WO1999043195A2 - Catalyseur a base de titane et procede de preparation dudit catalyseur - Google Patents

Catalyseur a base de titane et procede de preparation dudit catalyseur Download PDF

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Publication number
WO1999043195A2
WO1999043195A2 PCT/IL1998/000091 IL9800091W WO9943195A2 WO 1999043195 A2 WO1999043195 A2 WO 1999043195A2 IL 9800091 W IL9800091 W IL 9800091W WO 9943195 A2 WO9943195 A2 WO 9943195A2
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WO
WIPO (PCT)
Prior art keywords
catalyst composition
composition according
novel catalyst
titanium dioxide
catalyst
Prior art date
Application number
PCT/IL1998/000091
Other languages
English (en)
Inventor
Ya'acov Mirsky
Original Assignee
Rotem Amfert Negev Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rotem Amfert Negev Ltd. filed Critical Rotem Amfert Negev Ltd.
Priority to AU62284/98A priority Critical patent/AU6228498A/en
Priority to PCT/IL1998/000091 priority patent/WO1999043195A2/fr
Publication of WO1999043195A2 publication Critical patent/WO1999043195A2/fr

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Classifications

    • 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
    • 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
    • B01J35/31—Density
    • 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
    • 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

Definitions

  • the present invention relates to a novel catalyst. More particularly, the invention relates to a novel catalyst, based on titanium dioxide to be most useful for the sulfur recovery in various processes.
  • the novel catalyst according to the present invention can be used in various processes and particularly in the sulfur recovery and various reactions which involve sulfur constituents, such as hydrogen sulfide reaction with sulfur dioxide (known as Claus reaction), carbonyl sulfide hydrolysis, carbonyl disulfide hydrolysis and direct oxidation of hydrogen sulfide with air and tail gases treatment (for example "Sulfreen” process).
  • the catalyst can be used also in other catalytic processes in which titanium dioxide imparts catalytic activity, such as: carbon monoxide oxidation, nitrogen oxide reduction with ammonia, total oxidation of organic compounds, etc.
  • titania-based catalyst preparation According to the U.S. Patent No.
  • 4,388,288, a shaped titanium dioxide catalyst or a carrier is described.
  • this material appears as a powder which is a partially crystalline anatase, being mainly used as a white titanium pigment.
  • the powder has a weight loss on ignition in the range of between 1% to 50%, generally being mixed with water in the range of between 1% to 15% by weight and from 0% to 15% by weight of a shaping additive. The resulted mixture is shaped and the obtained article is dried and calcined.
  • a poor crystallized anatase can also be obtained by the hydrolysis of titanium compounds having the general formula TiCl 4 -n(OR) n wherein "n" is in the range of between 0 to 4 and R is an alkyl radical. Another way to obtain this anatase is by precipitation of a titanium salt with a base constituent such as ammonia.
  • a catalyst for the hydrolysis of carbonyl sulfide.
  • the catalyst was prepared in the form of porous blocks or granules, wherein the main constituent of the blocks is titanium dioxide mixed with reinforcing materials, selected from silica, aluminium oxide, clay or aluminosilicate.
  • the amount of reinforcing material used is limited up to 30% by weight; no data are mentioned on the properties of the specific reinforcing materials and their combination with the titanium dioxide.
  • the materials mentioned in the various Examples are spherical carrier comprising Titanium dioxide up to 93%, SiO 2 up to 34% and AI 2 O 3 3% (all by weight).
  • the catalysts contain also metal oxides in the range of between 0.5% to 10% by weight, the metal being selected from Li, Na, K, Cs, Mg, Ca, Ba, Zn, Cd. Sn, Pb or the like.
  • a shaped titanium dioxide catalyst is obtained by the same procedure as described in the U.S. Patent No. 4,388,288 but comprises besides titanium dioxide, a sulfate of an alkaline earth metal selected from the group consisting of calcium, barium, strontium and magnesium.
  • a sulfate of an alkaline earth metal selected from the group consisting of calcium, barium, strontium and magnesium.
  • Three methods of the addition of the alkaline earth metal sulfate may be used.
  • a shaped titanium dioxide body is successively impregnated with a compound which provides the sulfate anion and then with a compound which provides the alkaline earth metal cation.
  • the above mentioned compounds are transformed into the respective constituents to be incorporated in the mixture of titanium dioxide, water and shaping additive, before the step of this mixture shaping.
  • a catalyst for production of sulfur from a gas containing hydrogen sulfide is described.
  • the catalyst comprises a porous matrix associated with metal compounds, such as Fe, Cu, Zn, Cd, Mo, W, and optionally a noble metal.
  • the porous matrix comprising silica, titanium dioxide, zirconium dioxide, zeolites or alumina, are obtained by precipitating a hydrogel of silica, titanium or zirconium oxyhydrate from the respective solutions, followed by their transformation in pellets or beads being further dried and calcined.
  • a mixed matrix can be produced by mixing the selected oxides prepared separately by a respective co-precipitation. According to the PCT patent application WO87/02654 a process is described for the removal of sulfur-containing compounds from residual gas, using three groups of catalyst:
  • titanium extrudates are prepared from rutile and anatase in the form of shapable dough containing a mixture of titania with alkanolamine or ammonia, which are dried and calcined. It is mentioned the option to incorporate into the dough also other oxides, such as silica or zirconia and crystalline silicates.
  • the resulted titania extrudates are suggested to be used as carriers for catalysis in hydrogenation processes and hydrocarbon conversion processes.
  • an extrudable dough formed by a mixture of titanium dioxide, monoethanolamine, water, a powdery silica, zirconium dioxide and zeolite.
  • the invention relates to a novel catalyst composition based on a modified titanium dioxide as a catalytic active component, as described in our copending PCT patent application No. and comprises at least 3% by weight of said catalytic active component, an inert filler selected from siliceous materials, most preferably being diatomaceous earth.
  • a binder component such a sol of silicic acid may be used to prepare a catalyst generally in the form of extrudates.
  • extrudates possess a hardness above that of a commercial Claus catalyst, optimum macropore and mesopore structure and a high thermal stability as measured by a specific surface area up to 130 m 2 /g for a catalyst composition , comprising 45% by weight of the above mentioned modified titanium dioxide calcined at 800°C for three hours and a high hydrothermal stability.
  • the above novel catalyst was found to be most useful in the sulfur recovery processes, such as Claus reaction, carbonyl sulfide hydrolysis, carbon disulfide hydrolysis and "Sulfreen" process.
  • the catalyst composition contains between 3% to 100% (by weight) of an active component which is selected from modified titanium dioxides or titanium hydroxides (calculated as titanium dioxides) as described in our copending PCT patent application No or their mixture in any proportion. Also useful, is a mixture of aforesaid modified titanium dioxide with another titanium dioxide or titanium hydroxide produced by any method, present in the mixture in a quantity of between 0% to 80% by weight, the balance being a filler with or without a binder material. In the catalyst composition, optionally a binder constituent in an amount of between 0% to 20% by weight may be introduced.
  • Different colloidal sols or hydrogels of silicic acid can be used as a binder component, but this catalyst can be also prepared without any binder.
  • Different silica materials can be used as a filler, a preferable one being a natural silica-diatomaceous earth such as, or preliminary purified by an acid treatment from impurities of sodium, potassium, calcium, magnesium, and aluminium. Common mineral acids, such as hydrochloric acid or sulfuric acid can be used for this purpose.
  • the acid treatment has to be carried out at an elevated temperature in the range of between 60°C-100°C for 0.5-3 hours and the diatomaceous earth has to be washed from the acid solution.
  • This diatomaceous earth can be used in the form of a water suspension, wet cake, or dried material.
  • Another silica material which can be used as a filler is selected from precipitated silica or silica hydrogels. If these materials contain even a small amount of sodium or potassium (about 1% by weight) it is advisable to eliminate these impurities by an acid treatment or with any other known method.
  • the main components of this catalyst are: titanium dioxide and silica filler; titanium dioxide imparts a catalytic activity, while the silica filler imparts the necessary pore structure which causes a high rate of reagents diffusion inside the granules, the shaped catalyst and also to the reaction products outside the catalyst structure.
  • diatomaceous earth porous structure consisting of macropores with diameter about 1 micrometer, is the best filler.
  • Precipitated silica with low surface area and without a developed micropore structure and silica hydrogel with similar properties can also be used as fillers.
  • the catalyst obtained can be granulated into extrudates, beads, tablets, granules, or formed into honeycomb blocks or blocks with any suitable shape.
  • the novel catalyst is prepared according to the following main steps:
  • the modified titanium dioxide can be used in the form of a titanium hydroxide wet cake as taken from a filter, in the form of partially dried wet cake, or in the form of a completely dried, or calcined material.
  • the filler component may be used also either in the form of a wet cake, partially dried cake, or a completely dried material.
  • the main object of this step is to obtain a mixture possessing the following properties: - a high extent of homogeneity;
  • the prepared dough forms after the thermal treatment, granules with a high hardness even without using a binder in the stage of dough preparation.
  • sols of silicic acid may be added during the process up to 20% by weight calculated on the SiO 2
  • the resulted wet granules may be kept in air for some time or may be put into a drier immediately.
  • Different types of dryers can be used for this purpose and the drying process can be conducted at a wide range of temperatures, such as between the ambient one and up to 300°C.
  • the wet granules are dried first at 100°C-150°C until the granules become hard enough to be loaded into a calcination kiln at a temperature of about 400°C for about 1 to 10 hours, but sometimes the temperature of calcination may be increased up to 800°C.
  • a calcination kiln at a temperature of about 400°C for about 1 to 10 hours, but sometimes the temperature of calcination may be increased up to 800°C.
  • the aims of these Examples are to show the advantages of the novel catalyst in comparison with commercial ones in respect to: hardness, thermal and hydrothermal stability, mesopore and macropore structures and a smaller quantity of active component than in the known catalysts but at the same extent of catalytic activity.
  • Example 1 Two groups of Examples are shown: in Examples 1 and 2 the catalysts were prepared in a laboratory, while in Examples 4 to 13, the catalysts were prepared in a pilot plant.
  • the Example 3 is presented for comparative purpose.
  • This example demonstrates the preparation of the catalyst with the modified titanium dioxide as an active component, powdery precipitated silica as a filler and silica sol as a binder material, possessing a high catalytic activity in the Claus reaction.
  • the modified titanium dioxide and powdery silica were dried at 105°C for 24 hours. After drying, the two materials had losses on ignition values (LOI) as shown in Table 1.
  • Acidic sol of silicic acid was prepared from sodium sol of silicic acid using a cation exchange resin C-100 produced by PUROLITETM.
  • the paste was passed through a laboratory extruder obtaining extrudates with a diameter of 3.0 mm.
  • the extrudates were dried at 120°C for 3 hours in a laboratory dryer and then calcined at 400°C for 3 hours in a laboratory muffle.
  • the structural properties of the catalyst obtained are given in Table 3.
  • the quantity of titanium dioxide present in 1 m 3 of catalyst bed is only 140 Kg which is less than the quantity 777-900 kg present in a commercial catalyst (see Table 5).
  • these were crushed and the fraction between 8 and 12 mesh was separated by sieving and then tested in a bench scale pilot plant using the conditions as for the Claus process. The results of the tests are given in Table 4.
  • EXAMPLE 2 EXAMPLE 2.
  • modified titanium dioxide can be calcined before its incorporation in the mixture with the other components of the catalyst.
  • the paste mixture was prepared from this titanium dioxide, siliceous filler and a binder in a laboratory mortar (see Table 1); the composition of this paste, calculated on dry basis is given in Table 2.
  • Example 2 The paste had been formed into the same extrudates as in Example 1 in a laboratory extruder and then the extrudates were dried and calcined as in Example 1.
  • the structural properties of the prepared catalyst are given in Table 3.
  • the extrudates were crushed and the fraction with sizes of crumbs between 8 and 12 mesh, was tested in a bench scale pilot plant using the conditions as for Claus process. The results are given in Table 4.
  • This catalyst was introduced in the same reactor as in Examples 1 and 2.
  • the amount of the titanium dioxide used in this case was substantially the same as in Example 1. According to Table 4 it can be noticed that the difference in carbon disulfide conversion is equal to 10% which shows that the titanium dioxide present in the novel catalyst is more active than the same amount of titanium dioxide present in a commercial catalyst.
  • Water absorption (% by weight) 280 As natural diatomaceous earth contains some undesirable impurities, such as sodium, potassium, iron, aluminum, it was preliminary purified by an acid treatment. For this purpose hydrochloric or sulfuric acid having a concentration of 15%-20% was used, the temperature during this treatment being between 90°-98° C for about 3 hours. The purified diatomaceous earth was filtered, washed with demineralized water and used for the preparation of shapable dough in the form of wet cake or as a dried material. In some cases diatomaceous earth can be used as a filler without a preliminary purification.
  • hydrochloric or sulfuric acid having a concentration of 15%-20% was used, the temperature during this treatment being between 90°-98° C for about 3 hours.
  • the purified diatomaceous earth was filtered, washed with demineralized water and used for the preparation of shapable dough in the form of wet cake or as a dried material. In some cases diatomaceous earth can be used as a
  • Example 4 the purified diatomaceous earth was used .
  • the titanium dioxide from Example 1 in our above mentioned copending patent application was used as an active component in Examples 4-6 using silica hydrogel as a binder material, prepared by the following procedure: Basic silica sol prepared in its sodium form, having an initial concentration of about 3% (calculated as SiO2) was evaporated to an extent that its concentration increased to 20-30% by weight. Then this sol was treated with a cation exchanger in order to eliminate the sodium and accordingly to
  • the resulted acidic sol was treated with an aqueous solution of ammonia until its pH increased up to 7 and then it was heated. During the heating a coagulation of the sol into hydrogel took place and was used in the mixing with the other components.
  • the modified titanium dioxide in the form of a wet cake, a purified and dry diatomaceous earth and silica hydrogels were mixed in a double shaft mixer-sigma blade (produced by Sepor). After obtaining a homogeneous mixture, it was slightly dried in order to obtain a proper consistency suitable for extrusion.
  • the extrudates having a diameter of 3.6 mm, were obtained with a piston extruder, dried at 120°C for about two hours and calcined at 450 °C for 3 hours.
  • the catalyst consists of two components: the modified titanium dioxide (as prepared according to our above mentioned copending patent application) and as an inert filler, a purified diatomaceous earth (as obtained in Examples 4-6). Losses on ignition for the components are shown in Tablel and the compositions of the catalysts are given in Table 2.
  • the active component was mixed with the inert filler and the resulted mixture was malaxated thus producing a shapable dough using a double shaft mixer, as described in Examples 4 to 6 and a piston extruder as used in a process of granulation.
  • Example 7 diatomaceous earth was introduced as a wet cake after filtration, containing 35% of dry material. The paste was partially dried to a
  • diatomaceous earth was used in the form of a dried material (120°C) having a loss on ignition between 5%to 6% (see Table 1).
  • compositions of catalysts prepared in laboratory and in a pilot plant on the basis of precipitated modified titanium dioxides (% by weight calculated on dry basis)
  • Adsorption pore volume formed bv pores with diameter: less than 100 nm greater than 4.1 nm greater than 3.5 nm
  • Example No. of starting catalyst m 2 g "1 500 °C 700 °C 800 °C 900 °C

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
PCT/IL1998/000091 1998-02-24 1998-02-24 Catalyseur a base de titane et procede de preparation dudit catalyseur WO1999043195A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU62284/98A AU6228498A (en) 1998-02-24 1998-02-24 A catalyst based on titanium and method for its preparation
PCT/IL1998/000091 WO1999043195A2 (fr) 1998-02-24 1998-02-24 Catalyseur a base de titane et procede de preparation dudit catalyseur

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Application Number Priority Date Filing Date Title
PCT/IL1998/000091 WO1999043195A2 (fr) 1998-02-24 1998-02-24 Catalyseur a base de titane et procede de preparation dudit catalyseur

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7431904B2 (en) 2003-10-15 2008-10-07 Haldor Topsoe A/S Catalyst support material, catalysts prepared therefrom and process for the treatment of a flue gas
JP2014503443A (ja) * 2010-10-12 2014-02-13 エギシュ ヂョヂセルヂャール ニルヴァーノサン ミケデ レースヴェーニタールササーグ 薬学的使用に適する賦形剤の調製方法
CN106563475A (zh) * 2016-11-04 2017-04-19 昆明理工大学 一种同时催化水解羰基硫和二硫化碳的改性硅基催化剂的制备方法
WO2017066246A1 (fr) * 2015-10-13 2017-04-20 Imerys Filtration Minerals, Inc. Compositions et procédés pour protéger des plantes contre des organismes
CN106824149A (zh) * 2017-03-02 2017-06-13 太原理工大学 钛硅复合羰基硫水解催化剂及其制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7431904B2 (en) 2003-10-15 2008-10-07 Haldor Topsoe A/S Catalyst support material, catalysts prepared therefrom and process for the treatment of a flue gas
JP2014503443A (ja) * 2010-10-12 2014-02-13 エギシュ ヂョヂセルヂャール ニルヴァーノサン ミケデ レースヴェーニタールササーグ 薬学的使用に適する賦形剤の調製方法
WO2017066246A1 (fr) * 2015-10-13 2017-04-20 Imerys Filtration Minerals, Inc. Compositions et procédés pour protéger des plantes contre des organismes
CN106563475A (zh) * 2016-11-04 2017-04-19 昆明理工大学 一种同时催化水解羰基硫和二硫化碳的改性硅基催化剂的制备方法
CN106563475B (zh) * 2016-11-04 2020-04-03 昆明理工大学 一种同时催化水解羰基硫和二硫化碳的改性硅基催化剂的制备方法
CN106824149A (zh) * 2017-03-02 2017-06-13 太原理工大学 钛硅复合羰基硫水解催化剂及其制备方法
CN106824149B (zh) * 2017-03-02 2019-10-15 太原理工大学 钛硅复合羰基硫水解催化剂的制备方法

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Publication number Publication date
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