easy to disperse and cannot be recycled.
The preparation method of the catalyst for hydrogen production by hydrolysis of the nickel-loaded CoFeB sodium borohydride has the advantages of short preparation time, simple preparation process and low requirements on preparation conditions, and is suitable for large-scale popularization and production.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
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| CN115007152A (en) * | 2022-07-22 | 2022-09-06 | 成都大学 | A kind of hydrolysis hydrogen production catalyst and preparation method and application thereof |
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| CN116161616B (en) * | 2022-12-30 | 2024-04-19 | 合肥工业大学 | A method for rapidly producing hydrogen at low temperature by catalyzing sodium borohydride with a non-metallic catalyst |
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