CN112844397B - Cerium-samarium solid solution nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen - Google Patents
Cerium-samarium solid solution nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen Download PDFInfo
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Abstract
The invention relates to a nickel-based mesoporous composite oxide solid solution catalyst for autothermal reforming of acetic acid to produce hydrogen. Aiming at the problems of carbon deposition, sintering and the like of the existing catalyst, the invention adopts a sol-gel method to prepare the mesoporous composite oxide solid solution Ni/Sm-Ce-O x Catalyst, molar composition is (NiO) a (SmO 1.5 ) b (CeO 2 ) c Wherein a is 0.13-0.17, b is 0.38-0.50, c is 0.01-0.12; sm-Ce-O formation in catalysts x The composite oxide solid solution utilizes the synergistic effect of Ce-Sm, induces the absorption and conversion of acetic acid through the interaction of an active component Ni and a solid solution carrier, strengthens the activation effect on the acetic acid and water, and has the characteristics of carbon deposition resistance, sintering resistance, stable structure and the like in the autothermal reforming process of the acetic acid.
Description
Technical Field
The invention relates to a cerium-samarium solid solution nickel-based catalyst for preparing hydrogen by autothermal reforming of acetic acid, belonging to the field of hydrogen preparation by autothermal reforming of acetic acid.
Background
The hydrogen is used as an environment-friendly clean energy source, and has good application prospect in the fields of traffic, power generation, aerospace and the like. In the current hydrogen production process route, about 80% to 85% of hydrogen is produced from fossil fuels such as natural gas through a reforming process. In order to achieve the purposes of energy conservation and emission reduction, renewable biomass resources are used to obtain biomass oil through a fast pyrolysis process, and acetic acid with the proportion of 30% in water-phase components of the biomass oil is used as a raw material to prepare hydrogen, so that the method is an attractive hydrogen preparation process with a renewable approach.
The acetic acid steam reforming is a common hydrogen production mode, and high hydrogen yield can be obtained because the reactant steam can participate in the reaction; however, the process is endothermic and requires constant supply of heat from the outside to maintain the reaction. Partial oxidation reforming is another way, oxygen or air is introduced into the raw material, and the reactant acetic acid and the oxygen or the air undergo partial oxidation reaction to release heat, so as to maintain the reaction; in this process, acetic acid tends to be deeply oxidized into carbon dioxide and water, resulting in a decrease in hydrogen yield.
Compared with the two reforming hydrogen production modes, the autothermal reforming combines the endothermic steam reforming process and the exothermic partial oxidation reaction process, and the heat balance of the whole reaction, namely CH, can be realized by adjusting the oxygen-carbon ratio to change the reaction degree of the partial oxidation reforming 3 COOH+xO 2 +yH 2 O→aCO+bCO 2 +cH 2 (Δ H =0 kJ/mol), while maintaining a high hydrogen yield, significantly reduces the dependence on external heat sources, and has significant advantages in the hydrogen production process.
The production of hydrogen from an autothermal catalytic reforming process is particularly important to the choice of catalyst. Traditional noble metal catalysts such as platinum, palladium, rhodium, ruthenium and the like have high catalytic activity, but the high price also limits the wide application of the traditional noble metal catalysts. Among non-noble metal catalysts, the nickel-based catalyst has stronger capability of activating C-C bonds and C-H bonds, and has better application prospect. However, in the autothermal reforming of acetic acid, the acetic acid may be subjected to dehydrogenation, dehydroxylation, etc. (CH) 3 COOH→CH 3 COO*→CH 3 CO*/CH 3 COOH→CH 3 CO) and ketonization (CH) 3 CO*+CH 3 *→CH 3 COCH 3 ) This generates a large amount of CH 3 CO*、CH x And C, and the like, and the intermediate species are subjected to condensation polymerization to form carbon deposit which is accumulated on the surface of active metal nickel crystals to deactivate the nickel-based catalyst. Meanwhile, in the process of autothermal reforming, because oxygen is mainly consumed at the front end of the fixed bed reactor, local high temperature at the front end can be generated and can reach 1000 ℃,leading to aggregate sintering deactivation of the nickel-based catalyst; the oxidative atmosphere of the autothermal reforming process also initiates oxidative deactivation of the active component nickel.
In order to solve the problems in the autothermal reforming process of acetic acid, the invention introduces Sm-Ce-O into the nickel-based catalyst x A solid solution composite oxide. In the composite oxide, oxide CeO 2 Has typical fluorite structure, good thermal stability and Ce 3+ And Ce 4+ Has excellent oxygen storage and oxygen migration capacity, forms oxygen vacancy through oxygen species migration in crystal lattices, and is beneficial to the transfer and transfer of active O. By this route, the catalyst can promote carbon oxidation (CH) by oxygen migration from the crystal lattice for acetic acid derived carbon-containing species 3 *→C*+O*→CO*+O*→CO/CO 2 ) The carbon deposit is gasified, so that the carbon deposit on the surface of the catalyst is inhibited, and the carbon deposit resistance of the catalyst in the self-heating reforming process of acetic acid is improved. At the same time, ceO 2 The Ce-Ni composite material has a discrete molecular orbit, can generate a coupling effect with an electronic state on the surface of a loaded active metal to generate a charge transfer or polarization effect, shows an electron donating effect of low-electronegativity Ce on high-electronegativity Ni to form a strong interaction between Ce and Ni, and can improve the oxidation resistance and stability of active component nickel particles and inhibit oxidation and sintering.
However, the oxygen storage and oxygen transfer characteristics of ceria are not satisfactory for use in autothermal reforming of acetic acid. Because ceria consists of eight oxy cations coordinated at the cube corners, each anion is tetrahedrally coordinated by four cations, which makes the structure of ceria more stable and to some extent suppresses Ce 4+ To Ce 3+ Thereby inhibiting the oxygen transport capacity, resulting in inefficient transfer of the actual O species and reduced capacity to mitigate carbon deposition by carbon oxidation reactions.
Thus, the characteristics and CeO for autothermal reforming of acetic acid 2 The invention creatively introduces Sm 2 O 3 And construct Sm-Ce-O x A solid solution composite oxide. The solid solution has good thermal stability and good stability,more importantly, in the solid solution structure, sm-Ce-O x The crystal lattice distortion of the composite oxide forms a large number of crystal plane defects, and more oxygen vacancies (Ce) are formed on the surface of the composite oxide carrier 4+ -Ov-Sm 3+ ) Thereby effectively promoting the conversion of acetic acid molecules into CH in the process of autothermal reforming of acetic acid 3-x * And CO, and the like to generate CO/CO 2 And the like. Meanwhile, sm is added to form Sm 2 O 3 -Sm 2 O 3 CO 3 Catalytic cycle (Sm) 2 O 3 +CO 2 →Sm 2 O 3 CO 3 ，Sm 2 O 3 CO 3 +C*→Sm 2 O 3 +2 CO), while being able to convert C species more efficiently, CO 2 The adsorption activation also promotes gasification of the carbonaceous material during autothermal reforming of acetic acid, thereby inhibiting the formation of carbon. In addition, sm-Ce-O is used in autothermal acetic acid reforming x Sm in solid solution 2 O 3 The species efficiently activates water molecules in the feed, facilitating the Water Gas Shift Reaction (WGSR) to proceed in the forward direction (H) 2 O+CO→H 2 +CO 2 ) The yield of the hydrogen is effectively improved. In addition, CO and CO are generated in the autothermal reforming of acetic acid 2 Methanation, and the preceding small molecule CH 3 * The intermediate product combines with H previously produced by dehydrogenation of macromolecules to form CH as a by-product 4 In the presence of Sm-Ce-O x Basic Sm in solid solution 2 O 3 Species activate methane by adsorption to form ═ CH x Methyl free radical of (A), effectively increasing CH x Activity of cracking and conversion to CO/CO promoted by the active metal Ni 2 Thereby promoting the methane reforming reaction (CH) 4 +H 2 O→3H 2 + CO) is carried out in the forward direction, increasing the yield of hydrogen.
Therefore, the cerium-samarium solid solution nickel-based catalyst provided by the invention utilizes the synergistic effect of Ce-Sm, effectively improves the oxygen storage and oxygen transfer performance and the electron transfer capacity, and oxygen vacancies formed in large amount in the catalyst can effectively induce H in the autothermal reforming reactant of acetic acid 2 O and O 2 Adsorption activation of(ii) a Simultaneously Sm in the catalyst 3+ And Ce 4+ The reaction forms Lewis alkali site, further increases the integral alkalinity of the catalyst, inhibits the ketonization of acetic acid and enhances the reaction of CO 2 The adsorption and activation function of the catalyst can promote the gasification of carbon-containing products so as to reduce carbon deposition; the cerium-samarium solid solution nickel-based catalyst has the advantages of high catalytic activity on H 2 Activation of O can also promote the water gas reaction to increase hydrogen yield. These physicochemical properties effectively improve the autothermal reforming reaction of acetic acid on H 2 Has good thermal stability and is excellent in the autothermal reforming reaction of acetic acid.
Therefore, the catalyst has innovation in component and structure, and the carbon deposit resistance, sintering resistance and thermal stability of the catalyst in the autothermal reforming reaction of acetic acid are improved. The activity test result of the catalyst applied to the autothermal reforming reaction of acetic acid also shows that the catalyst has excellent activity, selectivity and stability.
Disclosure of Invention
The invention aims to solve the technical problems of low activity, poor stability, serious carbon deposition and sintering intolerance of the existing catalyst in the autothermal reforming reaction of acetic acid, so as to cause the inactivation of the catalyst, and provides a novel catalyst which has stable activity, carbon deposition resistance, sintering resistance and stable structure. The invention takes nickel as an active component, introduces Ce and Sm components, and adopts a sol-gel method to create the nickel-based mesoporous composite oxide solid solution Ni/Sm-Ce-O x A catalyst; the catalyst is used in the reaction of autothermal reforming of acetic acid to prepare hydrogen, the conversion rate of acetic acid is close to 100 percent under the condition that the reaction temperature is 650 ℃, and the hydrogen yield can be stabilized at 2.61mol-H 2 mol-HAc. The results of activity test and phase analysis and the like carried out on the catalyst prove that the catalyst has the advantages of carbon deposition resistance, sintering resistance, stable structure and activity.
The technical scheme of the invention is as follows:
the invention aims at the characteristic of autothermal reforming of acetic acid and prepares Ni/Sm-Ce-O by a sol-gel method x A mesoporous composite oxide solid solution catalyst. The chemical composition of the catalyst of the invention is (NiO) a (SmO 1.5 ) b (CeO 2 ) c Wherein a is 0.13-0.17, b is 0.38-0.50, c is 0.01-0.12; comprises the following components in percentage by weight: 10.0 to 13.0 percent of nickel oxide, 66.8 to 87.8 percent of samarium oxide and 1.9 to 20.9 percent of cerium oxide; wherein the preferred typical catalyst CDUT-NSC10 comprises the following components in percentage by weight: 12.1 percent of nickel oxide, 77.5 percent of samarium oxide and 10.4 percent of cerium oxide.
The specific preparation method comprises the following steps:
1) According to the proportion of each component (NiO) in the catalyst a (SmO 1.5 ) b (CeO 2 ) c Wherein a is 0.13-0.17, b is 0.38-0.50, c is 0.01-0.12, nickel nitrate, samarium nitrate and cerous nitrate are dissolved in deionized water to prepare a mixed solution #1;
2) Preparing a mixed solution #2 of citric acid and ethylene glycol according to the total molar ratio of citric acid to ethylene glycol to metal nitrate of 1; mixing the solution #1 and the solution #2, keeping the water bath heating at 60 ℃, continuing stirring until gel appears, moving the gel into an oven, and foaming and expanding the sample at the temperature of 105 ℃ for 12 hours;
3) Crushing the sample obtained in the step 2), putting the crushed sample into a tube furnace for roasting, heating the sample from room temperature to 600-800 ℃ at the heating rate of 10 ℃/min, and keeping the roasting for 4 hours to obtain the Ni/Sm-Ce-O alloy of the invention x The typical crystal structure of the composite oxide solid solution catalyst is shown as an XRD pattern in figure 1 and is represented as a main component Sm 2 O 3 Doped CeO 2 Phase, formation of Ce species intercalated Sm 2 O 3 Composite oxide solid solution Sm-Ce-O with structure x And the NiO phase is weak, which indicates that Ni is highly dispersed and embedded into a solid solution Sm-Ce-O x The crystal structure of (a); the typical BJH pore size distribution is shown as figure 2, and Sm-Ce-O with a mesoporous structure is formed x A solid solution;
4) The catalyst is used at the temperature of 600-800 ℃ and the flow rate of H of 30mL/min 2 Reducing the mixture for 1h, then purging the mixture by nitrogen, and passing the mixture through a catalyst bed layer to perform autothermal reforming reaction by using mixed gas with the molar ratio of acetic acid/water/oxygen = 1/(1.3-5.0)/(0.21-0.35), wherein the reaction temperature is 500-800 ℃, the normal pressure and the space velocity is 20000-60000 mL/(g-catalyst · h).
The invention has the beneficial effects that:
1) The invention prepares Sm-Ce-O by taking Ni as an active component and introducing Sm and Ce components through a sol-gel method x The composite oxide solid solution nickel-based catalyst has the advantages that in the solid solution, the Ce-Sm doping causes lattice defects to form more oxygen vacancies on the surface of a carrier, and the oxygen vacancies are generated to H 2 O、O 2 The oxygen-containing species have excellent adsorption and activation capabilities, and can be converted into O species, and the O species promote the gasification of intermediate products such as carbon deposition precursors C and CO, so that carbon deposition is reduced.
2) Sm-Ce-O constructed by the catalyst of the invention x In the solid solution, ce has an electron donating effect on Ni with high electronegativity, so that the Ce and the Ni load metal have strong interaction, the stability of the nano nickel particles is improved, and the nano nickel particles are prevented from sintering due to agglomeration.
3) Sm-Ce-O constructed by the catalyst of the invention x Solid solution, existing stable Sm 3+ Cation, obviously improves the alkalinity of the whole catalyst, and can effectively inhibit CH x * And CH 3 Acetone (CH) formed by CO bonding 3 CO*+CH 3 *→CH 3 COCH 3 ) Promoting the reaction pathway to CH 3 CO*→CH 3 * + CO transfer, promoting subsequent gasification to CO/CO 2 Reducing the reaction activity reduction caused by carbon deposition; at the same time, sm-Ce-O x The solid solution effectively activates acetyl and methyl free radicals generated after acetic acid dehydrogenation and O, inhibits acetone generation and promotes CH x Converting with small molecules such as CO;
4) Sm-Ce-O constructed by the catalyst of the invention x Solid solution of Sm having high dispersibility and good stability 3+ Species, capable of efficiently passing Sm 2 O 3 Adsorption of CO 2 Form Sm 2 O 3 CO 3 And combining the C species to generate CO to form a catalytic cycle, effectively converting the C species serving as the carbon deposition precursor, and reacting the CO 2 The adsorption activation also promotes the gasification of the carbonaceous material during the autothermal reforming of acetic acid; at the same time Sm 3+ The species effectively promote and activate water molecules, and further promote the water-gas shift reaction activityAnd the hydrogen yield is improved.
5) The catalyst of the invention synthesizes Ni/Sm-Ce-O by a sol-gel method x The XRD patterns of the composite oxide solid solution catalyst are shown as figures 1, 3 and 4, and Sm is shown after roasting, reduction and reaction 2 O 3 Ce is embedded into Sm as main phase 2 O 3 A stable solid solution structure is formed in the structure, and Ni enters Sm-Ce-O x The stability of the crystal lattice of the solid solution is improved; as shown in figure 2, a BJH aperture distribution diagram forms a mesoporous structure, the overall specific surface area of the catalyst is increased, and meanwhile, the porous structure and the pore channels with developed interior are suitable for the transmission and diffusion of reactant and product molecules, so that the thermal stability of the catalyst is improved.
6) The Ni/Sm-Ce-O formed after the roasting of the invention x The composite oxide solid solution catalyst utilizes the synergistic effect of Ce-Sm to promote the active component nickel, can induce acetic acid to carry out efficient adsorption conversion in the acetic acid conversion process, and effectively inhibits ketonization reaction, thereby inhibiting the generation of byproducts such as acetone, ketene and methane, and the like, and has the characteristics of carbon deposition resistance, sintering resistance, stable activity, high hydrogen yield and the like.
Drawings
FIG. 1: x-ray diffraction spectrum of calcined catalyst
FIG. 2: BJH pore size distribution diagram of catalyst of the invention
FIG. 3: x-ray diffraction spectrogram after catalyst reduction
FIG. 4: x-ray diffraction spectrum of catalyst after reaction
Detailed Description
Reference example 1
Weighing 1.889gNi (NO) 3 ) 2 ·6H 2 O、0.195gCe(NO 3 ) 2 ·6H 2 O and 8.763gSm (NO) 3 ) 3 ·9H 2 O, adding 27mL of deionized water to prepare a solution #1; weighing 5.602gC 6 H 8 O 7 ·H 2 O and 1.655g (CH) 2 OH) 2 Adding 113ml of deionized water to prepare a solution #2;mixing the solutions #1 and #2, and continuously stirring the mixture at the constant-temperature water bath of 60 ℃ until green gel is formed; then drying the gel in a drying oven at 105 ℃ for 12 hours; after the dried and foamed sample is crushed, the temperature is raised from room temperature to 650 ℃ at the heating rate of 10 ℃/min, and the CDUT-NSC2 catalyst is obtained after the roasting and the holding time is 4 h. The molar composition of the catalyst is (NiO) 0.16 (SmO 1.5 ) 0.49 (CeO 2 ) 0.01 The composite material comprises the following components in percentage by weight calculated on oxides: 12.1 percent of nickel oxide, 85.9 percent of samarium oxide and 2.0 percent of cerium oxide.
Evaluation of the activity of the autothermal reforming reaction of acetic acid was carried out in a continuous flow fixed bed reactor. Grinding and tabletting the catalyst, sieving into 20-40 mesh granules, placing into a reaction tube, and feeding into a reaction tube at 600-800 deg.C and with a flow rate of 30mL/min H 2 Reducing for 1h in the flow, injecting the mixed solution of acetic acid and water into a vaporizer by a constant flow pump for vaporization, mixing oxygen, and taking nitrogen as internal standard gas to form a molar composition of CH 3 COOH/H 2 O/O 2 Reaction raw material gas of which the ratio is 1/(1.3-5.0)/(0.21-0.35) is introduced into a reaction bed layer to carry out the autothermal reforming reaction of acetic acid, the reaction conditions are 500-800 ℃, normal pressure and space velocity 20000-60000 mL/(g-catalyst.h), and the reaction is carried out on-line analysis by adopting a gas chromatograph.
The CDUT-NSC2 catalyst is subjected to activity investigation through an autothermal reforming reaction of acetic acid, and has the reaction conditions of normal pressure, space velocity of 50000 mL/(g-catalyst.h), reaction temperature of 650 ℃ and feeding ratio of CH 3 COOH/H 2 O/O 2 The catalyst has acetic acid conversion rate of about 96.2% and hydrogen yield of 2mol-H when the reaction time is 10H and is 1/4.0/0.28 2 /mol-HAc，CO 2 The selectivity is about 59.5 percent, the CO selectivity is about 38.5 percent, and CH 4 The selectivity is between 0.5% and 1.5%, and the selectivity of the byproduct acetone is about 0.2%.
Example one
1.880gNi (NO) was weighed 3 ) 2 ·6H 2 O、1.053gCe(NO 3 ) 2 ·6H 2 O and 7.902gSm (NO) 3 ) 3 ·9H 2 O, adding 27mL of deionized water to prepare solution #1; weighing 5.604gC 6 H 8 O 7 ·H 2 O and 1.655g (CH) 2 OH) 2 Adding 113ml of deionized water to prepare a solution #2; the subsequent steps are the same as the reference example 1, and the Ce species embedded main body Sm is obtained after roasting for 4 hours at 650 DEG C 2 O 3 Mesoporous composite oxide solid solution Ni/Sm-Ce-O with structure x The typical structure of the catalyst, namely the CDUT-NSC10 catalyst, is shown in figure 1, and the typical pore size distribution of the mesoporous structure is shown in figure 2; the molar composition of the catalyst is (NiO) 0.16 (SmO 1.5 ) 0.44 (CeO 2 ) 0.06 The composite material comprises the following components in percentage by weight calculated on oxides: 12.1 percent of nickel oxide, 77.5 percent of samarium oxide and 10.4 percent of cerium oxide.
The CDUT-NSC10 catalyst is subjected to activity investigation through an autothermal reforming reaction of acetic acid, and has the reaction conditions of normal pressure, space velocity of 50000 mL/(g-catalyst.h), reaction temperature of 650 ℃ and feeding ratio of CH 3 COOH/H 2 O/O 2 The catalyst has acetic acid conversion rate of about 99.4% and hydrogen yield of 2.61mol-H when the reaction time is 10H and the reaction time is 1/4.0/0.28 2 /mol-HAc，CO 2 The selectivity is about 60 percent, the CO selectivity is about 39.5 percent, and CH 4 The selectivity approaches to 0, and the selectivity of the byproduct acetone is only about 0.02%. The catalyst activity remained stable as the reaction proceeded. The NSC10 catalyst is characterized by low-temperature nitrogen adsorption as shown in the attached figure 2, and the result is that: the specific surface area is 7.83m 2 Pore volume of 0.044 cm/g 3 (ii)/g, average pore diameter 9.3nm. The catalyst after reaction is characterized, as shown in XRD spectrogram of the catalyst after reduction in figure 3 and reaction in figure 4, the catalyst also keeps stable formation of Ce species embedded in Sm after reduction 2 O 3 Composite oxide Sm-Ce-O formed by structure x The existence of solid solution structure, weak phase Ni also indicates the high dispersion of the active component nickel and enters Sm-Ce-O x Solid solution structure, no coalescence, no carbon deposition species found; the reacted catalyst also shows stable Ni/Sm-Ce-O x Composite oxide solid solution structure. From the results, it is understood that the catalyst of the present invention has anti-carbon deposition property in the autothermal reforming reaction of acetic acidThe sintering resistance, the hydrogen yield is high, the structure is stable, and the like.
Example two
Weighing 1.891gNi (NO) 3 ) 2 ·6H 2 O、2.061gCe(NO 3 ) 2 ·6H 2 O and 6.876gSm (NO) 3 ) 3 ·9H 2 O, adding 27ml of deionized water to prepare a solution #1; weighing 5.615gC 6 H 8 O 7 ·H 2 O and 1.659g (CH) 2 OH) 2 Adding 114ml of deionized water to prepare a solution #2; the subsequent steps are the same as the reference example 1, and the Ni/Sm-Ce-O is obtained after roasting for 4 hours at the temperature of 650 DEG C x A composite oxide solid solution catalyst, namely a CDUT-NSC20 catalyst, the typical structure of which is shown in figure 1; the catalyst is a mesoporous material, and the typical pore size distribution of the catalyst is shown in figure 2; the molar composition of the catalyst is (NiO) 0.16 (SmO 1.5 ) 0.38 (CeO 2 ) 0.12 The composite material comprises the following components in percentage by weight calculated on oxides: 12.1 percent of nickel oxide, 67.5 percent of samarium oxide and 20.4 percent of cerium oxide.
The CDUT-NSC20 catalyst is subjected to activity investigation through an autothermal reforming reaction of acetic acid, and has the reaction conditions of normal pressure, space velocity of 50000 mL/(g-catalyst.h), reaction temperature of 650 ℃ and feeding ratio of CH 3 COOH/H 2 O/O 2 The catalyst has the acetic acid conversion rate of about 99.7 percent and the hydrogen yield of 2.59mol-H when the reaction time is 10 hours is 1/4.0/0.28 2 /mol-HAc，CO 2 The selectivity is about 59 percent, the CO selectivity is about 40 percent, and CH 4 The selectivity to acetone is close to 0. The overall activity of the catalyst is stable during the test. The CDUT-NSC10 catalyst was BET characterized and the results were: the specific surface area is 2.74m 2 Per g, pore volume of 0.016cm 3 G, average pore diameter of 10.9nm.
As can be seen from the activity test results, the catalyst of the invention has the acetic acid conversion rate approaching 100% in the autothermal reforming reaction of acetic acid, and the hydrogen yield of the catalyst reaches 2.61mol-H 2 mol-HAc, and keeps stable; the active component Ni of the catalyst can be effectively dispersed in the cerium samarium solid solution by combining the characteristics of XRD, BET and the like, and the valenceStable state, and has the characteristics of carbon deposition resistance, sintering resistance and the like.
Claims (4)
1. The application of the cerium samarium solid solution nickel-based catalyst in the process of autothermal reforming of acetic acid to prepare hydrogen is characterized in that: 0.1-0.2g of catalyst in H 2 Reducing for 1h at 600-800 ℃, and introducing CH with a molar ratio 3 COOH/H 2 O/O 2 The mixed gas of = 1/(1.3-5.0)/(0.21-0.35) is processed by the self-heating reforming reaction of acetic acid through a catalyst bed layer, and the reaction temperature is 500-800 ℃; the catalyst is prepared by the following method: preparing a mixed solution #1 of nickel nitrate, samarium nitrate and cerium nitrate; preparing a mixed solution #2 of citric acid and ethylene glycol according to the total molar ratio of citric acid to ethylene glycol to metal nitrate of 1; mixing the solution #1 and #2, continuously stirring in a constant temperature water bath at 60 ℃ until gel is formed, drying at 105 ℃ for 12 hours, and then roasting at 600-800 ℃ for 4 hours to obtain the Sm with the Ce species embedded in the main body 2 O 3 Structurally formed Ni/Sm-Ce-O with mesoporous structure x The composite oxide solid solution catalyst comprises the components with the molar ratio of (NiO) a (SmO 1.5 ) b (CeO 2 ) c Wherein a is 0.13-0.17, b is 0.38-0.50, c is 0.01-0.12; the weight percentage composition calculated by oxide is as follows: nickel oxide (NiO) 10.0-13.0 wt%, and samarium oxide (Sm) 2 O 3 ) 66.8 to 87.8 percent of cerium oxide (CeO) 2 ) 1.9 to 20.9 percent.
2. The use of a samarium-cerium solid solution nickel-based catalyst in autothermal reforming of acetic acid as defined in claim 1, wherein the samarium-cerium solid solution nickel-based catalyst comprises: the catalyst comprises the following components in percentage by weight: 12.1 percent of nickel oxide, 85.9 percent of samarium oxide and 2.0 percent of cerium oxide.
3. The use of a samarium-cerium solid solution nickel-based catalyst in autothermal reforming of acetic acid as defined in claim 1, wherein the samarium-cerium solid solution nickel-based catalyst comprises: the catalyst comprises the following components in percentage by weight: 12.1 percent of nickel oxide, 77.5 percent of samarium oxide and 10.4 percent of cerium oxide.
4. The application of the samarium cerium solid solution nickel-based catalyst in the autothermal reforming of acetic acid to produce hydrogen according to claim 1, wherein the samarium cerium solid solution nickel-based catalyst comprises the following components in percentage by weight: the catalyst comprises the following components in percentage by weight: 12.1 percent of nickel oxide, 67.5 percent of samarium oxide and 20.4 percent of cerium oxide.
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| CN114308056B (en) * | 2022-01-07 | 2023-02-10 | 成都理工大学 | Samarium-manganese-mullite-type nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN115920917B (en) * | 2023-01-12 | 2024-04-05 | 成都理工大学 | Titanium-containing oxide supported nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN115945197B (en) * | 2023-01-13 | 2024-04-05 | 成都理工大学 | Y for autothermal reforming of acetic acid to produce hydrogen x Pr 2-x O 3-δ Solid solution cobalt-based catalyst |
| CN116273019B (en) * | 2023-02-01 | 2024-06-14 | 成都理工大学 | Cerium-yttrium solid solution structured nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN116037133B (en) * | 2023-02-01 | 2024-06-25 | 成都理工大学 | Samarium praseodymium solid solution nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010013958A2 (en) * | 2008-08-01 | 2010-02-04 | 현대중공업 주식회사 | Catalyst for preparing synthesis gas from natural gas and carbon dioxide, and preparation method thereof |
| CN103521162A (en) * | 2013-10-11 | 2014-01-22 | 南京理工大学 | Cerium modified calcium-based bifunctional particle, and preparation method and application thereof |
| CN103769107A (en) * | 2014-02-24 | 2014-05-07 | 南京理工大学 | Biomass hydrogen production composite difunctional particle and preparation method and application thereof |
| CN106391036A (en) * | 2016-10-28 | 2017-02-15 | 成都理工大学 | Solid solution catalyst for acetic acid self-heating hydrogen production by reforming and preparation method |
| CN107042111A (en) * | 2017-01-11 | 2017-08-15 | 成都理工大学 | The laminated perovskite type catalyst and preparation method of a kind of acetic acid self-heating reforming hydrogen manufacturing |
| CN111111686A (en) * | 2020-01-17 | 2020-05-08 | 成都理工大学 | Ba-Mn perovskite type cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN111111674A (en) * | 2020-01-17 | 2020-05-08 | 成都理工大学 | Ni/La for autothermal reforming of acetic acid to produce hydrogen2X2O7Catalyst and process for preparing same |
| CN111111684A (en) * | 2020-01-17 | 2020-05-08 | 成都理工大学 | Mesoporous silica-loaded tungsten-promoted nickel-based catalyst for autothermal reforming of acetic acid |
-
2021
- 2021-01-22 CN CN202110085626.7A patent/CN112844397B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010013958A2 (en) * | 2008-08-01 | 2010-02-04 | 현대중공업 주식회사 | Catalyst for preparing synthesis gas from natural gas and carbon dioxide, and preparation method thereof |
| CN103521162A (en) * | 2013-10-11 | 2014-01-22 | 南京理工大学 | Cerium modified calcium-based bifunctional particle, and preparation method and application thereof |
| CN103769107A (en) * | 2014-02-24 | 2014-05-07 | 南京理工大学 | Biomass hydrogen production composite difunctional particle and preparation method and application thereof |
| CN106391036A (en) * | 2016-10-28 | 2017-02-15 | 成都理工大学 | Solid solution catalyst for acetic acid self-heating hydrogen production by reforming and preparation method |
| CN107042111A (en) * | 2017-01-11 | 2017-08-15 | 成都理工大学 | The laminated perovskite type catalyst and preparation method of a kind of acetic acid self-heating reforming hydrogen manufacturing |
| CN111111686A (en) * | 2020-01-17 | 2020-05-08 | 成都理工大学 | Ba-Mn perovskite type cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN111111674A (en) * | 2020-01-17 | 2020-05-08 | 成都理工大学 | Ni/La for autothermal reforming of acetic acid to produce hydrogen2X2O7Catalyst and process for preparing same |
| CN111111684A (en) * | 2020-01-17 | 2020-05-08 | 成都理工大学 | Mesoporous silica-loaded tungsten-promoted nickel-based catalyst for autothermal reforming of acetic acid |
Non-Patent Citations (4)
| Title |
|---|
| Auto-thermal reforming of acetic acid for hydrogen production by ordered mesoporous Ni-xSm-Al-O catalysts: Effect of samarium promotion;Zhou et al.;《Renewable Energy》;20190718;第145卷;第2317页左栏第2-3段 * |
| Hydrogen generation by acetic acid steam reforming over Ni-based catalysts derived from La1-xCexNiO3 perovskite;Lin Li et al.;《International Journal of Hydrogen Energy》;20180313;第43卷(第14期);第6795-6803页 * |
| 乙酸自热重整用 Ni-Mg-Cr-O 和Ni/La2X2O7催化剂的研究;谢星月;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20210415(第4期);B015-63 * |
| 生物质油自热重整转化制氢的镍基催化剂研究;钟心燕;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170315(第3期);B014-942 * |
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