• 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:
    1531595 Group VIII metal catalyst STAMICARBON BV 11 March 1976 [13 March 1975] 09836/76 Heading B1E [Also in Division Cl] An active group VIII noble metal catalyst on a porous carbon carrier is prepared by adsorbing on the carrier surface a soluble salt of the catalytically active metal from its solution, hydrolysing the salt to oxide or hydroxide, and reducing to the metal when the porous carbon contains macro-pores of radius above 10<SP>3</SP>Š, intermediate pores 20-10<SP>3</SP>Š and micropores not greater than 20Š, with the ratio of the combined pore volume of macro-plus intermediate pores to total pore volume is 0.6 to 1.0, and the hydrolysis of the salt and reduction of oxide or hydroxide are carried out in a single step using liquid hydrolysing and reducing agents. The preparation of Pd and Pd, Pt on carbon catalysts is exemplified using sodium bicarbonate and methanol for hydrolysis and reduction respectively.
    公开号:SU772469A3
    申请号:SU762331207
    申请日:1976-03-11
    公开日:1980-10-15
    发明作者:Фан Монфор Абрахам；Йоханнес Францискус Схольтен Йозеф
    申请人:Стамикарбон Б.Ф. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of preparation of noble metal catalysts for the synthesis of hydroxylamine.
    A known method for the preparation of a catalyst based on noble metals of group VIII of the activated carbon periodic system, comprising contacting the starting hydroxy, hydroxyl activated carbon with a soluble salt of the noble metals in an aqueous medium, the stage of hydrolysis and reduction in a liquid medium at elevated temperature, separation of the catalyst activated carbon 15 followed by drying.
    The disadvantage of this method is that · the activity of the catalyst in the synthesis of hydroxylamine is 17.5 g of hydroxylamine per 1 noble metal in 1 hour
    Closest to the invention in technical essence and the achieved effect is a method of preparing a catalyst for the synthesis of hydroxylamine by dispersing activated carbon in water, impregnating it with palladium chloride and / or platinum, followed by liquid phase reduction. £ 2]. The catalyst obtained by this method has a relatively low activity — in the synthesis of hydroxylamine, equal to 18 g of hydroxylamine per 1 g of a noble metal in 1 hour
    The aim of the invention is to obtain a catalyst with increased activity.
    A method of preparing a catalyst for the synthesis of hydroxylamine is proposed, which consists in dispersing activated carbon in water, impregnating it with palladium chloride and / or platinum, followed by liquid phase reduction, filtration, washing and drying. At the same time, activated carbon is preliminarily subjected to heat treatment in the temperature range of 100-150 ° C for 5-25 hours before dispersion and it is loaded onto dispersion with a temperature of 95-100 ° C.
    Distinctive features of the invention are the preliminary heat treatment of activated carbon before dispersing in the temperature range 100-150 ° C for 5-25 hours when loading it on dispersion with a temperature of 95-100 ° C.
    7 2 4 6 9
    As a result of using the proposed method, the activity of the catalyst averages 23 g of hydroxylamine per 1 g of palladium in 1 h, increasing by 28%.
    Example 1. 95 g 'activated carbon brand Norit SX with an inner surface of 1090 m ^ / g (BET), in which the ratio of the volume of macropores and average pores to the total pore volume is 0.76, is subjected to heat treatment at 120 ° C for 20 h in the dryer. Heat-treated coal with a temperature of 98 ° C, with stirring, was dispersed in 500 cc of distilled water Oe for 30 minutes, the pH of the medium was adjusted to 1.5 by addition of hydrochloric acid. Then, constantly stirring, add a solution of 20 g * PdC & 2 in 20 cm 3 HC & (specific gravity 1.19) and 50 cm® of distilled water at room temperature. Continue to stir for a further 2 hours. The resulting catalyst mass is separated from the liquid on a glass filter and dried at 120 ° C for 20 hours. With continuous stirring, the mass is fed into 800 ml of distilled water at 90 ° C containing 50 g of NaHC0 3 and 100 ml of methanol. Stirring is continued for 1 hour. The resulting catalyst is filtered on a glass filter, washed to the absence of chloride ions and dried in air at 120 ° C. for 20 hours.
    The resulting catalyst, containing 9.5 wt.% Pd, is used to produce hydroxylamine from nitrate ions at 3 ° C. In this case, hydrogen gas (80 l / h) is introduced into 1 l of an aqueous buffer solution that contains 207 cm3 of phosphoric acid (85%), 82 g of sodium hydroxide and 198 g of NaNO ^ and in which 750 mg of catalyst are dispersed. The activity of the catalysts is determined in grams of hydroxylamine / g Pd hour. It is 23 g / 'g Pd-h.
    Example 2. Repeat example 1 with the difference that the heat treatment of the source of activated carbon is carried out at 100 ° C for 25 hours, and for dispersion. The heat-treated carbon is served with a temperature of 95 ° C. The activity of the catalyst is 22.1 g of hydroxylamine / g Pd-h.
    Example 3. Example 1 is repeated with the difference that the heat treatment of the initial activated carbon is carried out at 150 ° С for 5 h, and the heat treated activated carbon is fed to dispersion at a temperature of 100 ° С. The activity of the catalyst is 23.9 g of hydroxylamine / g Pd-h.
    PRI me R 4. Repeat example 1 with the difference that an aqueous solution of platinum chloride is used. In this case, the catalyst activity is 22.8 g of hydroxylamine / g Pt h.
    Example 5. Example 1 is repeated with the difference that an aqueous solution of palladium and platinum chlorides is used in an amount providing a catalyst containing 8.3 wt.% Pd and 1.7 wt.% Pt. The activity of the catalyst is 44 g of hydroxylamine / g (Pd + Pt) -4.
    Example 6. Repeat example 1 with the difference that the heat-treated activated carbon with a temperature of 90C is dispersed in distilled water. The activity of the catalyst is 18.3 g of hydroxylamine / g Pd-h.
    Example 7. Repeat example 1 with the difference that the heat treatment of the source of activated carbon is carried out at 95 ° C for 25 hours, and for dispersion the heat-treated angle is served at a temperature of 95 ° C. The activity of the catalyst is 18.5 g of hydroxylamine / g Pd h
    Example 8. Repeat example 1 with the difference that the heat treatment of the source of activated carbon is carried out at 150 ° C for 4 hours, and the dispersed heat-treated carbon is fed with a temperature of 10 ° C. The activity of the catalyst is 18.9 g of hydroxylamine / g Pd '4.
    Example 9. Repeat example 1 · with the difference that the heat treatment of the source of activated carbon is carried out at 150 ° C for 5 hours, and the dispersed heat-treated activated carbon is served at a temperature of 110 ° C. The activity of the catalyst is 19.2 g of hydroxylamine / g Pd-h.
    Example 10, Example 1 is repeated with the difference that the heat treatment of the source of activated carbon is carried out at 160 ° C for 5.5 hours, with the heat-treated activated carbon being dispersed at a temperature of 100 ° C for dispersion.
    The activity of the catalyst is 22.4 g of hydroxylamine / g Pd -h.
    权利要求:
    Claims (4)
    [1]
    (54) METHOD FOR PREPARING A CATALYST FOR HYDROXYLAMINE SYNTHESIS The invention relates to the preparation of noble metal catalysts for the synthesis of hydroxylamine. A known method of preparing a catalyst based on noble metals of group VIII of the periodic system on activated carbon, including contacting the starting hydroxyl activated carbon with a soluble salt of noble metals in an aqueous medium, hydrolysis and reduction stage in a liquid medium at elevated temperature, separating the catalyst on the activated carbon with subsequent drying 1. The disadvantage of this method is that the activity of the catalyst in the synthesis of hydroxylamine is 17.5 g of hydroxylamine per 1 noble metal per hour. The closest to the invention in its technical essence and the achieved effect is the method of preparation of the catalyst for the synthesis of hydroxylamine by dispersing the activated carbon in water, impregnating it with palladium chloride and / or platinum, followed by a liquid phase reduction, filtration, washing and drying 2j. The catalyst obtained by this method has a relatively low activity - in the synthesis of hydroxylamine, equal to 18 g of hydroxylamine per 1 g of noble metal in 1 hour. The purpose of the invention is to obtain a catalyst with increased activity. A method of preparing a catalyst for the synthesis of hydroxylamine is proposed, which consists in dispersing the activated carbon in water, impregnating it with palladium chloride and / or platinum, followed by liquid-phase reduction, filtration, washing and drying. At the same time, before dispersing, the activated carbon is preliminarily subjected to heat treatment in the temperature range of 100–150 s for 5–25 h and loaded for dispersion with a temperature of 95–100 ° C. Distinctive features of the invention are the preliminary heat treatment of activated carbon before dispersing in the temperature range of 100-150s for 5-25 hours when it is loaded for dispersion with a temperature of 95-100s. In pesyjbTaTe using the proposed method, the catalyst activity averages 23 g of hydroxylamine per g of palladium per hour, increasing by 28%. Example 1. 95 g activated carbon of the brand Norit SX with an inner surface of 1090 (BET), in which the ratio of the volume of macropores and average pores to the total volume is 0.76, is subjected to heat treatment at L20 ° C in for 20 h in the dryer. Heat-treated coal with a temperature while stirring is dispersed with B 500 cm of distilled water for 30 minutes, the pH of the medium being adjusted to 1.5 with the addition of hydrochloric acid. Then, stirring constantly, add a solution of 20 g of PdCB in 20 (unit weight 1.19) and 50 cm of distilled water at room temperature. Continue to stir for a further 2 hours. The resulting catalyst mass is separated from the liquid on a glass filter and dried at 120 ° C for 20 h. With continuous stirring, the mass is fed into 800 ml of distilled water at 90 ° C, containing 50 g of NaHCOo, and 100 ml of methanol , Continue to stir for 1 hour. The resulting catalyst is filtered on a glass filter, washed until no chloride ions are present and dried in air at 120 ° C for 20 hours. The resulting catalyst, containing 9.5% by weight Pd, is used to obtain hydroxylamine from ions nitrate at. At the same time, hydrogen gas (80 l / h) is introduced into 1 liter of an aqueous buffer solution, which contains 207 cm -fsphoric acid (85%), 82 g of sodium hydroxide and 198 g of NaNO, j and in which 750 mg are dispersed catalyst. The activity of the catalysts is determined in grams of hydroxylamine / g Pd per hour. It is 23 g / g Pd.4. Example
    [2]
    2. Repeat the example with the difference that the heat treatment of the original activated carbon is carried out at 25 hours, and for dispersion. The heat-treated coal is fed at a temperature. The activity of the catalyst is 22.1 g of hydroxylamine / g of Pd-h. Example
    [3]
    3. Repeat the example with the difference that the heat treatment of the original activated carbon is carried out at 150 ° C for 5 hours, moreover, the thermally treated activated carbon is fed at a temperature to disperse. The activity of the catalyst is 23.9 g of hydroxylamine / g of Pd-h. EXAMPLE 4 An example is repeated with the difference that an aqueous solution of platinum chloride is used. The activity of the catalyst is 22.8 g of hydroxylamine / g Pt h. Example 5. Example 1 is repeated, with the difference that an aqueous solution of palladium and platinum chlorides is used in an amount that provides a catalyst that contains 8.3 wt. % Pd and 1.7 wt.% Pt. The activity of the catalyst is 44 g of hydroxylamine / g (Pd + Pt) -
    [4]
    4. Example 6. Example 1 is repeated with the difference that Thermo-treated activated carbon with a temperature of 9 ° C is dispersed in distilled water. The katg activity is 18.3 g hydroxylamine / g Pd-h. Example 7. Example 1 is repeated, with the difference that the heat treatment of the original activated carbon is carried out at 95 ° C for 25 hours, with the heat-treated angle being fed to the dispersion with a temperature of 95 ° C. The activity of the catalyst is 18.5 g of hydroxylamine / g Pd h. Example 8. Example 1 is repeated with the difference that the heat treatment of the original activated carbon is carried out at 150 ° C for 4 hours, and for dispersion Heat-treated carbon is fed at a temperature of 100 ° C. At the same time, the catalyst activity is 18.9 g of hydroxylamine / g Pd Part C. Example 9. An example is repeated with the difference that the heat treatment of the source activated carbon is carried out at 150 ° C for 5 hours, with dispersion heat treated activated carbon by ayut a temperature of 110 ° C. The activity of the catalyst is 19.2 g of hydroxylamine / g Pd4. Example 10 Example 1 is repeated, with the difference that the heat treatment of the original activated carbon is carried out at 160 ° C for 5.5 h, and the heat-treated activated carbon is fed to the dispersion at a temperature of lOO-c. The activity of the catalyst is 22.4 g of hydroxylamine / g Pd. Particle of the invention. Method of preparation of the catalyst for the synthesis of hydroxylamine by dispersing activated carbon in water, impregnating it with palladium chloride and / or palatina followed by liquid phase reduction, filtration, burning and drying, characterized in that, in order to obtain a catalyst with increased activity, the coal is preliminarily heat treated in a temperature range of 100-150 ° C for 5 to 25 hours and loaded for dispersion with a temperature of 95-100 ° C. Sources of information taken into account in the examination 1. US patent 3663166, cl. C 01 G 1/00, omission. 1G.OS.71. 2, USSR Author's Certificate 137913, cl. From 07 to Lu / 17, opuolik. 07/14/60 (prototype).
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    同族专利:
    公开号 | 公开日
    JPS5323274B2|1978-07-13|
    FR2303598A1|1976-10-08|
    IT1078732B|1985-05-08|
    BE839524A|1976-09-13|
    CA1071617A|1980-02-12|
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    法律状态:
    优先权:
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