CN107321352B - Circulating fluidized bed nickel-based reforming catalyst and preparation method and application thereof - Google Patents
Circulating fluidized bed nickel-based reforming catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN107321352B CN107321352B CN201710592195.7A CN201710592195A CN107321352B CN 107321352 B CN107321352 B CN 107321352B CN 201710592195 A CN201710592195 A CN 201710592195A CN 107321352 B CN107321352 B CN 107321352B
- Authority
- CN
- China
- Prior art keywords
- nickel
- fluidized bed
- active metal
- catalyst
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a nickel-based reforming catalyst of a circulating fluidized bed, and a preparation method and application thereof, wherein the nickel-based reforming catalyst comprises a carrier and active metal nickel loaded on the carrier, the carrier is active alumina microspheres, the particle size of the active alumina microspheres is 50-500 um, the D50 is 80-300 um, and the specific surface area is more than or equal to 50m2Per g, total pore volume is more than or equal to 0.1cm3G, abrasion index less than 0.1%/h. The method comprises 1) dissolving nickel salt and second active metal salt in water to prepare mixed salt solution; 2) dissolving hexamethylenetetramine in an organic solvent to prepare a precipitator solution; 3) mixing the mixed salt solution and the precipitant solution, and then adding the activated alumina microspheres for impregnation to enable active metal nickel and a second active metal to be loaded on the surface and in the pore channels of the alumina; 4) adding a precipitant solution into the suspension, and refluxing or crystallizing; 5) low temperature drying and high temperature calcining. The catalyst has high reforming activity, low abrasion and good wear resistance.
Description
Technical Field
The invention relates to a catalyst production technology, in particular to a nickel-based reforming catalyst of a circulating fluidized bed, a preparation method and application thereof.
Background
The utilization of biomass resources is one of important ways for solving the crisis of fossil energy and slowing down global climate deterioration caused by carbon dioxide emission. The biomass gasification technology is used for producing synthesis gas, the synthesis gas is used as a raw material to produce liquid fuel through technologies such as Fischer-Tropsch synthesis, methanol synthesis and synthesis gas-to-gasoline, or the gasification gas is used as a fuel to generate electricity through a gas turbine, so that the biomass gasification technology is two important ways for large-scale utilization of biomass raw materials, and is widely applied and developed.
The prior mature and economical biomass fluidizationIn the bed gasification process, the crude synthesis gas product usually contains 10-100 g/Nm3The tar and 5-20% of low carbon hydrocarbon. The tar in the crude synthesis gas easily causes the problems of equipment scaling, pipeline blockage and the like in the cooling process of the gas. At the same time, the residual biomass tar can cause poisoning of the downstream synthesis catalyst.
In addition, methane and hydrocarbons with carbon number of above 2 contained in the raw synthesis gas are used as inert gases, and cannot participate in the synthesis reaction to generate the target product, so that the carbon efficiency of the system is reduced. The method is an important technical approach for improving the biomass gasification indirect liquefaction process, and can remove tar in the crude synthesis gas and effectively convert hydrocarbon compounds in the crude synthesis gas into effective synthesis gas. Steam reforming is the primary means of converting tar and lower hydrocarbons into an efficient syngas.
The raw synthesis gas produced by the fluidized bed gasification technique usually used contains not only tar and low carbon hydrocarbon but also 30mg to 10g/Nm3Mainly gasification by-product solid coke and dust used as heat carrier in the gasification process. The industrial mature fixed bed catalytic steam conversion is utilized to carry out tar removal and hydrocarbon conversion on the crude synthesis gas, solid impurities easily cause bed layer blockage, and meanwhile, tar impurities taking polycyclic aromatic hydrocarbon as a main component easily cause catalyst carbon deposition, so that the catalyst is inactivated and the bed layer pressure drop is improved, and the economy of purifying the crude synthesis gas by the fixed bed catalytic steam conversion is limited.
In response to the foregoing problems, RenTech corporation, usa, has conducted a series of studies, such as: US8591610 proposes a process for purifying a biomass gasification raw synthesis gas product by means of a circulating fluidized bed technique, which solves the above-mentioned problems of catalyst deactivation, bed plugging, etc. in a fixed bed reactor by means of a cyclic regeneration of the catalyst. The circulating fluidized bed process comprises two fluidized bed reactors, namely a reforming reactor and a regeneration reactor, wherein a solid catalyst is rapidly circulated between the two reactors, so that the effect of reforming and activating is achieved, heat transfer can be realized, the requirements of regeneration and reaction heat supply are met, and the circulating fluidized bed process is a reforming process with the most application prospect.
Although the prior literature has many researches on nickel-based reforming catalysts, most of the nickel-based reforming catalysts screened from fixed bed reactors are not common, and the nickel-based reforming catalysts suitable for circulating fluidized beds have the following disadvantages when used for the circulating fluidized beds: 1) it is difficult to compromise the reforming activity and fluidization of the nickel-based reforming catalyst; 2) in the circulating fluidized bed, abrasion is easily generated due to the friction between catalyst particles and a reaction device, a fluidized medium and the catalyst particles, so that the particle size of the catalyst is reduced, and the problems of agent leakage, product pollution, frequent catalyst supplement and the like are caused. Such as: U.S. Pat. No. 4,795,15196 discloses a dual fluidized bed biomass gasification tar reforming catalyst, which is prepared by screening a series of industrial alpha-alumina microspheres produced by CoorsTek, a United states alumina manufacturer, selecting a microsphere carrier with good wear resistance and appropriate specific surface area, and loading nickel, magnesium, potassium and platinum with different contents as active substances by an impregnation method.
Chinese patent CN1751789A discloses a method for preparing a nickel-based microspherical catalyst suitable for a fluidized bed, which comprises loading a nickel-based complex onto alumina microspheres or silica gel microspheres by an impregnation method, wherein the prepared nickel-based microspherical catalyst has the characteristic of high dispersion, but the nickel-based microspherical catalyst adopts an organic or inorganic coordination nickel ion solution as a precursor, thereby greatly increasing the production cost of the catalyst, and the nickel crystal grains prepared by the impregnation method are more easily sintered at high temperature to cause inactivation.
In the chinese patent CN104368345, nickel and other metal precipitates are loaded on alumina microspheres by using urea, and the catalyst is applied to a first-stage selective hydrogenation reaction of pyrolysis gasoline.
Disclosure of Invention
The invention aims to provide a nickel-based reforming catalyst of a circulating fluidized bed, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the nickel-based reforming catalyst for the circulating fluidized bed comprises a carrier and active metal nickel loaded on the carrier, wherein the carrier is an active alumina microsphere, the particle size of the active alumina microsphere is 50-500 um, the D50 is 80-300 um, and the specific surface area is more than or equal to 50m2Per g, total pore volume is more than or equal to 0.1cm3G, abrasion index less than 0.1%/h.
Further, a second active metal is loaded on the carrier, the active metal nickel accounts for 0.5-20% of the total weight of the catalyst, the molar ratio of the second active metal to the active metal nickel is 0.01-1, and the balance is an active alumina microsphere carrier.
Furthermore, the content of gamma-alumina in the activated alumina microspheres is more than 90%, the particle size is 50-300 um, the D50 is 100-200 um, and the specific surface area is 160-170 m2Per gram, total pore volume is not less than 0.3cm3/g。
Further, the active metal nickel is selected from anhydrous nickel chloride, hydrated nickel chloride, nickel nitrate, nickel sulfate or nickel acetate, and accounts for 1-15% of the weight of the catalyst.
Further, the second active metal is selected from anhydrous nitrate, hydrated nitrate, chloride salt, sulfate or acetate, and the molar ratio of the second metal to the active metal nickel is 0.1-1.
Further, the second active metal is one or more of cobalt, copper and zinc.
The preparation method of the nickel-based reforming catalyst of the circulating fluidized bed is characterized by comprising the following steps: the method comprises the following steps:
1) dissolving nickel salt and second active metal salt in water to prepare mixed salt solution;
2) dissolving hexamethylenetetramine in an organic solvent to prepare a precipitant solution;
3) mixing the mixed salt solution and the precipitant solution, adding active alumina microspheres to form a suspension, and fully soaking to enable active metal nickel and a second active metal to be loaded on the surface and in the pore channel of the alumina;
4) adding the precipitant solution into the suspension, refluxing or crystallizing, and washing the filtrate to neutrality after suction filtration;
5) and sequentially drying the washed filter-out material at low temperature and calcining the filter-out material at high temperature to obtain the nickel-based reforming catalyst of the circulating fluidized bed.
Further, in the step 3), the molar ratio of hexamethylenetetramine to metal ions is 0.5-3.
Further, in the step 4), the reflux or crystallization temperature is 80-150 ℃, and the reflux or crystallization time is 3-10 hours.
Further, in the step 5), a two-stage temperature rise program is adopted for high-temperature calcination, the temperature is raised to 300-450 ℃ at a temperature rise rate of 1-10 ℃/min, the temperature is kept for 0.5-3 h, then the temperature is raised to 600-800 ℃ at a temperature rise rate of 0.5-5 ℃/min, and the temperature is kept for 0.5-3 h.
Further, in the step 5), the drying temperature is 80-120 ℃, and the drying time is 3-10 hours.
The application of the nickel-based reforming catalyst of the circulating fluidized bed is characterized in that: the catalyst is applied to the preparation of synthesis gas by reforming methane water in a circulating fluidized bed, and the process conditions are as follows: the reaction temperature is 700-900 ℃, the reaction pressure is 0.1-0.5 MPa, and the airspeed is 10000-1200000 h-1The water-carbon ratio is less than 3: 1.
Compared with the prior art, the invention has the following advantages:
firstly, the catalyst carrier adopts active alumina microspheres with proper particle size range and high physical strength, and the standard wear index of the prepared high-wear-resistance nickel-based microsphere catalyst is less than 0.1%/h; the gas velocity required for causing the catalyst microspheres to break and wear is measured in the wear index tester to be more than 100m/s, and the wear resistance is excellent, so that wider choices are provided for catalyst preparation equipment and a fluidized bed reactor, and industrial production is easy to realize.
Secondly, the invention loads nickel and second metal (cobalt, copper and zinc) on the surface and in the pore canal of the industrial formed alumina microsphere carrier with high mechanical strength and good wear resistance by a uniform precipitation method, and forms the microspherical composite metal oxide catalyst containing nickel and second metal ions after low-temperature drying and high-temperature calcination.
Thirdly, the method utilizes the characteristic that the precipitant is neutral at low temperature and decomposed into the precipitant at high temperature, hexamethylenetetramine can be slowly hydrolyzed under the heating condition to release ammonia water, and the ammonia water is ionized to generate OH-So that the pH of the solution is uniformly increased, and homogeneous crystal nuclei and crystallization are induced to be generated. Due to the precipitation of ionic OH-The method is characterized in that hexamethylenetetramine is hydrolyzed and is gradually generated through ammonia water ionization reaction, so that agglomeration or uneven components caused by overhigh local concentration in the adding process of a precipitator are effectively avoided, and the growth rate of crystal nuclei of the solution is slow in a low-saturation state, so that the method is favorable for forming a crystal product with larger grains, high crystallinity and uniform appearance. The catalyst prepared by the method has good catalytic activity and abrasion resistance to the synthesis gas prepared by reforming methane water, and can be used under the condition of high space velocity (1.1 multiplied by 10)6h-1) The catalyst can be recycled, the conversion rate of methane is maintained to be more than 70%, the standard abrasion index is less than 0.1%/h, and the catalyst can keep activity after being recycled and regenerated, can be used for the methane reforming process and the catalytic reforming process of coke-containing gases such as coal, biomass gasified gas, coke oven tail gas and the like, and is particularly suitable for the catalytic reforming process of a circulating fluidized bed.
Fourthly, the catalyst of the invention has good fluidization property, wear resistance and high stability, and avoids the problems of catalyst leakage, product pollution, need of regular catalyst supplement and the like.
Drawings
FIG. 1 is a graph of attrition indices for the catalyst prepared in example 1 at different gas velocities.
Detailed Description
The invention will be more clearly understood from the following detailed description of the invention taken in conjunction with the accompanying drawings and specific examples, which are not to be construed as limiting the invention. (reagents used in the following examples and comparative examples were chemically pure reagents unless otherwise specified.)
Example 1
2.919g of nickel nitrate hexahydrate are dissolved in 4ml of deionized water; dissolving 0.704g of HMT (hexamethylenetetramine) in 6ml of deionized water/ethanol mixed solution with the same volume; mixing the two solutions, adding 10g of activated alumina microspheres, and soaking for 1h to form a suspension; adding an equivalent HMT solution into the suspension, refluxing for 5 hours at 100 ℃, performing suction filtration, and fully washing the microspheres to be neutral by deionized water and ethanol to obtain a catalyst precursor; then the catalyst precursor is placed in an oven to be dried for 5h at 100 ℃, and then is calcined in a muffle furnace by temperature programming, the temperature is increased to 350 ℃ at 3 ℃/min and stays for 1h, and then the temperature is increased to 650 ℃ at 0.5 ℃/min and stays for 2h, and the supported Ni/Al is prepared2O3Microspherical catalyst 1.
The particle size of the active alumina microspheres of the catalyst 1 is 50-300 um, the D50 is 111.8um, and the specific surface area is 169.7m2(g) total pore volume of 0.3cm3The standard wear index at 84m/s gas velocity was 0.08%/h.
Example 2
2.919g of nickel nitrate hexahydrate are dissolved in 4ml of deionized water; dissolving 0.704g of HMT (hexamethylenetetramine) in 6ml of deionized water/ethanol mixed solution with the same volume; mixing the two solutions, adding 10g of activated alumina microspheres, and soaking for 1h to form a suspension; adding an equivalent HMT solution into the suspension, transferring the suspension into a high-pressure kettle, crystallizing, precipitating, heating at 120 ℃ for 5 hours, performing suction filtration, and fully washing the microspheres with deionized water and ethanol until the microspheres are neutral to obtain a catalyst precursor; then the catalyst precursor is placed in an oven to be dried for 5h at 100 ℃, and then is calcined in a muffle furnace by temperature programming, the temperature is increased to 350 ℃ at 3 ℃/min and stays for 1h, and then the temperature is increased to 650 ℃ at 0.5 ℃/min and stays for 2h, and the supported Ni/Al is prepared2O3 Microspherical catalyst 2.
The particle size of the active alumina microspheres of the catalyst 2 is 50-300 um, the D50 is 115.3um, and the specific surface area is 169.1m2(g) total pore volume of 0.3cm3The standard abrasion index at 84m/s gas velocity was 0.08%/h.
Example 3
3.156g of nickel nitrate hexahydrate and 1.580g of cobalt nitrate hexahydrate were dissolved in 4ml of deionized water; 1.141g HMT was dissolved in 6ml of equal volume of deionized waterA water/ethanol mixed solution; mixing the two solutions, adding 10g of active alumina microspheres, and soaking for 1h to obtain a suspension; adding an equivalent HMT solution into the suspension, refluxing for 5 hours at 100 ℃, performing suction filtration, and fully washing the microspheres to be neutral by deionized water and ethanol to obtain a catalyst precursor; drying the catalyst precursor in an oven at 100 ℃ for 5h, then carrying out temperature programming calcination in a muffle furnace, firstly heating to 350 ℃ at 3 ℃/min and staying for 1h, then heating to 650 ℃ at 0.5 ℃/min and staying for 2h, and preparing the supported Ni-Co/Al2O3A microspherical catalyst 3.
The particle size of the active alumina microspheres of the catalyst 3 is 50-300 um, the D50 is (110.0) um, and the specific surface area is (162.9) m2(g), total pore volume of (0.3) cm3The standard abrasion index at 84m/s gas velocity was (0.08)%/h.
Example 4
3.156g of nickel nitrate hexahydrate and 1.318g of copper nitrate trihydrate were dissolved in 6ml of deionized water; adding 10g of active alumina microspheres for dipping for 1 hour to obtain a suspension; 1.835g of HMT is dissolved in a mixed solution of 4ml of deionized water and 6ml of ethanol to form a precipitant solution; adding the precipitant solution into the suspension, refluxing for 5h at 100 ℃, performing suction filtration, and fully washing the microspheres to be neutral by deionized water and ethanol to obtain a catalyst precursor; drying the catalyst precursor in an oven at 100 ℃ for 5h, then carrying out temperature programming calcination in a muffle furnace, firstly raising the temperature to 350 ℃ at 3 ℃/min and staying for 1h, then raising the temperature to 650 ℃ at 0.5 ℃/min and staying for 2h, and preparing the supported Ni-Cu/Al2O3A microspherical catalyst 4.
The particle size of the active alumina microspheres of the catalyst 4 is 50-300 um, the D50 is 111.3um, and the specific surface area is 161.3m2(g) total pore volume of 0.3cm3The standard abrasion index at 84m/s gas velocity was 0.08%/h.
Example 5
3.043g of nickel nitrate hexahydrate and 1.557g of zinc nitrate hexahydrate are dissolved in 4ml of deionized water; dissolving 1.101g of HMT in 8ml of deionized water/ethanol mixed solution with the same volume; mixing the two solutions, adding 10g of activated alumina microspheres, and soaking for 1h to obtain a suspension; adding equivalent HMT solution into the suspension, refluxing at 100 deg.C for 5 hr, vacuum filtering, and washing with deionized water and ethanolThe ball is neutralized to obtain a catalyst precursor; drying the catalyst precursor in an oven at 100 ℃ for 5h, then carrying out temperature programming calcination in a muffle furnace, firstly raising the temperature to 350 ℃ at 3 ℃/min and staying for 1h, then raising the temperature to 650 ℃ at 0.5 ℃/min and staying for 2h, and preparing the supported Ni-Zn/Al2O3Microspherical catalyst 5.
The particle size of the active alumina microspheres of the catalyst 5 is 50-300 um, the D50 is 132.9um, and the specific surface area is 160.6m2(g) total pore volume of 0.3cm3The standard abrasion index at 84m/s gas velocity was 0.08%/h.
Comparative example
Comparative catalysts were prepared according to the catalyst preparation method disclosed in patent US 7915196.
Determination of abrasion index:
in the invention, the abrasion index of the catalyst is measured by a straight tube method by adopting the standard Q/TSH 3490909-2006 of catalyst division of China petrochemical company Limited. The method comprises the following specific steps: 10g of the catalyst was charged to an attrition measuring device and the catalyst was purged through an attrition tube with a small hole in the bottom after humidification of air at different flow rates. The fine powder generated by abrasion is collected by a powder collecting and filtering device above the abrasion pipe. After continuously purging for 1 hour, weighing the collected fine powder; the purging was continued for 4h and the blown fine powder was weighed. The catalyst attrition index was calculated as the percentage of fines blown off over 4 hours based on the total weight of the catalyst.
The attrition indexes of the catalyst 1 and the comparative catalyst were measured at gas velocities of 24m/s, 50m/s, 84m/s, 114m/s and 120m/s, respectively, using an attrition index measuring instrument, and as a result, see fig. 1, it can be seen from fig. 1 that the standard attrition index of the catalyst 1 is less than 0.1%/h and lower than that of the comparative catalyst at the same gas velocity. It is generally believed that the attrition of the alumina particles is dominated by two attrition mechanisms, namely a delamination mechanism and a fracture mechanism. The abrasion resistance of the microsphere catalyst can be characterized by an abrasion index, and can also be linearly fitted by the abrasion index under different gas velocities, and the intersection point of two straight lines respectively representing the abrasion of the stripping layer of the particles and the abrasion of the fracture of the particles obtained by fitting is defined as the critical gas velocity from the stripping layer to the fracture of the microsphere. The higher the critical gas velocity, the greater the gas velocity required to force the catalyst particles to break, and the greater the attrition resistance. As can be seen from FIG. 1, the critical gas velocity of the catalyst of the comparative example is 107m/s, and the attrition index of the catalyst 1 is not significantly changed in the above gas velocity range, which indicates that the critical gas velocity of the catalyst 1 with fracture and breakage is more than 107m/s, and the attrition resistance of the catalyst 1 is obviously better than that of the catalyst of the comparative example.
Evaluation of catalyst Activity:
in the tar reforming and methane conversion reaction of the crude synthesis gas, the tar reforming is easier to realize than the methane conversion, so that the method for screening the catalyst suitable for the tar removal and the hydrocarbon conversion of the crude synthesis gas of the circulating fluidized bed is an effective catalyst research and development method by taking the methane conversion capability of the catalyst as an evaluation index. The catalyst with excellent methane steam conversion performance can meet the technological requirements of circulating fluidized bed crude synthesis gas tar removal and hydrocarbon conversion.
The catalyst prepared in the embodiment 1-5 is used for the reaction of preparing synthesis gas by reforming methane at the reaction temperature of 850 ℃, normal pressure and space velocity of 1.1 multiplied by 106h-1And the reforming performance of the catalyst is tested under the condition that the water-carbon ratio is 2.8: 1. The method comprises the following specific steps:
1) 0.05g of catalyst is weighed, 10g of carrier is added as diluent to be uniformly mixed with the catalyst, the mixture is placed in a normal-pressure micro fluidized bed reactor, and 5 percent of H is introduced2Ar completely reduces the catalyst at 850 ℃.
2) CH with the flow rate of 100ml/min and 334ml/min is introduced into the reactor respectively4And N2And mixing with 280ml/min of water vapor, preheating to 850 ℃ and reacting for 30 min.
3) 4% H with a flow rate of 300ml/min was passed in2/3％O2/93％N2And (3) regenerating the catalyst by using regenerated gas at 850 ℃, wherein the regeneration period is 8 min. After regeneration was complete, a nitrogen purge was applied at 300 ml/min.
4) The CH flows of 100ml/min and 334ml/min are again respectively4And N2Introducing into a reactor, mixing with 280ml/min of water vapor, preheating to 850 ℃, and reacting for 30 min.
5) And (3) repeating the steps 3) and 4), and carrying out 6-cycle tests to simulate the process of 'reaction-regeneration-reaction-regeneration' of the catalyst in the circulating fluidized bed reactor.
The composition of the reaction product was determined using an american ARI raman spectroscopy on-line gas analyzer. The methane conversion, hydrogen yield and carbon monoxide yield were calculated using the following formulas (where out represents the outlet gas and in represents the inlet gas):
XCH4＝(FCO,out+FCO2,out)/FCH4,in×100％
YH2＝FH2,out/(3×FCH4,in)×100％
YCO＝FCO,out/FCH4,in×100％
the average values of the methane conversion, hydrogen yield and carbon monoxide yield over the reforming reaction period (30min) were taken as the reactivity, and the results are summarized in Table 1 below.
TABLE 1
As can be seen from the data in Table 1, the nickel-based reforming catalyst prepared by the method of the invention has high catalytic activity, and the reforming activity of the catalysts of examples 1-5 is obviously higher than that of the catalysts of comparative examples.
Claims (6)
1. A circulating fluidized bed nickel-based reforming catalyst comprising a support and an active metallic nickel supported on the support, characterized in that: the carrier is an active alumina microsphere, the particle size of the active alumina microsphere is 50-500 mu m, the D50 is 80-300 mu m, and the specific surface area is more than or equal to 50m2Per g, total pore volume is more than or equal to 0.1cm3G, abrasion index is less than 0.1%/h;
a second active metal is also loaded on the carrier, the molar ratio of the second active metal to the active metal nickel is 0.01-1, and the balance is an active alumina microsphere carrier;
the content of gamma-alumina in the activated alumina microspheres is more than 90 percent;
the second active metal is selected from anhydrous nitrate, hydrated nitrate, chloride salt, sulfate or acetate; the active metal nickel is selected from anhydrous nickel chloride, hydrated nickel chloride, nickel nitrate, nickel sulfate or nickel acetate, and accounts for 1-15% of the weight of the catalyst;
the second active metal is one or more of cobalt, copper and zinc;
the preparation method of the nickel-based reforming catalyst of the circulating fluidized bed comprises the following steps:
1) dissolving nickel salt and second active metal salt in water to prepare mixed salt solution;
2) dissolving hexamethylenetetramine in an organic solvent to prepare a precipitant solution;
3) mixing the mixed salt solution and the precipitant solution, adding active alumina microspheres to form a suspension, and fully soaking to enable active metal nickel and a second active metal to be loaded on the surface and in the pore channel of the alumina;
4) adding the precipitant solution into the suspension, refluxing or crystallizing, and washing the filtrate to neutrality after suction filtration;
5) sequentially drying the washed filter-out material at low temperature and calcining the filter-out material at high temperature to obtain the nickel-based reforming catalyst of the circulating fluidized bed;
in the step 3), the molar ratio of hexamethylene tetramine to metal ions is 0.5-3.
2. A method of preparing the circulating fluidized bed nickel-based reforming catalyst of claim 1, comprising: the method comprises the following steps:
1) dissolving nickel salt and second active metal salt in water to prepare mixed salt solution;
2) dissolving hexamethylenetetramine in an organic solvent to prepare a precipitant solution;
3) mixing the mixed salt solution and the precipitant solution, adding active alumina microspheres to form a suspension, and fully soaking to enable active metal nickel and a second active metal to be loaded on the surface and in the pore channel of the alumina;
4) adding the precipitant solution into the suspension, refluxing or crystallizing, and washing the filtrate to neutrality after suction filtration;
5) sequentially drying the washed filter-out material at low temperature and calcining the filter-out material at high temperature to obtain the nickel-based reforming catalyst of the circulating fluidized bed;
in the step 3), the molar ratio of hexamethylene tetramine to metal ions is 0.5-3.
3. The method for preparing a circulating fluidized bed nickel-based reforming catalyst according to claim 2, wherein: in the step 4), the reflux or crystallization temperature is 80-150 ℃, and the reflux or crystallization time is 3-10 h.
4. The method for preparing a circulating fluidized bed nickel-based reforming catalyst according to claim 2, wherein: in the step 5), a two-stage temperature rise program is adopted for high-temperature calcination, the temperature is raised to 300-450 ℃ at the temperature rise rate of 1-10 ℃/min, the temperature is kept for 0.5-3 h, the temperature is raised to 600-800 ℃ at the temperature rise rate of 0.5-5 ℃/min, and the temperature is kept for 0.5-3 h.
5. The method for preparing a circulating fluidized bed nickel-based reforming catalyst according to claim 2, wherein: in the step 5), the drying temperature is 80-120 ℃, and the drying time is 3-10 h.
6. Use of a circulating fluidized bed nickel-based reforming catalyst according to claim 1, wherein: the catalyst is applied to the preparation of synthesis gas by reforming methane water in a circulating fluidized bed, and the process conditions are as follows: the reaction temperature is 700-900 ℃, the reaction pressure is 0.1-0.5 MPa, and the airspeed is 10000-1200000 h-1The water-carbon ratio is less than 3: 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710592195.7A CN107321352B (en) | 2017-07-19 | 2017-07-19 | Circulating fluidized bed nickel-based reforming catalyst and preparation method and application thereof |
| PCT/CN2018/095551 WO2019015528A1 (en) | 2017-07-19 | 2018-07-13 | Nickel-based reforming catalyst for circulating fluidized bed, preparation method therefor, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710592195.7A CN107321352B (en) | 2017-07-19 | 2017-07-19 | Circulating fluidized bed nickel-based reforming catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107321352A CN107321352A (en) | 2017-11-07 |
| CN107321352B true CN107321352B (en) | 2021-04-09 |
Family
ID=60226740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710592195.7A Active CN107321352B (en) | 2017-07-19 | 2017-07-19 | Circulating fluidized bed nickel-based reforming catalyst and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN107321352B (en) |
| WO (1) | WO2019015528A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3805149B1 (en) * | 2019-10-08 | 2022-04-20 | C&CS Catalysts and Chemical Specialties GmbH | Fluidizable steam reforming catalyst and use of a catalyst in methane steam reforming |
| CN111841550B (en) * | 2020-08-18 | 2022-12-30 | 中国科学技术大学 | Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst |
| CN113318590B (en) * | 2021-07-05 | 2022-12-02 | 烟台大学 | Preparation method and application of high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent |
| CN117399014B (en) * | 2023-12-15 | 2024-04-23 | 乌镇实验室 | Preparation method and application of finite field ammonia decomposition catalyst |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1751789A (en) * | 2005-09-02 | 2006-03-29 | 浙江大学 | Prepn. method and application of high-dispersion loading type nickel-based catalyst |
| US7915196B2 (en) * | 2005-10-07 | 2011-03-29 | Alliance For Sustainable Energy, Llc | Attrition resistant fluidizable reforming catalyst |
| CN101352686B (en) * | 2008-09-05 | 2010-10-27 | 华东理工大学 | Catalyst used for hydrogen production by catalyzing and hydrogen production method by catalyzing |
| EP2379447B1 (en) * | 2009-01-21 | 2016-06-08 | Res Usa, Llc | System and method for dual fluidized bed gasification |
| CN101954288B (en) * | 2010-09-27 | 2013-01-23 | 上海华谊（集团）公司 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
| CN102464299B (en) * | 2010-10-28 | 2013-06-26 | 中国石油化工股份有限公司 | Method for producing hydrogen through fluidized-bed methane steam reforming |
| CN103170349B (en) * | 2011-12-23 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of carbon four that mixes is selected copper catalyst of hydrogenation and preparation method thereof |
| CN104368345A (en) * | 2014-11-20 | 2015-02-25 | 北京化工大学 | Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst |
| CN104801333B (en) * | 2015-03-03 | 2017-12-19 | 新奥科技发展有限公司 | A kind of preparation method of loading type nickel-based catalyst |
| CN105688916B (en) * | 2016-02-23 | 2018-10-26 | 中国科学院上海高等研究院 | A kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst and its application |
| CN106391028B (en) * | 2016-10-31 | 2019-09-24 | 中国海洋石油集团有限公司 | A kind of methanation catalyst and preparation method thereof for fluidized bed |
| CN106902829B (en) * | 2017-04-01 | 2019-08-23 | 太原理工大学 | A kind of load type double-metal reforming catalyst and its preparation method and application |
-
2017
- 2017-07-19 CN CN201710592195.7A patent/CN107321352B/en active Active
-
2018
- 2018-07-13 WO PCT/CN2018/095551 patent/WO2019015528A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019015528A1 (en) | 2019-01-24 |
| CN107321352A (en) | 2017-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107321352B (en) | Circulating fluidized bed nickel-based reforming catalyst and preparation method and application thereof | |
| Lebarbier et al. | Sorption-enhanced synthetic natural gas (SNG) production from syngas: a novel process combining CO methanation, water-gas shift, and CO2 capture | |
| WO2017173791A1 (en) | Cobalt carbide-based catalyst for direct preparation of olefin form synthesis gas, preparation method therefor and application thereof | |
| Feng et al. | Carbon deposition on Ni-based catalyst with TiO2 as additive during the syngas methanation process in a fluidized bed reactor | |
| CN109894133B (en) | Preparation method of supported Ni-MoCx catalytic material and application of supported Ni-MoCx catalytic material in preparation of synthesis gas by chemical-looping dry gas reforming | |
| CN107597119B (en) | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof | |
| CN114522688B (en) | Porous carbon supported bimetallic catalyst and preparation and application thereof | |
| CN101219392B (en) | Catalyst for producing gas rich in hydrogen with coke oven gas and method for producing the same | |
| Wang et al. | Hydrogen production from catalytic steam reforming of toluene over trace of Fe and Mn doping Ni/Attapulgite | |
| Wang et al. | Understanding relationship of sepiolite structure tailoring and the catalytic behaviors in glycerol steam reforming over Co/sepiolite derived Co-phyllosilicate catalyst | |
| CN104888783A (en) | Methanation catalyst, preparation method and application thereof | |
| KR102035714B1 (en) | Nickel catalysts for reforming hydrocarbons | |
| US7470647B2 (en) | Nickel oxide nanoparticles as catalyst precursor for hydrogen production | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN105771993A (en) | Fischer-Tropsch synthesis catalyst for preparing liquid hydrocarbon from syngas and preparation method of Fischer-Tropsch synthesis catalyst | |
| CN104984769A (en) | Synthesis-gas carbon-based catalyst preparation method by reforming methane and carbon dioxide | |
| Liu et al. | Inherently separated syngas production from plastic waste fast pyrolysis integrated with volatile chemical looping conversion with CO2 splitting | |
| CN113117712A (en) | Methane dry reforming reaction under microwave condition and catalyst thereof | |
| CN103230800B (en) | A kind of containing gallium iron-base fischer-tropsch Catalysts and its preparation method | |
| CN113058604A (en) | Flower-shaped catalyst, preparation method and application thereof | |
| CN105358477A (en) | Method for pre-reforming olefin-containing hydrocarbon streams, pre-reforming catalyst and method for preparing the catalyst | |
| WO2005030391A1 (en) | Catalyst and method for the generation of co-free hydrogen from methane | |
| CN113952970A (en) | Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof | |
| WO2007100333A1 (en) | Nickel oxide nanoparticles as catalyst precursor for hydrogen production | |
| CN104046399B (en) | Sulfur-tolerant methanation process for preparing natural gases from coke oven gases |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |