CN106563451B - The Co-B amorphous alloy porous microsphere catalyst and preparation method thereof of hydrogen is explained for ammonia borine alcohol - Google Patents
The Co-B amorphous alloy porous microsphere catalyst and preparation method thereof of hydrogen is explained for ammonia borine alcohol Download PDFInfo
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- CN106563451B CN106563451B CN201611003929.5A CN201611003929A CN106563451B CN 106563451 B CN106563451 B CN 106563451B CN 201611003929 A CN201611003929 A CN 201611003929A CN 106563451 B CN106563451 B CN 106563451B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 50
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910020674 Co—B Inorganic materials 0.000 title claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 24
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 24
- 239000004005 microsphere Substances 0.000 title claims abstract description 24
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 20
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 19
- 239000012279 sodium borohydride Substances 0.000 claims description 19
- 150000001868 cobalt Chemical class 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- HZEIHKAVLOJHDG-UHFFFAOYSA-N boranylidynecobalt Chemical compound [Co]#B HZEIHKAVLOJHDG-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 238000004513 sizing Methods 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000011232 storage material Substances 0.000 abstract description 6
- 238000001311 chemical methods and process Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000006140 methanolysis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910003207 NH4BO2 Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of Binary Amorphous Alloys porous microsphere type effective catalysts and preparation method thereof that hydrogen is explained suitable for hydrogen storage material ammonia borine catalytic alcohol, and the chemical formula of the catalyst can be abbreviated as CoxB1‑x, the molar ratio of Co and B are x:(1-x), x value 0.15 ~ 0.85, the catalyst has unformed Amorphous Phase structure, and appearance is in evenly dispersed microspheroidal, and microspherulite diameter is 200 ~ 300nm, and micropore is distributed in surface, and specific surface area is 45 ~ 60 m2·g‑1；The present invention uses liquid phase chemical technique, and process relative ease is not related to the reaction and treatment process of high temperature and pressure, and the time is shorter, easily controllable, and preparation process does not have environmental pollution；By liquid phase chemical process, so that Co-B amorphous alloy product still keeps certain magnetic characteristic, thus convenient for the recycling of the quick separating of catalyst, regeneration and multiplexing, facilitate the operating cost for reducing catalytic reaction process.
Description
Technical field
The present invention relates to catalyst preparation technical fields, specifically a kind of to be suitable for hydrogen storage material ammonia borine catalytic alcohol
Explain the Binary Amorphous Alloys porous microsphere type effective catalyst and preparation method thereof of hydrogen.
Background technique
The theoretical hydrogen of ammonia borine (Ammonia Borane, abbreviation AB) is up to 19.6wt.%, is to be found so far
The highest hydride type hydrogen storage material of hydrogen content.AB is stable white crystal at normal temperatures and pressures, non-volatile, non-toxic,
Thermal stability is stronger, water-soluble and certain organic solvents.Under suitable catalyst and reaction condition auxiliary, AB can pass through heat
The modes such as solution, hydrolysis or alcoholysis controllably release hydrogen.The pyrolysis of AB is released hydrogen point multistep and is carried out, and induction period is longer, releases completely
Hydrogen needs 500 DEG C or more of temperature, and with the generation of the toxic gases such as boron azine.Liquid phase release hydrogen include hydrolysis and alcoholysis, two
Person is that current mainstream releases hydrogen research direction.By catalyst appropriate, it is milder that hydrogen process is released in the hydrolysis of AB, releases hydrogen speed
Rate is very fast, but by-product NH4BO2It there is no feasible Regeneration Ways, thus application cost is higher.The alcohol of AB explains that hydrogen process is most
It is carried out in methanol system, by the auxiliary of appropriate catalysts, can equally realize at a lower temperature and quickly controllably discharge hydrogen
Gas, releases hydrogen amount and hydrolysis is substantially suitable, and harmful side product is relatively fewer, and has theoretically more feasible technological approaches,
Realize alcoholysis by-product NH4B(OCH3)4Regeneration, be conducive to recycling for AB, reduce the application cost of AB.
In recent years the study found that being generated non-in conjunction with the nonmetalloids such as the non-noble metal j elements such as Co and Ni and B, P
Crystal alloy has preferable catalytic hydrogenation or dehydrogenation activity.Amorphous alloy has isotropic space atomic arrangement, place
In shortrange order, " glassy state " metastable structure of longrange disorder, surface has the stronger unsaturated coordination field of force, active sites
Point is more, is easy to adsorption reaction object molecule, thus unique micro-structure make amorphous alloy catalytic activity and selectivity compared with
General crystalline material is more excellent.Experimental fact proves, atom combination, mixing ratio and its microcosmic shape of amorphous alloy
Looks have very important influence to its catalytic performance.Therefore, seek base metal (such as Co, Ni) as basic active constituent
New amorphous state alloy catalyst carries out its preparation, evaluation and application study, has very important theory significance and applies valence
Value.
Summary of the invention
It is an object of the present invention to which the characteristics of explaining hydrogen reaction process for AB alcohol, provides a kind of suitable for hydrogen storage material
The Binary Amorphous Alloys porous microsphere type effective catalyst and preparation method thereof of ammonia borine catalytic alcohol explanation hydrogen.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of Co-B amorphous alloy porous microsphere catalyst for explaining hydrogen for ammonia borine alcohol, the chemical formula of the catalyst
It can be abbreviated as CoxB1-x, the molar ratio of Co and B are x: (1-x), and x value 0.15 ~ 0.85, which has unformed non-
Crystalline state phase structure, appearance are in evenly dispersed microspheroidal, and microspherulite diameter is 200 ~ 300nm, and micropore, specific surface area is distributed in surface
For 45 ~ 60 m2·g-1。
A kind of preparation of Co-B amorphous alloy porous microsphere catalyst as described above that explaining hydrogen for ammonia borine alcohol
Method, the preparation method the following steps are included:
Step 1: the cobalt salt solution of polyvinylpyrrolidone dispersion is prepared: under room temperature, polyvinylpyrrolidone is molten
Enter in water, ultrasonic disperse handles 30min, sufficiently dissolves, and obtaining concentration is 10 ~ 20gL-1The homogeneous water of polyvinylpyrrolidone
Then soluble cobalt is added in solution, continue ultrasonic treatment to Quan Rong, obtain Co2+Ion concentration is 0.5 ~ 1.0 molL -1And
It is dispersed with the transparent cobalt salt solution of polyvinylpyrrolidone；
Step 2: sodium borohydride solution containing surfactant is prepared: under the conditions of ice-water bath, to concentration be 0.05 ~
0.15mol·L-1Soluble diamine solution in be added quaternary ammonium salt cationic surfactant, ultrasonic disperse handles 30min,
Sufficiently dissolution, obtaining surface-active contents is 0.01 ~ 0.03 molL-1Solution, then add sodium borohydride solids, after
Continuous ultrasonic treatment obtains BH to Quan Rong4 -Concentration is 0.5 ~ 1.0 molL -1Alkaline sodium borohydride solution, be kept in dark place spare；
Step 3: the preparation of Co-B amorphous alloy porous microsphere catalyst: according to cobalt boron molar ratio [n (Co2+)/n
(BH4 -)] it is equal to x/(1-x), wherein the material proportion relationship of x=0.15 ~ 0.85 pipettes pre- given x value respectively
The cobalt salt solution and sodium borohydride solution of calculation amount, by nitrogen protection, at room temperature by the alkaline sodium borohydride solution of amount of budget
It is slowly added drop-wise in cobalt salt solution, is stirred simultaneously, be added dropwise, the reaction was continued no longer generates bubble into solution and be
Only, the suspension for being dispersed with black particle is obtained；
Step 4: the leaching and separation of Co-B amorphous alloy catalyst product: preparation after reaction, to suspension into
Row centrifugation, is isolated black solid, is quickly dissolved in black solid in dehydrated alcohol with the ratio of solid-to-liquid ratio 1 (g)/20 (mL),
Ultrasonic disperse handles 30 ~ 60min, and then 10 ~ 15h of reflow treatment at 60 ~ 80 DEG C, is then centrifuged, successively with steaming
Distilled water and dehydrated alcohol wash 3 ~ 5 times respectively, collect solids, are dried in vacuo 10h under the conditions of 50 DEG C to get black micro mist shape
Co-B amorphous alloy porous microsphere catalyst.
Soluble cobalt is cobalt acetate, cobalt chloride or cobaltous sulfate in the step 1.
The model K30 of polyvinylpyrrolidone, molecular weight Mw=1 × 10 in the step 14。
Quaternary ammonium salt cationic surfactant is cetyl trimethylammonium bromide, myristyl three in the step 2
Methyl bromide ammonium or dodecyl trimethyl ammonium bromide.
Soluble diamines refers to ethylenediamine or 1,2- propane diamine in the step 2.
It is 240w that power is selected in the ultrasonic disperse processing, the supersonic generator that frequency is 40kHz.
Beneficial effects of the present invention:
The Binary Amorphous Alloys porous microsphere provided by the invention that hydrogen is explained suitable for hydrogen storage material ammonia borine catalytic alcohol
Type effective catalyst, active constituent are collectively constituted by Co and B, have certain magnetism, convenient for magnetic separation recovery with recycle,
And can be used to controllably adjust alcoholysis reaction releases hydrogen rate；Select base metal Co as catalyst chief active at
Point, replace the noble metals such as the common Pt and Pd of dehydrogenation, so that the preparation cost of catalyst is greatly reduced；
The Binary Amorphous Alloys porous microsphere provided by the invention that hydrogen is explained suitable for hydrogen storage material ammonia borine catalytic alcohol
The preparation method of type effective catalyst, using liquid phase chemical technique, process relative ease is not related to reaction and the place of high temperature and pressure
Reason process, the time is shorter, easily controllable, and preparation process does not have environmental pollution；By liquid phase chemical process, so that
Co-B amorphous alloy product still keeps certain magnetic characteristic, thus convenient for the recycling of the quick separating of catalyst, regeneration and answers
With, facilitate reduce catalytic reaction process operating cost；
Catalyst obtained by the present invention is the amorphous alloy constituted with base metal Co and nonmetallic B, it has original
Expect inexpensive, simple process, easily controllable, the characteristics of cost is relatively low；This catalyst has certain magnetism, convenient for quick separating and
Recycling facilitates the use cost for reducing catalytic reaction process；Co-B amorphous alloy product has microcellular structure, and presentation is compared
It is uniform spherical, be conducive to expand specific surface area, increase active site, improves catalytic activity；According to surveying and determination, present invention gained catalysis
The average grain diameter of agent microballoon is 250nm, and average specific surface area is 52.5 m2·g-1, catalyst is used for 0.5wt.% at 25 DEG C
The Methanolysis of ammonia borine (AB) release hydrogen, averagely releasing hydrogen rate is 8265.2 mlmin-1·g-1, release the flat of hydrogen reaction
Equal apparent activation energy is 48.27 kJmol-1。
Specific embodiment
The present invention is further elaborated With reference to embodiment.
A kind of Co-B amorphous alloy porous microsphere catalyst for explaining hydrogen for ammonia borine alcohol, the chemical formula of the catalyst
It can be abbreviated as CoxB1-x, the molar ratio of Co and B are x: (1-x), and x value 0.15 ~ 0.85, which has unformed non-
Crystalline state phase structure, appearance are in evenly dispersed microspheroidal, and microspherulite diameter is 200 ~ 300nm, and micropore, specific surface area is distributed in surface
For 45 ~ 60 m2·g-1。
Embodiment 1
A kind of preparation method of Co-B amorphous alloy porous microsphere catalyst that explaining hydrogen for ammonia borine alcohol, including with
Lower step:
Step 1: at room temperature, 10g polyvinylpyrrolidone (PVP) being dissolved in 100mL water, is ultrasonically treated 30min, is filled
Divide dissolution, add cobalt acetate 0.05mol, continues ultrasonic treatment to Quan Rong, obtain transparent cobalt salt solution；
Step 2: being 0.05 molL to 100mL, concentration under the conditions of ice-water bath-1Ethylenediamine solution in be added
The cetyl trimethylammonium bromide of 0.001mol, ultrasonic disperse handle 30min, sufficiently dissolve, then add 0.05mol's
NaBH4Solid continues ultrasonic treatment to Quan Rong, obtains NaBH4Alkaline solution is kept in dark place；
Step 3: according to n (Co2+)/n(BH4 -)=0.18 pipettes 15mL cobalt salt solution and the alkaline NaBH of 85mL respectively4
Solution, by nitrogen protection, at room temperature by NaBH4Solution is slowly added drop-wise in cobalt salt solution, while continuous magnetic agitation,
The reaction was continued after being added dropwise, and until no longer generating bubble, obtains black suspension；
Step 4: isolating black solid after centrifugal treating suspension, will be black in the ratio of solid-to-liquid ratio 1 (g)/20 (mL)
Color solid quickly dissolves in dehydrated alcohol, and ultrasonic disperse 30min, then the reflow treatment 10h at 60 DEG C, then carries out centrifugation point
From, washed respectively 3 times with distilled water and dehydrated alcohol, collect solids, at 50 DEG C be dried in vacuo 10h to get black micro mist
The Co-B amorphous alloy porous microsphere catalyst of shape.
Through measuring, the average grain diameter of the catalyst is 280nm, specific surface area 46.5m2·g-1；For at 25 DEG C,
The Methanolysis of the ammonia borine (AB) of 0.5wt.% releases hydrogen, and releasing hydrogen rate is 7866.5 mLmin-1·g-1, release the table of hydrogen reaction
Sight activation energy is 50.63 kJmol-1。
Embodiment 2
A kind of preparation method of Co-B amorphous alloy porous microsphere catalyst that explaining hydrogen for ammonia borine alcohol, including with
Lower step:
Step 1: at room temperature, 20g PVP being dissolved in 100mL water, is ultrasonically treated 30min, is sufficiently dissolved, add chlorine
Change cobalt 0.1mol, continues ultrasonic treatment to Quan Rong, obtain transparent cobalt salt solution；
Step 2: being 0.15 molL to 100mL, concentration under the conditions of ice-water bath-11,2- propane diamine aqueous solution in
The tetradecyltrimethylammonium bromide of 0.003mol is added, ultrasonic disperse handles 30min, sufficiently dissolves, then add
The NaBH of 0.1mol4Solid continues ultrasonic treatment to Quan Rong, obtains NaBH4Alkaline solution is kept in dark place；
Step 3: according to n (Co2+)/n(BH4 -)=5.70 pipette 85mL cobalt salt solution and the alkaline NaBH of 15mL respectively4
Solution, by nitrogen protection, at room temperature by NaBH4Solution is slowly added drop-wise in cobalt salt solution, while continuous magnetic agitation,
The reaction was continued after being added dropwise, and until no longer generating bubble, obtains black suspension；
Step 4: isolating black solid after centrifugal treating suspension, will be black in the ratio of solid-to-liquid ratio 1 (g)/20 (mL)
Color solid quickly dissolves in dehydrated alcohol, ultrasonic disperse 60min, then the reflow treatment 15h at 80 DEG C, centrifugation, with distilled water and
Dehydrated alcohol washs 5 times respectively, collects solids, is dried in vacuo 10 h at 50 DEG C to get the Co-B amorphous of black micro mist shape
State alloy porous microspherical catalyst.
Through measuring, the average grain diameter of the catalyst is 220nm, specific surface area 53.7m2·g-1；For at 25 DEG C,
The Methanolysis of the ammonia borine (AB) of 0.5wt.% releases hydrogen, and releasing hydrogen rate is 8433.62 mLmin-1·g-1, release hydrogen reaction
Apparent activation energy is 45.06 kJmol-1。
Embodiment 3
A kind of preparation method of Co-B amorphous alloy porous microsphere catalyst that explaining hydrogen for ammonia borine alcohol, including with
Lower step:
Step 1: at room temperature, 15g PVP being dissolved in 100mL water, is ultrasonically treated 30min, is sufficiently dissolved, add sulphur
Sour cobalt 0.075mol continues ultrasonic treatment to Quan Rong, obtains transparent cobalt salt solution；
Step 2: being 0.10 molL to 100mL, concentration under the conditions of ice-water bath-1Ethylenediamine solution in be added
The dodecyl trimethyl ammonium bromide of 0.002mol, ultrasonic disperse handle 30min, sufficiently dissolve, then add 0.075mol
NaBH4Solid continues ultrasonic treatment to Quan Rong, obtains NaBH4Alkaline solution is kept in dark place；
Step 3: according to n (Co2+)/n(BH4 -)=2.90 pipette 74.5mL cobalt salt solution and the alkalinity of 25.5mL respectively
NaBH4Solution, by nitrogen protection, at room temperature by NaBH4Solution is slowly added drop-wise in cobalt salt solution, while continuous magnetic force
Stirring, is added dropwise, the reaction was continued, until no longer generating bubble, obtains black suspension；
Step 4: isolating black solid after centrifugal treating suspension, will be black in the ratio of solid-to-liquid ratio 1 (g)/20 (mL)
Color solid quickly dissolves in dehydrated alcohol, ultrasonic disperse 45min, then the reflow treatment 12h at 70 DEG C, after centrifugation with distilled water and
Dehydrated alcohol alternately washs each 4 times, collects solids, is dried in vacuo 10h at 50 DEG C to get the Co-B amorphous of black micro mist shape
State alloy porous microspherical catalyst.
Through measuring, the average grain diameter of the catalyst is 230nm, specific surface area 49.8m2·g-1；For at 25 DEG C,
The Methanolysis of the ammonia borine (AB) of 0.5wt.% releases hydrogen, and releasing hydrogen rate is 8061.26 mLmin-1·g-1, release hydrogen reaction
Apparent activation energy is 48.73 kJmol-1。
Claims (6)
1. a kind of preparation method for the Co-B amorphous alloy porous microsphere catalyst for explaining hydrogen for ammonia borine alcohol, the catalyst
Chemical formula can be abbreviated as CoxB1-x, the molar ratio of Co and B are x: (1-x), x value 0.15 ~ 0.85, which has nothing
The Amorphous Phase structure of sizing, appearance are in evenly dispersed microspheroidal, and microspherulite diameter is 200 ~ 300nm, and micropore is distributed in surface,
Specific surface area is 45 ~ 60 m2·g-1, which is characterized in that the preparation method the following steps are included:
Step 1: the cobalt salt solution of polyvinylpyrrolidone dispersion is prepared: under room temperature, polyvinylpyrrolidone being dissolved in water
In, ultrasonic disperse handles 30min, sufficiently dissolves, and obtaining concentration is 10 ~ 20gL-1Polyvinylpyrrolidone homogeneous phase aqueous solution,
Then soluble cobalt is added, continues ultrasonic treatment to Quan Rong, obtains Co2+Ion concentration is 0.5 ~ 1.0 molL -1And disperse
There is the transparent cobalt salt solution of polyvinylpyrrolidone；
Step 2: sodium borohydride solution containing surfactant is prepared: under the conditions of ice-water bath, to concentration be 0.05 ~
0.15mol·L-1Soluble diamine solution in be added quaternary ammonium salt cationic surfactant, ultrasonic disperse handles 30min,
Sufficiently dissolution, obtaining surface-active contents is 0.01 ~ 0.03 molL-1Solution, then add sodium borohydride solids, after
Continuous ultrasonic treatment obtains BH to Quan Rong4 -Concentration is 0.5 ~ 1.0 molL -1Alkaline sodium borohydride solution, be kept in dark place spare；
Step 3: the preparation of Co-B amorphous alloy porous microsphere catalyst: according to cobalt boron molar ratio [n (Co2+)/n(BH4 -)]
Equal to x/(1-x), wherein the material proportion relationship of x=0.15 ~ 0.85 pipettes amount of budget for given x value respectively
Cobalt salt solution and sodium borohydride solution, by nitrogen protection, at room temperature slowly by the alkaline sodium borohydride solution of amount of budget
Be added drop-wise in cobalt salt solution, be stirred simultaneously, be added dropwise, the reaction was continued no longer generate bubble into solution until, obtain
It is dispersed with the suspension of black particle；
Step 4: the leaching and separation of Co-B amorphous alloy catalyst product: preparation after reaction, to suspension carry out from
The heart isolates black solid, is quickly dissolved in black solid in dehydrated alcohol with the ratio of solid-to-liquid ratio 1g/20mL, ultrasonic disperse
30 ~ 60min is handled, then 10 ~ 15h of reflow treatment at 60 ~ 80 DEG C, is then centrifuged, and successively uses distilled water and nothing
Water-ethanol washs 3 ~ 5 times respectively, collects solids, and it is non-to get the Co-B of black micro mist shape that 10h is dried in vacuo under the conditions of 50 DEG C
Crystal alloy porous microsphere catalyst.
2. the preparation of the Co-B amorphous alloy porous microsphere catalyst of hydrogen is explained for ammonia borine alcohol as described in claim 1
Method, it is characterised in that: soluble cobalt is cobalt acetate, cobalt chloride or cobaltous sulfate in the step 1.
3. the preparation of the Co-B amorphous alloy porous microsphere catalyst of hydrogen is explained for ammonia borine alcohol as described in claim 1
Method, it is characterised in that: the model K30 of polyvinylpyrrolidone, molecular weight Mw=1 × 10 in the step 14。
4. the preparation of the Co-B amorphous alloy porous microsphere catalyst of hydrogen is explained for ammonia borine alcohol as described in claim 1
Method, it is characterised in that: quaternary ammonium salt cationic surfactant is cetyl trimethylammonium bromide, ten in the step 2
Tetraalkyl trimethylammonium bromide or dodecyl trimethyl ammonium bromide.
5. the preparation of the Co-B amorphous alloy porous microsphere catalyst of hydrogen is explained for ammonia borine alcohol as described in claim 1
Method, it is characterised in that: soluble diamines refers to ethylenediamine or 1,2- propane diamine in the step 2.
6. the preparation of the Co-B amorphous alloy porous microsphere catalyst of hydrogen is explained for ammonia borine alcohol as described in claim 1
Method, it is characterised in that: it is 240W that power is selected in the ultrasonic disperse processing, the supersonic generator that frequency is 40KHz.
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| A novel perspective for hydrogen generation from ammonia borane (NH3BH3) with CoeB catalysts:"Ultrasonic Hydrolysis";Aysel Kanturk Figen等;《Hydrogen Energy》;20130109;第38卷;第2824-2835页 |
| Co-B非晶态合金催化剂用于乳酸乙酯液相加氢制1,2-丙二醇;马晓雨等;《精细化工》;20140430;第31卷(第4期);第452-457页 |
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