CN113522328A - Nano solid-phase catalyst for hydrogen production from formic acid and preparation method thereof - Google Patents
Nano solid-phase catalyst for hydrogen production from formic acid and preparation method thereof Download PDFInfo
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- CN113522328A CN113522328A CN202010290458.0A CN202010290458A CN113522328A CN 113522328 A CN113522328 A CN 113522328A CN 202010290458 A CN202010290458 A CN 202010290458A CN 113522328 A CN113522328 A CN 113522328A
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- catalyst
- metal
- carrier
- hydrogen production
- formic acid
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000001257 hydrogen Substances 0.000 title claims abstract description 78
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 51
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000007790 solid phase Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002407 reforming Methods 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- -1 biimidazole Chemical compound 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 2
- ULUNQYODBKLBOE-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)-1h-pyrrole Chemical compound C1=CNC(C=2NC=CC=2)=C1 ULUNQYODBKLBOE-UHFFFAOYSA-N 0.000 description 1
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical compound N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HCAUQPZEWLULFJ-UHFFFAOYSA-N benzo[f]quinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=N1 HCAUQPZEWLULFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- FKZFOHABAHJDIK-UHFFFAOYSA-K trichloroscandium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Sc+3] FKZFOHABAHJDIK-UHFFFAOYSA-K 0.000 description 1
- RYYVLZVUVIJVGH-UHFFFAOYSA-N trimethylxanthine Natural products CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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Abstract
The invention provides a nano solid-phase catalyst for hydrogen production by formic acid, which is supported nano RuxMyThe N-C catalyst comprises a carrier and a carrier. The general formula of the load is RuxMyThe load contains bimetal Ru and M, and the load is roasted to form nano alloy which is fixed on nitrogen and/or carbon sites (N-C)) The metal M is an oxophilic metal. The catalyst improves the dehydrogenation efficiency of the formic acid and reduces the generation of by-product CO. The invention also provides a preparation method of the catalyst, which takes a homogeneous metal organic complex as an impregnation liquid, and greatly improves the distribution uniformity of metal ruthenium and metal M in the catalyst. Meanwhile, nitrogen and carbon sites formed in the roasting process of the organic complex are used as metal fixing sites, so that the dispersity of metal and the specific surface area of the catalyst are improved, and the catalyst has high-efficiency hydrogen production activity.
Description
Technical Field
The invention relates to the technical field of solid phase catalysts, in particular to a nanometer solid phase catalyst for hydrogen production by formic acid and a preparation method of the catalyst.
Background
Formic acid is one of organic liquid media capable of producing hydrogen under the conditions of normal temperature and normal pressure, and has the good properties of low toxicity, low harm, nonflammability and the like, so that the formic acid becomes an excellent hydrogen energy carrier and can meet the requirements of people on mobile hydrogen storage. Under the circumstance that automobile energy development begins to advance to hydrogen fuel cell technology, the hydrogen production technology by formic acid reforming has been greatly improved in recent years, but the overall performance of the hydrogen production reactor does not meet the requirement of large-scale commercial application. One of the limiting factors is that the performance of the formic acid reforming catalyst is still in the technical critical stage, and the main problems of low catalytic efficiency, poor stability, difficult control of conversion rate and the like are faced at present.
Ruthenium is being investigated as an element which is relatively frequently used in formic acid reforming catalysts to improve the performance thereof. Ruthenium-based formic acid reforming catalysts are mainly classified into two major classes, homogeneous catalysts and solid-phase catalysts. The phosphine-coordinated homogeneous ruthenium catalyst is one of reported catalysts capable of efficiently preparing high-purity hydrogen, and the homogeneous catalyst has a large contact area with formic acid, so that the conversion speed is high. However, the effective separation of the formic acid liquid phase system and the catalyst is difficult to realize, so that the conversion speed is difficult to control, and the requirement of quick start and stop cannot be realized. Compared with a homogeneous catalyst, the ruthenium-based heterogeneous catalyst has the greatest advantage of high stability, and can meet the hydrogen supply requirement of quick start and stop, so that the reformer is safer and more easily controlled, and the practicability is stronger. Meanwhile, compared with other noble metal catalysts such as nano palladium, nano iridium, nano palladium-gold alloy and the like, the ruthenium metal has obvious advantage in cost. However, the method has the defects of low hydrogen production speed of the catalyst per unit mass, high catalyst consumption for improving the hydrogen production amount and the like, and has the problem of high relative content of the byproduct CO, thereby limiting the application of the method. As in the literature (Ruthenium Clusters on Carbon Nanofibers for chemical Acid composition: Effect of Doping the Support with Nitrogen, ChemCat chem2015,7,2910-2917.), a Carbon nanofiber supported Ruthenium cluster catalyst was prepared with a Carbon monoxide selectivity as high as 8%. Meanwhile, in the aspect of performance evaluation of the catalyst, the evaluation basis mainly focuses on the hydrogen production efficiency under a short-time test, and the evaluation on the aspects of stability and the like is rarely reported.
Therefore, in order to overcome the defects of the ruthenium-based solid-phase catalyst, the overall performance of the ruthenium-based solid-phase catalyst needs to be improved from multiple aspects of optimizing the active composition, improving the dispersion degree and specific surface area of the active components, improving the stability of the active components and the like, so that the industrial process of the hydrogen production technology by formic acid reforming is accelerated.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a nano solid-phase catalyst for hydrogen production from formic acid.
The second object of the present invention is to provide a method for preparing the above catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a nano solid-phase catalyst for hydrogen production by formic acid, which is a supported nano RuxMyA/N-C catalyst comprising a support and a carrier, the support being supported on the carrier, the support having the general formula RuxMyN-C, wherein 0<x<1,0<y is less than or equal to 0.5, the load contains bimetal Ru and M, the metal M carries out active modification on the metal ruthenium, and the nanometer Ru is formed after roasting treatmentxMyThe alloy is fixed on nitrogen and/or carbon sites (N-C), and the metal M is an oxophilic metal selected from any one of Ti, V, Sc and W.
Preferably, the ratio of x to y is 1 (0.001-0.3).
Preferably, the sum of the mass of the metal ruthenium and the mass of the metal M accounts for RuxMy0.1 to 40 percent of the total mass of the/N-C, preferably 10 to 35 percent.
Preferably, theIn the catalyst, the RuxMyThe mass of the/N-C accounts for 0.05-50% of the total mass of the catalyst.
Preferably, the nitrogen and/or carbon sites (N-C) are derived from a heterocyclic compound containing a nitrogen heteroatom, the heterocyclic compound being selected from any of 2,2' -bipyridine, 4' -bipyridine, 2':6', 2' -terpyridine, 2' -bipyridine, 4' -bipyridine, 2-bipyridine, 1, 10-orthophenanthrene.
Preferably, the carrier is at least one selected from carbon powder, activated carbon particles, carbon felt, porous ceramic, diatomite and kaolin.
The invention also relates to a preparation method of the nano solid-phase catalyst for hydrogen production from formic acid, which comprises the following steps:
1) preparing a metal precursor solution: dissolving a compound containing a metal element in a solvent, adding a complex, and stirring until the complex is dissolved.
Preferably, the compounds containing the metal element are ruthenium-containing compounds and M-containing compounds, and the molar ratio of the metal element to the complex is 1 (1-5).
Preferably, the complex is a heterocyclic compound containing a nitrogen heteroatom, the heterocyclic compound being selected from any one of 2,2 '-bipyridine, 4' -bipyridine, 2':6',2 ″ -terpyridine, 2 '-bipyridine, 4' -bipyridine, 2-bipyridine, 1, 10-phenanthridine.
Preferably, the solvent is a mixed solvent containing water and an organic solvent.
Preferably, the organic solvent is selected from any one of alcohol, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and acetonitrile; the alcohol is at least one selected from methanol, ethanol, ethylene glycol, glycerol and butanediol.
Preferably, the volume ratio of the water to the organic solvent in the mixed solvent is 1 (1-50).
2) Pretreatment of the carrier: and (3) pickling and drying the carrier, roasting, and then cooling to room temperature for later use.
Preferably, the pickling is carried out with an acid solution selected from HNO3、HCl、H2SO4And at least one of HF, the concentration of the acid solution is 0.1-3mol/L, the acid washing time is 5-120min, and the roasting is carried out in the air atmosphere for 1-4 h.
3) Carrier impregnation: and under an inert atmosphere, putting the pretreated carrier into a metal precursor solution for dipping, and then drying.
Preferably, the impregnation is carried out under reflux conditions, the temperature of condensation reflux is 40-120 ℃, the reflux time is 3-12h, and the drying temperature is 50-150 ℃.
4) Roasting and acid washing: roasting the impregnated carrier in an inert atmosphere, and then carrying out acid washing to obtain the nano solid-phase catalyst for hydrogen production by formic acid.
Preferably, the acid washing is to soak the roasted carrier in acid liquor, stir and wash the carrier, then wash the carrier by deionized water until the carrier is neutral, and then dry the carrier;
preferably, the acid liquor is selected from HNO3、HCl、H2SO4At least one of HF and HCOOH, wherein the acid solution concentration is 0.05-20mol/L, the acid pickling temperature is 10-90 ℃, and the acid pickling time is 0.5-10 h;
preferably, the roasting temperature is 400-800 ℃, and the inert atmosphere is selected from any one of nitrogen, argon and helium.
The invention has the beneficial effects that:
the invention provides a nano solid-phase catalyst for hydrogen production from formic acid, which comprises a load and a carrier, wherein the general formula of the load is RuxMythe/N-C, the load contains bimetal Ru and M, and the metal is fixed on nitrogen and/or carbon sites after roasting treatment. The oxophilic metal M is used for carrying out active modification on the metal Ru, and by means of the strong binding force of the oxophilic metal and the oxygen element in the formic acid, the dehydrogenation efficiency of the formic acid is improved, and the generation of a byproduct CO is reduced.
The invention also provides a preparation method of the catalyst, which takes a homogeneous metal organic complex as an impregnation liquid, and greatly improves the distribution uniformity of metal ruthenium and metal M in the catalyst. Meanwhile, nitrogen and carbon sites formed in the roasting process of the organic complex are used as metal fixing sites, so that the dispersity of metal and the specific surface area of the catalyst are improved, and the catalyst has high-efficiency hydrogen production activity. Meanwhile, the utilization rate of metal is improved, the dosage of the catalyst is reduced, and the preparation cost is effectively reduced.
In addition, the benzene heterocyclic organic ligand in the complex is cracked after being roasted in inert atmosphere and polymerized on the surface of the carrier, so that the surface immobilization of metal elements is stabilized, and the long-term stability of the catalyst is improved.
Drawings
FIG. 1 is a RuV carbon powder load0.1Transmission electron microscope picture of the/N-C catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
[ catalyst ]
The embodiment of the invention relates to a nano solid-phase catalyst for hydrogen production by formic acid, which is supported nano RuxMya/N-C catalyst. The catalyst can stably exist in the air for a long time, and keeps good activity and stability.
Specifically, the catalyst comprises a carrier and a support supported on the carrier. The general formula of the load is RuxMyN-C, wherein 0<x<1,0<y is less than or equal to 0.5, and the load contains bimetal Ru and M. Wherein, ruthenium metal is an active component, and the metal M carries out active modification on ruthenium. Nano-grade Ru formed after roasting treatmentxMyThe alloy is fixed on nitrogen and/or carbon sites (N-C).
In the support, the metal M is an oxophilic metal and is selected from any one of Ti, V, Sc and W. The affinity between the metal and oxygen is stronger, and the formed oxide is more stable. The oxophilic metal has stronger binding force with oxygen element in formic acid, so that the dehydrogenation efficiency of the formic acid can be improved, and the generation of by-products CO is reduced.
x and y are relative molar amounts of Ru and M, and the ratio of x to y is preferably 1 (0.001-0.3).
In one embodiment of the present invention, the sum of the mass of the metal ruthenium and the metal M accounts for RuxMy0.1-40% of the total mass of the/N-C. That is, the total mass of the ruthenium metal and the M metal in the supported material is 0.1 to 40%, preferably 10 to 35% of the total mass of the supported material.
RuxMyThe mass of the catalyst is 0.05-50% of the total mass of the catalyst.
In one embodiment of the invention, the nitrogen and/or carbon sites (N-C) are derived from heterocyclic compounds containing a nitrogen heteroatom. The heterocyclic compound is selected from any one of bipyridine, bipyrimidine, dipyrrole, biimidazole, azaphenanthrene, azaindene and derivatives thereof, and is specifically selected from any one of 2,2' -bipyridine, 4' -bipyridine, 2':6', 2' -terpyridine, 2' -bipyrimidine, 4' -bipyrimidine, 2-dipyrrole and 1, 10-o-diazaphenanthryl.
In one embodiment of the present invention, the carrier is selected from at least one of carbon powder, activated carbon particles, carbon felt, porous ceramic, diatomaceous earth, kaolin.
[ catalyst preparation ]
The invention also relates to a preparation method of the nano solid-phase catalyst for hydrogen production from formic acid, which comprises the following steps:
1) preparing a metal precursor solution: dissolving a compound containing a metal element in a solvent, adding a complex, and stirring until the complex is dissolved.
Further, the ruthenium-containing compound and the M-containing compound are dissolved in a solvent in a molar ratio of metal ruthenium to metal M.
In one embodiment of the present invention, the molar ratio of the metal element to the complex is 1 (1-5), and the metal is the sum of the metal ruthenium and the metal M.
In one embodiment of the present invention, the ruthenium-containing compound is a water-soluble salt of ruthenium, and may be selected from any one of chlorides, sulfates, nitrates, and acetates of ruthenium. The M-containing compound is a water-soluble salt of metal M, and can be selected from any one of chloride, sulfate, nitrate and acetate of M.
In one embodiment of the invention, the complex is a heterocyclic compound containing a nitrogen heteroatom, the heterocyclic compound being selected from any one of 2,2 '-bipyridine, 4' -bipyridine, 2':6',2 ″ -terpyridine, 2 '-bipyridine, 4' -bipyridine, 2-bipyrrole, 1, 10-phenanthridine.
In one embodiment of the present invention, the solvent is a mixed solvent containing water and an organic solvent, and functions to allow the inorganic metal compound and the organic complex to be simultaneously dissolved to form a highly dispersed uniform phase.
In one embodiment of the present invention, the organic solvent is selected from any one of alcohol, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile; the alcohol is at least one selected from methanol, ethanol, ethylene glycol, glycerol and butanediol.
In one embodiment of the present invention, the volume ratio of water to the organic solvent in the mixed solvent is 1 (1-50).
2) Pretreatment of the carrier: and (3) pickling and drying the carrier, roasting, and then cooling to room temperature for later use.
In one embodiment of the invention, the pickling is carried out with an acid solution selected from HNO3、HCl、H2SO4At least one of HF, acid solution concentration of 0.1-3mol/L, acid washing time of 5-120min, roasting in air atmosphere at 300-700 deg.c for 1-4 hr.
3) Carrier impregnation: and under an inert atmosphere, putting the pretreated carrier into a metal precursor solution for dipping, and then drying.
In one embodiment of the present invention, the impregnation is performed under an inert atmosphere, which is intended to isolate air and prevent the valence state change of ruthenium ions in the metallic ruthenium ion complex.
In one embodiment of the invention, the impregnation is carried out under reflux conditions, the temperature of condensation reflux is 40-120 ℃, the reflux time is 3-12h, and the drying temperature is 50-150 ℃.
4) Roasting and acid washing: roasting the impregnated carrier in an inert atmosphere, and then carrying out acid washing to obtain the nano solid-phase catalyst for hydrogen production by formic acid.
In one embodiment of the invention, the impregnated carrier is roasted in an inert atmosphere and then is subjected to acid washing, so that metallorganics which are not completely decomposed in the roasting process and metal M which is separately formed in the roasting process can be removed, and then the nano solid-phase catalyst for hydrogen production by formic acid is obtained.
In one embodiment of the invention, the acid washing is to soak the calcined carrier in acid liquor, stir and wash the calcined carrier, then wash the calcined carrier with deionized water until the calcined carrier is neutral, and then dry the calcined carrier. The acid solution is selected from HNO3、HCl、H2SO4At least one of HF and HCOOH, wherein the acid liquor concentration is 0.05-20mol/L, the acid pickling temperature is 10-90 ℃, and the acid pickling time is 0.5-10 h;
in one embodiment of the present invention, the calcination temperature is 400-800 ℃, and the inert atmosphere is selected from any one of nitrogen, argon and helium.
In one embodiment of the present invention, the catalyst is prepared by the following steps: 1) pretreatment of a catalyst carrier: pickling the carrier in 0.1-3mol/L nitric acid solution at room temperature for 5-120min, drying, roasting at the temperature of 300-700 ℃ in air atmosphere for 1-4h, and cooling to room temperature for later use. 2) Preparing and impregnating a metal precursor solution: weighing a ruthenium-containing compound and a M-containing compound according to the molar ratio of metal ruthenium to metal M, dissolving the ruthenium-containing compound and the M-containing compound in a mixed solvent containing water and an organic solvent, adding a complex, and stirring until the complex is dissolved. Adding the pretreated carrier, condensing and refluxing at 40-120 deg.C for 3-12h under the protection of inert atmosphere, and oven drying at 50-150 deg.C. 3) Roasting: roasting and acid washing the dried carrier in inert atmosphere to directly obtain the carrier-supported nano RuxMyThe catalyst can also be obtained by further acid washing after roasting.
The invention also relates to a hydrogen production method by formic acid, which adopts the nano solid-phase catalyst for hydrogen production by formic acid provided by the invention to decompose formic acid in a water phase system, thereby obtaining hydrogen.
Example 1
Ultrasonically soaking carbon powder in a nitric acid solution with the concentration of 0.5mol/L for 1h, repeatedly cleaning and drying the carbon powder by using deionized water, and roasting the carbon powder in a muffle furnace for 2h at the temperature of 400 ℃ under the air condition for later use. Then 0.45g of anhydrous ruthenium trichloride, 0.034g of vanadium trichloride and 1.12g of bipyridine are weighed according to the molar ratio of 1:0.1 of metal ruthenium to metal vanadium and the molar ratio of total metal to bipyridine is 1:3, and are stirred and dissolved in a mixed solvent consisting of 6ml of deionized water and 28ml of N, N-dimethylformamide. Adding 1g of treated carbon powder into the mixed solvent, condensing and refluxing for 5h under the protection of argon at 50 ℃, filtering out the carbon powder and drying at 70 ℃. Weighing 1.19g of the powder, placing the powder in a tubular furnace, introducing Ar gas for protection, roasting the powder at 550 ℃ for 2 hours, soaking the powder in 3mol/L formic acid solution, stirring the solution at 50 ℃ for 5 hours, filtering the solution, washing the solution with deionized water to be neutral, and drying the solution to obtain RuV loaded with 1.11g of carbon powder0.1and/N-C. FIG. 1 is a transmission electron microscope image of the substance, and it can be known that Ru and V in the catalyst prepared by the invention are both in nanometer level.
Prepared 1.11g of carbon powder loaded nanometer RuV0.1the/N-C catalyst is filled in a reactor, formic acid solution is prepared by using 85 mass percent of formic acid and potassium formate, wherein the molar ratio of the formic acid to the potassium formate is 3: 1. Adding 50ml of formic acid solution into a reaction kettle, controlling the reaction temperature to be 95 ℃, and after hydrogen production is started, continuously dropwise adding 85% formic acid to maintain the molar ratio of formic acid to potassium formate in the reaction kettle to be 3: 1. The generated mixed gas passes through an activated carbon adsorption column to remove formic acid vapor, passes through an alkali absorption tank to remove carbon dioxide, and then the hydrogen production rate is measured by a drainage method. Detection of H by gas chromatography2Volume fraction of CO by-product in the gas volume.
Table 1 shows the performance of the catalyst for producing hydrogen for 48 hours. Wherein the hydrogen production rate is RuV0.1Calculated as hydrogen production per mass of metal in the N-C catalyst, the percentage by volume of CO is calculated as CO in H2And the volume fraction of the total gas volume of CO. As can be seen from Table 1, the percentage by volume of CO is low within 1h of start-up and rises slowly with timeThen, the concentration is maintained below 0.0034%, and the hydrogen production rate is maintained at about 0.25 ml/min/mg.
TABLE 1 carbon powder loaded RuV0.1Performance of N-C catalyst for preparing hydrogen for 48h
Time/h | Hydrogen production rate/ml/min mg | Content of CO/%) |
1 | 0.254 | 0.0014 |
5 | 0.248 | 0.0021 |
12 | 0.252 | 0.0034 |
24 | 0.247 | 0.0031 |
36 | 0.251 | 0.0029 |
48 | 0.252 | 0.0031 |
Comparative example 1
0.45g of anhydrous ruthenium trichloride and 1.02g of bipyridine are weighed according to the molar ratio of the metal ruthenium to the bipyridine of 1:3, and are stirred and dissolved in a mixed solvent consisting of 6ml of deionized water and 28ml of N, N-dimethylformamide. 1.06g of a Ru/N-C catalyst supported on carbon powder was obtained in the same manner as in example 1 by adding 1g of carbon powder pretreated in the same manner as in example 1.
The catalyst was filled in a reactor, and hydrogen gas was produced by the same operation and hydrogen production conditions as in example 1. Table 2 shows the performance of the catalyst for producing hydrogen for 48 hours, the hydrogen production speed fluctuates about 0.14 ml/min-mg in 48 hours, and the volume percentage content of the impurity CO is up to 0.05%.
TABLE 2 carbon powder loaded Ru/N-C catalyst hydrogen production time 48h performance
Time/h | Hydrogen production rate/ml/min mg | Content of CO/%) |
1 | 0.14 | 0.053 |
5 | 0.142 | 0.049 |
12 | 0.145 | 0.05 |
24 | 0.138 | 0.041 |
36 | 0.143 | 0.048 |
48 | 0.137 | 0.044 |
Example 2
0.45g of anhydrous ruthenium trichloride, 0.06g of titanium tetrachloride and 1.06g of bipyridine are weighed respectively according to the molar ratio of the metal ruthenium to the metal titanium of 1:0.15 and the molar ratio of the total metal to the bipyridine of 1:3, and are stirred and dissolved in a mixed solvent consisting of 4ml of deionized water and 30ml of N, N-dimethylformamide. Adding 1g of carbon powder pretreated according to the method of the embodiment 1, condensing and refluxing for 8 hours under the protection of argon at 50 ℃, filtering out the carbon powder and drying. Weighing 1.23g of RuTi, placing in a tube furnace, introducing Ar gas for protection, and roasting at 500 deg.C for 2h to obtain 1.16g of carbon powder loaded RuTi0.15a/N-C catalyst.
The catalyst was filled in a quartz tube reactor, and hydrogen was produced by the same operation and hydrogen production conditions as in example 1. Table 3 shows that the catalyst has the performance of producing hydrogen for 48h, the hydrogen production speed is more than 0.22 ml/min. mg within 48h, the hydrogen production speed is relatively stable, and the volume percentage content of impurity CO is less than 0.0051%.
TABLE 3 carbon powder loaded RuTi0.15The hydrogen production time of the N-C catalyst is 48h
Time/h | Hydrogen production rate/ml/min mg | Content of CO/%) |
1 | 0.22 | 0.0041 |
5 | 0.21 | 0.0051 |
12 | 0.227 | 0.0043 |
24 | 0.236 | 0.0041 |
36 | 0.225 | 0.0049 |
48 | 0.217 | 0.0044 |
Example 3
According to the molar ratio of metal ruthenium to metal vanadium of 1:0.3 and the molar ratio of total metal to bipyridine of 1:3, 0.45g of anhydrous ruthenium trichloride, 0.1g of vanadium trichloride and 1.31g of bipyridine are respectively weighed, stirred and dissolved in a mixed solvent consisting of 4ml of deionized water and 30ml of N, N-dimethylformamide, 1g of carbon powder pretreated according to the method in the embodiment 1 is added, and the carbon powder is filtered after condensation and reflux are carried out for 5 hours under the protection of argon gas at the temperature of 50 ℃.Weighing 1.24g after drying, placing the powder in a tube furnace, introducing Ar gas for protection, roasting the powder for 2 hours at 550 ℃, then carrying out acid cleaning on the roasted carbon powder according to the method in the embodiment 1, and drying the powder to obtain RuV loaded by 1.2g of carbon powder0.3a/N-C catalyst.
The catalyst was filled in a quartz tube reactor, and hydrogen was produced by the same operation and hydrogen production conditions as in example 1. Table 4 shows the performance of the catalyst for preparing hydrogen for 48 hours, the hydrogen production speed is maintained to be more than 0.18ml/min & mg, and the CO content is reduced to be less than 0.0021 percent.
TABLE 4 carbon powder loading RuV0.3Performance of N-C catalyst for preparing hydrogen for 48h
Time/h | Hydrogen production rate/ml/min mg | Content of CO/%) |
1 | 0.176 | 0.0024 |
5 | 0.184 | 0.0021 |
12 | 0.186 | 0.0024 |
24 | 0.181 | 0.0026 |
36 | 0.179 | 0.0023 |
48 | 0.182 | 0.0021 |
Example 4
A metal precursor solution was prepared according to the method of example 1, wherein phenanthroline was used as a complex, and the molar ratio of the total metal to phenanthroline was 1: 3. 1g of carbon powder pretreated according to the method of example 1 was added thereto, and then, the mixture was condensed and refluxed for 4 hours under the protection of argon gas at 50 ℃ and the carbon powder was filtered out. Weighing 1.36g, placing in a tube furnace, introducing Ar gas for protection, and calcining at 650 deg.C for 2h to obtain 1.25g of RuTi loaded with carbon powder0.05a/N-C catalyst.
The catalyst was filled in a quartz tube reactor, and hydrogen was produced by the same operation and hydrogen production conditions as in example 1. Table 5 shows the performance of the catalyst for producing hydrogen for 48 hours, the hydrogen production speed is maintained to be more than 0.22 ml/min. mg, and the CO content is as low as 0.0071%.
TABLE 5 carbon powder loaded RuT0.05Performance of N-C catalyst for preparing hydrogen for 48h
Time/h | Hydrogen production rate/ml/min mg | Content of CO/%) |
1 | 0.226 | 0.0071 |
5 | 0.224 | 0.0073 |
12 | 0.221 | 0.0074 |
24 | 0.223 | 0.0079 |
36 | 0.219 | 0.0081 |
48 | 0.22 | 0.008 |
Example 5
According to the molar ratio of metal ruthenium to metal scandium of 1:0.1 and the molar ratio of total metal to bipyridine of 1:3, 0.45g of anhydrous ruthenium trichloride, 0.056g of scandium trichloride hexahydrate and 1.12g of bipyridine are respectively weighed, stirred and dissolved in a mixed solvent consisting of 5ml of deionized water and 20ml of nitrogen-methyl pyrrolidone, 1g of carbon powder pretreated according to the method of example 1 is added, the mixture is condensed and refluxed for 5 hours under the protection of argon gas at 50 ℃, the carbon powder is filtered out, and the dried mixture is weighed to have the mass of 1.46 g. Then placing the mixture in a tube furnace, introducing Ar gas for protection, and roasting the mixture for 2 hours at the temperature of 600 ℃ to obtain 1.32g of RuSc loaded by carbon powder0.1a/N-C catalyst.
The catalyst was filled in a reactor, and hydrogen gas was produced by the same operation and hydrogen production conditions as in example 1. Table 6 shows the performance of the catalyst for producing hydrogen for 48 hours, the hydrogen production rate is maintained to be more than 0.4 ml/min. mg, and the CO content is as low as 0.01 percent.
TABLE 6 RuSc carbon powder Loading0.1Performance of N-C catalyst for preparing hydrogen for 48h
Time/h | Hydrogen production rate/ml/min mg | Content of CO/%) |
1 | 0.436 | 0.011 |
5 | 0.424 | 0.013 |
12 | 0.415 | 0.010 |
24 | 0.417 | 0.009 |
36 | 0.390 | 0.011 |
48 | 0.40 | 0.008 |
The above examples and test results show that the nano solid-phase catalyst for hydrogen production from formic acid can efficiently catalyze the decomposition of formic acid to generate hydrogen and carbon dioxide under the conditions of low temperature, normal pressure and water phase. Due to the presence of the bimetallic in the catalyst, a gas mixture was obtained with a CO content of < 0.015%. While comparative example 1 does not use oxophilic metals, the CO content in the hydrogen production product is > 0.04%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The nanometer solid-phase catalyst for hydrogen production from formic acid is characterized in that the catalyst is supported nanometer RuxMyan/N-C catalyst comprising a support and a carrier, the support being supported on the carrier,
the general formula of the load is RuxMyN-C, wherein 0<x<1,0<y is less than or equal to 0.5, the load contains bimetal Ru and M, the metal M carries out active modification on the metal ruthenium, and the nanometer Ru is formed after roasting treatmentxMyThe alloy is fixed on nitrogen and/or carbon sites;
the metal M is an oxophilic metal and is selected from any one of Ti, V, Sc and W.
2. The nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the ratio of x to y is 1 (0.001-0.3).
3. The nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the sum of the mass of metal ruthenium and metal M is RuxMy0.1 to 40 percent of the total mass of the/N-C, preferably 10 to 35 percent.
4. According toThe nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the Ru is contained in the catalystxMyThe mass of the/N-C accounts for 0.05-50% of the total mass of the catalyst.
5. The nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the nitrogen and/or carbon site N-C is derived from a heterocyclic compound containing nitrogen heteroatom, and the heterocyclic compound is selected from any one of 2,2 '-bipyridine, 4' -bipyridine, 2':6',2 "-terpyridine, 2 '-bipyridine, 4' -bipyridine, 2-bipyridine, and 1, 10-phenanthridine.
6. The nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the carrier is at least one selected from carbon powder, activated carbon particles, carbon felt, porous ceramic, diatomaceous earth, and kaolin.
7. The preparation method of the nano solid-phase catalyst for hydrogen production from formic acid as defined in any one of claims 1 to 6, comprising the steps of:
1) preparing a metal precursor solution: dissolving a compound containing metal elements in a solvent, adding a complex, and stirring until the complex is dissolved;
2) pretreatment of the carrier: pickling and drying the carrier, roasting, and then cooling to room temperature for later use;
3) carrier impregnation: under inert atmosphere, putting the pretreated carrier into a metal precursor solution for dipping, and then drying;
4) roasting and acid washing: roasting the impregnated carrier in an inert atmosphere, and then carrying out acid washing to obtain the nano solid-phase catalyst for hydrogen production by formic acid.
8. The preparation method according to claim 6, wherein in the step 1), the molar ratio of the metal element to the complex is 1 (1-5);
and/or the complex is a heterocyclic compound containing nitrogen heteroatom, the heterocyclic compound is selected from any one of 2,2' -bipyridine, 4' -bipyridine, 2':6', 2' -terpyridine, 2' -bipyridine, 4' -bipyridine, 2-dipyrrole and 1, 10-o-diazaphenanthryl;
and/or the solvent is a mixed solvent containing water and an organic solvent, and the volume ratio of the water to the organic solvent in the mixed solvent is 1 (1-50).
9. The preparation method according to claim 6, wherein in the step 3), the impregnation is performed under reflux conditions, the temperature of condensation reflux is 40-120 ℃, the reflux time is 3-12h, and the drying temperature is 50-150 ℃.
10. The preparation method according to claim 6, wherein in the step 4), the acid washing is to soak the roasted carrier in acid liquor, stir and wash the carrier, then wash the carrier with deionized water to be neutral, and then dry the carrier;
and/or the acid liquor is selected from HNO3、HCl、H2SO4At least one of HF and HCOOH, wherein the acid solution concentration is 0.05-20mol/L, the acid pickling temperature is 10-90 ℃, and the acid pickling time is 0.5-10 h;
and/or the roasting temperature is 400-800 ℃, and the inert atmosphere is selected from any one of nitrogen, argon and helium.
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