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WO2008058425A1 - Procédé destiné à convertir un gaz de synthèse en composés oxygénés - Google Patents

Procédé destiné à convertir un gaz de synthèse en composés oxygénés Download PDF

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Publication number
WO2008058425A1
WO2008058425A1 PCT/CN2006/003064 CN2006003064W WO2008058425A1 WO 2008058425 A1 WO2008058425 A1 WO 2008058425A1 CN 2006003064 W CN2006003064 W CN 2006003064W WO 2008058425 A1 WO2008058425 A1 WO 2008058425A1
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WIPO (PCT)
Prior art keywords
catalyst
hydrogen
carbon monoxide
sulphur
reaction
Prior art date
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Ceased
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PCT/CN2006/003064
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English (en)
Inventor
Hengyong Xu
Yuchun Ma
Qingjie Ge
Wenzhao Li
Andreas Josef Goldbach
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Dalian Institute of Chemical Physics of CAS
BP PLC
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Dalian Institute of Chemical Physics of CAS
BP PLC
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Priority to PCT/CN2006/003064 priority Critical patent/WO2008058425A1/fr
Priority to PCT/GB2007/004243 priority patent/WO2008059208A1/fr
Priority to CN2007800422533A priority patent/CN101646641B/zh
Publication of WO2008058425A1 publication Critical patent/WO2008058425A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to the field of catalysis, more specifically to a catalysed process in which the catalyst is resistant to deactivation by sulphur.
  • Coal is a widely used fuel for power generation. However, it tends to be disfavoured over other fuels, such as crude oil-derived fuels or natural gas, as the energy liberated on its combustion is typically lower on a weight basis. Additionally, coal tends to have relatively larger quantities of sulphur, which can often act as a poison to catalysts in processes which use coal-derived feedstocks, and can reduce catalyst lifetime and activity. Consequently, in many cases, high-sulphur feedstocks have to be pre-treated in order to remove sulphur to below permissible levels.
  • feedstock pre-processing requires significant capital expenditure and operating costs. Additionally, as sulphur removal often uses a sacrificial absorbent such as zinc oxide, increased waste is generated by the process. A catalyst that can tolerate relatively high sulphur levels would therefore be advantageous by mitigating or even eliminating the need for such pre-processing.
  • Methanol is an important high volume commodity chemical, and is typically manufactured from syngas (a mixture of hydrogen and carbon monoxide).
  • Syngas can be produced from a variety of starting materials, in particular hydrocarbon sources such as natural gas, heavy oils, coal, and also biomass.
  • hydrocarbon sources such as natural gas, heavy oils, coal, and also biomass.
  • currently used catalysts such as Cu/ZnO/ Al 2 O 3 are highly sensitive to the presence of sulphur in the syngas feedstock, and will typically deactivate even in the presence of sulphur levels of as low as 0.5ppm.
  • Typical syngas feedstocks, particularly when coal derived can have sulphur levels in the range of from 10 to lOOppm. Therefore, a need remains for a process for the conversion of syngas to oxygenates which is tolerant to the presence of sulphur in the feedstock.
  • a process for the production of one or more oxygenated hydrocarbons from hydrogen and carbon monoxide comprises contacting a catalyst with a reaction composition comprising carbon monoxide, hydrogen and one or more reduced sulphur compounds under conditions sufficient to produce one or more oxygenated hydrocarbon, which catalyst comprises a metal active for the conversion of hydrogen and carbon monoxide to one or more oxygenated hydrocarbons and a support comprising a semiconducting inorganic oxide that is capable of catalysing the oxidation of reduced sulphur compounds, characterised in that the concentration of the one or more reduced sulphur compounds in the reaction composition is greater than 0.5ppm by weight expressed as elemental sulphur.
  • synthesis of oxygenated hydrocarbons from carbon monoxide can be carried out in a relatively high sulphur environment, at concentrations of greater than 0.5ppm expressed as elemental sulphur, by using a catalyst with a support that has an inorganic oxide with semiconducting properties, and which is capable of oxidising reduced sulphur compounds, in that the product of the sulphur oxidation comprises sulphur in an increased oxidation state.
  • An example of such a sulphur oxidation reaction would be the oxidation H 2 S or COS, both having sulphur oxidation numbers of -2, to sulphur dioxide or sulphur trioxide, which have oxidation numbers of +4 and +6 respectively.
  • the present invention solves this problem by providing a support which is capable of oxidising the reduced sulphur species, typically into one or more oxides of sulphur such as sulphur dioxide or sulphur trioxide, henceforth referred to as SO x .
  • SO x oxides of sulphur
  • the inorganic semiconducting oxide can donate framework oxygen to the reduced sulphur compounds in order to oxidise them.
  • activity of the catalyst can actually be enhanced by the presence of reduced sulphur compounds, in contrast to the deactivating effect of sulphur on Cu ZnO/Al 2 O 3 , for example, which deactivates rapidly even in the presence of sulphur concentrations of as low as 0.5ppm.
  • the metal can be any metal that is active for the synthesis of an oxygenated hydrocarbon from hydrogen and carbon monoxide.
  • the metal is selected from one or more of Cu, Cr, Co, Mo, Pt, Pd and Rh, and is preferably Cu and/or Pd.
  • the catalyst of the present invention may optionally comprise additional components, such as promoter or stabiliser components, which may comprise, for example, one or more elements from the group comprising alkali metals, alkaline earth metals, Sc, Y, La, Nd, Mn, Zn and Al.
  • the support comprises one or more inorganic semiconducting compounds that are capable of catalysting the conversion of reduced sulphur-containing compounds into oxidised sulphur compounds such as SO x under the reaction conditions.
  • the semiconducting inorganic oxide is doped to impart or improve its semiconducting properties or ability to create oxygen vacancies.
  • the inorganic semiconducting oxide is selected from one or more of lanthanide oxides, TiO 2 , ZrO 2 and ThO 2 .
  • the support comprises one or more of ZrO 2 , TiO 2 or CeO 2 , and most preferably comprises CeO 2 and/or ZrO 2 .
  • the one or more semiconducting compounds can be mixed with one or more non-semiconducting compounds, for example CeO 2 / Al 2 O 3 and ZrO 2 / Al 2 O 3 .
  • the support may additionally comprise other components, such as binder materials.
  • An inorganic oxide support may be made by a precipitation route, wherein a soluble and/or colloidal precursor of an inorganic oxide is treated so as to produce a solid oxide. If more than one oxide is present in the support, then a co-precipitation route may be employed, in which a mixture of soluble and/or colloidal precursors of each oxide are precipitated together to produce a solid mixed oxide.
  • the metal is precipitated together with the one or more oxide precursor materials to form the supported catalyst.
  • Composite or mixed oxides may be produced by co- precipitation, or by precipitating a precursor of one of the oxides onto the other oxide.
  • Catalyst lifetime can be further extended in the presence of reduced sulphur compounds when the total catalyst metal to the semiconducting inorganic oxide molar ratio is above a certain threshold value. This value is typically greater than 0.05:1. If palladium is present, the ratio of palladium to the semiconducting inorganic oxide is preferably preferably greater than 0.09: 1 , whether present as the only catalyst metal or in combination with another catalyst metal. For copper, when present as the only catalyst metal, the ratio is preferably in excess of 0.22:1.
  • the catalyst when used in a process for the conversion of hydrogen and carbon monoxide into one or more oxygenated hydrocarbons, may be used without pre-treatment, or may alternatively be reduced, for example in a flow of hydrogen gas or a mixture of hydrogen in nitrogen, in order to reduce the active catalyst metal component before use.
  • a reaction mixture comprising hydrogen and carbon monoxide is contacted with the catalyst to produce one or more oxygenated hydrocarbons, such as alcohols, esters, carboxylic acids and ethers.
  • the process is the production of one or more alcohols from hydrogen and carbon monoxide, and is preferably a process for the production of methanol and/or dimethyl ether.
  • Reaction temperatures typically in the range of from 100 to 45O 0 C, preferably from 170 to 300 0 C, are employed.
  • Reaction pressures typically in the range of from 1 to 100 bara (0.1 to 10 MPa), preferably from 10 to 60 bara (0.1 to 6 MPa), are employed.
  • Syngas is a convenient source of hydrogen and carbon monoxide.
  • Syngas can be prepared from a variety of substances, such as natural gas, liquid hydrocarbons, coal or biomass.
  • the catalyst of the present invention being sulphur-tolerant, is particularly suitable for syngas comprising relatively high sulphur levels, for example when derived from coal.
  • the catalysts of the present invention are tolerant to sulphur levels in excess of 0.5 ppm (expressed as elemental sulphur), for example 3ppm or more, or lOppm or more.
  • the catalyst is tolerant to sulphur levels in the range of from 10 to lOOppm.
  • the carbon monoxide to hydrogen (CO : H 2 ) molar ratio in the reaction composition is typically in the range of from 10 : 1 to 1 : 10, and is preferably in the range of 5 : 1 to 1 : 5, such as in the range of from 3 : 1 to 1 : 3.
  • the ratio is in the range of from 1 : 1 to i : 3.
  • the reaction composition preferably comprises a source of oxygen, for example water, oxygen or carbon dioxide.
  • a source of oxygen for example water, oxygen or carbon dioxide.
  • molecular oxygen is present in syngas that may be fed to the process.
  • oxygen is deliberately added to the reaction composition.
  • the presence of oxygen, either as molecular oxygen or in the form of an oxygen-containing compound such as water or carbon dioxide, is advantageous, as it can facilitate the formation of SO x and can also enable oxide vacancies in the support to be removed, thus facilitating the sulphur tolerance of the catalyst. This can therefore benefit both catalytic activity and lifetime.
  • the concentration of molecular oxygen is typically in the range of up to lwt%, for example up to 0.5 wt%. Preferably the molecular oxygen concentration is above lOppm.
  • Carbon dioxide can be present in the reaction composition, either as a constituent of one or more of the feedstock components (e.g. syngas), or produced during the reaction, or separately added to the reaction composition. Carbon dioxide can also assist in the conversion of reduced sulphur compounds to oxidised sulphur compounds, and in reoxidising the inorganic oxide. When present, its concentration in the reaction composition may be in the range of up to 15wt%, such as up to 10wt%. The carbon dioxide concentration is typically above lOppm.
  • Figure 1 illustrates one proposed reaction scheme by which catalyst deactivation in the presence of sulphur is inhibited
  • Figure 2 illustrates a second proposed reaction scheme by which catalyst deactivation in the presence of sulphur is inhibited
  • Figure 3 is a plot of catalytic activity of a PdZAl 2 O 3 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 3ppm H 2 S
  • Figure 4 is a plot of catalytic activity of a PdZCeO 2 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 3ppm H 2 S;
  • Figure 5 is a plot of the carbon monoxide conversion over PdZCeO 2 catalysts with different palladium loadings in the production of methanol from hydrogen and carbon monoxide in the presence of 1 lppm H 2 S;
  • Figure 6 is a plot of the methanol selectivity OfPdZCeO 2 catalysts with different palladium loadings in the production of methanol from hydrogen and carbon monoxide in the presence of 1 lppm H 2 S;
  • Figure 7 is a plot of catalytic activity of a Pd/CeO 2 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 2.2ppm COS and O. ⁇ ppm H 2 S;
  • Figure 8 is a plot of catalytic activity of a Pd/CeO 2 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 30ppm H 2 S;
  • Figure 9 is a plot of catalytic activity of a PdZZrO 2 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 36ppm H 2 S;
  • Figure 10 is a plot of catalytic activity of a Cu/ZnO catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 36ppm H 2 S
  • Figure 11 is a plot of catalytic activity of a Cu/CeO 2 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 30ppm H 2 S;
  • Figure 12 is a plot of catalytic activity of a Cu/ZrO 2 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 36ppm H 2 S;
  • Figure 13 is a plot of carbon monoxide conversion against copper content for Cu/ZrO 2 catalysts
  • Figure 14 is a plot of catalytic activity of a Pd/CeO 2 / Al 2 O 3 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 1 lppm H 2 S;
  • Figure 15 is a plot of catalytic activity of a Pd-Cu/CeO 2 catalyst in the production of methanol from hydrogen and carbon monoxide in the presence of 2.2ppm COS and 0.8ppm H 2 S.
  • the reaction scheme illustrated in Figure 1 shows a forward reaction, 1, and reverse reaction, 2, and a catalyst 3 comprising a metal E, 4, active for the conversion of hydrogen and carbon monoxide to oxygenated hydrocarbons supported on a semiconducting inorganic oxide support 5.
  • H 2 S reacts with the inorganic oxide, resulting in sulphur being incorporated, 6, into the support and the release of water.
  • the reverse reaction the sulphur is removed by reaction with oxygen present in the reaction composition, resulting in the release of SO x and the re-introduction of oxygen into the support.
  • the reaction scheme of Figure 2 shows the creation of an oxygen vacancy 7 in the oxide instead of the formation of a sulphided inorganic oxide.
  • oxygen is extracted from the support to form SO x , the vacancy being removed by reaction with oxygen.
  • a catalyst was prepared by treating 22.5mL of an aqueous solution comprising palladium(II) chloride (having 20mg palladium per mL) and 18.765g A1(NO 3 ) 3 .9H 2 O with a solution of 25g Na 2 CO 3 in 6OmL water as a precipitating agent. A pH of between 8 and 9, and a temperature of 55 0 C were maintained. A precipitate formed which was aged for 2 hours, before being filtered, washed with distilled water, dried overnight at 12O 0 C, and calcined in air at 36O 0 C for 6 hours.
  • the Pd: Al mole ratio of the catalyst was 0.34 : 1.
  • Example 2 the Pd: Ce mole ratio of the catalyst was 0.29 : 1. The ratios for
  • Examples 3 and 4 were 0.18 : 1 and 0.09 : 1 respectively.
  • ceria is a semiconducting oxide capable of catalysing the oxidation of reduced sulphur compounds.
  • a catalyst was prepared using the same procedure as Example 1, except that 3OmL of the palladium solution and 2Og Na 2 CO 3 in 4OmL water were used. Additionally, 11.846g Zr(NO 3 ) 4 .5H 2 O were used in place of the aluminium nitrate. The Pd:Zr mole ratio of the catalyst was 0.20 : 1.
  • Processes using this catalyst can be in accordance with the present invention, as palladium is active for the conversion of syngas to oxygenated hydrocarbons, and zirconia is a semiconducting oxide capable of catalysing the oxidation of reduced sulphur compounds.
  • the resulting precipitate was aged for 2 hours before being filtered, washed with distilled water, dried overnight 12O 0 C and calcined in air at 36O 0 C for 6 hours.
  • the Cu:Zn mole ratio of the catalyst was 2 : 1. Processes using this catalyst are not in accordance with the present invention, as zinc oxide does not catalyse the oxidation of reduced sulphur compounds.
  • Processes using this catalyst can be in accordance with the present invention, as copper is active for the conversion of syngas to oxygenated hydrocarbons, and ceria is a semiconducting oxide capable of catalysing the oxidation of reduced sulphur compounds.
  • Example 8 The same procedure as Example 8 was used, except that the quantities of materials listed in table 2 were used.
  • Example 16 PdZCeO 2 ZAl 2 O 2 .
  • Example 2 The same procedure as Example 2 was used, except that 45mL of the palladium solution, a solution of 3OgNa 2 CO 3 in 5OmL water, and 11.206g Ce(NO 3 ) 3 .6H 2 O were used. Additionally, 4.841g A1(NO 3 ) 3 .9H 2 O were added to the solution.
  • the Pd:Ce:Al mole ratio of the catalyst was 0.33 : 1 : 0.5.
  • Processes using this catalyst can be in accordance with the present invention, as palladium is active for the conversion of syngas to oxygenated hydrocarbons, and the support comprises ceria, which is a semiconducting oxide capable of catalysing the oxidation of reduced sulphur compounds.
  • ceria which is a semiconducting oxide capable of catalysing the oxidation of reduced sulphur compounds.
  • Example 2 The same procedure as Example 2 was used, except that 19.6mL of the palladium solution, a solution of 2Og Na 2 CO 3 in 5OmL water and 6.45g Ce(NO 3 ) 3 .6H 2 O were used. Additionally, 0.222g Cu(NO 3 ) 2 .3H 2 O were added to the solution. The Pd:Cu:Ce mole ratio of the catalyst was 0.25 : 0.06 : 1.
  • Samples of powdered catalyst were compressed into a disc at a pressure 20MPa, and were subsequently crushed and sieved to provide particle sizes of between 20 and 40 mesh.
  • 0.4g of the sieved particles were diluted with 1.Og quartz particles, and charged to a 140mm long stainless steel fixed-bed tube reactor with an inner diameter of 14mm. The resulting height of the catalyst bed was approximately 5mm.
  • the catalyst was reduced in a flow of 100% hydrogen (6.67mL/min) at a specified temperature for 8 hours.
  • a reaction composition comprising hydrogen and carbon monoxide with a molar CO : H 2 ratio of 1 : 2 was then fed to the catalyst at a specified reaction temperature, a pressure of 3.0 MPa absolute, and a GHSV (gas hourly space velocity) of 1000 h "1 , corresponding to a combined CO and H 2 flow rate of 6.67mL/min.
  • the feed gases also comprised CO 2 at 5% by volume, and N 2 at 2.3% by volume. Sulphur was also present in the feed gases in the form OfH 2 S or a combination of COS and H 2 S at various concentrations.
  • the quantity of methanol in the product stream from the tube reactor was determined by on-line gas chromatography equipped with a 1.5m long carbon molecular sieve column using a high purity helium carrier gas.
  • the PdZCeO 2 catalyst of Example 2 was pre-reduced at 300 0 C. It was studied at a reaction temperature of 24O 0 C, with a feedstock comprising 3ppm H 2 S. O 2 was also added to the feedstock at a concentration of 0.5% by volume.
  • Figure 4 shows the results of CO conversion and methanol selectivity over a period of 100 hours. After an initial period of instability during the first 20 hours of reaction, both parameters level out and begin to increase with time. This indicates that a Pd catalyst with a CeO 2 support is tolerant to the presence of sulphur.
  • the Pd/Ce ⁇ 2 catalyst of Example 2 was pre-reduced at 300 0 C. It was studied at a reaction temperature of 24O 0 C, with a feedstock comprising 0.8ppm H 2 S and 2.2ppm COS. O 2 was also added to the feedstock at a concentration of 0.5% by volume.
  • Figure 7 shows the results of CO conversion and methanol selectivity over a period of 100 hours. After an initial period of activity reduction over the first 20 hours of reaction, the activity begins to increase with time. This experiment demonstrates that the PdZCeO 2 catalyst is tolerant to the presence of different sulphur compounds.
  • the Pd/CeO 2 catalyst of Example 2 was pre-reduced at 24O 0 C. It was studied at a reaction temperature of 24O 0 C, with a feedstock comprising 30ppm H 2 S. No molecular oxygen was added to the reactor.
  • Figure 8 shows the results of CO conversion and methanol selectivity over a period of 100 hours. After an initial period of activity reduction over the first 20 hours of reaction, the activity begins to increase with time. This experiment demonstrates that the Pd/CeO 2 catalyst is tolerant to the presence of large concentrations of sulphur in the feedstock.
  • Example 5 The Pd/ZrO 2 catlayst of Example 5 was pre-reduced at 24O 0 C. It was studied at a reaction temperature of 24O 0 C, with a feedstock comprising 36ppm H 2 S. No molecular oxygen was added to the reactor.
  • Figure 9 shows the results of CO conversion and methanol selectivity over a period of 10 hours. High CO conversions are exhibited. This experiment demonstrates that ZrO 2 is also an effective support which has tolerance to high concentrations of sulphur.
  • the Cu/CeO 2 catalyst of Example 7 was pre-reduced at 22O 0 C, and tested at a reaction temperature of 22O 0 C for 8 hours, and 24O 0 C for a further period of 7 hours in the presence of a feedstock comprising 30ppm H 2 S. No molecular oxygen was added to the reactor.
  • Figure 11 shows the results of CO conversion and methanol selectivity over a period of 15 hours. No loss in activity was observed, and activity increased at the higher reaction temperature.
  • the Experiment shows that a CuZCeO 2 catalyst is also resistant to deactivation by sulphur even at high sulphur concentrations.
  • the CuZZrO 2 catalyst of Example 8 was pre-reduced at 22O 0 C, and tested at a reaction temperature of 24O 0 C over a period of 100 hours in the presence of a feedstock comprising 36ppm H 2 S. No molecular oxygen was added to the reactor.
  • Figure 12 shows the results of CO conversion and methanol selectivity over a period of 100 hours. Activity remained steady with only a small degree of deactivation observed.
  • the Experiment shows that a CuZZrO 2 catalyst is also resistant to deactivation by sulphur even at high sulphur concentrations.
  • Cu/ZrO 2 catalysts of Examples 8 to 15 were pre-reduced at 22O 0 C, and tested at a reaction temperature of 22O 0 C over a period of 10 hours in the presence of a feedstock comprising 36ppm H 2 S. No molecular oxygen was added to the reactor.
  • Figure 13 shows the results of CO conversion after 10 hours for each of the catalysts (the data point labels represent the Example number of the catalyst used). The Experiment shows that ZrO 2 -supported catalysts with Cu:Zr mole ratios of greater than 1.33 and less than 17.95 show the highest activity.
  • the Pd/CeO 2 /Al 2 O 3 catalyst of Example 16 was pre-reduced at 300 0 C, and tested at a reaction temperature of 24O 0 C over a period of 27 hours in the presence of 1 lppm H 2 S. O 2 was also added to the feedstock at a concentration of 0.5% by volume.
  • Figure 14 shows the results of CO conversion and methanol selectivity over a period of 27 hours. The results demonstrate that a catalyst with a support comprising a semiconducting oxide and a non-semiconducting oxide can still be sulphur resistant.
  • the Pd-Cu/CeO 2 catalyst of Example 17 was pre-reduced at 300 0 C, and tested at a reaction temperature of 24O 0 C over a period of 29 hours in the presence of 0.8ppm H 2 S and
  • Figure 15 shows the results of CO conversion and methanol selectivity over a period of 29 hours. The results show that a catalyst comprising both Pd and Cu catalyst metals is also active and resistant to presence of sulphur concentrations of greater than 0.5ppm.
  • the PdZAl 2 O 3 and PdZCeO 2 catalysts of Examples 1 and 2 respectively were analysed by X-Ray diffraction and X-ray fluorescence both before and after reaction for 100 hours on stream in an atmosphere comprising 30ppm H 2 S. Results are shown in Table 4.
  • the alumina-supported catalyst after use has significantly higher levels of sulphur than the ceria-supported catalyst, indicating a lower level of catalyst poisoning by sulphur in the ceria-supported catalyst.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé destiné à produire des hydrocarbures oxygénés à partir de monoxyde de carbone et d'hydrogène en présence d'un ou plusieurs composé(s) soufré(s) réduit(s). Dans ledit procédé, une composition réactive comprenant du monoxyde de carbone, de l'hydrogène et un ou plusieurs composé(s) soufré(s) réduit(s) est mise en contact avec un catalyseur comprenant un métal actif dans la production d'hydrocarbures oxygénés à partir de monoxyde de carbone et d'hydrogène et un support d'oxyde semi-conducteur inorganique susceptible de catalyser l'oxydation de composés soufrés réduits. Dans ledit procédé, la concentration du ou des composé(s) soufré(s) réduit(s) dans la composition réactive est supérieure à 0,5 ppm en poids, sur la base du soufre élémentaire.
PCT/CN2006/003064 2006-11-14 2006-11-14 Procédé destiné à convertir un gaz de synthèse en composés oxygénés Ceased WO2008058425A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/CN2006/003064 WO2008058425A1 (fr) 2006-11-14 2006-11-14 Procédé destiné à convertir un gaz de synthèse en composés oxygénés
PCT/GB2007/004243 WO2008059208A1 (fr) 2006-11-14 2007-11-08 Procédé pour la conversion de syngaz en oxygénats
CN2007800422533A CN101646641B (zh) 2006-11-14 2007-11-08 用于将合成气转化成含氧化合物的方法

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CN111569888A (zh) * 2020-06-02 2020-08-25 瓮福（集团）有限责任公司 一种耐硫、耐高温型中空核壳结构甲醇催化剂的制备方法

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CN106268856A (zh) * 2015-05-22 2017-01-04 中国科学院大连化学物理研究所 合成气一步法制乙醇用的铑基催化剂及其制备方法和应用
CN118976481B (zh) * 2024-08-01 2025-08-12 宁夏大学 一种金属复合改性的钙钛矿型氧化锆催化剂及其制备方法、应用

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CN111569888A (zh) * 2020-06-02 2020-08-25 瓮福（集团）有限责任公司 一种耐硫、耐高温型中空核壳结构甲醇催化剂的制备方法

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