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    • 专利摘要:
    The invention relates to a new process for the preparation of a supported metal catalyst containing at least one metal belonging to Group A and optionally at least one metal belonging to Group B, wherein Group A encompasses the metals palladium, rhodium, ruthenium, platinum, iridium, osmium, silver, gold and cadmium and Group B encompasses the metals zinc, mercury, germanium, tin, antimony and lead. According to the invention, the metal(s) is (are) applied onto the support in the presence of at least one compound of the general formula (I), <IMAGE> (I) wherein R1, R2, R3 and R4 each stands for a straight-chained or branched C1-20 alkyl group, a C1-4 hydroxyalkyl group or a phenyl-(C1-4 alkyl) group optionally having additional substituents, preferably C1-4 alkyl groups, on the phenyl ring, and X is hydroxy group or the residue of an organic or mineral acid. According to the invention, highly active catalysts can be prepared by an easy and economical process.
    公开号:SU1060096A3
    申请号:SU802926552
    申请日:1980-05-20
    公开日:1983-12-07
    发明作者:Мате Тибор；Тунглер Антал；Петро Йожеф
    申请人:Мадьяр Тудоманьош Академиа Кезпонти Хиватала (Инопредприятие)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing supported catalysts and can be used for the hydrogenation, dehydrogenation, hydrodemetry, hydrocycling and dehydrocyclization of organic compounds. A known method for producing a mash by impregnating the dioxide of the cream with an aqueous solution of nickel nitrate with ethylene diamine, followed by washing, drying, calcining and reduction with hydrogen at elevated temperature. In this case, silicon dioxide is previously subjected to cation exchange with sodium ions ij. However, the method is different in duration and complexity of performance and gives a catalyst with unstable activity. The closest to the proposed technical essence and the achieved effect is a method for producing a catalyst for hydrogenation processing of aliphatic and aromatic compounds containing unsaturated C — C bonds, oxo group, carbonyl, nitro, nitrile, chlorine or acyl, which includes impregnation of the carrier with a solution of metal, washing, drying and recovery of the catalyst mass of water comes from. In this case, silica gel is used as a carrier and platinum – ammonium hydroxide complex is used as a metal compound. The catalyst mass is first washed and dried, and then heated in a stream of nitrogen as the temperature rises to, then reduced, gradually increasing the hydrogen concentration 2J. The disadvantages of the method are the difficulty of implementation and the preparation of a catalyst with insufficiently high activity. The method requires the introduction of additional heat treatment in an atmosphere of nitrogen, which serves to decompose the platinum tetrammine complex. The activity of the catalysts obtained by this method is small and amounts, for example, during the hydrogenation of acetophenone to 12 ml / min (the activity is estimated from the rate of hydrogen absorption). Conditions guide. Survey: 1 g of 10%, 10 g of acetophenone in 100 ml of ethanol at atmospheric pressure and room temperature. The purpose of the invention is to simplify the process and obtain a catalyst with increased activity. This goal is achieved according to the method for preparing the catalyst | For hydrogenating processing of aliphatic and aromatic compounds containing unsaturated C — C bonds, oxo group, carbonyl, nitro group, nitrile, chlorine or acyl, including impregnation of the carrier, which is activated carbon, aluminum oxide. or silicon dioxide, with a solution of a compound of a metal, which is used as an inorganic salt or oxide of a metal of group VIII or a metal selected from the group comprising silver, gold, copper, the mixtures and or mixtures thereof, in a weight ratio based on 10-1: 1 metal, or a mixture of inorganic salts or an inorganic salt and oxide of a platinum group metal: with a metal selected from the group including zinc, mercury, germanium, tin, antimony, lead, in a weight ratio of 5-1: 1 per metal, in the presence of a quaternary ammonium compound of the general formula K -TG-VA: - Br - where - C | -C t-alkyl, C-C-oxyalkyl or phenyl ( C; (- C4-alkyl); X is hydroxyl, a carboxylic acid residue or a nitrogen, sulfur or halide-containing mineral acid, followed by reduction the catalyst mass is hydrogen in the reaction medium at IS – SO C, and then washed and dried or first washed and; drying followed by reduction with an increase in terahertura up to. Distinguishing features of the invention are the use of activated carbon or alumina or silica as a carrier and, as a metal compound, the above metal compounds or a mixture of metal compounds taken in a weight ratio calculated on a metal 10-1: 1 or 5-1. : 1, carrying out the impregnation of the carrier in the presence of a quaternary ammonium compound of the general formula -R 1 + L RZ J with the above values and X, the order of operations: first, reduction of the catalyst mass with hydrogen in the reaction oh medium under IS-SO C and then washing and drying or drying and proyvanie first and then restoring the temperature rises to 480 ° C, use of the proposed Images Retenu enables to obtain the following beneficial effects. By eliminating additional heat treatment under a nitrogen atmosphere, the process is simplified. The activity of the catalyst obtained by the proposed method increases. Thus, under identical conditions for the hydrogenation of acetophenone, the catalyst activity is 180 ml / min (instead of 12 ml / min in the prototype). Example 1. Palladium catalyst in activated carbon carrier. A 40% aqueous solution of 120 g of benzyltrimethylammonium bromide is added to 1000 ml of distilled water. 90 g of activated carbon with a particle size of less than 100 µm (fraction per surface 1150) is added to the resulting solution with constant stirring. After 0.5 stirring, an aqueous solution of palladium chloride is added and the resulting suspension is stirred for another 2 h. The aqueous solution of palladium chloride is prepared by dissolving 16.69 g of palladium chloride in 20 ml of a 36% aqueous salt solution. lots and diluting the solution with water to 150 ml. The suspension is poured into a hydrogenator mounted on a vibrator, and the mixture is saturated with hydrogen at 18–25 ° C and atmospheric pressure. The solution is shaken with an intensity of 100 rpm. After the uptake of hydrogen is complete (i.e., after the absorption of 12 liters of hydrogen), the residue is filtered on a glass filter made of sinter powder and rinsed a little with distilled water. The catalyst is dried in vacuum (20 mm Hg) at. The resulting catalyst contains 10 wt.% Metallic palladium. The dispersion calculated by the adsorption of carbon monoxide, measured at 20 ° C, is 0.51 i.e. more than half of the palladium atoms are present on the surface. Therefore, a very thin layer of palladium is distributed over the surface of the substrate (the dispersion of industrial palladium catalysts with 10% by weight of metal is 0.080, 15). The catalysts show high activity during the hydrogenation of several compounds in the liquid phase. To demonstrate the activity of the catalyst, the following reactions should be indicated: acetophenone (10 g) was hydrogenated quantitatively in ethylbenzo in the presence of a catalyst (1 g) at a pressure of 1 bar and 25 ° C (using a conventional catalyst), a greater amount of 1-phenylethanol is obtained as compared to ethylbenzene ; reaction time 1800 s; cinnamic aldehyde was hydrogenated to obtain propylene benzene as the final product 100% yield (using a conventional catalyst, a mixture of cinnamic aldehyde, hydrochloric alcohol and cinnamon alcohol is obtained), the reaction time is 3%; The catalyst showed a particularly high efficiency in the hydrogenation of 2-.nitro-4-chloroaniline (100 g) and beta-naphthol. The hydrogenation of 2-nitro-4-chloroaniline is carried out according to the following procedure. A 500 ml flask equipped with a stirrer, a tube for supplying hydrogen, a reflux condenser, a thermometer and a device for dispensing powder, 250 ml of I-butanol and 5 g of catalyst are loaded. With constant stirring (the speed of the stirrer is 500 rpm), hydrogen is supplied to the reactor through a supply tube mounted with a mixer at a speed of 50 ml / min and in the meantime the suspension is heated to 82 ° C. At this temperature, 85 g of 2- nitro-4-chloraniline in powder form for 2 hours. According to the chromatographic analysis of the sample taken from the reaction mixture 15 minutes after the end of the addition, it can be established that the reaction is completely complete, the conversion is 100%. The catalyst is then filtered off from the reaction mixture and o-phenylenediamine is isolated in 98.5% yield. The catalyst can be used 10 more times under the conditions mentioned above to obtain o-phenylene diamine from 2-nitro-4-chloroaniline. The yield of o-phenylenediamine is 98.5-99.4%. During the first ten consecutive experiments, the reaction time does not change, only in one experiment, it slightly increases (by 4.5%). The dispersion of the metal palashi is then determined by the adsorption of carbon monoxide on the spent catalyst; this value is equal to 0.49. The above data shows that the activity of the catalyst is very stable and its dispersion does not change even with frequent use. For comparison, a catalyst containing 10 wt.% Pszchladi and silica gel as a carrier is prepared according to the known (2J method. The catalyst is tested under conditions identical to those described for hydrogenating 2-nitro-4-chloroaniline. On this catalyst, the complete hydrogenation of the nitro group requires 8.6 h, and the reaction mixture contains takak 26.4% chlorophenylenediamine, the amount of which cannot be reduced by further hydrogenation.The catalyst is again used for this hydrogenation, and the time required for the complete hydrogenation of the nitro group during grows to 10.4 hours, and the reaction mixture contains 91.2% chlorophenylenediamine. If we compare these results with those obtained on a catalyst prepared in accordance with the invention, we can assume that the activity of the catalyst obtained by method iz is significantly lower during hydrogenation nitro groups: when used a second time, it decreases and it is no longer suitable for dehydrohalogenation; p-naphthol is hydrogenated in a heated autoclave made of acid-resistant steel and equipped with a magnetic stirrer and an Pressure regulator with a capacity of 1 l. 55 g of 5-naphthol in a mixture of 250 ml of methanol and 6 ml of acetic acid are dissolved in the autoclave and 2.5 g of catalyst are charged. Hydrogenation is carried out at a pressure of 5 bar and with stirring at a speed of 2000 rpm. The absorption of hydrogen ceases after 5 hours. According to a gas chromatographic analysis, it can be established that the conversion (α-naphthol is 100% and 5,6,7,8-tetrahydro-2 naphthol is formed with a selectivity of 90%. The catalyst is mentioned 5 times more. of the new condition (i-naphthol.) and in all cases the reaction proceeds with a conversion of 100% in 5 hours. Consequently, the catalyst activity remains stable.
    For comparison, a catalyst prepared according to method 2J and containing 100% by weight palladium on silica gel was tested in this reaction. Under the same reaction conditions as above, the reaction time required for 100% conversion of R-naphthol is 33 hours with a selectivity of 80.5%. If the catalyst is used a second time, the reaction time is 33 hours at a conversion of 82.7%. Therefore, the activity of the catalyst is reduced.
    In an autoclave, o-nitrophenylethyl alcohol is hydrogenated under the following conditions. 10 g of catalyst are added to 500 g of o-nitrophenyl ethyl alcohol and hydrogenated at 10 bar hydrogen pressure. In 4 hours, O-aminophenyl ethyl alcohol is formed in 100% yield. The catalyst recovered from the reaction mixture can be used in 10 consecutive experiments without any loss of activity. It is impossible to hydrate O-nitrophenyl ethyl alcohol without using the solvent on the catalyst prepared according to method 2, the said catalyst contains 10 wt.% Palladium on silica gel as a carrier. This catalyst is active only when O-nitrophenylethyl alcohol is reduced as a 20% solution in ethanol. All other reaction conditions were the same as described above. The reaction time required for complete conversion is 21.4 hours. Therefore, when using the catalyst obtained by the proposed process, it is not only time. reactions become significantly less, but the costs of solvent removal are eliminated.
    The hydrogenation of acetophenone and cinnamon aldehyde is investigated in a hydrogenation reactor mounted on a shaking unit. The hydrogen consumption during the hydrogenation reaction at atmospheric pressure and room temperature is measured using a gas burette attached to the hydrogenation reactor. The hydrogenation of acetophenone is examined under the following conditions: 10 g of acetophenone is dissolved in 100 ml of ethanol, 1 g of catalyst is added and hydrogenation is carried out at a shaking speed of 150 rotations per minute. In the case of the catalyst prepared according to the method described in this example, the consumption rate of hydrogen is 180 ml / min and the final reaction product is ethylbenzene. In the case of the catalyst prepared according to method 2, the hydrogen uptake rate is 12 ml / min, and the final reaction product is phenylethyl alcohol. This fact proves the high activity and special properties of the catalyst prepared by the proposed method, since no alcohol is formed from the carbonyl group. hydroxyl group, and CHj, -group.
    The hydrogenation of cinnamon aldehyde was investigated under the same conditions as acetophenone. Use 10 g of cinnamon aldehyde, 100 ml of ethanol, 1 g of catalyst, atmospheric pressure; temperature 25 ° C, shaking speed 150 vibrations per minute. The initial rate of hydrogen uptake is 260 ml / min, the final reaction product consists of 80% propyl benzene and 20% g hydrochloric alcohol. C. The case of the catcher prepared according to method 2 is the start of the hydrogen absorption rate at 28 ml / min, while the final reaction product is a mixture of hydrochloric aldehyde, hydrochloric alcohol and cinnamon alcohol. Therefore, as in the case of acetophenone, when using this catalyst, a CH-group is not formed from the carbonyl group as a sub-element. The hydrogenation of 2-methyl-3-bugin-2-ol was investigated under the same conditions as acetophenone. Using the catalyst prepared by the inventive method, the initial rate of hydrogen uptake, which characterizes the activity of the catalyst, is 225 ml / min, while the final reaction product consists of 2-methylbutane (75%) and 2-methyl butan-2-ol (25%). %). In the case of the catalyst prepared according to method 2, the initial absorption rate of hydrogen is 20 ml / min, while the final reaction product is a mixture of 2-methylbutan-2-ol (32%) and 2-methylbutan-2-ol. Consequently, on the catalyst prepared by the proposed method, the C – C triple bond is hydrogenated completely, whereas on the catalyst prepared according to method 21, this does not occur. PRI mme R 2. Palladium catalyst on a carrier of activated. New coal The palladium chloride solution prepared according to the method of Example 1 was added to 250 g of a 40% (weight by weight) solution of benzyltrimethylammonium. After dissolving, the solution formed is first diluted to. 1000 ml, 90 g of finely ground activated carbon with a specific surface area of 1800 is added. The resulting suspension is stirred for 0.5 h and the pH of the mixture is adjusted in the range of 9-11 with potassium hydroxide solution. Hydrogen is passed through the mixture at a rate of 1–15 l / h and the suspension is stirred for another 2 hours. With this, the flow of hydrogen is turned off, nitrogen is passed through the mixture, and the suspension is stirred for 15 minutes. The catalyst is filtered off, washed with distilled water and dried. The resulting catalyst contains 10 wt.% Metallic palladium with a dispersion of 0.55. This catalyst showed itself to be very active in the hydrogenation of 2 nitro-4-chloroaniline and p-naphthol, as well as in the dehydrogenation of indoline to indole. In the study of the hydrogenation of 2-nitro-4-chloroaniline and | 3-naphthol according to the procedure described in Example 1, the activity and stability of the activity of the catalyst are almost identical even after several experiments. When acetophenone is hydrogenated, the rate of hydrogen uptake is 192 ml / min. When using the catalyst of this example, indoline is dehydrogenated in the reactor described in example 1 and equipped with a stirrer. 75 g of indoline is dissolved in -250 mp of xylene, and 2 g of catalyst are introduced into the reactor. Argon is passed through the suspended mixture and the dehydrogenation is carried out at 150 ° C. According to the gas chromatographic analysis, the dehydrogenation of indoline to indole takes place completely within 78 minutes. When using the catalyst obtained by method 2j, 388 minutes is required to complete the reaction. When using this catalyst in the reaction once more, the reaction time increases to 426 minutes, however, with the catalyst obtained according to the invention, no changes are observed in 15 consecutive experiments. Example Palladium catalyst supported on alumina. 100 g of gsuminium mixed oxide with a solution of 4 g of benzyl trimethylammonium chloride in 200 ml of distilled water. Then a solution of 0.83 g of palladium chloride in 10 g of a 40% (weight percentage) aqueous solution of benzyltrimethylammonium chloride is added and the resulting suspension is evaporated at a pressure of 200 mm Hg. The impregnated substrate is loaded into a tubular reactor equipped with a heating jacket, and a stream of hydrogen is passed through the reactor, while the temperature is gradually increased to 200 ° C for 2 hours. This temperature is maintained for another 1 h to complete the reduction. which contains 0.5 wt.% palladium, is very active when hydrogenating benzene to cyclohexane and phenol to cyclohexanone. Investigate the hydrogenation of benzene and phenol in an integral tubular reactor, using 5 g of catalyst. When benzene is hydrogenated, the temperature is 100 ° C, the benzene feed rate is:
    0.25 mol / h and the molar ratio hydrogen; ben evil 4: 1. Conversion of benzene 100%. When using a catalyst containing 0.5% by weight of palladium on silica gel carrier and prepared according to method 2, the conversion is 46%, 4% under identical conditions.
    When phenol is hydrogenated, the temperature is 150 ° C, CKOpocytb of phenol feed is 0.195 mol / h and the molar ratio of hydrogen: phenol is 1: 5. The conversion of phenol is 98.6%. When using the catalyst prepared according to method 2j, conversion was 48.75%, cyclohexanone selectivity was 91.2%.
    The catalyst activity does not decrease during 500 hours of continuous operation, whereas for the catalyst prepared according to method 2j, the conversion is reduced to 12.5% after 40 hours of use.
    Example 4. A palladium catalyst supported on silica.
    100 g of a tableted silica is mixed with a mixture of 20 ml of a 40% (percentage by weight ratio) solution of tetramethylammonium hydroxide and 180 ml of distilled water, then 1.258 g of Pd (NO () 2 2 H2O) dissolved in 16 ml of 40% is added .- The resulting suspension is stirred for 2 hours, after which the impregnated substrate is filtered and loaded into the tubular reactor of example 3. A stream of hydrogen is passed through the reactor and the temperature of the catalyst layer is gradually increased to t for 3 hours. The temperature was maintained for a further 1 hour to complete the reduction. The resulting catalyst, which contained 0.5 wt.% palladium, is highly active in the hydrogenation of ash bin in cyclohexane and o-nitroetilbenzola in o-ethylaniline.
    When hydrogenating benzene using a catalyst under the conditions described in the previous example, the conversion is 99.64%. I.
    Investigate the hydrogenation of o-nitroethylbenzene in an integral tubular reactor with 5 g of catalyst. The reaction temperature is 180c, the feed rate of O-nitrosylbenzene is 0.18 mol / h, the molar ratio hydrogen: O-nitroethylbenzene is 4: 1. Conversion equal to 97.6% with a selectivity for o-ethylaniline 99.5%. When using the catalyst obtained by the t2J method, the conversion is equal to 38.4% and this value decreases to 21.6% in 4 hours. .
    PRI me R 5. Platinum catalyst on a carrier of activated carbon.
    99 g of finely ground activated carbon is mixed with a solution of 30 g of benzyl trimethylammonium chloride in 900 ml of distilled water. The suspension is stirred for 0.5 h / solution i, 1.727 g of platinum tetrachloride in 50 m of distilled water is added. After stirring for 1 h, 1.6 g of hydrazine monochloride is added and then 12 g of sodium bicarbonate is added, the suspension is poured into a hydrogenator mounted on a vibrator. The reactor is shaken at 250 rpm and the suspension is saturated with hydrogen. After the uptake of hydrogen is complete, the catalyst is filtered off and dried. The resulting catalyst contains 1% by weight of platinum.
    This catalyst is very active during the hydrogenation in the liquid phase of 2-nitro-4-chloroaniline, R-naphthol and cinnamic aldehyde.
    The hydrogenation of 2-nitro-4-chloroaniline is investigated by the method of example, with the only difference that 10 g of catalyst are used; reaction time is 4 hours with selectivity in o-phenylenediamine 93.5%. During the ten subsequent experiments, the catalyst activity is not reduced. When using a catalyst prepared according to method 2 and containing 1% by weight of platinum on a silica gel carrier, the reaction time is 14.6 hours, the reaction mixture will contain 31.3% chlorophenylene diamine. Therefore, this catalyst is not suitable for quantitative dehydrogenation and, therefore, it is much superior to the catalyst prepared according to the invention. .
    Investigate the hydrogenation of /} -naphthol with 5.5 g of catalyst. The reaction time required for a 100% pure was 8.2 hours with a selectivity of 5.6 to 7.8-tetrahydro-2-naphthol 81.4%. When using a catalyst prepared according to the f2j method and containing 1 wt% platinum on a silica gel carrier, the conversion is 73.6% after 32 hours of reaction. Therefore, in this reaction, this catalyst is indeed much less active than the catalyst prepared according to the invention.
    PRI me R 6. Rhodium catalyst on a carrier of activated carbon.
    99 g of finely ground activated carbon is mixed with a solution of 12 g of benzyl chloride: rimethylammonium in 850 g of distilled water. After stirring for 0.5 hour, a solution of 2.085 g of rhodium chloride in 50 ml of distilled water is added. After that, the procedure of Example 1 is used to catalyze a catalyst containing 1 wt.% Of rhodium. This catalyst is very active in hydrogenating cinnamic aldehyde to acetophenone. The hydrogenation of cinnamic aldehyde to acetophenone using the catalyst prepared in this example is investigated as described in Example 1, but 2.5 g of catalyst are introduced into the hydrogenation reactor. Hydrogen uptake rate 85 ml / min. When using a catalyst prepared according to method D, containing 1% by weight of rhodium and having silica gel as a carrier, the absorption rate of hydrogen is 7.5 ml / min. Example. Ruthenium catalyst on an activated carbon carrier. 10.26 g of ruthenium chloride is dissolved in 50 ml of distilled water, and the solution is added to 120 g of a 40% (weight by weight) solution of benzyltrimethylammonium chloride. After dissolving the initially formed precipitate, the solution is diluted to 1000 ml and 95 g of finely ground activated carbon is added. After that, the procedure of Example 2 is used to prepare a catalyst containing 5% by weight of ruthenium. The catcher is especially active in the hydrogenation of R-naphthol. 5 g of catalyst are introduced into the autoclave. Hydrogenation of 5-naphthol is carried out for 5 hours, with a conversion of 100% at a selectivity of 92.4%. When using the catalyst prepared according to method 2, containing 5 wt.% Ruthenium, on a silica gel carrier, the conversion is equal to 43.2% after 32 hours of reaction. PRI me R 8. Iridium catalyst on a carrier of activated carbon. 0.27 g H. IrC8j. 6H2O is dissolved in 25 ml of distilled water, and the solution is added to 25 g of a 40% (weight ratio) solution of benzyltrimethylammonium hydroxide. After dissolving the initially formed precipitate, the solution is added to 120 ml and 10 g of finely ground activated carbon is added. The procedure of Example 2 is used to prepare a catalyst which contains 1% by weight of iridium. This catalyst is active in the hydrogenation of cinnamon aldehyde on 4 catalyst, the rate of hydrogen uptake is 6.5 ml / min. EXAMPLE 9 Silver catalyst supported on activated carbon. 15.749 g of silver nitrate is dissolved in 150 g of a 40% -nog (weight percentage) solution of tetrapropylammonium hydroxide. After the dissolution of the initially formed precipitate is complete, the solution is diluted to 600 ml and 90 g of activated carbon (particle size 2-3 mm) is added. After stirring for 1 hour, 15 ml of hydrazine hydrate is added to the mixture and stirring is continued for another 2 hours. Thereafter, the catalyst is filtered off, washed with distilled water until it becomes neutral, and dried. The resulting catalyst contains 10 wt.% Silver. This catalyst is very active and. stable during the vapor phase dehydrogenation of cyclohexanol to cyclohexanone. The dehydrogenation of cyclohexanol is examined in an integral tubular reactor using 10 g of catalyst at. Cyclohexanol is fed at a rate of 0.16 mol / h, argon is used as the diluent gas. The cyclohexanol conversion is 98.4%, and the product leaving the tubular reactor contains 90.4% cyclohexanone. On catalysts prepared according to method 2j, the conversion of cyclohexanol is 5.2% under conditions identical to those described above. Therefore, Method 2 is not suitable for producing silver catalysts with industrially acceptable activity. I'll try it on. Gold catalyst on a carrier of activated carbon. 1.38 g of gold chloride is dissolved in 12 g of a 40% (weight percentage) solution of benzyltrimethylammonium chloride. After the dissolution of the initially formed mass is completed, the solution is diluted to 120 ml and 9 g of finely ground activated carbon is added. After that, the procedure of Example 2 is used to obtain a catalyst containing 10% by weight of gold. This catalyst is active in the hydrogenation of cinnamon aldehyde at a pressure of about 25 atm. The hydrogenation of cinnamon aldehyde catalyst is investigated at a pressure of 50 bar in an autoclave. After 8 hours, 83.5% of the hydocoric aldehyde is formed. Approx. 11. Copper catalyst supported on alumina. 26.19 g of 2% 0 are dissolved in 70 g of a 40% (weight ratio) solution of benzyltrimethylammonium chloride, the resulting solution is diluted to 120 ml. 90 g of alumina pellet are added to the solution and the suspension is stirred for 1 hour. Then a solution of 10 g
    Potassium hydroxide in 50 ml of distilled water is added to the mixture, evaporated at 50 ° C and a pressure of 20 mm Hg. The impregnated substrate is placed in a tubular reactor through which hydrogen is passed, the catalyst layer is gradually heated to 350 ° C. 2 h. This temperature is maintained for 4 h.
    The resulting catalyst, containing 10 wt.% Copper, is very active during vapor phase hydrogenation.
    -nitroethylbenzene in one-step production of indole from O-nitrophenyl-ethanol.
    Hydrocyclization of o-nitrophenyl ethanol is investigated in an integral tubular reactor using 10 g of catalyst at 230 ° C. The feed rate of 6-nitrophenyl ethanol is 0.27 mol / h, the molar ratio of hydrogen: substrate is 3: 1. The mixture leaving the reactor contains 91.2% of indole at a conversion of 100%, by-products are aminophenyl ethanol, phenylethanol and ethyl benzyl. When using a catalyst prepared according to method 2, containing 10% by weight of copper on a silica gel carrier, the conversion of 0-nitrophenylzanol is 31.3%, and the mixture leaving the reactor contains less than 1% indole, and it contains mainly 28.4% O-aminophenyl ethanol. Therefore, the known catalyst is not suitable for this special hydrocyclization reaction.
    For example 12. Ka; s1miy catalyst on a carrier of activated carbon,
    19.51 g CdC2. 2HjiO is dissolved in 45 g of a 40% (weight ratio) solution of benzyltrimethylammonium chloride, the resulting solution is diluted to 120 ml. 90 g of activated carbon (particle size 2-3 ml) are added.
    The suspension is stirred for 1 hour, after which a solution of 8 g of potassium hydroxide in 40 ml of distilled water is added. The resulting mixture is evaporated, and the dry, impregnated under- spoon is placed in a tubular reactor. Hydrogen is passed through the reactor, the temperature is gradually raised to .290 ° C over 3 hours. The catalyst is reduced at the same temperature over 2 hours to obtain a catalyst with a cadmium content of 10% by weight.
    This catalyst is active and selective when hydrogenating in the liquid phase of cinnamic aldehyde to cinnamon alcohol at 150 ° C and 65 bar pressure.
    Investigate the hydrogenation of cinnamon aldehyde in an autoclave. 50 g of cinnamon aldehyde dissolved in 250 ml of ethanol and 15 g of catalyst are loaded. Conducts hydrogenation
    About at 150 ° C and 65 bar. For 100% conversion, a reaction time of 8 hours is required, the selectivity to cinnamic alcohol is 94.5%.
    Example 13. Nickel catalysts on activated carbon media.
    20.24 g of Nice-2- is dissolved in 60 g of a 40% (weight percentage) solution of benzyltrimethylammonium chloride, and the resulting
    the solution is diluted to 80 ml. 45 g of activated carbon (particle size 2-3 mm) are added to the solution. The resulting suspension was stirred for 1 hour and 10 g of potassium hydroxide dissolved in 50 ml of distilled water was added. Then the water is evaporated at 50 ° C and a pressure of 20 mm Hg. The substrate coated with the nickel compound is entrained into the tubular reactor j as in Example 3. Hydrogen is fed through the reactor, the temperature of the catalyst bed is gradually increased to 460 ° C over 4 hours. The resulting catalyst, containing 10 wt.% Ni, is very active in the hydrogenation in the vapor phase of benzene.
    The hydrogenation of benzene is carried out as described in Example 3, using the catalyst of this example with the difference that the reaction is carried out at
    . At this temperature, the conversion of benzene is 100%.
    PRI me R 14. Cobalt catalyst on a carrier of activated carbon.
    20.28 g of СоСЕ2 6HyjO is dissolved in 50 g of a 40% (weight percentage) solution of benzyltrimethylmloni chloride, the resulting solution
    diluted to 100 ml. 45 g of activated carbon (particle size 2-3 mm) are added to the solution. After that, the procedure of Example 13 is used, with the difference that the activation is carried out at 480 ° C for 8 hours.
    The resulting catalyst with a cobalt content of 10 wt.% Is active during the hydrogenation in the liquid phase of benzyl cyanide at a temperature of more than
    and pressure over 50 atm.
    To study the hydrogenation of benzyl cyanide, 50 g of benzyl cyanide dissolved in 250 ml of ethanol and 15 g of catalyst are loaded into an autoclave.
    RI 120-C and pressure (50 bar conversion
    Benzyl cyanide is 100% in 8.5 hours.
    PRI me R 15. Iron catalyst on a carrier of activated carbon.
    24.95 g of FeSO-7HlO are dissolved in 55 g of a 40% (weight percentage) solution of benzyl trimethlammonium chloride. The procedure of Example 13 is then used to prepare a catalyst with an iron content of 10% by weight.
    This catalyst is very active in the vapor phase nitrobenzene hydrogenation.
    Investigate the hydrogenation of nitrobenzene in an integrated tubular reactor using 10 g of the catalyst of the example at 175 ° O. The feed rate of nitrobenzene is 0.11 mol / h, the molar ratio of hydrogen: substrate is 5: 1. Conversion 100% with aniline selectivity of 94.5%.
    Example 16. Rhenium catalyst supported on alumina.
    1.3 g of rhenium anhydride is dissolved in 10: from 40% (weight percentage) solution of tetrapropylammonium hydroxide, the resulting solution is diluted to 25 ml. Then 9 g of alumina pellet are added to the solution. The mixture is stirred for 0.5 hours, after which the water is evaporated, the resulting impregnated substrate is placed into the tubular reactor of Example 3. Hydrogen is fed through the reactor, the temperature of the catalyst bed is gradually increased to 420 ° C for 2 hours. The catalyst is activated at this temperature for 4 hours.
    The resulting catalyst with a rhenium content of 1 wt.% Is very active during the hydrogenation in the vapor phase of 0-nitroethylbenzene. In addition to o-amine ethyl benzene, a significant amount of aniline was obtained in this reaction. This catalyst has also been successfully used in the demethylation of skatole to indole. Indole was obtained with a selectivity of about 90% at a temperature exceeding 40 ° C. .
    Hydrogenation of n-nitroethylbenzene is investigated, as described in the example. At a conversion, the 100% mixture leaving the reactor contains 46.4% aniline and 53.6% 0-aminoethylbenzene. I Investigate the hydrodemethylation of methylindole in the following conditions. 10 g of catalyst are placed in an integral tubular reactor, the feed rate of a 25% -sized solution of methyl indol (skatole) in xylene is 26.5% mol / h, the diluent gas is argon, temperature. Conversion .katol 100% with a selectivity in 1indole 96.4%.
    Example 17. Pschladium-copper catalyst on a carrier of activated carbon.
    16.9 g of palladium chloride are dissolved in 20 ml of 36% (w / w) hydrochloric acid, and the resulting solution is diluted to 120 ml. Then 250 g, 40% (weight ratio) solution of benzyltri0 methyl ammonium chloride is added. The precipitate obtained is dissolved, 2.62 g of CuCl2H2O in 50 ml of distilled water is added to the solution, and the resulting solution is diluted to 1000 ml. 90 g of finely powdered is added to a solution of up to 5, then the mixture is treated according to the procedure of Example 2..
    The resulting catalyst containing 10 wt.% Palladium and 1 wt.%
    0 copper, very active and selective in hydrogenation of chloride 3,4,5trimethoxybenzoyl.
    The selectivity of hydrogenation of 3,4,5-trimethoxybenzoyl chloride in an autoclave, similar to that described in Example 1 and equipped with a stirrer and a supply of hydrogen, is investigated. 85 g of the acid chloride, dissolved in 300 ml of xylene, and 4 g of the catalyst of the example are charged into the autoclave.
    0 Conducts hydrogenation at atmospheric suppression and. After 4 hours, the conversion of said acid chloride is 100% with a selectivity of 3,4,5-trimethoxybenzyldehyde 94.8%.
    5 The catalyst can be used fifteen times.
    When using a catalyst prepared according to method 2, containing 10% by weight palladium and
    0 1 wt.% Copper on silica gel carrier, the selectivity for the same aldehyde is 41.2%.
    Example 18. Osmium catalyst supported on activated
    5 ang.
    0.231 g of (NH4) OsCe is dissolved in 30 g of a 40% (weight ratio) solution of benzyltrimethylammonium hydroxide, and the resulting solution is diluted to 50 ml. Then in
    9.9 g of finely powdered activated carbon are added to the solution. After that, the procedure of Example 1 is used to obtain a catalyst with an osmium content of 1% by weight.
    five
    This catalyst is active in the hydrogenation of cinnamon aldehyde.
    The hydrogenation of cinnamon aldehyde is investigated under conditions identical to example 10. The reaction time required for 100% conversion is 6.5 hours.
    PRI me R 19. Platinum-palladium catalyst on a carrier of activated carbon.
    5 9b g of finely powdered activated carbon is mixed with a solution of 45 g of benelyltrimethylamoni chloride in 1000. ml of distilled water. After stirring for 0.5 h, 1.669 g of palladium chloride dissolved in a mixture of 5 ml of 36% hydrochloric acid (50% distilled water and then 1.727 g of platinum tetrachloride dissolved in 50 ml) are added. distilled water. Following this, the procedure of Example 5 is used to obtain a catalyst containing 1% by weight of platinum and 1% by weight of palladium. The activity of the catalyst was investigated according to the procedure of Example 1 and when hydrogenating cinnamic aldehyde, the absorption rate of hydrogen is 125 ml / min. The reaction time required for complete B-naphthol conversion is 10.5 hours, while the liquid phase hydrogenation of o-nitrophenylethanol takes 6.2 hours. The liquid phase hydrogenation of 1-hexene-5-one is investigated in the same way as the hydrogenation of acetophenone. The initial rate of hydrogen uptake is 185 ml / min. At the time of the dependence of the absorption of hydrogen, different from 30-35 ml / min. The activity of the phase can be well defined ((hydrogenation of the carbonyl group). The final product of the reaction is hexane-5-ol. X Example 20. Palladium-ruthenium catalyst is supported on activated carbon. 16.69 g of palladium chloride are dissolved in 20 ml of 36% (weight ratio) of hydrochloric acid, the resulting solution is diluted to 80 MP. 10.25 g of ruthenium chloride is dissolved in the BOGDL of distilled water. These solutions are added to 280 g of 40% (% weights) solution of benzyltrimethylammonium chloride, the resulting mixture diluted to 1000 ml. Then 85 g of finely powdered activated carbon is added to the solution, followed by the procedure of Example 2 to obtain a catalyst containing 10. aa.% palladium and 5% by weight of ruthenium. The activity of the catalyst is investigated as described in Example 1, when hydrogenating cinnamon aldehyde, the rate of hydrogen uptake is 235 ml / min; when hydrogenating acetophenone, 255 ml / min; when hydrogenating 1-hexa-5-one — 265 ml / m, the reaction time required for complete conversion (5-naphthol, 3.6 h. Hydrogenation of dimethyl ether, itaconic to The acid was investigated in a hydrogenation reactor equipped with a shaking device. 10 g of itaconic acid dimethyl ester are dissolved in 100 ml of ethanol and 1 g of the catalyst of the example is added. The hydrogen uptake rate is 260 ml / min. Primer p.21. Palladium-rhodium catalyst on a carrier of activated carbon. 98 g of finely ground activated carbon are mixed with a solution of 25 g of benzyltrimethylammonium chloride in 900 ml of distilled water. After stirring for 0.5 h, a solution of 1.669 g of palladium chloride in 36% (w / w) hydrochloric acid dissolved in 50 ml is added. Then the palladium is reduced by the procedure of Example 2. After the reduction is completed, a solution of 2.085 g of rhodium chloride in 50 ml of distilled water is added to the suspension, and the mixture is again reduced by the procedure of Example 2. The resulting catalyst contains 1% by weight of palladium and 1% by weight of rhodium. The catalyst activity is 85 ml / min in the hydrogenation of cinnamic aldehyde, in the hydrogenation of itaconic acid dimethyl ester, it is 90 ml / min. The reaction time required for complete conversion of 2-nitro-4-chloroaniline and 0-nitrophenyl ethanol is 5.2 and 5.5 hours, respectively. EXAMPLE 22 Palladium-silver catalyst supported on activated carbon. 2.516 g of Pd (NO) 2-2H20 and 0.787 g of silver nitrate are dissolved in 50 ml of a 40% (weight percent) solution of tetraethylammonium hydroxide, the resulting solution is diluted to 100 ml, then 8.5 g are added to the solution finely ground activated carbon. After that, the procedure of Example 1 is used to obtain a catalyst containing 10 wt.% Palladium and 3 wt.% Silver. When using a catalyst, the reaction time required for complete conversion of 3,4,5-trimethoxybenzoyl chloride is 4.5 hours with a selectivity for the appropriate aldehyde of 95.6%. . PRI me R 23. Palladium-gold catalyst on a carrier of activated carbon. 8.5 g of finely ground charcoal is mixed with 50 g of 40% (weight by weight) benzyltrimethylammonium chloride dissolved in 100 ml of distilled water. After stirring, a solution of 1.669 g of palladium chloride in 36% (weight ratio) of hydrochloric acid, diluted in 50 ml, and then a solution of 0.77 g of gold chloride in 50 ml of distilled water. Then, the procedure of Example 2 is used to obtain a catalyst containing 10% by weight of palladium and 5% by weight of gold. The activity and selectivity of this catalyst are almost identical to the activity and selectivity of the catalyst prepared according to the previous example. Example 24. Palladium-cadmium activated carbon catalyst. 8.5 g of finely ground activated carbon is mixed with 25 g of a 40% weight percentage of ammonium chloride-benzyltrimethyl ammonium dissolved in 100 ml of distilled water. After stirring a solution of 1.669 g of palladium chloride in 36% (weight ratio) of hydrochloric acid, diluted in 50 ml, and then a solution of 0.985 g of 2H2O in 50 ml of distilled water are added for 0/5 hours. Then, the procedure of Example 2 is used to obtain a catalyst containing 10 wt.% Palladium and 5 wt.% Cadmium. When using a catalyst, the reaction time required for the complete conversion of 3,4,5-trimethoxybenzoyl chloride is 5 hours with a selectivity of the corresponding aldehyde of 94.4%. The acid chloride of 4-chlorobasic acid is hydrated in the apparatus described previously. A solution of 100 g of the indicated acid chloride in 330 ml of toluene and 4.5 g of the catalyst of the example are loaded into a hydrogenation reactor. The hydrogenation temperature is 62 ° C. After 3.5 hours, the conversion of chlorohydride to hydride is 100% with selectivity for 4-chloro-aldehyde 93.4%. PRI me R 25. Palladium catalyst on a carrier of activated carbon. 12 g of (+) - 1-phenylethyltrimethyl ammonium iodide was dissolved in 250 g of a 40% (weight ratio) aqueous solution of benzyltrimethylammonium. The resulting solution is diluted to 1000 ml and 90 finely ground particles are added; activated carbon After stirring for 0.5 h, 16.69 g of palladium chloride dissolved in 20 g of 36% (w / w) hydrochloric acid diluted in was added. 100 ml. The procedure of Example 2 is then used to prepare a catalyst containing 10% by weight of palladium. This catalyst is active in the hydrogenation of cinnamon aldehyde. In addition, the catalyst was used in stereoselective or enantioselective hydrogenation processes, i.e. when stereoselective hydrogenation in the phase of 6-dimethyl-6deoxy-6-methylene-5-hydroxy-tetracycline and pyridine acetic acid ethyl ester. The hydrogenation of 6-dimethyl-6-deoxy-6-methylene-5-oxytetracycline is examined under the following conditions. 25 g of this substrate, dissolved in 250 ml of a mixture of 2: 1 dimethylformamide and water, and g of an example catalyst are loaded into an autoclave. The hydrogenation is carried out at a pressure of 3 bar. After 2.5 hours of reaction, the conversion is equal to 100%. L-6-deoxy-5-oxytetracycline is formed with a selectivity of 95.%. When using the catalyst mentioned in the example and prepared without any optically active compound, two stereoisomers () are obtained in a 1: 1 ratio. - PRI me R 26. Palladium-zinc catalyst on a carrier of activated carbon. 80 MP of a 40% (weight percent) aqueous solution of chloride benzyltrimethylammonium are added to 900 ml of distilled water, with constant stirring, 94 g of finely ground activated carbon are added. After stirring for an hour, a solution of metal chloride (prepared by dissolving 8.35 g of palladium chloride in 10 ml of 36 wt.% Hydrochloric acid, diluted to 100 ml and stirring it with 2.085 g of zinc chloride dissolved in 20 ml is added to the suspension. distilled water). The procedure of Example 2 is then used to prepare a catalyst containing 5% by weight of palladium and 1% by weight of zinc. When using a catalyst, the reaction time required for the complete conversion of 4-chloromethyl acid chloride and 3,4,5-trimethoxybenzoyl chloride is 4.2 and 6.5 hours. The selectivity for the corresponding aldehydes is 95.6% and 96.8%, respectively . Example 27. Palladium-mercury catalyst on a carrier of activated carbon. The catalyst was prepared according to the procedure of Example 26 with the difference that 1.35 g of mercury chloride dissolved in 40 ml of distilled water was added to the palladium chloride solution (instead of zinc chloride). The resulting catalyst contains 5 wt.% Palladium and 1 wt.% Mercury. The activity of the catalyst of the example is identical to the activity of the catalyst obtained in accordance with the preceding example, but is less selective. At measure 28. Palladium-germanium catalyst of activated carbon carrier. 1.669 g of palladium chloride are dissolved in 3 ml of 36% (w / w) hydrochloric acid. Excess hydrochloric acid is removed by evaporation, 25 ml of 40% (w / w) tetrapropylammonium hydroxide solution is added . Chlo reed palladium is dissolved in this raster thief by gentle heating. 1.44 g of germanium oxide is dissolved separately in 20 ml of a 40% (weight percentage) solution of tetrapropylammonium hydroxide. The two solutions are then combined and diluted to 250 ml with distilled water. Then 8 g of finely ground activated carbon is added to the resulting solution. The suspension is heated to with constant stirring, at this temperature hydrogen is supplied through the suspension for 6 hours. Then the flow of hydrogen is turned off and nitrogen is fed through the suspension, the suspension is gradually cooled to room temperature. The reduced catalyst is filtered off, washed with distilled water and dried. The resulting catalyst contains 10 wt.% Palladium and. 9.6 wt.% Germanium. When using a catalyst, the reaction time required for complete conversion in the hydrogenation of 2-nitro-4-chloroaniline is 85 minutes. Under these conditions, 2,6-dinitrotoluene can be hydrogenated to 2,6-diaminotoluene for a minute. Example 29. Palladium-tin catalyst on a carrier of activated carbon. A solution of palladium chloride in a solution of tetrapropylammonium hydroxide is prepared according to the procedure of Example 28-. 1.597 g of tin chloride is dissolved separately in 15 ml of a 40% (weight by weight) solution of tetramethylammonium hydroxide with gentle heating. Two solutions are combined. Then, the procedure of Example 29 is used to obtain a lysator catalysts containing 10% by weight of palladium and 9.7% of tin. The catalyst is selectively hydrogenated with the C-C-double bond of brown aldehyde and l-reKceH-S-oHa. The hydrogen uptake rate is 105 and 96 ml / min, respectively. Example 30. Palladium-antimony catalyst on a carrier of activated carbon. The procedure of Example 29 is used with the exception that 1.87 g of antimony trichloride is dissolved in 20 ml of a 40% (weight by weight) solution of tetramethylammonium hydroxide instead of tin chloride. A catalyst is obtained containing 10% by weight of palladium and 9.8% by weight of antimony. This catalyst is selective in the hydrogenation in the liquid phase of cinnamic aldehyde. The activity and selectivity of the catalyst are almost identical to those of the catalyst described in Example 29. Example 31. Palladium-lead catalyst is supported on activated carbon. 30 ml of a 40% (weight percent) solution of benzyltrimethylammonium chloride are diluted to lOO ml with distilled water, and 8 g of finely divided activated carbon is added to the solution. After stirring for 0.5 h, a solution of metal salt, prepared by dissolving 1.669 g of palladium chloride in 3 ml of 36% (weight by weight) hydrochloric acid, diluting the solution to 80 ml and stirring it, is added to the suspension. with 1.60 g of lead nitrate. The procedure of Example 2 is then used to prepare a catalyst containing 10 wt.% Palladium and 8.5 wt.% Lead. When using a catalyst, the initial rate of hydrogen uptake is 65 ml / min with hydrogenation of 2-methyl-3-butyn-2-ol. On this catalyst, the C-Harmonous compound of the said compound is hydrogenated to a C-C-double bond with a selectivity of more than 90%. PRI me R 32. Platinum-rhenium catalyst on a carrier of alumina. 0.13 g of rhenium anhydride and 0.103 platinum tetrachloride are dissolved in 15 ml of a 40% (weight ratio) solution of tetrapropylammonium hydroxide, and the resulting solution is diluted to 25 ml. 10 g of alumina pellets are added to the solution, the mixture is stirred for 2 hours. Then the water is evaporated under vacuum, the substrate impregnated with rhenium and platinum is placed in the tubular reactor of example 2. A stream of hydrogen is passed through the reactor while the temperature gradually increases to 360 ° within 4h The catalyst is activated at this temperature for 4 hours. After this reduction step, a catalyst containing 0.6% by weight of platinum and 0.5% by weight of rhodium is obtained.
    Examine the dehydrocyclization of h-hesane in an integral tubular reactor using 6 g of the catalyst according to the invention at 365 ° C. The feed rate of n-hexane is 0.26 mol / h, argon is used in the dilution gas. Conversion is 94.5% with a benzene selectivity of 91.3%.
    Example 33. Platinum-zinc catalyst on an activated carbon carrier.
    35 ml of a 40% (weight percent) solution of the back-methyltrimethylammonium chloride solution is added to 800 ml of distilled water. Then 98.5 g of finely ground activated carbon are added to the solution, the resulting solution is stirred for 0/5 h, after which 1.727 g of platinum tetrachloride and 1.04 zinc chloride dissolved in 50 ml are added. distilled water. Then, the procedure of Example 5 is used to obtain a catalyst containing 1% by weight of platinum and 0.5% by weight of zinc.
    When using a catalyst, the reaction time required for the complete conversion of 4-chloromethyl acid chloride and 3,4,5-trimethoxybenzene chloride is 3.8 and 5.2 hours, respectively. The selectivity for the corresponding aldehydes is 87.6 and 91.2% respectively.
    PRI me R 34. Pal. Padium catalyst on a substrate of activated carbon.
    The method of Example 1 is repeated, with the difference that 103 g of benzyltrimethylammonium sulfate is used in the form of a 40 wt.% Aqueous solution. The catalyst thus obtained has the same activity as the catalyst prepared in accordance with the method described in Example 1.
    PRI me R 35. Palladium catalyst on an activated carbon substrate.
    The method of example 1 is repeated with the difference that 111 g of benzyltrimethylammonium nitrate is used in the form of a 40 wt.% Aqueous solution. The catalyst thus obtained has the same activity as the catalyst obtained in accordance with the method described in Example 1.
    Example 36. Paladium katashzor on an activated carbon substrate.
    The method of Example 1 is repeated with the difference that d09 g of benzyltrimethylammonium acetate is used in the form of a 40 wt.% Aqueous solution. Received so
    the catalyst has the same activity as the catalyst obtained in accordance with the method described in example 1.
    Example 37. Palladium catalyst on an activated carbon substrate.
    The method of example 2 is repeated with the difference that benzyldyrmethylhexadecylammonium chloride is used
    0 in the form of 560 g of a 40 wt.% Aqueous solution. The resulting catalyst contains 10 wt.% Psadi, the dispersion of which is 0.3.
    When using the received
    5 catalyst, the reaction time required for complete conversion is 4.2 hours with liquid phase hydrogenation of o-nitrophenyl ethanol.
    Example 38: Palladium catalyst on an activated carbon substrate.
    The method of example 1 is repeated with the difference that tetrahexylammonium bromide is used in the form of 590 g of a 40 wt.% Aqueous solution.
    5 The resulting catalyst contains 10% by weight of palladium, the dispersion of which is 0.28.
    The catalyst is unusually active when saturated with double bonds,
    0 for example in the case of unsaturated aliphatic ketones.
    So, when using the catalyst of this example, the initial absorption rate of hydrogen is equal to
    5 190 ml / min, with liquid phase hydrogenation of 1-hexene-5-one.
    Example 39. Palladium-silver catalyst on an activated carbon substrate.
    0
    The method of example 22 is repeated with the difference that 2-hydroxyethyltrimethylammonium hydroxide is used in the form of a 40 ml 50 wt.% Aqueous solution. The resulting catalyst contains 10 wt.% Paladi and 3 wt.% Silver.
    five
    When using a catalyst, the reaction time required for complete conversion of 3,, 4,5-trimethoxybenzoyl chloride is 4.5 hours with a selectivity for the corresponding
    0 aldehyde 94.6%.
    I
    PRI me R 40, Catalyst - palladium on activated carbon.
    Work according to the method of example 2
    5 with the difference that 295 g of benzyltrimethylammonium perchlorate are used in the form of a 40 wt.% Solution in water. The catalyst thus obtained contains 10% by weight of palladium, its dispersion is 0.52. Catalyst activity .192 NUI / MIN in the hydrogenation of acetophenone.
    Example 41. The catalyst is palladium on activated carbon.
    65
    Work according to the method of example 2 with the difference that they use 318 g of benoneyl trimethylammonium phosphate in the form of a 40 wt.% Aqueous solution. The resulting catalyst contains 10 wt.% Palladium, its dispersion is equal to 0.54. The activity of the catalyst is 196 ml / min during the hydrogenation of acetophenone.
    PRI me R 42. The catalyst is palladium on activated carbon.
    The catalyst was prepared according to the procedure of Example 2 with the difference that 324 g of benzyltrimethylammonium oxalate were used as 40% by weight of aqueous
    solution. The resulting catalyst contains 10 wt.% Palladium and its dispersion is equal to 0.50. Catalyst activity 190 ml / min in the hydrogenation of acetopheone.
    The proposed method has a wide range of applications and can be used to prepare catalysts of various composition, including metal compounds from the Pa to Group VIII of the Periodic System. In this case, the high activity of the catalyst is manifested not only in the use of noble metals, but also in the iron group metals
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING A CATALYST FOR HYDROGENIZATION PROCESSING OF ALIPHATIC AND AROMATIC COMPOUNDS containing unsaturated C-C bonds, oxo group, carbonyl, nitro group, nitrile, chlorine or acyl, including impregnation of the carrier with a solution of the metal compound, washing with a catalyst, washing with hydrogen, washing with a catalyst, washing with hydrogen and moreover, in order to simplify the process and to obtain a catalyst with increased activity, activated carbon, alumina, or silicon dioxide are used as a carrier, and as a metal compound is an inorganic salt or metal oxide of the XW group or a metal. selected from the group comprising silver, gold, copper, cadmium and rhenium or a mixture thereof, in a weight ratio of 10-1: 1 metal, or a mixture of inorganic salts or an inorganic salt and metal oxide of the platinum group with a metal selected from the group comprising zinc, mercury, germanium, tin, antimony and lead, in a weight ratio of 5-1: 1 metal, and the carrier is impregnated in the presence of a quaternary compound ammonium of the general formula
    T r _ J where Rj-R ^> * c < -c f6 -alkyl, C “-C4-hydroxyalkyl or phenyl- (C-alkyl);
    X is hydroxyl, the remainder of a carboxylic acid, or nitrogen, sulfur, or halide-containing mineral acid, and the catalytic mass is first reduced in the reaction medium at 18-80 ° C, and then washed and dried, or first washed and dried, followed by reduction with increasing temperature up to 480 ° C.
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    同族专利:
    公开号 | 公开日
    CH644770A5|1984-08-31|
    JPS5921660B2|1984-05-21|
    GB2052294A|1981-01-28|
    JPS55155746A|1980-12-04|
    DE3019582A1|1980-12-04|
    HU177860B|1982-01-28|
    GB2052294B|1983-02-16|
    DE3019582C2|1989-12-07|
    US4361500A|1982-11-30|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    HU79MA3151A|HU177860B|1979-05-22|1979-05-22|Method for producing carrier metal catalyzers|
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