CN111939907A - Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof - Google Patents
Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof Download PDFInfo
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- CN111939907A CN111939907A CN202010995233.5A CN202010995233A CN111939907A CN 111939907 A CN111939907 A CN 111939907A CN 202010995233 A CN202010995233 A CN 202010995233A CN 111939907 A CN111939907 A CN 111939907A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000354 decomposition reaction Methods 0.000 title claims description 36
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002905 metal composite material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 238000003756 stirring Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 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
- B01J23/38—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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention discloses a catalyst for preparing hydrogen by decomposing ammonia at low temperature, a preparation method and application thereof, wherein the catalyst comprises a carrier, an active component and a selectively added cocatalyst; the active component is ruthenium, the cocatalyst is one or two of alkali metal, alkaline earth metal and rare earth metal oxide, and the carrier is metal composite oxide M2Ce2O7M is La, Sm or Y. The invention adopts citric acid complexation method to prepare metal composite oxide M2Ce2O7Then loading ruthenium to prepare Ru/M2Ce2O7CatalysisAnd (3) preparing. The catalyst prepared by the invention has the advantages of high mechanical strength, good thermal stability, simple preparation process, low production cost, high low-temperature catalytic activity and the like, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a catalyst for hydrogen production by low-temperature ammonia decomposition and a preparation method and application thereof.
Background
Energy is a material basis of the rapid development of social economy, and with the increasing exhaustion of non-renewable energy sources such as fossil fuel, people are urgently required to develop a material capable of replacing fossilClean energy of fuel. Hydrogen energy is known as the secondary energy with the greatest development prospect in the 21 st century, H2The combustion enthalpy of the boiler is 142MJ/kg, the combustion product is water, and the boiler accords with the concepts of green chemistry, no pollution and zero emission.
Ammonia decomposition hydrogen production (2 NH)3＝N2+3H2) Compared with hydrogen production by using hydrogen storage raw materials such as natural gas, liquefied petroleum gas, methanol and the like, the method has the advantages of (1) NH3Can be stored and transported in liquid state at 20 deg.C and 0.8 MPa; (2) NH (NH)3Has a greater energy density (3000Wh/kg) and a higher hydrogen capacity (17 wt.%); (3) NH (NH)3The decomposition products are only hydrogen and nitrogen, and no CO is generatedxAnd NOxSelecting proper absorbent, non-decomposed NH3Can be effectively absorbed; (4) NH (NH)3The production, storage and transportation technology of the method is mature. Thus, NH3Is a carrier for hydrogen production, storage and transportation with high efficiency, cleanness and safety.
The ammonia decomposition hydrogen production catalyst mainly includes non-noble metal catalysts (Co, Mo, etc.) represented by Fe and Ni and noble metal catalysts (Ir, Pt, etc.) represented by Ru. At present, the industrial ammonia decomposition nickel-based catalyst has the problems of high energy consumption, high equipment manufacturing cost and the like when the use temperature is over 800 ℃.
Chinese patent 201910125806.6 discloses a method for preparing iron catalyst by melting method, the catalyst has low activity of ammonia decomposition at low temperature, and the space velocity is 7800h-1At 450 ℃ the conversion of ammonia was 58.05%, and at 500 ℃ the conversion of ammonia was 99.6%. The Chinese patent 201910538492.2 adopts a sol-gel method to prepare a catalyst precursor, the catalyst precursor is nitrided for 2-6h at the temperature of 500 ℃ and 800 ℃ under the atmosphere of mixed gas of hydrogen and nitrogen to prepare the ammonia decomposition catalyst, the ammonia conversion rate of the catalyst at 600 ℃ is 79.8-88.7%, and the ammonia conversion rate at 800 ℃ is about 99%. Chinese patent 201910532838.8 discloses a method for preparing a catalyst containing one or two of nickel and ruthenium as active components, one or more of alkali metal, alkaline earth metal and rare earth oxide as cocatalyst, and yttria-stabilized zirconia or BaCe0.7Zr0.1Y0.2O3-A supported catalyst, which has ruthenium as an active component and has an ammonia conversion rate of 550 DEG C90.6-98.9%; when nickel is used as an active component, the conversion rate of ammonia at 650 ℃ is 93.4-98.4%; when two components of nickel and ruthenium are used as active components, the conversion rate of ammonia at 550 ℃ is 93.2-98.8%, and the conversion rate of ammonia at 650 ℃ is more than 99%. Chinese patent 201811411804.5 discloses a method for preparing rare earth metal oxide-supported ruthenium catalyst 5 wt% Ru/CeO by deposition precipitation2The catalyst had an ammonia conversion of 76.4% at 450 ℃. Chinese patent 201911214086.7 discloses M/ABO prepared by loading metal M on ABOx composite metal oxide as carrierXCatalyst (A, B represents three-four valent metal, M represents Ru, Fe or Ni) with ruthenium as active group and potassium promoter added at 2600 hr-1And the highest ammonia conversion rate is 88.7 percent under the condition of 450 ℃.
In conclusion, the existing ammonia decomposition hydrogen production catalyst has the defects of high temperature, low-temperature activity, high production energy consumption and the like.
Therefore, the development of the catalyst for hydrogen production by ammonia decomposition with high activity and high stability under low temperature condition has very important significance.
Disclosure of Invention
Aiming at the defects in the field, the invention provides the catalyst for preparing hydrogen by decomposing ammonia at low temperature, which has the characteristics of low ammonia decomposition temperature, high ammonia conversion rate, high stability, low production energy consumption and low cost besides high mechanical strength, good thermal stability and simple preparation process, and has good industrial application prospect.
A catalyst for preparing hydrogen by decomposing ammonia at low temperature comprises a carrier, an active component and a selectively added cocatalyst;
the active component is ruthenium, the cocatalyst is one or two of alkali metal, alkaline earth metal and rare earth metal oxide, and the carrier is metal composite oxide M2Ce2O7M is La, Sm or Y.
Preferably, the vector M is2Ce2O7The supported amount of the active component is 0.1-5 parts by mass and the supported amount of the cocatalyst is 4-20 parts by mass.
Preferably, the active ingredient is preceded byThe driver is Ru3(CO)12、RuCl3·3H2O or K2RuO4One kind of (1).
Preferably, the precursor of the promoter is nitrate, hydroxide or oxide of alkali metal, alkaline earth metal or rare earth metal.
More preferably, the precursor of the cocatalyst is KOH or Ba (OH)2、KNO3、BaNO3One or two of them.
Preferably, the metal composite oxide M2Ce2O7The method comprises the following steps: the precursor of Ce is one of ammonium ceric nitrate, cerium acetate or cerium nitrate, and the precursor of M is one of oxides, nitrates or acetates of La, Sm or Y.
The invention also provides a preferable preparation method of the catalyst for preparing hydrogen by decomposing ammonia at low temperature, which comprises the preparation of metal composite oxide and the loading of active components, and specifically comprises the following steps:
(1) adding cerium salt into the precursor solution of M for dissolving to prepare a solution A;
(2) adding a complexing agent into the solution A, evaporating the solution to be viscous liquid at 60-90 ℃, drying at 100-120 ℃ to obtain a solid sample, grinding into powder, and roasting at 300-1000 ℃ for 2-10h to obtain the metal composite oxide M2Ce2O7；
The complexing agent is one of citric acid, urea or ethylene diamine tetraacetic acid;
(3) mixing the obtained metal composite oxide M2Ce2O7Adding the precursor of the active component into tetrahydrofuran solution, soaking at room temperature for 4-10h, evaporating the solvent to dryness at 50-80 ℃, and drying at 100-120 ℃ to obtain Ru/M2Ce2O7A catalyst.
The cerium salt in the step (1) can be one of ammonium cerium nitrate, cerium acetate or cerium nitrate.
Preferably, the preparation method further comprises the following steps:
(4) the obtained Ru/M2Ce2O7With addition of co-catalystDipping the precursor solution for 1-10h at room temperature, and then drying the precursor solution at the temperature of 100 ℃ and 120 ℃ to obtain the Ru-cocatalyst/M2Ce2O7A catalyst.
The invention also provides the application of the low-temperature ammonia decomposition hydrogen production catalyst in the ammonia decomposition hydrogen production reaction, wherein the low-temperature ammonia decomposition hydrogen production catalyst is firstly subjected to the reaction of 450 ℃ and 500 ℃ and H before the ammonia decomposition hydrogen production reaction2Reducing for 2-6h under the atmosphere; the pressure of the ammonia decomposition hydrogen production reaction is normal pressure, and the temperature is 350-500 ℃.
Compared with the prior art, the invention has the main advantages that:
1. the invention adopts the complexation method of citric acid and the like to prepare the metal composite oxide as the carrier, and then loads ruthenium to prepare Ru/M2Ce2O7Catalyst with high low-temperature catalytic activity, NH at 450 DEG C3The conversion rate reaches more than 99 percent and is close to the equilibrium conversion rate at the temperature.
2. The catalyst of the invention has NH3High conversion rate, high mechanical strength, good thermal stability, simple preparation process, low energy consumption for hydrogen production, low production cost and the like.
3. The catalyst provided by the invention can be applied to the field of hydrogen production by ammonia decomposition, and has good industrial application prospect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 12% Ru/La2Ce2O7Preparation of the catalyst
(1) Weighing 2g of La2O3Dissolving in diluted nitric acid, and adding 5g (NH)4)2Ce(NO3)6After stirring and dissolving, adding 20g of solid citric acid for dissolving to obtain a mixed solution;
(2) evaporating the mixed solution prepared in the step (1) at 80 ℃ to form viscous liquid, and drying at 110 ℃ for 12h to obtain a light yellow solid sample;
(3) grinding the light yellow solid sample obtained in the step (2) into powder, putting the powder into a muffle furnace, heating to 800 ℃ at a heating rate of 10 ℃/min, and roasting for 5 hours to obtain La2Ce2O7；
(4) 0.21g of Ru was weighed out3(CO)12Dissolved in 50ml of Tetrahydrofuran (THF), and 5g of La was weighed2Ce2O7Adding into the mixture, stirring, evaporating the solvent to dryness at 66 deg.C, and drying at 110 deg.C for 12 hr to obtain 2% Ru/La2Ce2O7A catalyst.
Example 24% Ru/La2Ce2O7Preparation of the catalyst
(1) Weighing 2g of La2O3Dissolving in diluted nitric acid, and adding 5g (NH)4)2Ce(NO3)6After stirring and dissolving, adding 20g of solid citric acid for dissolving to obtain a mixed solution;
(2) evaporating the mixed solution prepared in the step (1) at 80 ℃ to form viscous liquid, and drying at 110 ℃ for 12h to obtain a light yellow solid sample;
(3) grinding the light yellow solid sample obtained in the step (2) into powder, putting the powder into a muffle furnace, heating to 800 ℃ at a heating rate of 10 ℃/min, and roasting for 5h to obtain La2Ce2O7；
(4) 0.42g of Ru was weighed out3(CO)12Dissolved in 50ml of Tetrahydrofuran (THF) and 5g of La was weighed out2Ce2O7Adding the carrier into the mixture, stirring for a period of time, evaporating the solvent at 66 ℃, and drying at 110 ℃ for 12 hours to obtain 4% Ru/La2Ce2O7A catalyst.
Example 34% Ru/Y2Ce2O7Preparation of the catalyst
(1) Weighing 5g Y (NO)3)3·6H2O is made into a solution, and 5g (NH) is added4)2Ce(NO3)6Stirring and dissolving, and then adding 20g of solid citric acid into the mixture to dissolve to obtain a mixed solution;
(2) evaporating the solution prepared in the step (1) at 80 ℃ to form viscous liquid, and drying at 110 ℃ for 12h to obtain a solid sample;
(3) grinding the solid sample obtained in the step (2) into powder, putting the powder into a muffle furnace, heating to 800 ℃ at a heating rate of 10 ℃/min, and roasting for 5h to obtain Y2Ce2O7A carrier;
(4) 0.42g of Ru was weighed out3(CO)12Dissolved in 50ml of Tetrahydrofuran (THF) and weighed 5g Y2Ce2O7Adding the carrier into the mixture, stirring for a period of time, evaporating the solvent at 66 ℃, and drying at 110 ℃ for 12 hours to obtain 4% Ru/Y2Ce2O7A catalyst.
Example 44% Ru/Sm2Ce2O7Preparation of the catalyst
(1) Weighing 5g Sm (NO)3)3·6H2O is made into a solution, and 5g (NH) is added4)2Ce(NO3)6After stirring and dissolving, adding 20g of solid citric acid into the mixture to obtain a solution after dissolving;
(2) evaporating the mixed solution prepared in the step (1) at 80 ℃ to form viscous liquid, and drying at 110 ℃ for 12h to obtain a solid sample;
(3) grinding the solid sample obtained in the step (2) into powder, putting the powder into a muffle furnace, heating to 800 ℃ at a heating rate of 10 ℃/min, and roasting for 5h to obtain Sm2Ce2O7；
(4) 0.42g of Ru was weighed out3(CO)12Dissolved in 50ml of Tetrahydrofuran (THF), 5g of Sm were weighed out2Ce2O7Adding the carrier into the mixture, stirring for a period of time, evaporating the solvent to dryness at the temperature of 66 ℃, and drying at the temperature of 110 ℃ for 12 hours to obtain 4 percent Ru/Sm2Ce2O7A catalyst.
Example 54% Ru-14% K/La2Ce2O7Preparation of the catalyst
(1) Weighing 2g of La2O3Dissolving in diluted nitric acid, and adding 5g (NH)4)2Ce(NO3)6Stirring the mixture to dissolve the mixture,then 20g of solid citric acid is added into the mixture to be dissolved to obtain a mixed solution;
(2) evaporating the mixed solution prepared in the step (1) at 80 ℃ to form viscous liquid, and drying at 110 ℃ for 12h to obtain a light yellow solid sample;
(3) grinding the light yellow solid sample obtained in the step (2) into powder, putting the powder into a muffle furnace, heating to 800 ℃ at a heating rate of 10 ℃/min, and roasting for 5h to obtain La2Ce2O7；
(4) 0.42g of Ru was weighed out3(CO)12Dissolved in 50ml of Tetrahydrofuran (THF) and 5g of La was weighed out2Ce2O7Adding the carrier into the mixture, stirring for a period of time, evaporating the solvent at 66 ℃, and drying at 110 ℃ for 12 hours to obtain 4% Ru/La2Ce2O7A sample;
(5) weighing 1g of KOH, dissolving in water to prepare a solution, and adding the 4 percent Ru/La solution obtained in the step (4)2Ce2O7The sample is stirred for 3h and dried for 12h at 110 ℃ to obtain 4 percent Ru-14 percent K/La2Ce2O7A catalyst.
Example 64% Ru-4% Ba/La2Ce2O7Preparation of the catalyst
(1) Weighing 2g of La2O3Dissolving in diluted nitric acid, and adding 5g (NH)4)2Ce(NO3)6Stirring for dissolving, and adding 20g of solid citric acid into the solution for dissolving to prepare a solution;
(2) evaporating the solution prepared in the step (1) at 80 ℃ to form viscous liquid, and drying at 110 ℃ for 12h to obtain a light yellow solid sample;
(3) grinding the light yellow solid sample obtained in the step (1) into powder, putting the powder into a muffle furnace, heating to 800 ℃ at a heating rate of 10 ℃/min, and roasting for 5h to obtain La2Ce2O7；
(4) 0.42g of Ru was weighed out3(CO)12Dissolved in 50ml of Tetrahydrofuran (THF) and 5g of La was weighed out2Ce2O7Adding the carrier, stirring for a period of time, evaporating the solvent at 66 deg.C, and drying at 110 deg.C for 12 hr to obtain 4％Ru/La2Ce2O7A sample;
(5) 0.46g of Ba (OH) is weighed2Dissolving the mixture in water to prepare a solution, and adding the 4 percent Ru/La obtained in the step (4)2Ce2O7The sample is stirred for 3h and dried for 12h at 110 ℃ to obtain 4 percent Ru-4 percent Ba/La2Ce2O7A catalyst.
Comparative example 14% Ru/AC catalyst
(1) 0.1552g of RuCl were weighed out3·3H2Dissolving O in 2.4ml of water, dropwise adding into 1.5g of Activated Carbon (AC) while stirring, soaking at room temperature for 12h, and drying at 120 ℃ for 12 h;
(2) adding 25ml of 10% ammonia water by volume into the dried sample obtained in the step (1), standing for 12h, and washing with water until AgNO is used3Drying the solution at 120 ℃ for 12h after no Cl & lt- & gt is detected, and obtaining the 4% Ru/AC catalyst.
Comparative example 24% Ru/CNTs catalyst
(1) 0.1552g of RuCl were weighed out3·3H2O was dissolved in 2.4ml of water, and 1.5g of Carbon Nanotubes (CNT) were added dropwise while stirringS) Soaking at room temperature for 12h, and drying at 120 ℃ for 12 h;
(2) adding 25ml of 10% ammonia water by volume into the dried sample obtained in the step (2), standing for 12h, and washing with water until AgNO is used3Drying the solution at 120 ℃ for 12h after the solution is not detected to be Cl < - >, and obtaining the 4 percent Ru/CNTs catalyst.
Comparative example 34% Ru/MgO catalyst
(1) 2g of MgO and 0.18g of Ru are weighed out3(CO)12Mixing the two solutions, and grinding in a mortar for 30 min;
(2) and tabletting the ground sample, and taking the particle size of 18-40 meshes (0.069mm-1mm) to obtain the 4% Ru/MgO catalyst.
Application example
The ammonia decomposition hydrogen production performance evaluation was performed on the ammonia decomposition catalysts prepared in the above examples 1 to 6 and comparative examples 1 to 3, and the test procedures were as follows: loading 0.5ml of 18-40 mesh catalyst into a fixed bed reactor, and introducing H with the flow rate of 100ml/min2After reduction for 2h at 450 ℃, under normal pressure and space velocity of 7800h-1The ammonia decomposition activity of the catalysts of the above examples and comparative examples was tested under the conditions shown in table 1.
TABLE 1 evaluation results of catalyst Activity
As can be seen from Table 1, the comparison of examples 1-2 shows that the NH content at low temperature increases from 2% to 4% with the Ru loading3The conversion rate has a great influence, NH at 500 DEG C3The conversion rate can reach more than 99 percent; comparison of examples 2 to 4 shows that, when the M elements in the metal composite oxide are La, Y and Sm, respectively, NH at 450 ℃ is present3The conversion rates were 98.36%, 94.92% and 92.49%, respectively, in terms of La2Ce2O74% Ru/La prepared as support2Ce2O7Catalyst NH3The conversion rate is highest; 4% Ru/La prepared in example 22Ce2O7Respectively adding K and Ba promoters on the basis of the catalyst to prepare 4 percent Ru-14 percent K/La of the embodiment 5-62Ce2O7And 4% Ru-4% Ba/La2Ce2O7The catalyst can be found by comparison, 4 percent of Ru/La added with K cocatalyst2Ce2O7Catalyst NH at 400 ℃ and 450 DEG C3The conversion rates are respectively increased from 72.96 percent and 98.36 percent to 88.18 percent and 99.28 percent, and NH is added after Ba cocatalyst is added3The conversion rate is reduced to 40.21% and 78.12%, respectively, which may be caused by the low melting point of the K promoter, the high mobility, the sufficient contact with Ru, the electron transfer from K to Ru surface, the promotion of N-H bond cleavage or N-H bond cleavage2The dissociation and adsorption of the catalyst can improve the ammonia decomposition activity, while the Ba cocatalyst has high melting point and low mobility, and part of Ru can not participate in the reaction because of being coated by Ba, so that the activity of the catalyst is reduced, and the catalyst in the embodiment 5 containing the K cocatalyst has the highest ammonia decomposition activity; comparative examples 1-3 are 4% Ru/AC, 4% Ru/CNTs and 4% Ru/MgO catalysis prepared by respectively using Activated Carbon (AC), Carbon Nanotubes (CNTs) and magnesium oxide (MgO) as carriers and keeping the loading of Ru constant at 4%Agent, NH of which under the same evaluation conditions3The conversion rate is obviously lower than that of the catalyst prepared by taking the metal composite oxide as a carrier. Therefore, the catalyst has the highest ammonia decomposition activity, and has normal pressure and high space velocity (7800 h)-1) At 450 ℃ NH3The conversion rate can reach 99.28 percent (example 4), is close to the equilibrium conversion rate at the temperature, can greatly reduce the decomposition temperature of ammonia and the energy consumption thereof, and has good industrial application prospect.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. The catalyst for preparing hydrogen by decomposing ammonia at low temperature is characterized by comprising a carrier, an active component and a selectively added cocatalyst;
the active component is ruthenium, the cocatalyst is one or two of alkali metal, alkaline earth metal and rare earth metal oxide, and the carrier is metal composite oxide M2Ce2O7M is La, Sm or Y.
2. The catalyst for low-temperature ammonia decomposition to produce hydrogen according to claim 1, wherein the carrier M is2Ce2O7The supported amount of the active component is 0.1-5 parts by mass and the supported amount of the cocatalyst is 4-20 parts by mass.
3. The catalyst for low-temperature ammonia decomposition to produce hydrogen according to claim 1 or 2, wherein the precursor of the active component is Ru3(CO)12、RuCl3·3H2O or K2RuO4One kind of (1).
4. The catalyst for low-temperature ammonia decomposition hydrogen production according to claim 1 or 2, wherein the precursor of the promoter is nitrate, hydroxide or oxide of alkali metal, alkaline earth metal or rare earth metal.
5. The catalyst for low-temperature ammonia decomposition and hydrogen production according to claim 4, wherein the precursor of the promoter is KOH, Ba (OH)2、KNO3、BaNO3One or two of them.
6. The catalyst for low-temperature ammonia decomposition to produce hydrogen according to claim 1 or 2, wherein the metal composite oxide M is2Ce2O7The method comprises the following steps: the precursor of Ce is one of ammonium ceric nitrate, cerium acetate or cerium nitrate, and the precursor of M is one of oxides, nitrates or acetates of La, Sm or Y.
7. The preparation method of the catalyst for low-temperature ammonia decomposition hydrogen production according to any one of claims 1 to 6, which comprises the preparation of metal composite oxide and the loading of active components, and specifically comprises the following steps:
(1) adding cerium salt into the precursor solution of M for dissolving to prepare a solution A;
(2) adding a complexing agent into the solution A, evaporating the solution to be viscous liquid at 60-90 ℃, drying at 100-120 ℃ to obtain a solid sample, grinding into powder, and roasting at 300-1000 ℃ for 2-10h to obtain the metal composite oxide M2Ce2O7；
The complexing agent is one of citric acid, urea or ethylene diamine tetraacetic acid;
(3) mixing the obtained metal composite oxide M2Ce2O7Adding the precursor of the active component into tetrahydrofuran solution, soaking at room temperature for 4-10h, evaporating the solvent to dryness at 50-80 ℃, and drying at 100-120 ℃ to obtain Ru/M2Ce2O7A catalyst.
8. The method of claim 7, further comprising the steps of:
(4) the obtained Ru/M2Ce2O7Catalyst and process for preparing sameAdding into the precursor solution of the cocatalyst, soaking at room temperature for 1-10h, and drying at 100-120 ℃ to obtain the Ru-cocatalyst/M2Ce2O7A catalyst.
9. The application of the catalyst for low-temperature ammonia decomposition hydrogen production in the ammonia decomposition hydrogen production reaction according to any one of claims 1 to 6, wherein the catalyst for low-temperature ammonia decomposition hydrogen production is first subjected to the ammonia decomposition hydrogen production reaction at a temperature of 450 ℃ and a temperature of H2Reducing for 2-6h under the atmosphere; the pressure of the ammonia decomposition hydrogen production reaction is normal pressure, and the temperature is 350-500 ℃.
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