WO2012043905A1 - Catalyseur de déplacement au gaz à l'eau à sorption améliorée et procédé de préparation de celui-ci - Google Patents

Catalyseur de déplacement au gaz à l'eau à sorption améliorée et procédé de préparation de celui-ci Download PDF

Info

Publication number
WO2012043905A1
WO2012043905A1 PCT/KR2010/006682 KR2010006682W WO2012043905A1 WO 2012043905 A1 WO2012043905 A1 WO 2012043905A1 KR 2010006682 W KR2010006682 W KR 2010006682W WO 2012043905 A1 WO2012043905 A1 WO 2012043905A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide
water gas
gas shift
catalyst
group
Prior art date
Application number
PCT/KR2010/006682
Other languages
English (en)
Korean (ko)
Inventor
이중범
류청걸
김경숙
제갈성
양석란
백점인
엄태형
류정호
Original Assignee
한국전력공사
최동혁
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 한국전력공사, 최동혁 filed Critical 한국전력공사
Publication of WO2012043905A1 publication Critical patent/WO2012043905A1/fr

Links

Images

Classifications

    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/72—Copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • 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
    • C01B2203/1094—Promotors or activators
    • 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

Definitions

  • One or more active ingredients selected from the group consisting of copper oxide, zinc oxide and cerium oxide; Support; Inorganic binders; And
  • a water gas shift reaction catalyst comprising at least one promoter selected from the group consisting of calcium oxide, barium oxide, strontium oxide, magnesium oxide, zirconium oxide and barium titania, and a method for producing the same.
  • the catalyst according to the invention can be prepared by spray drying.
  • CCS carbon capture and storage
  • CO2 capture technology includes pre-combustion, in-combustion and post-combustion technologies.
  • pre-combustion CO 2 capture technology partially oxidizes (gasifies) various fossil fuels to produce a synthesis gas composed mainly of hydrogen and carbon monoxide. It is a technique for preparing and separating the hydrogen and carbon dioxide after conversion to hydrogen and carbon dioxide through a water gas conversion reaction.
  • the technique is a technique for capturing carbon dioxide before using the synthesis gas for various applications (fuel cell technology, coal liquefaction technology, compound production, etc.).
  • the pre-combustion carbon dioxide capture technology can use coal, biomass and organic waste as raw materials to prepare for oil depletion and high oil prices, and the synthesis gas as a product can be utilized in various ways such as power generation, fuel cells, and synthetic raw materials production.
  • high temperature, and it is possible to recover the CO 2 at a high pressure can reduce the efficiency reduction of the technology, it is possible to lower the cost of compressing the large reduction potential of the CO 2 capture technology costs.
  • the pre-combustion CO 2 capture technique includes a technique using a PSA process and a wet physiological absorber such as Selexol and Rectisol, and a membrane separation technique.
  • the technology using the PSA process and physical absorbents such as Selexol and Rectisol has a problem of low energy efficiency and high energy consumption due to low thermal efficiency and high energy consumption.
  • the existing commercial wet process requires at least four stages of process configuration, such as two-stage water gas conversion (WGS), heat exchange, and low temperature CO 2 absorption, and requires at least two stages of compression for storage due to low pressure of recovered CO 2 . Do.
  • WGS water gas conversion
  • the cost and efficiency loss due to reheating at the front of the gas turbine are high.
  • Membrane separation technology has high energy efficiency because it can be operated at high pressure, but there is a limit to apply to large industrial process due to its small capacity.
  • Sorption Enhanced Water Gas Shift is a technology that can effectively capture and separate CO 2 while maintaining the high temperature and high pressure conditions of the syngas produced in the gasifier.
  • This technology can promote CO conversion rate by simultaneous process with water gas conversion (WGS) reaction, and can be separated into high concentration of CO 2 during regeneration, and applied as pre-combustion CO 2 capture technology aiming to use clean energy. It is possible.
  • the fluidized bed SEWGS process is capable of a one-loop process of conversion / absorption-regeneration and is suitable for large-capacity CO 2 recovery.
  • the absorbent and the catalyst are continuously circulated between two reactors composed of a fluidized bed reactor, and the first reactor produces a high concentration of hydrogen by performing a carbon dioxide capture reaction simultaneously with a carbon monoxide conversion reaction.
  • absorbents that capture carbon dioxide can be regenerated by water vapor and additional heat sources to separate high concentrations of carbon dioxide.
  • the catalyst and the absorbent circulate the two reactors continuously and repeatedly, so that the continuous process is possible, making it easy to apply to large industrial processes such as coal gasification combined cycle power generation.
  • This technology uses solid particles, so there is little waste water, less corrosion problems, and it is possible to use various inexpensive materials.
  • the absorbent can be regenerated and used repeatedly, it is a technology having great potential for use as a future low-cost carbon dioxide recovery and hydrogen production technology.
  • JP 378231 proposes a catalyst containing a lithium oxide and a complex oxide of iron oxide-chromium oxide for use in a fixed bed multistage reactor, and the production method uses a supported method.
  • US 6692545 and US 7354562 propose an absorbent consisting of potassium carbonate, magnesium, manganese oxide, lanthanum oxide, clay and an iron-chromium oxide catalyst which is a high temperature conversion catalyst, but the patent proposes a supporting method.
  • US 7083658 proposes a calcium oxide absorber that can be used at high temperatures without mentioning a catalyst, and JP 2000-262837 and JP 2005-041749 propose iron and chromium composite oxide catalysts in various lithium compound forms.
  • the present invention relates to a technique for effectively capturing and separating carbon dioxide contained in syngas using a fluidized bed accelerated water gas shift reaction process.
  • problems such as particle size and abrasion exist, and an object of the present invention is to provide a suitable catalyst for the fluidized bed process. It is done.
  • a catalyst that satisfies the same conditions (particle size, particle distribution, strength and packing density) in a fluidized bed process, and which can be applied to a synthesis gas of high temperature (200 ° C. to 650 ° C.) and high pressure (more than 20 bar) in the same reactor. It aims to provide.
  • the catalyst according to the present invention can be utilized for coal gasification combined cycle, fuel cell, coal liquefaction technology and synthesis of compounds such as hydrogen.
  • the present invention as a means for solving the above problems, at least one active ingredient selected from the group consisting of copper oxide, zinc oxide and cerium oxide; Support; Inorganic binders; And
  • a water gas shift reaction catalyst composition comprising at least one promoter selected from the group consisting of calcium oxide, barium oxide, strontium oxide, magnesium oxide, zirconium oxide and barium titania is provided.
  • the present invention provides a slurry composition comprising a solid material and a solvent containing a water gas shift reaction catalyst composition.
  • the present invention as another means for solving the above problems, (A) drying the slurry composition described above by spray drying to prepare a solid particle; And
  • (B) it provides a method for producing a water gas shift reaction catalyst comprising the step of preparing a catalyst by dry baking the prepared solid particles.
  • the present invention is another means for solving the above problems, one or more active ingredients selected from the group consisting of copper oxide, zinc oxide and cerium oxide; Support; Inorganic binders; And
  • a water gas shift reaction catalyst comprising at least one promoter selected from the group consisting of calcium oxide, barium oxide, strontium oxide, magnesium oxide, zirconium oxide and barium titania is provided.
  • the present invention provides a first step of converting carbon monoxide into carbon dioxide and hydrogen using a catalyst and simultaneously collecting the converted carbon dioxide in the absorbent;
  • the catalyst comprises at least one active ingredient selected from the group consisting of copper oxide, zinc oxide and cerium oxide; Support; Inorganic binders; And
  • a fluidized bed accelerated water gas shift process comprising at least one promoter selected from the group consisting of calcium oxide, barium oxide, strontium oxide, magnesium oxide, zirconium oxide and barium titania.
  • the catalyst according to the present invention has excellent physical properties such as packing density and wear resistance and CO conversion.
  • mass production is easy, and the production yield is high and the cost is low, so it can be used as a low cost pre-combustion CO 2 recovery technology for coal gasification combined cycle, fuel cell, coal liquefaction process, compound production process.
  • high temperature and high pressure of the synthesis gas can be used as it is to minimize the reduction in efficiency due to the CO 2 recovery, it is possible to significantly reduce the compression cost can recover CO 2 at a low cost.
  • FIG. 1 is a process chart showing a process for preparing a water gas shift reaction catalyst according to the present invention.
  • FIG. 2 is a process chart illustrating a process of preparing a mixture of a solid raw material and a solvent into a slurry.
  • FIG. 3 is a process chart showing a process of forming a solid particle by spray drying the slurry.
  • Figure 4 is a process chart showing a process of producing a catalyst by dry baking the solid particles molded by the spray drying method.
  • FIG. 6 is a graph showing the CO conversion rate of the catalyst prepared according to the embodiment of the present invention.
  • One or more active ingredients selected from the group consisting of copper oxide, zinc oxide and cerium oxide; Support; Inorganic binders; And
  • a water gas shift reaction catalyst composition comprising at least one promoter selected from the group consisting of calcium oxide, barium oxide, strontium oxide, magnesium oxide, zirconium oxide and barium titania.
  • the present invention relates to a catalyst composition used in the process of promoting a water gas shift reaction
  • the catalyst composition may include an active ingredient, a support, an inorganic binder, and an accelerator.
  • the active ingredient of the catalyst composition is a material that effectively converts carbon monoxide and water contained in the synthesis gas into hydrogen and carbon dioxide.
  • the type of the active ingredient one or more selected from the group consisting of copper oxide (CuO, Cu 2 O), zinc oxide (ZnO), and cerium oxide (CeO 2 ) may be used.
  • the content of the active ingredient is not particularly limited, and may include 10 parts by weight to 80 parts by weight, and preferably 10 parts by weight to 70 parts by weight with respect to the catalyst composition.
  • the content is less than 10 parts by weight, there is a fear that the conversion rate of carbon monoxide is lowered, when it exceeds 80 parts by weight, there is a fear that the physical properties (ex, wear resistance and packing density, etc.) required in the fluidized bed accelerated aqueous conversion reaction process is lowered. have.
  • the purity of the active ingredient is preferably 98% or more.
  • the support included in the catalyst composition is a substance that makes the active ingredient well distributed in the catalyst particles, thereby increasing the utility of the active ingredient and providing pores and surface areas necessary for the reaction.
  • the type of the support is not particularly limited as long as it has a large specific surface area, and at least one selected from the group consisting of alumina, hydrotalcite, silica, ceramic, and magnesia may be used, and preferably, from the group consisting of alumina and hydrotalcite.
  • One or more selected may be used, more preferably alumina.
  • the alumina used may have an Al 2 O 3 content of about 99.8% and a specific surface area of 150 to 250 m 2 / g.
  • the hydrotalcite may have a MgO content of 20% or more and a specific surface area of 100 to 300 m 2 / g or more.
  • the content of the support is not particularly limited, and may include 5 parts by weight to 70 parts by weight, and preferably 5 parts by weight to 60 parts by weight with respect to the components constituting the catalyst. If the content is less than 5 parts by weight, physical properties such as abrasion resistance and packing density required in the fluidized bed accelerated aqueous conversion reaction process may be lowered. If the content is more than 70 parts by weight, performance may be reduced due to the reduction of the relative active ingredient. There is.
  • Inorganic binder included in the catalyst composition in the present invention is a material that binds the active ingredient and the support to impart strength to the catalyst and enables the catalyst to be used without loss due to prolonged wear.
  • the type of the inorganic binder is not particularly limited, and may be used at least one selected from the group consisting of cements, clays, ceramics, and the like, preferably at least one selected from the group consisting of clays and ceramics. Can be used.
  • specific types of the clays include bentonite or kaolin
  • specific types of ceramics include alumina sol, silica sol or boehmite, and the like. Silicates, calcium aluminate, and the like.
  • the content of the inorganic binder is not particularly limited, and may include 3 parts by weight to 70 parts by weight, and preferably 3 parts by weight to 60 parts by weight with respect to the components constituting the catalyst. If the content is less than 3 parts by weight, there is a risk that the physical properties are lowered due to a decrease in the bonding strength between the raw materials, if the content exceeds 70 parts by weight, the performance as a catalyst may be lowered due to the relative content of the active ingredient.
  • the promoter included in the catalyst composition is a material that improves the performance of the catalyst and allows the repeated use without deterioration of reactivity due to long-term use.
  • the accelerator may include at least one selected from the group consisting of calcium oxide (CaO), barium oxide (BaO), strontium oxide (SrO 2 ), magnesium oxide (MgO), zirconium oxide (ZrO 2 ), and barium titania (BaTiO 3 ). Can be used.
  • the content of the accelerator is not particularly limited, and may include 3 parts by weight to 70 parts by weight, and preferably 3 parts by weight to 60 parts by weight with respect to the components constituting the catalyst. If the content is less than 3 parts by weight, there is a fear that the effect of using the accelerator is insignificant, and if it exceeds 70 parts by weight, the performance as a catalyst may be lowered due to the relative decrease in the content of the active ingredient.
  • the present invention is a catalyst composition as described above, namely.
  • a composition comprising an active ingredient, a support, an inorganic binder and an accelerator as a solid raw material, and a slurry composition comprising the solid raw material and a solvent.
  • the active ingredient, the support, the inorganic binder, and the accelerator may be used without limitation the above-described type, and the content thereof may also be used in the above-mentioned amount.
  • the kind of the solvent is not particularly limited, and a solvent generally used in the art may be used. Specifically, water or alcohol may be used, and water is preferably used.
  • the content of the solid raw material in the present invention may be included, for example, 20 to 50 parts by weight with respect to 100 parts by weight of the solvent, preferably 20 to 40 parts by weight.
  • the content of the solid raw material is less than 20 parts by weight, the amount of the slurry for preparing the catalyst may be relatively increased, thereby reducing the production efficiency.
  • the content of the solid material exceeds 50 parts by weight, the fluidity may be increased due to an increase in the viscosity of the slurry due to an increase in concentration. This decreases, so that it is difficult to transport through the pump during spray drying and the workability may decrease.
  • the slurry composition according to the present invention further comprises at least one organic additive selected from the group consisting of dispersants, antifoaming agents and organic binders for controlling homogenization of solid raw materials, concentration, viscosity, stability, flowability and strength and density of slurry. It may include.
  • a dispersant is used to prevent agglomeration between particles in the grinding process, which will be described below. That is, in the pulverization process for controlling the particle size of the solid raw materials constituting the catalyst, the dispersant may be used to prevent the reduction of the pulverization efficiency due to the aggregation of the pulverized fine powder particles.
  • dispersant in the present invention for example, at least one selected from the group consisting of anionic dispersants, cationic dispersants, amphoteric dispersants and nonionic dispersants may be used, and preferably anionic dispersants and nonionics.
  • Systemic dispersants can be used.
  • anionic dispersant polycarboxylic acid, polycarboxylic acid amine, polycarboxylic acid amine salt, polycarboxylic acid soda salt, or the like may be used.
  • nonionic dispersant a fluorine-based surfactant may be used.
  • the anionic dispersant may be used in an amount of 0.1 to 10 parts by weight based on a solid raw material, and a nonionic dispersant may be used in an amount of 0.01 to 0.3 parts by weight based on a solid raw material. In this range, the dispersion effect of the particles is excellent.
  • a defoamer may be used to remove bubbles in the slurry to which the dispersant and the organic binder are applied.
  • the antifoaming agent may include, for example, at least one selected from the group consisting of silicone, metal soap, amide, polyether, polyester, polyglycol, organophosphoric acid and alcohol.
  • a metal soap type and polyester type nonionic surfactant can be used.
  • the antifoaming agent may be used in an amount of 0.01 to 0.2 parts by weight based on the solid raw material.
  • the organic binder imparts plasticity and fluidity to the slurry and ultimately gives strength to the solid particles formed during spray drying, thereby facilitating handling of the particles before drying and firing.
  • the type of the organic binder for example, one or more selected from the group consisting of polyvinyl alcohol, polyglycol, and methyl cellulose may be used.
  • the content of the organic binder may be, for example, 0.5 to 5 parts by weight based on the solid raw material. If the content is less than 0.5 parts by weight, it may be difficult to maintain the spherical shape until the drying and firing due to the decrease in the bonding strength of the spray-dried solid particles, if the content exceeds 5 parts by weight of the final material by the residual ash after firing There is a risk of deterioration in performance.
  • a pH adjusting agent may be further used.
  • organic amine or ammonia water can be used, for example.
  • the pH adjusting agent may be used in an amount of 0.01 to 10 parts by weight based on the solid material.
  • the method for producing the water gas shift reaction catalyst according to the present invention is not particularly limited.
  • (B) it may be prepared by a method comprising the step of preparing a catalyst by dry baking the prepared solid particles.
  • the slurry composition may be prepared by mixing the aforementioned solid raw material in a solvent.
  • the solid raw material may include an active ingredient, a support, an inorganic binder, and an accelerator, and the active ingredient, the support, an inorganic binder, and an accelerator may be used without limitation the above-described type, and the content thereof is also within the aforementioned content range.
  • an active ingredient a support, an inorganic binder, and an accelerator
  • the active ingredient, the support, an inorganic binder, and an accelerator may be used without limitation the above-described type, and the content thereof is also within the aforementioned content range.
  • the slurry composition according to the present invention comprises the steps of preparing a mixture of a solvent and a solid raw material
  • the mixture may be prepared by stirring and grinding.
  • the solvent may be used in the above-described kind, and specifically, water may be used.
  • the content of the solid raw material in the present invention may be 20 to 50 parts by weight based on 100 parts by weight of the solvent.
  • the organic additive in the step of adding the organic additive to the mixture of the present invention, one or more selected from the group consisting of a dispersant, an antifoaming agent, and an organic binder may be used.
  • a dispersant an antifoaming agent and an organic binder
  • a pH adjusting agent may be further added to the mixture.
  • the dispersant, the antifoaming agent, and the organic binder may be used in the above-mentioned kinds and contents.
  • the stirring may be performed in the process of adding the components included in the mixture, and / or in a state where all of them are added, and may be performed using a stirrer.
  • the type of the stirrer used is not particularly limited, and a general stirrer, a double helix mixer, a high speed emulsifier, a homogenizer, a high shear blender or an ultrasonic homogenizer may be used. homogenizer) and the like, and may be selectively used depending on the amount of raw material to be added.
  • the solid raw material particles can be finely ground and homogeneously dispersed.
  • an additional antifoaming agent and a dispersant may be used as necessary during the grinding, and a stable slurry may be prepared using an additional pH adjusting agent.
  • a wet milling method may be used to improve the grinding effect and to solve problems such as blowing of particles generated during dry grinding.
  • the grinding is performed using a grinder, and the type of the grinder used is not particularly limited.
  • a roller mill, a ball mill, an attrition mill, A planar mill, bead mill, or high energy bead mill can be used.
  • a high energy bead mill can be preferably used.
  • the filling amount of the bead (grind), which is the pulverization medium is preferably 60% to 80% based on the volume of the grinding container when grinding and homogenizing.
  • Beads, which are grinding media may use Yttria stabilized zirconia beads, which are excellent in strength and stability.
  • the size of the ball is preferably 0.3 to 1.25 mm.
  • the grinding may be performed two or more times to produce a homogeneous slurry.
  • a dispersant and an antifoaming agent may be added to the slurry (mixture) in order to perform the next pulverization, thereby controlling the fluidity of the slurry to facilitate the transfer through the pump.
  • an organic binder may be added prior to final grinding to uniformly mix the slurry.
  • the average diameter of the particles in the ground mixture may be 3 ⁇ m or less, preferably 1 ⁇ m or less.
  • the slurry composition which has been ground, can be used to adjust specificity such as concentration and viscosity by using a dispersant, an antifoaming agent or an additional solvent.
  • the grinding process may be omitted.
  • Preparation of the slurry composition of the present invention may further comprise the step of removing the foreign matter contained in the slurry after preparing the slurry composition.
  • the step of removing the foreign matter there is a sieve method or a vacuum sieve method.
  • Drying the slurry composition of the present invention into a solid particle by spray drying may be performed using a spray dryer.
  • the drying is performed by transferring the slurry composition to the spray dryer using a pump, and then spraying the transferred slurry into the spray dryer through a pump or the like to form solid particles by the drying.
  • the viscosity of the slurry transferable to the said pump can be sprayed as 300 cP or more, for example.
  • the operating conditions of the spray dryer for forming the catalyst particles in the spray dryer in the present invention may apply the operating conditions generally used in this field.
  • the spray method of the slurry composition in the present invention may use a countercurrent spray method for spraying in the direction opposite to the flow of the drying air using a pressure nozzle. That is, in order to control the average particle size of the particles in the spray dryer and increase the residence time of the particles sprayed in the dryer, a countercurrent spray method may be used in which a pressurized nozzle is installed at the bottom of the dryer.
  • the shape, particle size, particle distribution and structure of the catalyst particles are affected by the concentration, viscosity, dispersion degree of the slurry composition, injection pressure of the slurry composition, injection amount, drying capacity and temperature of the spray dryer, the spray dryer
  • the structure and spray form of can be adjusted to suit.
  • the injection pressure of the spray dryer may be 4 to 15 kg / cm 2
  • the inner diameter of the pressure nozzle is 0.4 to 1.6 mm
  • the inlet temperature of the dryer 240 to 300 °C and the outlet temperature may be 90 to 180 °C.
  • the particle size distribution of the solid particles produced in this step is preferably 30 to 500 ⁇ m.
  • step (B) is a step of producing a catalyst particle by dry firing the solid particles prepared in step (A).
  • step (B) the solid particles may be dried and then calcined to prepare catalyst particles.
  • Drying in the present invention may be carried out by drying the molded solid particles in a reflux dryer of 100 to 120 °C for 2 hours or more. At this time, drying is performed in an air atmosphere.
  • the dried particles are placed in a high temperature firing furnace to raise the final firing temperature to 350 to 1000 ° C. at a rate of 0.5 to 10 ° C./min, and then fired for 2 hours or more.
  • the stagnation section of each 30 minutes or more at a stagnation temperature of two or more steps up to the final firing temperature may be fired.
  • firing may use a firing furnace such as a muffle furnace, a tubular furnace, or a kiln.
  • a firing furnace such as a muffle furnace, a tubular furnace, or a kiln.
  • the method of firing the solid particles is not particularly limited, and the method of firing the solid particles by fluidization, the method of firing without fluidization, or the method of rotating and firing the particles in a cylindrical kiln such as Rotary Kiln may be used. .
  • the firing may be performed in an atmosphere of air, nitrogen, hellum, hydrogen, water, or reducing gas, and the flow rate of the atmospheric gas may be variously applied according to the type and size of the firing furnace, for example , 60 ml / min or more.
  • the upper limit of the flow rate is not particularly limited.
  • the organic additives (dispersant, antifoaming agent and organic binder) introduced during the preparation of the slurry by the firing are burned, and the strength of the particles is improved by bonding between the raw materials.
  • the present invention also relates to a water gas shift reaction catalyst.
  • the catalyst according to the invention comprises at least one active ingredient selected from the group consisting of copper oxide, zinc oxide and cerium oxide; Support; Inorganic binders; And
  • promoters selected from the group consisting of calcium oxide, barium oxide, strontium oxide, magnesium oxide, zirconium oxide, and barium titania.
  • the catalyst may have a spherical shape. If the shape is not spherical, but donut-shaped or grooved, the wear loss of the particles is increased.
  • the particle size and particle distribution of the catalyst may be 80 ⁇ m to 180 ⁇ m and 30 ⁇ m to 500 ⁇ m, respectively.
  • the packing density of the catalyst of the present invention may be 0.7 g / cc or more.
  • the upper limit of the filling density is not particularly limited and is preferably less than 2.0 g / cc.
  • the wear resistance is represented by the wear index (AI), the lower the wear index means that the wear resistance is better.
  • the wear resistance of the catalyst is not particularly limited and may be 80% or less, and preferably 8% to 68%. When the wear resistance exceeds 80%, a lot of fine powder may be generated, which may make it difficult to use the fluidized bed promoted water gas shift reaction process.
  • the carbon monoxide conversion of the catalyst at 300 ° C or higher may be 60% or more.
  • the carbon monoxide conversion rate refers to the rate at which carbon monoxide is converted to carbon dioxide and hydrogen by reaction with water.
  • the invention also includes a first step of using a catalyst to convert carbon monoxide to carbon dioxide and hydrogen while simultaneously collecting the converted carbon dioxide into the absorbent;
  • the catalyst comprises at least one active ingredient selected from the group consisting of copper oxide, zinc oxide and cerium oxide; Support; Inorganic binders; And
  • a fluidized bed accelerated water gas shift process comprising at least one promoter selected from the group consisting of calcium oxide, barium oxide, strontium oxide, magnesium oxide, zirconium oxide and barium titania.
  • Syngas produced in a gasifier or the like contains carbon monoxide and hydrogen as main components.
  • the conversion of carbon monoxide may be activated by a catalyst.
  • the catalyst is one or more active ingredients selected from the group consisting of copper oxide, zinc oxide and cerium oxide; Supports, inorganic binders and
  • promoters selected from the group consisting of calcium oxide, barium oxide, strontium oxide, magnesium oxide, zirconium oxide, and barium titania.
  • Carbon dioxide produced by the reaction may be captured by the absorbent.
  • the kind of the absorbent is not particularly limited.
  • an absorbent including a metal oxide containing an active ingredient, a support, an inorganic binder, and a transition metal can be used.
  • the active ingredient of the absorbent in the present invention is at least one selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal carbonates, alkaline earth metal bicarbonates, alkali metal hydroxides, alkaline earth metal hydroxides and carbonate precursors
  • alkali metal oxides alkaline earth metal oxides
  • alkali metal carbonates alkali metal bicarbonates, alkaline earth metal carbonates, alkaline earth metal bicarbonates, alkali metal hydroxides, alkaline earth metal hydroxides and carbonate precursors
  • the carbonate precursor means a material that can be converted to carbonate.
  • one or more selected from the group consisting of alumina, hydrotalcite, silica, ceramic, and magnesia may be used as the support of the absorbent, and the inorganic binder may be one selected from the group consisting of cements, clays, ceramics, and the like.
  • the clays include bentonite or kaolin
  • specific types of ceramics include alumina sol, silica sol or boehmite, and the like.
  • Silicates, calcium aluminates, and the like can be used.
  • the metal oxide containing a transition metal is stabilized titanium oxide, zirconium oxide, barium titania (BaTiO 2 ), molybdenum oxide, nickel oxide, cobalt oxide, iron oxide, copper oxide, zinc oxide and yttria stabilization.
  • zirconia Yttria-stabilized zirconia
  • TiO 2 titanium dioxide
  • ZnO zinc oxide
  • the absorbent of the present invention may use 5 to 70 parts by weight of an active ingredient, 5 to 70 parts by weight of a support, 5 to 70 parts by weight of an inorganic binder and 5 to 70 parts by weight of a metal oxide containing a transition metal.
  • the method for preparing the absorbent according to the present invention is not particularly limited, the method comprising: (a) drying the slurry composition to prepare solid particles; And
  • (B) it can be prepared by a method comprising the step of preparing a water absorbent by drying and firing the prepared solid particles.
  • the slurry composition in the present invention comprises the steps of preparing a mixture of a solvent and a solid raw material
  • the mixture may be prepared by a method including stirring and pulverizing.
  • the solid raw material includes a metal oxide containing the active ingredient, support, inorganic binder, and transition metal described above.
  • the type and content of the metal oxide containing the active ingredient, the support, the inorganic binder, and the transition metal included in the solid raw material are as described above.
  • water may be preferably used as the solvent.
  • the step of adding the organic additive and the stirring and pulverizing the mixture may be performed as described above in the preparation of the catalyst.
  • step of preparing the absorbent by dry firing the prepared solid particles of step (b) can also be carried out in the same manner as in step (B) described above in the preparation of the catalyst.
  • the absorbent prepared by the method may have a spherical shape, the particle size and the particle distribution may be 100 to 150 ⁇ m and 30 to 303 ⁇ m, respectively, and the packing density may be 0.6 to 2.0 g / cc.
  • the wear resistance of the absorbent may be 40% or less, the absorption capacity may be 3 to 10% by weight, the regeneration performance may be 70% or more.
  • the second step is to regenerate the absorbent trapped carbon dioxide, the regeneration may be carried out by reacting the absorbent with water vapor.
  • Feeding the absorbent with water vapor and additional heat sources separates the carbon dioxide in the absorbent and regenerates the absorbent.
  • the absorbent regenerated in the present invention may be carried out again in the first step of capturing carbon dioxide.
  • FIG. 1 is a process chart showing a process for preparing a water gas shift reaction catalyst according to the present invention.
  • Figure 2 of the present invention is a process chart showing a process for producing a mixture of a solid raw material and a solvent as a slurry.
  • the slurry is prepared by mixing a solid material in water (solvent) to prepare a mixture (11), adding an organic additive, etc. to the mixture (12), stirring the mixture ( 13) pulverizing and homogenizing the solid raw material 14 and removing the foreign matter contained in the slurry (15).
  • organic additive one or more selected from the group consisting of a dispersant, an antifoaming agent, and an organic binder may be used, and preferably all may be used.
  • FIG. 3 is a process chart showing a process of forming a solid particle by spray drying the slurry.
  • the spray drying of the slurry to form the solid particles comprises a step 21 of transferring the slurry to the spray dryer and a step 22 of spraying the transferred slurry into the spray dryer.
  • Figure 4 is a process chart showing a process of producing a catalyst by dry baking the solid particles molded by the spray drying method.
  • the solid particles (catalyst) primarily dried in the spray drying step are prepared as a final catalyst through a calcination process 32 after the drying process 31.
  • a solid slurry was added to water while stirring with a stirrer to prepare a mixed slurry.
  • the content of the solid raw material was 33.2 parts by weight based on 100 parts by weight of the mixed slurry.
  • the dispersant was added prior to the input of raw materials for easy mixing and dispersion of the solid material, or a small amount of the dispersant was added depending on the viscosity of the mixed slurry and the degree of agitation in the sequential loading of the raw materials.
  • the antifoaming agent was added in small amounts depending on the degree of bubbles generated after the dispersant or stirring the slurry.
  • the slurry was sufficiently stirred for 10 minutes or more at a speed of 10000 rpm to 25000 rpm using a double spiral stirrer to prevent sedimentation of particles having a relatively high specific gravity or large sizes in the solid raw material.
  • the slurry was pulverized and homogenized using a high energy bead mill two or more times to prepare a final slurry.
  • additional water, a dispersant, an antifoaming agent, and a pH adjusting agent (organic amine) were added to control the properties of the slurry, such as the viscosity of the slurry, the concentration of the solid raw material and the pH, or to facilitate the operation.
  • Polyethylglycol as an organic binder was added before final grinding to homogeneously disperse the slurry.
  • the final slurry obtained through the characteristics control of the slurry as described above was sieved to remove foreign matter that can be introduced during the manufacturing process.
  • the prepared slurry was dried at 120 ° C. for 2 hours or more in an air atmosphere dryer, and then heated at a heating rate of 0.5 ° C./min to 10 ° C./min to a final firing temperature of 500 ° C. to 650 ° C. in a Muffle Furnace. After the final temperature was maintained for 2 hours or more to prepare a final catalyst.
  • each was maintained at 200 ° C., 400 ° C. and 500 ° C. for 1 hour before reaching the final firing temperature.
  • the shape of the catalyst was measured using a naked eye, an industrial microscope or an electron scanning microscope (SEM).
  • Average particle size and particle size distribution of the catalyst were measured according to the standard method ASTM E-11. At this time, 10g of the catalyst sample was sieved in a sieve shaker for 30 minutes, and then the average particle size and size distribution were calculated according to the calculation method presented.
  • the packing density of the catalyst was measured according to the apparatus and method presented in the standard specification ASTM D 4164-88.
  • Abrasion resistance of the catalyst was measured in accordance with the test method and sequence proposed in the specification using a 3-hole attrition tester manufactured in accordance with ASTM D 5757-95.
  • the wear index (AI) calculated according to the method proposed by ASTM, is expressed as the ratio of the initial sample volume (50 g) of fine powders generated due to abrasion in wear tubes for 5 hours at a flow rate of 10 slpm (standard liters per minute).
  • One of the important indicators of the (fluidized bed or high velocity fluidized bed) process is less than 30% in the fluidized bed process.
  • the wear index (AI) expressed in wear resistance indicates that the smaller the value, the higher the wear strength.
  • CO conversion of the prepared catalyst was carried out using a Batch fluidized bed (2 cm ID) reactor. The conversion was measured at 20 bar and reaction conditions of 300 ° C. to 420 ° C.
  • the gas composition used in the reaction is a simulation of the synthesis gas produced by coal gasification, and the volume percentage is 29.8% carbon monoxide, 13.4% hydrogen, 4.9% carbon dioxide, and 59.1% nitrogen, which is a balance gas. Water was added by steam to adjust the volume ratio of water and carbon monoxide from 1: 1 to 5: 1.
  • Figure 5 shows the shape of the catalyst prepared by the embodiment, the shape of the catalyst prepared by the preparation example is spherical.
  • FIG. 6 is a graph showing the carbon monoxide conversion rate of the catalyst prepared in Preparation Example 9 (the ratio of water and carbon monoxide to steam is 1: 5 when measuring the conversion rate). As shown in the graph, the conversion at 283 ° C or higher indicates a high value of 98% or higher.
  • the water gas shift catalyst prepared by the preparation example of the present invention has a spherical shape, particle size 120 ⁇ 180 ⁇ m, particle distribution 30 ⁇ 330 ⁇ m, filling density 0.7g / cc or more, CO in a temperature range of 300 or more Since the conversion rate is 60% or more and the wear resistance is 80% or less, it not only satisfies the physical properties required in the fluidized bed process, but also has excellent CO conversion rate, so that it can be usefully used for the fluidized bed promoted water gas shift reaction.
  • gamma alumina ⁇ -Al2O3
  • a solid slurry was added to water while stirring with a stirrer to prepare a mixed slurry.
  • the content of the solid raw material was about 25 parts by weight based on 100 parts by weight of the mixed slurry.
  • the dispersant was added prior to the input of raw materials for easy mixing and dispersion of the solid material, or a small amount of the dispersant was added depending on the viscosity of the mixed slurry and the degree of agitation in the sequential loading of the raw materials.
  • the antifoaming agent was added in small amounts depending on the degree of bubbles generated after the dispersant was added or during the stirring of the slurry.
  • the slurry was sufficiently stirred for 10 minutes or more at a speed of 10000 to 25000 rpm using a double spiral stirrer to prevent sedimentation of particles having a relatively high specific gravity or large sizes in the solid raw material.
  • the slurry was pulverized and homogenized using a high energy bead mill two or more times to prepare a final slurry.
  • additional water, a dispersant, an antifoaming agent, and a pH adjusting agent (organic amine) were added to control the properties of the slurry, such as the viscosity of the slurry, the concentration of the solid material, and the pH, or to facilitate the operation.
  • Polyethylglycol as an organic binder was added before final grinding to homogeneously disperse the slurry.
  • the final slurry obtained through the characteristics control of the slurry as described above was sieved to remove foreign matter that can be introduced during the manufacturing process.
  • the final temperature After drying the prepared slurry for 2 hours or more at 120 °C in a dryer of an air atmosphere, the final temperature after raising the temperature at a heating rate of 0.5 to 10 °C / min to a final firing temperature 500 °C to 650 °C in a Muffle Furnace (Muffle Furnace)
  • the final absorbent was prepared by maintaining at least for 2 hours.
  • each was maintained at 200 ° C., 400 ° C. and 500 ° C. for 1 hour before reaching the final firing temperature.
  • Table 4 shows the results measured by measuring the physical properties and carbon dioxide reaction characteristics of the absorbent (A ⁇ M) prepared in Preparation Example 10.
  • FIG. 8 is a graph showing the results of evaluating absorbency for the absorbent prepared by Preparation Example 10. Evaluation of the absorbency was measured using a pressurized thermogravimetric analysis.
  • the CO 2 absorption capacity has a high value of 6 wt% or more even when the absorbent is reused several times.
  • Absorbent according to Preparation Example 10 of the present invention has a spherical shape, the particle size of 100 to 180 ⁇ m, particle distribution 30 to 330 ⁇ m, filling density 0.5g / cc or more, CO 2 absorption capacity 6 to 17% by weight, regeneration performance More than 60% and wear resistance of less than 40% to meet all the physical properties required in the fluidized bed accelerated water gas shift process, it can be easily used in the fluidized bed accelerated water gas shift reaction. .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un catalyseur destiné à un déplacement au gaz à l'eau à sorption améliorée comprenant : un ou plusieurs composants actifs choisis dans un groupe constitué de l'oxyde de cuivre, l'oxyde de zinc et l'oxyde de cérium ; un support ; un liant inorganique ; et un ou plusieurs accélérateurs choisis dans un groupe constitué de l'oxyde de calcium, l'oxyde de baryum, l'oxyde de strontium, l'oxyde de magnésium, l'oxyde de zirconium et le dioxyde de titane baryum, et un procédé de préparation de celui-ci. Selon la présente invention, le catalyseur possède d'excellentes propriétés physiques telles que la densité de charge, la résistance à l'abrasion et similaires et un taux de conversion élevé du CO, ce qui capture et sépare efficacement le dioxyde de carbone. De plus, il est facile de produire le catalyseur en grandes quantités en appliquant une technique de pulvérisation, et les coûts sont bas du fait d'un rendement élevé de production, et ainsi le catalyseur peut être utilisé dans une technique de capture de CO2 à précombustion à faible coût dans un cycle combiné de gazéification intégré, une pile à combustible, un procédé de liquéfaction du charbon, un procédé de fabrication de composé, et similaires.
PCT/KR2010/006682 2010-09-29 2010-09-30 Catalyseur de déplacement au gaz à l'eau à sorption améliorée et procédé de préparation de celui-ci WO2012043905A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100094732A KR101790066B1 (ko) 2010-09-29 2010-09-29 촉진수성가스전환 반응 공정용 촉매 및 그 제조 방법
KR10-2010-0094732 2010-09-29

Publications (1)

Publication Number Publication Date
WO2012043905A1 true WO2012043905A1 (fr) 2012-04-05

Family

ID=45893328

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2010/006682 WO2012043905A1 (fr) 2010-09-29 2010-09-30 Catalyseur de déplacement au gaz à l'eau à sorption améliorée et procédé de préparation de celui-ci

Country Status (2)

Country Link
KR (1) KR101790066B1 (fr)
WO (1) WO2012043905A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105478131A (zh) * 2014-10-09 2016-04-13 中国石油化工股份有限公司 Co中高压低温耐硫预变换催化剂及其制备方法
WO2016154514A1 (fr) * 2015-03-26 2016-09-29 Basf Corporation Catalyseurs d'hydrogénolyse présentant une grande tolérance aux acides
CN109867290A (zh) * 2019-04-21 2019-06-11 左海珍 一种化学机械抛光液用硅溶胶及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101460911B1 (ko) * 2013-09-30 2014-11-13 한국전력공사 고 열전도성 유동층용 수성가스전환 촉매 조성물 및 이를 포함하는 수성가스전환 촉매
KR101585792B1 (ko) 2014-09-29 2016-01-14 한국전력공사 이산화탄소 중온 활성 고체 흡수제, 슬러리 조성물 및 이의 제조방법
KR102438144B1 (ko) * 2020-06-16 2022-09-01 연세대학교 산학협력단 알칼리 토금속 기반 수성 가스 전환 반응용 촉매 및 이의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010092261A (ko) * 1999-03-18 2001-10-24 이마이 기요스케 수성가스 시프트 반응 촉매, 수소가스중의 일산화 탄소제거방법 및 연료전지 발전(發電) 시스템
US6627572B1 (en) * 2002-03-22 2003-09-30 Sud-Chemie Inc. Water gas shift catalyst
KR20050103568A (ko) * 2004-04-26 2005-11-01 한국과학기술연구원 고성능 수성가스 전환 반응용 촉매와 이의 제조방법
KR20090057554A (ko) * 2007-12-03 2009-06-08 주식회사 에코프로 수성가스 전환반응을 위한 촉매, 이의 제조방법 및 이를이용한 수성가스 전환 방법
KR20090072534A (ko) * 2007-12-28 2009-07-02 삼성전자주식회사 비자연발화성 수성가스 쉬프트 반응 촉매 및 그 제조 방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7238333B2 (en) * 2004-03-18 2007-07-03 General Motors Corporation High activity water gas shift catalysts with no methane formation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010092261A (ko) * 1999-03-18 2001-10-24 이마이 기요스케 수성가스 시프트 반응 촉매, 수소가스중의 일산화 탄소제거방법 및 연료전지 발전(發電) 시스템
US6627572B1 (en) * 2002-03-22 2003-09-30 Sud-Chemie Inc. Water gas shift catalyst
KR20050103568A (ko) * 2004-04-26 2005-11-01 한국과학기술연구원 고성능 수성가스 전환 반응용 촉매와 이의 제조방법
KR20090057554A (ko) * 2007-12-03 2009-06-08 주식회사 에코프로 수성가스 전환반응을 위한 촉매, 이의 제조방법 및 이를이용한 수성가스 전환 방법
KR20090072534A (ko) * 2007-12-28 2009-07-02 삼성전자주식회사 비자연발화성 수성가스 쉬프트 반응 촉매 및 그 제조 방법

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105478131A (zh) * 2014-10-09 2016-04-13 中国石油化工股份有限公司 Co中高压低温耐硫预变换催化剂及其制备方法
CN105478131B (zh) * 2014-10-09 2018-09-21 中国石油化工股份有限公司 Co中高压低温耐硫预变换催化剂及其制备方法
WO2016154514A1 (fr) * 2015-03-26 2016-09-29 Basf Corporation Catalyseurs d'hydrogénolyse présentant une grande tolérance aux acides
CN107635660A (zh) * 2015-03-26 2018-01-26 巴斯夫公司 具有高酸耐受性的氢解催化剂
US10350577B2 (en) 2015-03-26 2019-07-16 Basf Corporation Hydrogenolysis catalysts with high acid tolerance
US11077428B2 (en) 2015-03-26 2021-08-03 Basf Corporation Hydrogenolysis catalysts with high acid tolerance
CN109867290A (zh) * 2019-04-21 2019-06-11 左海珍 一种化学机械抛光液用硅溶胶及其制备方法
CN109867290B (zh) * 2019-04-21 2020-11-27 徐州天骋智能科技有限公司 一种化学机械抛光液用硅溶胶及其制备方法

Also Published As

Publication number Publication date
KR20120033129A (ko) 2012-04-06
KR101790066B1 (ko) 2017-10-26

Similar Documents

Publication Publication Date Title
WO2012043904A1 (fr) Particule hybride destinée à un procédé de réaction de déplacement au gaz à l'eau à sorption sur lit fluidisé améliorée et procédé de préparation de celle-ci
WO2012043905A1 (fr) Catalyseur de déplacement au gaz à l'eau à sorption améliorée et procédé de préparation de celui-ci
WO2012033250A1 (fr) Absorbant de dioxyde de carbone et son procédé de fabrication
WO2013065880A1 (fr) Absorbant solide de dioxyde de carbone comprenant une amine ou un composé de cette amine, destiné à être utilisé dans le procédé de capture du dioxyde de carbone par voie sèche, et procédé de fabrication dudit absorbant
WO2013048191A2 (fr) Absorbant de dioxyde de carbone, et son procédé de préparation
WO2012043960A1 (fr) Particules transporteurs d'oxygène et leur procédé de fabrication
WO2016052838A1 (fr) Sorbant solide actif mésophile du dioxyde de carbone, composition de suspension et son procédé de préparation
WO2015046715A1 (fr) Composition pour absorbant solide de dioxyde de carbone et absorbant solide de dioxyde de carbone contenant la composition
AU2012317149B2 (en) Fluidized bed aqueous gas-converting catalyst
US20080119356A1 (en) Highly attrition resistant and dry regenerable sorbents for carbon dioxide capture
CN101759430B (zh) 一种制备多孔莫来石的方法
KR101790065B1 (ko) 촉진수성가스전환반응 공정용 하이브리드 입자 및 그 제조 방법
WO2012036336A1 (fr) Agent de désulfuration et procédé de préparation de celui-ci
WO2018066751A1 (fr) Matière première solide pour absorbant de dioxyde de carbone, composition de l'absorbant de dioxyde de carbone la comprenant, et absorbant de dioxyde de carbone préparé à l'aide de celle-ci
WO2018056766A1 (fr) Composition de matière première pour préparer des particules de transport d'oxygène, particules de transport d'oxygène préparées à l'aide de celle-ci, et procédé de préparation de particules de transport d'oxygène
JP2010053016A (ja) 粉体状炭酸カルシウムの焼成方法
JP5412584B2 (ja) 噴霧乾燥方法で成形された亜鉛系脱硫剤及びその製造方法
WO2020004751A1 (fr) Composition de matière première pour la fabrication de particules de transfert d'oxygène, particules de transfert d'oxygène fabriquées à l'aide de celle-ci, et méthode de fabrication de particules de transfert d'oxygène
KR101790068B1 (ko) 촉진수성가스전환반응 공정용 하이브리드 입자 및 그 제조 방법
WO2016140428A1 (fr) Briquette de charbon, son procédé de fabrication, son dispositif de fabrication, procédé de fabrication d'acier doux et dispositif de fabrication d'acier doux
WO2011052825A1 (fr) Particules donneuses d'oxygène pour combustion ou reformage en boucle chimique, et procédé de préparation de ces dernières
JP4181132B2 (ja) 高強度乾式再生用ｃｏ２吸収剤
KR20140080810A (ko) 배가스를 이용한 일산화탄소의 제조방법 및 이의 활용 방법
WO2019078413A1 (fr) Composition de matériau pour préparer des particules de transfert d'oxygène, particules de transfert d'oxygène préparées à l'aide de celle-ci, et méthode de préparation de particules de transfert d'oxygène
KR101191086B1 (ko) 분무건조방법으로 성형된 아연계 탈황제 및 그 제조 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10857906

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10857906

Country of ref document: EP

Kind code of ref document: A1