WO2006082019A1 - Catalyseur de desulfuration - Google Patents

Catalyseur de desulfuration Download PDF

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Publication number
WO2006082019A1
WO2006082019A1 PCT/EP2006/000817 EP2006000817W WO2006082019A1 WO 2006082019 A1 WO2006082019 A1 WO 2006082019A1 EP 2006000817 W EP2006000817 W EP 2006000817W WO 2006082019 A1 WO2006082019 A1 WO 2006082019A1
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Prior art keywords
desulfurization catalyst
desulfurization
catalyst according
catalyst
molybdenum
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PCT/EP2006/000817
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German (de)
English (en)
Inventor
Friedrich Schmidt
Franz Grossmann
Richard Fischer
Michael Rau
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Süd-Chemie AG
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Publication of WO2006082019A1 publication Critical patent/WO2006082019A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8873—Zinc, cadmium or mercury
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/34—Mechanical properties
    • B01J35/36—Mechanical strength
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding

Definitions

  • the invention relates to a desulfurization catalyst, as used for the desulfurization of hydrocarbon streams.
  • catalysts especially those containing transition metals, are poisoned by organic sulfur compounds, thereby losing their activity.
  • hydrocarbon conversion processes such as the reforming of methane or other hydrocarbons, for example, in the production of synthesis gas for methanol synthesis or for power generation from methanol or other hydrocarbons in fuel cells, it is necessary to reduce the sulfur content in the hydrocarbon stream to the ppb range lower.
  • the gas stream is fed to a second reactor, in which the hydrogen sulfide originally contained in the gas or formed in the reduction of organic sulfur compounds is absorbed at a suitable absorber.
  • a suitable absorber usually, the hydrocarbon stream passes through the bed of a solid absorber, for example a zinc oxide absorbent bed.
  • No. 4,613,724 proposes a process for removing carbonyl sulfide (COS) from hydrocarbon streams, wherein the hydrocarbon stream is passed over an absorber containing zinc oxide and a promoter selected from the group of alumina, aluminum silicates and mixtures thereof.
  • a promoter selected from the group of alumina, aluminum silicates and mixtures thereof.
  • calcium oxide may also be contained as a promoter.
  • the proportion of the promoter on the absorber material is preferably at most 15 wt. -%.
  • the specific surface area of the absorber material is preferably 20 to 100 m 2 / g.
  • the particle size of the absorber material is preferably less than 2 mm, and more preferably between 0.5 and 1.5 mm.
  • the absorber material contains 85 to 95 wt. -% zinc oxide, 3 to 10 wt. -% alumina or Aluminum silicates and 0 to 5 wt. -% calcium oxide.
  • a catalyst for the desulfurization of hydrocarbon streams which as the hydrogenating component 4 to 10 wt. -% of a molybdenum compound, calculated as molybdenum oxide and 0, 5 to 3 wt. % of a cobalt compound calculated as cobalt oxide.
  • the catalyst comprises a carrier component which contains 0, 5 to 50 wt. -% of a magnesium compound and 0, 3 to 10 wt. % of a sodium compound, each calculated as an oxide.
  • the specific surface area of the catalyst is not less than 268 m 2 / g and the average pore diameter is not more than 300 ⁇ .
  • the catalyst can be prepared by, for example, impregnating the support with aqueous solutions of the salts of the active metal components.
  • the degree of desulfurization in hydrodesulfurization depends on the sulfur content of the gas stream to be desulphurized, the temperature at which the process is operated, and the activity of the catalyst.
  • Typical catalysts for hydrodesulfurization are prepared by impregnation of supports such as alumina, with molybdenum or tungsten, which are treated with promoters such as cobalt or nickel.
  • Typical catalysts for the hydrodesulfurization are, for example, mixtures of cobalt and molybdenum on alumina, nickel on alumina, or mixtures of cobalt and molybdenum, which are promoted with nickel and supported on alumina.
  • the desulfurization catalyst of the present invention comprises a hydrogenation component for hydrogenating organic sulfur-containing compounds and an absorber component for absorbing hydrogen sulfide.
  • the catalyst according to the invention can hydrogenate both sulfur-containing organic compounds and also absorb the hydrogen sulfide formed in the hydrogenation.
  • the catalyst according to the invention takes on both functions required for the hydrodesulfurization of hydrocarbon streams. Therefore, only one reactor is required for desulfurization of the hydrocarbon stream, which simplifies desulfurization and reduces the cost of the process.
  • the absorber component is formed from zinc oxide.
  • Zinc oxide is a low-cost substance. It has a high affinity for hydrogen sulphide, so that the sulfur content in a hydrocarbon stream to be desulphurised can be lowered to values of less than 5 ppm, in particular up to the ppb range. Zinc sulfide gives virtually no sulfur under the conditions of hydrodesulfurization and can only be converted back to the oxide under severe reaction conditions.
  • the hydrogenation component preferably contains at least one element from the group of copper, molybdenum, tungsten, iron, nickel and cobalt.
  • the hydrogenation component can be formed by only one element of this group, for example molybdenum, or also comprise a plurality of elements of the group, for example cobalt and molybdenum or nickel and tungsten.
  • the elements of the group are present in the desulfurization catalyst generally at least proportionally in the form of their oxides.
  • the desulfurization catalyst according to the invention contains a binder.
  • a binder can be provided, for example, when the catalyst is provided in the form of extrudates to achieve the required lateral compressive strength.
  • the desulfurization catalyst of the present invention may also be provided in the form of tablets. These generally do not require a binder in order to achieve a side pressure resistance required for use in a reactor. Tablet-like desulfurization catalysts in their oxidic form usually contain only small amounts of a lubricant, such as graphite, in addition to the hydrogenation component and the absorber component.
  • the proportion of the binder is preferably chosen so high that a sufficient strength of the catalyst body is achieved and, on the other hand, the fraction of the binder is as low as possible, since the binder does not contribute to the catalytic activity of the catalyst or acts as an absorber.
  • the binder is preferably present in an amount of less than 18% by weight, preferably less than 15% by weight, particularly preferably less than 10% by weight.
  • the proportion of binding agent is preferably more than 5% by weight, in each case based on the weight of the desulfurization catalyst according to the invention (calcined to constant weight at 600 ° C.).
  • the copper is preferably contained in an amount of 0.5 to 5% by weight, particularly preferably 1 to 2.5% by weight, calculated as copper oxide and based on the total weight of the desulfurization catalyst.
  • the molybdenum is preferably in a proportion of 0.5 to 5 wt. %, more preferably 3 to 4, 5 wt .-%, calculated as molybdenum oxide and based on the weight of the desulfurization catalyst.
  • the catalyst according to the invention in its embodiment with zinc oxide as absorber component and copper and molybdenum compounds as hydrogenation components has very good properties in the desulfurization of hydrocarbon streams. It allows the simultaneous reduction of sulfur-containing organic compounds and the absorption of the resulting hydrogen sulfide.
  • the sulfur is bound by the zinc oxide in close proximity to the hydrogenation-active metal compounds.
  • the molybdenum must be present at least in proportions in the form of the sulfide. If the catalyst is operated for a long time in a hydrocarbon stream which is free of sulfur-containing organic compounds, the molybdenum compound depletes of sulfur and is thus deactivated. There However, in the desulfurization catalyst according to the invention, the sulfur remains bound by the zinc oxide, the sulfur is available, so that the catalyst is immediately active again when again hydrocarbon streams are passed, containing sulfur-containing organic compounds.
  • the catalyst according to the invention has a multiplicity of defects in the crystal lattice.
  • the inventors believe that the stresses generated thereby in the crystal lattice during the absorption of the sulfur constantly create new fracture surfaces in the zinc oxide, which are then available for a further absorption of hydrogen sulphide.
  • the desulfurization catalyst according to the invention on the one hand has a very high affinity for hydrogen sulfide and on the other hand a high absorption capacity for hydrogen sulfide, since the zinc oxide can be used to a very high proportion for the absorption of hydrogen sulfide.
  • the invention should not be limited by this theory.
  • the high number of defects in the lattice of the zinc oxide manifests itself in a broadening of the X-ray reflection in the X-ray diffractogram.
  • a half-width is understood as the width of an X-ray reflex in 50% of the height of the reflex.
  • the catalyst according to the invention preferably has a high specific surface area, which leads to a high catalytic activity.
  • the catalyst preferably has a specific surface area of more than 5 m 2 / g, preferably more than 20 m 2 / g, particularly preferably more than 50 m 2 / g.
  • the specific surface can be determined with a BET method. A suitable method for determining the specific surface area will be described below.
  • the catalyst preferably has a total pore volume, as measured by Hg intrusion, of at least 30 mmVg, preferably at least 80 mm 3 / g and more preferably at least 100 mmVg and preferably at most 500 mirVVg, preferably at most 250 mm 3 / g and more preferably of at most 210 mm 3 / g.
  • the fraction of the pore volume of the catalyst, measured by Hg intrusion, in the range of 3.7 to 7 nm is preferably at least 3 mm 3 / g, preferably at least 15 mmVg, more preferably at least 30 mmVg and preferably at most 80 mm 3 / g , preferably at most 70 mm 3 / g and particularly preferably at most 60 mm 3 / g.
  • the fraction of the medium transport pores in the range from 875 nm to 40 nm, measured by Hg intrusion preferably has at least a volume of 2 mm 3 / g, preferably at least 10 mm 3 / g and more preferably at least 20 mm 3 / g and preferably at most 100 mm 3 / g, whereas the fraction of small transport pores is in the range from 40 nm to 7.5 nm, measured by Hg.
  • Intrusion preferably at least a volume of 80 mm 3 / g, preferably at least 100 mm 3 / g and more preferably at least 150 mm 3 / g and preferably at most 300 m ⁇ vVg on.
  • the desulfurization catalyst according to the invention is constructed from approximately spherical particles, which preferably have a mean diameter D 50 in the range of 0.5 to 50 ⁇ m, particularly preferably 1 to 10 ⁇ m.
  • D 50 mean diameter
  • the suspension of thermally decomposable copper compound, thermally decomposable molybdenum compound, and solid zinc compound before the thermal decomposition is finely ground and the suspension is dried after thermal decomposition by spray drying.
  • the desulfurization catalyst according to the invention is free of alumina and / or magnesium oxide.
  • the desulfurization catalyst according to the invention can be prepared by conventional methods.
  • the hydrogenation components can be deposited on the absorber component. Subsequently, it is generally still calcined in order to convert the components of the catalyst into the form of their oxides.
  • the starting components can be kneaded with the addition of water, with compounds selected as starting components which can be converted into the corresponding oxides by calcination, that is, for example, the carbonates or nitrates of the metals contained in the catalyst.
  • Another object of the invention relates to the use of the above-described desulfurization catalyst for the desulfurization of hydrocarbon streams.
  • the desulfurization is carried out in the usual manner by the hydrocarbon Ström is passed with the addition of a small amount of reducing agent, in particular hydrogen gas, over a bed of the catalyst.
  • the desulfurization is carried out under normal conditions.
  • the reaction may suitably be in a temperature range of 260 to 550 ° C, a hydrogen partial pressure from 0, 3 to 4 barg and a LHSV (liquid hourly space velocity) in the range of 0, 1 to 20 are performed.
  • the desulfurization catalyst can be in the form of shaped articles, for example tablets or extrudates, or else in the form of granules.
  • the diameter of the shaped bodies or granules is preferably selected in the range of 3 to 10 mm.
  • the catalyst of the invention is particularly suitable for the desulfurization of hydrocarbon streams having a sulfur content of less than 500 ppm, more preferably less than 400 ppm.
  • hydrocarbon streams are formed, for example, by natural gas or associated gas in the crude oil production.
  • FIG. 1 an electron micrograph of a spray-dried catalyst before shaping and calcining
  • the surface was coated according to DIN 66131 on a fully automatic nitrogen porosimeter from Micromeritics, type ASAP 2010, Right .
  • the pore volume was determined using the BJH method (E, P. Barrett, L, G. Joyner, P, P. Haienda, J. Am., Chem. Soc. 73 (1951) 373). Pore volumes of certain pore size ranges are determined by summing up incremental pore volumes, which are obtained from the evaluation of the adsorption isotherm according to BJH.
  • the total pore volume according to the BJH method refers to pores with a diameter of 1.7 to 300 nm.
  • the bulk density was determined according to DIN ISO 903.
  • a known amount of the sample to be measured was weighed in a ceramic boat and the sample was then placed in a heatable tube through which a stream of hydrogen sulfide (100%) was passed. The sample was left at 350 ° C. under the hydrogen sulfide stream for 6 hours. The sample was then removed from the tube and cooled to room temperature with exclusion of air and moisture. The sample was weighed again and the sulfur uptake calculated from the weight difference.
  • Example 1 was repeated except that the suspension was kept at 50 ° C. for 240 minutes prior to thermal decomposition.
  • Table 1 physical characterization of the catalysts from Examples 1 and 2
  • Example 2 The catalysts obtained in Examples 1 and 2 do not differ significantly in their physical properties. In Example 2, a lower pore volume was measured. This decrease is attributed to the longer aging time of the suspension, through which the specific surface area decreased. The cat lysator from Example 2 shows the higher absorption capacity for sulfur.
  • Example 1 was repeated, but after decomposition, the obtained suspension was aged for one week at room temperature.
  • Example 1 was repeated, but after decomposition, the obtained suspension was aged for 24 hours at room temperature.
  • Example 5 was repeated, but before the decomposition, the suspension was ground five times with an annular gap mill. For this purpose, the suspension was passed through the annular gap mill five times. After decomposition, the suspension was aged at room temperature for 72 hours.
  • Example 3 Due to the longer aging time in Example 3, the specific surface area decreased from 47 to 34 m 2 / g and the pore volume decreased from 210 to 170 mrrvVg. By grinding in Examples 5 and 6, the specific surface area increased significantly as compared to samples that were not ground. Furthermore, the pore volume increased in the range of 3, 7 to 7 nm.
  • Fig. 1 shows an electron micrograph of the catalyst obtained in Example 6, recognizing the approximately spherical shape of the particles.
  • FIG. Figure 2 shows the particle size distribution of the catalyst obtained in Example 5.
  • the D 50 value is 2.36 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur de désulfuration, comprenant un composant d'hydratation permettant d'hydrater des composés organiques contenant du soufre et un composant d'absorption permettant d'absorber de l'acide sulfhydrique ainsi que l'utilisation dudit catalyseur de désulfuration permettant de désulfurer les flux d'hydrocarbure, en particulier un flux de méthane. Le composant d'hydratation correspondant est formé à partir de cuivre et de molybdène, et le composant d'absorption utilisé est l'oxyde de zinc.
PCT/EP2006/000817 2005-01-31 2006-01-31 Catalyseur de desulfuration WO2006082019A1 (fr)

Applications Claiming Priority (2)

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DE102005004368.2 2005-01-31
DE102005004368A DE102005004368A1 (de) 2005-01-31 2005-01-31 Entschwefelungskatalysator

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1852182A1 (fr) * 2006-05-01 2007-11-07 Engelhard Corporation Catalyseur Fischer Tropsch contenant du cobalt et de l'oxyde de zinc
CN103785393A (zh) * 2012-10-31 2014-05-14 湖南长岭石化科技开发有限公司 芳烃加氢脱硫催化剂及其制备方法和应用和芳烃加氢脱硫的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009036203A1 (de) * 2009-08-05 2011-02-17 Süd-Chemie AG Verfahren zur Herstellung eines bruchfesten Katalysators zur Entschwefelung von Gasen
GB201112606D0 (en) 2011-07-22 2011-09-07 Johnson Matthey Plc Desulphurisation materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1011001A (en) * 1962-06-29 1965-11-24 Azote Office Nat Ind Desulphurisation catalysts for industrial gases and vapours
DE2029074A1 (de) * 1969-07-07 1971-01-21 Azote Et Produits Chimiques S.A., Toulouse (Frankreich) Desulfunerungsmassen auf der Basis von Zinkoxyd
DD116208A1 (fr) * 1974-08-27 1975-11-12
DE10352104A1 (de) * 2003-11-04 2005-06-02 Basf Ag Verfahren zur Entfernung von Schwefelverbindungen aus kohlenwasserstoffhaltigen Gasen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1011001A (en) * 1962-06-29 1965-11-24 Azote Office Nat Ind Desulphurisation catalysts for industrial gases and vapours
DE2029074A1 (de) * 1969-07-07 1971-01-21 Azote Et Produits Chimiques S.A., Toulouse (Frankreich) Desulfunerungsmassen auf der Basis von Zinkoxyd
DD116208A1 (fr) * 1974-08-27 1975-11-12
DE10352104A1 (de) * 2003-11-04 2005-06-02 Basf Ag Verfahren zur Entfernung von Schwefelverbindungen aus kohlenwasserstoffhaltigen Gasen

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1852182A1 (fr) * 2006-05-01 2007-11-07 Engelhard Corporation Catalyseur Fischer Tropsch contenant du cobalt et de l'oxyde de zinc
WO2007130908A2 (fr) * 2006-05-01 2007-11-15 Basf Catalysts Llc Catalyseur fischer-tropsch
WO2007130908A3 (fr) * 2006-05-01 2008-01-10 Basf Catalysts Llc Catalyseur fischer-tropsch
CN103785393A (zh) * 2012-10-31 2014-05-14 湖南长岭石化科技开发有限公司 芳烃加氢脱硫催化剂及其制备方法和应用和芳烃加氢脱硫的方法
CN103785393B (zh) * 2012-10-31 2016-12-07 湖南长岭石化科技开发有限公司 芳烃加氢脱硫催化剂及其制备方法和应用和芳烃加氢脱硫的方法

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