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WO1995032049A1 - Support pour sorbants chimiques - Google Patents

Support pour sorbants chimiques Download PDF

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Publication number
WO1995032049A1
WO1995032049A1 PCT/US1995/006449 US9506449W WO9532049A1 WO 1995032049 A1 WO1995032049 A1 WO 1995032049A1 US 9506449 W US9506449 W US 9506449W WO 9532049 A1 WO9532049 A1 WO 9532049A1
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WO
WIPO (PCT)
Prior art keywords
sorbent
production
mixture
coated
geode
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.)
Ceased
Application number
PCT/US1995/006449
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English (en)
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WO1995032049A9 (fr
Inventor
Robert J. Copeland
Jianhan Yu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDA Research Inc
Original Assignee
TDA Research Inc
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Filing date
Publication date
Application filed by TDA Research Inc filed Critical TDA Research Inc
Priority to AU26002/95A priority Critical patent/AU2600295A/en
Publication of WO1995032049A1 publication Critical patent/WO1995032049A1/fr
Publication of WO1995032049A9 publication Critical patent/WO1995032049A9/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • 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
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0222—Compounds of Mn, Re
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
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    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/024—Compounds of Zn, Cd, Hg
    • B01J20/0244—Compounds of Zn
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
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    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
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Definitions

  • This invention relates to high temperature hydrogen sulfide removal from coal-derived fuel gases, including the use of a new structure for carrying a regenerable sorbent agent for absorbing hydrogen sulfide while recovering elemental sulfur.
  • the new structure is identified as a "geode", more particularly, the geodes of this invention provide a very long-lived sorbent for multiple regeneration cycles under the conditions expected in a high temperature plant.
  • the geodes of this invention have particular utility for the removal of sulfur contaminants from the gaseous product of coal fueled power plants and coal synthetic fuels plants.
  • Coal gasification plants carry the promise of highly efficient utilization of coal.
  • Electrical energy for example, can be generated by the partial oxidation of coal in a gasifier/molten carbonate fuel cell system (MCFC) or in an integrated gasification combined cycle (IGCC) plant.
  • An IGCC plant generates power by the direct contact of hot coal-derived gases with turbine blades, and is one of the most promising new technologies for the production of base-load electric power from coal.
  • Coal-derived gases contain particulates, tars, ammonia, alkali metals, and sulfur. These materials are not only pollutants, but can cause corrosion, erosion or deposition on the turbine blades of a power plant.
  • Coal-derived gases contain significant levels of sulfur contamination. When coal is gasified, most of the total sulfur content is converted to hydrogen sulfide (H 2 S) .
  • the hydrogen sulfide concentration in the coal gas depends on the amount of sulfur initially present in the coal and on the nature of the coal gasification process used. Gas-phase concentrations of hydrogen sulfide on the order of several thousand parts per million (ppm) are typical, and 2,000 to 10,000 ppm is not unusual. Sulfur contamination of the coal gas is an environmental problem and also an operational problem. Because sulfur is a useful chemical, its recovery is also worthwhile economically.
  • sulfur is valuable as a constituent of sulfuric acid, the largest single chemical consumed in the United States (over 11 million long tons of sulfur consumed in 1988) .
  • elemental sulfur is typically recovered by steam injection from underground deposits, but this is thermally inefficient.
  • Natural gas and petroleum processing is another large source, but these show signs of decline in the United States. Accordingly, if elemental sulfur were to be re- covered as a by-product of the desulfurization of coal gas, the recovered sulfur would have a ready market.
  • an IGCC plant To recover sulfur from the coal gas stream and to minimize the emission of sulfur compounds, an IGCC plant typically operates with a reaction step and a separate sulfur removal step.
  • reaction step coal is converted to product gas (synthesis gas, or "syngas") at high temperature.
  • sulfur removal step physi ⁇ cal solvents are generally used to remove sulfur products and other contaminants from the crude syngas.
  • An IGCC plant has the potential for higher conversion efficiency, lower capital costs, and lower pollution impacts than pulverized coal-fired combustion even when used with cold gas cleanup systems.
  • a "hot gas” cleanup system capable of removing sulfur from the coal gas stream at high temperatures, in the range of 500 - 800°C.
  • hot gas cleanup can reduce capital costs and improve overall conversion cycle efficiency by elim- inating the need to cool and reheat the gasifier outlet gases. It can also reduce wastewater disposal costs.
  • Other coal gasification technologies besides IGCC and MCFC applications that would significantly benefit from hot gas cleanup include gasifier/diesel engine combina- tions, and processes for producing synthetic fuels from coal.
  • the most developed candidate is zinc ferrite (ZnFe 2 0 « ) : which reacts as follows with the hydrogen sul ⁇ fide (H 2 S) contaminant of coal-derived gases to form zinc and iron sulfides (ZnS and FeS) :
  • Sulfur dioxide is a contaminant that must then be disposed of itself.
  • the standard recovery method is to react the sulfur dioxide with limestone, producing ash.
  • DSRP Direct Sulfur Recovery Processes
  • a successful sorbent must, therefore, be able to remove sulfur so as to leave sulfur levels in the gas stream of 20 ppm or less (a recovery rate greater than 99.8%); and it must also have physical and chemical stability in gas atmospheres of 500°C and above. A sorbent pellet will be reused in successive absorption cycles.
  • the pellet must be long-lived or, if short ⁇ lived, must be easily refabricated.
  • the sorbent's physical characteristics affect its suitability for use in high temperature desulfurization. Among the relevant characteristics are durability, temperature stability, life span, and rate of utilization. Sorbent pellets are subject to physical and chemical degradation over successive process cycles: they may be broken by mechanical transport, fractured by multiple chemical reactions, and contaminated by gasifier ash, which is not removed by upstream filtering.
  • the desired process would subject the sorbent pellets used in the system to conditions of heat, chemical reaction and pulverizing forces, which tend to degrade the pellets, there is an additional need for a suitable pellet. If a long-lived pellet is not commer ⁇ cially feasible, the desired pellet must be one that is short-lived. The desired short-lived pellet must be ca- pable of being refabricated. Accordingly, a method for the inexpensive recovery and reuse of the tin (or other metal species) from the degraded sorbent pellets is de ⁇ sirable. The desired method would involve the periodic removal of degraded pellets, the chemical recovery of the metal species from the degraded pellet, and the re- fabrication of the high surface area tin oxide (or other metal oxide) in a new pellet.
  • a unique chemical feature of the system of United States Patent No. 5,271,907 is that, after the stannic oxide and zinc ferrite absorb the sulfur contaminants from the hot gas stream, the two sorbents can be regen ⁇ erated in two stages.
  • the zinc ferrite is regenerated, forming a sulfur dioxide (S0 2 ) by-product.
  • the tin oxide is regenerated. Because sulfur dioxide is one of the required species for the regeneration of the tin oxide, this otherwise unde- sirable species is consumed as part of the reaction, producing the regenerated tin oxide and elemental sulfur, which can be reclaimed and resold.
  • a system for refabricating the sorbent pellets is also described in United States Patent No. 5,271,907.
  • the instant invention relates to solving the problems of a long-lived pellet suitable for use in the system of United States Patent No. 5,271,907, and this invention should be understood with reference to the prior disclosures of United States Patent No. 5,271,907 and of United States Patent Application No. 08/170,580, both of which are incorporated herein by reference.
  • This invention includes a new sorbent fabrication method.
  • the new method creates a heterogeneous mixture of two components: a chemically active material (stannic oxide, zinc oxide, zinc ferrite, or other first or second sorbents) in the preferred embodiment of this invention within the system of United States Patent No. 5,271,907 and an inert binder material.
  • a chemically active material stannic oxide, zinc oxide, zinc ferrite, or other first or second sorbents
  • a "geode" pellet is formed.
  • the geode has an inner core and an exterior shell.
  • the inner core of the geode is constituted by the sorbent (that is, the chemically active material) and the exterior shell is constituted by the support material (that is, the binder) .
  • the chemically active material needs to carry little or no structural load because it is supported by the shell.
  • the exterior shell is porous (to allow gases to diffuse to the inner core of chemically active material) , inert (to retain its mechanical strength through multiple cycling) , durable, and strong.
  • the chemically active material is shaped and formed into a sphere or like shape, and the shell made of inert material is applied as a coating around the inner core.
  • the chemically active material is mixed with an oil (or water) and the inert material is mixed with water (or oil) and the two materials are then mixed together. Since the oil and the water will not mix, two phases form in the final mixture which yields a sorbent that is strong and has small regions of chemically active material surrounded by a matrix of the strong inert material.
  • the geodes of this invention can produce a sorbent with high strength and durability of a supported sorbent, accompanied by a relatively higher chemical content (in the inner core material) and relatively low costs.
  • the geode sorbents of this invention should have a useful life of 200 to 300 cycles within the conditions in the system for high temperature sulfur removal system by regenerable agents as described in United States Patent No. 5,271,907.
  • FIG. 1 is a schematic view of the first embodiment of a geode produced according to this invention.
  • FIG. 2 is a chart showing experimental results of testing on a second embodiment of a geode produced according to this invention.
  • a 275.5 g sample was tested at 130 psia at a temperature of 573°-727° with 78% of the H 2 S removed and a sulfur loading at 8.4% at the end of the test.
  • FIG. 3 is a chart showing experimental results of additional testing on the geode of FIG. 2 at a 0.4763% per cycle mass loss rate.
  • FIG. 4 is a schematic cross-sectional view of a portion of an alternate embodiment of a geode produced according to this invention.
  • Adding chemically active material to a performed inert pallet, or extrudate, or agglomerate is a well established procedure for both catalyst and chemical sorbent. (The result produced by this known procedure will be referred to as a "supported sorbent".)
  • the performed inert material supports the mechanical loads cn the sorbent and eliminated any need for the chemically active material to contribute to the mechanical strength of the sorbent.
  • the sorbent can change radically during application without affecting the life of the sorbent pellet.
  • Still others could be loaded with high quantities of stannic oxide and remain strong, but the pores were too large to retain the stannic oxide when handled (e.g., during shipping the stannic oxide would fall out) . All of these supported sorbents were relatively expensive and the process to load the stannic oxide was even more expensive.
  • the sorbent fabrication method of this invention produces sorbent with the strength and durability of a supported sorbent but with the higher chemical content (i.e., stannic oxide) and lower costs associated with a sorbent formed by mixing metal oxides before firing.
  • the new fabrication method of this invention provides a structurally durable support, using a shaped heterogenous mixture of two components: a chemically active material (stannic oxide) and an inert material (binder) .
  • the chemically active material [stannic oxide (Sn0 2 ) or zinc oxide (ZnO) ] is shaped and formed into a soft or weak inner core.
  • the inner core carries little or no structural load.
  • the binder material is shaped and formed into an exterior shell, which is porous, chemically inert, and strong.
  • the exterior shell provides the structural strength to support the sorbent.
  • sorbent made by this method is called a "geode", since natural geodes have similar aspects, i.e., a hard, strong outer shell with a hollow interior.
  • the same geode technique can be applied to zinc oxide, zinc ferrite, copper oxide, and other sorbents for H 2 S and other gases (e.g., HC1) for gasified coal, biomass, and other applications.
  • Geodes were formed by two different methods: (a) Type 1 -- coating a formed inner core of chemically active, but weak sorbent (stannic oxide) with an exterior shell of a strong, porous, inert material and firing the composite to a strong form and, (b) Type 2 -- mixing the chemically active material with an oil (or water) and the inert material with water (or oil) and then mixing the two materials together; since the oil and water will not mix, two phases form in the final mixture, and firing that mixture then produces a sorbent which is strong with small regions of chemically active material surrounded by a matrix of the strong inert material.
  • the Type 1 geode forms an exterior shell around a previously formed inner core pellet or spheroid of chemically active material.
  • the coating or exterior shell 12 must be porous to allow gases to diffuse to the interior and it must be chemically inert to retain its mechanical strength with multiple cycling.
  • the inner core 14 is a weak preformed stannic oxide pellet or spheroid with or without a binder used in its preparation. Since it is desirable to maximize the stannic oxide content of the geode, a 100% stannic oxide pellet or extrudate or agglomerate fired at low temperature (i.e., 900°C or lower) to maximize surface area of the sorbent is preferred.
  • structurally weak inner core spheroids 14 formed by agglomeration (2.6 lb £ crush strength with 100% Sn0 2 ) are coated with an outer shell 12 of bentonite (a low cost mineral) forming the strong, chemically inert, and porous outer shell.
  • the resulting geode pellet was fired at 900°C containing 44% Sn0 2 by weight, and had crush strengths > 3 lb f and >30% void volume.
  • the Type 2 method as illustrated in Fig. 4 does not have a single soft or weak inner core of chemically active material (e.g., stannic oxide Sn0 2 ) , but rather has a large array of inner cores 16 formed at one time and a matrix of the inert material 18 (e.g., bentonite, or talc, etc.) forms the structure of the shell, like a honeycomb surrounding the inner cores.
  • the method produces a structure that is rather similar to a honeycomb panel but much smaller and three dimensional.
  • the Type 2 geode inert shell forms the webs of the panel and the voids are filled by the sorbed material.
  • the requirements for the binder material to be used as the shell for both types of geodes are defined as follows. To assure that the binder permits transfer of the molecules, the void fraction of the binder must be moderately high (e.g., >20% of the volume occupied by the inert) . Since the binder must have high strength, it must be fired to sinter it into a load bearing matrix; however, if the chemically active material were also sintered at the same time, the sorbent would lose its surface area and become inactive (thus, for stannic oxide the temperature must be less than 1,000°C, 1,832°F, to prevent sintering) .
  • the void fraction of the binder must be moderately high (e.g., >20% of the volume occupied by the inert) . Since the binder must have high strength, it must be fired to sinter it into a load bearing matrix; however, if the chemically active material were also sintered at the same time, the sorbent would lose its surface area and become inactive
  • Firing temperatures for the binder must also be significantly higher than the expected operating temperature of the application (e.g., 570°C, 1,058°F for hot gas cleanup of gasified coal). If the binder continuously sinters during use, it would lose its porosity and prevent reactants from reaching the chemically active inner core material (stannic oxide) . Thus, and to summarize the foregoing requirements, in a stannic oxide inner core, the required firing temperature of the binder to be used as the shell is above 800°C (1,472°F) and below 1,000°C (1,832°F).
  • the chemically active inner core material must represent a significant fraction of the mass of the geode (e. g. , >25% stannic oxide by weight) .
  • Other sorbents e. g. , ZnO, Fe 2 0 3 , CuO, MnO, V 2 0 s or mixtures of these metal oxides with Sn0 2
  • Requirements of geodes made with zinc oxide, copper oxide, etc. would be somewhat different and would vary with the operating temperature of the application, such requirements could be readily ascertained by one skilled in the art without undue experimentation.
  • the geodes of this invention are a new type of sorbent structure
  • development of the geode structure was conducted in two steps, a) first, the inert binder shell material, firing temperature and porosity were developed, and b) second, the heterogenous geode structure, including the commercially reactive inner core and the inert shell was tested.
  • binders were tested and selections of preferred materials made.
  • Bentonite (HPM 20)TM, Polargel TTM, and VolclagTM had a high crush strength but a low porosity.
  • Graphite added to the inert shell material before mixing with the chemically active material (stannic oxide) increases the porosity of the inert materials with high strength.
  • Two types of bentonites (HPM-20 and Polargel) were tested both with and without graphite. Adding graphite to the binder increased porosity; nevertheless, a high crush strength can still be retained as shown below:
  • binder graph wt % porosity crush cc/g strength lb/mm
  • Suitable binders include borax, silica, alumina, alumina-silicates, sodium silicates, and mixtures of these in any proportion.
  • Type 2 geodes The materials required to prepare the above Type 2 geodes are: graphite powder, an oil mix (kerosene mixed with or without a surfactant, mixed in the oil) , talc, and the high surface area chemical in reactive inner core material (stannic oxide) or chemical precursor (stannous sulfate) .
  • stannic oxide reactive inner core material
  • stannous sulfate stannous sulfate
  • the Y0121-1 is made by first mixing Polargel-T with graphite; 500 g of Polargel are mixed with 56 g of graphite making a 10% by weight mixture of two dry powders. 62 g of water are added, making a 10% by weight mixture with the mixed dry powders. To the 618 g of Polargel mixed with graphite and water, 1,235 g cf stannic oxide mixed with kerosene are added. Due to the presence of the graphite, the mixture will exhibit a predominantly black color but small areas of the white stannic oxide may be seen. The mixing continues until there is no further change in the appearance of the mixture. Water and MethocelTM are added to the composite mixture to help it extrude.
  • Y0121-3 and Y0121-5 geodes have the same formulations and preparation procedures through the green state but are fired at different temperatures, 900°C and 950°C respectively.
  • No graphite was used in the preparation of this material, since the talc (3MgO*4Si0 2 *H 2 0) produces sufficient porosity due to the water contained within the crystal.
  • the talc produces 3 moles of MgSi0 3 with 1.0 mole of excess Si0 2 and this insures that all of the MgO is locked up with silica during regeneration. Equilibrium calculations show that no side reactions should be executed to occur in either absorption or regeneration with the MgSi0 3 or Si0 2 .
  • the preparation of these geodes with talc is as follows. To 500 g of talc, 56 g of water are added and well mixed giving 556 g of damp powder. To the talc plus water mix, 556 g of the stannic oxide mixed with kerosene were added. The 1,112 kg mixture is pressed with added water and MethocelTM as required to extrude a good green pellet. When pressed, small regions of white stannic oxide forming the inner cores within the matrix of the slightly darker talc shell may be seen. The pellets are dried at 125°C for several hours or until the water and kerosene evaporates. The Y0121-3 pellets are fired at 900°C; JY0121-5 is fired at 950°C. No intermediate firing at 600°C is required with these formulations since no graphite is present.
  • Breakthrough characteristics of a Type 2 geode were measured at high pressure and high temperature. This geode was identified as BW0121-1 and is made in the same manner as Y0121-1, but by a different person.
  • H 2 S concentration 78% of the H 2 S was removed was sustained for a very long period of time.
  • the calculated sulfur loading was 8.4%. The data demonstrate that very high loadings can be achieved with this material in high temperature use, even after many previous cycles have been accumulated on the same batch of pellets.
  • the reactor contained 400 grams of the material and was tested both at high space velocity (3450 h" 1 ) with simulated KRW gases and at lower space velocities (2000 h" 1 ) with simulated Texaco gases, diluted with steam (lower space velocity and higher H 2 S concentration) to load the sorbent to the maximum extent, simulating the inlet region of a fixed bed reactor.
  • the inlet region of the reactor was simulated because it has been shown to have the highest sulfur loading, which creates the greatest expected potential for damage to the sorbent with cycling.
  • the geode pellets were removed from the reactor and the mass of whole geode pellets remaining was weighed. Some whole geode pellets were removed and analyzed for the properties of the sorbent. The remaining geode pellets were again weighed before returning them to the reactor.
  • the properties of the BW0121-1 with cycling are given below:
  • the loss rates for a zinc titanate sorbent are also shown in Figure 3; the data are for TRZ-21 as reported by Jung et al . 1 .
  • the zinc titanate sorbents were tested under simulated inlet conditions and Jung et al. report that the zinc titanate is rapidly destroyed under these conditions (2.5% per cycle) .
  • the stannic oxide sorbent losses were very low (0.48%/cycle) , which is most probably a direct result of the geode structure of this invention.
  • the source of the stannic oxide can affect both the cost and properties of the sorbent. By starting with a material that is partially refined and contains significant quantities of impurities, the cost of the stannic oxide
  • stannic oxide (or other chemical sorbent) can be greatly reduced (by avoiding the costs for the purification) .
  • the impact on the properties of the sorbent can also be favorable.
  • a geode was fabricated in the same manner as BW0121-1 but using an impure source of stannic oxide (76% Sn0 2 by weight) . That geode had a strength of 19.7 lb/mm versus 4.6 lb/mm for the same geode made with a pure source of stannic oxide.
  • Several different sorbents were then fabricated with that material and the properties of new and sulfided pellets are shown below:
  • the reduced strength and porosity are typical of the sulfided stannic oxide and other tests have shown that the material regains its strength when regenerated.
  • the testing of the sorbents has also used steam dilution to change the temperature and composition of the modelled coal gas stream.
  • the un-diluted gas stream would reduce Sn0 2 to metallic tin (melting point of 232°C) , a liquid at the operating temperatures of an anticipated hot gas cleanup system (e.g. , 570°C) .
  • the 1529-48-0 extruded geodes were tested with a gas composition, which simulated a low steam KRW gasifier.
  • the gas was 57.5% N 2 , 30.6% H 2 and 11.9% C0 2 with no steam or CO or H 2 S (calculating the reducing potential at 2.57 and equal to a 5% steam gasifier as reported by Gupta (1991) 2 ).
  • H 2 reduced extrudates identified as 1529-48-H2R
  • 1529-48-H2R were then sulfided. After sulfidation they were strong, porous, and had high sulfur loadings; again the bentonite sin ⁇ tered and had a surface area of 1.1 m 2 /g.
  • a geode in zinc oxide was also prepared.
  • the zinc oxide geodes used talc 3 as the inert binder and a mixture of ZnO and Sn0 2 as the sorbent .
  • This geode identified as TZSN40-359 , contained 27.1% ZnO, 8 .67% Sn0 2 , 0 .16% NiO
  • Talc is 3MgO*4Si0 2 *H 2 0 and forms 3MgSi0 3 + SiO- when fired at 900 "C.
  • Talc makes an effective inert binder for SnO.
  • thermodynamic calculations indicate that MgSiO- is inert but that the SiO- will react and form ZnSi0 3 , a compound that does not react with H,S .
  • the zinc silicate removes some of the capacity to remove HJS and may have limited the conversion in this preliminary test . enhancer, and 64.07% talc and other inerts.
  • the geode could absorb up to 13.9% (wt.) S, if 100% of the sorbent is converted to the sulfide, of which 1.9% is due to the Sn0 2 and enhancer and 12.0% to ZnO.
  • the geode was fired at 900°C (1,652°F), which is higher than most zinc oxide based sorbents. We are able to fire at lower temperatures. However, to decompose zinc sulfate, which will form during regeneration, the commercial sorbent will be heated to >.700°C at the end of each regeneration cycle. We fired at 200°C higher
  • the geode was exposed to simulated gases from a KRW gasifier containing 1.0% H 2 S in H 2 , CO, C0 2 , H 2 0, and N 2 for 5 hours at 570°C.
  • the zinc oxide geode absorbed 4.0% S (wt.) or 31.6% of theoretical.
  • the crush strength was 3-5 lb/mm with a porosity of 0.16 cc (water)/g.
  • the data demonstrate that a strong, porous, and chemically active zinc oxide geode can be made.
  • Ti0 2 may also be mixed with the ZnO to form a zinc titanate sorbent, the .addition of Ti0 2 stabilizes the ZnO, especially during high temperature operation (i . e. , to minimize zinc loss by vaporization).

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Abstract

L'invention concerne un procédé pour la désulfurisation à température élevée de gaz dérivés du charbon, utilisant des absorbants chimiques pouvant être regénérés. Une nouvelle structure pour un absorbant chimique, appelée 'géode', comporte une partie centrale intérieure (14) et une enveloppe extérieure (12). La partie centrale intérieure (14) de la géode est constituée par un matériau chimiquement actif, et l'enveloppe extérieure (12) est constituée d'un matériau de support. Le matériau chimiquement actif ne doit porter qu'une charge structurelle faible ou nulle car il est supporté par l'enveloppe extérieure (12). L'enveloppe extérieure (12) est poreuse (de manière à permettre aux gaz de se diffuser vers la partie centrale intérieure (14) du matériau chimiquement actif), inerte (pour conserver sa résistance mécanique pendant de multiples cycles), durable et résistante. La géode permet de regénérer le matériau chimiquement actif de la partie centrale intérieure (14) dans diverses conditions de traitement. La géode permet également de produire des supports de catalyseurs très résistants à grande surface.
PCT/US1995/006449 1994-05-23 1995-05-22 Support pour sorbants chimiques Ceased WO1995032049A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
FR2794993A1 (fr) * 1999-06-18 2000-12-22 Air Liquide Utilisation d'un adsorbant particulaire non homogene dans un procede de separation de gaz
FR2843049A1 (fr) * 2002-08-01 2004-02-06 Inst Francais Du Petrole Adsorbant non homogene et son utilisation dans des procedes de separation diffusionnelle
US20130204065A1 (en) * 2012-02-06 2013-08-08 Uop Llc Protected Adsorbents for Mercury Removal and Method of Making and Using Same
CN104190434A (zh) * 2014-08-22 2014-12-10 哈尔滨工业大学 Fe3O4-MnO2复合催化剂的制备及利用其去除印染废水中有机染料的方法

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US3755202A (en) * 1971-07-01 1973-08-28 Inst Neftechimicheskogo Sintez Method for reactivation of oxide catalysts
US4143123A (en) * 1976-06-25 1979-03-06 Atomic Energy Of Canada Limited Process for the exchange of hydrogen isotopes between streams of gaseous hydrogen and liquid water
US4442078A (en) * 1982-07-07 1984-04-10 The United States Of America As Represented By The United States Department Of Energy Method of removing hydrogen sulfide from gases utilizing a zinc oxide sorbent and regenerating the sorbent
US4729889A (en) * 1985-03-29 1988-03-08 California Institute Of Technology High temperature regenerative H2 S sorbents
WO1990014876A1 (fr) * 1989-05-29 1990-12-13 Haldor Topsøe A/S Purification de gaz contenant du sulfure
US5182016A (en) * 1990-03-22 1993-01-26 Regents Of The University Of Minnesota Polymer-coated carbon-clad inorganic oxide particles
US5248489A (en) * 1989-06-07 1993-09-28 Phillips Petroleum Company Selective removal of hydrogen sulfide over a zinc oxide and silica absorbing composition

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US3755202A (en) * 1971-07-01 1973-08-28 Inst Neftechimicheskogo Sintez Method for reactivation of oxide catalysts
US4143123A (en) * 1976-06-25 1979-03-06 Atomic Energy Of Canada Limited Process for the exchange of hydrogen isotopes between streams of gaseous hydrogen and liquid water
US4442078A (en) * 1982-07-07 1984-04-10 The United States Of America As Represented By The United States Department Of Energy Method of removing hydrogen sulfide from gases utilizing a zinc oxide sorbent and regenerating the sorbent
US4729889A (en) * 1985-03-29 1988-03-08 California Institute Of Technology High temperature regenerative H2 S sorbents
WO1990014876A1 (fr) * 1989-05-29 1990-12-13 Haldor Topsøe A/S Purification de gaz contenant du sulfure
US5248489A (en) * 1989-06-07 1993-09-28 Phillips Petroleum Company Selective removal of hydrogen sulfide over a zinc oxide and silica absorbing composition
US5182016A (en) * 1990-03-22 1993-01-26 Regents Of The University Of Minnesota Polymer-coated carbon-clad inorganic oxide particles

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2794993A1 (fr) * 1999-06-18 2000-12-22 Air Liquide Utilisation d'un adsorbant particulaire non homogene dans un procede de separation de gaz
FR2843049A1 (fr) * 2002-08-01 2004-02-06 Inst Francais Du Petrole Adsorbant non homogene et son utilisation dans des procedes de separation diffusionnelle
WO2004012835A3 (fr) * 2002-08-01 2004-07-22 Inst Francais Du Petrole Adsorbant non homogene et son utilisation dans des procedes de separation diffusionnelle
US7435699B2 (en) 2002-08-01 2008-10-14 Institut Francais Du Petrole Heterogeneous adsorbent and the use for diffusional separation methods
US20130204065A1 (en) * 2012-02-06 2013-08-08 Uop Llc Protected Adsorbents for Mercury Removal and Method of Making and Using Same
US9006508B2 (en) * 2012-02-06 2015-04-14 Uop Llc Protected adsorbents for mercury removal and method of making and using same
CN104582834A (zh) * 2012-02-06 2015-04-29 环球油品公司 用于汞脱除的保护吸附剂及其制备和使用方法
CN104190434A (zh) * 2014-08-22 2014-12-10 哈尔滨工业大学 Fe3O4-MnO2复合催化剂的制备及利用其去除印染废水中有机染料的方法

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