• 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:
    1458704 Acrylic acid NIPPON SHOKUBAI KAGAKU KOGYO CO Ltd 18 March 1974 [22 March 1973] 11920/74 Heading C2C [Also in Division B1] Acrylic acid is made by contacting a gas containing 1-10% v acrolein, 1-15% v O 2 , 5-60% v H 2 O and 20-80% v inert gas at 200-350‹ C., 1-10 atm. and a space velocity of 500-8000 hr.<SP>-1</SP> (NTP) with a catalyst comprising an inert porous carrier and catalytic material of empirical formula wherein a=12, b=2-14, c=0À1-6, d=0-12 and e = 0-6, d + e> 0 and Z is an alkaline earth metal.
    公开号:SU1032999A3
    申请号:SU742011058
    申请日:1974-03-21
    公开日:1983-07-30
    发明作者:Вада Масахиро；Янагисава Исао；Ниномия Мичикадзу；Охара Такаси
    申请人:Ниппон Шокубаи Кагаку Когио Ко.,Лтд (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of acrylic acid by catalytic vapor phase oxidation of acrolein with oxygen-containing gas. In order to obtain acrylic acid by catalytic vapor phase oxidation of acrolein, a catalytic composition is usually required, which ensures a high degree of conversion of acrolein and high selectivity with respect to acrylic acid, is relatively easy to produce and maintains a stable catalytic capacity in temenia of a long time period. The catalytic 1 composition should also provide high quality, easily cleaned acrylic acid. Conventional acrylic acid, obtained by catalytic vapor phase oxidation of propylene or acrolein, contains traces of contaminants that cannot be removed by conventional purification methods; The presence of such contaminations often causes unexpected complications. For example, it may take a long time or the same to carry out the polymerization reaction. the required reaction time may be too wide and it may be difficult to add an initiator to the polymerization process or to obtain a high-quality polymer of high molecular weight. Therefore, special methods are needed for the purification of acrylic acid obtained as a result of the catalytic vapor-phase reaction of acrolein oxidation. A number of catalysts for the production of acrylic acid by catalytic vapor-phase oxidation of acrolein are known. Thus, it is known for using a catalyst containing molybdenum and vanadium J. A method is also known using a catalyst containing molybdenum, vanadium h, tungsten and silica gel. However, these methods ensure insufficient product yield. The maximum yield per pass does not exceed 87%. There are known methods using a catalyst containing molybdenum, vanadium, silver and copper f3 of a catalyst containing molybdenum, vanadium, tungsten and maranets 3, as well as a catalyst containing molybdenum, vanadium and antimony L5J. These methods provide increased product yield in a single run. The disadvantages of these methods are due to the difficulty of catalyst preparation, the use of precious metal, as well as the low level of spatial velocity, oxidation. The closest to the proposed technical essence and the achieved result is a method for producing acrylic acid by a phase-by-phase oxidation of a gas mixture containing, obd: acrolein 1-10; oxygen 1-15; steam 5-60 and 41ert gas 20-80, by passing it at 200-350С and a flow rate of 500-8000 using catalysts containing oxygen-containing molybdenum, vanadium, tungsten and / or copper compounds deposited on porous inert carrier 6j, However The known method does not provide a sufficiently high quality acrylic acid. The purpose of the invention is to improve the quality of the target product. The goal is achieved by the fact that according to the method of producing acrylic acid by vapor-phase oxidation of a gas mixture containing,% by volume: acrolein 1-10, oxygen 1-15, steam 5-60 and inert gas 20-80 by passing it at 200-350 ° C and a space velocity of 500-8000 tc — over a molybdenum-vanadium-tungsten-copper oxygen-containing catalyst deposited on a porous inert carrier, as the molybdenum-vanadium-tungsten-copper oxygen-containing catalyst, a catalyst is used, additionally containing an oxygen-containing compound alkaline-earth- metal at the atomic ratio of molybdenum: vanadium | y.: alkaline earth metal: tungsten: copper, equal to 12: 2-14: 0.1-6: 0-12: 0-6, provided that the composition of the catalyst is includes oxygen-containing compound of tungsten and / or copper. Oxygen is present in the catalyst in the form of a complex metal oxide or its acid salts. The oxygen content in the catalyst depends, therefore, on the atomic ratio. various metal elements c. catalytic oxide. A useful inert porous carrier: a body for the catalyst used may be a powder or granulated product: 0-alumina, silicon carbide, pumice, silica, zirconium oxide or titanium oxide. The material of the carrier can also be used material that in the process of granulation of pre. rotates into porous granules, such as glass. The support should have a surface area of no more than 2 porosities of 10-b5 and a pore size distribution such that at least 80 of all pores have particles 1-1500 microns in diameter. Particularly preferred carriers have a surface area of no more than 1 m / g, a porosity of 30-651 and no less than 90% of all. The pores have particles with a diameter of 1-1500 m. The catalyst used is prepared, for example, by introducing a carrier into an aqueous solution in which the molybdenum compound is dissolved, for example, ammonium molyb, a vanadium compound, for example ammonium metavanadate, and an alkaline earth metal compound, for example strontium, tungsten dinenera, for example ammonium paratungstate, and a copper compound such as copper nitrate. The aqueous solution is evaporated to dryness and the dried product is calcined at 300 SOO C, preferably 350-600 ° C. The initial metal compounds can be not only ammonium salts or nitrates, it is also acceptable to use: any oxholes metaxhov, organic acid metal salts, nonorigate salts: metal, complex metal compounds, organic metallic compounds mt.d., if only they form during calcination catalytically active oxide. Acrolein-containing gas from direct oxidation of propane or its mixture with air or oxygen may be used as the source gas. The byproducts found in such acrolein-containing gas, such as acrylic acid, acetaldehyde, acetic acid, carbon dioxide, carbon monoxide, or unreacted substances, such as propylene or propane, do not adversely affect the process. The process can be carried out not only using a fixed but also a fluidized bed of catalysis; torus. The acrylic acid obtained by the proposed method is of good quality. It is easily cleaned with conventional cleaning methods to produce acrylic acid that does not contain contaminants. The degree of conversion, selectivity, and the output per run are defined. Lena follows. The number of reactivePerebrate is 35 eo ein ...,. Calling Number of moles of acrolein injected Number of moles of the formed acSelek-Eilic acid. - a, tivnost Number of reactive l. Acrolein mol of moles Number of acrylic acid moles formed by yield, PLO ONE ------- C ------ x100 mol% gon Moles of acrolein Example 1. Preparation of the catalyst. B 20 (W ml of heated water with stirring injected 52 g of ammonium paratungstate, k3 g of ammonium metavanadate, 169 g of ammonium molybdate and 8.6 g of strontium nitrate. The resulting solution was mixed with an aqueous solution of 3 g of copper nitrate in 500 ml of water. Formed the mixture is poured into a porcelain evaporator over a water bath and, with stirring, 500 ml of a carrier consisting of granules of α-alumina with a particle size of 3-5 mm are introduced. The mixture is evaporated to dryness so that all these compounds are deposited on the carrier and then the material is calcined. in t For 5 hours at kOO ° C. The resulting catalytic oxide (It has the following composition: IV4. V a, 4, 2. The surface area of the used carrier is not more than 1 m / g, the porosity is 2%, and the pore distribution is such that 92 of all pores falls on particles .30-250 microns. Carrying out the reaction. O-shaped stainless steel tube with a diameter (
    25 ml are charged with tOO ml of the obtained catalyst and immersed in a saltpeter bath (molten salt of nitric acid) heated to 25 $ C. A gas mixture containing vol,% of acrolein, 51 vol. air and 5% vol. steam. The reaction is carried out with a speed of 3000 (at normal pressure).
    The results are presented in table 1.
    Cleaning up Formed in. as a result of the reaction, the gas is passed through a condenser-collector in order to obtain an approximately aqueous solution of crude acrylic acid. The condensed liquid is extracted with ethyl acetate at a 1: 1 volume ratio of liquid to solvent. The resulting organic liquid phase is sent to a distillation column, where the solvent and low-grade components are distilled off. The crude components obtained at the bottom of the column are sent to a distillation column with 10 plates. In the cleaning process, the pressure at the top of the columns is 70 mmHg The temperature above is 77.5 ° C and the reflux ratio is 1: 1.

    Polymerization test. The obtained purified acrylic acid 1 containing 100 h / MPS. used as a stabilizer hydroquinone monomethyl ether is diluted with 50 vol. deionized water and placed in an experimental tube with a diameter of 16 and a length of 180 mm together with and, by weight of acrylic acid used as the initiator of the polymerization of ammonium persulfate. The polymerization is carried out in an oil bath, the temperature of which is maintained equal. The time from immersion of the pilot tube into the oil bath until the maximum heat generating temperature is reached is 15 minutes.
    The verification of polymerizability indicates that the lower required for achieving the maximum calming temperature for such acrylic acid, the acid is more stable during storage and contains less contaminating impurities. The use of high-quality acrylic acid with a shorter time to reach the maximum heat-generating temperature ensures high
    material conversion rate during polymerization. At a low catalyst concentration, a high molecular weight polymer is obtained.
    Stability test 8 och obtained as described (O, acrylic acid is added with O,% hydrochlorinone monomethyl ether, and the mixture is placed in a sealed tube with a diameter of 16 and a length of 120 mm. The tube is lowered into the oil bath. No polymer was detected after this.
    Example 2. (comparative). Example 1 is repeated, except that ammonium paratungstate, strontium nitrate and copper nitrate are not used. Get the catalyst next. th composition:
    with the catalyst, the reaction described in example 1 is repeated.
    Example 3 (Comparative) Repeat Example 1, but ammonium para-tungstate and copper nitrate are not used. The catalyst is obtained as a catalytic oxide of the following soil:
    Sr.
     Che
    0.5
    Repeat the reaction described in Example 1.
    Example h (comparative) Repeat the experiment described in Example 1, except that strontium nitrate is not used to form the catalyst. Get the catalyst having the following composition:
    °, Le A: L
    With this composition, the reaction described in example 1 is carried out.
    The results are presented in Table 1.
    Untreated acrylic acid is purified as described in Example 1. Purified acrylic acid is tested for polymerization and stability as in Example 1 ,. It turns out that the time to achieve maximum max: heat transfer temperature is equal to (3 min. The polymer does not form even after 9 hours.
    Example 5 The reaction described in example 1 was carried out, with the exception that the temperature of the saltpeter bath was kept equal and the spatial velocity h. The degree of acrolein conversion was 95.0, the acrylo-i selectivity of acid was 37.0%, and the yield of acrylic acid for one run 96.3%. The condensed liquid is purified from the reaction gas as in Example 1. The purified acrylic acid is tested for polymerization and stability, as described in Example 1. The time to reach the maximum heat transfer temperature is 15 minutes. No polymer formation is observed even after 9h. ... Example 6. The reaction described in example 1 is repeated, except that the temperature of the saltpeter bath is 25 ° C and the spatial velocity is 5000 hours. The conversion of acrolein is 97.5, the selectivity for acrylic acid is 98.5, the yield of acrylic acid is in. one run 9b, 0. The condensed liquid obtained from the reaction gas is purified as in Example 1. The purified acrylic acid is tested for polymerization and stability as in Example 1. At the same time, the time to reach the maximum heat generating temperature is 20 minutes, and the formation of the polymer is not observed even after 9 hours. Example 7: The reaction described in example 1 is repeated, except that a gaseous mixture of 5 vol.% Is used. ak zolein, 50 vol. air and kS vol.% steam at a spatial velocity of 3000 hours. The degree of acrolein conversion reaches 100%, the selectivity for acrylic acid is 97.3%. The condensed liquid obtained from the reaction gas is cleaned, the CCP is described in Example 1, and the purified acrylic acid is tested for polymerization and stability, as in Example 1. At the same time, the time required to reach the maximum heat generating temperature is 15 minutes. it is observed even after 9 hours. Example 8. The reaction is carried out analogously to example 1, except that the gaseous mixture consists of 7 vol.% acrolein, A8 vol.% air and 5 vol% steam. The conversion ratio of acrolein is 99.1%, the selectivity for acrylic acid 998 acid is 97.0, and the yield of acrylic acid per run is 96.1%. The condensed liquid from the reaction gas is purified as in Example 1, and the resulting acrylic acid 71 is tested for polymerization and stability, as in Example 1. It turns out that the time required to reach the maximum heat generating temperature is 20 minutes, and polymer formation is not observed even after 9 hours . Example 9-15. The catalysts are prepared analogously to example 1, but using different alkaline earth metals. The reaction is carried out in various modes. The results obtained are presented in Table 2 (for quality of the component. Z, fine powdered manganese oxide, beryllium, calcium, barium, and strontium are introduced as nitrate salts). In each of examples 9-15, the liquid condensed from the reaction gas is cleaned as described in Example 1. The purified acrylic acid is tested for polymerization and stability, similar to riipHMepy 1. At the same time, the time required to achieve the maximum heat generating temperature is 16, 18 , 20, 18, 17, 18 and 1b min, respectively. In all examples of polymer formation, it is not observed even after 9 hours. EXAMPLE 16 The procedure of Example 1 is repeated, with the exception that a carrier is used which is silicon carbide granules with a diameter of 3-5 mm and a specific surface area not more than 1, porosity 41, and such a pore distribution that 90% of all pores are particles with a diameter of 5-100 microns. The conversion rate of acrolein is 99.5%, the selectivity to acrylic acid is 97%, and the yield per acrylic acid is 96.9%. The condensed liquid obtained from the reaction gas is purified as in Example 1. The purified acrylic acid is tested for polarizability and stability as in Example 1. The time required to reach the maximum heat generating temperature is 15 minutes, and polymer formation is not observed even after 9 m of aging. Example 17. By catalytic vapor-phase oxidation of commodity propylene (more pure), a molybdenum bismuth catalyst gives a gaseous mixture of the following composition,% by volume: Acrolein 5 01 Propylene + propane 0.58 Acrylic acid + acetic acid O., 60 Nitrogen 51 Oxygen . . 6.50 ParZ, 0 Other2.31 The gaseous mixture is introduced into a reaction tube filled with the same catalytic composition as in Example 1, the reaction is carried out at a spatial velocity of 3000 hours at a saltpetre bath temperature of 255 ° C, the conversion rate of acrolein is 99.7, the selectivity to acrylic acid 97.5t, the yield of acrylic acid in one pass is 97.2%. When calculating these indicators, it is assumed that propylene, propane and acrylic acid do not enter into a mutual reaction. The condensed liquid obtained from the reaction gas is purified as described in Example 1. The purified acrylic acid is tested for polymerization and stability as in Example 1. The time for reaching the maximum heat generating temperature is 21 minutes. Polymer formation is not observed even after 9 hours. Example 18-21. The pharmaceutical compositions are prepared in the same way as Example 1, except that. The carriers indicated in Table 3 are used. The catalysts are used, the reaction is carried out as in Example 1. The purification procedures, tests for polymerization and stability are compromised as in the example. 1. The results obtained are summarized in table. - Examples 22-33. The reaction is carried out analogously to Example 1, with the exception that various mixtures or catalysts of different composition are used. The results are summarized in Tables 5 and 6. 9910 Primer. The reaction is carried out analogously to example 1, then with the exception that the source gas is a reaction gas formed during the oxidation of a gas mixture consisting of 5 parts of propylene, IP obd of oxygen; 10 vol% water vapor; about. nitrogen; 0.75 about L carbon dioxide and 0.35 about. carbon monoxide, in reaction-. torus filled with catalyst composition. K orb,. when for 2.7 s. The feed gas has the composition., Vol.%: Acrolein, 3, acrylic acid 0.3, propylene 0.2, oxygen, 5, water vapor 15, nitrogen 73.9, carbon dioxide 1.09 and carbon monoxide 0.51 . The conversion rate of the original acrolein is 99.5%. acrylic acid selectivity 97 ,, acrylic acid yield per one run of 96.9% Acrylic acid, obtained by the proposed method, has a higher quality than the second slot obtained by a known method. The improved quality of acrylic acid can be judged on the basis of polymerization tests, at which the time required to achieve maximum temperature under purified polyacrylate acid is determined under polymerization conditions. The shorter the time needed to achieve maximum heat generation temperatures, the more significant the advantage is in terms of more conversion to a polymer with a high molecular weight at low concentrations. catalyst. In accordance with the proposed method, the time required to reach the temperature at which maximum heat generation is achieved is 15-20 minutes, i.e. about a third of the time required for acrylic acid of its own, obtained by no known method. In addition, the acrylic acid obtained by the proposed method is highly stable. Stability tests determine whether or not any polymer is formed upon prolonged exposure in the presence of a hydrbhinonone monoethyl ether. The data obtained show that the acrylic acid obtained by the proposed method does not form a poly; after 9 hours of exposure;
    Table 3
    18 ot- Aluminum oxide. 1 (50) silicon carbide
    o-alumina
    (75%) silica
    20 Silicon Carbide
    21 oi.-Aluminum oxide
    (BS%) "cl 35
    silicon oxide
    "(75-1000 microns)
    3-5 95
     G kQ (50-1200 microns)
    3-5 95
    1 55 (75-500 microns) 3-5 93
    (20-180 microns) 3-5 100
    III
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    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING ACRYLIC ACID by vapor-phase oxidation of a gas mixture containing, vol.%: Acrolein 1-1.0; oxygen 1-15; steam 5 * 60 and inert gas 20-80, by transmitting it at 200-350 v and a space velocity of 500-8000 H- 4 over molybdenum vanadium-tungsten-copper oxygen-gas. with a supported catalyst supported on a porous inert support, and so on; in order to improve the quality of the target product, a catalyst additionally containing an oxygen-containing compound is used as the molybdenum-vanadium-tungsten-copper oxygen-containing catalyst alkaline earth metal with an atomic ratio of molybdenum: vanadium: alkaline earth metal: tungsten: copper, equal to 12: 2-14: 0.1 -6: 0-12: '0-6, provided that the composition of the catalyst. The oxygen-containing compound of tungsten and / or copper is necessarily included.
    "3 1 1032999
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    同族专利:
    公开号 | 公开日
    GB1458704A|1976-12-15|
    CS185221B2|1978-09-15|
    AU6680574A|1975-09-25|
    JPS5246208B2|1977-11-22|
    NL158162B|1978-10-16|
    DE2413206A1|1974-10-10|
    NL7403773A|1974-09-24|
    BE812613A|1974-07-15|
    JPS49117419A|1974-11-09|
    US3954855A|1976-05-04|
    IT1005874B|1976-09-30|
    FR2222349B1|1978-06-02|
    DE2413206B2|1978-03-09|
    BR7402283D0|1974-11-19|
    CA1029393A|1978-04-11|
    DE2413206C3|1978-11-16|
    FR2222349A1|1974-10-18|
    PL89868B1|1976-12-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3567773A|1966-05-21|1971-03-02|Nippon Kayaku Kk|Production of unsaturated aliphatic acids|
    JPS4911371B1|1970-10-23|1974-03-16|Nippon Catalytic Chem Ind|
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    US3799978A|1971-12-23|1974-03-26|Nippon Catalytic Chem Ind|Process for the preparation of unsaturated carbonyl compounds|JPS533369B2|1973-03-30|1978-02-06|
    US4163862A|1974-09-13|1979-08-07|Standard Oil Company |Preparation of unsaturated acids|
    US4138366A|1976-05-05|1979-02-06|The Standard Oil Company|Process for producing unsaturated aliphatic acids and catalysts therefore|
    US4532365A|1982-09-20|1985-07-30|The Halcon Sd Group, Inc.|Conversion of alkanes to unsaturated aldehydes|
    US5177260A|1989-11-06|1993-01-05|Nippon Shokubai Kagaku Kogyo Co., Ltd.|Method for production of acrylic acid|
    DE4431949A1|1994-09-08|1995-03-16|Basf Ag|Process for the catalytic gas-phase oxidation of acrolein to acrylic acid|
    DE19622331A1|1996-06-04|1997-12-11|Basf Ag|Process of heterogeneously catalyzed gas phase oxidation of propane to acrolein|
    FR2760009A1|1997-02-27|1998-08-28|Atochem Elf Sa|PROCESS FOR MANUFACTURING ACRYLIC ACID FROM ACROLEIN BY REDOX REACTION AND THE USE OF A SOLID COMPOSITION OF MIXED OXIDES AS A REDOX SYSTEM IN THE SAID REACTION|
    US6384275B2|1998-09-23|2002-05-07|Lg Chem, Ltd.|Method of producing acrylic acid using a catalyst for acrolein oxidation|
    KR100204729B1|1997-03-17|1999-06-15|성재갑|Preparation of ctalyst for partially oxidizing of acrolein|
    JP3943284B2|1999-05-27|2007-07-11|株式会社日本触媒|Acrylic acid production method|
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    RU2361853C2|2003-08-14|2009-07-20|Басф Акциенгезельшафт|Method of producing acrolein and/or acrylic acid|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP3183073A|JPS5246208B2|1973-03-22|1973-03-22|
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