• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    Process for steam dealkylation of alkylaromatic hydrocarbons, particularly useful to produce benzene from toluene and to de-alkylate the alkylaromatic hydrocarbons contained in the effluents from catalytic reforming and aromatic production units, wherein the catalyst contains, in addition to an alumina carrier (a) at least one metal selected from ruthenium, rhodium, palladium, osmium, iridium and platinum (b) rhenium and (c) an alkali metal selected from lithium, sodium, potassium, rubidium and cesium.
    公开号:SU1087071A3
    申请号:SU792734660
    申请日:1979-02-21
    公开日:1984-04-15
    发明作者:Курти Филипп；Ле Паж Жан-Франсуа；Сюжье Андре；Козин Жан
    申请人:Энститю Франсэ Дю Петроль (Фирма)；
    IPC主号:
    专利说明:

    2. Method POP.1, I differ by the fact that they use a catalyst containing, in mass,%: 0.50, 54 rhodium, 0.56-0.6 rhenium, 1.0 potassium, supported on alumina with a specific surface of 210-220.
    3. Method POP.1, I differ by the fact that they use ka1087071
    catalyst, containing, wt.%: 0,230, 35 rhodium, 0.41-0.8 metal a, selected from the group consisting of platinum, ruthenium, palladium, 1.1-1.48 potassium, 0.51-0.6 rhenium deposited on alumina with a specific surface area of 210-260.
    I
    This invention relates to the reaction of toluene dialkylation with steam to produce benzene.
    A known method for producing benzene by demethylation of toluene on a catalyst containing rhodium and nickel supported on alumina 1.
    There is also known a method for producing benzene by demethylation of toluene on a catalyst that represents a platinum group metal (platinum, palladium, rhodium, iridium, ruthenium.) On a carrier that is alumina or a combination of alumina with nickel or cobalt C2.
    There is also known a method for producing benzene by demethylation of toluene on a catalyst containing alumina, a platinum group metal, and a metal chosen among vanadium, niobium, and tantalum C3.
    The catalysts used in the known processes possess sufficiently good properties in terms of activity.
    However, their stability is insufficient, the selectivity is not high enough, when toluene is converted to benz8l, side reactions of hydrocracking and / or cracking with water vapor of the aromatic core are observed, which leads to undesirable gaseous products, such as CO, CO2, CH, syrup in aromatic hydrocarbons.
    Closer to the invention is a method for producing benzene by demethylation of toluene in the presence of water vapor at 300-600 ° C using a catalyst containing 0.5-1.03% by weight of a metal selected from the group containing rhodium, palladium, platinum, ruthenium or their mixture, and 1-1.5 wt.% potassium, which are deposited on a carrier based on alumina with a specific surface of 210-250 C4J.
    The disadvantages of the method are the reduced yield of benzene and the low selectivity of the process.
    The purpose of the invention is to increase the yield of the target product and increase the selectivity of the process ..
    This goal is achieved by the fact that according to the method of producing benzene by demethylation of toluene in the presence of water vapor at COO-BOO C using a catalyst containing 0.5-1.03 wt.% Metal selected from the group containing rhodium, palladium, platinum , ruthenium or their mixture and 1-1.5 wt.% potassium, which are supported on an alumina-based carrier with a specific surface of 210-250, use a catalyst, additionally containing 0.51-0.6 wt.% rhenium.
    It is preferable to use a catalyst containing, in wt.%: 0.50, 54 rhodium, 0.56-0.6 rhenium, 1.0 potassium, supported on alumina with a specific surface of 210-220. ; It is preferable to use a catalyst containing, in wt.%: 0,250, 35 rhodium, 0.41-0.8 metal selected from the group containing platinum ruthenium, palladium, 1.1-1.48 potassium, 0.51-0.6 rhenium deposited on alumina with a specific surface area of 210250.
    The process is carried out between 300 and 600 ° C, preferably between 350 and, under pressure from 1 to 20 atm, preferably between 3 and 10 atm, with a bulk velocity lying between 0.1 and 10 volumes of hydrocarbons per volume of catalyst 1 hour, preferably between 1 and 20, preferably between 3 and 15. The catalysts used in the proposed method allow to obtain high yields of benzene with one time degree of decomposition of the aromatic core and the hydrogen-rich reaction gas (containing about 50-70% hydrogen by volume), easily estimated. They have excellent stability in more severe conditions of work. The catalyst carrier is preferably selected from eta-cubic H, gamma-cubic j., Gamma-tetragonal j, chi-cubic x, kappa orthorhombic 1, theta-monoclinic c, delta-orthorhombic c, and po-amorphous p aluminum oxide. Preferably, the specific surface area is 210-250, and the total pore volume is from 30 to 150 ml / 100 g. Any known catalyst preparation method can be used. The active elements are applied either simultaneously or separately to the carrier by impregnation with soluble solutions or solutions of soluble active elements in a suitable solvent. Impregnation can be carried out either dry, filling the pore volume of the carrier with an equal volume of the impregnating solution, then after maturing in some cases, drying the specified carrier, or with an excess of solution, bringing the carrier into contact with the solution that exceeds the volume of the pore of the specified carrier, and waiting the amount of time for fixing the metal ions contained in the solution, for example by exchange reaction with the carrier. As the soluble salts of these active elements, the following can be mentioned: for noble metals of group VIII, for rhenium and for potassium, halides, nitrates, acetates, alkali carbonates, formats, oxalates, citrates, chlorometal acids and their ammonium and amine salts, complexes
    containing at least one of the previously mentioned metals, with oxalic acid and oxalates. one
    place the carrier with this solution, then dry and calcine and / or restore it under the conditions specified previously. 714 citric acid and citrates, tartaric acid and tartrates, with other polyacids, hydroxy acids, amino acids and their salts, acetylacetonates. Rhenium is most commonly used in the form of perrhenic acid or ammonium or potassium perrhenate. For example, the carrier can be impregnated with a solution containing at least one platinum-group metal (group VIII), dried, for example between 100-250 ° C for at least 1 hour, in some cases thermally activated (calcination for at least 1 hour). at a temperature between about 300 and), impregnate with a solution containing rhenium compound and in some cases potassium, dry, in some cases, calcine and / or restore for at least 1 hour at 300 ° C in the presence of gas containing at least 10% hydrogen finally in some In some cases, soak (if this has not yet been done) with a solution containing potassium, dry, then calcine and / or restore as previously indicated. It is also possible, for example, to impregnate the carrier with a solution containing a rhenium compound and in some cases at least one alkali metal, dry and calcine between 200-350 ° C for at least 1 hour and in some cases recover after calcination at least at least for 1 hour at ZOO-BOO C, the carrier impregnated with these metals is then impregnated with a solution containing at least one platinum group metal (group VIII), dried and activated and / or restored, as described earlier, then, finally, in some cases pr they are fired (if this has not yet been done) with a solution containing an alkali metal, dried, calcined and / or reduced, as mentioned earlier. It is also possible, for example, to prepare a solution containing at least one platinum group metal (group VIII), at least one rhenium compound and at least one alkali metal, and propium. Another way to prepare a catalyst is to administer rhodium as chlorodioic acid, (Obtained by dissolving trichloride in hydrochloric acid, and at the same time, rhenium is introduced as a hydro-acidic solution of ammonium perrhenate, potassium perrhenate or perrhenic acid, into an oxide carrier. Both metals (rhodium and rhenium) are They can be reliably in the form of anions and they can be preferably introduced into the exchange reactions with an alumina carrier upon homogeneous impregnation of the carrier indicated. Any method that allows such homogeneity to be obtained can be used.The carrier impregnated with rhenium and rhodium is allowed to drain, dry at 100200 C for 1 hour or more, in some cases, calcined in the presence of air at 200-400С for 1 hour or more, then impregnated with at least one alkali metal, dried, in some cases, crystallized as before at -bound metals, then finally reduced with a gas containing at least 10% hydrogen, preferably dry, i.e. containing less than 0.5% by weight of water vapor, at a temperature of ZOO-TOO C, preferably 320-550 ° C for at least 1 hour. Preferably, before any contacting with toluene, a reduction treatment of the catalyst is carried out by passing a stream of hydrogen at 100-500 ° C. Example 1. A carrier in the form of commercial u-alumina, which is a ball of 1.6-2.5 mm in diameter with a specific surface of 210 and a volume of 63 ml / 100 g, previously held in a drying cabinet at 70 ° C. the atmosphere is saturated with water vapor, impregnated as follows. 1000 g of dry carrier, overpowered. in a drying oven, in contact with 1500 ml of a solution containing 5.1 g of rhodium in the form of hydrated rhodium trichloride, 40 ml of hydrochloric acid, p.a. (,nineteen). After depletion of the solution, it is observed that rhodium is evenly distributed in the carrier beads. After draining, it is dried at 100 ° C for 1 hour, npiT for 2 hours, then calcined at 1 hour. Then, the catalyst is contacted with 1400 ml of a solution containing 9.4 g of ammonium turrenate and 20 ml of hydrochloric acid. After exhaustion, this solution is dried after falling at 100 ° C for 1 hour, at 200 ° C for 2 hours, then calcined at 5 hours in the presence of air. Then the catalyst is impregnated dry with 560 ml of a solution containing 10.2 g of potassium in the form of nitrate, dried at 1 hour, then 5 hours at 200 ° C and reduced directly with dry hydrogen at 300 ° C for 30 minutes, then at 1 hour. Catalyst A is obtained which contains 0.5% rhodium, 0.6% rhenium and 1% potassium. Example 2 (comparative). The operation is carried out according to the procedure of Example 1 before calcination, and the wire is kept at 1 hour (after impregnation with rhodium). Then, 10.2 g of potassium is impregnated on dry basis, dried and reconstituted as in Example 1. Catalyst B is obtained, which contains, by weight, 0.5% rhodium and 1% potassium. This catalyst does not contain rhenium. Example 3. Commercial alumina (100 g) is used as a carrier. It is an extrudate with a diameter of 1.2 mm, a length of 5-7 mm, a specific surface of 250 and a total pore volume of 54 ml, pre-moistened with a drying cabinet at 70 ° C (water vapor pressure — saturation pressure). 1000 g of this carrier is impregnated with immersion in 1300 ml of a solution containing 3.6 g of rhodium (in the form of trichloride) and 4.2 g of palladium (in the form of chloride) and 44 ml of hydrochloric acid, p.a. (, l9). After depletion of the solution, it is established that palladium and rhodium are evenly distributed in the carrier beads. After draining, the impregnated carrier is dried at 5 hours, then it is contacted with 1300 ml of a solution containing 7.4 g of perrhenic acid and 20 ml of hydrochloric acid. After depletion, the solution is dried after falling at 100 ° C for 1 h, at 160 ° C5 h, then calcined at 3 h in the presence of air. Finally, the catalyst is impregnated with a drying of 510 ml of a solution containing 11.6 g of potassium as carbonate. dried at 10 hours, then activated at 2 hours and finally reduced in a stream of dry hydrogen at 300 ° C, 50 minutes, then at 1 hour. Catalyst C is obtained, which contains 0.35% by weight, 0.41% palladium, 0.53% rhenium and 1.1% potassium. Example 4. It works according to the method of example 3, replacing 4.2 g of palladium with 4.6 g of platinum in the form of chloroplatinic acid. The rest of the procedure is identical. Catalyst D is obtained, which contains by weight 0.35% rhodium, 0.44% platinum, 0.51% rhenium and 1.1% potassium. Example 5. 1000 g of the carrier described in Example 1, pre-moistened, as indicated above, are contacted with 1400 ml of a solution containing 8.3 g of ruthenium (in the form of trichloride), 2.6 g of rhodium in the form of trichloride, 50 ml of salt Acidic acid, analytical grade, 300 ml of ethanol and 50 g of citric acid monohydrate. After depletion of the solution, it is observed that ruthenium and rhodium are evenly distributed in the carrier beads. Dried after the drain at 130 ° C for 10 h, then calcined at 350 C for 3 h in the presence of air. Then the catalyst is placed in a drazer, then 600 ml of a solution containing 6.3 rhenium in the form of ammonium perrhenate, 15.3 g of potassium in the form of nitrate, and 50 g of citric acid monohydrate are impregnated with a drier. After 4 hours of ripening in air, the catalyst is dried at 180 ° C for 10 hours, calcined in air at 300 ° C for 4 hours, then reduced in the presence of dry hydrogen at 30 minutes, at 30 minutes and at 90 minutes. Catalyst E is obtained, which contains, by weight, 0.8 % ruthenium, 0.23% rhodium, 0.6% rhenium and 1.48% potassium. Example 6 (comparative). The procedure of Example 5 is repeated, but
    ,, entered toluene + entered xylene- (derived entered tolyoJJ +
    toluene + xylenes removed
    The xylenes entering. The reaction property is determined as follows.
    Selr
    Selectivity
    toluene and xylene conversion
    the resulting benzene 18 did not add rhenium. The impregnating solution for dry impregnation, used in the second part of the procedure, then does not contain potassium. Catalyst F is obtained, which contains, by weight, 0.8% ruthenium, 0.23% rhodium and 1.5% potassium. Example 7. 1000 g of commercial - {pC-alumina as a carrier, representing balls of 1.6-2.5 mm in diameter with a specific surface of 220 and a total pore volume of 60 ml / 100 g, previously aged in a drying cabinet at 70 C in an atmosphere of saturated water vapor, in contact with 1600 ml of a solution containing 5.6 g of rhodium in the form of trichloride, 8.5 g of ammonium perrhenate and 30 ml of hydrochloric acid, p.a. (,nineteen). After depletion of the solution, it is observed that rhodium and rhenium are evenly distributed in the carrier. It is dried at 120 ° C for 2 h, then 500 ml of solution containing 10.5 g of potassium in the form of carbonate are impregnated with dry land in a drazhyrator. The catalyst is finally dried at 100 ° C for 1 hour, at 200 ° C for 3 hours, then reduced by dry hydrogen at 300 ° C for 30 minutes, then at 500 ° C for 1 hour. The catalyst G is obtained, containing, by weight, 0.54% rhodium, 0.56 % rhenium and 1% potassium. Example 8. In this example, the characteristics given by the standard test for the dialkylation of toluene, catalysts A and B are compared. The conditions of the experiments are as follows: load: toluene 98.2% by weight, xylenes 1.8% by weight; volume rate 2 load volumes per catalyst volume per 1 hour; water ratio: H20 / TOLUOL 6 mol / mol; pressure: 7 atm, relative; amount of catalyst: 750 g / 1 l /. Thus, the molar conversion of the charge is determined: The yield of benzene is equal to the product of conversion to selectivity. The characteristics of catalysts A and presented in FIG. 1 and 2. (Fig. For each catalyst A and B shows molar conversion with respect to the load, obtained as a function of the temperature of the experiment; Fig. 2 is presented for each of the catalysts A and B according to the algae molar conversion of the load, and ordinate, the resulting selectivity to benzene). With each of the catalyst & A and B work for 50 hours at. Then, with each of the catalysts B and A, several two-hour experiments were carried out, each at different temperatures. For each experiment, the conversion, selectivity, and yield of benzene are determined. The curve, which describes the selectivity as the 20 function of the conversion, allows you to compare
    0.5 Rh; 0.6 Re; IK 0.5 Rh; 1 TO
    0.35 Rh; 0.41 Pd; . 0.53 Re; 1.1 K
    0.35 Rh; 0.44 Pt; 0.51 Re; 1.1 K
    0.80 Ru; 0.23 Rh; 0.6 Re; 1.48 K
    0.80 Ru; 0.23 Rh; 1.5 K
    0.54 Rh; 0.56 Re; 1 TO
    470 61 95.8 58.4 464 61 89.2 54.4
    49.4
    95.1
    52
    53.7
    56.8 94.5
    64.5
    92.1
    70
    474 70 83.2 58.2 472 71.2 95.0 67.6 both are catalysts for isoconversion. It can be seen that the proposed catalyst (catalyst A), used for the same conversion, gives 4-8 points with a higher conversion depending on temperature than catalyst B, which does not contain rhenium. Example 9. This example describes the characteristics inherent in the catalysts of examples 1-7 with the same loads and under the same operating conditions as in example 8. Catalysts B and F are not part of the invention. The table shows the characteristics of catalysates. These tables confirm the superiority of the proposed catalysts.
    Table continuation
    }
    WO A
    ZV80
    SB6070
    thirty
    %
    ui.2
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING BENZENE by demethylation of toluene in the presence of water vapor at a temperature of 300-600 ° C using a catalyst containing May 0.5-1.03% of a metal selected from the group consisting of rhodium, palladium, platinum, ruthenium or their a mixture, and 1-1.5 wt.% potassium, which are supported on an alumina-based carrier with a specific surface area of 210-250 m 2 / g, characterized in that, in order to increase the yield of the target product and increase the selectivity of the process, a catalyst is used optionally containing 0.51-0.6 wt.% rhenium.
    SU w, 1087071
    [2]
    2. The method according to claim 1, characterized in that the use of a catalyst containing, wt.%: 0.50.54 rhodium, 0.56-0.6 rhenium, 1.0 potassium deposited on alumina with a specific surface area of 210 -220 m 2 / g.
    [3]
    3. The method according to claim 1, characterized in that the use of a catalyst containing, wt.%: 0.230.35 rhodium, 0.41-0.8 metal selected from the group containing platinum, ruthenium, palladium, 1, 1-1.48 potassium, 0.51-0.6 rhenium deposited on alumina with a specific surface area of 210-260 m 2 / g
    I
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    同族专利:
    公开号 | 公开日
    DE2906389A1|1979-09-06|
    FR2434131B1|1981-03-06|
    IT1112021B|1986-01-13|
    GB2015028A|1979-09-05|
    IT7920483D0|1979-02-23|
    BE874319A|1979-08-21|
    DE2906389C2|1987-09-10|
    JPS6225128B2|1987-06-01|
    NL7901426A|1979-08-28|
    GB2015028B|1982-06-03|
    US4199437A|1980-04-22|
    FR2434131A1|1980-03-21|
    JPS54122230A|1979-09-21|
    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR787805367A|FR2434131B1|1978-02-24|1978-02-24|
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