CN112871173A - Preparation method of reaction catalyst for preparing synthesis gas by dry reforming of methane and carbon dioxide - Google Patents

Preparation method of reaction catalyst for preparing synthesis gas by dry reforming of methane and carbon dioxide Download PDF

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CN112871173A
CN112871173A CN202110148404.5A CN202110148404A CN112871173A CN 112871173 A CN112871173 A CN 112871173A CN 202110148404 A CN202110148404 A CN 202110148404A CN 112871173 A CN112871173 A CN 112871173A
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catalyst
preparing
methane
carbon dioxide
synthesis gas
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肖进彬
王文博
聂宁
刘振
张璐璐
方玉美
任秋鹤
王品胜
刘晓杰
王晓雅
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Henan Hi Tech Industry Co ltd
Henan Academy of Sciences
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Henan Hi Tech Industry Co ltd
Henan Academy of Sciences
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • 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
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Abstract

The invention belongs to the technical field of industrial catalyst preparation, and particularly relates to a preparation method of a reaction catalyst for preparing synthesis gas by dry reforming of methane and carbon dioxide, which comprises the following steps: 1) preparation of powder catalyst: dissolving active metal soluble salt and auxiliary agent soluble salt into deionized water, mixing with solid carrier powder after heating pretreatment by an isometric immersion method, and obtaining catalyst powder after ultrasonic stirring, standing for aging, drying and roasting; 2) and (3) catalyst molding: uniformly stirring and mixing the catalyst powder prepared in the step 1) with a binder, an extrusion aid and deionized water, and ageing, pugging, extruding, forming and roasting to obtain the formed catalyst. The preparation method of the reaction catalyst for preparing the synthesis gas by dry reforming of the methane and the carbon dioxide is simple and easy for large-scale preparation, and the alkaline sites on the surface of the formed catalyst are increased, so that the catalyst shows excellent catalytic activity and carbon deposition resistance in the reaction of preparing the synthesis gas by reforming of the methane and the carbon dioxide.

Description

Preparation method of reaction catalyst for preparing synthesis gas by dry reforming of methane and carbon dioxide
Technical Field
The invention belongs to the technical field of industrial catalyst preparation, and particularly relates to a preparation method of a reaction catalyst for preparing synthesis gas by dry reforming of methane and carbon dioxide.
Background
With the rapid development of global economy, the demand of people for traditional fossil fuels such as coal, petroleum and the like in daily life and production increases year by year, and energy shortage is caused. While fossil fuel consumption emits large amounts of greenhouse gases (CH)4、CO2、N2O), is one of the main causes of global warming, sea level elevation, polar glaciers melting, and extreme weather frequency. The methane and carbon dioxide reforming technology can convert two greenhouse gases of methane and carbon dioxide into synthesis gas (CO + H) with industrial value2) And the synthesis gas can be used for the synthesis of long-chain hydrocarbons or oxygen-containing compounds. The methane and carbon dioxide reforming is not only beneficial to relieving the greenhouse effect, but also can realize the high-efficiency utilization of methane resources. Thus, methane carbon dioxideReforming is receiving much attention as an efficient green technology.
The methane carbon dioxide dry reforming reaction is an endothermic reaction and needs to be carried out at high temperature, and the catalyst is easily deactivated by carbon deposition and sintering. In addition, the research on the methane and carbon dioxide dry reforming catalyst is mostly focused on a powder catalyst, the powder catalyst can only be used for researching the activity of the catalyst on a laboratory bench due to a series of factors such as high back pressure and the like, and in the actual industrial production, the catalyst is often required to have fixed shape and mechanical strength, so that through the improvement of a preparation method and a catalyst forming formula, the development of a catalyst which has strong carbon deposition resistance and good thermal stability and has an important effect on the breakthrough of the methane and carbon dioxide reforming reaction.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a reaction catalyst for preparing synthesis gas by dry reforming methane and carbon dioxide, which can effectively overcome the problems of easy sintering, easy carbon deposition, difficult molding and the like of the existing catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a reaction catalyst for preparing synthesis gas by dry reforming methane and carbon dioxide, which comprises the following steps:
1) preparation of catalyst powder: dissolving active metal soluble salt and auxiliary agent soluble salt into deionized water, mixing with solid carrier powder after heating pretreatment by an isometric immersion method, and obtaining catalyst powder after ultrasonic stirring, standing for aging, drying and roasting;
2) and (3) catalyst molding: uniformly stirring and mixing the catalyst powder prepared in the step 1) with a binder, an extrusion aid and deionized water, and ageing, pugging, extruding, forming and roasting to obtain the formed catalyst.
Preferably, in the step 1), the active soluble salt is at least one soluble salt of nickel, cobalt or iron, wherein Ni, Co and Fe are used as active metal components, and more preferably, the nickel, cobalt and iron soluble salt is nitrate, acetate or chloride.
Preferably, in the step 1), the active metal component accounts for 5 to 30 percent of the mass of the catalyst powder, and more preferably, the active metal component accounts for 8 to 15 percent of the mass of the catalyst powder.
Preferably, in the step 1), the soluble salt of the auxiliary agent is at least one soluble salt of lanthanum, cerium or samarium, wherein La, Ce and Sm are used as the auxiliary agent, and more preferably, the soluble salt of lanthanum, cerium or samarium is nitrate, acetate or chloride.
Preferably, in the step 1), the auxiliary agent accounts for 0-8% of the catalyst powder by mass, and more preferably, the auxiliary agent accounts for 2-6% of the catalyst powder by mass.
Preferably, in the step 1), the solid carrier powder is at least one of alumina, titania, silica and zirconia, and the temperature of the heating pretreatment of the solid carrier powder is 200-400 ℃ and the heating pretreatment time is 2-3 h.
Preferably, in the step 1), the standing and aging time is 1-3 h, the roasting temperature is 400-700 ℃, the roasting time is 3-5 h, more preferably, the roasting temperature is 600 ℃, and the roasting time is 4 h.
Preferably, in the step 2), the binder is one or more of alkaline silica sol, alkaline alumina sol, water glass and sodium aluminosilicate, and the solid content of the alkaline silica sol and the alkaline alumina sol is 30-50%. The solid content of the alkaline silica sol refers to the content of silica in the alkaline silica sol, and the solid content of the alkaline alumina sol refers to the content of alumina in the alkaline alumina sol.
Preferably, in the step 2), the extrusion aid is one or more of sesbania powder, dry starch and glycol.
Preferably, in the step 2), the mass ratio of the catalyst powder, the binder, the extrusion aid and the deionized water is 100: 40-70: 5-12: 20-30, and more preferably, the mass ratio of the catalyst powder, the binder, the extrusion aid and the deionized water is 100: 55-57: 5.5-8.5: 22.5 to 27.5.
The dosage of the binder, the extrusion aid and the deionized water can affect the forming effect and the physical and chemical parameters of the formed catalyst, thereby affecting the performance of the supported catalyst. For example, if the amount of the binder added is too small, the catalyst powder cannot be molded well; when the addition amount of the binder is too much, the viscosity of the powder is too high, so that the powder is difficult to strip, the strip-extruding speed is slow, the power load of the strip extruder is seriously increased, and on the other hand, the excessive binder causes that active particles of the dried catalyst are seriously wrapped by the binder, the specific surface area of the catalyst is reduced, and the activity of the catalyst is reduced. The friction between material particles and between the material particles and forming equipment can be obviously reduced by adding the extrusion aid, the forming extrusion speed can be accelerated, cracks and burrs on the surface of the formed catalyst can be reduced, but when the addition of the extrusion aid is too large, the strip discharging speed is too high when the strip is extruded, the toughness is poor, the strip is easy to break, and the side pressure strength of the formed catalyst is low. The water powder ratio plays a decisive role in the molding of the catalyst, when the water powder quality is smaller, the molded catalyst is drier, and the materials are not compact and are too loose during kneading; when the water powder has a large mass, the molded catalyst becomes wet and slippery due to an excessively large amount of water, and flows around during kneading.
Preferably, in the step 2), the extrusion molding method is a conventional method in the field, and a screw rod extruder or a piston rod extruder can be used for extrusion molding.
Preferably, in the step 2), the roasting temperature is 200-400 ℃, the roasting time is 2-4 h, and more preferably, the roasting temperature is 400 ℃, and the roasting time is 2 h.
In the present invention, unless otherwise specified, the starting materials used are all those conventionally available commercially in the art or those prepared by methods well known to those skilled in the art.
The invention has the beneficial effects that:
(1) the invention makes the carrier load the specific active component by the dipping method, further forms the powder catalyst, then adopts the blending extrusion forming mode to form the catalyst powder, prepares the formed catalyst with the specific shape and the larger mechanical strength, and solves the related scientific problem of the powder catalyst forming.
(2) The binder, the extrusion aid and the forming mode used by the invention can not damage the metal active center of the catalyst, and simultaneously increase the surface alkaline sites of the catalyst.
(3) The inorganic binder used in the invention can form silicon oxide, aluminum oxide or silicon aluminum oxide at high temperature, and the original oxide carrier particles loaded with active metal ions can be completely wrapped by the porous oxides with uniform sizes to form a core-shell structure. The core-shell structure limits the active metal in a closed shell layer, inhibits the sintering migration of the active metal, inhibits the growth of carbon deposition on the surface of the active metal and enables active metal particles to exist in a stable state at high temperature.
(4) Compared with the catalyst obtained by loading the active component to a commercial molded carrier, the molded catalyst prepared by the invention has the advantages of high mechanical strength, obviously improved catalytic activity and carbon deposition resistance, and higher selectivity.
(5) The preparation method of the formed catalyst is simple and is easy for industrial production.
Drawings
FIG. 1 is a flow chart of the preparation and formation of the catalyst of the present invention.
FIG. 2 shows catalyst A in example 8 of the present invention1And catalyst B from example 91H of (A) to (B)2-TPR spectrum.
FIG. 3 shows catalyst A in example 8 of the present invention1Catalyst B in example 91And gamma-Al2O3XRD pattern of (a).
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Preparation and forming of catalyst for dry weight integration of methane and carbon dioxide into synthesis gas
Example 1
1) 247.78gNi (NO)3)2·6H2Dissolving O in 250mL of deionized water, and then dissolving 450g of gamma-Al of 160-200 meshes2O3Adding the carrier into the salt solution (drying and pretreating at 300 ℃ for 2h) to fully soak the carrier. Ultrasonically shaking for 30min, standing at room temperature for 3h, and drying at 105 ℃. Finally, the sample was calcined at 600 ℃ for 4 hours in an air atmosphere to obtain 514.65g of a catalyst powder.
2) Taking 400g of the catalyst powder obtained in the step 1), adding 200g of 30% alkaline silica sol, 25g of sodium aluminosilicate, 30g of sesbania powder and 100g of deionized water, mixing and stirring uniformly, ageing, pugging on a vacuum pugging machine, and extruding the mixed material into strips and cutting strips with the thickness of 3mm on a piston type strip extruding machine. And naturally airing, drying in a 105 ℃ oven, and finally roasting in a 400 ℃ muffle furnace for 2h to obtain the formed catalyst, which is marked as catalyst A.
Example 2
1) 247.78g of Ni (NO)3)2·6H2O、77.93g La(NO3)2·6H2Dissolving O in 280mL of deionized water, and then dissolving 420g of gamma-Al of 160-200 meshes2O3Adding the carrier into the salt solution (drying and pretreating at 300 ℃ for 2h) to fully soak the carrier. Ultrasonically shaking for 30min, standing at room temperature for 3h, and drying at 105 ℃. Finally, the sample was calcined at 600 ℃ for 4 hours in an air atmosphere to obtain 521.28g of a catalyst powder.
2) Taking 400g of the catalyst powder obtained in the step 1), adding 200g of 30% alkaline alumina sol, 25g of water glass, 30g of sesbania powder and 100g H2And O, uniformly mixing, aging, pugging on a vacuum pugging machine, and extruding the mixed materials into strips with the thickness of 3mm and cutting the strips on a piston type strip extruding machine. And naturally airing, drying in a 105 ℃ oven, and finally roasting in a 400 ℃ muffle furnace for 2h to obtain a molded catalyst, which is marked as catalyst B.
Example 3
1)247.78g Ni(NO3)2·6H2O、77.50g Ce(NO3)2·6H2Dissolving O in 280mL of deionized water, and then dissolving 420 with 160-200 meshesgγ-Al2O3Adding the carrier into the salt solution (drying and pretreating at 300 ℃ for 2h) to fully soak the carrier. Ultrasonically shaking for 30min, standing at room temperature for 3h, and drying at 105 ℃. Finally, the sample was calcined at 600 ℃ for 4 hours in an air atmosphere to obtain 523.41g of a catalyst powder.
2) Taking 400g of the catalyst powder obtained in the step 1), adding 200g of 30% alkaline alumina sol, 25g of sodium aluminosilicate, 20g of sesbania powder, 5g of ethylene glycol and 90g of deionized water, mixing and stirring uniformly, ageing, pugging on a vacuum pugging machine, and extruding the mixed material into strips and cutting strips with the thickness of 3mm on a piston type strip extruding machine. And naturally airing, drying in a 105 ℃ oven, and finally roasting in a 400 ℃ muffle furnace for 2h to obtain the formed catalyst, which is marked as catalyst C.
Example 4
1) 72.36g Fe (NO)3)3·6H2O、247.78g Ni(NO3)2·6H2Dissolving O in 220mL of deionized water, and then dissolving 440g of gamma-Al of 160-200 meshes2O3Adding the carrier into the salt solution (drying and pretreating at 300 ℃ for 2h) to fully soak the carrier. Ultrasonically shaking for 30min, standing at room temperature for 3h, and drying at 105 ℃. Finally, the sample was calcined at 600 ℃ for 4 hours in an air atmosphere to obtain 519.87g of a catalyst powder.
2) Taking 400g of the catalyst powder obtained in the step 1), adding 200g of 30% alkaline silica sol, 15g of sodium aluminosilicate, 5g of water glass, 30g of sesbania powder and 90g of deionized water, mixing and stirring uniformly, ageing, pugging on a vacuum pugging machine, and extruding the mixed material into strips and cutting strips with the thickness of 3mm on a piston type strip extruding machine. And naturally airing, drying in a 105 ℃ oven, and finally roasting in a 400 ℃ muffle furnace for 2h to obtain a molded catalyst, which is marked as catalyst D.
Example 5
1) 247.78gNi (NO)3)2·6H2Dissolving O in 250mL of deionized water, and then dissolving 450g of TiO with the mesh size of 160-2002Adding the carrier into the salt solution (drying and pretreating at 300 ℃ for 2h) to fully soak the carrier. Ultrasonically shaking for 30min, standing at room temperature for 3h, and drying at 105 ℃. Finally, the sample is placed in the air atmosphere at the temperature of 600 ℃ for roasting for 4hTo obtain 516.72g of a catalyst powder.
2) Taking 400g of the catalyst powder obtained in the step 1), adding 200g of 30% alkaline silica sol, 25g of sodium aluminosilicate, 30g of sesbania powder and 100g of deionized water, mixing and stirring uniformly, ageing, pugging on a vacuum pugging machine, and extruding the mixed material into strips and cutting strips with the thickness of 3mm on a piston type strip extruding machine. And naturally airing, drying in a 105 ℃ oven, and finally roasting in a 400 ℃ muffle furnace for 2h to obtain a molded catalyst, which is marked as catalyst E.
Example 6
1) 247.78gNi (NO)3)2·6H2Dissolving O in 250mL of deionized water, and then dissolving 450g of ZrO with 160-200 meshes2Adding the carrier into the salt solution (drying and pretreating at 300 ℃ for 2h) to fully soak the carrier. Ultrasonically shaking for 30min, standing at room temperature for 3h, and drying at 105 ℃. Finally, the sample was calcined at 600 ℃ for 4 hours in an air atmosphere to obtain 518.19g of a catalyst powder.
2) Taking 400g of the catalyst powder obtained in the step 1), adding 200g of 30% alkaline alumina sol, 22g of water glass, 30g of sesbania powder, 3g of dry starch and 110g of deionized water, mixing and stirring uniformly, ageing, pugging on a vacuum pugging machine, and extruding the mixed material into strips and cut strips with the thickness of 3mm on a piston type extruding machine. And naturally airing, drying in a 105 ℃ oven, and finally roasting in a 400 ℃ muffle furnace for 2h to obtain the formed catalyst, wherein the label is catalyst F.
Example 7
1) 247.78gNi (NO)3)2·6H2Dissolving O in 250mL of deionized water, and then dissolving 450g of SiO with the mesh size of 160-2002Adding the carrier into the salt solution (drying and pretreating at 300 ℃ for 2h) to fully soak the carrier. Ultrasonically shaking for 30min, standing at room temperature for 3h, and drying at 105 ℃. Finally, the sample was calcined at 600 ℃ for 4 hours in an air atmosphere to obtain 520.47g of a catalyst powder.
2) Taking 400g of the catalyst powder obtained in the step 1), adding 200g of 30% alkaline silica sol, 25g of water glass, 30g of sesbania powder, 3g of dry starch and 110g of deionized water, mixing and stirring uniformly, ageing, pugging on a vacuum pugging machine, and extruding the mixed material into strips and cut strips with the thickness of 3mm on a piston type extruding machine. And naturally airing, drying in a 105 ℃ oven, and finally roasting in a 400 ℃ muffle furnace for 2h to obtain a molded catalyst, which is marked as catalyst G.
Comparative example 1
247.78g of Ni (NO)3)2·6H2O was dissolved in 200mL of deionized water, and then 3mm particles of 450g of gamma-Al were added2O3Adding the carrier into the salt solution (drying and pretreating at 300 ℃ for 2h) to fully soak the carrier. Ultrasonically shaking for 30min, standing at room temperature for 3h, and drying at 105 ℃. And finally, roasting the sample in an air atmosphere at 600 ℃ for 4 hours to obtain a catalyst, wherein the catalyst is marked as a catalyst H.
Secondly, the mechanical strength, the specific surface area and the pore volume of the catalyst prepared by the preparation method are improved.
TABLE 1 mechanical Strength and specific surface area of catalysts prepared by different methods
Figure BDA0002931120210000071
According to the method for measuring the mechanical strength of the catalyst, 80-120 samples are randomly selected according to a relevant method in a standard HGT 2782-2011 (measuring the crushing resistance of fertilizer catalyst particles), the length of each catalyst is measured, then a QJ-II intelligent particle strength tester is used for testing the strength of each catalyst, the strength data of each sample when the sample is crushed is recorded, and the average value of the strength data is taken as the mechanical strength of the sample prepared under the condition. The BET low-temperature nitrogen adsorption method is adopted to measure the specific surface area and the pore volume, and the analysis of experimental data in the table 1 shows that the mechanical strength of the catalyst prepared by adopting the process of loading before molding is higher than that of the catalyst prepared by adopting the comparative example 1, and the catalyst has higher specific surface area and larger pore volume.
And thirdly, the catalyst prepared by the preparation method is applied to dry reforming reaction of methane and carbon dioxide.
3mL of catalyst was taken and charged into a fixed bed reactor, and the catalyst was taken before use in H2Reducing for 0.5h at 700 ℃ in airflow. Then introducing feed gas with the volume ratio of CH4:CO21:1, space velocity 24000ml gcat -1·h-1The reaction temperature is 750 ℃, the reaction time is 10h, samples are taken once every 30min, the average value is calculated, and the result is shown in table 4.
Example 8
3mL of catalyst A was taken and charged in a fixed bed reactor, and the catalyst was taken before use in H2Reducing at 700 deg.C for 0.5h in gas stream, and labeling as catalyst A1Then introducing raw material gas with the volume ratio of CH4:CO21:1, space velocity 24000ml gcat -1·h-1The reaction temperature is 750 ℃, the reaction time is 10h, samples are taken once every 30min, and the average value is calculated.
Example 9
3mL of catalyst B was taken and charged in a fixed bed reactor, and the catalyst was taken before use in H2Reducing at 700 deg.C for 0.5h in gas stream, and labeling as catalyst B1Then introducing raw material gas with the volume ratio of CH4:CO21:1, space velocity 24000ml gcat -1·h-1The reaction temperature is 750 ℃, the reaction time is 10h, samples are taken once every 30min, and the average value is calculated.
Comparative example 2
3mL of catalyst H was taken and charged in a fixed bed reactor, and the catalyst was taken before use in H2Reducing at 700 deg.C for 0.5H in gas stream, and labeling as catalyst H1Then introducing raw material gas with the volume ratio of CH4:CO21:1, space velocity 24000ml gcat -1·h-1The reaction temperature is 750 ℃, the reaction time is 10h, samples are taken once every 30min, and the average value is calculated.
FIG. 2 shows H for catalysts of examples 8 and 92TPR spectrum, it is known that there is a large difference between the reduction peak temperature and the reduction peak pattern of the two catalysts. Catalyst A in example 81Mainly has 2 reduction peaks, the reduction temperature is 550 ℃ and 780 ℃, which respectively correspond to NiO and nickel aluminate spinel NiAl2O4Reduced peak of (2). Catalyst B in example 91Having 3 reductionsPeaks, the reduction peaks at 400 ℃ and 500 ℃ are respectively attributed to the reduction of free state NiO and cubic state NiO, and the reduction peak at 780 ℃ corresponds to the NiAl with a spinel structure formed by nickel oxide and a carrier2Reduction peak of O. According to an analysis curve, the optimal reduction temperature of the catalyst should be between 600 and 700 ℃.
FIG. 3 shows catalyst and support γ -Al of examples 8 and 92O3The XRD patterns of (1) are shown in the figure, and diffraction peaks at 19.9 degrees, 37.5 degrees, 39.4 degrees, 45.7 degrees and 67.2 degrees belong to gamma-Al2O3. With gamma-Al2O3XRD spectra of the catalyst A in example 81Diffraction peaks attributed to metallic Ni appeared at 44.4 ° and 52.1 °. Catalyst B in example 91XRD pattern of (1) and catalyst A of example 81The diffraction peaks of (A) were identical and no diffraction peak attributed to La was observed, which is likely to be caused by the support of example 9 supporting less La or Al2O3The surface is in single-layer distribution, but the addition of the metal lanthanum is beneficial to forming independent NiO and reducing nickel aluminate spinel NiAl2O4Thereby obtaining more Ni active center sites in the subsequent reduction treatment.
In order to detect that the surface of the catalyst has an acid site and a basic site, NH is adopted3TPD and CO2TPD the catalysts A, B of examples 1 and 2 and their powder catalysts before shaping were tested for their acid-base performance by testing for NH3TPD and CO2Integration of the TPD peak areas, the central acid or base amounts of the corresponding weak, medium and strong acid or base on each catalyst were calculated and the results are shown in tables 2 and 3.
From the data in Table 2, it can be seen that the formed catalysts A and B in examples 1 and 2 and their powder catalysts before forming have three significant NH3And (3) desorption peaks, wherein the peak near 100 ℃ is the desorption peak of a weak acid center on the surface of the catalyst, the peak near 350 ℃ is the desorption peak of a strong acid center in the surface of the catalyst, and the peak near 590 ℃ is the desorption peak of a strong acid center on the surface of the catalyst. The total acid content of the molded catalyst A was 0.68 mmol/g-1The total acid amount of the powdery catalyst before molding is 0.88 mmol/g-1Reduced by 0.20 mmol/g-1The total acid content of the molded catalyst B was 0.70 mmol/g-1The total acid amount of the powdery catalyst before molding is 0.84 mmol/g-1Reduced by 0.14 mmol/g-1。
From the data in Table 3, it can be seen that the molded catalysts A and B in examples 1 and 2 and their powder catalysts before molding showed two distinct CO2Desorption peak, peak near 65 ℃ is corresponding to CO on weak base site2The peak at about 350 ℃ corresponds to CO at a medium-strong basic site2The total alkali content of the molded catalyst A was 0.44 mmol/g-1The total alkali content of the powdery catalyst before molding is 0.33 mmol/g-1Increased by 0.11 mmol/g-1The total alkali content of the molded catalyst B was 0.43 mmol/g-1The total alkali content of the powdery catalyst before molding is 0.36 mmol/g-1Reduced by 0.07 mmol/g-1。
Therefore, the reduction of the total acidity and the increase of the total alkalinity before and after the catalyst is molded are attributed to the addition of the binder and the extrusion aid, and the inorganic polymer binder can form oxides after being calcined at high temperature, so that the alkaline sites on the surface of the catalyst are increased.
Table 2 NH of catalysts in example 1 and example 23Amount of TPD acid
Figure BDA0002931120210000101
Table 3 CO of catalysts in example 1 and example 22Amount of TPD base
Figure BDA0002931120210000102
As can be seen from the evaluation data in Table 4, example 8 catalyst A1And example 9 catalyst B1Comparative example 2 catalyst H1In CH4With CO2The dry reforming reaction shows excellent catalytic performance, and the conversion rate of methane and the conversion rate of carbon dioxide are excellent in activity tests of example 8 and example 9In comparative example 2, the amount of carbon deposition was lower, and in examples 8 and 9, H2The molar ratio of/CO is close to the theoretical value 1, while comparative example 2H2The ratio/CO deviates significantly from the theoretical value of 1, indicating that the catalyst H of comparative example 21The side reactions above are severe.
In addition, it is inferred that the increase of the alkaline sites after the catalyst is molded and the silicon, aluminum or silicon aluminum oxide formed by high-temperature roasting of the inorganic high molecular binder wraps oxide carrier particles loaded with active metal ions, so that the migration and agglomeration of the active metal particles in the interlayer on the surface of the carrier are hindered, the dispersion degree of the active metal particles is improved, the active metal particles are always kept in a smaller particle size in a high-temperature reaction, and further the growth of carbon deposition on the surface of the active metal is inhibited, which are the main reasons for the excellent catalytic activity of the molded catalyst prepared by the invention.
In conclusion, the catalyst with a specific shape obtained by preparing the powder catalyst and then molding has stronger mechanical strength, and also has good catalytic activity, carbon deposition resistance and sintering resistance. Therefore, the formed catalyst prepared by the invention has excellent industrial application prospect in the dry reforming reaction of methane.
Table 4 comparative table of reaction effect of catalysts of example 8, example 9 and comparative example 2
Figure BDA0002931120210000111
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a reaction catalyst for preparing synthesis gas by methane and carbon dioxide dry reforming is characterized by comprising the following steps:
1) preparation of catalyst powder: dissolving active metal soluble salt and auxiliary agent soluble salt into deionized water, mixing with solid carrier powder after heating pretreatment by an isometric immersion method, and obtaining catalyst powder after ultrasonic stirring, standing for aging, drying and roasting;
2) and (3) catalyst molding: uniformly stirring and mixing the catalyst powder prepared in the step 1) with a binder, an extrusion aid and deionized water, and ageing, pugging, extruding, forming and roasting to obtain the formed catalyst.
2. The method for preparing the reaction catalyst for preparing the synthesis gas by dry reforming of the methane and the carbon dioxide according to claim 1, wherein in the step 1), the soluble salt of the active metal is at least one soluble salt of nickel, cobalt or iron, wherein Ni, Co and Fe are used as active metal components.
3. The method for preparing the reaction catalyst for preparing the synthesis gas by dry reforming of the methane and the carbon dioxide according to claim 2, wherein in the step 1), the soluble salt of the nickel, the cobalt and the iron is nitrate, acetate or chloride.
4. The method for preparing the reaction catalyst for preparing the synthesis gas by dry reforming of the methane and the carbon dioxide according to claim 2, wherein in the step 1), the active metal component accounts for 5-30% of the catalyst powder by mass.
5. The method for preparing a catalyst used in the reaction of dry reforming methane and carbon dioxide to prepare the synthesis gas according to claim 1, wherein in the step 1), the soluble salt of the auxiliary agent is at least one soluble salt of lanthanum, cerium or samarium, and wherein La, Ce or Sm is used as the auxiliary agent.
6. The method for preparing a catalyst used in the reaction of preparing the synthesis gas by dry reforming of methane and carbon dioxide according to claim 5, wherein in the step 1), the soluble salt of lanthanum, cerium or samarium is a nitrate, an acetate or a chloride.
7. The method for preparing the reaction catalyst for preparing the synthesis gas by dry reforming of methane and carbon dioxide according to claim 5, wherein in the step 1), the auxiliary agent accounts for 0-8% of the catalyst powder by mass.
8. The method for preparing the reaction catalyst for preparing the synthesis gas by dry reforming of methane and carbon dioxide according to claim 1, wherein in the step 1), the solid carrier powder is at least one of alumina, titania, silica and zirconia, and the temperature of the heating pretreatment of the solid carrier powder is 200-400 ℃ and the heating pretreatment time is 2-3 h.
9. The preparation method of the reaction catalyst for preparing the synthesis gas by dry reforming of methane and carbon dioxide according to claim 1, wherein in the step 1), the standing and aging time is 1-3 h, the roasting temperature is 400-700 ℃, and the roasting time is 3-5 h, and in the step 2), the roasting temperature is 200-400 ℃ and the roasting time is 2-4 h.
10. The method for preparing the reaction catalyst for preparing the synthesis gas by dry reforming of the methane and the carbon dioxide according to claim 1, wherein in the step 2), the mass ratio of the catalyst powder, the binder, the extrusion aid and the deionized water is 100: 40-70: 5-12: 20-30%, the binder is one or more of alkaline silica sol, alkaline alumina sol, water glass and sodium aluminosilicate, the solid contents of the alkaline silica sol and the alkaline alumina sol are 30-50%, and the extrusion aid is one or more of sesbania powder, dry starch and glycol.
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