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WO2018013009A1 - Catalyseur d'oxydation sélective de sulfure d'hydrogène (et variantes) et différents processus l'utilisant - Google Patents

Catalyseur d'oxydation sélective de sulfure d'hydrogène (et variantes) et différents processus l'utilisant Download PDF

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WO2018013009A1
WO2018013009A1 PCT/RU2017/000497 RU2017000497W WO2018013009A1 WO 2018013009 A1 WO2018013009 A1 WO 2018013009A1 RU 2017000497 W RU2017000497 W RU 2017000497W WO 2018013009 A1 WO2018013009 A1 WO 2018013009A1
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catalyst
hydrogen sulfide
oxidation
vol
sulfur
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PCT/RU2017/000497
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Russian (ru)
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Наиля Самильевна САКАЕВА
Сергей Петрович КИЛЬДЯШЕВ
Ольга Анатольевна КЛИМОВА
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Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор"
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Priority claimed from RU2016127910A external-priority patent/RU2632014C1/ru
Priority claimed from RU2016127911A external-priority patent/RU2629193C1/ru
Application filed by Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" filed Critical Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор"
Publication of WO2018013009A1 publication Critical patent/WO2018013009A1/fr

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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
    • B01D53/34—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
    • 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
    • B01J21/02—Boron or aluminium; 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • 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

Definitions

  • the invention relates to a catalyst for the selective oxidation of hydrogen sulfide to sulfur in gases of various origin containing 0.3-15.0% vol. Hydrogen sulfide, and can be used in enterprises of gas processing, petrochemical and other industries, in particular, for the purification of process exhaust gases Klaus, low-sulfur natural and associated petroleum gases, emissions from chemical industries, for the purification of biogas.
  • a catalyst for the selective oxidation of hydrogen sulfide to sulfur in gases of various origin containing 0.3-15.0% vol. Hydrogen sulfide can be used in enterprises of gas processing, petrochemical and other industries, in particular, for the purification of process exhaust gases Klaus, low-sulfur natural and associated petroleum gases, emissions from chemical industries, for the purification of biogas.
  • Process and natural gases containing hydrogen sulfide are multicomponent gas mixtures, and may contain H 2 S (0.3-15 vol.%), S0 2 , organosulfur sulfur compounds (mercaptans, COS, CS 2 ), water vapor (3-40 vol.%), Carbon monoxide, carbon dioxide, hydrogen, saturated and / or aromatic hydrocarbons, nitrogen.
  • H 2 S 0.3-15 vol.%
  • S0 2 organosulfur sulfur compounds
  • COS carbon dioxide
  • CS 2 water vapor
  • Carbon monoxide carbon dioxide
  • hydrogen hydrogen
  • saturated and / or aromatic hydrocarbons nitrogen.
  • various gas purification options are possible - catalytic, adsorption, adsorption-catalytic.
  • the main parameters that determine the optimal technology for processing sulfur-containing gases are the composition of the gases (especially the content of hydrogen sulfide and water vapor) and the properties of the catalysts used.
  • the catalyst In the presence of certain impurities in the gas composition — saturated and / or aromatic hydrocarbons, carbon monoxide, and hydrogen, the catalyst can be deactivated due to soot deposits in the pores of the catalyst.
  • the oxidation of hydrogen sulfide to sulfur is carried out in one step at temperatures of 200-300 ° C. In cases of hydrogen sulfide content of more than 2.5 vol.% (Up to 15 vol.%), The process is carried out in several successive reactors, or in one multisection reactor with a batch supply of oxygen to each reactor or section, or in a reactor with a fluidized bed of catalyst.
  • the exhaust gases from Klaus plants may contain: 1-2 vol.% H 2 S, 1 vol.% SO2, up to 0.4 vol.% COS and up to 0.3 vol.% CS 2 , steam sulfur (1-8 g / m 3 ), and water vapor up to 40 vol.%.
  • the level of global sulfur recovery requires at least 99.5%
  • Processes of this type are widely known - the process Catasulf ® company BASF, the process BSR / Selectox ® company Unocal, Modop ® process company Mobil Oil, processes Superclaus 99 and Superclaus 99.5 company Jacobs Nederland BV ( «World sulfur, N, P and K ', J42 4, 1994, p. 32).
  • a known method of conducting the process of selective oxidation of hydrogen sulfide, when the stage of selective oxidation of hydrogen sulfide is carried out in an inert liquid medium at temperatures of 120-160 ° C (US patent 5897850, IPC B01D53 / 52, B01D53 / 86, C01B17 / 04, publ. 27.04.1999).
  • the disadvantage of this process is the technological difficulties of conducting liquid phase oxidation, the presence of acidic effluents, corrosion of equipment, and the high cost of the technology.
  • a gas containing less than 1 vol.% H 2 S, hydrogen and about 5 vol.% H 2 0 is reheated to 230 ° C, mixed with air and fed to a catalytic oxidation reactor, where hydrogen sulfide is oxidized to sulfur in the presence of a catalyst for selective oxidation of hydrogen sulfide (patent US 5037629, IPC B01D53 / 86, B01J23 / 745, B01J23 / 86, B01J35 / 10, C01B17 / 04, C10K1 / 34, publ. 08/08/1991; patent RU 2232128, IPC C01B17 / 04, B01D53 / 86, published July 10, 2004).
  • the process of removing elemental sulfur from gas streams is known, in which, in the first stage, hydrogen sulfide and sulfur vapor are oxidized to S0 2 , in the second stage, all sulfur dioxide is reduced to hydrogen sulfide in the presence of a hydrogenation / hydrogenation catalyst, and then, in the third stage, selective oxidation of hydrogen sulfide to sulfur in the presence of a selective oxidation catalyst (patent RU 2438764, IPC B01D53 / 86, publ. 10.01.2012).
  • a cost-effective process is the selective oxidation of hydrogen sulfide in the exhaust gases of the Claus process, in which the oxidation of hydrogen sulfide to sulfur is carried out in a gas stream with a controlled hydrogen sulfide content in the range of 0.8-3.0 vol.%, Preferably containing hydrogen sulfide - less than 1.5 vol. % and water vapor - not more than 30% vol.
  • the catalyst To achieve high rates of gas purification from hydrogen sulfide, the catalyst must provide a sulfur yield of at least 85% in the operating temperature range of 200-300 ° C. It is known that vanadium-containing catalysts are characterized by a high degree of H 2 S conversion in the temperature range 200–300 ° C.
  • Known oxidation catalyst H 2 S which is an oxide and / or vanadium sulfide on a non-alkaline refractory carrier
  • vanadium-containing catalysts are usually active in hydrocarbon oxidation reactions, which leads to rapid deactivation due to soot deposits on the catalyst surface.
  • titanium-containing catalysts are highly active in the selective oxidation of hydrogen sulfide, but only when the water vapor content is not more than 10 vol.% (Patent SU 1837957, IPC B01J21 / 06, C01B17 / 04, publ. 30.08.1993, patent EP 0078690 , IPC B01J21 / 06, B01D53 / 86, ⁇ 01 ⁇ 17/04, ⁇ 1J, B01D, publ.
  • Iron-containing catalysts are known to be highly effective catalysts for the oxidation of hydrogen sulfide, and in terms of the sum of their properties — high activity, selectivity, low toxicity, low cost, and high strength, these catalysts are of the greatest interest. Massive and supported type iron-containing catalysts are known for the selective oxidation of hydrogen sulfide to sulfur.
  • iron-containing catalysts supported on a SiC-2 carrier US patent 6207127, IPC B01J23 / 76, ⁇ 01 ⁇ 17 / 04, publ. 03/27/2001.
  • the proposed catalysts are characterized by a content of catalytically active material of 0.1-50 wt.%, Specific surface area of 20-350 m 2 / g, a total pore volume of 0.6-0.7 cm 3 / g, an average pore radius of 40-500 A.
  • the active material may contain iron and chromium compounds in an amount of 0.1-40 wt.% (patent US 5352422, IPC B01D53 / 52, B01D53 / 86, B01J21 / 08, B01J23 / 70, B01J23 / 74, B01J23 / 745, B01J23 / 85, B01J23 / 86, B01J27 / 185, B01J35 / 10, C01B17 / 04, C10K1 / 34, publ.
  • Known supported type catalyst for the selective oxidation of H 2 S in sulfur for purification of exhaust gases of the Claus process (patent US 6083473, IPC C01B17 / 00, B01J21 / 00, C01B17 / 04, C01B17 / 02, B01J21 / 16, publ. 07/04/2000) containing iron oxides on a Si0 2 support and oxides of other compounds, for example: chromium, manganese, cobalt and / or nickel in an amount of from 0.1 to 10 wt.% And additionally containing phosphorus and / or sodium compounds.
  • Known supported type catalyst (patent RU 2405738, IPC ⁇ 01 ⁇ 17 / 04, B01J37 / 02, B01J37 / 08, published December 10, 2010) intended for the oxidation of hydrogen sulfide by oxygen or air at a temperature of 180-320 ° C, and representing a salt or a mixture of salts on a silicon-containing carrier, where salts are used phosphates, or fluorides, or borates of metals selected from the group: iron, cobalt, nickel, copper or a mixture thereof, and including hydroxyl groups in the range of 0.05-20 ⁇ mol / g.
  • the catalysts are characterized by low bulk density, and very low mechanical strength. It is known that supported type iron oxide catalysts are rapidly deactivated due to the conversion of iron oxide to surface iron sulfates ("Deactivation of Claus tail-gas treating Catalysts, Cat. Deact.”, Berben PH, Scholten A., Titulaer MK, Brahma N., Van der Wal WJJ and Geus JW, 1987, p. 303-319). In addition, in the presence of aromatic hydrocarbons (1000 ppmv) in acid gas, carbonization of the catalyst is observed. Water vapor also has a deactivating effect, leading to a sharp decrease in strength due to hydrothermal aging (Ind.Eng.Chem.Res. 2007, 46, 6338-6344).
  • Massive type iron-containing catalysts are active and more resistant to the reaction medium.
  • Massive type catalysts are known, which mainly include iron oxide (patent SU 871813, IPC ⁇ 01 ⁇ 17 / 04, B01J23 / 745, publ. 15.10.1981), or iron compounds and other metals, for example iron, magnesium, zinc and chromium - Fe A MgBZn with CrD (patent US 5603913, IPC B01J23 / 86, C01B17 / 00, C01B17 / 16, C01B17 / 04, B01J 23/76, publ.
  • the closest technical solution to the claimed invention is a catalyst for the selective oxidation of hydrogen sulfide and the process of selective oxidation of hydrogen sulfide with oxygen in the presence of 0-30 vol.% Water vapor, in the temperature range 200-300 ° C at a gas flow rate of 900-4000 hours "1 , providing a sulfur yield of at least 85% under the specified operating conditions (patent RU 2288888, IPC ⁇ 1 ⁇ 17/04, B01D53 / 86, B01J27 / 18, B01J37 / 04, B01J37 / 08, published December 10, 2006).
  • Catalyst for selective oxidation hydrogen sulfide includes iron compounds and modifying add Ku, which is used as oxygen-containing phosphorus compounds, especially phosphoric acid, has the following composition, wt% based on the oxides:.. Fe 2 March 83-89, P 2 0 5 11-17
  • the catalyst is not sensitive to water, it is not need to condense during operation.
  • the main disadvantage of this catalyst is its non-optimized texture, namely: high bulk density, low total pore volume, minimum pore volume with a radius of 100-1000 A. These characteristics reduce the efficiency of catalyst use in processes based on the use of the selective hydrogen sulfide oxidation reaction.
  • the basis of the invention is the task of developing an effective iron-containing catalyst for selective oxidation hydrogen sulfide with an optimized structure and oxidation of hydrogen sulfide on iron-containing catalysts with an optimized texture in multicomponent gas mixtures containing H2S 0.3-15 vol.%, S0 2 , water vapor up to 40 vol.%, carbon monoxide, carbon dioxide, hydrogen, hydrocarbons nitrogen; with a ratio of 0 2 / H 2 S in the range of 0.15-5.0.
  • the problem is solved using a variant of the catalyst for the selective oxidation of hydrogen sulfide into elemental sulfur, including iron compounds and oxygen-containing non-metal compounds.
  • the catalyst additionally contains silicates and / or aluminosilicates in an amount of 1.0-40.0 wt.%,
  • the catalyst as oxygen-containing non-metal compounds contains phosphorus and / or boron compounds and has the following composition, in terms of oxide, wt.%:
  • silicates and / or aluminosilicates 1.0-40.0 silicates and / or aluminosilicates 1.0-40.0.
  • the problem is solved using the second version of the catalyst for the selective oxidation of hydrogen sulfide in elemental sulfur, including iron compounds, oxygen-containing non-metal compounds.
  • the catalyst additionally contains silicates and / or aluminosilicates in an amount of 1.0-40.0 wt.% And at least one metal compound selected from the group: cobalt, manganese, zinc, chromium, copper, nickel, titanium, molybdenum, tungsten, vanadium in an amount of 0.1-30.0 wt.%, the catalyst as oxygen-containing non-metal compounds contains phosphorus and / or boron compounds and has the following composition, in terms of oxide, wt.%:
  • the catalyst contains synthetic and / or natural aluminosilicates, silicates, or mixtures thereof, selected from the group: kaolinite, bentonite, montmorillonite, bidellite, argillite, vermiculite, phyllosilicate, amorphous silica.
  • the total pore volume of the catalyst is 0.10-0.40 cm 3 / g
  • the BET specific surface area is 3-60 m 3 / g.
  • the strength of the catalyst is 3-12 MPa.
  • the strength of the catalyst is 4-6 MPa.
  • the catalyst has an average pore diameter of 300-1800 A.
  • the catalyst contains a metal in the form of oxide and / or phosphorus salts and / or boron salts.
  • the catalyst contains a catalytically active material in an amount of not less than 60 wt.% And mainly in the form of a mixture of metal oxides and phosphates / borates.
  • the catalytically active catalyst material contains predominantly iron phosphates with a crystallite size of 1-70 nm and iron oxides with a crystallite size of 20-100 nm.
  • the catalyst is in the form of a handle, sphere, ring, honeycomb block.
  • the catalyst has a granule size of 2-12 mm.
  • the catalyst does not have activity in the Klaus reaction, as well as in the reactions of deep oxidation of hydrocarbons, hydrogen, carbon monoxide at temperatures up to 400 ° C.
  • the problem is solved using the process of oxidation of hydrogen sulfide by passing a gas mixture comprising hydrogen sulfide and oxygen over an iron-containing catalyst.
  • the oxidation is carried out in the presence of catalysts containing silicates and / or aluminosilicates in an amount of 1.0-40.0 wt.% And oxygen-containing compounds of phosphorus and / or boron and the catalyst has the following composition, in terms of oxide, wt.%:
  • the catalyst has the following composition, in terms of oxide, wt.%:
  • P 2 0 5 / B 2 0 5 14.0-25.0 at least one compound of an additional metal selected from the group: cobalt, manganese, zinc, chromium, copper, nickel, titanium, molybdenum, tungsten, vanadium, in terms of oxide 0.1-30.0 wt.%.
  • silicates and / or aluminosilicates 1.0-40.0 silicates and / or aluminosilicates 1.0-40.0.
  • the process of selective oxidation of hydrogen sulfide to elemental sulfur is carried out at a temperature of 200-300 ° C, followed by separation of the formed sulfur.
  • the hydrogen sulfide oxidation process is carried out at a hydrogen sulfide content of 0.3-15% by volume.
  • the hydrogen sulfide oxidation process is carried out at a hydrogen sulfide content of 0.8-1.5 vol.%.
  • the hydrogen sulfide oxidation process is carried out with a hydrogen sulfide content of 0.3-15 vol.% And a ratio of 0 2 / H 2 S in the range 0.15-5.0.
  • the hydrogen sulfide oxidation process is carried out at an O2 / H2S ratio in the range of 0.55-1.0.
  • the volumetric transmission rate of the gas mixture is 450-9000 hours 1 .
  • the volumetric flow rate of the gas mixture is 450-1800 hours 1 .
  • the hydrogen sulfide oxidation process is carried out in the presence of water vapor with a water vapor content of up to 40 vol.%.
  • the process is used for desulfurization of the Claus process exhaust gas, purification of biogas, natural gas, fuel gas, coke oven gas, chemical plant exhaust gas.
  • the process is carried out in the third and / or fourth reactor of the sulfur production unit according to the Klaus process after the preliminary stage of reduction of sulfur compounds: SO2, sulfur vapor, mercaptans, COS, CS 2 to hydrogen sulfide in the presence of a hydrogenation-hydrogenation catalyst at a temperature of 200-350 ° C.
  • the process is carried out in the presence of a catalyst by passing a gas mixture with a H 2 S content of 0.3-15 vol.%, Water vapor up to 40 vol. % in a cascade of reactors arranged in series, while air is supplied separately to each reactor in an amount corresponding to the oxygen supply at an O2 / H2S ratio in the range 0.15-5.0.
  • the process is carried out at a temperature of more than 350 ° C. to oxidize hydrogen sulfide to sulfur dioxide with an O2 / H2S ratio of more than 2.0, with a volumetric flow rate of the gas mixture of 450-6000 hr '1 , with a water vapor content of up to 30 vol.%
  • the process is used for purification of the tail gases of the Claus process, where the complete oxidation of H 2 S to SO2 is carried out in the first stage, all sulfur compounds are reduced to H 2 S in the second stage, and selective oxidation in the presence of the iron-containing catalyst described above is carried out in the third stage .
  • the technical result of the proposed solution is an iron-containing catalyst for the selective oxidation of hydrogen sulfide into elemental sulfur, which is characterized by an optimized texture: reduced bulk density, increased pore volume, average pore diameter of 300-1800 A, and providing a sulfur yield of at least 85% in the temperature range 200-300 ° C in multicomponent gas mixtures containing H 2 S 0.3-15 vol.%, Water vapor up to 40 vol.%, Sulfur dioxide, carbon monoxide, carbon dioxide, hydrogen, hydrocarbons, nitrogen; with a ratio of 0 2 / H 2 S in the range 0.15-5.0, variants of iron-containing catalysts for the selective oxidation of hydrogen sulfide and oxidation processes of hydrogen sulfide on iron-containing catalysts with an optimized texture that can be used, depending on the conditions of the processes in various technologies - for the desulfurization of the exhaust gases of the Klaus process, the purification of biogas, natural gas, fuel gases, coke oven gases, waste gases from chemical plants.
  • the method of preparation of the catalyst options is based on mixing iron compounds in the form of oxides, hydroxides, salts and / or mixtures thereof with oxygen-containing compounds of phosphorus and / or boron, porous structures and / or plasticizing additives, aluminosilicates / or silicates.
  • At least one metal selected from the group of cobalt, manganese, zinc, chromium, copper, nickel, titanium, molybdenum, tungsten, and vanadium is additionally introduced into the composition of the catalyst. After mixing all the components, extrusion, drying and heat treatment are carried out at temperatures of 300-750 ° C.
  • the proposed iron-containing catalysts are characterized by an optimized texture, which allows to achieve a high initial catalytic activity and minimize catalyst deactivation due to sulfur deposits in the pores of the catalysts, which increases the period of effective operation.
  • the proposed iron-containing catalysts are characterized by minimal activity in the Klaus reaction, which allows to achieve high selectivity of the process of oxidation of hydrogen sulfide at a temperature of 200-300 ° C.
  • the granules of the catalysts have high mechanical strength (on average 4 MPa), which is important for maintaining their integrity during transportation and loading into the reactor, and also minimizes the growth of hydrodynamic resistance to flow due to the destruction of the granules during operation of the catalysts.
  • Tables 1-2 show the compositional options and physicochemical properties of the obtained catalysts and prototype.
  • the specific surface area for nitrogen was measured on a GC-1 gas meter according to GOST 23401 for nitrogen adsorption by the BET method.
  • the crushing strength of the catalyst along the generatrix (MPa) was determined on the MP-9C instrument by the ultimate fracture force, referred to the conditional cross section of the granule.
  • the pore size distribution was measured by the method of mercury porosimetry on a poromer 2000 of the Caglio Erba company (Italy). Measurement of the mass fractions of the components of the catalysts was carried out on a Spectroscan instrument.
  • X-ray analysis of the samples was carried out on a D8 Advance powder diffractometer (Vgakeg company) in CUKO radiation, in the following modes: scanning step - 0.1 °, signal accumulation time 7 sec / point, voltage and incandescent current 40 kV and 40 tA, respectively.
  • the interpretation of the obtained diffraction patterns was carried out using the 2006 ICDD powder diffraction database.
  • the catalytic activity was measured in a laboratory setup using a flow-type quartz reactor, and the reaction mixture was analyzed by chromatographic method.
  • the mass is mixed, molded in the form of a shank with a diameter of 5 mm, dried, calcined.
  • the catalyst has an average pore diameter of 550 A.
  • the catalytically active catalyst material contains iron ortho-phosphate, iron borate and iron oxide with a crystal size of 55 nm.
  • Example 2 The preparation of the catalyst is analogous to example 1.
  • the loading of the starting components is carried out based on so that the finished catalyst is characterized by the following content of components, in terms of oxide, wt.%:
  • the catalyst has the shape of a shank with a diameter of 5 mm and a length of 5-6 mm.
  • the catalyst has an average pore diameter of 843 A.
  • the catalytically active catalyst material contains iron ortho-phosphate with a crystallite size of 25 nm and iron oxide with a crystallite size of 75 nm.
  • the catalyst is prepared analogously to example 1.
  • the loading of the starting components is carried out from the calculation so that the finished catalyst is characterized by the following content of components, in terms of oxide, wt.%:
  • the catalyst has the shape of a shank with a diameter of 5 mm and a length of 5-6 mm.
  • the catalyst has an average pore diameter of 933 A.
  • the catalytically active material contains iron orthophosphate with a crystallite size of 30 nm, chromium orthophosphate with a crystallite size of 22 nm, and alpha iron oxide with a crystallite size of 75 nm.
  • the preparation of the catalyst is analogous to example 1.
  • the loading of the starting components is carried out on the basis of such that the finished catalyst is characterized by the following content of components, in terms of oxide, in May. %:
  • the catalyst has the shape of a shank with a diameter of 5 mm and a length of 5-6 mm.
  • the catalyst has an average pore diameter of 1710 A.
  • the preparation of the catalyst is analogous to example 1.
  • the loading of the starting components is carried out based on so that the finished catalyst is characterized by the following content of components, in terms of oxide, wt.%:
  • the catalyst has an average pore diameter of 460 A.
  • the catalytically active catalyst material contains iron ortho-phosphate with a crystallite size of 33 nm, copper ortho-phosphate with a crystallite size of 24 nm, and iron oxides with a crystallite size of 58 nm.
  • the preparation of the catalyst is analogous to example 1.
  • the loading of the starting components is carried out based on so that the finished catalyst is characterized by the following content of components, in terms of oxide, wt.% .:
  • Aluminosilicate - 35 Aluminosilicate - 35.
  • the catalyst has an average pore diameter of 1649 A.
  • the catalytically active catalyst material contains non-stoichiometric phosphates of iron, vanadium and copper, and iron oxide with a crystallite size of 67 nm.
  • the preparation of the catalyst is analogous to example 1.
  • the loading of the starting components is carried out based on so that the finished catalyst is characterized by the following content of components, in terms of oxide, wt.% .:
  • the catalyst has an average pore diameter of 330 A.
  • the preparation of the catalyst is analogous to example 1.
  • the loading of the starting components is carried out based on so that the finished catalyst is characterized by the following content of components, in terms of oxide, wt.% .:
  • the catalyst has an average pore diameter of 331 A.
  • the preparation of the catalyst is analogous to example 1.
  • the loading of the starting components is carried out based on so that the finished catalyst is characterized by the following content of components, in terms of oxide, wt.% .:
  • Aluminosilicate - 36 Aluminosilicate - 36.
  • the catalyst has an average pore diameter of 300 A.
  • the preparation of the catalyst is analogous to example 1.
  • the loading of the starting components is carried out based on so that the finished catalyst is characterized by the following content of components, in terms of oxide, wt.% .: Fe 2 0 3 - 36;
  • Aluminosilicate - 36 Aluminosilicate - 36.
  • the catalyst has an average pore diameter of 309
  • the data (tables 1-2) indicate that a change in the chemical composition of the catalyst — the simultaneous introduction of compounds of phosphorus (and / or boron), aluminosilicates (and / or silicates) and modifying metals allowed us to optimize the texture of the catalyst — increase the specific surface area, increase total pore volume and pore volume with a diameter of 100-1000 A, reduce bulk density.
  • the strength of the catalysts in examples 1-10 was at least 4 MPa, which is sufficient strength for industrial applications.
  • Tables 3-10 provide data on the catalytic properties of the catalysts (tables 1-2) depending on the process conditions.
  • hydrogen sulfide-containing gases can be roughly divided into two main groups — gases containing 10-40 vol.% Water vapor, for example, exhaust gases from the Klaus process (examples 11-14, tables 3-6) and natural gases origin containing less than 7 vol. % water vapor (examples 15-18, tables 8-10).
  • Example 11 Catalytic properties in the Claus reaction.
  • Table 3 shows the catalytic properties of the catalysts prepared according to examples 1, 2, 6 (see table 1-2), operated under the conditions of the Claus reaction at a temperature of 220 ° C and a gas composition: 2% H 2 S, 1% S0 2 , 30% H 2 0, the rest is nitrogen.
  • Example 12 The effect of hydrothermal aging on the strength of the catalysts.
  • Table 4 presents data on the strength of the catalysts prepared according to examples 1-10 (see table 1-2) after hydrothermal aging, carried out at a temperature of 350 ° C and a gas composition: 40% NgO, the rest is nitrogen, the total duration is 24 hours . (Previously, it was found that noticeable changes in the properties of the catalysts occur rapidly in the first three hours of the test, and after 10 hours a stationary state is already established).
  • Example 13 Catalytic properties in the conditions of purification of exhaust gases of the Claus process.
  • the catalytic properties of the catalysts prepared according to examples 1-6 are presented under the conditions of purification of exhaust gases from the Klaus process.
  • the gas composition simulates the use of catalysts in the reactor of the sulfur production unit (OPS) after the preliminary stage of reduction of sulfur dioxide and sulfur vapor in the presence of a hydrogenation-hydrogenation catalyst known from the prior art at a temperature of 200-350 ° C.
  • the data show the advantage of the proposed catalyst in comparison with the prototype for the conversion of hydrogen sulfide, selectivity and sulfur output in the temperature range 220-280 ° C.
  • Example 14 Catalytic properties in the conditions of purification of exhaust gases of the Claus process.
  • the catalytic properties of the catalysts prepared according to example 2 are presented under the conditions of purification of exhaust gases from the Claus process in the fourth reactor of the sulfur production unit (OPS), while the gas composition is different low hydrogen sulfide content, includes SO 2 and contains 35-40 vol.% water vapor.
  • OPS sulfur production unit
  • the data presented indicate the possibility of effective sulfur recovery in the presence of the proposed catalyst in the fourth reactor of the UPS at a space velocity of 900 hours "1 s in the temperature range of 220-250 ° C and a water vapor content of up to 35 vol.%.
  • An increase in the content of water vapor up to 40% leads to reduce the temperature range in which the sulfur yield of more than 85% is achieved, and it is 220-250 ° C.
  • the advantage of the proposed process is the ability to supply air for the oxidation of hydrogen sulfide in a small excess compared with stoichiometry, which prevents the occurrence of side reactions of oxidation and simplifies process control in conditions of fluctuations in the composition and flow rate of the reaction mixture.
  • Example 15 The catalytic properties of the catalysts in the treatment of industrial, natural or associated petroleum gases. The process is carried out in a flow reactor with a stationary catalyst bed.
  • Table 7 presents the catalytic properties of the catalysts prepared according to examples 7-10 (see table 1-2), operated in a gas mixture containing water vapor — 3 vol.%.
  • Example 16 The catalytic properties of the catalysts in the purification of industrial, natural or associated petroleum gases.
  • the catalytic properties of the catalyst prepared according to example 3 are presented (see table 1-2).
  • the oxidation of hydrogen sulfide is carried out in a gas stream, vol.%: H 2 S - 1.7, 0 2 - 5, methane - 20, propane - 3, benzene vapor - 0.4, water vapor - 3-5, hydrogen - 0, 5, ⁇ - 1, the rest is nitrogen.
  • Example 17 The catalytic properties of the catalysts in the purification of industrial, natural or associated petroleum gases.
  • the process is carried out in three successive reactors with a stationary catalyst bed with intermediate sulfur removal.
  • the catalytic properties of the catalysts prepared according to examples 5 and 6 are presented under conditions of purification of natural gases with a gas composition at the inlet of the reactor: hydrogen sulfide content of 9 vol.% And water vapor content of 3 vol.%.
  • the test simulates the process of hydrogen sulfide oxidation in three successive reactors with intermediate sulfur removal, while in the first two reactors the O2 / H2S ratio is set lower than stoichiometrically necessary to avoid overheating, and in the third reactor, O2 / H2S is 0.65.
  • Example 18 The catalytic properties of the catalyst under conditions of oxidation of hydrogen sulfide to S0 2 .
  • the process is carried out in a flow reactor with a stationary catalyst bed.
  • the catalyst is characterized by low sensitivity to the content of water vapor, which allows the processing of gases of various origins and the technological design of the process does not require the removal of water before the stage of selective oxidation of hydrogen sulfide.
  • the catalyst is inert with respect to the reactions of deep oxidation of hydrocarbons, CO and hydrogen in the temperature range 200-400 ° C, which allows it to be used to purify gases of various origins from hydrogen sulfide.
  • the catalyst is characterized by low sensitivity to changes in the ratio 0 2 / H 2 S in the range of 0.55-1.0, which prevents the occurrence of adverse reactions in the temperature range 200-300 ° C and allows to achieve high sulfur yields; in addition, these process conditions minimize catalyst deactivation by means of surfactation and sulfidation, which increases the effective life of the catalyst.
  • the catalyst oxidizes hydrogen sulfide to sulfur dioxide without the formation of sulfur trioxide. This is a property of the catalyst. allows you to use it in technologies based on the reaction of oxidation of hydrogen sulfide to S0 2 .
  • the catalyst for the selective oxidation of hydrogen sulfide can be used at gas processing, petrochemical and other industries using various processes with its application, in particular, for purification of exhaust gases from the Claus process, low-sulfur natural and associated petroleum gases, emissions from chemical industries, for purification biogas.

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Abstract

L'invention porte sur des catalyseurs pour l'oxydation sélective de sulfure d'hydrogène en soufre et en hydrogène dans des gaz de différentes origines contenant 0,3-15,0 vol. % d'hydrogène sulfuré, et sur des processus utilisant les catalyseurs. Le catalyseur comprend des composés de fer, des silicates et/ou des aluminosilicates dans des quantités de 1,0-40,0 en % en masse, des composés de phosphore et/ou de bore et possède la composition suivante, en termes d'oxyde, en % en masse: Fe2O3 36,0-85,0 P2O5/B2O5 4,0-25,0 silicates et/ou aluminosilicates 1,0-40,0. Dans une deuxième variante, le catalyseur comprend au moins un composé de métal sélectionné dans le groupe: cobalt, manganèse, zinc, chrome, cuivre, nickel, titane, molybdène, tungstène, vanadium dans des quantités de 0,1-30,0 % en masse. Le résultat technique de la solution proposée consiste en un catalyseur contenant du fer d'oxydation sélective d'hydrogène sulfuré en soufre élémentaire qui est caractérisé par une texture optimisée: un faible poids en vrac, une taille de pores plus importante, un diamètre moyen des pores de 300-1800 Å, et qui assure un rendement minimal en soufre de 85% dans l'intervalle des températures 180-300ºC dans des mélanges gazeux à composants multiples contenant H2S 0,3-15 vol. %, et de la vapeur d'eau jusqu'à 40 en vol. %, du dioxyde de soufre, de l'oxyde de carbone, de l'hydrogène, des hydrocarbures, de l'azote; avec un rapport de O2/H2S dans des limites de 0,15-5,0, des variantes de catalyseurs contenant du fer, d'oxydation sélective de sulfure d'hydrogène et des processus d'oxydation d'hydrogène sulfuré sur des catalyseurs contenant du fer à texture optimisée qui peuvent être utilisés en fonction des conditions de réalisation de processus selon des technologies différentes pour la désulfuration des gaz d'échappement du procédé Claus, pour la purification de biogaz, des gaz d'origine naturelle, des gaz combustibles, des gaz de fours à coke, des gaz d'échappement d'usines chimiques.
PCT/RU2017/000497 2016-07-11 2017-07-07 Catalyseur d'oxydation sélective de sulfure d'hydrogène (et variantes) et différents processus l'utilisant WO2018013009A1 (fr)

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RU2016127910A RU2632014C1 (ru) 2016-07-11 2016-07-11 Процесс окисления сероводорода
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RU2016127911A RU2629193C1 (ru) 2016-07-11 2016-07-11 Катализатор для селективного окисления сероводорода (варианты)
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CN112517008A (zh) * 2020-12-29 2021-03-19 福州大学 一种Fe掺杂的镁铝尖晶石催化剂的制备方法及其在脱硫领域的应用
CN113277639A (zh) * 2021-03-31 2021-08-20 李晟贤 一种试气污水处理方法
CN114849739A (zh) * 2021-02-03 2022-08-05 威水星空（北京）环境技术有限公司 一种铁硼硫化钼复合多孔催化剂及其制备方法与应用

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RU2070089C1 (ru) * 1989-07-21 1996-12-10 ВЕГ-Газинститут Н.В. Катализатор для селективного окисления соединений серы и способ селективного окисления соединений серы до элементарной серы
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CN105126850A (zh) * 2015-08-21 2015-12-09 山东迅达化工集团有限公司 选择氧化h2s生产硫磺的催化剂及其制备方法

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Publication number Priority date Publication date Assignee Title
CN112517008A (zh) * 2020-12-29 2021-03-19 福州大学 一种Fe掺杂的镁铝尖晶石催化剂的制备方法及其在脱硫领域的应用
CN112517008B (zh) * 2020-12-29 2023-10-27 福州大学 一种Fe掺杂的镁铝尖晶石催化剂的制备方法及其在脱硫领域的应用
CN114849739A (zh) * 2021-02-03 2022-08-05 威水星空（北京）环境技术有限公司 一种铁硼硫化钼复合多孔催化剂及其制备方法与应用
CN114849739B (zh) * 2021-02-03 2023-08-18 威水星空（北京）环境技术有限公司 一种铁硼硫化钼复合多孔催化剂及其制备方法与应用
CN113277639A (zh) * 2021-03-31 2021-08-20 李晟贤 一种试气污水处理方法

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