• 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:
    The invention relates to aldehydes, in particular to the preparation of methacrolein or acrolein, which are used in the synthesis of polymers. The goal is to increase the selectivity of the process. The preparation is carried out by catalytic oxidation of isobutylene or propylene with atmospheric oxygen on a shell catalyst. The latter consists of an inert carrier with a grain size of 4 mm and the shell of the active catalyst substance of composition NI 4.5-6 , CO 0.6-2 , FE 1.6-2 , BI 0.8, surrounding it and firmly associated with it. -2 , P 0.8-1 , MO 12 O 45.9-52.5 and additionally 0.2-5 wt.% Samarium per SM 2 O 3 and 0.17-0.3 wt.% Alkaline metal per oxide. The catalyst has a calcined steatite carrier with an average surface roughness of 25 microns according to DIN 4768/1, measured with a Hommel profiler, and a continuous shell of containing layered silicate or its mixture with highly dispersed silicon oxide in a 1.3: 1 mass ratio of active catalyst substance. The oxidation process is carried out at 345-367 ° C, a pressure of 1-1.5 atm with a molar ratio of olefin to oxygen and water of 1: (1.7-2.2) :( 2.1-2.3). The method provides an increase in the selectivity of up to 82.3-84.3% against 80% in the known method.
    公开号:SU1604154A3
    申请号:SU823479652
    申请日:1982-05-27
    公开日:1990-10-30
    发明作者:Арнтц Дитрих；Прешер Гюнтер；Хайлос Йоханнес
    申请人:Дегусса Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the synthesis of aldehydes, in particular, to an improved method for the preparation of methacrolein or acrolein, which are used in the production of polymers.
    The purpose of the invention is to increase the selectivity of the process.
    Example 1. The starting material for the preparation of the active phase of a catalyst is obtained by the fact that to a solution of 1.31 kg of nickel nitrate Ni (NO) j, 0.01 kg K1Hy, 0.17 cobalt nitrate
    Co (Shz) 2 6H.jO and 0.65 kg of iron nitrate He (Shz) s 9H2 0 in 3.04 kg of water are added successively with potent i iSII solution, 0.0005 kg of samarium oxide in 0.005 kg 38% - nitric acid, as well as a solution of 2.12 kg of ammonium molybdate (W4) bMo702D H2O in 2.41 kg of 3.0% phosphoric acid, a solution of 0.39 kg of bismuth nitrate B1 (KO) s 0.7. kg 0.8% nitric acid and 0.6 kg pyrogenic silicic acid (Aerosil 200). The resulting material is an additical 4
     about
    the roller coil is dried and calcined for 5 hours at 545 ° C in a bushing, and then ground in a pin mill. Thus obtained powder of the preliminary stage of the catalytically active material has a particle size distribution from 5 to 80 µm (90%) with a maximum of 32 µm and a coefficient of thermal expansion Q at 88 ,.
    The composition of the active phase is as follows: Ni / j.s:; WITH 0.6; Fe.6; j Ro, and i Mo ,, 2. O45,) 0.17 mWd of alkali metal oxide +0.2 wt.% 15
    By suspending 7.5 kg of this preliminary-stage powder with 6.2 kg of water with the addition of 0.6 kg of glucose as a binder and 0.5 kg of pentaerythritol as a poro-20 body, a suspension is prepared for the starting shell material. As carriers for this material of the first stage, burned steatite beads with a diameter of 4 mm are taken, which 25 have practically no pores, and the surface of the balls is rough (average roughness value is 25 µm according to DICK 4768/1) and their coefficient of thermal linear expansion with a ra-JQ veins 90..10 / ° C.
    6 kg of this carrier is loaded into the dryacoater 500 and in it by blowing in air preheated to 80 ° C at a speed of 2 m / min, and also due to the rotation of the drum at 20 rpm, the material is mixed and liquefied.
    The material put into such a movement is sprayed with JQ spray for 2 minutes using a double nozzle 0.4 l. The application of the remaining suspension by spraying is controlled by the temperature of the air leaving the boiler; that the same humidity is observed in the shell 45 all the time. In this case, the temperature of the exhaust air is first reduced from 39 ° C at the end of the suspension application (after 70 minutes) and the application of the suspension is increased from 0.096 to 0.104 eg l / min.
    After the suspension process has been completed, the compaction phase is carried out for 5 minutes while the drum continues to rotate for 5 minutes, and after that the 20-minute drying phase of the rotation of the drum is 1 rpm. After drying overnight, the blowing agent is decomposed under bushing with an average processing time of 35
    55
    Q
    five
    0 5 Q
    Q 5 g
    five
    five
    ki 15 min Catalyst activation is also carried out in bushing at 550 ° C for 15 minutes.
    The coefficient of thermal expansion of the preliminary catalytic mass is 10 / ° C, the carrier coefficient is steatite 90jlO / ° C, if 90.-10 is 100%, then 88-10 is 97%, the difference is 3%.
    The shell catalyst obtained in this way has a hard shell without cracks. The average diameter of the resulting shell catalysts is 5.25 mm with a deviation from the standard of 0.3 mm. The abrasion is determined in the Friabil torus of La Roche by obkutyuan and falling at 20 rpm and it is less than 2 after 7 minutes, i.e. less than 0.2 wt.%. After heat treatment. During the .100 cycles of heating and cooling, in which the catalyst is heated for 250 to 400 seconds and cooled for half an hour, cooling does not significantly deteriorate to abrasion and is 0.2%.
    . In the fall test, i.e. with a free fall of 100 ml of catalyst through a tube 3.4 m long, having an internal diameter of 20 mm on a solid base, the proportion of faults to less than 2 mm is 0.03%.
    50 ml of the prepared catalyst is loaded into a tubular reactor with an inner diameter of 16 mm, heated by the Left bath to (at pressure il, 0 atm). With the introduction of 0.25 mol per hour; propene, 46 nl of air and 9.5 g of water / (molar, the ratio of olefin to oxygen and water is 1: 1.7: 2.1):. the conversion is 96.5%, i.e. the yield of acrolein (based on the used propylene) is 84.3%, and the total selectivity for acrolein and acrylic acid (based on the used propylene) is 95.9%,
    PRI mme R 2. A pre-stage powder is prepared according to the method described in Example 1. To do this, to a solution of 1.75 kg of nickel nitrate Ni (NOa) 2 X6H2.0, 0.03 kg KNOj, 0.6 kg Cobalt nitrate Co (NOg) and 0.81 kg of iron nitrate Fe (Shz) s1 3.04 kg of water are sequentially added with stirring a solution of 0.147 kg of samarium oxide SmgOj, in 1.591 kg of pollutant% nitric acid, solution 2, 1 kg of ammonium molybdate (III) HolO fl: {gO in 2.41
    ten
    a mash consisting of an inert carrier with a grain size of 4 mm and the surrounding and tightly bound shell of active catalyst substance of the composition .5-6.0, 6-Z, .6-Z ,,, 8
    Mo g045Я-52, y also additionally 0.2-5 wt.% Samarium calculated on SffljOj and 0.17-0.3 wt.% Of an alkali metal calculated on oxide, characterized in that, in order to increase the selectivity process, the oxidation is carried out on a shell catalyst of annealed steatite carrier with an average surface roughness of 25 µm according to DIN 4768/1, measured by a profiler
    . , -, -7 7P Hommel, and a continuous shell of co
    Atit is the same 90 10 / C, 82, 10 containing layered silicate or its pressure is from 90% to 90%, the difference is 9%. mixture with highly dispersed oxide cream- The composition of the active phase is as follows:
    Ni, 6.o; content; him; R.O. m, 205-.5 +
    +0.3 wt.% Alkali metal oxide + + 5 wt.%.
    Out of 5.5 kg of this preliminary stage powder with the addition of 0.4 kg of glucose in 4.5 kg of water and 6 kg of steatite carrier, respectively, are prepared.
    kg of 3.4% phosphoric acid, a solution of 0.97 kg of bismuth nitrate BKNOj) 5H2iO in 0.7 kg of 0.8% of nitric acid, 0.7 kg of montmorillonite and 0.6 kg of pyrogenic silicic acid (Aero- forces 200). The resulting material is dried on a roller dryer at 140 ° C for 5 hours at 535 ° C, calcined in a bushing, and then ground in a pin mill. The powder produced in this way has a particle size distribution from 5 to 80 µm (90%) with a maximum of 35 µm and a coefficient of thermal expansion equal to 82 1-0-L C.
    The coefficient of thermal expansion of the preliminary catalytic mass, the ratio of the carrier ST15
    nor in a mass ratio of 1.3: 1 active catalyst substance prepared by mechanically shaking a portion of the carrier and simultaneously loosening by blowing upwards at 39-48 C of a fluidized gas stream, which strengthens the sheath catalyst resistant by stirrer 1 in the dryacater 500. The abrasion in the L-Rosh freeabel torus is 0.25 wt.%.
    Test 50 ml manufactured ka30
    spraying the carrier in countercurrent to the gas previously obtained by suspension of the active catalyst substance containing a binder and a preformer, in increasing quantity - as - as the shell thickens from
    the catalyst is carried out in the same way as the catalyst substance, and partly as in example 2, but only the temperature removal and application of the salt bath spray is 367 ° C, and the suspension is maintained at a pressure of 1.5 atm, the molar ratio determined by the ratio of olefin to oxygen and the mixture of carrier and active catalysis is 1: 2.2: 2.3. The conversion is 0 mash, and the coefficients are 95.1%, the yield of methacrolein (in thermal expansion of the carrier and calculated per used isobutylene) of the powdered product is 82.1%, and the total selection is selected from each other by 3 -9%, and the potency for methacrolein and methacrylogenesis and spraying of an acid sheath (in terms of use, is compacted by continuation of the strengthened foam isobutylene) is 84% stirring, then the mechanical re-suggested method allows for increased stop mixing, mater al dried
    in the flowing gas stream and after decomposition of the added blowing agent 50, it is held for 15 minutes at
     and carry out the oxidation process at a temperature of 345-367 C and a pressure of 1-1.5 atm with a molar ratio of olefin to oxygen and water equal to
    to increase the selectivity to 82.3 - 84.3% against 80% in the known method.
    权利要求:
    Claims (1)
    [1]
    The invention The method of producing methacrolein or acrolein by catalytic oxidation of isobutylene or propylene with oxygen of the air on the shell of the catalyst is 55 1: 1.7-2.2: 2.1-2.3.
    1604154
    ten
    15
    holding layered silicate or its mixture with highly dispersed oxide of cream-
    nor in a mass ratio of 1.3: 1 active catalyst substance prepared by mechanical shaking of the carrier portion and simultaneous loosening by blowing upwards at 39-48 ° C with a pseudo-fluid stirred-gas 30
    类似技术:
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    同族专利:
    公开号 | 公开日
    DE3125061A1|1983-01-13|
    ES512340A0|1983-07-01|
    EP0068193A1|1983-01-05|
    DE3260134D1|1984-06-07|
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    BR8203690A|1983-06-21|
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    JPH0427973B2|1992-05-13|
    US4442308A|1984-04-10|
    ES8307700A1|1983-07-01|
    DE3125061C2|1984-03-15|
    引用文献:
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    ES2027712T3|1987-02-17|1992-06-16|Nippon Shokubai Kagaku Kogyo Co., Ltd|CATALYST FOR THE OXIDATION OF AN OLEPHINE OR A TERTIARY ALCOHOL.|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE3125061A|DE3125061C2|1981-06-26|1981-06-26|Process for the production of acrolein or methacrolein by catalytic oxidation of propylene or isobutylene or tertiary butanol in oxygen-containing gas mixtures|
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