CN116139910A - New use of nickel-based re-hydroxylation silicon-based catalyst - Google Patents

New use of nickel-based re-hydroxylation silicon-based catalyst Download PDF

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CN116139910A
CN116139910A CN202310114670.5A CN202310114670A CN116139910A CN 116139910 A CN116139910 A CN 116139910A CN 202310114670 A CN202310114670 A CN 202310114670A CN 116139910 A CN116139910 A CN 116139910A
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catalyst
nickel
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methane
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CN116139910B (en
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何德东
武少杰
罗永明
梅毅
张宜民
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Kunming University of Science and Technology
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
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    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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    • 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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    • 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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    • 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
    • C01B2203/1082—Composition of support materials
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Abstract

The invention discloses an application of a nickel-based re-hydroxylation silicon-based catalyst in preparing synthesis gas by dry reforming of methane; the nickel-based re-hydroxylation silicon-based catalyst is prepared by placing a silicon-based carrier in hydrogen peroxide solution with the volume concentration of 2% -10%, soaking at room temperature for 10-15h, separating solid from liquid, washing the solid with deionized water until washing liquid is neutral, drying to obtain a silicon-based-OH carrier, grinding and screening the silicon-based-OH carrier, mixing the silicon-based-OH carrier with nickel acetylacetonate, placing the mixture in methane dry reforming equipment, calcining in situ in an anhydrous air atmosphere, and reducing the calcined product in a hydrogen atmosphere at 700-800 ℃; the catalyst prepared by the invention has high active metal utilization rate, strong anti-sintering capability and excellent reaction activity and stability in the dry reforming reaction of methane; the catalyst is stable and catalytic at 750 ℃ for 150 hours without obvious deactivation, and the nickel particle size is kept smaller after the reaction, so that the catalyst has certain significance and good application prospect in the aspects of energy and environment.

Description

New use of nickel-based re-hydroxylation silicon-based catalyst
Technical Field
The invention belongs to the field of energy and environmental catalysts, and particularly relates to application of a nickel-based re-hydroxylation silicon-based catalyst in preparation of synthesis gas by dry reforming of methane.
Background
Methane Dry Reforming (DRM) is a very promising reaction that allows the conversion of two major greenhouse gases CH 4 And CO 2 Conversion to valuable synthesis gas CO and H 2 . Product synthesis gas is an important industrial intermediate that can be preferentially used to synthesize valuable energy chemicals such as olefins, alkanes, and liquid hydrocarbons. Ni-based catalysts have high catalytic activity and cost effectiveness, and are the preferred catalysts for DRM reactions. Since the DRM reaction is a strong thermodynamic endothermic reaction, it needs to be performed at high temperature. However, the high temperature not only promotes sintering of Ni nanoparticles, but also accelerates CH 4 Decomposition produces carbon deposition. Both of which can lead to rapid deactivation of the nickel-based catalyst. To avoid sintering and coking, the highly dispersible Ni particles and the strong metal-support interaction are considered to be effective methods of providing efficient and stable DRM catalysts.
Silicon-based supports, especially ordered SBA-15 materials, are considered ideal supports for Ni nanoparticles, which can provide high specific surface area and rich pore structure that can constrain the effect to inhibit metal particle aggregation. Although much research is currently being conducted in this area, the preparation of such catalysts remains challenging. The Ni/SBA-15 catalyst is prepared by impregnating the support with an aqueous solution of nickel. However, this method allows a portion of the nickel particles to deposit on the outer surface of the silica and to aggregate easily. Therefore, if simple impregnation is used, the impregnated catalyst is calcined at high temperature and under reaction conditions, the metal is easily nickel-sintered, resulting in deactivation of the catalyst.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a new application of a nickel-based reslurrying silicon-based catalyst, namely the application of the nickel-based reslurrying silicon-based catalyst in preparing synthesis gas by dry methane reforming, wherein a silicon-based carrier is placed in hydrogen peroxide solution with the volume concentration of 2% -10%, the silicon-based reslurrying silicon-based catalyst is soaked at room temperature for 10-15h, after solid-liquid separation, solid is washed with deionized water until washing liquid is neutral, the silicon-based-OH carrier is obtained after drying, the silicon-based-OH carrier is mixed with nickel acetylacetonate after grinding and screening, the mixture is placed in reaction equipment, anhydrous air is introduced for in-situ calcination, and a calcined product is subjected to reduction treatment at the temperature of 700-800 ℃ under the hydrogen atmosphere, so that the nickel-based reslurrying silicon-based catalyst is prepared; in the invention, nickel is uniformly distributed on the surface of silicon-based-OH and in the pore canal by a gas phase diffusion method under the action of hydroxyl, and in a methane dry reforming performance test of 150 hours, the nickel-based re-hydroxylation silicon-based catalyst shows high DRM conversion rate and excellent DRM stability;
the mass ratio of the nickel acetylacetonate to the silicon-based-OH carrier is 0.05-0.3:1.
The calcination is carried out under the condition that the temperature is raised to 300-500 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 1-3h, then the room temperature is reduced, and the anhydrous air is continuously introduced at the flow rate of 8-12mL/min in the calcination process.
The silicon-based carrier is selected from SBA-15 and SiO 2 MCM-41, a commercially available product or a reagent prepared by a conventional method.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the catalyst is simple and easy to implement, the repeatability is high, and the silicon-based carrier is subjected to the re-hydroxylation treatment and then is mixed with the active metal nickel to prepare the high-performance methane dry reforming catalyst;
2. the catalyst well solves the problems of catalyst sintering deactivation, low conversion rate and the like in the prior methane dry reforming reaction, and the high-performance nickel-based re-hydroxylation silicon-based catalyst prepared by re-hydroxylation treatment obtains higher catalytic activity and ultra-long stability in the methane dry reforming reaction and is at a higher level compared with the prior literature;
3. the catalyst has low preparation cost and is suitable for industrial production and market popularization and application.
Drawings
FIG. 1 shows the methane conversion (panel a) and carbon dioxide conversion (panel b) of the catalysts prepared in the different methods of example 1, for dry reforming of methane;
FIG. 2 is a schematic diagram of H for methane dry reforming reactions using catalysts prepared according to the different methods of example 1 2 Schematic of CO results;
FIG. 3 is a schematic illustration of H of the catalyst prepared by the different methods of example 1 2 -a TPR profile;
FIG. 4 is a schematic illustration of H of the catalyst of example 1 2 -chemisorption calculated nickel dispersity (a plot) and nickel particle size (b plot);
FIG. 5 is a graph showing methane and carbon dioxide conversion results for catalyst 5Ni/SBA15-OH of example 2;
FIG. 6 is H of catalyst 5Ni/SBA15-OH of example 2 2 Schematic of CO results.
Detailed Description
The present invention will be further described in detail by way of examples, but the scope of the invention is not limited to the above description, where the methods are conventional unless otherwise specified, and the reagents are conventional reagents or reagents formulated according to conventional methods;
in the following examples SBA15 was prepared by dissolving 24g Pluronic P123 triblock polymer (PEO-PPO-PEO, aldrich) in a mixture of distilled water (650 mL) and hydrochloric acid (140 mL), stirring at room temperature for 30min until P123 was completely dissolved, then adding 55mL Tetraethylorthosilicate (TEOS) drop by drop with continuous stirring, and stirring for 24h; then, putting the mixture into a baking oven at 90 ℃ for crystallization for 24 hours, filtering and washing the reaction product, drying the reaction product at 80 ℃ for 24 hours, and finally heating the reaction product to 550 ℃ at a speed of 1 ℃/min and roasting the reaction product for 6 h to obtain the catalyst;
example 1
1. 5g of SBA15 is placed in 100mL of 2% hydrogen peroxide solution, after soaking treatment for 12h at room temperature, solid-liquid separation is carried out, solid deionized water is washed until washing liquor is neutral, SBA15-OH carrier is prepared by drying for 12h at room temperature, and SBA15-OH is ground and sieved to 40-60 meshes; weighing 0.11g of nickel acetylacetonate, adding 1g of SBA15-OH carrier after sieving, and uniformly mixing; placing 0.1g of the mixture in the center of a quartz tube of a reaction furnace, and heating to 300deg.C at a heating rate of 10deg.C/min under anhydrous air atmosphere (10 mL/min flow rate continuously)120min, heating to 750deg.C at 10deg.C/min under nitrogen atmosphere, and heating with 10% H 2 Pre-treating for 1h by argon reduction to prepare a nickel-based re-hydroxylation SBA15 catalyst (Ni/SBA 15-OH);
simultaneously preparing a Ni/SBA15 catalyst and a Ni/SBA15-IWI catalyst as a control;
wherein the Ni/SBA15 catalyst is prepared by grinding and sieving common SBA15 to 40-60 meshes; weighing 0.11g of nickel acetylacetonate, adding 1g of SBA15 carrier after sieving, and uniformly mixing; placing 0.1g of the mixture in the center of a quartz tube of a reaction furnace, heating to 300 ℃ at a heating rate of 10 ℃/min, and keeping for 120min to obtain a catalyst Ni/SBA15;
the Ni/SBA15-IWI catalyst is prepared by weighing 0.13g of nickel nitrate hexahydrate, dissolving in 2mL of deionized water, then adding 1g of common SBA15, stirring for 30min by using a glass rod, drying the solid at 80 ℃ for 12h, placing the product in a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, maintaining for 360min, grinding and screening to 40-60 meshes;
2. application of nickel-based re-hydroxylation SBA15 catalyst
(1) After synthesizing the nickel-based re-hydroxylation SBA15 catalyst in a quartz tube, methane-carbon dioxide-nitrogen mixture (CH) was fed at a flow rate of 60mL/min 4 :CO 2 :N 2 =1:1:1) is introduced into a quartz tube in a reactor, methane dry reforming is carried out to prepare synthesis gas under the conditions of 750 ℃ and reaction pressure of 0.1M Pa and reaction space velocity of 36000mL/g/h, sampling is carried out every 2h, and the total reaction time is 150h; measuring CH by gas chromatograph FID and TCD 4 、CO 2 、H 2 Peak area of CO, processing the data, calculating conversion and H 2 a/CO ratio;
the results are shown in FIGS. 1 and 2, and it can be seen from FIGS. 1 and 2 that the Ni/SBA15-OH catalyst, CH, is used in methane reforming 4 And CO 2 88% and 96% respectively, and no significant deactivation in the long-term reaction at 150h, CH at 150h 4 And CO 2 The catalyst has stable catalytic activity, which shows that small particles and high-dispersion nickel play an important role in catalytic performance, and the catalyst is respectively reduced by 2.8 percent and 2.0 percent; initial H of Ni/SBA15-OH catalyst 2 CO connectionNear 1, indicating that substantially no side reactions occurred during the reaction;
CH of catalyst (Ni/SBA 15) with ordinary SBA15 as carrier 4 And CO 2 The conversion of (C) is significantly lower than that of the Ni/SBA15-OH catalyst, the initial conversion is 73.2% and 82.8%, respectively, and relatively rapid deactivation occurs in the 100h reaction, CH at 100h 4 And CO 2 Respectively 7.7 percent and 7.3 percent, and the initial H is reduced 2 the/CO is also lower, 0.91; CH of Ni/SBA15-IWI catalyst by impregnation method 4 And CO 2 The initial conversion of (2) was 78.8% and 86.9%, respectively, CH at 100h 4 And CO 2 Respectively reduced by 24.6% and 24.1%, and serious inactivation occurred, which indicates that the surface nickel is unstable, the initial H2/CO is 0.93, and the H is increased with time 2 the/CO drop is also faster.
（2）H 2 TPR test
H is carried out by adopting Tianjin Pengxiang PX200 adsorption instrument 2 TPR test by which the effort of the metal support is explored, the adsorber is equipped with a Thermal Conductivity Detector (TCD), 50mg of catalyst is placed between quartz wool in a U-tube, pretreated with argon (30 mL/min) at 150℃for 1 hour to remove physically adsorbed water; then after cooling the catalyst to 50 ℃, the temperature is increased from 50 ℃ to 800 ℃ at a heating rate of 10 ℃/min, and meanwhile, 10% H is introduced at a flow rate of 30mL/min 2 Simultaneously recording TCD signal variation data.
The results are shown in FIG. 3, and it can be seen from the graph that the reduction temperatures of the Ni/SBA15 catalyst and the Ni/SBA15-IWI catalyst are low, and the main peak positions are respectively 350 ℃ and 338 ℃, which indicates that the interaction between the common untreated SBA15 carrier and nickel is weak, and the stability of nickel cannot be ensured. The Ni/SBA15-IWI shows a reduction peak at 383 ℃, which proves that the Ni/SBA15-OH catalyst has stronger metal-carrier interaction force, and the reduction peak area at 383 ℃ is larger than that of the Ni/SBA15 catalyst and the Ni/SBA15-IWI catalyst, which means that the nickel on the Ni/SBA15-OH catalyst has stronger force with the carrier and better dispersibility;
（3）H 2 chemisorption experiments
To obtain a catalyst surface active Ni dispersionInformation on the degree and average particle size, H was carried out on the catalysts prepared in the different methods of example 1 on a Tianjin Pengxiang PX200 adsorbent instrument 2 Chemisorption experiments, 100mg of catalyst were run in U-tubes at 10% H before the experiment 2 Ar (30 mL/min) was reduced at 750℃for 1h to give metallic Ni, which was purified with Ar at 1h and cooled to 50 ℃. Subsequent sustain pulse H 2 The flow, until adsorption is saturated, the pulse peak area remains unchanged.
The nickel dispersion and nickel particle size obtained by data processing are shown in FIG. 4, and the nickel particle dispersion histogram of FIG. 4a shows that the nickel dispersion of the three catalysts Ni/SBA15-OH, ni/SBA15 and Ni/SBA15-IWI are 37.2%, 19.6% and 12.1%, respectively, and the nickel particle size information of the three catalysts Ni/SBA15-OH, ni/SBA15 and Ni/SBA15-IWI of FIG. 4b is also regular, 2.2 nm, 3.9nm and 6.6nm, respectively, which all demonstrate that loading nickel on the re-hydroxylated SBA15 by the weather diffusion method can promote the nickel dispersion, form small nickel particles, and thus enhance the methane performance.
Example 2
1. 5g of SBA15 is placed in 100mL of hydrogen peroxide solution with the concentration of 2%, after soaking treatment for 12 hours at room temperature, solid-liquid separation is carried out, solid deionized water is washed until washing liquid is neutral, SBA15-OH carrier is prepared by drying for 12 hours at room temperature, and SBA15-OH is ground and screened to 40-60 meshes; weighing 0.22g of nickel acetylacetonate, adding 1g of SBA15-OH carrier after sieving, and uniformly mixing; placing 0.1g of the mixture in the center of a quartz tube of a reaction furnace, continuously introducing anhydrous air at a flow rate of 10mL/min, simultaneously heating to 300 ℃ at a heating rate of 10 ℃/min and maintaining for 120min, heating to 750 ℃ at a heating rate of 10 ℃/min under nitrogen atmosphere, and finally using a reaction kettle containing 10% H 2 Pre-treating for 1h by argon reduction to obtain a nickel-based re-hydroxylation SBA15 catalyst (5 Ni/SBA 15-OH);
2. application of nickel-based re-hydroxylation SBA15 catalyst
After synthesizing the nickel-based re-hydroxylation SBA15 catalyst in a quartz tube, methane-carbon dioxide-nitrogen mixture (CH) was fed at a flow rate of 60mL/min 4 :CO 2 :N 2 =1:1:1) was introduced into a quartz tube in a reactor at 750 ℃The reaction pressure is 0.1M Pa, the reaction space velocity is 36000mL/g/h, methane dry reforming is carried out to prepare synthesis gas, sampling is carried out every 2h, and the total reaction time is 20h; measuring CH by gas chromatograph FID and TCD 4 、CO 2 、H 2 Peak area of CO, processing the data, calculating conversion and H 2 a/CO ratio; the results are shown in FIG. 5, and it can be seen from FIG. 5 that the 5Ni/SBA15-OH catalyst shows better catalytic performance in methane reforming, CH 4 And CO 2 The initial conversion of (2) reached 91% and 96%, respectively, and there was no tendency to drop in the reaction for 20H, as can be seen from FIG. 6, H of 5Ni/SBA15-OH 2 The CO reached 1 with substantially no side reactions, which also demonstrated that loading nickel on the re-hydroxylated SBA15 by gas phase diffusion still produced uniformly dispersed nickel at high metal loadings and maintained stable catalytic activity.

Claims (4)

1. Application of nickel-based re-hydroxylation silicon-based catalyst in preparing synthesis gas by dry reforming of methane;
the nickel-based re-hydroxylation silicon-based catalyst is prepared by placing a silicon-based carrier in hydrogen peroxide solution with the volume concentration of 2% -10%, soaking at room temperature for 10-15h, separating solid from liquid, washing the solid with deionized water until washing liquid is neutral, drying to obtain a silicon-based-OH carrier, grinding and screening the silicon-based-OH carrier, mixing the silicon-based-OH carrier with nickel acetylacetonate, placing the mixture in methane dry reforming equipment, calcining in situ in an anhydrous air atmosphere, and reducing the calcined product in a hydrogen atmosphere at 700-800 ℃;
and (3) preparing the synthesis gas by performing methane dry reforming in situ after the catalyst is prepared.
2. The use according to claim 1, characterized in that: the mass ratio of the nickel acetylacetonate to the silicon-based-OH carrier is 0.05-0.3:1.
3. The use according to claim 1, characterized in that: the calcination is carried out by treating at 300-500 deg.C for 1-3h, cooling to room temperature, and continuously introducing anhydrous air at a flow rate of 8-12mL/min during calcination.
4. The use according to claim 1, characterized in that: the silicon-based carrier is selected from SBA-15 and SiO 2 、MCM-41。
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