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    • 专利摘要:
    Catalytic process for steam dealkylation of a charge containing at least one alkyl aromatic hydrocarbon, such as a charge issued from effluents of units for catalytic reforming or for producing aromatic hydrocarbons, wherein the catalyst contains an alumina carrier, from 0.1 to 1% of rhodium, from 0.05 to 1% of TiO2 and optionally from 0.1 to 1% of ruthenium, palladium, iridium, platinum or osmium and/or from 0.01 to 5% of lithium, sodium, potassium, rubidium or cesium.
    公开号:SU888813A3
    申请号:SU792705002
    申请日:1979-01-05
    公开日:1981-12-07
    发明作者:Курти Филипп；Мартино Жермэн；Ле Паж Жан-Франсуа
    申请人:Энститю Франсэ Дю Петроль (Инофирма)；
    IPC主号:
    专利说明:

    (5V) METHOD OF OBTAINING BENZENE
    I
    ; The invention relates to a method for producing benzog., In particular, by dealkylation in water vapor of toluene and other alkyl benzenes.
    For the dealkylation of aromatic hydrocarbons in vapor, many catalysts have been proposed, including a porous support and at least One metal supported on this support. For example, a catalysts are known, consisting of rhodium, nickel and alumina Cl3, or a catalyst that contains noble metals of the platinum group (platinum, palladium, rhodium, iridium and ruthenium) 15 on a substrate composed of alumina or a mixture of oxides aluminum with nickel or cobalt G23.
    The closest to the invention to the technical essence and reach-
     My result is a method of producing benzene by dealkylation of toluene in the presence of water vapor at elevated temperature using a catalyst containing 25
    0.1-1.0 relative to the weight of the carrier rhodium and 0.01-5.0 relative to the weight of the carrier alkali metal, which is deposited on the carrier, based on alumina 3.
    According to a known method, the dealkylation of toluene is carried out at a temperature of AOO-600 ° C, the molar ratio of hydrocarbons: water vapor, in the presence of a catalyst containing 0.1-1.0% relative to the weight of the rhodium carrier, 0.01-5.0 in relation to the weight of the carrier of an alkali metal.
    However, such a catalyst has low stability, which leads to rapid deactivation and acceleration of its mechanical decomposition.
    The aim of the invention is to increase the stability of the catalyst.
    The goal is achieved by the fact that in carrying out the method for producing benzene by dealkylation of toluo ;.a in the presence of water vapor at elevated temperature using a catalyst containing 0.1-1.0% 3 relative to the weight of the carrier and 0.01-5 , 0 in relation to the weight of the carrier of an alkali metal, which are supported on a carrier based on alumina, use a carrier that additionally contains 0,, 0 in relation to the weight of the carrier of titanium dioxide. Distinctive features of the proposed method are the use of the carrier mentioned above. The technology for this method is as follows. The process is carried out at a temperature of 300-600, preferably 350550 ° C, at a pressure of 1-20, preferably atm, the flow rate of the feed is 0.1-10, preferably 1-5, the molar ratio of water to carbon and hydrogen to 1-20, preferably B the process produces both common dealkylation products, e.g. benzols, and partial dekylation products, e.g. toluene from xylene. The selective catalysts used in the invention contain a substrate i 0.1 - 1.0, preferably 0.2 0.8, preferably 0,, b5 with respect to the total weight of the catalyst; 0.05-1.0, preferably 0, 0.5, preferably 0.07-0.5 titanium dioxide with respect to the total catalyst. Preferably, the selective catalysts of the invention comprise a support comprising 0.05-1.0, preferably 0.06-0.5, preferably 0.07-0.3 titanium oxide and O, 1-1, 0, preferably 0.2 -0.8, predominantly 0.25-0.65 relative to the weight of the catalyst rhodium. In addition, three preferred types of catalysts can be used: Catalyst No. 1. Catalysts that, in addition to titanium and rhodium, contain a catalyst of 0.1-1.0, preferably 0.2-0.8, preferably 0.25-0 , 65 single and noble metals from the group; ruthenium, palladium, iridium, platinum and osmium; Ruthenium, palladium and platinum are the preferred metals. Catalyst No. 2. Catalysts other than titanium and rhodium contain 0.01-5% by weight of at least one catalyst. 4 alkali metals selected from the group: lithium, sodium, potassium, rubidium and cesium; rubidium, especially potassium and sodium, are the preferred metals. Catalyst No. 3- Catalysts that, in addition to titanium and rhodium, simultaneously contain another noble metal, as catalyst No. 1, and alkali metal, as catalyst No. 2. To each catalyst No. 1, 2 and 3, you can add 0, C1-6 relative to to the weight of the catalyst of at least one filler metal or a filler metal compound selected from indium, zirconium, thorium, germanium, tin, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt and nickel. Preferred metals are indium, tungsten, tantalum, tin, manganese, chromium, molybdenum and iron, especially niobium, cobalt, vanadium, nickel, germanium and rhenium. Alumina is used as a substrate. It can be obtained using alkaline etching of bauxite-type minerals, for example, by the Bayer method or acid etching of clay or shale rocks by the Peshnein method, as well as by dissolving aluminum in alcohol with subsequent conversion by hydrolysis to alcohol. Aluminum oxide is preferably prepared by hydrolysis of aluminum oxyalcohols, obtained by the addition of ethylene hydrocarbons to triethylaluminum, and the oxidation of polyalkylaluminum to polyalkoxy aluminum. The catalysts used in the proposed method are prepared by first adding 0.05-1 titanium dioxide to the alumina support. Titanium dioxide is added by any known method, for example, by dissolving a titanium compound in a solution containing an aluminum compound under conditions that allow both alumina and titanium hydroxide to precipitate. It is also possible to add titanium compounds from the compounds taken from the group consisting of titanium dioxide in the form of rutile or anatase to hydrated alumina in the form of a gel {(i-trihydrate, 6-trihydrate or aluminum i-monohydrate). Or TiO and Jiiji Oj, titanic acids, alkaline, alkaline earth and ammonium titans and soluble
    five
    and insoluble organic and inorganic titanium salts.
    A method can be used where a molded alumina support is impregnated with a solution of an organic or inorganic titanium salt. Thus, the addition of titanium can be carried out before molding, during molding, or after molding the catalyst support.
    The preferred method is to add an organic titanium compound, for example tetraethoxytitanium, to the organic-based solution (for example, an alcoholic organic aluminum compound (for example, alkoxyaluminium, such as aluminum isopropylate), and then hydrolyze the solution thus obtained.
    Titanium can also be introduced in the form of an easily hydrolyzable inorganic compound, such as titanium tetrachloride.
    Another preferred method
    consists of adding controlled amounts of organic compound based on titanium, for example alkoxytitanium, such as tetraethyl titanium, and / or inorganic compound
    titanium (for example, titanium trichloride) during Ziegler synthesis of polyalkoxyaluminium by the reaction of alkyl aluminum (for example, aluminum triethyl), ethylene, and one of the mentioned compounds
    titanium. Polymerization followed by oxidation prepares said polyalkoxy aluminum, which will be hydrolyzed to polyalkyl and hydrated alumina containing titanium.
    It has been experimentally established that this method leads to an increased dispersion of titanium ions in the matrix of alumina obtained after the hydrolysis of alkoxyaluminium or polyalkoxyaluminium. The preferred method of impregnation with titanium allows, if the substrate is prepared in the form of balls or extruded globules, etc., the floor is a constant content of the ball to the ball and from globule to globule, i.e. if the average desired concentration is C%, then. the concentration C from one ball to another and from one globule to another using preferred methods of the invention will remain within C ± S% of this concentration, as well as within 3
    Lax ± 3 wt.%. Even better results are obtained when using a catalyst support containing from 0.06 to 0.51 TiO ..
    According to the invention, the catalyst support is selected from ethacubic alumina, gamma-cubic, gamma-tetragonal fc -cubic, kappa-orthorhombic 3J-, theta-monoclinic 9, delta-orthorhombic a and 8-amorphous alumina. It has a specific surface area from 2 to too m / g, preferably from 50 to 350 m / g, and a total pore volume from 30 to 150 ml / 100 g.
    In addition, the substrate contains from 0.05 to 1.0, more precisely from 0.06 to 0.5 and preferably from 0.07 to 0.3 wt.% Of TU .. This oxide of titanium is introduced into the substrate before it is impregnated with rhodium aqueous solution, then the substrate is dried, subjected to thermal activation (calcination and / or reduction), dried and impregnated with an alkali metal. The final drying is carried out after thermal activation (calcination and / or reduction). For example, drying is carried out at 100 ° C, then at 200 ° C for 1 hour or more, calcining at 300-500 ° C for 1 hour or more, and reduction at 200-tOO ° C in the presence of gas containing at least 10% HQ, for 1.h or more.
    During the dealkylation reaction, the catalysts maintain a conversion at a constant level of from 0 to 75 mol. with a gradual increase in temperature. The deactivation rate, for example, for 2000 hours of operation is determined in ° C / 1000 hours and is expressed by the following relationship:
    Y% сО - °°°
    As an example, for a catalyst operating for 2000 hours at a temperature from hOQ (TCD) to 500 ° C (dec).
    Y 5 | 0 Ord 5H / 1000 h
    Example 1. Preparation of the substrate SA / j -SA- ;.
    An alumina support consisting of extruded alumina Tc and Tt specific surface.  7 of 230 nVr, with a pore volume of 5A i vi / 100 g, diameter 1.2 mm and length mm, divided into 7 fractions of 100 g each (SA -SA-f).  A part of SA-i is calcined for 1 h at 500 ° С, a part of SAt is impregnated with O, g of an aqueous plant.  the thief oxalate decahydrate titanium (o, 0b g TiOij), then dried for 1 hour at 100 ° C, for 1 hour and calcined at 500 ° C for 1 hour.  SAj-SA substrates are prepared in a similar manner with varying amounts of titanium oxalate, which results in different final TiOo contents. .  The characteristics of the substrates are as follows: Ti oxalate weight: TiOn content of tan, gves.  SA5, 0.680.10 5Ab 3, SA SA-5.1 SA2. ° 0.0 The TU content varies very much from one batch of extruded particles to another, deviating no more than 5 pounds relative to the average Ti-On content.  X Example 2.  Test Series A Substrates are impregnated with the active substance as follows.  100 g of the substrate is immersed in distilled water, then dried to reduce the water content to 5 wt. .  Next, the substrate is mixed with 100 ml of a solution containing O, 6 g of rhodium in the form of trichloride and rhodium and i ml of pure hydrochloric acid (d (. .  1.19), after depletion of the solution (rhodium is not detected when tin chloride is added to the solution), the catalyst is filtered, dried for h at 100 ° C, 2 hours at and heated: dan hydrogen for 1 hour at.  The recovered catalyst is impregnated with 1 Bec. t Krjp, taken in the form of an aqueous solution of potassium carbonate, then dried 2 m at 100 C and 2 at.  Activate for 2 hours at 38. The operation is repeated 7 times; catalysts are obtained, which thus contain 0.06 wt. % Rhodi and 1 weight and, in addition, the above amounts of titanium.  SA -SA-j catalysts are tested for 1000 h in the presence of 99.9 wt.  pure toluene containing about 0.2 ppm of sulfur.  The results are shown in Table.  one.  Test conditions of series A: load - toluene (mol. Conversion 46), pressure 7 atm, L. H. S. V.  Toluene 1 volume / volume (catalyst / h, water / toluene 7 mol / mol, test duration 1000 h.  These results indicate that the addition of TiOo to the alumina support results in a decrease in the rate of deactivation of the catalyst.  Example 3  Seri Test B.  A series of comparative tests was carried out with a pair of rhodium-ruthenium bound to potassium.  The substrate used is SA-SA-j, the preparation of which is described in Example 1.  Reproduce the preparation of test series A with replacement of 0.6 g of rhodium with 0.3 g of rhodium and Q, k g of ruthenium in the form of trichloride and the addition of 5 ml of HC1 instead of k ML; drying and activation are the same.  Then it is impregnated with 1.8, taken in the form of potassium carbonate, dried for 2 m at 100 ° C and 2 hours at 200 ° C.  Activate in air for 2 m at.  The stabilizing effect of TiO is observed in a similar way (on activity (Table  2, series B).  Operate under test conditions of series A.  Example k.  Seri Test C.  Reproduce the preparation of test series B, replacing ruthenium with palladium and potassium with sodium.  For this, catalyst A is prepared, replacing 0.6 g of rhodium with 0.3 g of rhodium and 0, g of palladium in the form of chlorides and adding 3 ml of HC1 instead of k ml; drying and activation remain the same.  Then, 1.8% by weight of NajO is impregnated in the form of sodium carbonate, dried for 2 hours at 100 ° C and 2 hours at 200 ° C, activated for 1 hour in air.  Operate under test conditions of series A.  The results are shown in Table.  3, C series. , Example 5.  Test Series D.  Reproduce the preparation of the Ag catalyst of the A series, replacing part of the parent. iridium and potassium for rubidium.  For this, catalyst AJ is prepared, replacements of O, 6 g of rhodium, 0.3 g of rhodium and O, 4 g of iridium in the form of chlorometalic acids and added C, ml of HCl. Drying (for 2 hours) follows calcination at (OO for 2 hours, followed by resuming for 1 hour at.  The reduced catalyst is impregnated with O, 8 RbnO, taken as rubidium hydroxide, converted to carbonate in an alcohol solution, then dried for 2 hours and for 2 hours.  I activate 1 hour at 500 ° С.  The effect of rubidi is even more significant than the action of potassium, therefore, the content of RbnO is reduced from 1.8 to 0.8 °.  As before, titanium produces a stabilizing effect on activity.  Operate under the conditions of test series A (the results are shown in Table.  , series o).  Example 6  Test series E Using the substrate SA-j, reproduce the preparation of test series A, replace 0.6 g rhodi with 0.3 g rhodi and O, g platinum as chlorides and add ml HC1; drying was carried out at 100 ° C for 2 hours, then for 1 hour, then calcined in air for 2 hours.  The calcined catalyst is impregnated. In aqueous form, dried at 250 ° C for 2 hours and reduced in atmosphere i at 300 ° C for 1 hour.  The results are shown in Table.  5 (series E).  Example 7  Preparation of the SF series spoons. Preparation of the SF substrate. With stirring, the hydrolysis of aluminum triisopropoxide Al (CjH70) j pure for analysis, dissolved in +500 ml of isopropanol with 5000 ml of water, is performed.  The resulting precipitate is dried for 5 hours at 100 ° C and then placed in an agglomeration device and form balls of 1.8-3.0 mm in size.  Balls are released and then calcined for 4 hours.  After that, the granulometric 310 fraction of 1.6-2.5 mm is screened out.  In this way . 800 g balls are obtained; their porosity is 55 ml / 100 g, of which 10 ml / 100 g contain pores with a diameter greater than 100 A.  Their specific surface is 210 moog.  Substrate Preparation Sf.  Reproduce the preparation of the SF substrate prior to the hydrolysis step.  The resulting layer of hydrated alumina is mixed with 1 g in the form of a titanic acid gel i, obtained by oxidizing hydrolysis of a solution of titanium trichloride.  Wet mixing was carried out on a Hobbart mixer for 1 hour.  After stirring, the resulting mass, dried at 100 ° C for 8 hours, is turned into grits with a particle size less than 0.5 mm, and then it is agglomerated in an sintering machine into balls of 1.8-3.0 mm in size; after drying, the balls are calcined at 550 ° C for 3 hours.  Receive 805 g of balls (1.6-2.5 mm) containing O. 12% TiO (2 (average content).  Statistical analysis indicates that this content varies between 0.08 and 0.15%.  Their porosity is 50 ml / 100 g, of which 4 ml / 100 g contain more than 100 A. pore.  Specific surface 230.  Preparation of SFj substrate.  2.8 g of tetraethoxytitanium (o1 solo 0.97 g TiO) is dissolved in an alcohol solution of aluminum isopropylate, then hydrolysis is carried out as in the preparation of the SF substrate,. The rest, as in the preparation of the substrate SF.  Receive 803 g of balls (1.6-2.5 mm) containing 0.12 wt. % T i O.  Statistical analysis shows that this content is consistent from ball to ball.  A study of the cross section of the balls on the Kasten microprobe shows that TiOn is evenly distributed in each ball: from one ball to another, the concentration varies between 0.12 ± 0.2 weight. %  The porosity of the substrate SF} 5b ml / 100 g, of which 6 ml / 100 g have a pore diameter greater than 100 A.  The specific surface is 205 MVr.  Example 8  Test Series F.  Various catalysts are prepared on.  SF substrates. .  , SFp and SFj.  Preparation of catalyst f ,.  100 g of alumina (substrate) is immersed in distilled water.  then dried at 80 ° C so as to reduce the contained water to 6 weight D. This alumina is immersed in 100 ml of a solution containing 0.5 g of rhodium (in the form of hydrochloric acid) 0.3 g of indium (in the form of indium nitrate) and 3 ml clean. HC1 (d 1.19).  After depletion of the solution by more than 99%, the catalyst is sintered, dried for 2 hours at, then 3 hours at 200 ° C, calcined in air at 1 hour and reduced with hydrogen at 2 hours.  Then 1 NaoO is added in the form of aqueous carbonates, dried at, then at 200 ° C and calcium, nirovanny 2 C at it30 C.  The preparation of catalysts f and RZD is the same as in the preparation of catalyst F, but the corresponding SFo and SF substrates are used.  Catalysts of the series are tested under the following conditions: - loading - pure toluene 9918 weight L, containing 0.2 ppm of sulfur, pressure 5 atm, G. H. S. V toluene 2 volume / volume of catalyst / h, test duration 1000 h.  The results of catalytic tests (Table.  6, series F) confirmed the effect of the presence of TiOij. The SFj substrate, which does not contain an evenly scattered TU, has less good results than the SFj substrate containing 0.12 well distributed T 10 (2, Example 9.  Test Series G Compare SFv, (0 TiOi) and SF-J (0.12% TiOij) substrates with a catalytic formula including rhodium, ruthenium and germanium and prepared as follows.  Preparation of catalyst G).  100 g of the substrate SF, wetted by 0.3 weight.  In a sintering device, HtjO is impregnated with 55 ml of a solution containing 0.35 g of rhodium in the form of RhClj, 0.35 g of ruthenium in the form of RuCla, 5 g of monohydrated citric acid, and}% germanium in the form of germanyl citrate.  After exposure to air for 4 hours, the catalyst is dried at 100 ° C for 5 hours, then calcined for 2 m at itSOC in air and finally reduced to 2 m at, 12 Preparation of the catalyst.  Act as in the preparation of catalyst G, but use a substrate.  Comparative test (table.  4, series G) under conditions of series F shows the indisputable stabilizing effect of titanium on the results.  Example 10  Seri ProvetovN.  The same SF substrates are compared.  (0 and SF3 (0.3% TiO) with a catalytic formula containing rhodium, tin and potassium and prepared as follows.  Preparation of catalyst H  100 g of the substrate SF (0% TiO), wetted by 0.8; weight. % ON Oh, dry Q is impregnated,% of tin in the form of a hydrochloric acid solution of tin chloride containing moles of HC1 / l.  The product is dried for 2 hours at and activated for 2 hours by reacting with a 100 MP solution, including 0.7 g of rhodium in the form of YANCCI, 5 ml of HCl.  After fixation of O, 6 g of rhodium, by anion exchange, the substrate is washed with 2 times 200 ml of water, dried at, then at 200 ° C for 2 h, and reduced for 3 h with hydrogen at.  The substrate is finally impregnated with 0.2% in the form of potassium carbonate dissolved in alcohol, then activated in air for 2 hours.  Preparation of catalyst Hj.  Reproduce the preparation of catalyst H-I using an SFj substrate (0.12% TiOj).  Comparative test (table.  7, Series H), carried out under the conditions of Series F, showed a new effect of an SFg substrate containing titanium on the stability of the catalyst.  PRI me R 11.  Test Series I.  Again compare the substrate SF (0% TiOj. ) and SFj (0.12% TiOQ) with a catalytic formula containing rhodium, palladium and vanadium and prepared as described below.  Catalyst Preparation 1.  100 g of the substrate is impregnated with 5 wt. % vanadium pentoxide, taken as an aqueous solution of vanadium oxalate.  Then the catalyst is dried at 100 ° C, for 2 hours and reduced at 500 s for 3 hours (Hj, 30% in Nj).  The recovery catalyst is impregnated with 48 ml of a solution containing O + g of palladium and O, 3 g of rhodium, taken as chlorides and k ml of HC1.  After soaking for 3 hours, dry the ave.   within 6 hours and reduced for 1 hour with pure hydrogen at 350 ° C. Preparation of the catalyst Ij.  Reproduce the preparation of catalyst 1 using 100 g of SF, j substrates.  Comparative test under conditions of the F series (Table  Series 7 |) shows that these catalysts are especially active, but that they are stable enough only in the presence of titanium.  EXAMPLE 12.  Test series 1 Uses SFj (0.12 TiOjj) with a catalytic formula that differs from the catalyst formula in that palladium is replaced by platinum, and the aqueous solution of vanadium goxalate, corresponding to 5 alcohol solution containing 3% TELO and 2 bfjGf in the form chlorides.  The rest, as in the preparation of the catalyst series I.  The results are shown in Table.  eight.  In tab.  8, series K and I, the results obtained with catalysts containing a) 0.12 wt.  TiOii; b) 0.55 weight. % give birth; c) 1.5 weight. % KqO and d) chromium oxide (series K) or a mixture of MoO, | + WO (series L).  PRI me R 13.  Prepare a mixture of reference substrates SM / ,,.  Preparation substrate SM ,.  Polyalkoxyaluminum produced by Ziegler synthesis in the presence of aluminum triethyl, ethylene and the minimum amount of a homogeneous catalyst based on titanium (for example, TtCI-j) is hydrolyzed, washed, and then spray dried at 200 ° C.  A fine powder is obtained consisting of granules with a size of 20-150 µm and an accessory surface of 230.  This powder is agglomerated in an agglomeration device into balls with sizes of 1.8-3.0 mm.  The balls are quickly dried, then calcined at i 550C for hours.  The grain fraction of 1.6-2.5 mm is screened out.   The substrate thus obtained consists of a mixture of fc and Tu-alumina and contains 0.08 TiOrj; its specific surface is 205 m / g, the pore volume is 55 ml / 100 g.  Preparation of the substrate BM ,: The same synthesis is carried out with a larger amount of titanium on the catalyst.  A substrate is obtained, co1 4 holding 0.27% of TiOj, with a specific surface of 220 MVr and a pore volume of 52 ml / 100 g.  Preparation substrate SM.  With stirring, hydrolysis of 8200 g of aluminum triisopropoxide A1 () pure for analysis in 9000 ml of distilled water is carried out.  The resulting suspension is dried by spraying, agglomerated in an agglomeration device, as the substrate is drying and calcining are the same.  Get 1bOO g balls of porosity of 5 ml / VOO g, of which 11 ml / 100 g contain pores with a diameter greater than A.  The specific surface is 200 MVr, the substrate does not contain TiO / j.  Preparation substrate SMj.  Repeat the synthesis of the substrate SMj, a solution in an alcohol solution of aluminum isopropyl 4.2 g of tetraethoxytitanium (about 1.5 g of TiOg).  The rest of the preparation is the same.  Get 1605 balls containing O, 08% TiOQ, with a composition similar to the composition of the substrate SM, j.  Preparation of substrates SMc-SM. -.  A series of substrates prepared (Table.  9) in the same way as indicated above, vary the amount of TiO / i added to alumina.  The content in the substrates is SM-.  varies from 0.00 (substrate SM) to 1.01% (substrate) and is given in Table.  9.  In substrates with T10o, the content of the latter varies from ball to ball by no more than 2% relative to the average content of the substrate.  An example.  Seri Test M.  Based on the substrate, a catalytic formula of ML is prepared, containing rhodium, manganese and potassium.  Preparation of the catalyst M.  100 g balls SM. moistened with water at 1%, impregnated with 0.6 g of rhodium (RhClj) and 3 ml of HCl (d 1.19), dissolved in 100 ml of water.  After depletion of the solution, the catalyst is dried at 100 ° C for 6 hours, then reduced for 3 hours with hydrogen at 280 ° C.  The catalyst is impregnated with 6.91 g of a heat saturated aqueous solution of potassium permanganate; after drying at 150 ° C for 3 hours and recovering at it IOO ° C for 2 hours, a catalyst of composition is obtained, wt. %: Rh 0.6, MpO 3.0, 2.0.  The results of the tests, given the fs conditions indicated at the end of Example 8, are given in Table.  10, series M Example 15.  Seri Test N.  Based on the substrate SM, an N4 catalyst containing rhodium, ruthenium and rhenium was prepared.  100 g of substrate ZMts.  saturated with O, 6 g of ruthenium and 0.3 g of rhodium in the form of chloride in the presence of 6 ml of HCl (d 1.19).  After depleting the impregnating solution, the washed substrate is dried, at 100 ° C for 2 hours, activated in air at 00 ° C for 2 hours, impregnated with% rhenium in the form of ammonium perranate, dried for 5 hours at 100 ° C and restored for 2 hours at .  Get the catalyst composition, weight. %: 0.6 ruthenium, 0.3 rhodi, 1, O rhenium.  The results of the test carried out under conditions of the F series are given in Table.  10, Serie N, Example 1b.  Seri Testing Institute O.  - A catalytic formula containing rhodium, rubidium and iron is prepared in this way.  100 g of the SM4 substrate are mixed with O, 5 g of rhodium (RhCli,) and 5 ml of HC (d 1.19) in 100 ml of water.  After exhaustion of the solution ,. the catalyst is dried at and for hours, reduced to 2 hours at 300 ° C and impregnated in dry form with 5% ReLO, taken as an aqueous solution of iron chloride, then dried for 2 hours at 200 ° C and calcined for 2 hours at 50 ° C .  Finally, the substrate is impregnated with O, 8 | Rb (0 in the form of an aqueous solution of carbonized aluminum hydroxide, dried at 200 ° C and calcined at AOO ° C for 1 hour.  The test results for the F series are given in Table.  10, series 0.  PRI me R 17.  Test series P Examine the test results of a catalytic formula containing rd, nickel and potassium on a SMQ substrate. 100 g of an SMrj substrate is impregnated with 3 CoO (cobalt nitrate), then calcined for 10 hours at.  The catalyst is then treated at 80 ° C in an atmosphere of water vapor and mixed with O, 6 g of birth (RhCl) in an aqueous solution of hydrochloride (5 ml of HCl; 16 d 1,19) until the solution is exhausted.  After washing, drying at 200 ° C for 2 h and recovering at 100 ° C for.  For 1 hour, the catalyst is impregnated with 1.3 as potassium carbonate, dried and activated in nitrogen at 1 hour.  The results of catalytic tests carried out under test conditions of the F series are given in Table. 10, Serie R.  The results were exactly the same when replacing 3 CoO with 3 NiO.  Example 18 Test series R.  A catalytic formula containing rhodium, palladium, nickel, iron and potassium on substrates is prepared, as indicated below.  100 g of the substrate, pre-impregnated with U NiO (nitrate), then calcined - for 10 hours, impregnated with O, A g of palladium and O, g of rhodium (introduced in the form of their chlorides) in 100 ml of a solution containing 6 ml of HCl.  After depletion of the solution, the catalyst, dried at 150 ° C for 3 m and reconstituted at 350 ° C for 2 hours, is impregnated with 3 (in the form of chloride), dried at 100 ° C, then at 200 C for 2 hours, and finally calcined at for k hours  Next, finally impregnated with a catalytic mass obtained with 1.1% of Ki2. 0 (potassium carbonate), dried for 1 hour at 200 ° C and calcined at 350 ° C for 2 hours.  i Thus, receive catalysts R ,, composition weight. %: 0.4 palladium, 0.4 rhodi, 3.0, 3.0 NiO, 1.1.  The catalysts R, SM / | -R, SM, j are tested under the conditions of Example 8, Series F.  The temperature (t)) of the reaction is increased in such a way as to maintain the conversion at the level of 6S% for 1000 h.   .  Temperature increase (a. ) less can be achieved when the content of TiOij exceeds 0.051 (500 ppm) or 0.06 (600 ppm), preferably 0.07% (700 ppm).  dT increases slightly with a TiOfj content of more than 0.3 (3000 ppm) and increases when the content is 5000 ppm (0.51).  
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    权利要求:
    Claims (1)
    [1]
    The claims of the invention use a carrier, additionally
    The method of producing benzene by de-weight of the carrier of titanium dioxide, alkylation of toluene in the presence of
    water vapor at an elevated temperature
    catalyst using catalyst taken into account in the examination containing 0.1-1.0% in relation to 1. Patent of the USSR ff 213776,
    the weight of the carrier is rodi and 0.01-5.0%. C 07 C 15 / o4, 1971. Relative to the weight of the carrier alkaline 2. US patent No. 3595932,
    metals that are deposited on a carrier, ykl. 260-672, publ. 19b9. on the basis of aluminum, about tl and -3. US Patent No.
    charitable with the fact that 260 - 672, published-. 19b9 (to increase the stability of the catalyst, totype).
    containing 0.05-1.0 in relation to
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    同族专利:
    公开号 | 公开日
    DE2856863A1|1979-07-12|
    FR2414034A1|1979-08-03|
    IT7919092D0|1979-01-05|
    US4207169A|1980-06-10|
    IT1109943B|1985-12-23|
    NL7900049A|1979-07-10|
    FR2414034B1|1981-07-10|
    GB2011945B|1982-03-24|
    GB2011945A|1979-07-18|
    BE873180A|1979-06-29|
    JPS5531061A|1980-03-05|
    引用文献:
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    US3595932A|1968-08-20|1971-07-27|Gdal Nossonovich Maslyansky|Method of producing benzene and its low-molecular weight homologs|
    US3649706A|1969-06-27|1972-03-14|Universal Oil Prod Co|Steam dealkylation process|
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    JPS5720014B2|1974-10-01|1982-04-26|
    FR2317962A1|1975-07-15|1977-02-11|Raffinage Cie Francaise|Catalysts for steam dealkylation of alkyl aromatics - contg. rhodium and group VIB metal on non-cracking support|
    FR2355791B1|1976-06-22|1979-07-20|Rhone Poulenc Ind|FR2434131B1|1978-02-24|1981-03-06|Inst Francais Du Petrole|
    US4977129A|1989-03-13|1990-12-11|W. R Grace & Co.-Conn.|Auto exhaust catalyst composition having low H2 S emissions and method of making the catalyst|
    US5102853A|1989-11-22|1992-04-07|Ford Motor Company|Three-way catalyst for automotive emission control|
    US5492880A|1991-06-24|1996-02-20|University Of Pittsburgh Of The Commonwealth System Of Higher Education|Process for the inorganic chemical modification of rhodium alumina catalysts and automotive catalyst made by the process|
    US5714659A|1996-08-29|1998-02-03|Phillips Petroleum Company|Catalyst composition and processes therefor and therewith|
    US5714660A|1996-08-29|1998-02-03|Phillips Petroleum Company|Catalyst composition and processes therefor and therewith|
    CA2352171C|1998-11-26|2009-12-15|Idemitsu Kosan Co., Ltd.|Carbon monoxide oxidation catalyst, method for preparation of carbon monoxide oxidation catalyst and method for production of hydrogen-containing gas|
    JP2001232195A|1999-12-17|2001-08-28|Ngk Insulators Ltd|Catalyst body|
    SE517251C2|2000-08-30|2002-05-14|Gustav Berggren|Component for controlling exhaust gas reflux|
    US20040043898A1|2000-09-08|2004-03-04|Naomi Noda|Method for producing catalyst body and carrier having alumina carried thereon|
    US6589908B1|2000-11-28|2003-07-08|Shell Oil Company|Method of making alumina having bimodal pore structure, and catalysts made therefrom|
    KR100632591B1|2000-12-16|2006-10-09|에스케이 주식회사|Catalyst composition for dioxin removal and preparation method thereof|
    US6756340B2|2002-04-08|2004-06-29|Uop Llc|Dehydrogenation catalyst composition|
    US6713032B2|2002-04-12|2004-03-30|Matsushita Electric Works, Ltd.|Catalyst for removing carbon monoxide in hydrogen rich gas and production method therefor|
    US7220701B2|2003-11-24|2007-05-22|Exxonmobil Chemical Patents Inc.|Catalyst and process for selective hydrogenation|
    US7220700B2|2003-11-24|2007-05-22|Exxonmobil Chemical Patents Inc.|Catalyst and process for selective hydrogenation|
    US7199273B2|2003-11-24|2007-04-03|Exxonmobil Chemical Patents, Inc.|Selective hydrogenation of alkynes and/or diolefins|
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    DE102005053230A1|2005-11-06|2007-05-10|Basf Ag|Process for aromatizing non-aromatics and subsequent dealkylation of alkyl-substituted aromatic hydrocarbons with water vapor|
    TW200800387A|2006-06-01|2008-01-01|Ritek Corp|Catalyst for catalyzing carbon nanotubes growth|
    JP5314910B2|2008-03-26|2013-10-16|株式会社東芝|Methanol oxidation catalyst and method for producing the same|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7800335A|FR2414034B1|1978-01-06|1978-01-06|
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