WO2017211710A1 - Procédé de réduction de la teneur en soufre de l'oxyde de titane anastase et produit ainsi obtenu - Google Patents

Procédé de réduction de la teneur en soufre de l'oxyde de titane anastase et produit ainsi obtenu Download PDF

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WO2017211710A1
WO2017211710A1 PCT/EP2017/063439 EP2017063439W WO2017211710A1 WO 2017211710 A1 WO2017211710 A1 WO 2017211710A1 EP 2017063439 W EP2017063439 W EP 2017063439W WO 2017211710 A1 WO2017211710 A1 WO 2017211710A1
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PCT/EP2017/063439
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Ralf Becker
Regina Optehostert
Rolf Wittenberg
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Huntsman P&A Germany Gmbh
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Priority claimed from US15/173,801 external-priority patent/US20170348671A1/en
Priority to EP17736572.3A priority Critical patent/EP3464184A1/fr
Priority to US16/306,903 priority patent/US11135570B2/en
Priority to UAA201812723A priority patent/UA125691C2/uk
Priority to EA201892791A priority patent/EA201892791A1/ru
Priority to AU2017277063A priority patent/AU2017277063B2/en
Application filed by Huntsman P&A Germany Gmbh filed Critical Huntsman P&A Germany Gmbh
Priority to CA3025085A priority patent/CA3025085A1/fr
Priority to KR1020197000485A priority patent/KR102381005B1/ko
Priority to MYPI2018002314A priority patent/MY197671A/en
Priority to BR112018073994A priority patent/BR112018073994A2/pt
Priority to JP2019516072A priority patent/JP7181187B2/ja
Priority to CN201780035012.XA priority patent/CN109311695A/zh
Publication of WO2017211710A1 publication Critical patent/WO2017211710A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention relates to the field of heterogeneous catalysis.
  • it refers to a process for reducing the sulphur content of stabilized anatase titania, the so-obtained catalytic support materials and the use thereof for manufacturing of heterogeneous catalysts.
  • Titanium dioxide is a well-known material for the manufacturing of heterogeneous catalysts. It finds widespread application either as the catalytic material (e.g. Claus catalysis) or as a catalytic support (e.g. selective catalytic reduction of nitrous oxides, Fischer -Tropsch).
  • the catalytic material e.g. Claus catalysis
  • a catalytic support e.g. selective catalytic reduction of nitrous oxides, Fischer -Tropsch.
  • the predominant and in most cases preferred polymorph for heterogeneous catalysis is the anatase crystal phase.
  • the large industrial scale manufacturing of anatase type T1O2 relies on the so-called sulphate process in which titanium rich raw materials (ilmenite or Ti-slag) are firstly reacted with concentrated sulphuric acid to form TiOSO .
  • TiOSO titanium rich raw materials
  • a fine particulate anatase type TiO 2 with a high water content is obtained (so-called metatitanic acid with general formula TiO(OH) 2 ).
  • metatitanic acid with general formula TiO(OH) 2 is obtained after further purification steps which include reduction and washing procedures, a pure anatase T1O2 can be obtained.
  • the other large scale manufacturing process for T1O2 is the so-called chloride process which uses a raw material with very high Ti content (natural or synthetic rutile or Ti-slag), chlorine and carbon to produce in a first step TiCI 4 which can easily be purified by distillation. Upon burning in an oxygen rich flame, a pure Rutile T1O2 is obtained. A pure anatase T1O2 polymorph cannot be produced by this method.
  • Another procedure for the manufacturing of anatase type TiO 2 is the flame hydrolysis of TiCI 4 yielding a mixture of Rutile and anatase only.
  • heterogeneous catalysts often depends on the purity. Stray ions can affect the overall conversion of the catalytic process and/or the selectivity. Typical unwanted impurities are phosphorous, sulphur, heavy metals, alkaline and alkaline earth metals.
  • the Fischer-Tropsch synthesis of hydrocarbons from syngas is very sensitive towards sulphur impurities since the sulphur reacts with the catalytically active cobalt to form cobalt sulphides (Co x S y ) which in turn lead to drastic reduced catalytic performance.
  • Typical sulphur levels of FT- catalysts are below 150 ppm, preferably below 100 ppm.
  • the major impurity in the sulphuric acid process generated anatase TiO 2 is sulphur stemming from adherent sulphuric acid of the manufacturing process.
  • Other stray ion impurities are in the one or low two digit ppm range and typically are uncritical.
  • heterogeneous catalysts also depends on the physical properties. A very good dispersion of the catalytically active material on the support is often a prerequisite to observe high conversions. Typically large specific surface areas of the support are important to ensure maximum dispersion of the catalytically active centres.
  • anatase type TiO 2 is the sulphate process.
  • Major drawbacks of this process is the large sulphur content in the final product which is known to be detrimental for a lot of catalytic applications.
  • a process has to be found that allows for the large industrial scale production of an anatase type TiO 2 with high specific surface area (> 40 m2/g) and a low amount of sulphur ( ⁇ 150 ppm S). . .
  • Reacting the excess sulphuric acid with an appropriate base NaOH, aqueous ammonia solution etc.
  • an appropriate base NaOH, aqueous ammonia solution etc.
  • removing the salts formed by excessive washing with de-ionized water allows for significant lower sulphur levels of 0,03-0,2 wt.-%.
  • basic solutions of metals e.g. NaOH or KOH
  • Lowering the sulphur level can also be done by successive washing cycles by excess treatment with a strong base and successive removal of the metal ions by washing with an acid.
  • acids e.g. acetic acid
  • the sulphur is removed by thermal decomposition of the sulphuric acid.
  • temperatures exceeding 500 °C a significant reduction of the sulphate contaminations is observed, but during this heat treatment two processes also take place: i) the T1O2 particles undergo a particle growth which results in significantly and irreversible decrease of the specific surface area and ii) at these temperatures the phase transformation from the anatase to the rutile polymorph takes place.
  • BET surface area > 20 m 2 /g, preferably > 30 m 2 /g and more preferably > 40 m 2 /g
  • anatase type titanium dioxide doped with the appropriate amount of silica and/or an oxide of zirconium, and or an oxide of aluminium can be treated at temperatures high enough to decompose the sulphuric acid while maintaining substantially large specific surface areas.
  • thermal stabilization has to be understood that anatase type TiO 2 is stabilized in a manner that i) the rutilization temperature is shifted towards higher temperatures and ii) the tendency towards BET loss is reduced.
  • anatase type T1O2 having a content of 8 wt% SiO 2 is heated for one hour to temperatures as high as 1000°C.
  • the resulting powder exhibits BET surface areas of about 50-70 m 2 /g and residual sulphur contaminations of ⁇ 50 ppm.
  • the degree of resistance towards thermal aging of the anatase is strongly dependent on the amount of silica added. Small amounts only introduce a minor resistance, while larger amounts of silica have a strong effect on aging properties.
  • silica can also influence the catalytic properties of the final catalyst. It can change the overall performance by altering the selectivity and/or the conversion rate.
  • the right material and calcination conditions have to be individually adjusted to the . . respective intended use. In general, high calcination temperatures reduce both, residual S-levels and specific surface area.
  • any element that is able to stabilise the anatase polymorph can be used in terms of this invention.
  • typical elements for catalytic applications are Si, Al, Zr [J Mater Sci (201 1 ) 46:855-874].
  • the present invention is directed to an anatase titanium dioxide having a content of at least one compound selected from oxides of Si, Al, and Zr in an amount of 2-50 % b.w., preferably 2-30 % b.w., calculated as oxides, of the total weight of the oxides, and having a sulphur content of less than 150ppm, preferably less than 100ppm and more preferred of less than 80ppm referred to the total weight of the oxides.
  • the inventive anatase material has preferably an alkali content such as of Na + of below 200ppm, preferably below 100ppm in order to avoid any negative influences of the alkali on the stability of the material during use.
  • the anatase titanium dioxide is preferably obtained by the sulphate process which is obtained as titanium dioxide and hydrated forms thereof including meta-titanic acid. Meta-titanic acid and the hydrated forms of titania which are used here synonymously can be represented by the formula _ _
  • Said meta-titanic acid is then further treated to incorporate the stabilising agents selected from Si, Zr and/or Al in the form of the oxides and hydrated forms thereof and then subjected to the calcination treatment to decompose the sulphur-containing compound such as sulphuric acid as a remainder of the sulphate process.
  • the hydrated forms are converted to the oxides and the hydrate content will be reduced to zero which should be clear to the skilled man.
  • anatase titanium dioxide or anatase titania as used in accordance with the present invention means that at least 95% b.w., preferably 98% b.w. and most preferred 100% of the titania is present in the anatase form.
  • the anatase phase has crystallite sizes of 5 - 50 nm.
  • the crystalline phases of the particles are mostly present in the anatase phase, after drying at 105°C for at least 120 min before calcination and also after calcination due to the stabilisation. I.e.
  • the ratio of the height of the most intensive peak of the anatase structure (reflex (101 )) to the height of the most intensive peak of the rutile structure (reflex (1 10)) is at least 5:1 , preferably at least 10:1 .
  • the XRD analysis exclusively shows anatase peaks.
  • an X-ray is taken.
  • the intensities of the Bragg condition after diffracted at the lattice planes of a crystal X-rays are measured against the diffraction angle 2 Theta.
  • the X-ray diffraction is characteristic for the phase.
  • Drying as used in the context of the present invention means drying at temperatures above 105°C at ambient pressure. All large scale industrial techniques can be applied such as spin-flash or spray drying, but the drying is not limited to the techniques mentioned.
  • Calcining as used in accordance with the present invention means treating the stabilized anatase titania at an elevated temperature from above 500°C, preferably from 800°C up to 1200°C, for a time period sufficient to decompose the remaining sulphur containing compound such as sulphuric acid and thus to reduce the - - sulphur content to a level below 150ppm, preferably less than 100ppm and more preferred less than 80ppm referred to the total weight of the oxides, preferably for a time period of 30 min to 1200 min, while maintaining the titania in the anatase form.
  • Calcining can be carried out in a regular calcination device under atmospheric pressure so that the sulphur containing components can evaporate from the material.
  • the weight ratios, ppm-values or percentages as used in the present invention refer to the weight of the material after calcination.
  • the anatase T1O2 obtained can then serve as a catalytic support material which can further be treated with at least one compound of catalytically active metal selected from Co, Ni, Fe, W, V, Cr, Mo, Ce, Ag, Au, Pt, Pd, Ru, Rh, Cu, or mixtures thereof whereby a metal loaded material is obtained.
  • a precursor compound soluble in polar or non-polar solvents of a catalytically active metal selected from Co, Ni, Fe, W, V, Cr, Mo, Ce, Ag, Au, Pt, Pd, Ru, Rh, Cu, or mixtures thereof can be used. Treating the support material with one precursor compound or mixtures thereof of the catalytically active metals can be performed by various techniques.
  • Typical methods include incipient wetness or excess solvent method. Also deposition reactions such as hydrolysis can be applied to bring the catalytically active metal or precursors thereof into contact with the catalytic support material.
  • the compound of a catalytically active metal which are not particularly limited and may be selected from Co, Ni, Fe, W, V, Cr, Mo, Ce, Ag, Au, Pt, Pd, Ru, Rh, Cu, or mixtures thereof can be used in an amount to obtain a loading of 1 -50 % b.w,, preferably 5-30 % b.w., and more preferably 8-20 % b.w., calculated as oxides of the total weight of the final material. . .
  • the present invention covers an:
  • - anatase titanium dioxide having a content of at least one compound selected from oxides of Si, Al, and Zr in an amount of 2-50 % b.w., preferably 2-30 % b.w., calculated as oxides, of the total weight of the oxides, and having a sulphur content of less than 150ppm, preferably less than 100ppm and more preferred of less than 80ppm referred to the total weight of the oxides;
  • - anatase titanium dioxide having a content of at least one compound selected from oxides of Si, Al, and Zr in an amount of 3-20% b.w., more preferably 4- 12% b.w., calculated as oxides, of the total weight of the oxides and having a sulphur content of less than 150ppm, preferably less than 100ppm and more preferred of less than 80ppm referred to the total weight of the oxides;
  • - anatase titanium dioxide having a content of S1O2 in an amount of 2-30 % b.w., preferably 3-20% b.w., more preferably 4-12% b.w., calculated as oxide, of the total weight of the oxides, and having a sulphur content of less than 100ppm, preferably less than 80ppm referred to the total weight of the oxides;
  • anatase titanium dioxide having a content of at least one compound selected from oxides of Si, Al, and Zr in an amount of 2-50 % b.w., preferably 2-30 % b.w., more preferably 3-20% b.w., most preferably 4-12% b.w., calculated as oxides, of the total weight of the oxides , and having a sulphur content of less than 150ppm, preferably less than 100ppm and more preferred less than 80ppm, referred to the total weight of the oxides, wherein:
  • a titanium compound selected from metatitanic acid or titanylsulphate is mixed with at least one compound selected from oxides and/or hydroxides of Si, Al, and Zr or precursors thereof in an aqueous medium,
  • the product is optionally filtered, optionally washed with water, and optionally dried, _ _ the product is then subjected to a calcination treatment at a temperature of more than 500°C, preferably in the range of 800° to 1200°C, over a time period sufficient to decompose the remaining sulphur containing compound such as sulphuric acid to a level below 150ppm, preferably less than 100ppm and more preferred less than 80ppm referred to the total weight of the oxides, preferably over a time period of 0,5 to twelve hours,
  • an anatase titania having a content of a stabilizing agent is treated at a - - temperature more than 500°C, preferably in the range of 800° to 1200°C, over a time period sufficient to decompose a remaining sulphur containing compound such as sulphuric acid to a level below 150ppm, preferably less than 100ppm and more preferred less than 80ppm referred to the total weight of the oxides, preferably for a time period of at least 30 min, wherein the stabilizing agent is selected from oxides of Si, Al, and Zr and wherein the content of the stabilizing agent is in the range of 2-50 % b.w., preferably 2-30 % b.w., calculated as oxides, of the total weight of the oxides
  • anatase titanium dioxide of the invention obtainable according to the inventive processes, as a catalyst or catalyst support in catalysis reactions, gas-to-liquid reactions such as in particular Fischer-Tropsch catalysis, selective catalytic reduction (SCR), oxidation catalysis, photo catalysis, hydrotreating catalysis, Claus catalysis, phthalic acid catalysis.
  • gas-to-liquid reactions such as in particular Fischer-Tropsch catalysis, selective catalytic reduction (SCR), oxidation catalysis, photo catalysis, hydrotreating catalysis, Claus catalysis, phthalic acid catalysis.
  • Catalyst or catalyst support comprising the anatase titanium dioxide of the invention, obtainable according to the inventive processes.
  • x-ray diffraction (XRD) analysis is applied. This is done in a typical XRD set-up where the intensities of the diffracted x-rays are measured vs. the diffraction angle 2 Theta.
  • the material is digested in H 2 SO 4 /(NH ) 2 SO 4 , followed by dilution with de-ionized water.
  • the residue is washed with sulphuric acid and the SiO 2 content is obtained by weighing the filter cake after incineration.
  • S-contents were obtained by elemental analyzer Euro EA (Hekatech). The sample is burned in oxygen atmosphere and the gases are analyzed by gas chromatography. S-contents are calculated from the areas of the chromatogram.
  • the specific surface area was determined by nitrogen adsorption technique according to DIN ISO 9277 (BET method). 5 points between 0,1 and 0,3 p/po were evaluated. The equipment used was an Autosorb 6 or 6B (Quantachrome GmbH). - -
  • SiO 2 (13,1 % b.w.) was introduced by co-precipitation of TiO 2 and SiO 2 from TiOSO 4 - and Na 2 SiO 3 -solutions.
  • 352 I of Na 2 SiO 3 (94 g/l SiO 2 ) solution and 2220 I of TiOSO 4 (103 g/l TiO 2 ) solution were simultaneously pumped over a period of 270 minutes into a stirred reaction vessel containing 960 I water. During the reaction, the pH was kept at 5 with ammonia solution. After the addition was complete, the reaction was heated for 1 hour to 75°C to complete reaction. Afterwards a hydrothermal aging was performed for 4 hours at 9,5 - 10 bar and 170-180°C. Finally the resulting reaction mixtures was filtered and washed with de-ionized water. The product was obtained after spray drying at 350°C. BET was 100m 2 /g and S content 4000ppm.
  • a SiO 2 /TiO 2 powder having a SiO 2 content of 8,5% b.w. was prepared on the basis of metatitanic acid and Na 2 SiO3 following a sequence of pH-adjusting steps and final filtration and washing of the so-obtained material with de-ionized water.
  • the SiO 2 /TiO 2 powder obtained after drying had a BET of 334 m 2 /g and a sulphur content of 1 100 mg/kg.
  • Example 4 was produced in the same way as example 3 except that the sequence of ZrOCI 2 x8H 2 O and sodium silicate addition was changed. For example 4 first the - -
  • Hombikat 8602 was purified by neutralisation with NaOH and washing with deionized water. The resulting sulphur content before calcination was 0,2 wt.-% (2000ppm). and BET-surface area 351 m 2 /g.
  • a rutile suspension was prepared according to example 1 a in DE10333029A1 .
  • NaOH was added to a pH of 6,0 to 6,2 at 60°C, the solid was filtered and washed with deionized water to a filtrate conductivity of below 100pS/cnn.
  • the obtained filter cake was re-slurried and spray dried.
  • the BET surface area was 105m 2 /g and the S-content 70ppm
  • the FTS test were conducted using a 32-fold parallel reactor. The powders were compacted and subsequently crushed. The samples were lowed with Co(NO3)2 via impregnation in order to get a final Co loading of 10 wt.-% based on the total weight of the dried and reduced catalyst. For catalytic testing, the 125-160 ⁇ fraction was used and each catalyst unit was filled with an amount of catalyst to ensure 40mg Co-metal loading. Prior to the catalytic testing the catalyst was activated in diluted H 2 (25% in Ar) at 350°C (1 K/min heating ramp). The catalytic testing was then performed at 20 bar with a feed of 1 .56 L/h per reactor. The H 2 /CO ratio was 2 (10 % Ar in feed) and the temperature of the catalytic test was 220 °C.
  • the target of FTS is to produce long chain hydrocarbons. Especially hydrocarbons with more than 5 carbon atoms are of interest, because they serve as a feedstock e.g. for high quality Diesel, kerosene or long chain waxes.
  • Syngas H 2 /CO-mixtures
  • H 2 0 to yield CO and H 2 (steam reforming).
  • the reverse reaction would reduce the amount of CO and H 2 available for the FTS reaction.
  • High CH 4 - - selectivity in FTS indicates high conversion of CO and H 2 to CH 4 and vice versa. Therefore the CH 4 selectivity should be kept at lowest level possible.
  • CO can react with H 2 0 to form C0 2 and H 2 (water gas shift reaction). This would reduce the concentration of carbon atoms available for the FTS.
  • High C0 2 selectivity indicates high conversion of CO to C0 2 and vice versa. Thus C0 2 selectivity should be low for FTS catalysts.
  • CO conversion (the amount of CO converted) should be high and additionally the amount of hydrocarbons with more than 5 carbon atoms should also be high.
  • the latter parameter is indicated by the amount of hydrocarbons with more than 5 carbon atoms produced within one hour over one gram of Cobalt metal.
  • Table 3 clearly shows that the inventive products exhibit superior properties when used as catalytic supports in FTS.

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Abstract

La présente invention concerne le domaine de la catalyse hétérogène. Plus particulièrement, elle concerne un procédé de réduction de la teneur en soufre d'un oxyde de titane stabilisé, le matériau ainsi obtenu et son utilisation pour la fabrication de matériaux de support pour catalyseurs hétérogènes.
PCT/EP2017/063439 2016-06-06 2017-06-02 Procédé de réduction de la teneur en soufre de l'oxyde de titane anastase et produit ainsi obtenu WO2017211710A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
CN201780035012.XA CN109311695A (zh) 2016-06-06 2017-06-02 用于降低锐钛矿二氧化钛的硫含量的工艺及如此获得的产物
US16/306,903 US11135570B2 (en) 2016-06-06 2017-06-02 Process for reducing the sulphur content of anatase titania and the so-obtained product
UAA201812723A UA125691C2 (uk) 2016-06-06 2017-06-02 Діоксид титану анатазної форми зі зниженим вмістом сірки та спосіб його одержання
EA201892791A EA201892791A1 (ru) 2016-06-06 2017-06-02 Способ снижения содержания серы в диоксиде титана анатазной формы и полученный таким способом продукт
AU2017277063A AU2017277063B2 (en) 2016-06-06 2017-06-02 Process for reducing the sulphur content of anatase titania and the so-obtained product
EP17736572.3A EP3464184A1 (fr) 2016-06-06 2017-06-02 Procédé de réduction de la teneur en soufre de l'oxyde de titane anastase et produit ainsi obtenu
CA3025085A CA3025085A1 (fr) 2016-06-06 2017-06-02 Procede de reduction de la teneur en soufre de l'oxyde de titane anastase et produit ainsi obtenu
KR1020197000485A KR102381005B1 (ko) 2016-06-06 2017-06-02 아나타제 티타니아의 황 함량을 감소시키기 위한 방법 및 이렇게 수득된 생성물
MYPI2018002314A MY197671A (en) 2016-06-06 2017-06-02 Process for reducing the sulphur content of anatase titania and the so-obtained product
BR112018073994A BR112018073994A2 (pt) 2016-06-06 2017-06-02 processo para reduzir o teor de enxofre de titânia anatase e o produto assim obtido
JP2019516072A JP7181187B2 (ja) 2016-06-06 2017-06-02 アナターゼチタニアの硫黄含有量を低下させる方法及びそのようにして得られる生成物

Applications Claiming Priority (4)

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US15/173,801 2016-06-06
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GB2267905A (en) * 1992-06-20 1993-12-22 Tioxide Specialties Ltd Coating of anatase titanium dioxide particles
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GB1168136A (en) * 1966-06-22 1969-10-22 Nat Lead Co Photoreactive Titanium Dioxide Material
US5169821A (en) * 1991-11-14 1992-12-08 Exxon Research And Engineering Company Method for stabilizing titania supported cobalt catalyst and the catalyst for use in Fischer-Tropsch process
GB2267905A (en) * 1992-06-20 1993-12-22 Tioxide Specialties Ltd Coating of anatase titanium dioxide particles
WO1994020447A1 (fr) * 1993-03-10 1994-09-15 Amoco Corporation Catalyseur et procede pour purifier de l'acide terephtalique brut, de l'acide isophtalique brut ou un acide naphtalene dicarboxylique brut
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AU2017277063B2 (en) 2021-12-02
MY197671A (en) 2023-07-03
KR102381005B1 (ko) 2022-03-30
AU2017277063A1 (en) 2018-12-20
CN109311695A (zh) 2019-02-05
EP3464184A1 (fr) 2019-04-10
UA125691C2 (uk) 2022-05-18
JP2019518602A (ja) 2019-07-04
BR112018073994A2 (pt) 2019-02-26
JP7181187B2 (ja) 2022-11-30
KR20190017898A (ko) 2019-02-20

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