CN116037133A - Samarium praseodymium solid solution nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen - Google Patents
Samarium praseodymium solid solution nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen Download PDFInfo
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- CN116037133A CN116037133A CN202310049620.3A CN202310049620A CN116037133A CN 116037133 A CN116037133 A CN 116037133A CN 202310049620 A CN202310049620 A CN 202310049620A CN 116037133 A CN116037133 A CN 116037133A
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002453 autothermal reforming Methods 0.000 title claims abstract description 35
- 239000006104 solid solution Substances 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 15
- FLWCYCMGKSKYDB-UHFFFAOYSA-N [Sm].[Pr] Chemical compound [Sm].[Pr] FLWCYCMGKSKYDB-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000000975 co-precipitation Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 8
- 229940075630 samarium oxide Drugs 0.000 claims description 8
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 7
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000002431 foraging effect Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 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 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008021 deposition Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 3
- 238000002309 gasification Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000036961 partial effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Images
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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
-
- 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
-
- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a samarium praseodymium solid solution nickel-based catalyst for preparing hydrogen by autothermal reforming of acetic acid. Aiming at the deactivation problem of the catalyst in the autothermal reforming reaction of acetic acid, the invention provides a novel catalyst with stable structure, carbon deposit resistance and oxidation resistance. The molar composition of the catalyst according to the invention is (NiO) a (SmO 1.5 ) b (PrO 1.5 ) c Wherein a is 0.286-0.292, b is 0.368-0.708, c is 0-0.346 and is not 0. The invention adopts a coprecipitation method, takes Ni as an active component, introduces Sm element, and forms mesoporous Sm by partially replacing Sm with Pr element 2‑x Pr x O 3±δ The solid solution nickel-based catalyst promotes the adsorption and activation of reactant acetic acid, accelerates the gasification process of carbon deposition precursors, and improves the carbon deposition resistance, oxidation resistance and sintering resistance of the catalyst.
Description
Technical Field
The invention relates to a samarium praseodymium solid solution type nickel-based catalyst for producing hydrogen by autothermal reforming of acetic acid, belonging to the field of hydrogen production by autothermal reforming of acetic acid.
Background
The large consumption of the traditional fossil fuel brings about the problem of environmental pollution, and the hydrogen has the characteristics of high energy density, cleanness and the like, thereby being an important alternative energy carrier. Renewable biomass can be pyrolyzed to obtain biomass oil, and acetic acid (HAc) which is the main component of water phase in the biomass oil can be used as a hydrogen production raw material to prepare hydrogen through an autothermal reforming process.
The autothermal reforming process of acetic acid is generally classified into steam reforming, partial oxidation reforming, autothermal reforming, etc.; the acetic acid steam reforming hydrogen production process is a strong endothermic reaction, and has higher heat exchange requirement; only oxygen or air is introduced in the partial oxidation reforming reaction, and the hydrogen yield is low.
Autothermal reforming of acetic acid combines an endothermic steam reforming process with an exothermic partial oxidation reaction process to achieve a thermal balance of the overall reaction, i.e., CH, by varying the extent of the partial oxidation reforming reaction by adjusting the ratio of oxygen to reactants 3 COOH+xH 2 O+yO 2 →aCO 2 +bCO+cH 2 (ΔH＝0kJmol -1 ) Not only maintains high yield of hydrogen, but also reduces heat exchange requirements.
In the autothermal reforming of acetic acid to produce hydrogen, transition metals such as Ni, co, fe, cu, etc. are available as active components of catalysts in acetic acid reforming systems, while Ni-based catalysts are widely used in reforming processes due to their excellent ability to activate C-C and C-H bonds. However, acetic acid in Ni 0 CH formed by deoH at active site 3 The intermediate such as CO is further decomposed to generate CH 3 * The accumulation of dehydrogenated product C forms soot, which causes deactivation of the catalyst; on the other hand, the oxidizing atmosphere causes a rapid increase in the bed temperature of the fixed bed reactor, and the active component aggregates at this temperature to become large, resulting in a decrease in the conversion ability of large-sized Ni particles to acetic acid, and thus a decrease in activity.
In order to solve the problems of the Ni-based catalyst in the autothermal reforming process of acetic acid, the invention uses a coprecipitation method to prepare Ni/Sm 2-x Pr x O 3±δ The solid solution catalyst has excellent thermal stability, and can effectively relieve the problem of high-temperature sintering in autothermal reforming of acetic acid; the strong interaction with the active metal Ni inhibits the aggregation growth of Ni particles and improves the stability of the catalyst; more importantThe lattice defect in the formed solid solution structure can promote the formation of oxygen vacancies, thereby enhancing the adsorption activation of oxygen-containing species, accelerating the gasification process of the carbon deposition precursor and directionally improving the carbon deposition resistance of the Ni-based catalyst.
For active phase Ni 0 The invention creatively introduces Sm and Pr elements to form a solid solution structure, and utilizes the multivalent electron transfer capability of both Sm element and Pr element to inhibit active component Ni in the autothermal reforming process of acetic acid 0 Improves the oxidation resistance of the catalyst; furthermore, a unique Pr is constructed by adding Pr 4+ /Pr 3+ And Sm 3+ /Sm 2+ Redox electron pair (Sm) 3+ +Pr 3+ →Sm 2+ +Pr 4+ ) The electrons can be transferred through the bridge structure of Sm-O-Pr, O 2 Can be from Pr 3+ Electrons are obtained at the site to generate O 2- And Pr (Pr) 4+ May also be to Sm 3+ Transmitting electrons to generate O and Sm 2+ . The formation of this electron pair promotes charge recycling during the autothermal reforming reaction of acetic acid, enhancing the oxygen-containing species (CH 3 COO*、CH 3 CO*、CO 2 *、CO*、H 2 O, O) further improves the oxidation resistance of the catalyst from the acetic acid reaction pathway.
The invention is innovative in catalyst components and structures, improves the oxidation resistance, carbon deposition resistance and sintering resistance of the catalyst, improves the conversion rate of acetic acid, reduces the selectivity of byproduct methane, and shows excellent catalytic properties.
Disclosure of Invention
The invention aims to solve the technical problems of low activity and even deactivation of the catalyst caused by the fact that the existing catalyst is easy to accumulate carbon, poor in stability and easy to sinter in the autothermal reforming reaction of acetic acid, and provides a novel catalyst with high carbon accumulation resistance, high thermal stability and sintering resistance.
The invention takes Ni as an active component, introduces Sm and Pr elements, adopts a coprecipitation method to prepare Ni/Sm 2-x Pr x O 3±δ Mesoporous composite oxide solid solutionAnd (3) a catalyst, namely forming an active center of Ni-Sm-Pr-O. The catalyst of the invention is used in the reaction of autothermal reforming of acetic acid to produce hydrogen, the conversion rate of acetic acid (HAc) is close to 100% at 750 ℃, and the hydrogen yield is stable at 2.75mol-H 2 about/mol-HAc.
The technical scheme of the invention is as follows:
aiming at the characteristic of autothermal reforming of acetic acid, the invention adopts a coprecipitation method to prepare Ni/Sm 2-x Pr x O 3±δ The mesoporous composite oxide solid solution catalyst forms an active center of Ni-Sm-Pr-O, and improves the sintering resistance, thermal stability and carbon deposit resistance of the Ni-based catalyst in the acetic acid autothermal reforming reaction process. The molar composition of the catalyst of the invention is (NiO) a (SmO 1.5 ) b (PrO 1.5 ) c Wherein a is 0.286-0.292, b is 0.368-0.708, c is 0-0.346 and is not 0; the weight percentage composition in terms of oxide is: 13.0 to 15.9 percent of nickel oxide, 46.1 to 84.1 percent of samarium oxide, 0 to 40.5 percent of praseodymium oxide and other than 0 percent, and the sum of the weight percentages of the components is 100 percent; wherein the preferred catalyst comprises the following components in weight percent based on oxides: 15.0% of nickel oxide, 75.0% of samarium oxide and 10.0% of praseodymium oxide.
The preparation method comprises the following steps:
1) According to the mole ratio (NiO) of each component in the catalyst a (SmO 1.5 ) b (PrO 1.5 ) c Wherein a is 0.286-0.292, b is 0.368-0.708, c is 0-0.346 and is not 0, weighing a certain amount of nickel nitrate, samarium nitrate and praseodymium nitrate, and dissolving in deionized water to prepare mixed nitrate solution 1#;
2) According to [ OH - ]/[Sm 3+ +Pr 3+ ]＝1/8、[OH - ]/[CO 3 2- ]=1/16, formulate Na 2 CO 3 Mixed solution 2# with NaOH; then, slowly dripping and mixing the solution 1# and the solution 2# at 65 ℃ and the pH value of 10.0+/-0.5, performing coprecipitation reaction, and aging for 24 hours;
3) Filtering and washing the obtained precipitate for 3 times, and transferring the obtained precipitate into an oven at 80 ℃ for drying for 24 hours to obtain a catalyst precursor; placing the dried sample in a tube furnace, heating to 700 ℃ at a heating speed of 10 ℃/min, and keeping for 4 hours; finally, tabletting, crushing and screening the sample;
4) The structure of the obtained catalyst is shown as an XRD pattern in figure 1, and Ni/Sm with nickel species supported on samarium praseodymium solid solution structure is formed 2-x Pr x O 3±δ The composite oxide solid solution catalyst forms an active center of Ni-Sm-Pr-O, and typical BJH pore size distribution is shown in figure 2, so that a mesoporous structure is formed; the catalyst is H at 600-800 DEG C 2 Reducing for 1 hour in the atmosphere, using nitrogen as carrier gas, introducing mixed gas with the mole ratio of acetic acid/water/oxygen=1/(3.0-5.0)/(0.2-0.5), and carrying out acetic acid autothermal reforming reaction through a catalyst bed layer, wherein the reaction temperature is 600-800 ℃.
The invention has the beneficial effects that:
1) The invention takes Ni as an active component, introduces Pr component and embeds Sm 2 O 3 Lattice, partially substituting Sm component to form Ni/Sm with Ni-Sm-Pr-O as active center 2-x Pr x O 3±δ A solid solution nickel-based catalyst; wherein Sm is 2-x Pr x O 3±δ Sm in solid solution Structure 3+ Pr with smaller radius of ion (0.121 nm) 3+ Partial substitution of ions (0.113 nm) leads to reduction of the lattice spacing and contraction of the lattice of the unit cell, and the constructed lattice defect is beneficial to generation of oxygen vacancies; thus, on the one hand, promote lattice oxygen (O 2- ) Species generation, acceleration of O * The circulating flow process improves the oxygen storage and oxygen migration capacity of the catalyst, thereby being beneficial to the carbon deposition precursor CH x * Conversion of C to CO/CO 2 (C*+O*→CO，CO+O*→CO 2 ) Waiting for a target carbonaceous product; on the other hand, the generation of oxygen vacancies can increase H in the autothermal reforming process of acetic acid 2 O、O 2 The adsorption and activation capacities of the oxygen-containing species are changed into O species, so that gasification of intermediate products such as carbon deposition precursors C and CO is promoted, the carbon deposition amount on the surface of the catalyst is further reduced, and the carbon deposition resistance of the catalyst is improved.
2) Sm formed in the invention 2-x Pr x O 3±δ In the solid solution structure, the Sm element and the Pr element have multivalent electron transfer capability, which is beneficial to inhibiting active component Ni in the autothermal reforming process of acetic acid 0 Improves the oxidation resistance of the catalyst; and, by adding Pr, a specific Pr is constructed 4+ /Pr 3+ And Sm 3+ /Sm 2+ Redox electron pair (Sm) 3+ +Pr 3+ →Sm 2+ +Pr 4+ ) The electrons can be transferred through the bridge structure of Sm-O-Pr, O 2 Can be from Pr 3+ Electrons are obtained at the site to generate O - And Pr (Pr) 4+ May also be to Sm 3+ Transmitting electrons to generate O and Sm 2+ The method comprises the steps of carrying out a first treatment on the surface of the The formation of this electron pair promotes charge recycling during the autothermal reforming reaction of acetic acid, enhancing the oxygen-containing species (CH 3 COO*、CH 3 CO*、CO 2 *、CO*、H 2 O, O) further improves the oxidation resistance of the catalyst from the acetic acid reaction pathway.
3) The invention prepares Sm with mesoporous structure by coprecipitation method 2-x Pr x O 3±δ Solid solution supported nickel-based catalyst, which is reduced in 700 ℃ hydrogen atmosphere for 1h, active metal Ni 0 Highly dispersed in Sm 1-x Pr x O y Is a stable reaction interface of a carrier and promotes a reactant CH 3 COOH、H 2 O、O 2 Adsorption activation to H 2 、CO 2 Waiting for a target product; meanwhile, the catalyst mesoporous structure has a 'limiting function', so that a 'fast channel' is provided for the diffusion of reactant molecules and product molecules in the reforming process, the regular pore channel structure also has an inhibiting effect on the polymerization of macromolecular byproducts such as carbon precursor ketene and the like, and carbon deposition is further inhibited, so that the hydrogen yield and CO of the product are improved 2 Selectivity.
4) The characterization result related to autothermal reforming of acetic acid shows that the conversion rate of acetic acid is close to 100%, and the hydrogen yield can be stabilized at 2.75mol-H 2 and/mol-HAc, and can effectively inhibit the production of byproducts such as acetone, methane, etc., and has the characteristics of oxidation resistance, sintering resistance, carbon deposition resistance, stable activity, high hydrogen yield, etc.
Drawings
Fig. 1: x-ray diffraction pattern of the catalyst of the invention
Fig. 2: BJH pore size distribution diagram of the catalyst of the invention
Detailed Description
Reference example 1
2.336g of Ni (NO) 3 ) 2 .6H 2 O, 8.667g Sm (NO) 3 ) 3 .6H 2 O, adding a proper amount of deionized water to prepare nitrate solution #1; 8.811g of NaOH and 1.459g of Na were weighed out 2 CO 3 Adding a proper amount of deionized water to prepare solution # 2; then, slowly dripping and mixing the solution 1# and the solution 2# at 65 ℃ and the pH value of 10.0+/-0.5, performing coprecipitation reaction, and keeping the temperature for aging for 24 hours; filtering and washing for 3 times, and transferring the obtained precipitate into an oven at 80 ℃ to dry for 24 hours to obtain a catalyst precursor; placing the dried sample in a tube furnace, heating to 700 ℃ at a heating speed of 10 ℃/min, and keeping for 4 hours to obtain a CDUT-NS catalyst; the catalyst comprises the following components in percentage by weight in terms of oxide: 15.0% of nickel oxide and 85.0% of samarium oxide.
The acetic acid autothermal reforming reactivity evaluation was performed in a continuous flow fixed bed reactor. Grinding and tabletting the catalyst, sieving to obtain particles of 20-40 meshes, weighing 0.1-0.2g, mixing with quartz sand, loading into reactor, and heating at 600-800deg.C under H 2 Reducing for 1h; then injecting the acetic acid-water mixed solution into a vaporizer by a constant flow pump for vaporization, mixing with nitrogen, and forming a catalyst with the molar ratio of CH by taking the nitrogen as an internal standard gas 3 COOH/H 2 O/O 2 The reaction raw material gas of 1/(3.0-5.0)/(0.2-0.5) is introduced into a reaction bed, the reaction condition is 600-800 ℃, the normal pressure and the airspeed are 20000-60000 mL/(g-catalyst.h), and the reaction tail gas is analyzed on line by a gas chromatograph.
The activity of the CDUT-NS catalyst is examined through acetic acid autothermal reforming reaction, the reduction temperature is 700 ℃, the space velocity is 50766 mL/(g-catalyst h), the reaction temperature is 750 ℃, and the feeding mole ratio is CH 3 COOH/H 2 O/O 2 =1/4.0/0.28. The catalyst is used in acetic acidThe conversion of acetic acid during the autothermal reforming reaction was stabilized around 100% and the hydrogen yield was 2.25mol-H 2 about/mol-HAc. Carbon dioxide selectivity fluctuates around 60%; carbon monoxide selectivity fluctuates around 40%; methane selectivity fluctuates around 1%. The CDUT-NS catalyst is subjected to nitrogen low-temperature physical adsorption characterization, and the result is as follows: specific surface area of 7.5m 2 Per gram, pore volume of 0.038cm 3 The average pore diameter was 5.7nm.
Example 1
2.336g of Ni (NO) 3 ) 2 .6H 2 O, pr (NO) 1.055g 3 .6H 2 O, 7.647g Sm (NO) 3 ) 3 .6H 2 O, adding a proper amount of deionized water to prepare nitrate solution #1; 8.853g of NaOH and 1.466g of Na were weighed out 2 CO 3 Adding a proper amount of deionized water to prepare #2; then, slowly dripping and mixing the solution 1# and the solution 2# at 65 ℃ and the pH value of 10.0+/-0.5, performing coprecipitation reaction, and keeping the temperature for aging for 24 hours; filtering and washing for 3 times, and transferring the obtained precipitate into an oven at 80 ℃ to dry for 24 hours to obtain a catalyst precursor; placing the dried sample in a tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min, and maintaining for 4 hours to obtain the CDUT-NSP10 catalyst, thereby forming Ni/Sm with nickel species supported on samarium praseodymium solid solution structure 2-x Pr x O 3±δ The composite oxide solid solution catalyst forms an active center of Ni-Sm-Pr-O, the typical structure of which is shown in figure 1, and a mesoporous structure with the pore diameter intensively distributed near 5nm is formed, as shown in figure 2; the catalyst comprises the following components in percentage by weight in terms of oxide: 15.0% of nickel oxide, 75.0% of samarium oxide and 10.0% of praseodymium oxide.
The activity of the CDUT-NSP10 catalyst is examined through acetic acid autothermal reforming reaction, the reduction temperature is 700 ℃, the space velocity is 50766/(g-catalyst h), the reaction temperature is 750 ℃, and the feeding mole ratio is CH 3 COOH/H 2 O/O 2 =1/4.0/0.28. The catalyst has the conversion rate of acetic acid stabilized at 100% and hydrogen yield of 2.75mol-H in the process of autothermal reforming reaction of acetic acid 2 about/mol-HAc, the carbon dioxide selectivity fluctuates at about 67%Carbon monoxide selectivity fluctuates around 33% and methane selectivity fluctuates around 1%. The CDUT-NSP10 catalyst is subjected to nitrogen low-temperature physical adsorption characterization, and the result is that: specific surface area of 6.3m 2 Per gram, pore volume of 0.084cm 3 The average pore diameter was 6.8nm. XRD, BET and other characterizations find that the active component Ni of the catalyst is effectively dispersed in Sm 2-x Pr x O 3±δ In the samarium praseodymium solid solution skeleton structure, an active center of Ni-Sm-Pr-O is formed, and the valence state is stable, and the samarium praseodymium solid solution skeleton structure has the characteristics of carbon deposition resistance, sintering resistance and the like.
Example two
2.336g of Ni (NO) 3 ) 2 .6H 2 O, 4.221g Pr (NO) 3 .6H 2 O, 4.588g Sm (NO) 3 ) 3 .6H 2 O, adding a proper amount of deionized water to prepare solution #1; 8.979g NaOH and 1.487g Na were weighed out 2 CO 3 Adding a proper amount of deionized water to prepare solution # 2; then, slowly dripping and mixing the solution 1# and the solution 2# at 65 ℃ and the pH value of 10.0+/-0.5, performing coprecipitation reaction, and keeping the temperature for aging for 24 hours; filtering and washing for 3 times, and transferring the obtained precipitate into an oven at 80 ℃ to dry for 24 hours to obtain a catalyst precursor; placing the dried sample in a tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min, and maintaining for 4 hours to obtain the CDUT-NSP40 catalyst, wherein nickel species are loaded on Sm 2-x Pr x O 3±δ The mesoporous composite oxide samarium praseodymium solid solution structure forms an active center of Ni-Sm-Pr-O; the catalyst comprises the following components in percentage by weight in terms of oxide: 15.0% of nickel oxide, 45.0% of samarium oxide and 40.0% of praseodymium oxide.
The activity of the CDUT-NSP40 catalyst is examined through acetic acid autothermal reforming reaction, the reduction temperature is 700 ℃, the space velocity is 50766 mL/(g-catalyst h), the reaction temperature is 750 ℃, and the feeding mole ratio is CH 3 COOH/H 2 O/O 2 =1/4.0/0.28. The conversion rate of the catalyst to acetic acid in the autothermal reforming reaction process of acetic acid is stabilized near 100%, and the hydrogen yield reaches 2.50mol-H 2 the/mol-HAc, the carbon dioxide selectivity is fluctuated about 60%, and the carbon monoxide selectivity is fluctuated about 30%Methane selectivity fluctuates around 5%. The CDUT-NSP40 catalyst is subjected to nitrogen low-temperature physical adsorption characterization, and the result is that: specific surface area of 9.2m 2 Per gram, pore volume of 0.045cm 3 The average pore diameter was 6.3nm. XRD characterization results show that the catalyst has stable Ni/Sm 2-x Pr x O 3±δ Solid solution structure.
Claims (3)
1. The application of samarium praseodymium solid solution nickel-based catalyst in the process of autothermal reforming of acetic acid to prepare hydrogen is characterized in that: the catalyst is added in H 2 Reducing for 1h at 600-800 ℃ under atmosphere, and introducing a molar ratio of CH 3 COOH/H 2 O/O 2 The mixed gas of 1/(3.0-5.0)/(0.2-0.5) is subjected to acetic acid autothermal reforming reaction through a catalyst bed, and the reaction temperature is 600-800 ℃; the catalyst is prepared by the following method: according to the weight percentage of the catalyst, a certain amount of nickel nitrate, samarium nitrate and praseodymium nitrate are weighed and dissolved in deionized water to form a mixed nitrate solution 1#; according to [ OH ]]/[Sm 3+ +Pr 3+ ]＝1/8、[OH - ]/[CO 3 2- ]=1/16, formulate Na 2 CO 3 Mixed solution 2# with NaOH; then, slowly dripping and mixing the solution 1# and the solution 2# at 65 ℃ and the pH value of 10.0+/-0.5, performing coprecipitation reaction, and keeping the temperature for aging for 24 hours; filtering and washing for 3 times, and transferring the obtained precipitate into an oven at 80 ℃ to dry for 24 hours to obtain a catalyst precursor; placing the dried sample in a tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min, and maintaining for 4 hours to obtain Ni/Sm with mesoporous structure and forming Ni-Sm-Pr-O active center 2-x Pr x O 3±δ A solid solution nickel-based catalyst; the catalyst has the molar composition (NiO) calculated by oxide a (SmO 1.5 ) b (PrO 1.5 ) c Wherein a is 0.286-0.292, b is 0.368-0.708, c is 0-0.346 and is not 0; the weight percentage composition in terms of oxide is: 13.0 to 15.9 percent of nickel oxide, 46.1 to 84.1 percent of samarium oxide, 0 to 40.5 percent of praseodymium oxide and other than 0 percent, and the sum of the weight percentages of the components is 100 percent.
2. The use of the samarium praseodymium solid solution nickel based catalyst according to claim 1 in an autothermal reforming process of acetic acid to produce hydrogen, characterized in that: the catalyst comprises the following components in percentage by weight of oxide: 15.0% of nickel oxide, 75.0% of samarium oxide and 10.0% of praseodymium oxide.
3. The use of the samarium praseodymium solid solution nickel based catalyst according to claim 1 in an autothermal reforming process of acetic acid to produce hydrogen, characterized in that: the catalyst comprises the following components in percentage by weight of oxide: 15.0% of nickel oxide, 45.0% of samarium oxide and 40.0% of praseodymium oxide.
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