EP3958999A1 - Procédé de nettoyage de gaz de traitement corrosifs contenant du soufre - Google Patents

Procédé de nettoyage de gaz de traitement corrosifs contenant du soufre

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Publication number
EP3958999A1
EP3958999A1 EP20720055.1A EP20720055A EP3958999A1 EP 3958999 A1 EP3958999 A1 EP 3958999A1 EP 20720055 A EP20720055 A EP 20720055A EP 3958999 A1 EP3958999 A1 EP 3958999A1
Authority
EP
European Patent Office
Prior art keywords
gas
cleaning
sulfur compounds
maximum
hydrogen chloride
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.)
Pending
Application number
EP20720055.1A
Other languages
German (de)
English (en)
Inventor
Alexander LUEKEN
Michael Venz
Thomas Burbach
Andre Rittermeier
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.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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 Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3958999A1 publication Critical patent/EP3958999A1/fr
Pending legal-status Critical Current

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    • 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
    • B01D53/04—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 with stationary adsorbents
    • 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
    • B01D53/8609—Sulfur oxides
    • 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
    • B01D53/8615—Mixtures of hydrogen sulfide and sulfur oxides
    • 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
    • B01D53/8659—Removing 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
    • B01J20/06—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
    • 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
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/32—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
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • C01B7/0718—Purification ; Separation of hydrogen chloride by adsorption
    • 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
    • B01D2253/104—Alumina
    • 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
    • B01D2253/1124—Metal oxides
    • 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
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • 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
    • B01D2256/26—Halogens or 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/308—Carbonoxysulfide COS

Definitions

  • the invention relates to a method for cleaning corrosive process gases containing sulfur.
  • the invention further relates to the use of inorganic sorbents containing zirconium oxide and / or cerium oxide for the removal of sulfur compounds from sulfur-containing corrosive process gases.
  • the invention is based on purification methods known per se for corrosive process gases and, in particular, process gases containing hydrogen chloride.
  • WO2015198567 discloses a means for removing sulfur from liquids in a cleaning column that contains copper, silver or iron, in particular copper particles, as reactive components. The cleaning of corrosive gases is not mentioned in this document.
  • a method for removing SO x from gases has become known from WO2015085880, in which a polyethylene glycol solution is used as the adsorbent. This adsorbent can be regenerated by degassing.
  • a method for desulfurizing crude oil has become known, in which the crude oil is mixed with water and hydrogen and the resulting mixture is converted in contact with a catalyst mass under desulfurization conditions.
  • a supported catalyst with a catalytic component of at least one of the metals from groups Via and VIII of the periodic table on an alumina-silica support serves as the catalyst mass. The catalysis takes place in the presence of hydrogen.
  • the desulphurisation of corrosive raw gases is not mentioned here.
  • the object of the present invention is to provide a cleaning method for corrosive process gases containing sulfur compounds which overcomes the above disadvantages and enables sulfur compounds to be removed from the process gases as far as possible.
  • a special object of the invention is to provide a gas cleaning method that avoids the disadvantages of the known cleaning methods and in particular enables the cleaning of process gases for the catalytic gas phase oxidation of hydrogen chloride so that poisoning of the catalyst for the gas phase oxidation is avoided.
  • the object is achieved in that the corrosive process gas flow is passed over a chemically inert inorganic sorbent which absorbs the sorbable sulfur-containing components.
  • the invention relates to a method for cleaning corrosive process gases containing sulfur compounds, characterized in that a gas stream which contains corrosive gases is passed in a sorption phase at a defined temperature over a sorption material which absorbs at least one of the sorbable sulfur-containing components on the sorption material , and removes the gas stream depleted of sulfur compounds.
  • the absorption of the sorbable sulfur-containing components can in principle take place through an adsorption or an absorption process.
  • preferred sulfur compounds are one or more compounds from the series: SO x , preferably SO 2 and SO 3 , H 2 S, CS 2 , SOCI 2 , S 2 CI 2 , SCI 2 , COS and mercaptans.
  • the new process is particularly suitable for the purification of gas mixtures in which the sulfur compounds are present as trace gas, in particular in a concentration of a maximum of 10 ppm, preferably a maximum of 1 ppm, particularly preferably a maximum of 0.1 ppm.
  • the sorption material has at least one oxide or mixed oxide of cerium and / or zirconium and / or titanium, particularly preferably CeO 2 and / or ZrO 2 and / or TiO 2, as the active component.
  • Suitable carrier materials for the sorbent are, in particular, all known carrier materials that are chemically resistant to hydrogen chloride, in particular one or more carrier materials from the series: Al 2 O 3 , TiO 2 , ZnO 2 , SiO 2 , SnO 2 and ZrO 2 , the carrier material and the possible active components of the sorbent material are different.
  • Al 2 O 3 , TiO 2 , ZrO 2 are particularly preferred as the material for the carrier.
  • the sorbent comprises a supported cerium oxide catalyst, which is obtained in particular by applying a cerium compound, in particular a compound from the series: cerium nitrate, cerium acetate or cerium chloride in solution by means of dry impregnation to the carrier and the impregnated The carrier is then dried and calcined at an elevated temperature. Dry impregnation is understood here in particular to mean that the component to be applied is only dissolved in so much solvent that this solvent is completely absorbed by the carrier material.
  • the new method is preferably carried out in such a way that the corrosive process gas is cleaned at a temperature of a maximum of 420 ° C., preferably a maximum of 200 ° C., particularly preferably a maximum of 40 ° C.
  • the corrosive process gas is preferably cleaned at an elevated pressure, in particular of at least 1013 hPa, preferably at least 2026 hPa to 25,325 hPa.
  • the purification process is preferably controlled in such a way that the gas stream depleted of sulfur compounds has a residual content of sulfur compounds of at most 0.05 ppm, preferably at most 0.01 ppm, particularly preferably at most 1 ppb.
  • the corrosive process gas has at least hydrogen chloride or hydrogen chloride and chlorine as the corrosive component. Furthermore, inert components in the corrosive process gas, e.g. Contain nitrogen and carbon dioxide.
  • the new cleaning process is coupled with a downstream catalyzed process, in particular for converting the corrosive gases.
  • the gas stream depleted of sulfur compounds is particularly preferably fed to a downstream catalytic process, preferably a catalytic oxidation reaction, particularly preferably a thermocatalytic oxidation of hydrogen chloride gas.
  • the preferred coupled mode of operation described above is carried out in a preferred variant of the new process in such a way that the gas cleaning of the corrosive process gas is carried out in a reaction zone which is arranged in a reactor which is separated from a further downstream reactor and whose temperature and / or Pressure can be controlled independently of the other reactor.
  • the gas cleaning of the corrosive process gas is carried out in a reaction zone which is arranged in a reactor with several reaction zones, the reaction zone for cleaning being separated from at least one further downstream reaction zone for the gas phase reaction and the temperature and / or pressure in the reaction zone for gas cleaning can be controlled independently of the downstream reaction zone.
  • the catalytic process known as the Deacon process is preferably used.
  • hydrogen chloride is oxidized to chlorine with oxygen in an exothermic equilibrium reaction, with water vapor being produced.
  • the reaction temperature is usually 150 to 500 ° C., the usual reaction pressure is 1 to 25 bar. Since this is an equilibrium reaction, it is advisable to work at the lowest possible temperatures at which the catalyst still has sufficient activity.
  • oxygen in amounts greater than the stoichiometric amount compared to the hydrogen chloride. For example, a two to four-fold excess of oxygen is common. Since no losses in selectivity are to be feared, it can be economically advantageous to work at relatively high pressure and accordingly with a longer residence time compared to normal pressure.
  • Suitable preferred catalysts for the Deacon process contain ruthenium oxide, ruthenium chloride, ruthenium oxychloride or other ruthenium compounds on silicon dioxide, aluminum oxide, titanium dioxide, tin dioxide or zirconium dioxide as a carrier.
  • Suitable catalysts can be obtained, for example, by applying ruthenium chloride to the support and then drying or drying and calcining.
  • suitable catalysts can also contain compounds of other noble metals, for example gold, palladium, platinum, osmium, iridium, silver, copper or rhenium.
  • Suitable catalysts can also contain chromium (III) oxide.
  • the catalytic oxidation of hydrogen chloride can either be adiabatic or isothermal or approximately isothermal, but preferably adiabatically, batchwise or continuously, but preferably continuously as a fluidized or fixed bed process, preferably as a fixed bed process, particularly preferably in tube bundle reactors over heterogeneous catalysts at a reactor temperature of 180 to 500 ° C , preferably 200 to 400 ° C, particularly preferably 220 to 350 ° C and a pressure of 1 to 25 bar (1000 to 25000 hPa), preferably 1.2 to 20 bar, particularly preferably 1.5 to 17 bar and especially 2, 0 to 15 bar can be carried out.
  • a reactor temperature 180 to 500 ° C , preferably 200 to 400 ° C, particularly preferably 220 to 350 ° C and a pressure of 1 to 25 bar (1000 to 25000 hPa), preferably 1.2 to 20 bar, particularly preferably 1.5 to 17 bar and especially 2, 0 to 15 bar can be carried out.
  • reaction apparatus in which the catalytic oxidation of hydrogen chloride is carried out are fixed bed or fluidized bed reactors.
  • the catalytic hydrogen chloride oxidation can preferably also be carried out in several stages.
  • a device suitable for the Deacon process consists in using a structured catalyst bed in which the catalyst activity increases in the direction of flow.
  • Such structuring of the catalyst bed can take place by differently impregnating the catalyst support with active material or by differently diluting the catalyst with an inert material.
  • Rings, cylinders or balls made of titanium dioxide, tin dioxide, zirconium dioxide or mixtures thereof, aluminum oxide, steatite, ceramic, glass, graphite or stainless steel can be used as the inert material.
  • the inert material should preferably have similar external dimensions.
  • heterogeneous catalysts are ruthenium compounds or copper compounds on support materials, which can also be doped; optionally doped ruthenium catalysts are preferred.
  • Suitable support materials are, for example, silicon dioxide, graphite, titanium dioxide with a rutile or anatase structure, tin dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, preferably titanium dioxide, tin dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, particularly preferably tin dioxide, a- or g-aluminum oxide or their mixtures.
  • the supported copper or ruthenium catalysts can be obtained, for example, by impregnating the support material with aqueous solutions of CuCl or RuCl and, if appropriate, a promoter for doping, preferably in the form of their chlorides.
  • the shaping of the catalyst can take place after or preferably before the impregnation of the support material.
  • suitable catalysts can also contain compounds of other noble metals, for example gold, palladium, platinum, osmium, iridium, silver, copper, chromium or rhenium.
  • Metals or metal compounds of the metals are suitable as promoters for doping the catalysts: alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, particularly preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and Calcium, particularly preferably magnesium, rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yttrium, lanthanum and cerium, especially preferably lanthanum and cerium, or mixtures thereof.
  • Shaped bodies of any shape are suitable as shaped catalyst bodies, tablets, rings, cylinders, stars, wagon wheels or spheres are preferred, rings, cylinders or star strands are particularly preferred as the shape.
  • the shaped bodies can then be dried and optionally calcined at a temperature of 100 to 400 ° C., preferably 100 to 300 ° C., for example under a nitrogen, argon or air atmosphere.
  • the shaped bodies are preferably first dried at 100 to 150.degree. C. and then calcined at 200 to 400.degree.
  • the conversion of hydrogen chloride in a single pass can preferably be limited to 15 to 90%, preferably 40 to 85%, particularly preferably 50 to 70%. Unreacted hydrogen chloride can, after separation, be partially or completely returned to the catalytic hydrogen chloride oxidation.
  • the volume ratio of hydrogen chloride to oxygen at the reactor inlet is preferably 1: 1 to 20: 1, preferably 1: 1 to 8: 1, particularly preferably 1: 1 to 5: 1.
  • the heat of reaction of the catalytic hydrogen chloride oxidation can advantageously be used to generate high pressure steam. This can be used to operate a phosgenation reactor and / or distillation columns, in particular isocyanate distillation columns.
  • the invention also relates to the use of a sorbent material which comprises at least one oxide or mixed oxide of cerium and / or zirconium as the active component, preferably CeO 2 and / or ZrO 2, for removing sulfur compounds from corrosive process gas containing sulfur compounds, in particular at least hydrogen chloride or Corrosive process gas containing hydrogen chloride and chlorine.
  • a sorbent material which comprises at least one oxide or mixed oxide of cerium and / or zirconium as the active component, preferably CeO 2 and / or ZrO 2, for removing sulfur compounds from corrosive process gas containing sulfur compounds, in particular at least hydrogen chloride or Corrosive process gas containing hydrogen chloride and chlorine.
  • a ZrO 2 carrier material manufactured by Saint-Gobain NorPro, type: SZ 31163, extrudates with 3 - 4 mm diameter and 4 - 6 mm length
  • a ZrO 2 carrier material manufactured by Saint-Gobain NorPro, type: SZ 31163, extrudates with 3 - 4 mm diameter and 4 - 6 mm length
  • This ZrO 2 carrier material (SZ 31163) was crushed with a mortar and classified into sieve fractions. 1 g of the 100-250 mm sieve fraction was dried for 2 h at 160 ° C. and 10 kPa. 50 grams of cerium (III) nitrate hexahydrate was dissolved in 42 grams of deionized water. 0.19 ml of the cerium (III) nitrate solution prepared in this way was diluted with an amount of deionized water sufficient to fill the entire pore volume and placed in a beaded beaker and 1 g of the dried sieve fraction (100-250 mm) of the ZrO 2 - The catalyst support was stirred in until the solution was completely absorbed (dry impregnation method).
  • the impregnated ZrO 2 catalyst support was then dried for 5 h at 80 ° C. and 10 kPa and then calcined in air in a muffle furnace.
  • the temperature in the muffle furnace was increased linearly from 30 ° C. to 900 ° C. over the course of 5 h and held at 900 ° C. for 5 h.
  • the muffle furnace was then linearly cooled from 900 ° C. to 30 ° C. over the course of 5 hours.
  • the supported amount of cerium corresponds to a proportion of 7% by weight based on the calcined catalyst, the catalyst components being calculated as CeO 2 and ZrO 2 .
  • Example 3 0.5 g of the sorbent prepared in Example 1 were placed in a fixed bed in a quartz reaction tube (internal diameter 8 mm) and at a temperature of 20 ° C with a gas mixture of 2 L / h hydrogen chloride, 1 L / h oxygen, 2 L / h nitrogen and 5 ppm SO 2 flowed through for 336 h. The sulfur content on the sorbent was then determined by elemental analysis. The result is shown in Table 1.
  • Example 3 Example 3:
  • Example 1 0.5 g of the sorbent prepared in Example 1 was placed in a fixed bed in a quartz reaction tube (internal diameter 8 mm) and at a temperature of 260 ° C with a gas mixture of 2 L / h hydrogen chloride, 1 L / h oxygen, 2 L / h nitrogen and 5 ppm SO 2 flowed through for 336 h.
  • the quartz reaction tube was heated by an electrically heated oven.
  • the sulfur content on the sorbent was then determined by elemental analysis. The result is shown in Table 1.
  • Example 1 0.5 g of the sorbent prepared in Example 1 were placed in a fixed bed in a quartz reaction tube (internal diameter 8 mm) and at a temperature of 300 ° C with a gas mixture of 2 L / h hydrogen chloride, 1 L / h oxygen, 2 L / h nitrogen and 5 ppm SO 2 flowed through for 336 h.
  • the quartz reaction tube was heated by an electrically heated oven.
  • the S content on the sorbent was then determined by elemental analysis. The result is shown in Table 1.
  • Example 1 0.5 g of the sorbent prepared in Example 1 was placed in a fixed bed in a quartz reaction tube (internal diameter 8 mm) and at a temperature of 340 ° C with a gas mixture of 2 L / h hydrogen chloride, 1 L / h oxygen, 2 L / h nitrogen and 5 ppm SO 2 flowed through for 336 h.
  • the quartz reaction tube was heated by an electrically heated oven.
  • the S content on the sorbent was then determined by elemental analysis. The result is shown in Table 1.
  • Example 7 0.5 g of the sorbent prepared in Example 1 was placed in a fixed bed in a quartz reaction tube (internal diameter 8 mm) and at a temperature of 380 ° C with a gas mixture of 2 L / h hydrogen chloride, 1 L / h oxygen, 2 L / h nitrogen and 5 ppm SO 2 flowed through for 336 h.
  • the quartz reaction tube was heated by an electrically heated oven.
  • the S content on the sorbent was then determined by elemental analysis. The result is shown in Table 1.
  • Example 7 Example 7:
  • Example 1 0.5 g of the sorbent prepared in Example 1 was placed in a fixed bed in a quartz reaction tube (internal diameter 8 mm) and at a temperature of 420 ° C with a gas mixture of 2 L / h hydrogen chloride, 1 L / h oxygen, 2 L / h nitrogen and 5 ppm SO 2 flowed through for 336 h.
  • the quartz reaction tube was heated by an electrically heated oven.
  • the S content on the sorbent was then determined by elemental analysis. The result is shown in Table 1.
  • Example 8 A commercially available CeO 2 doped ZrO 2 carrier material (manufacturer: Saint-Gobain NorPro, type: SZ 61191, spheres with 3 mm diameter) in a tetragonal structure with the following specifications was used:
  • the ZrO 2 catalyst support was tested and analyzed in accordance with the sorbent in Examples 2-7. The result is shown in Table 1.
  • the ZrO 2 catalyst support was tested and analyzed in accordance with the sorbent in Examples 2-7. The result is shown in Table 1.
  • a ZrO 2 microparticle carrier material (manufacturer: Saint-Gobain NorPro, microparticles with 0.781 mm diameter) in a monoclinic structure with the following specifications was used:
  • ZrO2 carrier materials manufactured by Saint-Gobain NorProl in a tetragonal structure with the following specifications: Type: SZ 61152, spheres with a 3 mm diameter (example 111:
  • the sorption capacity is almost always below the sorption capacity of the CeO 2 -containing materials.
  • the pure ZrO 2 materials there is a linear trend towards the BET surface area with regard to the sorption capacity. The larger the BET surface area, the higher the sorbent capacity in most cases.
  • the sorbtion capacity of pure ZrO 2 materials increases linearly with the temperature of 260 ° C to 340 ° C at, after which the sorption capacity drops of pure ZrO 2 materials again. At the highest measured temperature (420 ° C) the sorption capacity is negligible and the sulfur concentration is even below the concentration of the starting materials.
  • ZrO 2 materials are generally suitable for the adsorption of sulfur species, but that the material must be selected depending on the sulfur contamination.
  • the same trend can be seen with increasing temperature as with the pure ZrO 2 materials.
  • the sorption capacity of the CeO 2 / ZrO 2 materials is much higher than that of the pure ZrO 2 materials.
  • the sorption capacity of the CeO 2 / ZrO 2 materials up to the temperature of 420 ° C continuously, in contrast to the pure ZrO 2 materials.

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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Gas Separation By Absorption (AREA)
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Abstract

L'invention concerne un procédé de nettoyage de gaz de traitement corrosifs contenant des composés du soufre, dans lequel un courant gazeux contenant des gaz corrosifs est passé dans une phase de sorption, sur un matériau de sorption inorganique qui absorbe au moins un des composants sorbables contenant du soufre sur le matériau de sorption, et rejette le courant gazeux appauvri en composés de soufre.
EP20720055.1A 2019-04-26 2020-04-23 Procédé de nettoyage de gaz de traitement corrosifs contenant du soufre Pending EP3958999A1 (fr)

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PCT/EP2020/061323 WO2020216837A1 (fr) 2019-04-26 2020-04-23 Procédé de nettoyage de gaz de traitement corrosifs contenant du soufre

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EP3403723A1 (fr) * 2017-05-19 2018-11-21 Covestro Deutschland AG Procédé de régénération d'un catalyseur contenant du ruthénium contaminé ou des composés de ruthénium

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WO2020216837A1 (fr) 2020-10-29
KR20220003017A (ko) 2022-01-07
CN113710347A (zh) 2021-11-26
US20220203300A1 (en) 2022-06-30
EP3730202A1 (fr) 2020-10-28

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