• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1487668 Silica-alumina catalyst support beads LABOFINA SA 17 Feb 1975 [18 Feb 1974] 6646/75 Heading B1E [Also in Division C1] A method for producing silico-alumina beads for use as a catalyst support containing silica and an at least equal amount of alumina comprises (a) forming an aqueous mixture comprising alumina hydrogel, alumina hydrosol, an alkali metal silicate or silica gel and a water-soluble ethylenic monomer whose homopolymer is water-soluble or forms a gel (the amount of alkali metal silicate, based on SiO 2 , not exceeding 20 wt.% of the total weight of SiO 2 and Al 2 O 3 and the total amount of alkali metal silicate and silica gel, when present, based on SiO 2 . not exceeding 50 wt. % of the total weight of SiO 2 and Al 2 O 3 ; (b) dispensing the mixture as droplets in a hot. substantially water miscible fluid and allowing the monomer in each droplet to polymerise and thus coagulate the alumina hydrogel and hydrosol to form beads which may be separated, dried and calcined, to form silico-alumina beads. Suitable hot, water immiscible fluids are (a) a current of hot dry gas through which the droplets are passed counter-current: (b) a column of liquid having a density lower than that of the final beads (such as paraffin oil) and downwardlv through which the hardening droplets fall: or (c) a column of liquid having a density higher than that of the final beads (such as chlorinated diphenyl) and upwardly through which the hardening droplets pass. In the production of catalysts, the beads may be impregnated with one or more active catalytic agents or one or more compounds which are capable of generating an active catalytic agent. No specific Examples are given. Specification 1487661 is referred to.
    公开号:SU795440A3
    申请号:SU752105557
    申请日:1975-02-17
    公开日:1981-01-07
    发明作者:Марк Каен Раймон；Морис Гислен Андре Жак；Робер Дебю Анри；Одон Ламмер Рене；Жоанн Ван Тийо Юго
    申请人:Лябофина С.А. (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to a method for producing aluminosilicate supports for heterogeneous catalysts.
    Methods are known for the preparation of aluminosilicate carriers by precipitating a gel-like precipitate from solutions of aluminum salts by alkali or ammonia 1.
    The closest technical solution to the present invention is a method for preparing a macrospherical alumina carrier by dispersing an aqueous suspension comprising alumina and a gelling component in a medium that is not miscible with water, at 50-105 ° C, followed by treatment with an aglmiac,
    Bitch and calcination 2.
    The disadvantage of the known method is the relatively low mechanical strength of the carrier beads, which is about 1.2 kg at a density of 0.77 g / l.
    In order to obtain a carrier with enhanced mechanical strength, it is dispersed in a water-immiscible medium, an aqueous suspension comprising alumina and containing additional sodium or potassium silicate, gel
    silicon oxide, a monomer dissolved in water with the general formula (1):
    Sn C (T1) - (CD
    where is R; H, CH ,;
    R ORj, R - oxyalkyl or polymerization methoxide, sodium persistent sulfate, with trace components,
    2.6-17 (counting on AljC
    0,65-2 cheat
    na) 0.1-1.5 (calculated on SiOij)
    2.35-2.94 (counted on SiOrj) 1.5-4
    0.24-0.5
    权利要求:
    Claims (2)
    [1]
    0.024-0.05 The remainder of the silicon added is 0.99-15% by weight of the total weight of silica and alumina introduced by the compounds forming these oxides and the total amount of silica introduced by alkaline silicate and silica gel, is 32.9549.84% by weight of the total weight of silica and alumina introduced by the compounds generating these oxides. The suspension is dispersed at the temperature of monomer polymerization. The carrier balls, obtained by this method, have a mechanical strength of 2.1 kg compared with a strength of 1.2 kg of carrier balls obtained by a known method. Example 1. Preparing an aqueous mixture containing, in wt.%: Hydrogel 8 (counting on ftRyO) aluminum Hydrosol 2 (counting on A8a.%} Aluminum, silicate, natO, 1 (counting on Abdry Acrylic acid Dioxyethylene-bis-acrylamide Ammonium persulphate Sodium bisulfite Water Else. Aluminum hydrogel is obtained by treating aluminum sulphate with caustic soda to pH 9. The resulting gel is cleaned with several washes and then dried and crushed and sieved. Aluminum hydrosol is obtained by leveling aluminum sawdust in an aqueous solution of aluminum chloride. drogel, hydrosol water and heated for 1 hour at 95 ° C with stirring. Then, alkaline silicate and acrylic acid are added to pH 3.1, then the other components are added. The resulting mixture is introduced in the form of drops into the upper the part of the column with paraffin oil, heated to. Balls collected in the lower part of the column are washed with water, dried at 110 ° C and calcined at. Thus, balls containing approximately 1% Si0 and 99% A1 0 are obtained. With apparent density 0.53g and crushing strength 2.5 kg. The amount of S i 0 (introduced by alkali silicate, 0.1%. The total amount of S Oi M introduced by the compounds forming these oxides / 10.1%. The ratio of SiOj introduced by alkali silicate is / 100 - about 99% 1 / 100 Example 2. According to the procedure of pria 1, an aqueous mixture is prepared, comprising: Hydrogel 8 (counted) aluminum Hydrosol 2 (counted) ala link Silicate 0.22 (counted on SiOa) sodium Acrylic acid 1.5 Dioxyethylene- ammonium bisacrylate ammonium persulfate bisulfite 0,024 sodium Else. Balls collected in the lower part filled with oil are washed, then kept for 5 h in 5.6% ammonia solution.Pushies and calcinations get shais containing approximately 2% Si Oj 8% AtijO. They have an apparent density of 0.52 g / ml and a resistance to pressure of 2 kg. The amount of S i Od introduced by alkali silicate is 0.22%. The total SIO and, represented by oxides forming compounds, 10.22%. The ratio of SiO introduced by alkali silicate is 0 22000 2.15%. Example 3. Using the procedure of method 1, the aqueous mixture is prepared: Hydrogen gel aluminum 16 (counted) Aluminum hydrosol 1.5 counted on MgO) Potassium silicate (i0, 45) (counted HaSiO} Metacrylic acid3, 25 0.15 Acrylamide 0.10 Glyoxal Sulfur persulfate P rsulfat ammonium bisulphate 0.034 sodium rest. The mixture in the form of droplets is introduced into the lower part of the column filled with phenol DR4 (chlorinated biphenyl, started up by Prozhil SA and eaten at a density of 1.39) heated to The balls collected on the surface of the liquid are washed with water, dried at IO-c and calcined at 700 s. These calcined balls contain 2, .5% SiOij and 97.5%,. They have toT crush strength, equal to 2.1 kg. The amount of S i 0. applied by alkali silicate, 0.45%. The total amount of SiO and introduced by the generators of these oxides is 17.95%. The ratio of Si On, introduced. 0.45 / 100 alkali, with silicate silicate, is 95/100 2.5%. Example 4. According to the procedure of Example 1, an initial aqueous mixture containing, wt%, is prepared: Aluminum hydrogel 7, 6 (counting on Aluminum Hydrosol 1.9 (counting on APjiD sodium silicate 0.5 (counting on Acrylic acid Ft, N - Ethylidene-bis-acryl imide 0.1 Ammonium persulphate 0.3 Sodium bisulphite 0.03 Water Else The collected balls are washed with water for 2 hours in a 5.5% solution of g1 miac, then dried and calcined in. The calcined balls contain 5% S i O, 2. and 95%. They have an apparent density of 0.50 g / ml and a crush strength equal to 4.7. The amount of S i Orj. 0.5%. The total amount of S1 and 10% of these oxyd generators. The ratio of SiO., alkali added to silicate silicate, e 5%. Example 5. According to the method of example 1, an initial aqueous mixture is prepared containing, in wt.% : Hydrogel 7.2 (counted on A (aluminum Hydrosol 1.6 (counted on M, gQj aluminum Silicate nat1, 0 (counted on GiO and Acrylic acid Dioxyethylene-bis-acrylamide Ammonium persulfate Bisulfite 0.023 sodium Else Balance) Water After adding acrylic acid pH: 3, 6. The balls obtained in the lower part of the Column are washed with water, kept for 20 h in 5.6% ammonia solution, then dried at and calcined at 7000 s. The calcined balls have an apparent density of 0.48 g / ml and a crush strength of 2.1 kg. They contain 10.2% S102. and 89.1% A | (OZ. The amount of Si 0 (1, added with alkali HbW silicate) is 1.10%. The total amount of SiOij and, introduced by oxides, 9.8%. Relation. SJ Og., introduced alkaline D1NYM silicate, 10.2%. I, o / c. Example 6. According to the procedure of Example 1, an initial aqueous mixture is prepared, containing, wt.%: Hydrogel 6.8 (calculated on aluminum. Hydrosol 1.7 (counting on aluminum. Silicate sodium, 5 (counted on IOa) acrylic acid 1.5 Dioxyethylene-bis-acrylamide Ammonium persulfate Bisulphite 0,024 sodium Else. Water After adding acrylic acid, the pH of the mixture is 3.3. The mixture is dispersed in the form of droplets in paraffin oil under pressure. The balls collected in the lower part of the column are washed with water and kept for 5 h in 5.6% ammonia solution. The dried and calcined balls contain 15% Si 0 and 85% They have a crush strength of 2.7 kg. The amount of SiO, introduced by alkaline silicate, is 1.5%. The total amount of S i 0 and introduced by the compounds forming these oxides is 10%. The ratio of S i Ojt, introduced by alkaline silicate, J-Vjf | Q - 15%. Example 7. According to the method of Example 1, an initial aqueous mixture is prepared containing, in wt.%: Aluminum hydrogel 4.2 fccc AB AB Aluminum hydrosol 1.05 (counting on A Silicon silica hydrogel (in 93% water) 2.35 (counting on SlOoJ Silicate sodium 0.23 (considered SiOot Acrylic acid 3 Dioxyethylene-bis-acrylamide 0.15 Ammonium persulphate 0.25 Sodium bisulfite 0.025 Water Else. After adding acrylic acid, the pH of the mixture is 3.6, Balls collected in the bottom parts of the column filled with oil, washed with water, incubated for 1 h in a water solution containing 0.05% HNLMS, with, then they are dried Calcined balls contain 32.4 510, and 67.6% Al, j, 0, they have a crush strength of 3.2 kg. The amount of SiO introduced by alkali silicate is 0.23%. Oa, introduced by alkaline silicate and helium of silica dioxide, 2.58%. The total amount of Si and Oj and introduced by the compounds forming these oxides is 7.83%. The ratio of SiOj, introduced by alkali silicate, is 0.23 / 100 2.9% .7.83 / 100 Ratio S i uj. Alkali silicate and helium dioxide 258/100 7.83 / 100 - e Example 8. An aqueous mixture is prepared containing, in wt%: Aluminum hydrogel 2.62 based on ASjO Silicon oxide hydrogel (in 93% water 2.94 (counted. SiO / j Silicate sodium 0.33 (counted on ScQz Acrylamide 4 Dioxyethylene bicacrylamide 0.2 Ammonium persulfate 0.5 Sodium bisulfite 0.05 Water Else. Mixed guide {aluminum gel, aluminum hydrosol and water and heated for 1 hour at 95. After settling, evaporated water is replaced and stirred vigorously. He added acrylamide, sodium silicate and gel and a They set the pH to 3.3 by adding hydrochloric acid. After maintaining the crosslinking agent and the catalytic system, the mixture is dispersed in the form of droplets in a column filled with arafin oil, and the balls collected in the bottom of the olon are kept for 1 hour in an aqueous solution containing 0, 05% pu, then they are dried at 120 ° C and calcined at. The calcined balls contain equal amounts of S i Ojj and AlrjO.OHH and have a crush strength of 1.7 kg. Amount. # Contributed by alkaline silicate, 0.33%. The amount of Si0 introduced by alkaline silicate and helium silicon dioxide, 3.27%. The total amount of Si 02 and AlijO contributed by the compounds forming these oxides is 6.56%. The ratio of S i 0 introduced by alkali, 33/100 nym silicate ,; 6.56 / 100 The ratio of SiC, introduced by alkaline silicate and gel of cream dioxide - W) - Accordingly, the ratio S i 0 is introduced by alkaline silicate between 0.99 and 15%, while the ratio S i is 0.2, introduced by alkali silicate and helium silica, between 32.95 and 49.84%. Claims of Invention A method of producing a microspherical silica-alumina carrier by dispersing an aqueous suspension comprising alumina in a medium. immiscible with water, followed by drying and calcining, characterized in that, in order to increase the mechanical strength, the suspension is further subjected to dispersion, additionally containing sodium or potassium silicate, silica gel, water-soluble monomer of the general formula G: CH2-C (R) where K: I.C is an oxyalkyl or methoxymethyl radical, as well as a catalyst for the polymerization of the monomer (.1), containing 1mmonium persulfate and sodium bisulfite, in the following ratio of components, wt.%; Aluminum hydrogel alumina 2.6-16 (counting on ASjOj / Hydrosol alumina 0.65-2 (counting on AEjCV Sodium or potassium silicate 0.1-1.5 (counting on SiO Silica gel 2.35-2.94 HaS Monomer (l) 1.5-4 Ammonium persulphate 0, 24-0.5 Sodium bisulfite 0.024-0.05 Water the Rest, and the amount of silica applied with alkaline silicate is 0.99-15% by weight of the total weights of silica and alumina introduced by the compounds forming these oxides, and the total amount of silica made by alkaline silicate and silica gel is 32.95-49.84% by weight of the total weight silica and alumina oxides introduced by compounds generating these oxides and the suspension is dispersed at the polymerization temperature of the monomer. Sources of information taken into account in the examination of 1. Thomas C. Industrial catalytic processes and efficient catalysts. M., Mir, 1973.
    [2]
    2. US patent number 3416888, cl. 23-143, 1968 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
    US2349243A|1944-05-23|Catalysis
    US4218307A|1980-08-19|Hydrocarbon cracking catalyst
    US4340465A|1982-07-20|Dual component crystalline silicate cracking catalyst
    SU795440A3|1981-01-07|Method of producing microspherical alumosilicate support for heterogenous catalysts
    US2477695A|1949-08-02|Treating hydrosols with fluorides to obtain improved gel catalysts
    US4010116A|1977-03-01|Fluid cracking catalysts
    JPH10146529A|1998-06-02|Meso-porous fluidized catalytic decomposition catalyst incorporated with gibbsite and rare earth oxide
    JPH09506596A|1997-06-30|Polyglycerol production
    GB2166970A|1986-05-21|Silica-alumina-rare earth cogels
    US4198319A|1980-04-15|Method of producing zeolitic catalysts with silica alumina matrix
    US3442821A|1969-05-06|Manufacture of spheroidal silica-alumina particles
    GB2044627A|1980-10-22|Hydrocarbon conversion catalyst preparation
    US4376039A|1983-03-08|Hydrocarbon conversion catalysts and processes utilizing the same
    IL23341A|1968-07-25|Process for preparing zeolites
    GB2085861A|1982-05-06|Thermally-stabilised/aluminium- exchanged type Y zeolite
    SU784751A3|1980-11-30|Method of producing silicon dioxide spherical particles
    RU2009125961A|2011-01-20|CATALYTIC CRACKING CATALYST COMPOSITIONS, ENSURING AN INCREASED TRANSFORMATION OF OIL RESIDUES
    US3364151A|1968-01-16|Catalyst containing silica-alumina and finely divided caf2, mgf2, srf2, alf3 or inf3
    US4239651A|1980-12-16|Cracking catalyst and method of producing the same
    US2506923A|1950-05-09|Conversion of hydrocarbons with silica-alumina catalyst
    US3433747A|1969-03-18|Method of preparing petroleum cracking catalysts
    CA2084929C|2000-01-25|Catalyst and process for cracking hydrocarbons with highly attrition resistant mesoporous catalytic cracking catalysts
    US3912619A|1975-10-14|Preparation of cracking catalyst
    US3356451A|1967-12-05|Method for producing molecular sieve zeolite particles
    US2526907A|1950-10-24|Coprecipitation of silica-alumina
    同族专利:
    公开号 | 公开日
    NL7501826A|1975-08-20|
    FR2261053A1|1975-09-12|
    DD117432A5|1976-01-12|
    JPS5818344B2|1983-04-12|
    IT1031787B|1979-05-10|
    AU7828675A|1976-08-19|
    US3993590A|1976-11-23|
    GB1487668A|1977-10-05|
    CA1055917A|1979-06-05|
    LU69405A1|1975-12-09|
    BE825562A|1975-05-29|
    FR2261053B3|1977-10-28|
    DE2506760A1|1975-09-25|
    JPS50119009A|1975-09-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2526907A|1948-09-29|1950-10-24|Universal Oil Prod Co|Coprecipitation of silica-alumina|
    US2966466A|1956-04-11|1960-12-27|Socony Mobil Oil Co Inc|Production of attrition-resistant silica-alumina gels|
    US3472791A|1966-09-12|1969-10-14|Universal Oil Prod Co|Method of spherical catalyst preparation|
    GB1231385A|1967-08-04|1971-05-12|
    US3746657A|1971-06-28|1973-07-17|Standard Oil Co|Catalyst manufacturing process|FR2443278B1|1978-12-08|1981-07-17|Uop Inc|
    FR2464745B1|1979-09-06|1982-09-03|Oxysynthese|
    US4714567A|1985-10-31|1987-12-22|Aluminum Company Of America|Reacting alumina hydrate sol and an organic material to form a stable monolithic gel|
    US4721696A|1987-03-11|1988-01-26|Phillips Petroleum Company|Silica-modified alumina and process for its preparation|
    US4785049A|1987-07-27|1988-11-15|Aluminum Company Of America|Forming clear gel and transparent film by reacting alumina hydrate with vinyl alcohol-vinyl acetate copolymer|
    US5045522A|1990-03-27|1991-09-03|Phillips Petroleum Company|Absorption composition comprising zinc titanate for removal of hydrogen sulfide from fluid streams|
    DE19639016A1|1996-09-23|1998-03-26|Basf Ag|Mesoporous silica, process for its production and use|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    LU69405A|LU69405A1|1974-02-18|1974-02-18|
    [返回顶部]