CN113019383A - Nickel/lanthanum oxide catalyst and preparation method and application thereof - Google Patents
Nickel/lanthanum oxide catalyst and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 229
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 90
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 41
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 39
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 32
- 238000006057 reforming reaction Methods 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 229910002226 La2O2 Inorganic materials 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002221 La2NiO4 Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 230000008021 deposition Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 63
- 229910021641 deionized water Inorganic materials 0.000 description 63
- 239000002244 precipitate Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000463 material Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 11
- 238000002407 reforming Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000003993 interaction Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910002249 LaCl3 Inorganic materials 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910018062 Ni-M Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003835 carbonate co-precipitation Methods 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/03—Precipitation; Co-precipitation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- 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
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Abstract
The invention discloses a nickel/lanthanum oxide catalyst and a preparation method and application thereof. The preparation method comprises the following steps: carrying out parallel-flow coprecipitation reaction on a mixed reaction system containing a precipitator, a nickel salt, a lanthanum salt and a solvent to obtain a catalyst precursor; and roasting the catalyst precursor to obtain the nickel/lanthanum oxide catalyst. The preparation of the catalyst disclosed by the invention is carried out in a narrow pH value range (7.5-8.5), the simultaneous precipitation of Ni and La is carried out, the high uniform dispersion of Ni in a carrier is ensured, the preparation steps are simple, the preparation process is green and energy-saving, the obtained nickel/lanthanum oxide catalyst has high activity and catalytic efficiency, when the nickel/lanthanum oxide catalyst is used in the dry reforming reaction of methane and carbon dioxide, the generation of carbon deposition is obviously inhibited, and the conversion rates of methane and carbon dioxide are high.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis, relates to a nickel/lanthanum oxide catalyst, a preparation method and application thereof, and particularly relates to a nickel/lanthanum oxide catalyst, a preparation method thereof and application of the catalyst in methane carbon dioxide dry reforming reaction.
Background
The synthetic gas composed of hydrogen and carbon monoxide is the raw material of Fischer-Tropsch synthetic liquid hydrocarbon fuel, is widely used for producing olefin, methanol, dimethyl ether and the like, can be used as the basic raw material for synthesizing chemicals containing oxygen, nitrogen and the like through carbonylation and hydroformylation, and has increasingly large application. There are two main sources of synthesis gas in industry, coal and natural gas, the latter of which is obtained by Steam Reforming of Methane (SRM). In order to better utilize this clean energy source of natural gas and reduce the energy consumption of the process, Partial Oxidation of Methane (POM), dry reforming of methane-carbon Dioxide (DRM) and autothermal reforming of methane (ATM) to synthesis gas have been studied extensively for a long time. In the DRM process, two reactants are both greenhouse gases and cheap carbon resources which are abundant in nature, and thus are in great interest.
Catalysts used in the dry reforming reaction of methane and carbon dioxide include noble metals (Ru, Rh, Pt, Pd, etc.) and non-noble metals (Ni, Co, Cu, etc.); although the noble metal catalyst has the advantages of high activity and good stability, the noble metal catalyst has scarce resources and high price and is difficult to use in large quantities in industry. Among non-noble metals, a catalyst using Ni as an active component is favored because it has high initial activity and is relatively inexpensive, but the problem of activity reduction due to sintering of the Ni active component at high temperature and catalyst carbon deposition becomes a bottleneck affecting its industrial application.
To understandIn order to solve the problems, various means and strategies are adopted, and the two aspects are summarized: 1) inhibiting the aggregation of Ni in the reaction process; 2) the catalyst carrier or the auxiliary agent is improved, and the dispersion and carbon containing capability of Ni are improved by adjusting the pH value to inhibit carbon deposition or adjusting the pore structure. For example, the size of Ni is stabilized by the use of the tunnel confinement effect (Significant rolls of media and basic modifier for ordered media Ni/CaO-Al)2O3 catalyst towards CO2 reforming ofCH4，Catalysis Science&Technology, 2014, 4, 1759-; the monatomic catalyst (atomic dispersed nickel as co-reactive sites for methane dry reforming, Nature Communications 2019, 10(1), 5181) and the like are formed by utilizing a strong metal-support interaction.
La in comparison with other basic carriers2O3The Ni-supported catalyst showed better stability because La was generated during the reaction2O3With CO2Can form La2O2CO3. Verykios et al were on La2O3The Ni-loaded catalyst has been studied in detail for the Carbon dioxide reforming reaction of methane (Carbon dioxide reforming of methane to synthesis gas over Ni/La)2O3 catalysts，Applied Catalysis A：General，1996，138，109-133；Kinetic study ofthe catalytic reforming of methane with carbon dioxide to synthesis gas over Ni/La2O3catalysis Today, 2001, 64, 83-90). In the prior published literature reports, Ni/La2O3The catalyst is usually prepared by an impregnation method or a precipitation method, for example, the Chinese patent invention 201811589656.6 discloses a nickel-loaded mesoporous lanthanum oxide catalyst and a preparation method thereof, wherein a nickel salt is used for impregnating a lanthanum oxide carrier; muller et al (Dry-reforming of methane over bimetallic Ni-M/La)2O3(M＝Co，Fe)：The effect of the rate of La2O2CO3formation and phase stability on the catalytic activity and stability, Journal of catalysis, 2016, 343, 208-214) use sodium carbonate co-precipitation to prepare bimetallicA nickel/lanthanum oxide catalyst. However, for a lanthanum oxide support having a relatively low specific surface area, the impregnation method does not easily result in uniformly dispersed Ni particles. When the catalyst is prepared by a precipitation method, the active components are uniformly distributed and have proper interaction with the carrier, but a precipitator containing sodium ions is generally selected, so that the influence of residual sodium is eliminated, the strict requirement on the washing of the catalyst in the preparation process is met, and the complexity and the energy consumption of the process are increased.
Disclosure of Invention
The invention mainly aims to provide a nickel/lanthanum oxide catalyst, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a nickel/lanthanum oxide catalyst, which comprises the following steps:
carrying out parallel-flow coprecipitation reaction on a mixed reaction system containing a precipitator, a nickel salt, a lanthanum salt and a solvent to obtain a catalyst precursor, wherein the pH value of the mixed reaction system is 7.5-8.5;
and roasting the catalyst precursor to obtain the nickel/lanthanum oxide catalyst.
The embodiment of the invention also provides a nickel/lanthanum oxide catalyst prepared by the method, and the phase of the nickel/lanthanum oxide catalyst comprises monoclinic La2O2CO3Hexagonal La2O2CO3、La2O3And La2NiO4The content of the nickel element in the nickel/lanthanum oxide catalyst is 0.1-5.0 wt%.
The embodiment of the invention also provides application of the nickel/lanthanum oxide catalyst in dry reforming reaction of methane and carbon dioxide.
The embodiment of the invention also provides a dry reforming reaction method of methane and carbon dioxide, which comprises the following steps:
preparing a nickel/lanthanum oxide catalyst by the method;
in a reducing atmosphere, carrying out reduction treatment on the nickel/lanthanum oxide catalyst at 600-800 ℃ for 1-3 h;
and continuously inputting methane and carbon dioxide into a tubular reactor provided with a nickel/lanthanum oxide catalyst subjected to reduction treatment, wherein the temperature is 600-800 ℃, and the space velocity is 10000-50000 h-1Under the conditions of (a) to produce carbon monoxide and hydrogen.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, ammonium carbonate and/or ammonium bicarbonate are/is used as a precipitator, the pH value in the precipitation process is controlled within a tiny fluctuation range (the pH value is 7.5-8.5), the uniform dispersion of nickel on a carrier is improved, the interaction between the nickel and the carrier is enhanced, and the stability of the nickel/lanthanum oxide catalyst at high temperature is improved;
(2) compared with the impregnation method, the method for preparing the nickel/lanthanum oxide catalyst has the advantage that lanthanum in the catalyst is La2O2CO3And La2O3In the form of a crystalline phase, nickel being in the form of La2NiO4The catalyst is in a form, so that the activation of carbon dioxide is facilitated and the sintering resistance of the active component of the catalyst at high temperature is maintained;
(3) when the nickel/lanthanum oxide catalyst is prepared, nitrate or chloride is washed, so that harmful gases such as nitrogen oxides and the like are not generated in the roasting process of the catalyst precursor, and the development trend of green chemistry is met;
(4) the preparation method is simple, and the prepared catalyst has the characteristics of high dispersion degree of active components and good stability, and can effectively solve the problems of high carbon deposition rate and poor stability in the methane carbon dioxide reforming reaction in the prior art;
(5) the nickel/lanthanum oxide catalyst prepared by the invention has higher catalytic activity, the nickel loading is as low as 1 wt%, the nickel/lanthanum oxide catalyst is used for dry reforming reaction, and under the condition of not using any diluent gas, the conversion rates of methane and carbon dioxide at 750 ℃ respectively reach 85% and 92%, and the conversion rates respectively reach 862 and 964 mmol.g-1·min-1。
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD pattern of a nickel/lanthanum oxide catalyst prepared in examples 1-4 of the present invention;
FIG. 2 is an XRD pattern of the nickel/lanthanum oxide catalysts prepared in comparative examples 1-3 of the present invention;
FIG. 3 shows H for NL-1 catalyst prepared in example 1 according to the invention and C-1 catalyst prepared in comparative example 12-a TPR map;
FIGS. 4 a-4 b are graphs showing the results of the performance of the dry reforming reaction of methane/carbon dioxide with reaction time using the NL-1 catalyst of example 1 and the C-1 catalyst of comparative example 1, respectively;
FIG. 5 is a TGA/DSC plot of NL-1 catalyst of example l of the present invention and C-1 catalyst of comparative example 1 after 100h of catalytic dry reforming of methane with carbon dioxide;
FIGS. 6 a-6 b are TEM images of NL-1 catalyst in example 1 of the present invention and C-1 catalyst in comparative example 1, respectively, after catalyzing a dry reforming reaction of methane with carbon dioxide for 100 h.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a method for preparing a nickel/lanthanum oxide catalyst, including:
carrying out parallel-flow coprecipitation reaction on a mixed reaction system containing a precipitator, a nickel salt, a lanthanum salt and a solvent to obtain a catalyst precursor;
and roasting the catalyst precursor to obtain the nickel/lanthanum oxide catalyst, wherein the pH value of the mixed reaction system is 7.5-8.5.
In the present invention, the nickel/lanthanum oxide catalyst is used in the dry reforming reaction of methane and carbon dioxide.
In some more specific embodiments, the preparation method specifically comprises:
dissolving nickel salt and lanthanum salt in water to form a first mixed solution;
dissolving a precipitant in water to form a precipitant solution;
and simultaneously dropwise adding the first mixed solution and the precipitant solution into a solvent at 20-50 ℃ to form the mixed reaction system, controlling the pH value of the mixed reaction system to be 7.5-8.5, stirring and reacting at 20-50 ℃ for 10-30 min, and standing for 10-30 min to obtain the catalyst precursor.
Further, the nickel salt includes any one or a combination of two or more of nickel chloride, nickel nitrate, nickel acetate, and nickel sulfate, and is not limited thereto.
Further, the lanthanum salt includes any one of lanthanum chloride and lanthanum nitrate or a combination of the two, and is not limited thereto.
Further, the precipitant includes any one of ammonium carbonate and ammonium bicarbonate or a combination of the two, and is not limited thereto.
Further, the solvent includes water and/or an aqueous ethanol solution, and is not limited thereto.
Further, the concentration of the ethanol water solution is less than 20 wt%.
Further, the molar ratio of the nickel salt to the lanthanum salt in the first mixed solution is 0.02-0.5: 1.
Further, the concentration of the precipitant in the precipitant solution is 0.1-2.0 mol/L.
Further, the volume ratio of the solvent to the sum of the first mixed solution and the precipitant solution is 1: 1-1: 2.
In some specific embodiments, the temperature of the roasting treatment is 600-800 ℃ and the time is 2-4 h.
In some more specific embodiments, the preparation method further comprises: and after the parallel-flow coprecipitation reaction is finished, filtering, washing and drying the obtained mixture.
Further, the drying treatment temperature is 80-120 ℃, and the drying treatment time is 8-12 hours.
In some more specific embodiments, the method of preparing the nickel/lanthanum oxide catalyst (co-current co-precipitation method) specifically comprises:
(1) dissolving nickel salt and lanthanum salt in deionized water to form a solution A, wherein the concentrations of the two salts are 0.002-0.2 mol/L and 0.1-3 mol/L respectively;
(2) dissolving carbonate (precipitant) in deionized water to form a solution B, wherein the concentration of the carbonate solution is 0.1-2 mol/L;
(3) adding deionized water into a container, stirring at 20-50 ℃, simultaneously dropwise adding the solution A and the solution B into the deionized water, wherein the volume ratio of the deionized water to the total volume of the solution A and the solution B is 1: 1-1: 2, and maintaining the pH value of the solution at 7.5-8.5;
(4) after the solution A and the solution B are dripped, continuously stirring for 10-30 min, and standing for 10-30 min;
(5) filtering the precipitate, washing with deionized water, drying to obtain catalyst precursor, roasting to obtain nickel/lanthanum oxide catalyst, and conventional use of H before catalytic reaction2And (5) carrying out reduction treatment.
Further, the nickel salt in the step (1) includes any one or a combination of two or more of nickel chloride, nickel nitrate, nickel acetate, and nickel sulfate, and is not limited thereto.
Further, the lanthanum salt in the step (1) includes any one of lanthanum chloride and lanthanum nitrate or a combination of two, and is not limited thereto.
Further, the carbonate in the step (2) includes any one of ammonium carbonate and ammonium bicarbonate or a combination of two of them, and is not limited thereto.
Further, the drying treatment in the step (5) is carried out at the temperature of 80-120 ℃ for 8-12 hours.
Further, the temperature of the roasting treatment in the step (5) is 600-800 ℃, and the time is 2-4 hours.
Further, the reducing treatment conditions in the step (5) include: and (3) in a hydrogen atmosphere, the temperature is 600-800 ℃, and the time is 1-3 h.
It is also an aspect of an embodiment of the present invention to provide a nickel/lanthanum oxide catalyst prepared by the foregoing method, the phase of the nickel/lanthanum oxide catalyst comprising monoclinic La2O2CO3(m-La2O2CO3) Hexagonal La2O2CO3(h-La2O2CO3)、La2O3And La2NiO4The content of the nickel element in the nickel/lanthanum oxide catalyst is 0.1-5.0 wt%.
Furthermore, the content of the nickel element in the nickel/lanthanum oxide catalyst is 0.2-4.0 wt%.
In another aspect of embodiments of the invention there is also provided the use of a nickel/lanthanum oxide catalyst as hereinbefore described in a dry reforming reaction of methane with carbon dioxide.
Another aspect of an embodiment of the present invention also provides a dry reforming reaction method of methane and carbon dioxide, including:
preparing a nickel/lanthanum oxide catalyst by the method;
in a reducing atmosphere, carrying out reduction treatment on the nickel/lanthanum oxide catalyst at 600-800 ℃ for 1-3 h;
and continuously inputting methane and carbon dioxide into a tubular reactor provided with a nickel/lanthanum oxide catalyst subjected to reduction treatment, wherein the temperature is 600-800 ℃, and the space velocity is 10000-50000 h-1Under the conditions of (a) to produce carbon monoxide and hydrogen.
Further, the reducing atmosphere includes a hydrogen atmosphere, and is not limited thereto.
Further, the molar ratio of methane to carbon dioxide is 1.0.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
EXAMPLE 1 preparation of a Nickel/lanthanum oxide catalyst
(1) 1.80g of Ni (NO)3)2·6H2O with 10.40g La (NO)3)3·6H2Dissolving O in 100ml of deionized water, and uniformly stirring to form a solution A;
(2) adding 7.50g of NH4HCO3Dissolving in 100ml deionized water to form solution B;
(3) adding 100ml of deionized water into a 500ml beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at room temperature (20-25 ℃), wherein the stirring speed is kept at 600 revolutions per minute, and the pH value of the solution is controlled to be 7.9;
(4) continuously stirring the material containing the precipitate in the step (3) for reaction for 15min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 120 ℃ for 12h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 700 ℃ for 3h to obtain the nickel/lanthanum oxide catalyst, wherein the mark is NL-1, and the Ni element content in the catalyst is 3.5 wt%.
EXAMPLE 2 preparation of a Nickel/lanthanum oxide catalyst
(1) 0.96g of Ni (NO)3)2·6H2O with 11.76g La (NO)3)3·6H2Dissolving O in 200ml of deionized water, and uniformly stirring to form a solution A;
(2) adding 8.30g of NH4HCO3Dissolving in 200ml deionized water to form solution B;
(3) adding 100ml of deionized water into a 1L beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at room temperature (20-25 ℃), wherein the stirring speed is kept at 580 revolutions per minute, and the pH value of the solution is controlled to be 7.8;
(4) continuously stirring the material containing the precipitate in the step (3) at room temperature for 30min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 120 ℃ for 12h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 700 ℃ for 3h to obtain the nickel/lanthanum oxide catalyst, which is marked as NL-2, wherein the Ni element content in the catalyst is 1.1 wt%.
EXAMPLE 3 preparation of Nickel/lanthanum oxide catalyst
(1) 0.81g of NiCl2·6H2O with 8.2g LaCl3·3H2Dissolving O in 100ml of deionized water, and uniformly stirring to form a solution A;
(2) 8.32g (NH)4)2CO3Dissolving in 100ml deionized water to form solution B;
(3) adding 100ml of deionized water into a 500ml beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at 50 ℃, wherein the stirring speed is kept at 550 revolutions per minute, and the pH value of the solution is controlled to be 8.5;
(4) continuously stirring the material containing the precipitate in the step (3) at 50 ℃ for reacting for 20min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 120 ℃ for 12h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 700 ℃ for 3h to obtain the nickel/lanthanum oxide catalyst, wherein the mark is NL-3, and the Ni element content in the catalyst is 1.8 wt%.
EXAMPLE 4 preparation of a Nickel/lanthanum oxide catalyst
(1) 0.288g of Ni (NO)3)2·6H2O with 15.84g La (NO)3)3·6H2Dissolving O in 200ml of deionized water, and uniformly stirring to form a solution A;
(2) 7.23g (NH)4)2CO3Dissolving in 200ml deionized water to form solution B；
(3) Adding 200ml of deionized water into a 1L beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at room temperature (20-25 ℃), keeping the stirring speed at 600 revolutions per minute, and controlling the pH value of the solution to be 7.8;
(4) continuously stirring the material containing the precipitate in the step (3) at room temperature for reaction for 10min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 100 ℃ for 12h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 750 ℃ for 3h to obtain the nickel/lanthanum oxide catalyst, wherein the mark is NL-4, and the Ni element content in the catalyst is 0.2 wt%.
EXAMPLE 5 preparation of Nickel/lanthanum oxide catalyst
(1) 0.58g of Ni (CH)3COO)2·6H2O with 9.29g LaCl3·3H2Dissolving O in 100ml of deionized water, and uniformly stirring to form a solution A;
(2) 8.25g (NH)4)2CO3Dissolving in 100ml deionized water to form solution B;
(3) adding 100ml of deionized water into a 500ml beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at 40 ℃, wherein the stirring speed is kept at 600 revolutions per minute, and the pH value of the solution is controlled to be 7.6;
(4) continuously stirring the material containing the precipitate in the step (3) at 40 ℃ for reacting for 20min, standing for 20min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 120 ℃ for 12h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 700 ℃ for 3h to obtain the nickel/lanthanum oxide catalyst, wherein the mark is NL-5, and the Ni element content in the catalyst is 0.9 wt%.
Comparative example 1 preparation of a nickel/lanthanum oxide catalyst by impregnation
(1) 24.68g La (NO)3)3·6H2Dissolving O in 200ml of deionized water, and uniformly stirring to form a solution A;
(2) 8.50g (NH)4)2CO3Dissolving in 200ml deionized water to form solution B;
(3) slowly dropwise adding the solution B into the solution A at room temperature (20-25 ℃), wherein the stirring speed is kept at 550 revolutions per minute, and the pH value of the solution is 7.6 after dropwise adding;
(4) continuously stirring the material containing the precipitate in the step (3) at room temperature for reaction for 30min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, drying the precipitate at 120 ℃ for 12h, and roasting at 700 ℃ for 3h to obtain La2O3A white powder;
(5) taking the La in the step (4)2O36.0g of white powder (NO) 2.76gNi3)2·6H2Soaking the solution of O dissolved in 15ml of deionized water at room temperature for 10min, then stirring at 90 ℃, evaporating to remove water to obtain light green powder, and drying at 120 ℃ for 12 h;
(6) and (3) placing the material obtained in the step (5) in a muffle furnace, and roasting at 700 ℃ for 3h to obtain a nickel/lanthanum oxide catalyst, wherein the mark is C-1, and the content of the Ni element in the catalyst is 4.1 wt%.
Comparative example 2 impregnation method for preparing a nickel/lanthanum oxide catalyst
(1) 14.96g of LaCl3·3H2Dissolving O in 200ml of deionized water, and uniformly stirring to form a solution A;
(2) 15.9g of Na2CO3Dissolving in 200ml deionized water to form solution B;
(3) dropwise adding the solution B into the solution A at room temperature (20-25 ℃), wherein the stirring speed is kept at 600 revolutions per minute, and the pH value of the solution is 8.5 after the dropwise adding is finished;
(4) filtering the material containing the precipitate in the step (3), washing the precipitate with deionized water until the pH value of the filtrate is 7, drying the precipitate at 120 ℃ for 12h, and roasting at 700 ℃ for 3h to obtain La2O3A white powder;
(5) taking the La in the step (4)2O36.0g of white powder, 1.38g of Ni (CH)3COO)2·6H2Soaking O in 15ml deionized water at room temperature for 10min, evaporating to remove water at 90 deg.C under stirring to obtain light green powder, and drying at 120 deg.CDrying for 12 h;
(6) and (3) placing the material obtained in the step (5) in a muffle furnace, and roasting at 700 ℃ for 3h to obtain a nickel/lanthanum oxide catalyst, wherein the mark is C-2, and the content of the Ni element in the catalyst is 4.5 wt%.
Comparative example 3 preparation of a nickel/lanthanum oxide catalyst by precipitation
(1) 0.44g of Ni (NO)3)2·6H2O with 11.76g La (NO)3)3·6H2Dissolving O in 100ml of deionized water, and uniformly stirring to form a solution A;
(2) 8.62g NaOH was dissolved in 100ml deionized water to form solution B;
(3) slowly dripping the solution B into the solution A at room temperature (20-25 ℃), wherein the stirring speed is kept at 600 revolutions per minute, and the pH value of the solution is 9.5 after the dripping is finished;
(4) continuously stirring the material containing the precipitate in the step (3) at room temperature for reaction for 10min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 120 ℃ for 12h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 700 ℃ for 3h to obtain the nickel/lanthanum oxide catalyst, wherein the mark is C-3, and the Ni content in the catalyst is 0.9%.
And (3) performance characterization:
the XRD patterns of the nickel/lanthanum oxide catalysts prepared in examples 1 to 4 of the present invention are shown in fig. 1, and those of the nickel/lanthanum oxide catalysts prepared in comparative examples 1 to 3 are shown in fig. 2, and it can be seen from the results of fig. 1 to 2 that: the phase mainly existing in the nickel/lanthanum oxide catalysts prepared in examples 1 to 4 of the present invention is monoclinic La2O2CO3Hexagonal La2O2CO3、La2O3And La2NiO4The difference is the proportion of each phase, which shows that by adopting the preparation method of the invention, Ni exists in the catalyst in a highly dispersed form and has strong interaction with the carrier; XRD in comparative examples 1-3 shows that Ni in the catalyst is other than La2NiO4NiO or NiCO3The form exists.
The inventionExample 1 and comparative example 1 preparation of catalyst H2The TPR diagram is shown in fig. 3, and it can be seen that: the Ni species in the nickel/lanthanum oxide catalyst NL-1 prepared by the embodiment of the invention is single, namely, the Ni almost completely interacts with the carrier strongly; while the catalyst prepared in comparative example 1 had three Ni species present, NiO nanoparticles (α), Ni (β) having a weak interaction with the support, and Ni (γ) having a strong interaction.
Comparative example 4 preparation of a Nickel/lanthanum oxide catalyst
(1) 1.80g of Ni (NO)3)2·6H2O with 10.40g La (NO)3)3·6H2Dissolving O in 100ml of deionized water, and uniformly stirring to form a solution A;
(2) 6.80g of NH4HCO3Dissolving in 100ml deionized water to form solution B;
(3) adding 100ml of deionized water into a 500ml beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at room temperature (20-25 ℃), wherein the stirring speed is kept at 600 revolutions per minute, and the pH value of the solution is controlled to be 7.0;
(4) continuously stirring the material containing the precipitate in the step (3) for reaction for 15min, standing for 30min, filtering, washing the precipitate with deionized water for 3 times, and drying the precipitate at 120 ℃ for 12h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 700 ℃ for 3h to obtain the nickel/lanthanum oxide catalyst, wherein the mark is C-4, and the content of the Ni element in the catalyst is 2.6 wt%.
Comparative example 5 preparation of a Nickel/lanthanum oxide catalyst
(1) 1.80g of Ni (NO)3)2·6H2O with 10.40g La (NO)3)3·6H2Dissolving O in 100ml of deionized water, and uniformly stirring to form a solution A;
(2) 13.50g of NH4HCO3Dissolving in 100ml deionized water to form solution B;
(3) adding 100ml of deionized water into a 500ml beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at room temperature (20-25 ℃), wherein the stirring speed is kept at 600 revolutions per minute, and the pH value of the solution is controlled to be 9.0;
(4) continuously stirring the material containing the precipitate in the step (3) for reaction for 15min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 120 ℃ for 12h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 700 ℃ for 3h to obtain the nickel/lanthanum oxide catalyst, wherein the mark is C-5, and the content of the Ni element in the catalyst is 1.5 wt%.
Example 6
The catalysts prepared in examples 1-5 and comparative examples 1-5 were used for dry reforming of methane and carbon dioxide under the following specific reaction conditions: 0.1g of the catalyst was diluted with 0.35g of quartz sand and placed in a fixed bed quartz tube reactor, and before the reaction was started, the catalyst was subjected to a reduction treatment, specifically, N2Under the atmosphere, the catalyst is heated to 700 ℃ and is introduced for 20mL min- 1H2Maintain for 2H, turn off H2Continue to use N2Purging for 30 min. Then introducing methane and carbon dioxide gas for reaction, controlling the molar ratio of the methane to the carbon dioxide gas to be 1, and introducing 5 ml/min into the raw material gas-1N2The product was analyzed on-line as an internal standard for analysis. The results of the test at 1h of reaction are shown in table 1:
TABLE 1 results of catalyst Performance testing
As can be seen from the data in Table 1, the results of the tests of examples 1-5 are superior to those of comparative examples 1-5 under the same reaction conditions, which shows that the nickel/lanthanum oxide catalyst prepared by the method of the present invention shows higher catalytic activity in the dry reforming reaction of methane and carbon dioxide. This is closely related to the high dispersion of Ni and the strong interaction with the support.
FIGS. 4 a-4 b further compare the catalysts prepared in example 1 and comparative example 1 at a reaction temperature of 700 ℃ and a space velocity of 15000ml g-1.h-1During the reaction, the conversion rate of methane and carbon dioxide changes with the reaction time within 210min,the C-1 catalyst in comparative example 1 showed a significant downward trend in methane and carbon dioxide conversion, whereas the NL-1 catalyst in example 1 showed a more stable performance.
FIG. 5 is a TGA/DSC plot of the NL-1 catalyst of example 1 and the C-1 catalyst of comparative example 1 after 100h of catalytic dry reforming of methane with carbon dioxide; FIGS. 6 a-6 b are TEM images of the NL-1 catalyst in example 1 and the C-1 catalyst in comparative example 1, respectively, after catalyzing a methane carbon dioxide dry reforming reaction for 100 h; as can be seen from FIG. 5, the weight loss of the catalyst after 100h reaction at 750 ℃ is significantly different from the exothermic case, the carbon deposition amount of the C-1 catalyst of comparative example 1 is 20 wt%, while the NL-1 catalyst of example 1 has almost no carbon deposition-induced weight loss, and FIGS. 6a to 6b also further show that the carbon deposition on the surface of the C-1 catalyst of comparative example 1 is mainly filamentous carbon, and no significant carbon deposition is observed in the NL-1 catalyst of example 1. The nickel/lanthanum oxide catalyst prepared by the method has better carbon deposition resistance and high-temperature stability.
EXAMPLE 7 preparation of Nickel/lanthanum oxide catalyst
(1) 0.96g of Ni (NO)3)2·6H2O with 11.76g La (NO)3)3·6H2Dissolving O in 200ml of deionized water, and uniformly stirring to form a solution A;
(2) adding 7.40g of NH4HCO3Dissolving in 200ml deionized water to form solution B;
(3) adding 100ml of deionized water into a 1L beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at room temperature (20-25 ℃), wherein the stirring speed is kept at 580 revolutions per minute, and the pH value of the solution is controlled to be 7.5;
(4) continuously stirring the material containing the precipitate in the step (3) at room temperature for reaction for 10min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 80 ℃ for 10h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 600 ℃ for 4h to obtain the nickel/lanthanum oxide catalyst, which is marked as NL-7, wherein the Ni element content in the catalyst is 0.8 wt%.
EXAMPLE 8 preparation of a Nickel/lanthanum oxide catalyst
(1) 0.81g of NiCl2·6H2O with 8.2g LaCl3·3H2Dissolving O in 100ml of deionized water, and uniformly stirring to form a solution A;
(2) 8.10g (NH)4)2CO3Dissolving in 100ml deionized water to form solution B;
(3) adding 100ml of deionized water into a 500ml beaker, slowly and dropwise adding the solution A and the solution B into the deionized water at 50 ℃, wherein the stirring speed is kept at 550 revolutions per minute, and the pH value of the solution is controlled to be 8;
(4) continuously stirring the material containing the precipitate in the step (3) for reaction for 10min, standing for 30min, filtering, washing the precipitate with deionized water until the pH value of the filtrate is 7, and drying the precipitate at 100 ℃ for 8h to obtain a catalyst precursor;
(5) and (3) placing the catalyst precursor in a muffle furnace, and roasting at 800 ℃ for 2h to obtain the nickel/lanthanum oxide catalyst, wherein the mark is NL-8, and the Ni element content in the catalyst is 1.7 wt%.
Comparative example 6 preparation of a nickel/lanthanum oxide catalyst by impregnation
(1) La was produced in the same manner as in steps (1) to (4) of comparative example 22O3；
(2) Taking the La in the step (1)2O3White powder 3.42g, using 9.09g Ni (NO)3)2·6H2Soaking the solution of O dissolved in 20ml of deionized water at room temperature for 10min, then stirring at 90 ℃, evaporating to remove water to obtain light green powder, and drying at 120 ℃ for 12 h;
(3) and (3) placing the material obtained in the step (2) in a muffle furnace, and roasting at 750 ℃ for 2h to obtain a nickel/lanthanum oxide catalyst, wherein the mark is C-6, and the content of the Ni element in the catalyst is 13.8 wt%.
Example 9
The catalysts prepared in examples 7-8 and comparative example 6 were used for dry reforming of methane and carbon dioxide under the following specific reaction conditions: diluting 0.1g of catalyst with 0.35g of quartz sand, loading the diluted catalyst into a fixed bed quartz tube reactor, and reducing the catalyst before the reaction starts, wherein the specific operation isAs in N2Under the atmosphere, the catalyst is heated to 750 ℃ and 10 mL/min is introduced-1H2，20·min-1N2Maintain for 2H, turn off H2Continue to use N2Purging for 30 min. Then introducing methane and carbon dioxide gas for reaction, controlling the molar ratio of the methane to the carbon dioxide gas to be 1, and introducing the raw material gas for 5min-1N2The product was analyzed on-line as an internal standard for analysis. The results of the test at 1h of reaction are shown in table 2:
TABLE 2 catalyst Performance test results
Example 10
The catalysts prepared in examples 1-3 were used in dry reforming of methane and carbon dioxide under the following specific reaction conditions: 0.1g of the catalyst was diluted with 0.35g of quartz sand and placed in a fixed bed quartz tube reactor, and before the reaction was started, the catalyst was subjected to a reduction treatment, specifically, N2Under the atmosphere, the catalyst is heated to 600 ℃, and 10 mL/min is introduced-1H2，20ml·min-1N2Maintaining for 3H, turning off H2Continue to use N2Purging for 30 min. Then introducing methane and carbon dioxide gas for reaction, controlling the molar ratio of the methane to the carbon dioxide gas to be 1, and introducing 5 ml/min into the raw material gas-1N2The product was analyzed on-line as an internal standard for analysis. The reaction temperature is 800 ℃, and the space velocity of the raw material is 30000m 1g-1·h-1Also, a good effect is obtained.
Example 11
The catalysts prepared in examples 1-3 were used in dry reforming of methane and carbon dioxide under the following specific reaction conditions: 0.1g of the catalyst was diluted with 0.35g of quartz sand and placed in a fixed bed quartz tube reactor, and before the reaction was started, the catalyst was subjected to a reduction treatment, specifically, N2Under the atmosphere, the catalyst is heated to 800 ℃ and 10 mL/min is introduced-1H2，20ml·min-1N2Maintaining for 1H, turning off H2Continue to use N2Purging for 30 min. Then introducing methane and carbon dioxide gas for reaction, controlling the molar ratio of the methane to the carbon dioxide gas to be 1, and introducing 5 ml/min into the raw material gas-1N2The product was analyzed on-line as an internal standard for analysis. The reaction temperature is 600 ℃, and the space velocity of the raw material is 20000ml g-1·h-1Also, a good effect is obtained.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for preparing a nickel/lanthanum oxide catalyst is characterized by comprising the following steps:
carrying out parallel-flow coprecipitation reaction on a mixed reaction system containing a precipitator, a nickel salt, a lanthanum salt and a solvent to obtain a catalyst precursor, wherein the pH value of the mixed reaction system is 7.5-8.5;
and roasting the catalyst precursor to obtain the nickel/lanthanum oxide catalyst.
2. The method according to claim 1, comprising:
dissolving nickel salt and lanthanum salt in water to form a first mixed solution;
dissolving a precipitant in water to form a precipitant solution;
and simultaneously dropwise adding the first mixed solution and the precipitant solution into a solvent at 20-50 ℃ to form the mixed reaction system, controlling the pH value of the mixed reaction system to be 7.5-8.5, stirring and reacting at 20-50 ℃ for 10-30 min, and standing for 10-30 min to obtain the catalyst precursor.
3. The method of claim 2, wherein: the nickel salt comprises any one or the combination of more than two of nickel chloride, nickel nitrate, nickel acetate and nickel sulfate;
and/or the lanthanum salt comprises lanthanum chloride and/or lanthanum nitrate;
and/or, the precipitant comprises ammonium carbonate and/or ammonium bicarbonate;
and/or, the solvent comprises water and/or aqueous ethanol; preferably, the concentration of the ethanol aqueous solution is less than 20 wt%.
4. The method of claim 2, wherein: the molar ratio of the nickel salt to the lanthanum salt in the first mixed solution is 0.02-0.5: 1;
and/or the concentration of the precipitant in the precipitant solution is 0.1-2.0 mol/L;
and/or the volume ratio of the solvent to the sum of the first mixed solution and the precipitant solution is 1: 1-1: 2.
5. The method of claim 1, wherein: the roasting treatment temperature is 600-800 ℃, and the roasting treatment time is 2-4 h.
6. The method of claim 1, further comprising: after the parallel-flow coprecipitation reaction is finished, filtering, washing and drying the obtained mixture; preferably, the drying treatment temperature is 80-120 ℃, and the drying treatment time is 8-12 h.
7. A nickel/lanthana catalyst prepared by the method of any one of claims 1-6, the phase of the nickel/lanthana catalyst comprising monoclinic La2O2CO3Hexagonal La2O2CO3、La2O3And La2NiO4The content of the nickel element in the nickel/lanthanum oxide catalyst is 0.1-5.0 wt%; preferably, the content of the nickel element in the nickel/lanthanum oxide catalyst is 0.2-4.0 wt%.
8. Use of the nickel/lanthanum oxide catalyst of claim 7 in a dry reforming reaction of methane and carbon dioxide.
9. A dry reforming reaction process of methane and carbon dioxide, characterized by comprising:
preparing a nickel/lanthanum oxide catalyst using the method of any of claims 1-6;
in a reducing atmosphere, carrying out reduction treatment on the nickel/lanthanum oxide catalyst at 600-800 ℃ for 1-3 h;
and continuously inputting methane and carbon dioxide into a tubular reactor provided with a nickel/lanthanum oxide catalyst subjected to reduction treatment, wherein the temperature is 600-800 ℃, and the space velocity is 10000-50000 h-1Under the conditions of (a) to produce carbon monoxide and hydrogen.
10. The dry reforming reaction process of claim 9, wherein: the reducing atmosphere comprises a hydrogen atmosphere;
and/or the molar ratio of methane to carbon dioxide is 1.0.
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