WO2015101768A1 - Sorbant pour composés halogénés - Google Patents

Sorbant pour composés halogénés Download PDF

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Publication number
WO2015101768A1
WO2015101768A1 PCT/GB2014/053672 GB2014053672W WO2015101768A1 WO 2015101768 A1 WO2015101768 A1 WO 2015101768A1 GB 2014053672 W GB2014053672 W GB 2014053672W WO 2015101768 A1 WO2015101768 A1 WO 2015101768A1
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Prior art keywords
sorbent
alkali metal
particulate
metal compound
calcium silicate
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PCT/GB2014/053672
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English (en)
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David Jonathan Davis
Michelle Taylor WILSON
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Johnson Matthey Public Limited Company
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Publication of WO2015101768A1 publication Critical patent/WO2015101768A1/fr

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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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/14—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 by absorption
    • 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
    • B01D53/68—Halogens or halogen compounds
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • 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
    • B01J20/28002—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
    • 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
    • B01J20/2803—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
    • 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
    • B01J20/3007—Moulding, shaping or extruding
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3028—Granulating, agglomerating or aggregating
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1122—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B01D2256/245—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • 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
    • B01D53/68—Halogens or halogen compounds
    • B01D53/685—Halogens or halogen compounds by treating the gases with solids

Definitions

  • This invention relates to sorbents for halogen compounds, and methods for making and using such sorbents, Sorbents for halogen compounds such as hydrogen chloride present in gaseous or liquid refinery streams may be removed using alkalised alumina or zinc oxide materials.
  • WO9522403(A1) discloses an absorbent for hydrogen chloride in the form of granules, preferably having a particle size greater than 2 mm and a BET surface area of at least 10m 2 /g, comprising an intimate mixture of an alumina component selected from alumina and/or hydrated alumina, an alkali component selected from sodium carbonate and/or sodium bicarbonate in weight proportions of 0.5 to 2 parts of said alkali component per part of said alumina component, and a binder, said granules containing from 5 to 20 % by weight of said binder and having an alkali component content such that, after ignition of a sample of the granules at 900 DEG C, the sample has a sodium oxide, Na 2 0, content of at least 20 % by weight.
  • W09939819(A1) discloses shaped absorbent units suitable for use as chloride absorbents comprising a calcined intimate mixture of an alkali or alkaline earth, zinc and aluminium components having an alkali or alkaline earth metal to zinc atomic ratio in the range 0.5x to 2.5x and an alkali or alkaline earth metal to aluminium atomic ratio in the range 0.5x to 1 .5x, where x is the valency of the alkali or alkaline earth metal, and containing from 5 to 20 % by weight of a binder.
  • Preferred compositions are made from sodium carbonate or bicarbonate, basic zinc carbonate or zinc oxide and alumina or hydrated alumina.
  • JP58177136(A) discloses a method to prepare a fluidisable absorbent for removing acidic gases from an exhaust gas, wherein an alkaline earth metal particle comprising a Ca compound such as limestone or quick lime or a Mg compound such as magnesium hydroxide and a cement such as Portland cement or alumina cement are kneaded and hydrated while hydroxide is partially liberated. These materials require insoluble alkaline earth components as the active sorbent material, which is used in a fluidised state in exhaust gas treatment.
  • JP2000288389 discloses a method for producing an adsorbent for a high temperature acidic exhaust gas in which a mixture of amorphous calcium silicate hydrate and sodium aluminate is subjected to hydrothermal treatment.
  • alkali metal compound-containing hydrated calcium silicate cement compositions are surprisingly effective sorbents for halogen compounds.
  • the invention provides a method for preparing a sorbent comprising the steps of:
  • the particulate alkali metal compound comprises an oxide, hydroxide, carbonate or hydrogen carbonate and the sorbent is shaped before and/or after the treatment with water.
  • the invention further provides a sorbent obtainable by the method in the form of a shaped unit comprising a hydrated calcium silicate cement and an alkali metal compound, and the use of the sorbent in removing halogen compounds from fluid streams, particularly refinery fluid streams.
  • absorbent we include absorbent and adsorbent.
  • calcium silicate cement we mean compositions containing one or more calcium silicates that react with water to form hardened solid masses.
  • a particularly suitable calcium silicate cement is Portland cement, which is the product of grinding Portland cement clinker (more than 90%), a limited amount of calcium sulphate (which controls the set time) and up to 5% minor constituents as allowed by various standards such as the European Standard EN 197-1 .
  • Portland cement clinker is a hydraulic material which consists of at least two-thirds by mass of calcium silicates (3 CaO Si0 2 and 2 CaO Si0 2 ), the remainder consisting of aluminium- and iron-containing clinker phases and other compounds.
  • the ratio of CaO to Si0 2 is not less than 2.0.
  • the magnesium oxide content (MgO) does not exceed 5.0% by mass.
  • Typical Portland cements comprise;
  • All types of Portland cement may be used to prepare the sorbent.
  • ASTM C150 Types I, II, III, IV and type V and EN 197-1 Types I, II, III, IV and V including ordinary Portland cement, Portland composite cement, blast-furnace cement, pozzolanic cement and composite cement, which may include artificial or natural pozzolans.
  • the particulate calcium silicate cement may have a broad particle size range.
  • Portland cements may comprise 15% by mass of particles below 5 ⁇ diameter, and 5% of particles above 45 ⁇ , i.e. 80% by mass of the particles have a particle size between 5 and 45 ⁇ .
  • the measure of fineness usually used is the specific surface area, which is the total particle surface area of a unit mass of cement.
  • the rate of initial reaction (up to 24 hours) of the cement on addition of water is directly proportional to the specific surface area. Typical values are 320-380 m 2 kg ⁇ 1 for general purpose cements, and 450-650 m 2 kg ⁇ 1 for "rapid hardening" cements.
  • Such calcium silicate cements are readily commercially available.
  • the particulate calcium silicate cement is mixed with a particulate alkali metal compound.
  • the particulate alkali metal compound may be a sodium compound, a potassium compound or a mixture of these.
  • the particulate alkali metal compound may be an oxide, hydroxide, carbonate or hydrogen carbonate. Alkali metal oxides, carbonates and hydrogen carbonates are preferred. Good results have been obtained simply using sodium carbonate and/or potassium carbonate.
  • the particulate alkali metal compound content of the mixture is in the range 5-90% by weight, more preferably 20-75% by weight, most preferably 30-60% by weight.
  • the particulate alkali metal compound content of the sorbent, which has been treated with water is in the range 3-86% by weight, more preferably 10-72% by weight, most preferably 15- 58% by weight.
  • the particulate alkali metal compound may be in the form of a powder, preferably with an average particle size, [D 50 ], in the range 5-100 ⁇ .
  • the mixture of particulate calcium silicate cement and particulate alkali metal compound may further comprise a binder, such as clays, including bentonite, sepiolite, minugel and attapulgite clays; calcium aluminate cements such as ciment fondu; and organic polymer binders such as cellulose binders, or a mixture thereof.
  • a binder such as clays, including bentonite, sepiolite, minugel and attapulgite clays; calcium aluminate cements such as ciment fondu; and organic polymer binders such as cellulose binders, or a mixture thereof.
  • the total amount of the binder in the sorbent may be in the range 2.5-30% by weight.
  • the binders are desirably in the form of powders, preferably powder with a D 50 particle size in the range 1 -100 ⁇ .
  • the sorbent may include a particulate support material.
  • the particulate support material may be any inert support material suitable for use in preparing sorbents.
  • Such support materials are known and include alumina, metal-aluminate, silicon carbide, silica, titania, zirconia, alumino-silicates, zeolites, carbon, or a mixture thereof.
  • Other supports include zinc compounds such as zinc oxide, zinc carbonate or zinc hydroxycarbonate.
  • a support material offers a means to adapt the physical properties of the sorbent to the duty.
  • the surface area, porosity and crush strength of the sorbent may suitably be tailored to its use.
  • support particles can increase the strength and durability of the sorbent composition by acting as a diluent.
  • Support materials are desirably oxide materials such as aluminas, titanias, zirconias, zinc oxides, silicas, zeolites and aluminosilicates, or mixtures of two or more of these. Hydrated oxides may also be used, for example alumina trihydrate or boehmite. Particularly suitable supports are aluminas and hydrated aluminas, especially alumina trihydrate.
  • the sorbent may comprise 2.5-30% by weight in total of one or more supports.
  • the support is desirably in the form of a powder, more preferably a powder with a D 50 particle size in the range 1 -100 ⁇ .
  • the sorbent consists essentially of hydrated calcium silicate cement and sodium carbonate (Na 2 C0 3 ) and/or potassium carbonate (K 2 C0 3 ).
  • the mixture comprising the particulate calcium silicate cement and particulate alkali metal compound, before and/or after shaping, is treated with water to hydrate the calcium silicate cement.
  • the treatment results in a chemical transformation and hardening of the cement.
  • the transformation is complex, but is believed to include the following reactions;
  • a benefit of using calcium silicate cement therefore appears to arise from the ability of the calcium hydroxide hydration product, in addition to the alkali metal compound, to trap halogen compounds such as hydrogen chloride.
  • Shaping of the sorbent may be by casting into moulds, pelleting, extruding or granulating.
  • castings of the sorbent may be made by forming a slurry comprising the calcium silicate cement and alkali metal compound in water and pouring it into moulds of predetermined shape to harden.
  • the sorbent may be cast as slabs, which after hardening, may be crushed and sieved to give particles of the sorbent according to a desired particle size range. It will be understood that in this case, although the hardening of the cement largely takes place after shaping, in forming the slurry the treatment with water is before shaping.
  • Sorbent pellets may be shaped by moulding a powder composition comprising the calcium silicate cement and alkali metal compound, generally containing a material such as graphite or magnesium stearate as a moulding aid, in suitably sized moulds, e.g. as in conventional tableting operation.
  • the pellets may then be subsequently treated with water.
  • sorbent extrudates may be formed by forcing a suitable composition comprising the calcium silicate cement and alkali metal compound and often a little water and/or a moulding aid as indicated above, through a die followed by cutting the material emerging from the die into short lengths.
  • extrudates may be made using a pellet mill of the type used for pelleting animal feedstuffs, wherein the mixture to be pelleted is charged to a rotating perforate cylinder through the perforations of which the mixture is forced by a bar or roller within the cylinder: the resulting extruded mixture is cut from the surface of the rotating cylinder by a doctor knife positioned to give extruded pellets of the desired length.
  • the amount of water used in extrusion may be sufficient to cause bulk hydration of the calcium silicate cement. Where this is not the case, the extrudates may be subsequently treated with water.
  • sorbent granules may be formed by mixing a powder composition comprising the calcium silicate cement and alkali metal compound with a little water, insufficient to form a slurry, and then causing the composition to agglomerate into roughly spherical, but generally irregular, granules in a granulator.
  • the amount of water used in granulation is generally insufficient to cause bulk hydration of the calcium silicate cement. Therefore granulate sorbents will typically require a subsequent, treatment with water.
  • the pellets, extrudates or granules preferably have a length and width in the range 1 to 25 mm, with an aspect ratio (longest dimension divided by shortest dimension) ⁇ 4.
  • the different shaping methods have an effect on the surface area, porosity and pore structure within the shaped articles and in turn this often has a significant effect on the sorption characteristics and on the bulk density.
  • beds of sorbents in the form of moulded pellets may exhibit a relatively broad absorption front, whereas beds of granulated agglomerates can have a much sharper absorption front: this enables a closer approach to be made to the theoretical absorption capacity.
  • agglomerates generally have lower bulk densities than tableted compositions.
  • a preferred shaping method involves granulating a mixture of particulate calcium silicate cement, particulate alkali metal compound and any other components in a granulator.
  • the amount of water used to granulate the mixture may be in the range 100-500 ml/kg of mixture, depending upon the composition.
  • Granules with a diameter in the range 1 -15 mm may be formed.
  • Granules of diameter 1 -5 mm are preferred for most duties.
  • the shaped sorbent is subjected to a water treatment, this may be performed by spraying the shapes with water or dipping the shapes in water, or a combination of both.
  • the water treatment of the shaped sorbent preferably uses a minimum amount of water and techniques to minimise leaching of the alkali metal compound from the sorbent.
  • the shaped units may be treated by an incipient wetness technique whereby the amount of water added is sufficient to fill the pores of the sorbent.
  • the amount of water should preferably be sufficient to fully hydrate the calcium silicates present in the cement.
  • the water used to treat prepare the sorbent may be mains water, demineralised water or water recovered from suitable industrial processes. It may be desirable to use water containing an alkali metal compound, such as an alkali metal carbonate. For example water containing dissolved alkali metal compound such as a carbonate at a concentration from ⁇ 1 % wt up to saturation may be used. Using water containing alkali metal compound such as a carbonate may allow for improved control of the alkali metal compound content of the sorbent.
  • an alkali metal compound such as an alkali metal carbonate.
  • the water treatment results in a hardening or setting of the cement in the sorbent as the calcium silicate hydration reactions proceed.
  • the water treatment is preferably performed at a temperature in the range 1 -95°C, more preferably 5-50°C.
  • the treatment may be continued for a period (a setting period) to harden the cement and generate the reactive sorbent.
  • the setting period may be from 0.1 to >100 hours depending upon the properties of the mixture and amount of water used.
  • the sorbent comprises water as the hydration product of the calcium silicate cement. Water may also be present in a hydration product of the alkali metal compound, and further as excess water adsorbed within the pore structure of the sorbent.
  • the amount of water in the sorbent may be in the range 4-50% by weight, preferably 10-45% by weight, more preferably 15-45% by weight on the sorbent. Where excess water in an amount beyond incipient wetness of the sorbent has been used, the excess water is preferably separated and the sorbent subjected to a drying step. Such a drying step removes free water within the sorbent but should be performed without substantial dehydration of the formed hydrated calcium silicate. We have found that the degree of hydration in the sorbent should be kept as high as possible. Therefore preferably the drying step is performed at 5-50°C, most preferably 5-35°C. The drying step may be performed at atmospheric pressure or under vacuum.
  • the sorbent thus obtainable by the method is in the form of a shaped unit comprising a hydrated calcium silicate cement and an alkali metal compound selected from an oxide, hydroxide, carbonate or hydrogen carbonate.
  • the invention includes a process for removing halogen compounds from a fluid stream by contacting the fluid stream with the sorbent.
  • the sorbents may be used absorb halogen compounds from gas streams to avoid corrosion problems during subsequent processing of the gas stream and/or to avoid poisoning of downstream catalysts.
  • the fluid stream may be a hydrogen gas stream comprising preferably >50% vol hydrogen, more preferably > 80% vol hydrogen, most preferably >90% vol hydrogen.
  • the fluid stream may be a synthesis gas stream comprising hydrogen, carbon monoxide and carbon dioxide.
  • the fluid stream may be a gas stream comprising a hydrocarbon such as a natural gas or a refinery off-gas, containing, for example, one or more hydrocarbons such as methane, ethane, propanes, or butanes and especially one or more alkenes such as ethane, propene and butenes.
  • Alkynes may also be present.
  • the hydrocarbon content may be in the range 0.1 -100% vol, but is preferably in the range 0.5-20% vol.
  • the fluid stream may be a liquid hydrocarbon stream.
  • Such streams include liquid natural gas, natural gas liquids, condensates , LPG, kerosene, cracked naphtha and diesel fuels.
  • the halogen compounds that may be removed by the sorbent may be bromine, chlorine, fluorine, or iodine compounds but more commonly are chlorine compounds.
  • the sorbent may be used to capture hydrogen chloride, hydrogen bromide, hydrogen iodide and hydrogen fluoride.
  • Organic halide compounds such as haloalkanes, including chloromethanes, chloroethanes, chloropropanes and chlorobutanes, as well as other longer chain chloroalkanes may also be removed from fluid streams using the sorbent.
  • the halogen compound is hydrogen chloride.
  • the amount of halogen compounds may vary depending upon the fluid stream but the present process is particularly effective where the hydrogen halide content of the process fluid fed to the sorbent is in the range 0.1 -20 ppm.
  • the sorbent may be placed in a sorption vessel and the fluid stream containing the halogen compound is passed through it.
  • the process may be operated at inlet temperatures in the range 10-400°C, but preferably in the range 5-100°C, more preferably 5-50°C and at pressures in the range 1 -100 bar abs.
  • the sorbent is placed in the vessel as one or more fixed beds according to known methods. More than one bed may be employed and the beds may be the same or different in composition.
  • the sorbent prepared by the present invention may be used to capture hydrogen halides in combination with other sorbents that capture organic halogen compounds to provide a total halogen compound removal system.
  • Example 1 The invention is further described by reference to the following Examples.
  • Example 1 The invention is further described by reference to the following Examples.
  • Example 1 Example 1 .
  • OPC ordinary Portland cement
  • the chloride content of the discharged samples was measured by coulometric analysis using silver electrodes in a Sherwood model 926 chloride analyser.
  • the method used was as follows; a weighed amount of ground sample was boiled with nitric acid to dissolve all acid soluble chloride. The solution was then made up to a standard volume with demineralised water. 0.5 ml of this solution was added to an acid buffer and placed in a Sherwood 926 analyzer. The analyzer automatically titrated the chloride ions by passing a known constant current between two silver electrodes which provides a constant generation of silver ions. These silver ions combine with the chloride in the sample and form insoluble silver chloride.
  • Comparative III 1 1 .0 The chloride saturation test was also performed on the parent Portland cement material without metal carbonate or a hydration step, resulting in a chloride pickup of ⁇ 1 wt.%. In comparison, the chloride removal capacity of Comparative III (1 1 .0 wt.%) clearly demonstrates that the chemical transformation occurring during the hydration step is facilitating chloride removal.
  • Sorbent (c) 480.4 g of Ordinary Portland cement was added to a powder mixer along with 120.6 g of Na 2 C0 3 and mixed thoroughly for 5 minutes. 100 g of the resulting mixture was removed and 120 g of demineralised water was added to the remaining mixture until it formed a paste. 60 g of the removed powder mixture was added to the paste to turn it into granules. The granules were sieved to a size fraction of 1 -2 mm and then left for 16 hours at room temperature (20°C) to set.
  • Sorbent (d) The above granulation procedure was repeated with a 50/50 w/w mix of Na 2 C0 3 and cement. In total 600 g of the Na 2 C0 3 /cement combination was mixed with 160 g of water to form a granular material. The granules were sieved to a size fraction of 1 -2 mm and then left for 16 hours at room temperature (20°C) to set.
  • the resulting granules were assessed for chloride removal capability using the chloride saturation test.
  • Samples of the granules were further treated with sufficient water to just exceed the water uptake capacity. In each case, the treated granules were left for 64 hours at room temperature to set. The treated granular sorbents were then re-assessed for chloride removal capability using the chloride saturation test. The results are presented in the table below. Sample Water treatment CI content (wt%)
  • a sorbent prepared according to WO95/22403 had a CI content of 25.7% wt following the chloride saturation test, and a sorbent prepared according to W099/39819 had a CI content of 33.1 % wt following the chloride saturation test.
  • the sorbent according to the present invention is able to match or surpass the absorbency of the prior art sorbents.

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Abstract

L'invention concerne un procédé de préparation d'un sorbant comprenant les étapes suivantes : (i) mélange ensemble d'un ciment de silicate de calcium particulaire et d'un composé de métal alcalin particulaire, et (ii) traitement du mélange avec de l'eau pour hydrater le ciment de silicate de calcium, le composé de métal alcalin particulaire comprenant un oxyde, un hydroxyde, un carbonate ou un hydrogénocarbonate et le sorbant étant façonné avant et/ou après le traitement avec de l'eau.
PCT/GB2014/053672 2014-01-03 2014-12-11 Sorbant pour composés halogénés WO2015101768A1 (fr)

Applications Claiming Priority (2)

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GBGB1400091.3A GB201400091D0 (en) 2014-01-03 2014-01-03 Sorbent for halogen compounds
GB1400091.3 2014-01-03

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WO2015101768A1 true WO2015101768A1 (fr) 2015-07-09

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017186478A1 (fr) 2016-04-28 2017-11-02 Unilever N.V. Composition granulaire et filtre pour la purification d'eau
CN112546844A (zh) * 2020-11-20 2021-03-26 沈阳三聚凯特催化剂有限公司 一种脱氯剂及其制备方法
WO2022162626A1 (fr) * 2021-01-29 2022-08-04 Sud Chemie India Pvt Ltd Nouvel adsorbant à faible coût ayant une capacité d'élimination de chlorure élevée

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WO1995022403A1 (fr) * 1994-02-21 1995-08-24 Imperial Chemical Industries Plc Absorbants
WO1999039819A1 (fr) * 1998-02-06 1999-08-12 Imperial Chemical Industries Plc Absorbants
US20060148642A1 (en) * 2005-01-04 2006-07-06 Chong-Kul Ryu Highly attrition resistant and dry regenerable sorbents for carbon dioxide capture
US20080179253A1 (en) * 2003-12-24 2008-07-31 Malcolm William Clark Porous Particulate Material For Fluid Treatment, Cementitious Composition and Method of Manufacture Thereof
EP2022553A1 (fr) * 2006-05-19 2009-02-11 Asahi Glass Company, Limited Procédé d'élimination d'un halogène gazeux et matière d'élimination pour un halogène gazeux
WO2013045883A1 (fr) * 2011-09-29 2013-04-04 Johnson Matthey Public Limited Company Procéde de purification

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JPH11262634A (ja) * 1998-03-17 1999-09-28 Asahi Chem Ind Co Ltd 塩化水素除去材
JP3302998B2 (ja) * 1999-03-31 2002-07-15 独立行政法人産業技術総合研究所 高温酸性排ガス吸収剤の製造方法及び高温酸性排ガスの除去方法

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Publication number Priority date Publication date Assignee Title
WO1995022403A1 (fr) * 1994-02-21 1995-08-24 Imperial Chemical Industries Plc Absorbants
WO1999039819A1 (fr) * 1998-02-06 1999-08-12 Imperial Chemical Industries Plc Absorbants
US20080179253A1 (en) * 2003-12-24 2008-07-31 Malcolm William Clark Porous Particulate Material For Fluid Treatment, Cementitious Composition and Method of Manufacture Thereof
US20060148642A1 (en) * 2005-01-04 2006-07-06 Chong-Kul Ryu Highly attrition resistant and dry regenerable sorbents for carbon dioxide capture
EP2022553A1 (fr) * 2006-05-19 2009-02-11 Asahi Glass Company, Limited Procédé d'élimination d'un halogène gazeux et matière d'élimination pour un halogène gazeux
WO2013045883A1 (fr) * 2011-09-29 2013-04-04 Johnson Matthey Public Limited Company Procéde de purification

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017186478A1 (fr) 2016-04-28 2017-11-02 Unilever N.V. Composition granulaire et filtre pour la purification d'eau
CN109071349A (zh) * 2016-04-28 2018-12-21 荷兰联合利华有限公司 用于纯化水的颗粒组合物和过滤器
CN109071349B (zh) * 2016-04-28 2021-04-09 荷兰联合利华有限公司 用于纯化水的颗粒组合物和过滤器
CN112546844A (zh) * 2020-11-20 2021-03-26 沈阳三聚凯特催化剂有限公司 一种脱氯剂及其制备方法
WO2022162626A1 (fr) * 2021-01-29 2022-08-04 Sud Chemie India Pvt Ltd Nouvel adsorbant à faible coût ayant une capacité d'élimination de chlorure élevée

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AR099026A1 (es) 2016-06-22
GB201400091D0 (en) 2014-02-19
GB2522989A (en) 2015-08-12

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