• 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:
    METHOD OF PREPARING CATALYST FOR oxidation of propylene to acrolein based on oxidic cobalt compounds, molybdenum or tungsten, iron and bismuth, comprising mixing an aqueous solution of ammonium heptamolybdate or ammonium tungstate with an aqueous solution of cobalt nitrate, bismuth and iron, drying and yrokalivanie, characterized in that, In order to improve working conditions and increase the safety of the process, an aqueous solution of ammonium hydroxide containing 50-250 g of ammonia per liter of solution is added to the resulting mixture of solutions at a rate of 20–200 g of ammonia per hour per liter of the mixture until a pH of 6–8 is reached, followed by exposure to the resulting suspension at 20–80 ° C for 2–24 h and filtered. ABOUT)
    公开号:SU1145916A3
    申请号:SU813276205
    申请日:1981-04-24
    公开日:1985-03-15
    发明作者:Деррьян Жан-Ив
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    four
    SP

    The invention relates to methods of preparing catalysts for the oxidation of propylene to acrolein, in particular catalysts based on oxides of cobalt, molybdenum or tungsten compounds, iron and bismuth. A known method of preparing a catalyst for the oxidation of propylene to acrolein based on oxide compounds of cobalt, iron, bismuth, tungsten, molybdenum, silicon, thallium, alkali or alkaline earth metal, consisting in mixing aqueous solutions of ammonium molybdate and para-tungstate ammonium with aqueous solutions cobalt nitrate, bismuth iron, thallium, and an alkaline or alkaline earth metal hydroxide or nitrate added to the resulting mixture. The water is evaporated and the resulting catalyst is calcined. 1. The closest in technical essence and the achieved result to the proposed method is a catalyst for the oxidation of propylene to acrolein based on either oxide compounds of cobalt, molybdenum or tungsten, iron and bismuth, which consists in mixing an aqueous solution of ammonium heptamolybdate or in the mixture of ammonium and aqueous ammonia. solution of cobalt, bismuth and iron nitrates, followed by evaporation of water, drying and calcining the catalyst mass, first at 450-500 ° C for -5 hours, then cooled to ambient temperature The medium is calcined again under the same conditions. A disadvantage of the known methods is the creation of hazardous working conditions due to the fact that the ammonium nitrate resulting from the reaction is an explosive that thermally decomposes at a temperature around the time of the last calcination. The purpose of the invention is to improve working conditions and improve the safety of the process. ,, This goal is achieved in that according to the method for preparing a catalyst for propylene β-oxidation to acrolein based on cobalt oxide compounds, yolib-Deen, or tungsten of iron and bismuth, which involves displacing an aqueous solution of ammonium heptamolybdate or ammonium jungrate with an aqueous solution of cobalt nitrate, i.e. Drying and calcining, to the resulting mixture of solutions is added an aqueous solution of ammonium hydroxide containing 50-250 g of ammonia per liter of solution, at a rate of 20-200 g of ammonia per hour per liter of mixture until p 6-8 followed vscherzhkoy the suspension at 20-80 C for 2-24 hours and filtered. The proposed method allows to improve the working conditions and increase the safety of the process by eliminating the formation of explosive ammonium nitrate. The method consists in displacing an aqueous solution of ammonium heptamolybdate or ammonium tungstate with an aqueous solution of cobalt, bismuth and iron nitrates, while the pH of the mixture drops to pH 1-2. This drop in pH, caused by the presence of nitrates in the second aqueous solution, is accompanied by the precipitation of a solid, a substance based on metals of iron and bismuth. When the pH is raised by the addition of ammonium hydroxide, in particular, to a value higher than the pH of the first original aqueous solution, precipitation of a cobalt-based solid is observed. At the end of the addition of ammonium oxide gvdrat and after filtration a solid phase is formed that does not contain ammonium nitrate, which is after the essence and the obukig. gives the desired catalyst. The liquid phase is an aqueous solution containing mainly formed ammonium nitrate, which also contains traces of metals that make up the active one. After the addition of ammonia has been completed and before filtration, the resulting suspension is heated to 20-180 ° C and maintained at this temperature for 2-24 hours. Heat treatment allowed; It increases the deposition of cobalt and molybdenum or tungsten. The precipitate is dried and calcined. The catalysts obtained by the inventive method (i) are melted in the process of propylene oxidation with air. Example 1, Obtaining a catalyst of the composition With MoCRE, B 1,, 0,. A first aqueous solution of ammonium heptamolybdate is obtained, a solution of 167.6 g (KJ) (MHtO in 760 cm H | p, 0 at ambient temperature 3), preparing a second aqueous solution of nitrates, mixing at ambient temperature the following three solutions: 38 , 4 g of Bi (N0,), 5Hjp in 28.5 cm, acidified in 4 cm of pure nitric acid; 32.1 g of FeCNOj)} x X 9HgO in 25 cm HgO; 230.2 g Co (NO X 6HjO in 150 cm HgO, strongly mix the second nitrate solution at ambient temperature, and add the nitrate solution in the heptamolybdate solution with strong mixing. At the end of the nitrate addition, the bismuth-based precipitate is noted. and iron. Then the solution is added (d 0.926, 184 g NHj / l) at a speed of 5 cm / min. When the pH reaches 6,, 9, i.e. when 1 46 ml of ScOH is added in 30 minutes, the addition is stopped. An additional cobalt-based sediment is noted. The resulting suspension is heated to 60 and maintained at that temperature for 4 hours. Then the suspension is filtered. A precipitate and a filtrate are obtained, the analysis of which reveals the presence of 156 g of NH, NOj, 5.4 g of Co, expressed as metal, and 2.6 g of Mo, expressed as metal Do not detect the presence of iron and bismuth in the filtrate. The precipitate is washed with 1 liter at ambient temperature. The cake is squeezed for 20 hours at 120 ° C, 226 g of solid product is obtained. Then, the dried product is burned at 40 ° C for 6 hours. 19.6 g. This weight loss corresponds to the decomposition products present in the dried product, part of which is ammonium nitrate, not removable in the filtrate. The resulting product has the formula Co, Mo, jFe, i ,, sQ. . The deposition coefficient for cobalt is 88.4%, for molybdenum it is 97% and for (iron and bismuth 100%. This solid product can then be crushed, deposited on a carrier and fired by known methods. Examples 2-4. The emission of various catalytic formulas by changing the pH achieved by adding ammonia.They work in the same way as in example 1, starting from the same solutions of heptamolybdates and metal nitrates, but 164 change the amount of added, and therefore the final pH. The results are shown in Tables 1 and 2. Examples 5-12. The effect of heat treatment after added and before filtering. Work as in Example 1 from the same ammonium heptamolybdate and nitrate solutions, but subjecting the resulting suspension to various heat treatments for 4 hours at different temperatures. Tables 3 and 4 show the results obtained. the absence of heat treatment (Example 9). Carry out the second series of tests, continue to change and maintain the temperature at a constant temperature (80 ° C). The results are shown in Table. 5 and 6. Example 13. Preparation of a catalyst of the formula Mo ", FeviBin /) x. Prepare the first aqueous solution of ammonium heptamolybdate, a solution of 167.6 g (NH) Mo, Og4. 4Ha6 in 760 cm HgO at ambient temperature. A second aqueous solution of nitrates is prepared by mixing at ambient temperature the following three solutions: 230.2 g of Co- (MSZ) j x X 6 Hjp in 100 cm HgO; 16.05 n Fe (NOj) 3 9HaO at 12.5 cm Na.O., 38.4 g of VCLVO5HgO in cm Hg9 | acidified with 4 cm of pure nitric acid. Mix these two solutions, as in example 1. The pH is reduced to 2.2. 125 cm (d 0.926, 114 g / l NHj) are then added at a speed of 5 cm / min. Stop the addition when the pH is -7. Then work as in example 1. The filtrate contains 149 g, 7.9 g of cobalt, expressed as metal fi, 2.4 g of molybdenum, melted in the form of metal, the content of iron and bismuth is below 0.01 g. The weight of solid product. drying at 218 g. The firing weight loss at 15.3g. The resulting product has the formula -9i "Mo, i, (. The precipitate ratio is 83% for cobalt, 97.3% for molybdenum and above 99.9% for iron and bismuth. Example 14: Preparation of a catalyst of formula Cp 1o “Re, 1. They work, as in Example 1, on the basis of the following solutions: 167.6 g (NH,), Sc.0 in 760 cm HgO; 230.2 g Co (NOj) 2 bNgO in 100 cm 16 , 05 g of FeCNO) - 9HgO in 12.5 cm H, 0, 19.2 g of Bi {NOa) 5 in 14.5 cm HgO,. . When both solutions are mixed, the pH drops to 2.35. Again add 120 cm (d 0.926, 184 g / l CW) with a speed of 5 to obtain a pH of 6.6. Then work as in Example 1. The filtrate contains 118 g of NH NOj; 4.2 g of cobalt and 3.41 g of molybdenum, and the content of iron and bismuth is below 0.01 g. The weight of the solid product after drying at 120 ° C is 232 g. The weight loss after calcination at 37 g. The resulting product has the formula Cc, Mo ,, 0. The deposition rate is 91% for cobalt, 96.5 for molybdenum and 99.9% for iron and bismuth. Example 15. The preparation of the catalyst of the formula Co, jMo ,,. Jpj (. Act the same as in example 1, based on the following solutions 167.6 g (t-14) b Mo 0 4-- 4НгО in 760 cm 3, 113 0, 184.2 g of Co (Shz) g of bNgO in 100 cm HgO; 32.1 g of Pe (Shz) g 9H O in 25 cm 38.4 g of BiCNOj}: in 28.5 cm of iHgO acidified with 4 ml of pure nitric acid. When mixed with two aqueous solutions, the pH drops to 1.5. 200 ml (d 0.926, 184 g / lcN3) are added again at a rate of 5 until a pFI of 8 is obtained. Then, it acts as in Example 1. The filtrate contains 134 g NH / jND, less than 0.02 g of cobalt, 16.8 g of molybdenum and less than 0.02 g of bismuth and glands Weight of solid product after drying 215 g. Weight loss after calcination at 32.2 g. The resulting product has the formula Co5, Mo4gr ,, gB1, gO. The deposition coefficient for cobalt is 99%, for molybdenum 80.5 and iron and bismuth are above 99.9% Example 16. Preparation of a Coa-Mo Fe jBi jt catalyst mix The first aqueous solution of ammonium heptamolybdate is obtained by dissolving 167.6 g (W Ob / Mo Ogc 4HtO in 760 cm of water at ambient temperature. A second aqueous solution of nitrates is obtained by crossing at the ambient temperature the following three solutions: 38.4 g of Bi (N03) jX X -5 HgO in 28.5 cm of water, acidified with 4 cm of pure nitric acid (d 1.33); 32.1 g Fe (N03) j 9HaO in 25 cm3 of water; 230.2 g of Co (Shz) d x X 6HgO in 100 cm of water. The second solution of nitrates is vigorously stirred at ambient temperature and added to the heptamolybdate solution with vigorous stirring. At the end of the addition of nitrates (pH 1.7), a precipitate based on bismuth and iron is observed. An ammonium hydroxide solution (d .0.926, 184 g of mH3 / l) is then added at a rate of 5 cm / min. When the pH reaches 6, i.e. after pouring 124 ml of ammonium hydroxide for 30 minutes, the addition is stopped. The addition of cobalt based precipitate is observed. After that, the obtained suspension is heated to 60 ° C and kept at this temperature for 4 hours. Then the suspension is filtered. A precipitate and a filtrate are obtained, the analysis of which shows a content of 220 g of ammonium nitrate J 8.4 g of cobalt per metallic cobalt and 2.6 g of molybdenum per metallic molybdenum. Neither iron nor nickel was detected in the filtrate. The precipitate is washed with 1 g of water at ambient temperature and dried for 20 hours at 120 s, 215 g of solid are obtained. Then the dried product is calcined at 400 ° C for 6 hours. A weight loss of 11.3 g is observed. This weight loss corresponds to the content in the dried product of decomposing substances, some of which are not converted to nitrate ammonium nitrate. The formula of the resulting product, iFe, jBi,. The deposition efficiency for cobalt is 82.0%, for molybdenum 97%, and for iron and bismuth 100%. In the future, this solid can be crushed, deposited on a carrier and calcined by known methods. Example 17. Obtaining a catalyst of the composition Co |, Mo, gRe, g.
    The first aqueous solution of ammonium heptamolybdate is obtained by dissolving 167.6 g (NH,) jMo, Oe4 AHgO in 760 cm of water at an ambient temperature. Prepare a second 5 aqueous solution of nitrates by mixing the following three solutions at ambient temperature: 38.4 g of BKNOj) -5 HjO in 28.5 cm of water, acidified with 4 cm of pure nitric acid 10 (a 1.38); 32.1 g Fe (NOs) 5 x X 9HgO in 25 cm of water; , 230.2 g Co (N05) j {per 100 cm of water.
    The second nitrate solution is vigorously stirred at ambient temperature and added to the heptamolybdate solution with energetic agitation.
    At the end of the supply of nitrates (pH 1.3), a precipitate of 20 based on bismois and iron is observed. An ammonium hydroxide solution (d 0.926, 184 g) is then added at a rate of 5. When the pH reaches 8, i.e. after pouring in 200 ml of ammonium hydroxide for 30 minutes, the addition is stopped. An additional cobalt based precipitate is observed. Then, the resulting suspension is heated to and settled at this temperature for 4 hours. After that, the suspension is filtered. A precipitate is obtained, and the filtrate analysis of which shows a content of 240 g of ammonium nitrate, O g of cobalt “per metallic cobalt and 16.8 g of molybdenum per metallic / n. Neither iron nor bismuth was found in the filtrate. The precipitate is rinsed with 1 liter of water at ambient temperature, dried for 20 hours at temperature of 120 ° C and 215 g of solid are obtained. Then, the dried product is calcined at 400 ° C for 6 hours, a loss of weight of 32 g is observed. This weight loss corresponds to the content of decaying substances in the dried product, some of which are not ammonium peroxidate.
    The formula of the obtained product
    Co, o, j.Fe, i Bi4,2 Oh,
    The deposition efficiency is 100% for cobalt, 82% for molybdenum and 100% for iron and bismuth. This solid can be further crushed, deposited on a carrier and calcined by known methods.
    Example 18. Obtaining a catalyst composition, 2.Re ,,.
     The first aqueous solution of ammonium heptamolybdate is obtained by dissolving 167.6 g of (NH) gMo 760 cm of water at ambient temperature. A second aqueous solution of nitrates is obtained by mixing at the ambient temperature the following three solutions: 38.4 g) X 5HjO in 28.5 cm of water, acidified with 4 cm of pure nitric acid (d 1.33); 32.1 g of Fe (NOj) 3 - 9НГО in 25 cm of water, 230.2 g of CoCNOj) - 6HjO in 100 cm of water.
    The second nitrate solution is vigorously stirred at ambient temperature and added to the heptamolybdate solution with vigorous stirring.
    I At the end of the addition of nitrates (pH 1.3), a precipitate based on bismuth and iron is observed.
    Then a solution of ammonium hydroxide (d 0; 926, 184 g NHj / l) is added at a rate of 5 cm / m3. When the pH reaches 6.9, i.e. after tinting; 146 ml of ammonium hydroxide for 30 minutes, the addition is stopped. An additional cobalt based precipitate is observed. Then, the resulting suspension is heated to and kept at this temperature for 24 hours. Then the filter suspension is heated. Get sediment / and filtrate, the analysis of which shows the content of 235 g of ammonium nitrate; 4.4 g of cobalt per metal and 6.2 g of molybdenum per metal. Neither lezo, nor bismuth were found in the filtrate. The precipitate is 1 liter of water at ambient temperature, dried for 20 hours at which 216 g of solid is obtained, then the eaten product is calcined at 6 hours. Watch; loss weight 15.8 g. This weight loss corresponds to the content in dried : Nominal product of decomposable substances, some of which are ammonium nitrate not transferred to the filtrate
    The formula of the obtained product
    .
    The deposition efficiency for cobalt is 90.6%, for molybdenum 93.2% and for iron and bismuth, t00%. In the future, this solid can
    be crushed, supported and calcined using known techniques
    Example 19. Obtaining catalyst composition Cc, Mo jiFe; ,,, iBi | (gi, 0 (.
    A first solution of ammonium heptamolybdate is obtained by dissolving 167.6 g (NH) .4 AHz.0 in 760 cm of water at ambient temperature. A second aqueous solution of nitrates is obtained by mixing the following three solutions at ambient temperature: 38.4 g of Bi (MOj) j X in 28.5 cm of water, acidified with 4 cm of pure nitric acid (d 1.33); 32.1 rFe (NOj) 3 in 25 cm of water, 230.2 g of CO 2 3) in 100 cm of water.
    The second nitrate solution is vigorously stirred at ambient temperature and added to the heptamolybdate solution with vigorous stirring.
    At the end of the addition of nitrates (pH 1.3), a precipitate based on bismuth and iron is observed.
    Ammonium hydroxide solution (d 0.926, 184 g W / l) is then added at a rate of 5. When the pH reaches 6.9, i.e. After boiling 146 ml of ammonium hydroxide for 30 minutes, the addition stops. Observe the appearance of additional sediment on the basis of cobalt. Then, the resulting suspension is heated to 80 ° C and the booster is heated at this temperature for 2 hours. Then the suspension is filtered. Poluchshbt oyadok and a filtrate, an analise of which shows the content of 230 g of nitrate ag moni, 4.8 g of cobalt per cobalt metal and 3.4 g of molybdenum per metal molybdenum. No iron or bismuth was detected in the filtrate. The precipitate is washed with 1 l of water at ambient temperature. The cake is dried for 20 hours at which 219 g of solid are obtained. Then the dried product is calcined at 400 ° C for 6 hours and a weight loss of 13.4 g is observed. This weight loss corresponds to the content of decomposable substances in the dried product, some of which are ammonium nitrate which has not been converted to the filtrate.
    The formula of the obtained product COyMo j, Fe,) (.
    Salt efficacy for cobalt is 89.7%; for molybdenum, 96.3%; and for iron and bismuth, 100%. This solid can then be crushed, deposited on a carrier and calcined by known techniques.
    Example 20. Obtaining a catalyst composition,) - Ox.
    An aqueous solution of ammonium tungsten is obtained by dissolving 248 g (NH) toWii04r 5H20 in 10 l of water; pH 6jO. To this solution is added a second solution, obtained by mixing 38.4 g of B1 (W3) from 5NYO to 28.5 cm of water, acidified with 3.5 cm of nitric acid (d 1.38), 32.1 g of Pe (NO ) s 9H2.0 in 25 cm of water; 230 g CoCNOj) ;, bNgR in 100 cm of water.
    After adding the second solution, the RC value of 6.5 is maintained by adding dropwise approximately 200 cm of ammonium hydroxide (d 0.920), a precipitate is formed from the beginning.
    The resulting suspension is then heated to 60 ° C for 4 hours, allowing the water to evaporate to a volume of 2.5 liters. The suspensions are allowed to cool, then fg-schrut.
    A precipitate and a filtrate are obtained, the analysis of which shows a content of 225 g. J 19.0 g of cobalt per metallic cobalt and 8.7 g of tungsten per metallic alfram. Neither iron nor bismuth was detected in the filtrate. The precipitate is washed with 1 liter of water at ambient temperature. The precipitate is dried, then calcined at 450 ° C for 6 hours. Weight 26 g; composition is as follows: GoejLW ,; , This solid can be crushed, applied to a carrier and calcined.
    Test catalysts.
    The various catalysts described in Examples 16-19 are tested to produce acrolein from propylene, air, water, or hydrogen in a reactor 50 cm high and 2.1 cm in diameter, containing 100 cm of catalyst consisting of alumina balls with a rough coated surface with an average diameter of 4.8 mm, covered with 23.1 wt.% of the active phase with respect to the total weight of the active phase + but: itel.
     Gaza; coming out of the reactor, representing a mixture consisting of gas, oxygen, water, propylene, rabbin, acrylic acid, vinegar 114591612
    hydrochloric acid, acetaldehyde and hydroxy- X (indicates the degree of conversion of carbon OB (CO, COg,), nor, i.e.,
    the number of moles of reacted propylene 21 g; the number of moles of propylene at the inlet of the reactor; S is the selectivity for product X, i.e. an attitude
    the number of moles of the resulting products, „1. "I
    the number of moles of converted propylene
    ft is the output of product X (this is what the proposed product means.: sob creates a safe environment for "XftSjf) yes by eliminating the formation of
    Test results 16-19 result of solid ammonium nitrate. In addition, deny in table. 7, where indicated. Provides the ability to accurately
    Cj is propylene; A - acrolein; AA control of the final composition of cataliac acrylic acid.
    Table 1
    21,648.4 2.6 th, 01 0.01 215
    3158 3.6 3.6, 01 0.01 227
    41532.4 3.6 0.01 0.01 / 233 T, С I Example The resultant catalysis is fo1 1ul 550C (Mo, 2Bi ,, Fe, 660C (Mo, Bi4,, Fe, o, .1 HLH,,
    table 2
    11.4 82 97.2 99.9 99.9 17.7 92.3 96 99.9 99.9 22.6 95 96 799.9 99.9 Table 3 The composition of the filtrate, g Co MoBi Fe 4.6 3, 60.01 0t 16242.3 0.01 0.01 1593.8 3.6 o, -01 o, from 1605.1 6.2 0.01 0.01
    13
    1145916
    U Table
    Table 5
    T a b l and c a 6
    99.9 99.9 99.9 99.9 99.9 99.9
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PREPARING THE CATALYST FOR THE OXIDATION OF PROPYLENE IN ACROLEIN based on oxide compounds of cobalt, molybdenum or tungsten, iron and bismuth, which includes mixing an aqueous solution of ammonium heptamolybdate or ammonium tungstate with an aqueous solution of cobalt nitrate, drying, bismuth, in order to improve working conditions and increase process safety, an aqueous solution of ammonium hydroxide containing 50–250 g of ammonia per liter of solution is added to the resulting mixture of solutions at a rate of 20–200 g ammonia per hour per liter of the mixture until pH 6-8 is reached, followed by exposure of the resulting suspension at 20-80 ° C for 2-24 hours and filtration.
    SU <„, 1145916 f 114591
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    同族专利:
    公开号 | 公开日
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    引用文献:
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    US3624146A|1965-08-25|1971-11-30|Grace W R & Co|Process for the production of acrylic acid from propylene|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8009314A|FR2481146B1|1980-04-25|1980-04-25|
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