• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    CATALYST FOR PREPARING 3-CYANPYRIPINE by reacting 3-methylpyridine with ammonia and oxygen, including an oxygen-containing compound of antimony, vanadium and titanium, containing components in atomic ot-. wearing antimony: vanadium: titanium 4:
    公开号:SU1189327A3
    申请号:SU823394504
    申请日:1982-02-25
    公开日:1985-10-30
    发明作者:Бешке Хельмут；Фридрих Хайнц；Хайлос Йоханнес
    申请人:Дегусса Аг (Фирма)；
    IPC主号:
    专利说明:

    I
    The invention relates to the field of catalysts for the preparation of 3-cyanomeridine.
    The purpose of the invention is to increase the activity and selectivity of the catalyst due to the additional content of montmorillonite and highly dispersed silicon dioxide in a certain ratio and certain physical characteristics of the catalyst.
    Example 1. Suspension 23.3 kg of antimony (III) oxide, 4.7 kg of ammonium metavanadate, 12.8 kg of titanium dioxide, 11.7 kg of montmorillonite and 5.8 kg of highly dispersed silicon dioxide with a surface of 200 to 140 liters of water, after which 1.6.4 L of 54% nitric acid is added to it. The mixture is slowly heated to boiling point, 7 l of water is added to boiling water, boiled for 2 hours, the pH is adjusted to 4.6 with ammonia, cooled, dried in a roller dryer, calcined in a rotary tube furnace and crushed into a steel mill type e to a particle size less than 0-, 5 mm. 4500 g of the catalyst mixture prepared in this way is thoroughly mixed with 225 g of graphite and 1700 g of a 20% aqueous solution of urea and then molded into extruded products with a diameter of 3 mm. The resulting products are heat treated in an atmosphere of air, keeping them for 15 hours at 120 ° C, 2 hours at 550 ° C, 1 hour at-650 ° C: And 3 hours at 770 ° C. The apparent catalyst density is 1.05 kg / l, the BET surface is 18 m / g, the pore volume is 0.28 cm / g, and the average pore diameter is 2.7-10 cm.
     The catalyst contains 20% mont-. morillonite, 10% highly dispersed silicon dioxide, and oxygen-containing compounds of antimony, vanadium, and titanium in the atomic ratio of 4: 1: 4, respectively.
    1050 g of the obtained catalyst was filled with a reaction tube 3000 mm long and an internal diameter of 20 mm. A preheated gas mixture is passed through the tube, to which / mountain per 1 mole of 3-methylpyridine has 6 mol of ammonia, 30 mol of air and 6 mol of water vapor. . The mixture is passed at a rate of
    893272
    calculating 1.34 moles of 3-methylpyridine per hour. The tube is heated with a molten salt with a temperature of 350 ° C. After passing the reaction tube, the gases are washed with water. Over 8 hours, an average of 94% of the starting 3-methylpyridine reacts, which corresponds to an average yield of 3-cyanopyridine of 89 mol.% Calculated on
    10 3-methylpyridine and a volumetric yield of 124 g / l h.
    Example 2. Using the same catalyst, the process is carried out as in Example 1, but at a temperature of molten salt of 360 C. For 8 hours, the conversion is on average 96%, the yield of 3-cyanopyridine is 98 mol%, and the volume yield is 129 g / l .
    Example 3. Apply the same
    0 catalyst, the process is carried out according to
    Example 1, but at a temperature of salt. 365C bath, and the gas mixture is fed at a rate of 1.47 mol 3-methylpyridine per hour. Behind
    5 3 h, the average conversion rate is 94%, the yield of 3-cyanpyridine is 90 mol.%, And the volume yield is 137 g / l h.
    Example 4. Apply the same catalyst, proceed through
    Q Example 1, but at a temperature of molten salt 365C and a gas mixture is passed through the reaction tube, in which only 4 mol of ammonia is used per 1 mole of 3-methylpyridine. For 8 h, the average degree of conversion of 93%, the yield of 3-cyanopyridine
    89 mol.%, And the volumetric yield 124g / lh.
    Example 5. 23.3 kg of antimony trioxide, 4.7 kg of ammonium metavanadate,
    0 12.8 kg titanium dioxide, 11.7 kg
    montmorillonite and 1.0 kg of highly dispersed silicon dioxide with a surface of 200 are suspended in 140 l of water, after which
    5 16.4 L 54% nitric acid. AT
    the rest in the manufacture of the catalyst is carried out according to example 1. The pressed catalysts are heated in an air stream, and during
    0 15 hours at a temperature of up to 120 ° С, 2 hours up to 550 ° С and 1 hour at a temperature up to БЗС and 700 ° С. It seems to have a density of 1.10 kg / l, a BET surface, a micropore volume of 0.25 cm- / g, and an average
    5 Pore radius 2, see Catalyst
    contains 22.25 wt.% montmorillonite and 1.85 wt.% highly dispersed silicon dioxide. The ratio of antimony: vanadium: titanium is 4: 1: 4. When reacting 3-methylpyridine with ammonia, it is received according to example 4. On average, 93% of the used 3-methylpyridine reacted within 8 hours. The yield of 3-cyanpyridine (based on the used 3-methylpyridine) is 89 mol.%, And the output is volume-time 122 g / l h. Example 6. 23.3 kg of antimony trioxide, 7.0 kg of ammonium metavanadate 6.4 of titanium dioxide , 11.7 montmorillonite and 1.0 kg of highly dispersed silicon dioxide with a surface of 200 are suspended in 140 l of water, after which 18.0 l of 54% nitric acid is added. Otherwise, in the manufacture of the catalyst, the procedure is the same as in Example 1, but the application of 1700 g of a 37% aqueous solution of urea. The apparent density of the catalyst is 1.03 kg / l, the BET surface is 35 m / g, the volume of micropores is 0.40 cm / g, the average pore radius is 3.2 cm. The catalyst contains 24.0% mont morillonite and 2% highly dispersed silicon dioxide, atomic ratio antimony: vanadium: titanium 4-: 1.5: 2.0 When reacting 3-methylpyridine with ammonia, proceed as in Example 1. On average, 96% of the 3-methylpyridine used reacted for 8 hours. The yield of 3-cyanpyridine (based on the used 3-metipyridine) is 88 mol.%, And the output is volume-time 124 g / lh. Example 7. 23.3 kg of antimony trioxide, 4.7 kg of ammonium metavanadate are mixed in 140 l of water , 16.0 kg of titanium dioxide, 11.7 kg of montmorillonite and 11.7 of fine silica with a specific surface area of 200. In the following, the process is carried out as in Example 1 with the difference that 1700-g of a 35% aqueous solution of urea is used. The bulk density of the catalyst is 1.03 kg / l, the specific surface area according to BET 43, the volume of macropores is 0.5, and the average pore radius is 4.0-10 cm. Antimony, vanadium and titanium are in the catalyst in an atomic ratio of 4: 1: 5 , The content of montmorillonite and fine silica on 17.5%. The reaction of 3-methylpyridine is carried out according to Example 1. An average conversion rate of 3-methylpyridine is 97%. The average yield of 3-cyanpyridine is 88 mol.% Based on the starting 3-methylpyridine, and the volumetric yield is 123 g / l h. Example 8. In a gallon of water a mixture of 23.3 kg of antimony trioxide, 4.7 kg of ammonium metavanadate, 12, 8 kg of titanium dioxide, 2.9 kg of montmorillonite and 5.8 kg of finely dispersed silicon dioxide with a specific surface of 200. In the following, the process is carried out as in Example 1. The bulk density of the catalyst is 1.12 kg / l, the BET specific surface area, macropore volume is 0.18, and the average pore radius is 2.0--10 cm. Antimony, vanadium and. titanium is in the catalyst in an atomic ratio of 4: 1: 4. Its content of montmorillonite is 6%, and that of fine silica is 12%. The conversion of 3-methylpyridine is carried out as in Example 1. The average conversion of 3-methylpyridine. 90%. The average yield of 3-cyanpyridine is 88 mol.% Based on the starting 3-methylpyridine, and the volumetric yield is 117 g / l h.
    权利要求:
    Claims (1)
    [1]
    CATALYST FOR PRODUCTION
    Z-DIANPYRIDIDINE by reacting 3-methylpyridine with ammonia and oxygen, including an oxygen-containing compound of antimony, vanadium and titanium, containing components in the atomic ratio of antimony: vanadium: titanium = = 4: (1.0-1.5) :( 2.0 -5.0) and oxygen to saturate the valency of the incoming elements, characterized in that, in order to increase the activity and selectivity of the catalyst, it additionally contains 18-35 wt.% Montmorillonite and highly dispersed silicon dioxide with a specific surface area of 200 m 2 / g with mass the ratio of montmorillonite to silicon dioxide (0.5 -12): 1, the catalyst has a BET surface of 7-43 m 2 / g, micropore volume of 0.18-0.5 cm 3 / g and an average pore radius of (2.0-4.0) 10 cm.
    SLL -. P8.9327
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    同族专利:
    公开号 | 公开日
    EP0059414B1|1985-10-30|
    AT16248T|1985-11-15|
    DE3267083D1|1985-12-05|
    US4447612A|1984-05-08|
    DE3107755A1|1982-09-16|
    EP0059414A2|1982-09-08|
    JPS57156038A|1982-09-27|
    JPH0596B2|1993-01-05|
    CA1164437A|1984-03-27|
    EP0059414A3|1983-01-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3259652A|1961-03-31|1966-07-05|Shell Oil Co|Oxidation of acrolein or methacrolein to the corresponding acid in the presence of an sn-sb-mo catalyst|
    GB1034914A|1964-02-05|1966-07-06|Distillers Co Yeast Ltd|Improvements in or relating to the production of unsaturated aliphatic acids|
    US3927007A|1970-08-08|1975-12-16|God Und Silber Scheideanstalt|Catalysts for the production of aromatic and heteroaromatic nitriles|
    DE2039497C3|1970-08-08|1974-01-17|Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt|Process for the production of antimony-containing catalysts and the use of the catalysts for the production of aromatic and heteroaromatic nitriles|
    CH582151A5|1973-08-10|1976-11-30|Lonza Ag|
    US4051140A|1976-07-01|1977-09-27|The Lummus Company|Preparation of pyridines and nicotinonitrile from piperidines|
    US4284781A|1977-07-28|1981-08-18|The Lummus Company|Supported vanadia catalyst and use thereof for nitrile production|US4876348A|1985-10-29|1989-10-24|The Standard Oil Company|Process for making 3-cyanopyridine|
    JP2615819B2|1988-04-28|1997-06-04|三菱瓦斯化学株式会社|Method for producing cyanopyridine|
    CN1044338C|1994-06-23|1999-07-28|化学工业部北京化工研究院|Catalyst for preparing cyanopyridine by ammoxidation of alkyl-pyridine and its application|
    DE19504283A1|1995-02-09|1996-08-14|Degussa|Process for the preparation of cyanopyridines and suitable catalysts therefor|
    US6200926B1|1995-12-22|2001-03-13|R. P. Fiber & Resin Intermediates|Ammoxidation catalysts for fluidized/moving bed reactors|
    FR2742678B1|1995-12-22|1998-02-20|Rhone Poulenc Fibres|PROCESS FOR THE PREPARATION OF AMMOXIDATION CATALYSTS FOR A FLUIDIZED BED OR TRANSPORTED BED REACTOR|
    US6187943B1|1996-10-24|2001-02-13|Mitsubishi Rayon Co., Ltd.|Process for preparing carbocyclic or heterocyclic nitriles by vapor phase ammoxidation|
    DE19647527C1|1996-11-16|1998-03-12|Degussa|Cyano compounds preparation|
    DE10305650A1|2003-02-12|2004-08-26|Reilly Industries, Inc., Indianapolis|Regeneration of antimony-vanadium-based mixed oxide catalyst e.g. for /gas phase production of nitriles, especially 3-cyanopyridine, by ammonoxidation, especially in situ regeneration, uses gas containing oxygen|
    DE10335454A1|2003-08-02|2005-02-24|Reilly Industries, Inc., Indianapolis|Novel VPO catalysts for use in production of cyanopyridines by ammoxidation reaction of methylpyridines also contain transition metals|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19813107755|DE3107755A1|1981-02-28|1981-02-28|CATALYSTS FOR THE PRODUCTION OF 3-CYANPYRIDINE|LV920369A| LV5194A3|1981-02-28|1992-12-22|Catalyst for 3-cyanopyridine production|
    LTRP520A| LT2108B|1981-02-28|1993-05-06|CATALYST 3-CYANOPIRIDINE GIVES|
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