JPH01500249A - Attrition-resistant catalyst compositions, manufacturing methods, and uses - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Attrition-resistant catalyst composition, manufacturing method, and application LLL field Catalysts containing titania have a variety of uses. The composition containing titania The reactions mediated include selective reduction of nitrogen oxides in the flue gas with ammonia (atmospheric (useful for pollution control), hydrodesulfurization (e.g. decomposition of thiophene in naphtha), Coal liquefaction by hydrogenation, butene isomerization, and hydrocarbon selective oxidation. selective oxidation of butadiene, 1-butene, and benzene to maleic anhydride. , naphthalene and. -Selective oxidation of xylene to phthalic anhydride, butene to acetic acid Selective oxidation, selective oxidation of acetaldehyde and methanol to formaldehyde (S, Mazda and A.

Kado, Applied Catalysis, 8, 14 9-165 (1983)).

Many reactions using titania catalysts are exothermic, so such reactions are It was advantageous to perform it on the floor. Unfortunately, some materials that contain large amounts of titania Traditionally, media have poor physical integrity and abrasion resistance when used in fluidized beds. There was the inconvenience of scarcity. Titania catalysts require the harsh treatment that occurs in fluidized beds. It tends to break down into smaller particles on impact, and from the fluidized bed These fine particle el trinusions result in large losses of catalyst. wear it.

Under certain circumstances, fine particles of titania are weakly held together by electrostatic forces. These particles are “sticky” and difficult to fluidize. difficult and results in poor fluidization.

Therefore, due to these deficiencies in the prior art, a satisfactory fluidized bed titania catalyst is not available. I can't do it. Titania catalyst or titanium catalyst with excellent attrition resistance for fluidized bed operation It is an object of the present invention to provide a method for preparing a catalyst support.

Titania catalyst that does not tend to "stick" in fluidized beds and exhibits excellent fluidization properties Another aspect of the present invention is to provide a method for preparing a catalyst support having titania. This is the purpose of

By the term "fluidization characteristics" we mean that the temperature is uniform throughout the fluidized bed and It is easy to maintain stable fluidized bed operation that is subject to only small pressure fluctuations. It shows.

Still another objective is to produce a titania-based material that exhibits substantially the chemical properties of bulk titania. The object of the present invention is to provide a fluidized bed catalyst or a catalyst support having as a fraction.

Other objects, features and advantages of the invention will be found in the specification, including the examples, and the claims. This will become clearer from the discussion.

jLLjL distortion As early as 1962, Japanese researchers decided that titania would be preferred over silica as a catalyst support. using. - Excellent results are obtained in the catalytic oxidation of xylene to phthalic anhydride. (H. Kakinoki et al., Catalyst, 4.113 (1962), This is Uniinwright (M, S, Wainwright) and Hoffman (T, N, Hoffman), The Canadian Journal of Chem ical Engineering, i+557-564 (October 1977 ), later, the increase in selectivity for phthalic anhydride was It was shown that it is associated with an increase in the amount of oxygen absorbed per unit (H, Kir et al., Academic Journal, 7 (3), 164 (1964) (M, S, Uniin Light and and T.N. Hoffmann, supra)). However, 15 years later, anhydrous M.S. Unii is a major researcher and commentator in the field of tarnic acid synthesis. Nright reported that the exact role of Titania is still not understood (M, S , Uniin Light and N, R, Foster (Foster) +Cata1. R ev, -5ci, Eng, ■(2), 211-292 (1979)), At the same time, Uniinlite believes that the "titania catalyst" tends to break down into fine particles. ``Therefore, unless a suitable carrier is found, 0-xylene cannot be There is no prospect that fluidized beds will be used to

Titanyl sulfate (TiO3O) has been previously mentioned in the catalyst literature with no examples. For example, there are various ways to add titanyl sulfate solutions to dry silica gel. See the method of U.S. Pat. No. 2,344,911 as amended in U.S. Pat. See also US Pat. No. 2,458,818.

Titanylammonium sulfate is disclosed in U.S. Patent No. 3926 to Ono et al. Used in the '846 specification. See also U.S. Pat. No. 3,948,807. sea bream.

Titanium dioxide occurs in three polymorphic forms: rutile, anatase, and brookite. Cheating. Anatase is stable at temperatures below 700’C and has a large specific surface area. Solid titania supports are usually prepared with anatase. Titania is typically Neutralizing acidic solutions of titanium salts to yield orthotitanic acid as an intermediate, or Hydrolyze salt or titanate to produce metatitanic acid as an intermediate. Then, this titanic acid is calcined at 300 to 600°C to produce anatase. Prepared by. At temperatures above about 700°C, anatase becomes sintered and its surface area becomes extremely large. It decreases dramatically and turns into rutile. However, recently, Nijimoto et al. Academic Journal, (2), 246-52 (1984) (Chemical Abstracts) , x12106a (1984))) hydrolyzes Ti(SO2)t. , the resulting Ti(OB)a slurry was heated in the temperature range of 170-1000°C. A series of titania powders were prepared by calcination at ambient temperature. You in this powder The carbon content and the corresponding crystallite size increase with temperature up to 700°C. It was a big deal. The transition from anatase to rutile occurs at approximately 740-830°C, and The sulfate ions in the resulting titania powder decrease linearly with increasing temperature. It disappeared slightly, and completely disappeared at temperatures higher than 800°C. on the surface of titania The amount of hydroxyl groups decreased monotonically with increasing temperature.

U.S. Patent Nos. 4,046,780, 4,284,571, and 4,481,304 The specification states that a significant portion of the anatase titania is a porous catalyst support of silicon carbide. Anhydrous made using titanium hydroxide and titanylammonium sulfate placed on top It is described as being retained in a phthalic acid catalyst. The anatase shape is also known as U.S. Pat. No. 397,768.

Titanyl sulfate is used in US Pat. No. 4,424,320, which describes a polymerization catalyst. It is reacted with peroxide prior to addition to the licagel.

However, all of the above-mentioned patent specifications describe No attrition resistant catalysts made from titanyl sulfate are described.

A method for producing supported catalysts for partial oxidation of aromatic hydrocarbons in a fluidized bed , :2 U.S. Patent No. 35 to Friedrichsen et al. No. 65919. This catalyst uses an inert support material as a titanium compound. and heated to 130-1300°C in the presence of oxygen; 7 with a solution or melt of a vanadium compound in the presence of oxygen. It is prepared by heating at 350-1100℃. This catalyst is described as ``wear-resistant.'' However, this claim is based on gas velocities in the range typically used in commercial operations. Not supported using data showing the rate at which this catalyst wears out in a fluidized bed. .

The teachings of U.S. Pat. No. 3,565,919 also provide a satisfactory titania catalyst support. It also lacks other qualities that are extremely important to . Only a monolayer of titania is obtained. , and this does not represent the chemistry of bulk titania. Friedrichsen Another significant limitation encountered according to the teachings of the patent specification is the thermal stability of the composition. It is a sexual restriction. The anatase phase of titania is the preferred phase for most applications. However, it is easily converted thermally to the less active rutile phase. Such a transformation , if the catalyst is prepared in less than 3 hours at 600 °C according to the teachings of Friedrichsen. occurs when the retention time of catalyst activity is used to apply the catalyst. It shows that even at lower temperatures it will be severely reduced.

light show According to the invention, catalysts or catalysts in commercial fluidized bed operations with titania Materials with acceptable attrition rates for use as carriers are abrasion-resistant fluidizable It is prepared by impregnating a support material with a soluble acid salt of titanium. protruding jaw The method used by Applicants provides titania in the stable anatase form and has an average pore volume of 0.1 CIA/ g, preferably greater than 0.4 cc/g, and a commercial fluidized bed A fluidizable support material having satisfactory abrasion resistance for use in Place Tarth-shaped Titania. The support material may be conditioned prior to impregnation. , and then this support material was added with titanium sulfate, which yields anatase titania when pyrolyzed. containing soluble salts or mixtures of salts such as ammonium titanyl or titanyl sulfate. impregnated with an aqueous solution of heat up. The above compound or mixture is then pyrolyzed to give the resulting Adjusting the condition of titania and supporting materials includes pre-calcination, steam calcination, and doping. Treatments such as blocking or blocking, i.e., relatively less Small amounts of selected compounds or drugs such as soluble metal salts, hydrates, or oxides and calcined for a relatively long time (i.e. 8-50 hours or more). This means filling the cavities of the support matrix with the components. Dopin The selection and amount of adhesive used are optional variables well known to those skilled in the art and are subject to change. Preliminary steps that can be used to prepare materials for impregnation (e.g. steaming at one temperature and then at another temperature for a specified period of time) It is also possible to program. Within the scope of the invention, the sieve portion or empty Depending on the mood class, a certain particle size fraction (e.g. "fines" or "dust" ”) is also included as an option. in this way," "Conditioning" means a one-meter task intended to prepare the supporting material for impregnation. It is an arbitrary and variable process.

Rutile form of titania is desirable for some applications in catalyst compositions containing titania. However, rutile titania is anhydrous phthalate of o-xylene and naphthalene. They are generally less active as catalysts for most applications such as oxidation to acids.

The method of this invention has, as one of its advantages, the initial attachment of anatase as A significant portion of the titania produced can be used without converting it to rutile. There is a thing called.

Unexpectedly, the stability of the anatase form in the products of the invention is extremely The composition with titania of the present invention has a high , showing no evidence of rutile formation when exposed to 900°C for 8 hours, 80 After 80 hours at 0°C, when the support material is prepared according to the teachings of the present invention, The resulting fluidizable tactile fluid was prepared with no detectable traces of rutile. The medium has a combination of titania's chemical properties and the starting support's physical properties. There is an advantage. Because of its relatively low densities, this material fluidizes well and forms bulk It is likened to titania, and the support material is covered with Ti1t, so it is It appears to be less likely to initiate solid state chemical reactions than if fully exposed. Ru. The treatment method of this disclosure is facilitated by a composition having titania or titania. Prepare catalysts useful for any chemical reaction requiring a support material with tania For example, the material prepared by Applicants' method is suitable for phthalic anhydride. Selective oxidation of 0-xylene and naphthalene or mixtures thereof to produce acids It is particularly suitable as a support for catalysts for It also contains cis of 1-butene It is also particularly suitable as a catalyst for the isomerization to /trans 2-butene.

The term "substrate" is used herein to refer to a type of metal oxide. or mixtures of oxides, carbides, silicates, and aluminates. used to designate an inorganic oxide material qualitatively comprising any of the above forms. In the case of silica, silica-alumina, alumina, magnesia, silica-mag nesia, calcium aluminate and calcium silicate, and silicon carbide. It is commonly used to prepare catalysts and catalyst supports.

The term "fluidizable support material" refers to materials that are in the form of particles and that a fluid can is supported freely by this fluid as it passes upward through the bed at a suitable speed. Any material such as means a material known to be capable of Typically a fluidizable support material The particle size ranges from 60 microns to 400 microns, and its appearance is dense. The degree is 0.5 to 2.0 g/cc.

Preferably, the support material is coated with titanyl sulfate or titanyl sulfate by an "initial wet" technique. impregnated with ammonium, i.e. the volume of the impregnating solution covers the pores of the material to be wetted. Approximately equal volume is used. The use of larger amounts of solution will result in less satellites in the product. Larger impregnated particles with excess unsupported titania present as a similar fine powder and as a result, the results of the abrasion test of the product are unsatisfactory. It becomes worth it.

adding the solution to the support material and mixing until the solution is uniformly distributed in the pores; The steps can be carried out batchwise or in a continuous manner. Examples of suitable mixing equipment is a Pfaudler or Abbe rotary mixer, ■ Includes type mixers, and drum mixers. Impregnating the support material with a spray dryer, e.g. Use by slurrying with a solution and feeding this slurry to a spray dryer. can do. Multiple impregnations allow water to evaporate in the middle of the impregnation prior to the final calcination step. and heat the titania-containing compound or mixture to the desired extent. This can be done by decomposition or pyrolysis, and in the final calcination step Thermal decomposition is completed and the composition stabilized. The final calcination temperature adopted is Depending on the particular impregnating agent used as the Tania source 7. natanyl ammonium sulfate, decomposes at about 575°C. Therefore, calcination or decomposition of this material is possible at this temperature or It must be carried out at a higher temperature.

At 575°C, thermal decomposition of the impregnating agent is completed and the composition remains stable. The temperature required to reach the temperature may be too long to be practical; The higher the temperature is above 75°C, the shorter the time required for processing. Dew.

Heating to temperatures above 900°C promotes sintering of titania, thereby reduces the surface area. For example, 37.5% TiO□ on a silica support. Calcining a composition for 8 hours at 950°C versus 900°C reduces the surface area by approximately 3 Decrease by 0%. Therefore, the resulting catalysts and compositions of this disclosure The combination of time and temperature for calcination can be adjusted to vary the surface area within limits. You may also use adjusting. Titanylammonium sulfate as a source of titania If so, the final charring is preferably carried out at 700-900°C for 0.5 hours or more. is preferably carried out for 1 to 10 hours.

Titanyl sulfate (not ammoniated) is , 450°C was discovered to convert to titania at lower temperatures. at 450℃ For this material calcined for 24 hours, X-ray diffraction was performed at a scan rate of 1 degree/min. Main peak of anatase with 1387 counts at d 3.52 and 6 at d 3.25 The main peak of rutile with 6 counts was shown. Therefore, titanium sulfate is a source of titania. Compositions utilizing tanyl should be calcined at temperatures of 450°C or higher. Therefore, the preferred temperature is 550 to 800°C.

If some rutile is desired in the catalyst or composition, the method described above It has been recognized that the final calcination of It will be done. This is done by adding rutile as a seed material to the initial titanyl sulfate. It would be the easiest to do. Sulphate buffer with sufficient amount added to titanyl sulphate. Other compounds such as nazils are the natural heat of titania defined in this disclosure. Presumably overcoming stability, it facilitates the metamorphosis of anatase into rutile, thereby It is also recognized that considerable rutile-type titanium will be produced during calcining. Ru.

Other ingredients may be added to the impregnating solution prior to impregnating the support to provide specific compositions or catalysts. It is also possible that the titania contained in the final composition can be obtained by the teachings of this disclosure. as long as it is made and within the compositional limits of TiO2 explained below. is within the scope of this invention. An example of an additive ingredient is sulfate buffer added to the impregnating solution. sodium, thereby depositing the V,Os-TiO□ composition on the starting support. arise.

Examples of starting supports that can be used for this invention include Wear resistance) All absorbent materials that have acidity and can be used in fluidized bed reactors. Includes quality. Common examples of such materials include silica gel, ground silica, synthetic and natural silicates, clay, alumina, magnesium oxide, zirconium oxide, Includes zeolites, silicon carbide, and others familiar to those skilled in the art. .

The term "titanyl sulfate" as used in the claims. Included within the scope is titanyl sulfate, as discussed above, as well as in the section below. does not include any of the impregnating solutions described in , especially titanyl sulfate, titanyl ammonium sulfate, their hydrates and acidic solutions , as well as titania hydrate valves.

Mackerel,, acid 793-fire 1 tempura, Mori (1 nail Σ-)-5Φ acid, sexual fluid this impregnation solution To prepare the solution, the first step was to hydrolyze TiCl, with water. messenger The device used was a machine that was stirred by a power stirrer and had a scale with a long discharge pipe. A 1500aJ Pyrex beaker equipped to receive liquid from a funnel. It was made up of several things. A cube of ice with a bulk volume of approximately 300 wJ is placed in a beaker. and then filled the interstitial spaces of the ice sheet with water.

Fill the addition funnel with 135- TiC1a, loosely cover the lid, and stir vigorously. Start and add TiCl4 to ice water over a period of about 10 minutes and TiCla to liquid. It was added while introducing it below the surface. During the addition, the temperature of the mixture should not exceed 75°C. Add more ice so that the volume of the mixture does not exceed 600 ml. I got it. After adding TiC1a, 67-ml concentrated sulfuric acid was added to the mixture.

Finally, 165 g of ammonium sulfate was heated and dissolved in 165-g of deionized water. and this solution was boiled and added to the mixture in the beaker. prepared solution The total volume of is 750-800 mZ, and the most bitter composition is as follows. Ta.

(NH4:h S04・Ti0SOa・2+(2038, 4% by weight water 42.8 HC118,2 The freshly prepared solution was allowed to cool slightly before being used for impregnation. but, Stock solutions are often stored for several days before use, and during this time the concentration of ATS will gradually increase. It decreased somewhat due to the crystallization that occurs.

Artificial canopy and μ lid bag swimming power Upon standing, an acidic solution of ATS prepared as described precipitates crystals. number The crystal clumps that accumulate over days do not dissolve easily in common solvents, however The newly deposited crystals were found to be water soluble and 96.5 wt% ATS water It seemed to be composed of Japanese materials. Then multiple batches of acidic solution of ATS Cool and separate the crystals, which are removed by filtration, and then prepare an aqueous solution of the crystals. used for impregnation.

Molten mold is added to the sulfurized chiyo of the pulp and is used for the composition of this disclosure. As a near source, Canada's National Lead As more exemplified, titania-containing ore or slag iron is digested with sulfuric acid to produce water. commercially by the sulfate Ti02 process to produce hydrated titanium sulfate (bulb). A manufactured titania hydrate valve may also be used. The resulting product is , a suspension of solids in an acidic solution, about 28.5% by weight by calcination. Produces TiO□.

Titanyl sulfate solution (TSS) is approximately 1 part commercial titania hydrate valve. It is prepared by cooking with about 4 parts of sulfuric acid and a glass fiber mat (watt GF/F) to generate titania. Removed non-digestible material that might give seeds a tendency towards rutile form. This melt The liquid contains about 10% TiO! by calcination. will occur.

Overuse hole tj port 1 mat dog engineer 33 This impregnation solution is made by adding 39-30% hydrogen peroxide to 30@l TSS. was prepared in the same manner as in U.S. Pat. No. 4,382,022. The color of the impregnating solution was reddish brown.

P Chinil゛Ha2 After several months of storage, the TSS described above converts the bulk of its solute into the water-soluble dihydrate TiOS. O4・2H! It was precipitated as 0. To prepare an aqueous solution of this dihydrate for impregnation , a large amount of crystals is separated by filtration, washed with acetone on the filter, and desorbed. Dissolved in ionized water. This solution does not contain sulfuric acid as a main component. It differs from TSS in this respect.

Coarse study 1hy Kyoso An aqueous solution of crude titanyl sulfate dihydrate was prepared as follows.

That is, the TSS is heated to evaporate a substantial portion of the acid and firmly form the dihydrate. and retained acid, leaving behind a solid residue. This residue was then treated with methanol. Extract to remove additional portion of acid and dissolve the extraction residue in water to form the impregnating solution. Prepared.

Folded Kai±Mata Sanbi 11 Exclusion Approximately 367 g of titania hydrate bulb containing 28% equivalent of Ti0z 250+nZ concentrated sulfuric acid was added. The mixture was maintained at 180° C. for approximately 1 hour; Most of the hydrate bulb was solubilized. This is cooled and calcined to 18 For this solution of wt% TiO2, dilute the titania hydrate bulb with water and and stir to ensure good dispersion of the bulbs. This solution as a source of titania is , a carrier with a large pore size, that is, about 500 angstroms, or Best suited for supporting materials.

The previously described variant of the titanyl sulfate solution impregnates the class of abrasion-resistant "starting supports" used to.

Ej Hida: Zusil' 5 Kuso2 1 group 1 Deaf - This disclosure's preferred supported titani The a composition exhibits a strong anatase X-ray peak with no trace of rutile, and The titanyl sulfate solution and titanyl ammonium sulfate solution mentioned above are used as impregnating agents. This could only be obtained if the

Main TiO anatase X-ray peak at d3.52 using CuK-a radiation The percentage of Ti01 in the composition is approximately 2%, which is the detectable limit of X-ray technology. It was observed when reaching Ti0z.

At a constant scanning speed, the peak magnitude increases with increasing TiO2 and For compositions calcined at higher temperatures, e.g. 800°C and above. becomes sharper, indicating the presence of large titania crystallites, and at lower temperatures, e.g. For example, for samples calcined at 600-650°C, it becomes wider and smaller. This showed the presence of fine microcrystals. Ti01 range for compositions encompassed by this disclosure The range is 2-95% Tilt, with a preferred range of 15-55%.

Abrasion resistance Attrition in fluidized bed reactors is the breakage of particles in the fluidized bed, thereby causing The trinion produces a fine powder that leaves the reactor. to el triny john The mechanism behind this is well clarified. Gas passing through a fluidized bed first turns into a solid forming a layer and transporting the fines to the surface where they are then picked up and transported out of the reactor. be taken away. Beds with larger particles have more voids and therefore The el trignesion rate increases as the fines present are more easily transported to the bed surface. can increase as the particle size of the bed ingredients increases. el trinion speed Furthermore, the particle density and particle size at the bed surface may be reduced or the flow velocity may be increased. It increases as time goes by. El trinosis velocity is related to Stokes' law Most correlations are between particle mass and diameter, fluid viscosity and velocity, and particle shape. reflects a drag coefficient that depends somewhat on the

The phenomenon of attrition depends not only on the system parameters but also on the mechanical strength of the particles and their physical shape. also depends. Milled particles with irregular shapes and rough edges are more sensitive than smooth spherical particles. They are also susceptible to high wear rates. H deceleration is determined by appropriate laboratory abrasion tests. One such industry-recognized abrasion test that must be measured is American Cyanamid Corporation 1957 edition pamphlet by d Corporation, ``Synthetic Fluid Decomposition "Test Methods for Catalysts" (pages 42-49), which is incorporated by reference. can be incorporated here.

In this test, three air jets at a velocity of approximately 890 ft/s bombarded the particles. imparting strong motion and creating collisions that cause wear. caused by this process Fine powder is conveyed from the unit by an el trinion. Wear per unit time The amount of material removed or overhead is defined as the wear rate.

This parameter determines the speed at which the catalyst is replenished due to attrition in commercial fluidized bed reactors. It can be related to degree. A device such as that described above can be used in accordance with the method of this disclosure. was used to measure the wear rate of materials manufactured by Examples 15-19 below are , listing the results of the abrasion test.

Although the standard exam time is 45 hours, there are some longer, 100+ hour exams. It was done. A 50 g sample was packed into the tube of the unit. These samples were The granules were pre-sized by sieving to -80, +325 mesh, but this was before breakage. of the initial particle size range for the fluidized bed catalyst. However, larger particles Some of the finer particles that cling to the particles may remain after sizing and may not pass through the test. The fine powder was first subjected to elution triguration. This will turn on after 5 hours. The substance was collected at the bar head. The attrition rate of the test material is determined by the initial fines Plot of weight % overhead versus time, after retrinification. The measurement was taken when an essentially constant speed was reached.

2 excretion R1 and 1λ Sized into approximately -80, +325 mesh, surface area approximately 230rrr/g , 85 g of crushed silica with a pore volume of 1.15 cc/g was added to titanium sulfate. Wet 4 times with acidic solution of Monium 1o3-11o3-191m7 and 81Il17 Impregnated by wetting, 740-75 after each of the first three wettings The absorbed solution is decomposed by placing the 171 substance in an oven at 0°C for 1 hour. The material was then calcined at 900° C. for 8 hours after the fourth wetting. TiO The proportion of □ was 38.6% by weight. The surface area of the most P-composition is 110rrr/g , and the pore volume was 0.66 cc/g.

Banmata 100 g of the silica used in Example 1 was mixed with sulfuric acid containing 1.1% vanadyl sulfate. Aqueous solution of titanylammonium acid and acid 133-1117-1105-192- Wetting 5 times at 1 and 78°C and heating at temperatures up to 200°C for 2.5 to 16 hours each time. It was then dried and finally calcined at 800°C for 4 hours. The final composition was 61.7% Si ng, 37.5% Tilt, and 1'2.1% VzOs. V / The Ti01% ratio is 0.049, and 4.6% of the starting silica is dehydroxylated. was written. Surface area, pore volume, and median pore size of the resulting composition are 119n(/g), 0.64cc/g, and 206 people, respectively. It was.

Master 150 g of the silica used in Example 1 was added to 1 liter of an acidic solution of titanylammonium sulfate. 80-118o-188! , 82-1 and 76-. The first four times After each wetting, the material was dried in a forced draft oven at 150°C for 1-1.5 hours. It was dried and then heated at 750° C. for 2 hours in air in an oven. After the final moistening, The material was dried at 150°C and calcined at 800°C in air for 7.5 hours. . This material contains 38.7% TiO□ and has a BET surface area of 111 m/g, average pore diameter of 202 people, and pore volume of 0.60 cc/g. X-ray diffraction is , 1333 anatase counts at d 3.52, with a scanning speed of 1 degree/min. and did not show any rutile count at d3.25.

, L4- 75 g of the silica used in Example 1 was mixed with titanyl ammonium sulfate prepared as described. It was moistened with an acidic solution of aluminum and placed in the air in a furnace at 750°C for 1 hour to undergo thermal decomposition. I let it go. Repeat this cycle three times using solutions of 90@l, 81-1 and 75-1. After the last cycle, the batch was calcined at 800°C for 8 hours in air. . The calcined material contains 38.9% TiO, and has a BET surface area of 13 8n? /g, the average pore diameter was 208 people, and the pore volume was 0.64 cc/g.

X-ray diffraction study showed anatase count of 1230, no rutile detected. It was.

1-Tamaichi You 50 g of the material of Example 4 was prepared using solutions of 33@l, 32-230aZ, and 28- wetted four more times, heated to decompose, then divided to give Example 5, Example 6, Example 7 was divided into portions and calcined in air for 8 hours, 16 hours, and 24 hours. . These materials contain about 51.7% TiO2 and have a range of 81-91 m/ BET surface area in g, average pore size of 211 people, and 0, 42 ~ 0, 43 c The pore volume was shown as c/g. The X-ray diffraction counts for anatase are No rutile was detected over the range 1346-1385.

L any well To prepare these compositions, 75 g of the silica used in Example 1 was first placed in air. Calcined at 800℃ for 64 hours, during this time it lost 6.37% weight and also its The pore volume decreased to 1.25 c, c/g. The calcined silica is then explained moistened with an acidic base solution of titanylammonium sulfate prepared as described above, and Heated at 750° C. for 1 hour in air. Repeat this wetting/1 hour heating procedure 8 times. Ta. The amount of solution used for the first four wettings was 90ml! , 90rn! , 81-1 so It was 75-. After the fourth wetting and decomposition, the resulting material 47 ．． 6 g was wetted four additional times with solutions of 33-132@l, 30-1 and 28- The pyrolysis was carried out after each wetting. After the last cycle, this Divide the material into portions as in Example 8, Example 9, and Example 10, and then heat them in air. Calcined at 00°C for 8 hours, 16 hours, and 24 hours, respectively. The three products are All contain about 52% Tie, with a BET surface area of about 83 m/g and 20 The average pore size ranged from 3 to 212 people. Anatase's X-ray count is 1292-14 No rutile was detected over a range of 79.

±month-''7eU To prepare these compositions, 100 g of the silica used in Example 1 was first added to the An acidic solution of titanyl ammonium sulfate prepared as described 120 Io! wet with and then heated to 1.50”C in a forced draft oven for 2.5-3.5 hours to dry. Sazeta. Add this cycle using a solution of 94-277m7, and 57aF. 2. After the fourth cycle, leave the material in air for 7.5 hours at 80 Calcined at 0°C. This first stage material contains 31% TiO2 and 14 Surface area of 6rn”/g, average pore size of 196 people, and pores of 0.74cc/g The volume is shown. X-ray diffraction shows 750 counts for anatase and rutile No figures were shown for this. Next, add 62-150d of this first stage material. , 36-1 and 23.5 m/l of titanyl ammonia sulfate, moistened four times with an acidic solution of and dried for 1 hour at 150'C after each wetting. After that Divide the batch into three parts, Example 11, Example 12, and Example 13, and were baked in air at 650"C for 2 hours, 4 hours, and 21 hours, respectively.

All three calcined materials contain 45-46% TiO2, approximately 115% ~118%/g (7) BET surface area, average pores of 200-212 people diameter, and a pore volume of 0.57 cc/g. At a scanning speed of 1 degree/min , all exhibit an X-ray count of about 1238 for anatase at d, 3.52, and d 3-25Q: No counts were shown for rutile.

Two bunches of the acidic solution of titanylammonium sulfate prepared as described above were poured into water. It was cooled in a bath 7 to precipitate crystals, which were filtered and taken out 7. This crystal is deionized. 50 containing 25.7% titanyl ammonium sulfate hydrate dissolved in water. ．． A 7% solution was created and used as the impregnating solution for the initial wetting. So Vanadyl sulfate is added to a portion of this first solution for use in subsequent wetting. The vanadyl acid concentration was adjusted to 2%, and the mixture was heated at 60-70 °C for several hours. A second impregnation solution was prepared by extracting the dark green solution.

60 g of the silica used in Example 1 was wetted with 80 ml of the first solution and then forced It was dried at 150° C. for 3 hours in a draft oven.

After that, the first of 60aF, 5[3mZ, 49d, 42-543-1 and 38- Six additional wettings were carried out using a solution of After that, it was dried in the same way. After the final wetting, the material was heated at 800°C for 4 hours in air. It was grilled. Analysis shows that the product contains 36.8% TiO□ and 1.5% vanadium. It has a BET surface area of 118 m/g, an average pore diameter of 222 m/g, and The pore volume was shown to be 0.60 cc/g. x1 diffraction is you shows 1285 counts for earth, and does not show any counts for rutile. won.

Qi 107 g of the silica used in Example 1 was mixed with titanyl ammonia sulfate prepared as described above. The sample was wetted three times with 1 of 1, 75-1 and 75+nZ. first After each of the two wettings, the material was dried for 1 hour at 150°C and It was heated at 750°C for 2 hours.

After the final wetting, the material was dried at 150°C and 750°C for 10 hours. Calcined. Surface area, pore volume, and median pores of the resulting composition The diameter is 100rrr/g, 0.49cc/g, and 208 people, respectively. there were. The X-ray count value of anatase at d 3.52 is 1 at a scanning speed of 1 degree/min. 657, and no rutile was detected.

50g of this composition, sized into -80, +325 sieves, was washed as described above. and an initial fines content of 4.2% and an attrition rate of 0 for this material. ．． 49%/h was measured.

withdrawal Titania permanent product received from NL Chemicals Dilute 397 g of Bulb (titanyl sulfate hydrate) with 121 g of deionized water, An impregnating solution with a density of 1.2 g/cc was made. 100gt of silica used in Example 1. Moisten this material with 120 ml of a thank you valve solution and heat it at 150°C for 2 hours. Allowed to dry for a while. This material was rewetted with a solution of 152- and heated to 150°C for 2 hours. It was dried, then calcined at 550°C for 2 hours. As a result, 49.2% The surface area, pore volume, and median pore size of the composition containing TiO□ are They were 154 M/g-, 1 Occ/g%, and 226 people, respectively. d　 The anatase X-ray count for this material measured at 3.52 is 905. , rutile was not detected.

A portion of the above dried, uncalcined composition was heated at 650°C for 2 hours. Calcined. - 50 g of this composition sized to 80, → 325 mesh was abraded as described above. When tested, this material had an initial fines content of 3.5% and an abrasion rate of 0.26. %/h was measured.

85g of silica from Example 1 was added to 1o3-11o3-191m! , and 85aF titanium sulfate Moisten with tanylammonium solution four times and heat for approximately 1 hour between wettings to test. Decomposed salts with tania.

The final composition was calcined at 900°C for 8 hours and contained 38.6% TiOz. So, the surface area, pore volume, and median pore diameter are each 110n?　／　g　、 A composition was made that was 0.62 cc/g and 232 people. -80, +325 meters 50g of granulated powder was packed into the abrasion test unit described above, and this material was An initial fines of 4.2% and an attrition rate of 0.36%/h were measured.

75 g of the silica of Example 1 was prepared according to the procedure described above, and also titanium sulfate J. 100 m of concentrated solution of '133al, 71. ml, 6】Tane! , and 5 times at 56- The humidity is seven. Heat the material at 650°C for 1 hour while moistening to form titania. The final calcination was at 650° C. for 4 hours. As a result, The resulting composition contained approximately 46.9% TiO2. -80, +3 Pack 50g of this material, sized into 25 pieces, into the 7-piece test unit described above, and This composition then had an initial fines content of 4.5% and an attrition rate of 0.4%/h. was measured.

"Hiki" 285 g of the silica used in Example 1 was first doped with titanyl sulfate. 380 liters of ammonium acidic solution! 1/1 and 64 hours at 800°C. was burned. The resulting material containing approximately 19% TiO□ , the above solutions 294 @l, 290-1 and 275m! Then add it and moisten it 3 times. Moisten and heat at 800℃ for 1 hour in the middle, then finally at 800'C for 8 hours. The resulting composition that is to be calcined contains 41.4% TiOz. It also has a surface area of 105 m/g, a pore volume of 0.6 cc/g, and a surface area of 221 people. It also shows the median pore size. 50g divided into -80, +325 mesh , then packed into the abrasion test unit described above, with an initial fines content of 5.1% and 0. An F'g deceleration of 3%/h was measured.

1 g of this composition was then added to a microcatalytic reactor (microcatalytic reactor). ctor) and heated to 280°C. Purge the reactor with nitrogen and (The ratio of the feed amount to the catalyst is 0.54wt/wt-ho) 1-butene on the catalyst I let it pass. 60 m melt coated with 5PB-1 dimethylpolysiloxane stationary phase. Decomposed silica can also be extracted from reactor exhaust gas by gas chromatography using a tube column. analyzed. A Flair ionization detector was used for analysis of hydrocarbon content.

The gas composition of the product was such that the conversion of 1-butene to 2-butene was approximately 82%. The trans isomer component is approximately 50% and the trans isomer component is approximately 32%. It was shown that

The reactor containing the catalyst composition described above was then removed and replaced with an empty tube.

This tube was then charged with 1-butene at the same volumetric flow rate and 280°C used with the catalyst. I let it pass.

The reactor exhaust gas was analyzed again using the chromatographic method described above to determine 1-butene. No conversion to 2-butene was shown.

international search report Ah’) IEX To’>’: E INTER, NATICNAL 5EAR C! (Continued from REPORT ON1 page ■Int, C1, 4 identification code Office reference number C07B 61100 300 Inventor: Sinoster, Nidward, United States of America, Junior St. REIT 734 Inventor: Jorgen, Tortus, G.A., USA, /11 Grace Tory Special edition Showa 64-500249 (9) Pennsylvania 15139. Oakmont, Eighth Kent Tara Key 41017 ．． Fort Mitchell.

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Claims (16)

[Claims] 1. A wear-resistant porous support material with a pore volume greater than 0.1 cc/g is made of titanium sulfate. The support is coated with a solution of 2-95% by weight based on the weight of the support. % of TiO2, dry this impregnated support material, and heat it to infiltrate titanium sulfate. decomposing the impregnating composition and calcining the resulting impregnating composition. A method for producing a catalyst or a catalyst carrier. 2. Claim 1, wherein the composition contains 15 to 55% TiO2. Method described. 3. the impregnating solution consists essentially of titanyl sulfate or titanylammonium sulfate, The method according to claim 1. 4. The calcined composition is characterized by the anatase X-ray peak at d3.52. A method according to claim 1, which exhibits the characteristic features of anatase titania. . 5. The calcined composition shows that the X-ray peaks at d3.52 and d3.25 Claims showing the characteristics of characterized anatase titania and rutile titania The method described in item 3 within the scope of 6. the titanyl sulfate is titanyl ammonium sulfate, and the calcination is minimal. A method according to claim 1, which is carried out at a temperature of at least 575°C. 7. the titanyl sulfate is not ammoniated; and wherein the calcination is carried out at a temperature of at least 450°C. Method. 8. The resulting final composition has an attrition rate of about 890 particles of this composition. less than 1%/h based on the collision of three air jets carrying a velocity of feet/second. The method according to claim 1, wherein the method comprises: 9. an average pore volume of at least 0.1 cm2/g and a weight of the impregnated support material; Fluidizable abrasion resistant support having from about 2 to about 95% TiO2 by weight A catalyst composition comprising. 10. 10. The composition of claim 9, wherein the TiO2 is in anatase form. 11. 10. The composition of claim 9, wherein the attrition rate is less than 1%/h. 12. Silica, silica-alumina, alumina, magnesia, silica-magnesia , calcium aluminate, calcium silicate, silicon carbide, and mixtures thereof in the form of fluidizable particles of at least 0.1 cm2/g anatase titania with an average pore volume of A catalyst composition comprising an impregnated support material. 13. Claim 1, wherein said anatase titania is derived from titanyl sulfate. Composition according to item 12. 14. the anatase titania is derived from titanylammonium sulfate; The composition according to claim 12. 15. The anatase titania is present in an amount of about 15% to about 55% of the composition. 13. The composition according to claim 12. 16. Claim characterized by anatase X-ray peak at d3.52 The composition according to item 12.