• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    1499020 Preparation of maleic anhydride NIPPON SHOKUBAI KAGAKU KOGYO CO Ltd 1 Dec 1975 [2 Dec 1974] 49309/75 Heading C2C [Also in Division B1] Maleic anhydride is made by the vapour phase oxidation of benzene at 330-450‹ C. with an O 2 -containing gas in the presence of a catalyst comprising a porous inert support having an alkali metal content, calculated as oxide, of at most 0-3 wt. per cent, an apparent porosity of 20-70%, a B.E.T. surface area of 0À01- 1 m.<SP>2</SP>/g., and supported thereon a catalytic composition comprising V, Mo, P, Na and K in the molar ratios, calculated as oxides of the elements in their highest valency states, of 1 : 0À3-1À2 : 0À005-0À05 : 0À03-0À2 : 0-0À05.
    公开号:SU728693A3
    申请号:SU752196603
    申请日:1975-12-01
    公开日:1980-04-15
    发明作者:Сузуки Хидео；Сато Такахиса；Кубота Тацуо；Осака Сигеми；Комацу Сигеру
    申请人:Ниппон Шокубаи Кагаку Когио Ко, Лтд (Фирма)；
    IPC主号:
    专利说明:

    one
    The present invention relates to the manufacture of catalysts for the production of maleic anhydride with 1 benzene oxide.
    A known catalyst for the oxidation of benzene to maleic anhydride, containing vanadium pentoxide, molybdenum trioxide, tungsten trioxide and phosphorus pentoxide on a carrier, molten alumina or silica gel 1.
    The known catalyst allows to obtain maleic anhydride in a yield of 84-95% by weight.
    The immediate solution of the problem is a catalyst for the oxidation of benzene to maleic anhydride containing vanadium pentoxide, molybdenum trioxide, phosphorus pentoxide, silver oxide and sodium oxide in a molar ratio of 1: (0.2-0.7): (0, 01-0.1) :( 0.01-0.05) :( 0.01-0.3) on the carrier, for example, pumice 2.
    The specified catalyst provides the yield of maleic anhydride in the oxidation of benzene at the level of 94100 wt.%. However, the known catalyst has the disadvantage that, despite its high initial yield level, it has a short lifetime and loses catalytic activity in a short period of time, for example, the optimum reaction temperature rises by about 1 g, and the yield drops by 3- 5 wt.%.
    The aim of the invention is to increase the stability of the catalyst.
    This goal is achieved by the fact that, as a carrier, the catalyst contains silicon carbide or oC-alumina with a content of 0.05-0.3% by weight of alkali metal oxide with a porosity and a surface area of 0.02-
    5 1 m / g with the following content of components, wt.%: Vanadium pentoxide 2,16-11,53; molybdenum trioxide 0.4-5-8.3; phosphorus pentoxide 0.01 - 0.5; sodium oxide is 0.02-1.03 and the carrier is the rest.
    The catalyst according to the invention provides maleic anhydride, read with a yield of 95-99 wt.%, While this output is maintained in
    5 for the duration of time.
    The catalyst was prepared as follows.
    The initial mixture of catalytic substance is added to the aqueous solution.
    0 hydrochloric acid, sulfuric acid or a similar inorganic acid, or oxalic acid or a similar organic P. acids to produce a solution of the catalytic substance. It is preferable to use a solution of the catalytic substance in the form of an aqueous solution; however, a mixture with an organic solvent such as dimethyl forms or ethane oxide can be used. Catalytic substances, contained in the catalyst solution, are applied to a sponge carrier by soaking this carrier with a solution and evaporating the solution before drying, and then the carrier is calcined in an oxidizing atmosphere to form an active catalyst. In addition, the same results can also be obtained by spraying a solution of catalytic substances on a neutral carrier, which is preheated in a cup for evaporation with a jacket or in a rotating drum. In this method of spraying, the carrier is thoroughly mixed so that the catalyst components evenly distributed and at the same time maintain the temperature of this carrier from 150 to, preferably from 200 to 250 ° C. Simultaneously with the deposition of the catalyst, the volatile components of the solution are evaporated and removed. The support thus treated is then subjected to calcination in an oxidizing gas stream, n-for example, air, in order to obtain an active catalyst. Calcination is performed at 300-BOO C, preferably at 400-500 ° C for 2--10 h, preferably 4-8 h. The amount of the catalytically active substance thus obtained which is on the completed cathode torus (most of these components are is in the form of oxides), is in the range of from 3 to 15 g, preferably from 7 to 12 g per 100 g of carrier. To obtain maleic anhydride using the catalyst of the invention, a reaction tube made of steel or stainless steel with an internal diameter of 15-35 mm, preferably 20-30 mm, is used in which the catalyst is packed and which is immersed in a bath of molten salt. oxygen passes through a layer of this catalyst in the pipe, where the oxidation of benzene to the vapor phase occurs. The temperature of the molten salt in the bath is maintained at a level of from 330 to, preferably from 350 to 420 ° C., air is usually used as a gas containing molecular oxygen, although gaseous oxygen diluted with an inert gas can be used, such as nitrogen gas, carbon dioxide. The concentration of the feed gas supplied to the reaction zone, in the case where air is used as the gas containing molecular oxygen, ranges from 15 to 40 liters of air / g of benzene, preferably from 20 to 30 liters of air / g of benzene, B In the case where gaseous oxygen diluted with an inert gas is used as the oxidizing agent, oxidation can occur under the same conditions. The volumetric rate of such a gas reaction mixture may be in the range of from 1500 to 4000, preferably (at a rate; 1 conditional 2000-3000 twi x). KaTajtn3aTOp according to the invention retains high activity and selectivity, which is characterized by a significant yield of mA. Either anhydride is from 95 to 100 wt.% for a significant period of time, of the order of 1 hour or more, and there is no need to increase the temperature of the salt melt. In the following examples and control runs, all the yields are calculated by the following equation: Yield (%) IfS - where benzene is used as a feedstock, which is calculated as 100% benzene. The carriers used in the invention are prepared as follows. Self-caking silicon carbide support. High-frequency silicon carbide in the form of granules with a particle size of 50 to 200 mesh with the addition of an organic binder, such as polyacrylic acid, starch or carboxymethylcellulose, is stirred, melted and heated to a temperature of 2100 to 2400 ° C to obtain sintering carbide particles silicon in the decomposition and recombination of part of silicon carbide. The carrier is made from C (, OXID aluminum. O.-High-purity aluminum oxide in the form of granules with particle sizes from 50 to: 200 mesh with the addition of the required amount of water, cellulosic material and 3-7 wt.%, Calculated on the weight of C.- aluminum oxide clay material containing silica, gamma alumina, calcium, magnesium and small amounts of alkali metals, mixed, melted and calcined at 1100-1400 s. During calcination, water and cellulosic material are burned to ensure the required properties and design of the finished carrier, wherein the pore diameter and pore volume are adjusted, and the clay material connects the particles of aluminum oxide. Example 1. In 1500 ml of distilled water, 272 g of oxalic acid is dissolved, then 230 g of ammonium metavanadate are added to this solution. 69.4 g of ammonium molybdate, 11.2 g of trisodium phosphate and 2.5 g of sodium nitrate are mixed to form a catalyst solution. Then this solution is sprayed onto 1.8 g of saturated silicon carbide in the form of spherical particles with an average diameter of 7 -8 mm in the heated from the outside rotating ms drum, and this carrier is maintained at 200-250 ° C, and then the carrier treated in this way is calcined for 8 hours in an air stream in order to obtain a finished catalyst, the composition of the catalyst in mole is as follows: V2.05: MoO3 Pa 5 : 1: 0.40: 0.015: 0.06, and the amount retained is 8 g / 100 g of carrier. The catalyst contains, wt.%: V2.O55,45 MoOz1,74 P2., 0,06, 11 Carrier Other The used carrier from silicon carbide has 98,7 wt.% Carbide krni, contains 0.4% of impurities silicon dioxide Si02, 0.3% alumina AC2O, j, 0.2% iron oxide 0.0 total and. This carrier has an apparent porosity of 38% and (BET) surface area of 0.05 m / g. The total volume of pores having a diameter of at least 10 μm reaches 95% of the volume of pores with a diameter of 100 μm and a less than 25 ml stainless steel reaction tube is placed in a salt bath with a catalyst so as to obtain a catalyst bed of height 2 , 5 m; at that, the temperature of the salt bath is set at 370 ° C, and the concentration of the supplied gas is 25 liters of air / g of benzene, and hectares are fed at a volumetric rate of 2500 hours for the oxidation reaction. With the passage of such a reaction, a yield of maleic anhydride of 95% by weight is obtained and this high yield is maintained for a long time. a continuous period of 1 year without the need to increase the temperature of the salt bath. Example 2. The same method is used as in example 1, except that ammonium molybdate is used in an amount of 130 g, and trisodium phosphate and sodium nitrate are replaced by 4.5 g of ammonium phosphate and 8.3 g of sodium carbonate, whereby a complete catalyst is obtained with the following molar composition: VuOs: MoO3: –1: 0.75: 0.02: 0.08, and the amount retained is 8 g / 100 g carrier. The catalyst contains, wt%: 4.53 2.69 0.07 0.12 Carrier 92.59 Benzene is oxidized on the thus obtained catcher in the same manner as in Example 1, except that the temperature of the salt bath is maintained at 380 ° C, while the yield of maleic anhydride is 99 wt.%. This output is maintained for a long period of continuous reaction lasting 1 year without the need to increase the temperature of the salt bath. Example 3. Using the same method as described in example 1, except that ammonium molybdate and trisodium phosphate are used in amounts of 156 g and 29.8 g, respectively, and sodium nitrate is excluded, a complete catalyst with a spatially molar composition is obtained :: MoO-j: P.: 1: O, 90: 0, 04: 0.12, and the amount retained is Bg / 100g of carrier. Catshizator contains, wt%: VgOg-4.15 MoOg2 94 0.13 0.17 Carrier 92.61 Oxidation of benzene is performed in the same way as in Example 1, except that the temperature in the salt bath is kept at level To obtain a yield of maleic anhydride of 96 wt.%. This output is maintained for a long time for a continuous reaction lasting 1 year without the need to increase the temperature of the salt bath. Control experiment 1. The catalyst was prepared in the same manner as in example 2, except that the carrier and the benzene oxidation process presented below were carried out under the same conditions as in example 2. The carrier used was spherical particles silicon carbide with an average diameter of 7-8 mm, which consists of, wt%: silicon carbide &amp; SiO 14,5; 3.9; FsyO 0.4; CaO 0.8; MgO 0.4 and NagO + 2.2. the carrier has an apparent porosity of 42% and (BET) surface area of 0.8 m / g, where the total pore volume with a diameter of at least 10 microns is 95% of the total pore volume with a diameter of 100 microns or less.
    Catalya-iTop contains, wt.%:
    5.08
    VgOj
    2, 96
    hOOg
    0.03

    Oh, Jaa „0
    Carrier91,75
    With a continuous cycle, the week is 1 IU at the temperature of the salt bath Z90c, the output of maleic anhydride ;; a 91 wt. after 3 months of operation, the temperatures of the salt bath rose to, and the yield decreased to 88 wt.%. The catalyst is then removed and the potassium and sodium content in the surface of the catalytic substance and the potassium content in the carrier are determined by using X-ray fluorescence analysis, atomic absorption analysis and using an X-ray microanalyzer to confirm that the concentration is
    potassium and sodium v.;; -; j; i. ; i iecKO i substance increases, while G-, while the concentration is 1;: - the amount in this carrier is significant5; about g ;; izahegs.
    Control experiments 2-6. The catalysts listed in Table 1 are prepared using starting compounds for preparing ataliators, such as ammonium metavanadate, ammonium molybdate, mono s-yunium phosphate, sodium nitrate and potassium nitrate, and also use Tafnl nosi-gel and , the same method as in example 1, the oxidation of benzene is performed using this catalysts in the same way as 5 as in example 1. The optimum temperature-g1 of the salt bath and the output of maleic 1hydride after a continuous cycle of 1 month for each reactions are given in table. one.
    t a b l i ts a. one
    Example 4, B150O ml of distilled water, dissolve 258 g of oxalic acid, then add and dissolve, g: amymonium metavanadate 230; Ammoy molybdate 139, trisodium phosphate 22.4; Sodium chloride 3.5 and kgssi sulfate 2.6, the solution is stirred and a solution of the catalytic substance is obtained This solution is then applied to an alumina carrier in the form of cylindrical granules with a diameter of .6 mm and a height of 6 mm by spraying onto 1.8 kg of carrier, which is maintained at 200-250 ° C in an externally rotating drum, and then is dripped into the air stream for 6 hours to obtain a complete catalyst with the following molar composition: MoO3: P, 0j: 1: 0.30: 0.03: O: 12: 0.015 and the applied amount is 10 g catalytic substance / 100 g of carrier.
    The catalyst contains, wt%: V2.O56,52
    MOS4,13
    PiOj- 0.15
    Na, 2.00,27
    .KgO0.05
    Media 88.88
    The carrier used from o (.- A € .jO.j contains 95.5 wt.% Alumina and as impurities,%: SiO / 2 3.5; Ge.2. Oz 0.2; Sar 0.2; MDO 0.1 and NajO + 0.15, while the apparent porosity is 55%, and (BE1) surface area is in the order of 0.07 m / g and the total pore volume with a diameter of at least 10 µm reaches 100% total pore diameter not exceeding 100 microns.
    A stainless steel reaction tube with an internal diameter of 25 mm is placed in a bath of molten salt and filled with catalyst to form a catalyst bed 2 m high, while the temperature of the melt is maintained at a level. The source gas mixture is introduced into this reaction tube at a volume velocity of 2800 at a benzene concentration of 25 liters of air / g to perform: acidification. During the continuous au. For 6 months, the yield of maleic anhydride in the order of 95 to 96 wt.% is maintained without increasing the temperature of the salt bath.
    Control experiment 7. The catalyst was prepared in the same manner as in Example 4, except that a different carrier was used, and the oxidation of benzene was carried out in the same manner as in Example 4.
    Use 1.8 kg of the carrier of aluminum oxide in the form of spherical particles with an average diameter of .5-6 mm, which consists of, wt.%: 203 SiO2l2; 0.15; CaO 0, B5; MDO 0.05 and + K ,, O 0.6. The apparent porosity of such a carrier is 59%, (BET) the surface area is about 0.1, and the total pore volume with a diameter of at least 10 microns is 95% of the total pore volume with a diameter not exceeding 10 microns
    The catalyst has a composition, wt.%: V20jr5,93
    3.76
    MOOS 0.14 0.24 0.46 Carrier 89.47.
    Control experiment 13. The catalyst was prepared in the same way as in example 2, except that a different carrier was used, and the oxidation of benzene was carried out in the same manner as in example 1. 2.3 kg of irregularly shaped particles were used as carrier. molten carrier of alumina with dimensions of 7-8 mm, which consists of, wt.%: with aluminum oxide 99.8; SiOg. 0.3; , 04 and + 0.05. Seemingly with the porosity of this carrier
    With a continuous cycle, the yield of maleic anhydride at the salt bath temperature of the S90s is 93% by weight after 1 month of work, although the optimum temperature of the salt bath has increased to 425 ° C, and the yield of mashainic anhydride has decreased to 88% by weight after 6 months. Thereafter, the catalyst is removed and analyzed for the content of potassium and sodium in the catalytic substance and for the content of potassium in this carrier in order to ensure that the content of potassium and sodium in the catalytic substance increases, while on the other hand, potassium content in a given
    5, the carrier is significantly reduced compared to the catalyst before it is used.
    Control experiments 8-12. The catalysts are given in table. 2, prepared
    0 using starting materials for catalysts: ammonium metavanadate, ammonium molybdate / monoammonium phosphate, trisodium phosphate, sodium chloride, potassium carbonate and use the same carrier as in example 4,
    5 and the same method as in Example 4. The oxidation of benzene is carried out using these catalysts. Optimum salt bath temperature and maleic anhydride yield
    0 after a continuous cycle of 1 month are summarized in table 2.
    table 2
    is 9%, and (BET) the surface area is about 0.01 m / g and the total pore volume with a diameter not exceeding 100 microns is very small. The catalyst contains weight. %: V, O 3.54; MoOj 2.1; P2 .Os 0.06; 0.09; carrier 94, 21. When using this catalyst, maleic anhydride is obtained 91% by weight at the temperature of the salt bath. In this catalyst, the catalytically active layer on the surface of the carrier is peeling so that after 6 months of continuous operation the reaction tube becomes unsuitable because of the extremely high pressure that occurs due to clogging of such a catalyst.
    Control experiments 14-17 (restriction MoO-s).
    Exit 1 month after the start of the reaction.
    Control experiments 18-21 {restriction PjOs The catalysts listed in Table. 4, obtained using different amounts
    Exit after 1 month from the start of the reaction.
    Control experiments 22-25 j adjusting the size of the oxide particles
    (restriction of porosity), aluminum, amount of cellulose
    Prepare a carrier consisting of dust and melting point. Catalyst.%: Alumina 95.5; SiOj 3.5; congestion indicated in Table 5 is prepared
    iPejOg 0.2; CaO 0.2; MDO 0.1 using such a carrier
    Na.j, D + K 0.15. In the process of the ego-cc, the porosity is varied by measure 1 in the same manner as in the feed.
    17
    As in example 1
    25
    23
    The catalysts shown in Table 3 are prepared using different amounts of ammonium molybdate in the same manner as in Example 1 and the addition of amounts of MoOj affects the catalytic activity and selectivity in the same manner as in Example 1.
    -Table
     in the same way as in Example 1, the same tests are carried out.
    The results are shown in table 4. Table 4
    Table 5
    400
    91
    0.05
    390
    95
    0.05
    Exit after 1 month from the start of the reaction.
    Control experiments 2b-29 (limited surface area).
    A. A spherical, self-caking Sic carrier having a porosity of 23% and a BET surface area of 0.01 m / g is prepared by adding cellulose powder to SiC powder with a particle size of 150 May and a purity of 98.7%, containing,% by weight: SiO20.4; ACgO 0.3; Ge20eO, 2; and + K, O 0.09, substances mixUEOT and sintered at 2300С.
    B. A spherical, self-caking Sic carrier with a diameter of b mm, having a porosity of 24% and 0.03 m / g BET surface area, is prepared by sintering at 2100 ° C in the same way as the carrier A.
    C. Aluminum powder having a particle size of 150 mesh, mixed with
    26
    As in example 1
    Exit after 1 month after the start of the reaction.
    Control experiments 30-31, jacnpeplot porosity).
    Catalysts are obtained with the use of Continuation of Table 5
    with a binding agent and a cellulosic powder, the mixture is molded into a sphere having a diameter of 6 mm, and the sphere is sintered at 1200 ° C. The composition of the carrier consists of, wt%: alumina 95.5; SiOi 3.5; 0.2; CaO 0,2; MgO 0.01 and NaoO + 0.15. The porosity is 35%, and the BET surface area is 0.85.
    D. A carrier having a porosity of 36% and a BET surface area of 1.25 is prepared by sintering at 1100 ° C in the same way as the carrier B.,
    The catalysts indicated in Table 6 are prepared using the above four types of carriers, respectively, in the same manner as in Example 1. The results are shown in Table 6.
    Table 6
    390
    92
    the names of the carriers, which are listed in table 7, respectively, in the same way as in example 1,
    Table 7
    Physical properties of carriers are given in table 8.
    Table 8
    The test results for catalysts are given in Table 9.
    The physical properties of the carriers are listed in Table I.
    Table 11
    The test results are given in table.
    T 1 b l and c and
    How in
    D
    390
    91.5 example 1
    31
    B
    375
    96.5
    Output after I g and with from the start of the reactions
    Control experiments 32-33 limiting alkali in the carrier),
    The catalysts are obtained by using the carrier indicated in table. respectively in the same way as in example 1.
    IO table
    Table 12
    Control experiments 34-37 (limiting the number of media). . Catalysts are prepared by varying the amount of support and are tested for initial activity and yield of catalysts.
    The results are shown in Table. 13.
    Table 13
    87.5
    430
    权利要求:
    Claims (2)
    [1]
    1. The patent of England No. 1205111,
    cl. C 2 C (C 07 C 51/54), published. 1968.
    [2]
    2. US patent 3535346, cl. 260-346.8, pub. 1970 (prototype).
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    同族专利:
    公开号 | 公开日
    GB1499020A|1978-01-25|
    PL105127B1|1979-09-29|
    IT1052463B|1981-06-20|
    IN142639B|1977-08-06|
    BE836017A|1976-03-16|
    JPS5164487A|1976-06-03|
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    FR2293430A1|1976-07-02|
    US4036780A|1977-07-19|
    FR2293430B1|1979-01-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2967185A|1957-05-29|1961-01-03|Scient Design Co|Preparation of maleic anhydride and catalyst thereof|
    US3156706A|1960-12-14|1964-11-10|Petro Tex Chem Corp|Production of dicarboxylic acid anhydrides by the catalytic oxidation of aliphatic hydrocarbons|
    US3226337A|1960-12-24|1965-12-28|Hoechst Ag|Process for producing a catalyst for the oxidation of olefins and diolefins to unsaturated dicarboxylic acids|
    FR1322127A|1961-02-01|1963-03-29|Scient Design Co|Catalyst used in particular for the preparation of maleic anhydride|
    US3211671A|1962-07-16|1965-10-12|Chemical Process Corp|Oxidation catalyst|
    US3255211A|1963-04-19|1966-06-07|Petro Tex Chem Corp|Preparation of dicarboxylic acid anhydrides|
    US3288721A|1963-10-02|1966-11-29|Petro Tex Chem Corp|Vanadium-phosphorus catalyst containing alkali metals|
    BE703829A|1966-09-14|1968-02-01|
    US3917655A|1969-10-22|1975-11-04|Prolizenz Ag|Oxidation of benzene to maleic anhydride using a new catalyst|JPS5519206B2|1976-09-06|1980-05-24|
    JPS5637050A|1979-09-04|1981-04-10|Ube Ind Ltd|Preparation of catalyst for preparing unsaturated acid|
    US4760153A|1985-03-26|1988-07-26|Nippon Shokubai Kagaku Kogyo Co., Ltd.|Process for producing maleic anhydride|
    EP1516659B1|1999-09-29|2006-12-13|Ibiden Co., Ltd.|Honeycomb filter and ceramic filter assembly|
    US20070105713A1|2005-11-10|2007-05-10|Intevep, S.A.|Hydrogenation catalyst with improved textural properties|
    CN104549544B|2013-10-29|2018-01-19|中国石油化工股份有限公司|Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application|
    FI127288B|2015-06-12|2018-03-15|Teknologian Tutkimuskeskus Vtt Oy|Method and apparatus for preparing a chemical compound|
    CN109201095A|2017-07-04|2019-01-15|中国石油化工股份有限公司|A kind of benzene oxidatoin catalyst for preparing cis-anhydride and the preparation method and application thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP13699574A|JPS555379B2|1974-12-02|1974-12-02|
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