EP1576076A1 - Procede pour retirer des composes soufres de gaz contenant des hydrocarbures - Google Patents

Procede pour retirer des composes soufres de gaz contenant des hydrocarbures

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Publication number
EP1576076A1
EP1576076A1 EP03789265A EP03789265A EP1576076A1 EP 1576076 A1 EP1576076 A1 EP 1576076A1 EP 03789265 A EP03789265 A EP 03789265A EP 03789265 A EP03789265 A EP 03789265A EP 1576076 A1 EP1576076 A1 EP 1576076A1
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EP
European Patent Office
Prior art keywords
weight
catalyst
catalysts
liter
composition
Prior art date
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EP03789265A
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German (de)
English (en)
Inventor
Helge Wessel
Markus HÖLZLE
Bernd Vogel
Roland HAGEBÖKE
Michael Hesse
Norbert Wilden
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BASF SE
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BASF SE
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Priority claimed from DE2002160028 external-priority patent/DE10260028A1/de
Priority claimed from DE2003131771 external-priority patent/DE10331771A1/de
Priority claimed from DE2003140251 external-priority patent/DE10340251A1/de
Priority claimed from DE2003152104 external-priority patent/DE10352104A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1576076A1 publication Critical patent/EP1576076A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas

Definitions

  • the present invention relates to a process for removing sulfur compounds from hydrocarbon-containing gases on catalysts, with the exception of activated carbons and zeolites, which contain copper, silver, zinc, molybdenum, iron, cobalt, nickel or mixtures thereof.
  • Coals hydrogen-containing gases - such as Natural gas - usually contain sulfur compounds or must be mixed with malodorous sulfur compounds for safety reasons. On an industrial scale, natural gas is e.g. hydrodesulfurized. However, this is not possible or useful for every application.
  • the hydrogen necessary for the operation of fuel cells is usually made up
  • natural gas has a high hydrogen / carbon ratio and thus enables the production of a hydrogen-rich reformer gas.
  • natural gas describes a large number of possible gas compositions that can vary widely depending on the location. Natural gas can consist almost exclusively of methane (CH 4 ), but in other cases it can also contain considerable amounts of higher hydrocarbons.
  • higher hydrocarbons is understood to mean all hydrocarbons from ethane (C 2 H 6 ), regardless of whether they are saturated, unsaturated or even cyclic hydrocarbons.
  • the proportions of the higher hydrocarbons in natural gas increase with increasing molecular weight and Ethane and propane are typically found in the percentage range, while hydrocarbons with more than ten carbons usually only have a few ppm in natural gas, and the higher hydrocarbons also contain cyclic compounds such as carcinogenic benzene, toluene and xylenes. Each of these compounds can be present in the natural gas in concentrations of> 100 ppm.
  • H 2 S hydrogen sulfide
  • COS carbon oxysulfide
  • CS 2 disulfide carbon
  • Methane or natural gas per se are odorless gases that are not toxic, but in combination with air can lead to ignitable mixtures.
  • a small concentration of malodorous substances is added to natural gas, which, as so-called odorants, cause the odor characteristic of natural gas.
  • the odorization of natural gas is required by law in most countries - together with the odorant to be used.
  • mercaptans such as tert-butyl mercaptan or ethyl mercaptan are used as odorants, while in the member states of the European Union mostly cyclic sulfur compounds such as tetrahydrothiophene are used. Together with the sulfur compounds that occur naturally in natural gas, this results in a large number of different sulfur compounds in natural gas.
  • the different regulations for the composition of natural gas usually allow up to 100 ppm sulfur in natural gas.
  • LPG liquefied petroleum gas
  • Liquefied petroleum gas which contains propane and butane as its main components, must be mixed with sulfur-containing molecules as odor markers, just like natural gas.
  • a procedure is preferred in which the hydrocarbon-containing gas is passed in a single pass at room temperature through an adsorber which completely removes all sulfur components as far as possible.
  • the adsorber should preferably be operable at room temperature and at normal pressure. Since the adsorber should be suitable for operating natural gases of different compositions, it is also important that only the sulfur-containing components are adsorbed from the natural gas and the co-adsorption of higher hydrocarbons is suppressed to a negligible extent. Only under these conditions is it possible to achieve high adsorption capacities for sulfur-containing compounds, which corresponds to a sufficiently long service life. In this way, the frequent exchange of the adsorber medium can be avoided.
  • EP-A-1 121 922 discloses the adsorptive removal of sulfur-containing organic components such as sulfides, mercaptans and thiophenes from natural gas with the aid of silver-doped zeolites at room temperature.
  • the high silver content is a disadvantage.
  • zeolites readily adsorb all of the higher hydrocarbons found in the gas stream in their pore system.
  • cyclic hydrocarbons such as. eg benzene are completely adsorbed and can be enriched in the zeolite in the range of a few% by weight.
  • the examples from EP 1 121 977 A2 also show the effectiveness of the catalysts according to the invention for the adsorption of organic sulfur compounds, but not for inorganic sulfur compounds such as H 2 S and COS.
  • US-A-2002/0159939 discloses a two-stage catalyst bed consisting of an X zeolite for removing odorants and then a nickel-based catalyst for removing sulfur-containing components from natural gas for operation in fuel cells.
  • a disadvantage of this process is that COS cannot be removed directly but only after hydrolysis to H 2 S.
  • the object of the present invention was therefore to remedy the disadvantages mentioned above and in particular to enable the use of hydrocarbon-containing gases contaminated with sulfur compounds for fuel cells.
  • the hydrocarbon-containing gas contaminated by sulfur compounds can be very particularly preferably at a temperature of (-50) to + 150 ° C., preferably (-20) to 80 ° C., particularly preferably 0 to 80 ° C., in particular 15 to 40 ° C. at room temperature and a pressure of 0.1 to 10 bar, preferably 0.5 to 4.5 bar, particularly preferably 0.8 to 1.5 bar, in particular at normal pressure, are passed over one or more catalysts according to the invention.
  • suitable hydrocarbon-containing gases contaminated with sulfur compounds are natural gas, town gas, biogas and liquefied petroleum gas (LPG), preferably natural gas and town gas, particularly preferably natural gas.
  • LPG liquefied petroleum gas
  • the contaminating sulfur compounds are generally COS, H 2 S, CS 2 as well as mercaptans and disulfides and for safety reasons, malodorous sulfur compounds such as tetrahydrothiophene, ethyl mercaptan, n-butyl mercaptan, t-butyl mercaptan or mixtures thereof.
  • Suitable catalysts according to the invention which can also act as an adsorbent, are those which contain 1 to 99.8% by weight, preferably 2 to 85% by weight, particularly preferably 3 to 75% by weight, in particular 5 to 70% by weight .-% copper, silver, zinc, molybdenum, iron, cobalt, nickel or mixtures thereof and 0.2 to 99 wt .-%, preferably 15 to 98 wt .-%, particularly preferably 25 to 97 wt .-%, in particular 30 to 95 wt .-% oxides from the group MB, IIIB, IVB, VIB, VIII, IIIA and IVA of the periodic table of the elements, which are at least up to 250 ° C solids, such as the oxides of magnesium, calcium, scandium, yttrium, lanthanum, titanium, zircon, chromium, tungsten, boron, aluminum, gallium, silicon, germanium and tin, preferably magnesium, calcium, lanthanum, titanium,
  • the catalysts according to the invention are copper-containing catalysts which contain 30 to 99.8% by weight, preferably 40 to 85% by weight, particularly preferably 50 to 75% by weight of copper oxide and 0.2 to 70% by weight, preferably 15 to 60 wt .-%, particularly preferably 25 to 50 wt .-% oxides from group IIB, IIIB, IVB, VIB, VIII, IIIA and IVA of the periodic table of the elements, which are at least up to 250 ° C solids, such as Zinc, scandium, yttrium, lanthanum, titanium, zirconium, chrome, molybdenum, tungsten, Iron, cobalt, nickel, boron, aluminum, gallium, silicon, germanium and tin, preferably zinc, lanthanum, titanium, zirconium, chromium, molybdenum, iron, cobalt, nickel, aluminum and silicon, particularly preferably zinc, lanthanum, titanium, zirconium , Nickel, aluminum and silicon contain, preferably consist of
  • molybdenum-containing catalysts are suitable which contain 1 to 80% by weight, preferably 2 to 60% by weight, particularly preferably 3 to 50% by weight of molybdenum oxide and 20 to 99% by weight, preferably 40 to 98 % By weight, particularly preferably 50 to 97% by weight, of oxides from the group MB, IIIB, IVB, VIB, VIII, IIIA and IVA of the Periodic Table of the Elements, which are solids at least up to 250 ° C., for example the oxides of magnesium, calcium, zinc, scandium, yttrium, lanthanum, titanium, zirconium, chromium, tungsten, iron, cobalt, nickel, boron, aluminum, gallium, silicon, germanium and tin, preferably magnesium, calcium, zinc, lanthanum, Contain titanium, zircon, chromium, iron, cobalt, nickel, aluminum and silicon, particularly preferably magnesium, calcium, zinc, titanium, zircon, cobalt, nickel, aluminum and silicon, particularly
  • a preferred embodiment are catalysts containing copper and molybdenum.
  • the copper- and molybdenum-containing catalysts can be used separately in any order or mixed, preferably homogeneously mixed or particularly preferably in the sequence of copper-containing before molybdenum-containing catalyst. Mixtures are usually the simplest variant of the invention and can preferably be used in small applications (e.g. in small fuel cells). In all other cases, it is generally advantageous to separate the catalysts in the order of copper-containing before molybdenum-containing catalyst. Further catalysts, as are known for example from EP-A-1 121 977, can be connected downstream.
  • the catalysts according to the invention can be prepared by generally known processes, for example by precipitation, impregnation, mixing, kneading, sintering, spraying, spray drying, ion exchange or electroless deposition, preferably by precipitation, impregnation, mixing, sintering or spray drying, particularly preferably by precipitation or Impregnation, especially by impregnation.
  • the powders of catalysts according to the invention generally obtained by precipitation can after the precipitation and the catalysts according to the invention produced by impregnation can, before or after the impregnation, optionally with pore formers such as cellulose, glycerol, urea, ammonium carbonate, ammonium nitrate, melamine, carbon fibers or mixtures thereof , mixed and tabletted with conventional auxiliaries, such as binders, for example formic acid, polyvinylpyrolidone (PVP), polysilicic acid or mixtures thereof and, if appropriate, lubricants such as graphite, stearic acid, molybdenum sulfide or their mixtures, or extruded into any shape and, if necessary, subsequently split are processed.
  • pore formers such as cellulose, glycerol, urea, ammonium carbonate, ammonium nitrate, melamine, carbon fibers or mixtures thereof
  • auxiliaries such as binders, for example
  • Non-zeolitic masses are suitable as catalysts of the invention, for example those without a channel structure; activated carbons and those that are doped are also excluded.
  • the catalysts according to the invention can optionally be activated before or after shaping at temperatures from 250 to 750 ° C., for example in the presence of hydrogen, carbon monoxide, nitrous oxide or mixtures thereof, or generally in a reducing gas atmosphere, in particular in the case of catalysts containing copper or molybdenum.
  • the method according to the invention can generally be connected upstream, i.e. that after the cleaning of the hydrocarbon-containing gas according to the invention, it can be used to obtain hydrogen which feeds the fuel cell.
  • the method according to the invention is suitable for all known types of fuel cells such as PEM fuel cells, phosphoric acid fuel cells (PAFC), MCFC fuel cells (molten carbonate) and high-temperature fuel cells (SOFC).
  • the method according to the invention is suitable for stationary and transient applications.
  • Preferred for use in the stationary area are, for example, in fuel cell systems for the simultaneous generation of electricity and heat (such as combined heat and power plants), preferably in the home energy supply.
  • the method for cleaning hydrocarbons for fuel cells in passenger cars (passenger cars), trucks (trucks), buses or locomotives, preferably passenger cars and trucks, particularly preferably passenger cars, can be used preferably for use in the transient area. It does not matter whether the fuel cells are only used to generate on-board electricity or for propulsion.
  • Composition 52.5% by weight CuO; 30% by weight of ZnO and 17.5% by weight of Al 2 O 3
  • a mixture of a nitric acid solution of 420 g copper (II) oxide, a nitric acid solution of 240 g zinc oxide and a nitric acid solution of 140 g aluminum nitrate nonahydrate was mixed with a solution of 474 g sodium carbonate in 2 liters of demineralized water in a 50 ° C kept water at a pH of about 6 precipitated and stirred for 3 h.
  • the precipitate was separated off, washed with sodium and nitrate ions with water, dried at 120 ° C. and calcined at 400 ° C. for 1 h.
  • Composition 40% by weight CuO; 40% by weight of ZnO and 20% by weight of Al 2 O 3
  • Composition 73.9% by weight CuO; 21.1% by weight of ZnO and 5% by weight of ZrO 2
  • Composition 50% by weight CuO; 30% by weight of ZnO and 17.5% by weight of Al 2 O 3 and 2.5% by weight of ZrO 2
  • Composition 60% by weight CuO; 20% by weight ZnO, 17.5% by weight Al 2 O 3 and 2.5% by weight ZrO 2
  • This catalyst was produced analogously to catalyst 4.
  • the compressive strength of the tablets was 100 N.
  • Catalyst 6 composition 67% by weight CuO, 26.4% by weight ZnO and 6.6% by weight Al 2 O 3
  • a solution of 320 g of Zn (NO 3 ) 2 "6 H 2 O and 336.4 g of Al (NO 3 ) 3 " 9 H 2 O in 600 ml of water and 2000 ml of a 20% by weight sodium carbonate solution were combined that the precipitation with stirring at a temperature of 50 ° C and a pH of 6.7 to 6.9 was carried out, stirred for 30 minutes, filtered, then washed free of sodium and nitrate, dried at 120 ° C. for 12 h and calcined at 350 ° C. for 2 h.
  • Composition 65% by weight CuO; 20 wt% ZnO; 6% by weight Al 2 O 3 ; 6% by weight of ZrO 2 and 3% by weight of La 2 O 3
  • the preparation was carried out analogously to catalyst 2 at a nitric acid solution of 215 g of CuO, 66 g of ZnO, 145 g of AI (NO 3) 3 '9H 2 0, 20 g of ZrO 2 and 10 g of La 2 O 3, but was at a temperature of 70 ° C. This gave 330 g of the mixed oxide, which was processed analogously to catalyst 1 into tablets with a lateral compressive strength of 80 N.
  • the BET surface area was 109 m 2 / g.
  • Composition 60% by weight CuO; 20 wt% ZnO; 10% by weight Al 2 O 3 ; 5 wt% ZrO 2 and 5 wt% MgO
  • the preparation was carried out analogously to catalyst 2 at a nitric acid solution of 231 g of CuO, 77 g of ZnO, 290 g of AI (NO 3) 3 '9H 2 0, 19.2 g of ZrO 2 and 19.5 g of MgO, however, was conducted at a Temperature of 70 ° C. This gave 350 g of the mixed oxide, which was processed analogously to catalyst 1 into tablets with a lateral compressive strength of 90 N.
  • the BET surface area was 96 m 2 / g.
  • Composition 60% by weight CuO; 20 wt% ZnO; 10% by weight Al 2 O 3 ; 5 wt% ZrO 2 and 5 wt% NiO
  • the preparation was carried out analogously to catalyst 2 at a nitric acid solution of 264 g of CuO, 88 g of ZnO, 323 g of AI (NO 3) 3 '9H 2 0, 22 g of ZrO 2 and 22 g of NiO, but was precipitated at a temperature of 70 ° C. 400 g of the mixed oxide were obtained, which was processed analogously to catalyst 1 into tablets with a lateral compressive strength of 80 N.
  • the BET surface area was 114 m 2 / g.
  • Composition 60% by weight CuO; 20 wt% ZnO; 10% by weight Al 2 O 3 ; 5% by weight of ZrO 2 and 5% by weight of SiO 2
  • the preparation was carried out analogously to catalyst 2 at a nitric acid solution of 200 g of CuO, 66 g of ZnO, 241 g of AI (NO 3) 3 '9H 2 0, 16.5 g of ZrO 2 and 16.5 g of SiO 2 (colloidal; Ludox TM; 50 wt .-% in water), but was precipitated at a temperature of 70 ° C.
  • This gave 300 g of the mixed oxide, which was processed analogously to catalyst 1 into tablets with a lateral compressive strength of 90 N.
  • the BET surface area was 125 m 2 / g.
  • Impregnation catalyst of the composition 14.6% by weight CuO, 7.4% by weight ZnO and 78% by weight Al 2 O 3
  • Impregnation catalyst of the composition 71, 15% by weight Al 2 O 3 , 18% by weight MoO 3 ,
  • a heatable tubular reactor with a diameter of 10 mm was each filled with 10 g of one of the previously described catalysts in split form (1 to 2 mm) and operated in a single pass.
  • the exit gas was fed to a gas chromatograph.
  • a flame ionization detector For the detection of organic carbon compounds by a flame ionization detector and for selective sulfur detection by a flame photometric detector.
  • Catalysts 1-15 were exposed to a stream of methane containing 1,000 ppm COS.
  • the gas space velocity, that is the volume of gas per volume of catalyst was 1000 " ⁇ h the reaction temperature was 25 ° C.
  • the experiment was terminated as soon as step ppm in the exit gas, the amount of COS1.
  • Table A summarizes the results of the sulfur content of the catalysts subsequently removed.
  • Catalysts 1 through 15 were exposed to a stream of methane containing 1000 ppm H 2 S.
  • the gas space velocity that is the volume of gas per volume of catalyst was 1000 h ' ⁇ the reaction temperature 25 ° C.
  • the experiment was stopped as soon as the amount of H 2 S exceeded 1 ppm in the exit gas.
  • Table A summarizes the results of the sulfur content of the catalysts subsequently removed.
  • Catalysts 1-15 were exposed to a stream of methane containing 500 ppm H 2 S and 500 ppm COS.
  • the gas space velocity that is the volume of gas per volume of catalyst was 1000 h " ⁇ the reaction temperature 25 ° C.
  • the test was canceled as soon as the amount of H 2 S and COS together exceeded 1 ppm in the outlet gas.
  • Table A summarizes the results of the sulfur content of the catalysts subsequently removed.
  • the catalysts 1 to 15 were exposed to a gas stream consisting of 60 vol.% Methane and 40% propane, which contained 500 ppm H 2 S and 500 ppm COS and additionally 2,000 ppm toluene.
  • the gas load that is to say the volume of gas per volume of catalyst, was 1000 l / the reaction temperature was 25 ° C. The experiment was stopped as soon as the amount of H 2 S and COS together exceeded 1 ppm in the exit gas.
  • Table A summarizes the results of the sulfur content of the catalysts subsequently removed.
  • Table A shows that regardless of the presence of higher hydrocarbons, COS and H 2 S were still completely adsorbed on the catalyst. Adsorption of the higher hydrocarbons (such as toluene) on the catalyst was not observed.
  • the catalyst was reduced at a temperature of about 200 ° C. and a gas stream of about 1% by volume of hydrogen in nitrogen.
  • the catalysts 1 to 15 reduced in this way were exposed to a stream of methane which contained 15 ppm by volume of tetrahydrothiophene (THT).
  • THT tetrahydrothiophene
  • the gas space velocity, that is the volume of gas per volume of catalyst was 1000 h ' ⁇ the reaction temperature 25 ° C.
  • the experiment was stopped as soon as the amount of THT in the outlet gas exceeded 1 ppm.
  • Table B summarizes the results of the adsorption capacity of the catalyst for THT until termination.
  • Table B summarizes the results of the adsorption capacity of the catalyst for THT until termination.
  • Table B shows that the adsorption was lower than in Application Example 5, in which the catalysts were used in reduced form.
  • Natural gas is used instead of methane. This essentially has the following composition: 84% by volume methane, 3.5% by volume ethane, 0.6% by volume propane, 9.3% by volume nitrogen, 1.6% by volume Carbon dioxide and a total of approx.3,500 ppm higher hydrocarbons (C 3 - C 8 ).
  • the following constituents are mixed into the natural gas: 20 ppm COS, 20 ppm H 2 S and 15 ppm THT.
  • the catalyst initially introduced is reduced by 80% in each case, so that approximately 80% of the catalyst bed are optimized for the absorption of THT, while the rest is available for the adsorption of COS and H 2 S.
  • the gas load that is to say the volume of gas per volume of catalyst, is again 1000 1 / l * h "1 ; the reaction temperature is 25 ° C.
  • the experiment is stopped when THT with> 1 ppm for the first time in the off-gas after the reactor
  • the adsorption capacity of the catalyst in g THT / liter of catalyst was calculated from the gas volume flow passed through the catalyst up to this point in time. In all cases, neither COS nor H 2 S was detectable in the exhaust gas of the reactor at this point in time.
  • Catalysts 1-15 were exposed to a stream of methane containing 1,000 ppm COS.
  • the gas space velocity, that is the volume of gas per volume of catalyst was 1000 " ⁇ h the reaction temperature was 25 ° C.
  • the experiment was terminated when 5 ppm exceed the amount of COS in the exit gas.
  • Table B summarizes the results of the adsorption capacities for sulfur-containing components.
  • the THT adsorption capacity of this activated carbon was 0.9 g THT per liter activated carbon.
  • the THT adsorption capacity of this activated carbon was 6.5 g THT per liter activated carbon.
  • the THT adsorption capacity of this activated carbon was 0.5 g THT per liter activated carbon.
  • the THT adsorption capacity of this activated carbon was 0.6 g THT per liter activated carbon.
  • the COS adsorption capacity of this activated carbon was 0.6 g COS per liter activated carbon.
  • the COS adsorption capacity of this activated carbon was 0.55 g COS per liter activated carbon.
  • Catalyst 13 composition 1.5% by weight of CoO, 7% by weight of MoO 3 and 91.5% by weight of Al 2 O 3
  • the strands obtained were treated by spraying a mixture of 102 g of a 15.9% strength by weight cobalt nitrate solution in 420 ml of water, dried again at 120 ° C. for 7 hours and calcined at 550 ° C. for 3 hours.
  • the catalyst obtained had a liter weight of 736 g / liter, a cutting hardness of 12.5 N, a BET surface area of 250 m 2 / g, an ignition loss (at 900 ° C.) of 1.4% by weight and a composition of 1.5% by weight of CoO, 7% by weight of MoO 3 and 91.5% by weight of Al 2 O 3 .
  • Composition 4.5% by weight CoO, 22% by weight MoO 3 and 73.5% by weight Al 2 O 3
  • the catalyst had a liter weight of 915 g / liter, a cutting hardness of 14.7 N, a BET surface area of 241 m 2 / g, an ignition loss (at 900 ° C.) of 2.7% by weight and one
  • Composition 3% by weight CoO, 15% by weight MoO 3 , 4.4% by weight SiO 2 and 77.6% by weight Al 2 O 3
  • the catalyst obtained had a liter weight of 770 g / liter, a cutting hardness of 14.8 N, a BET surface area of 307 m 2 / g, an ignition loss (at 900 ° C.) of 2.2% by weight and a composition of 3% by weight of CoO, 15% by weight of MoO 3 , 4.4% by weight of SiO 2 and 77.6% by weight of Al 2 O 3 .
  • Composition 3% by weight CoO, 15% by weight MoO 3 , 4.3% by weight SiO 2 and 77.7% by weight Al 2 O 3
  • the catalyst obtained had a liter weight of 602 g / liter, a cutting hardness of 3.95 N, a BET surface area of 265 m 2 / g, an ignition loss (at 900 ° C.) of 2.6% by weight and a composition of 3% by weight of CoO, 15% by weight of MoO 3 , 4.3% by weight of SiO 2 and 77.7% by weight of Al 2 O 3 .
  • Composition 3% by weight CoO, 15% by weight MoO 3 and 82% by weight Al 2 O 3 Analogous to catalyst 14, 1581 g of aluminum oxide (PURALOX® SCCa 5/150 of
  • Composition 3% by weight of CoO, 15% by weight of MoO 3 and 82% by weight of SiO 2
  • the strands obtained were treated by spraying a mixture of 780 g of a 15.9% strength by weight cobalt nitrate solution in 1106 ml of H 2 O, dried and calcined.
  • the catalyst obtained had a liter weight of 530 g / liter, a cutting hardness of 7.88 N, a BET surface area of 51.1 m 2 / g, an ignition loss (at 900 ° C.) of 6.2% by weight and a composition of 3% by weight of CoO, 15% by weight of MoO 3 and 82% by weight of SiO 2 .
  • Composition 3% by weight of CoO, 15% by weight of MoO 3 and 82% by weight of TiO 2
  • the catalyst obtained had a liter weight of 1142 g / liter, a cutting hardness of 5.0 N, a BET surface area of 72.7 m 2 / g, an ignition loss (at 900 ° C.) of 6.9% by weight and a composition of 3% by weight of CoO, 15% by weight of MoO 3 and 82% by weight of TiO 2.
  • Composition 3% by weight CoO, 15% by weight MoO 3 , 15.6% by weight CaO and
  • the catalyst obtained had a liter weight of 1134 g / liter, a BET surface area of 142.1 m 2 / g, an ignition loss (at 900 ° C.) of 6.0% by weight and a composition of 3% by weight.
  • Composition 3% by weight CoO, 15% by weight MoO 3 and 82% by weight ZrO 2
  • the catalyst obtained had a liter weight of 1134 g / liter, a BET surface area of 51.2 m 2 / g, an ignition loss (at 900 ° C.) of 1.7% by weight and a composition of 3% by weight CoO, 15 wt% MoO 3 and 82 wt% ZrO 2 .
  • Composition 3% by weight CoO, 15% by weight MoO 3 , 15.7% by weight MgO and
  • the catalyst obtained had a liter weight of 752 g / liter, a BET surface area of 179.2 m 2 / g, an ignition loss (at 900 ° C.) of 5.5% by weight and a composition of 3% by weight.
  • Composition 3% by weight CoO, 15% by weight MoO 3 and 82% by weight Al 2 O 3
  • the catalyst obtained had a liter weight of 977 g / liter, a BET surface area of 109 m 2 / g, an ignition loss (at 900 ° C.) of 1.8% by weight and a composition of 3% by weight of CoO, 15% by weight MoO 3 and 82% by weight Al 2 O 3 .
  • Catalyst 24 composition 3% by weight of CoO, 15% by weight of MoO 3 and 82% by weight of Al 2 O 3
  • SASOL company an aluminum oxide calcined for 8 hours at 975 ° C.
  • the catalyst obtained had a liter weight of 771 g / liter, a BET surface area of 99 m 2 / g, a loss on ignition (at 900 ° C.) of 3.4% by weight and a composition of 3% by weight of CoO, 15% by weight MoO 3 and 82% by weight Al 2 O 3 .
  • Composition 3.3% by weight CoO, 14% by weight Mo0 3 and 82.7% by weight Al 2 O 3
  • the strands obtained had a liter weight of 705 g / liter, a cutting hardness of 2.65 N, a BET surface area of 167 m 2 / g, a loss on ignition (at 900 ° C.) of 2.8% by weight and a composition of 3.3% by weight of CoO, 14% by weight of MoO 3 and 82.7% by weight of Al 2 O 3 .
  • the manufacturing process is repeated 6 times. 7420 g of these strands were ground into chips of 0.3-0.7 mm, mixed with 222.6 g of graphite and shaped into tablets with a diameter of 1.5 mm and a height of 2.5 mm.
  • the tablets had a lateral compressive strength of 40 N, a vibrating weight of 906 g / l, a surface area of 236 m 2 / g and a loss on ignition (at 900 ° C.) of 5.8% by weight.
  • Composition 3.3% by weight of CoO, 1% by weight of MoO 3 and 82.7% by weight of Al 2 O 3
  • phosphoric acid molybdenum solution prepared by reacting 600 kg of molybdenum trioxide (purity of 90%; powder) in 200 kg of orthophosphoric acid and 1500 liters of water, were 3 hours at 100 ° C. and 24 hours at 40 ° C. and filtering, kneaded for 2 hours, extruded into 1.7 mm round strands, dried at 120 to 150 ° C. and calcined at 550 ° C.
  • the catalyst obtained had a liter weight of 610 g / l, a cutting hardness of 5.3 N, a loss on ignition (at 900 ° C.) of 6.39% by weight and a composition of 3.3% by weight of CoO, 14 % By weight of MoO 3 and 82.7% by weight of Al 2 O 3.
  • Catalyst 27 composition 3.3% by weight of CoO, 14% by weight of MoO 3 and 82.7% by weight of Al 2 O 3
  • the preparation was carried out analogously to catalyst 26. In addition, post-heating was carried out at 500 ° C. for 2 h.
  • the catalyst obtained had a liter weight of 613 g / l, a cutting hardness of 5.1 N, a loss on ignition (at 900 ° C.) of 5.5% by weight and a composition of 3.3% by weight of CoO, 14 % By weight of MoO 3 and 82.7% by weight of Al 2 O 3.
  • Composition 3.3% by weight of CoO, 14% by weight of MoO 3 and 82.7% by weight of Al 2 O 3
  • the preparation was carried out analogously to catalyst 26. In addition, post-heating was carried out at 600 ° C. for 2 h.
  • the catalyst obtained had a liter weight of 627 g / l, a cutting hardness of 5.1 N, a loss on ignition (at 900 ° C.) of 4.6% by weight and a composition of 3.3% by weight of CoO, 14 % By weight of MoO 3 and 82.7% by weight of Al 2 O 3 .
  • Composition 3.3% by weight of CoO, 14% by weight of MoO 3 and 82.7% by weight of Al 2 O 3
  • the preparation was carried out analogously to catalyst 26. In addition, post-heating was carried out at 700 ° C. for 2 h.
  • the catalyst obtained had a liter weight of 644 g / l, a cut hardness of 4.3 N, a loss on ignition (at 900 ° C.) of 4.2% by weight and a composition of 3.3% by weight of CoO, 14 % By weight of MoO 3 and 82.7% by weight of Al 2 O 3.
  • Catalyst 30 composition 7.5% by weight of MoO 3 and 92.5% by weight of Al 2 O 3
  • Composition 24% by weight MoO 3 and 76% by weight Al 2 O 3
  • the catalyst obtained had a liter weight of 856 g / liter, a cutting hardness of 12.2 N, a loss on ignition (at 900 ° C.) of 9.35% by weight, a BET surface area of 252 m 2 / g and a composition of 24% by weight MoO 3 and 76% by weight Al 2 O 3 .
  • Composition 17% by weight MoO 3 , 5.4% by weight SiO 2 and 77.6% by weight Al 2 O 3
  • Catalyst 33 composition 16% by weight MoO 3 and 84% by weight SiO 2
  • a heatable tubular reactor with a diameter of 10 mm was each filled with 40 ml of one of the previously described catalysts and operated in a single pass.
  • the exit gas was fed to a gas chromatograph.
  • the GC has a flame ionization detector for the detection of organic carbon compounds and a flame photometric detector for selective sulfur detection.
  • the catalysts 13 to 33 were exposed to a gas stream consisting of 60% by volume methane and 40% propane, which contained 15 ppm tetrahydrothiophene (THT) and an additional 2,000 ppm toluene.
  • the gas load, ie the volume of gas per volume of catalyst was 7,000 h '1 , the reaction temperature 25 ° C.
  • the experiment was stopped as soon as the exit gas contained more than 100 ppb sulfur.
  • Table C The results are summarized in Table C.
  • the catalysts 13 to 33 became a gas stream consisting of natural gas (which in the present case is essentially 9.27% by volume of nitrogen, 1.64% by volume of carbon dioxide, 84.5% by volume of methane , 3.46 vol .-% ethane, 0.579 vol .-% propane and approx. 12000 ppm other C 2 - to C 8 -hydrocarbons), which contains 15 ppm tert-butyl-mercaptan and 15 ppm tetrahydrothiophene ,
  • the gas space velocity, that is the volume of gas per volume of catalyst was 7000 h ⁇ ⁇ , the reaction temperature 25 ° C.
  • the experiment was stopped as soon as the exit gas contained more than 200 ppb sulfur.
  • Table D The results are summarized in Table D.
  • a heatable tubular reactor with a diameter of 30 mm was filled with a total of 280 ml of two of the previously described catalysts and operated in a single pass.
  • the exit gas was fed to a gas chromatograph.
  • the GC has a flame ionization detector for the detection of organic carbon compounds and a flame photometric detector for selective sulfur detection.
  • a homogeneous mixture of equal parts by volume of a copper catalyst and a molybdenum catalyst was used.
  • THT tetrahydrothiophene
  • Catalyst 34 composition 10% by weight MoO 3 and 90% by weight Al 2 O 3 .
  • Composition 15% by weight MoO 3 and 85% by weight Al 2 O 3 .
  • the catalyst had a BET surface area of 289 m 2 / g, a liter weight of 884 g / liter and a pore volume of 0.40 ml / g.
  • Composition 20% by weight MoO 3 and 80% by weight Al 2 O 3 .
  • the catalyst had one BET surface area of 294 m 2 / g, a liter weight of 823 g / liter and a pore volume of 0.42 ml / g.
  • Catalyst 37 composition :! 5% by weight MoO 3 on aluminum oxide with 50% by weight coriderite.
  • Catalyst 38 composition 15% by weight MoO 3 and 85% by weight Al 2 O 3
  • These strands were impregnated with a 15.5% strength by weight solution of ammonium heptamolybdate, so that a Mo content of 15% by weight ultimately results (calculated as MoO 3 ).
  • the catalyst was dried at 200 ° C. for 4 hours and then calcined at 550 ° C. for 2 hours.
  • the strand catalyst had a BET surface area of 143 m 2 / g, a water absorption of 0.35 ml / g and a liter weight of 1028 g / liter.
  • Composition 15% by weight MoO 3 and 85% by weight Al 2 O 3
  • the preparation was carried out analogously to catalyst 38, but the aluminum oxide strands were calcined at 1050 ° C. for 2 hours.
  • the catalyst had a BET surface area of 87 m 2 / g, a water absorption of 0.25 ml / g and a liter weight of 1038 g / liter.
  • Composition 15% by weight MoO 3 and 85% by weight Al 2 O 3 .
  • 600 g of an extruded aluminum oxide support from BASF with a diameter of 3 mm (pore volume of 0.65 ml / g, BET surface area of 223 m 2 / g, vibrating weight of 649 g / l) were calcined at 750 ° C. for 2 hours , then with a 15.5% by weight Solution impregnated with ammonium heptamolybdate and then dried for 16 hours at 120 ° C. and calcined at 550 ° C. for 3 hours.
  • the catalyst had a BET surface area of 160 m 2 / g, a liter weight of 750 g and a pore volume of 0.5 ml / g.
  • Composition 15% by weight MoO 3 and 85% by weight Al 2 O 3 .
  • the preparation was carried out analogously to catalyst 40, but the aluminum oxide support was calcined at 1050 ° C. for 2 hours.
  • the catalyst had a BET surface area of 77 m 2 / g, a pore volume of 0.39 ml / g and a liter weight of 750 g / liter.
  • catalyst 19 495 g were impregnated with a 15.5% strength by weight solution of ammonium heptamolybdate, dried at 200 ° C. for 4 hours and calcined at 550 ° C. for 3 hours.
  • the catalyst had a water absorption of 0.24 ml / g, a BET surface area of 38 m 2 / g and a liter weight of 1248 g / liter.
  • a solution of 775 g of aluminum nitrate nonahydrate and 729 g of nickel nitrate in 2.5 liters of water was mixed with a solution of 1000 g of sodium hydroxide solution in 2 liters of water while stirring at 70 ° C. and a pH of 11, the precipitate with 50 liters of water washed, 4 h at 200 ° C for 4 h, calcined for 2 h at 500 ° C, with 3 wt .-% graphite mixed and compressed into tablets 4.75 x 2 mm.
  • the tablets had a lateral compressive strength of 41 N / tablet, a BET surface area of 142 m 2 / g and a pore volume of 0.23 ml / g.
  • a solution of 417 g of iron (III) nitrate nonahydrate in 1.5 liters of water and 1750 g of an aqueous solution of nickel nitrate with a Ni content of 13.5% by weight was stirred at 70 ° C and a pH of 11 mixed with a solution of 1000 g of sodium hydroxide solution in 2 liters of water, the precipitate washed with 50 liters of water, dried for 4 hours at 200 ° C., calcined for 2 hours at 500 ° C., mixed with 3% by weight of graphite and 4 , 75 x 2 mm tablets pressed.
  • the tablets had a lateral compressive strength of 43 N / tablet, a BET surface area of 142 m 2 / g and a pore volume of 0.23 ml / g.
  • a Na-Y zeolite (CBV® 100 from Zeolyst Int. With an Si / Al ratio of 5.1) were stirred with 2.5 l of a 0.5 molar solution of silver nitrate (424.6 g ), heated to 80 ° C for 4 h, the precipitate filtered off, washed once with 500 ml of water, dried for 2 h at 120 ° C, calcined for 4 h at 500 ° C (heating rate: 1 ° C / min), again with 2 , 5 l of a 0.5 molar silver nitrate solution heated to 80 ° C. for 4 hours, filtered off, with 500 ml of water, dried at 120 ° C. overnight. 372 g of the zeolite were obtained.
  • 253 g of the zeolite were heated with 1200 ml of a 10% ammonium nitrate solution at 80 ° C for 4 h, the precipitate was filtered off, a fresh 10% ammonium nitrate solution (1, 2 l) was added, the mixture was heated at 80 ° C for 4 h, which The precipitate is filtered off, washed twice with 500 ml of water, dried for 2 hours at 120 ° C., calcined for 5 hours at 450 ° C. (heating rate: 1 ° C./min). 100.2 g of the zeolite were obtained.
  • the activated carbon had a copper content of 4.5% by weight, a surface area of 1120 m 2 / g and a bulk density of approx. 550 g / liter.
  • a commercially available natural gas (from Linde) was used. This had the following composition: 84.5 vol.% Methane, 3.5 vol.% Ethane, 0.6 vol.% Propane, 1000 vol. Ppm butanes, approx. 1200 vol. Ppm higher hydrocarbons C 4 - KW; of which 100 ppm benzene; 9.3% by volume nitrogen and 1.7% by volume carbon dioxide.
  • the gas was passed over the catalyst at a volume flow of 240 liters per hour (space-time velocity of 6000 per hour). All measurements were made at standard pressure and room temperature.
  • the catalysts were not pretreated (eg reduction).
  • a commercial gas chromatograph was used to analyze the gas after the reactor, which had a two-column circuit and two detectors.
  • the first detector a flame ionization detector (FID)
  • FPD flame photometric detector
  • FPD flame photometric detector
  • Tetrahydrothiophene was chosen as the model substance for organic sulfur compounds, since it is known that, in contrast to terminal sulfur compounds, cyclic sulfur compounds are very difficult to remove by means of adsorption.
  • Test series 1 Adsorption of organic sulfur compounds using the example of THT
  • the catalysts of the comparative examples show an increase in the adsorption of benzene by a factor of 50.
  • the catalysts of the invention can also be used for the removal of inorganic sulfur compounds from natural gas. High sulfur loads can be achieved. At the same time, the co-adsorption of benzene remains low.

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Abstract

La présente invention concerne un procédé pour retirer des composés soufrés de gaz contenant des hydrocarbures, procédé selon lequel on utilise des catalyseurs, à l'exception du charbon actif et des zéolites, qui contiennent du cuivre, de l'argent, du zinc, du molybdène, du fer, du cobalt, du nickel ou des mélanges de ceux-ci, à une température comprise entre (-50) et 150 DEG C et à une pression comprise entre 0,1 et 10 bar.
EP03789265A 2002-12-19 2003-12-13 Procede pour retirer des composes soufres de gaz contenant des hydrocarbures Ceased EP1576076A1 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
DE10260028 2002-12-19
DE2002160028 DE10260028A1 (de) 2002-12-19 2002-12-19 Verfahren zur Entfernung von Schwefelverbindungen aus kohlenwasserstoffhaltigen Gasen
DE2003131771 DE10331771A1 (de) 2003-07-11 2003-07-11 Verfahren zur Entfernung von Schwefelverbindungen aus kohlenwasserstoffhaltigen Gasen
DE10331771 2003-07-11
DE10340251 2003-08-29
DE2003140251 DE10340251A1 (de) 2003-08-29 2003-08-29 Verfahren zur Entfernung von Schwefelverbindungen aus kohlenwasserstoffhaltigen Gasen
DE10352104 2003-11-04
DE2003152104 DE10352104A1 (de) 2003-11-04 2003-11-04 Verfahren zur Entfernung von Schwefelverbindungen aus kohlenwasserstoffhaltigen Gasen
PCT/EP2003/014193 WO2004056949A1 (fr) 2002-12-19 2003-12-13 Procede pour retirer des composes soufres de gaz contenant des hydrocarbures

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KR20070019428A (ko) * 2005-08-12 2007-02-15 에스케이 주식회사 유기황화합물 제거용 탈황제, 이의 제조방법 및 이를이용한 유기황화합물의 제거방법
CA2686526C (fr) * 2007-06-14 2015-10-06 Exxonmobil Upstream Research Company Procede de purification d'hydrocarbures
US20100233054A1 (en) * 2007-08-09 2010-09-16 Basf Se Catalyst and process for the desulfurization of hydrocarbon-comprising gases
GB0804572D0 (en) * 2008-03-12 2008-04-16 Johnson Matthey Plc Preparation of desulphurisation materials
GB0804570D0 (en) * 2008-03-12 2008-04-16 Johnson Matthey Plc Desulphurisation materials
US7981825B2 (en) * 2008-03-27 2011-07-19 Spansion Llc Fuel cell catalyst regeneration
CN102170953B (zh) * 2008-09-01 2015-02-04 巴斯夫欧洲公司 吸附剂材料和含烃气体脱硫的方法
DE102009046741A1 (de) 2008-11-18 2010-05-27 Helmholtz-Zentrum Für Umweltforschung Gmbh - Ufz Verfahren und Vorrichtung zur selektiven Entfernung von Schwefelkohlenstoff aus Strippgasen
CN102316959A (zh) * 2008-12-17 2012-01-11 巴斯夫欧洲公司 从含水的气流除去污染物的方法
DE102009036203A1 (de) * 2009-08-05 2011-02-17 Süd-Chemie AG Verfahren zur Herstellung eines bruchfesten Katalysators zur Entschwefelung von Gasen
KR101147545B1 (ko) * 2009-12-30 2012-05-17 한국가스공사 황 화합물 검지용 지시제 및 이를 이용한 황 화합물 흡착제
DE102013225724A1 (de) * 2013-12-12 2015-06-18 Evonik Industries Ag Reinigung flüssiger Kohlenwasserstoffströme mittels kupferhaltiger Sorptionsmittel
US10882801B2 (en) 2016-01-04 2021-01-05 Saudi Arabian Oil Company Methods for gas phase oxidative desulphurization of hydrocarbons using CuZnAl catalysts promoted with group VIB metal oxides
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AU2003293874A1 (en) 2004-07-14
JP4990529B2 (ja) 2012-08-01
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CA2511441A1 (fr) 2004-07-08
US20060035784A1 (en) 2006-02-16
CA2511441C (fr) 2011-03-22
US7837964B2 (en) 2010-11-23

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