• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    o f t h e D I S C L O S U R E The invention relates to an improved process for the production of a formamide, wherein a current of a gas containing carbon monoxide is reacted at elevated temperature (50-200.degree.C) and pressure (5-110 bars) in a reaction zone with a recycled current of liquid reaction mixture containinga) a nitrogen-containing compound selected from the group consisting of ammonia, a primary alkylamine and a secondary alkylamine(e.g. monomethylamine or dimethylamine);b) a methanolic solution of an alkali metal or earth metal methoxide as catalyst, andc) the formamide produced as reaction product, part of the current of liquid reaction mixture being withdrawn in order to recover the formamide therefrom. The characteristic feature of the invention consists in that the recycled liquid reaction mixture is used for sucking and dispersing the current of gas in the reaction zones. Advantages of the process are: excellent heat exchange, high productivity and yield, absence of solid deposits on the internal surfaces of the apparatus, lower operating pressures and temperatures, use of apparatus of smaller dimensions, suppression of recycling of carbon monoxide, continuous operation etc.
    公开号:SU725554A3
    申请号:SU772460652
    申请日:1977-03-11
    公开日:1980-03-30
    发明作者:Куто Вилли；Рамиуль Жан
    申请人:Юцб С.А. (Фирма)；
    IPC主号:
    专利说明:

    In this connection, over time, the formation of a solid precipitate of the catalyst occurs, which is the cause of blockage of pipelines and valves of the installation, as well as the formation of a solid scale on the heat exchange surfaces. Over time, the heat exchange from this deteriorates more and more. The third complication is that in the presence of moisture, alkaline or alkaline earth methylate reacts with carbon monoxide to form alkaline or alkaline earth formate, which also dissolves poorly in the reaction mixture and also creates manufacturing difficulties as described for alkali or alkaline earth methylate. In tab. 2 shows the solubility of sodium formate in the DMF / CH3OH system at room temperature.
    table 2
    The catalyst activity significantly loses its activity due to the transition to alkaline or alkaline earth formate, which does not catalyze the process. However, the relatively high pressure and process temperature significantly increases the investment and operating costs.
    The closest technical solution to the claimed is the method in which the reaction mixture is recycled between the reactor and the heat exchanger. Circulation is provided by a venturi tube into which, as a moving medium for a liquid amine – catalyst reaction mixture, the solvent is injected under pressure with carbon monoxide. The method provides an effective removal of the heat of reaction, but over time, catalyst precipitate begins to form, gradually reducing the throughput of the reaction mixture in the pipelines and reducing the heat transfer between the reaction mixture and the cooling surface of the heat exchanger. The dispersion of gas bubbles in a liquid medium becomes coarse, as a result of which the gas-liquid contact surface is insufficient. The process temperature is 50-200 ° C, the pressure is 5-110 atm.
    In this method, a reactor-heat exchanger-pump loop is used to circulate the fluid. The liquid mixture is pumped into the venturi pipe from the throughput
    ability not less than 50% higher than the capacity sucked at atmospheric pressure under the influence of only the force of suction of the gas stream of the liquid mixture. As a result, the distribution of gas bubbles is improved and their size is reduced, the contact between the liquid and gaseous phase is improved. Due to the presence of the pump, the tendency of solid deposits of the catalyst, 3, due to the turbulent nature of the flow, is reduced.
    However, on an Industrial scale, this method has disadvantages.
    Thus, the need arises to recycle unreacted carbon monoxide. However, before being re-introduced into the reactor, the residual carbon monoxide must be freed from the volatile components trapped by it. Then, before mixing with the fresh gas fed into the reactor, the exhaust gas must be re-compressed. This provides for additional investment, i.e., almost doubles the cost of installation. The consumption of energy by the compressor of the recirculation line is also significant, and the cost of the installation itself and its operation incur additional costs.
    Productivity is not optimal, and the temperature and pressure conditions are quite high.
    The aim of the invention is to simplify the process and increase its productivity.
    This goal is achieved in that the method of producing formamide, mono- or dimethylformamide is carried out in the reaction zone by reacting a carbon monoxide gas or gas containing it with a liquid mixture mixture containing ammonia, mono- or dimethylamine, an alkali metal methylate solution as a catalyst using the recycling of the product between the reactor and the heat exchanger and dispersion, at a temperature of 50-200 ° C and a pressure of 5-110 atm with the selection of part of the reaction product to isolate the target Recreatives Products. A distinctive feature of the process is the recycling of the liquid reaction product, which is used to suck and disperse the carbon monoxide gas stream in the reaction zone.
    Thus, in contrast to the known method, where carbon monoxide is used as the driving medium for the reaction mixture, the liquid reaction mixture is used as the driving medium for carbon monoxide (or its containing stream). This difference affects the cost of the method as well. as there is no need to recycle carbon monoxide. This eliminates significant investment and operational costs. In addition, the process is carried out at a more moderate pressure and temperature than in the known, with the best performance. 5. Target product yield It is obtained almost quantitative. The method can be carried out continuously. FIG. 1 shows the process; in fig. 2 shows a graph of the effect of co-10 sodium sodium methoxide on process performance. The apparatus consists of a reaction chamber 1, a circulation pump 2, a heat exchanger 3, a device 4 for suctioning 15 and dispersing carbon monoxide. The direction of circulation of the liquid reaction mixture is indicated by arrows. The device 4 comprises a perforated plate through which thin jets of the reaction-20 liquid mixture are passed, striking the impact plate and forming a mist with the gaseous phase. In this way, a close connection of the gaseous phase and the liquid phase is provided. The device is presented in the form of a Ven-25 tour tube, although it is possible to use any device capable of ensuring the aspiration of the gas phase by the liquid phase with obtaining an extremely close connection between the two phases. -30 Carbon monoxide (or its gas-containing mixture) is fed at a constant flow rate through conduit 5 to the intended: top of chamber 1 for the gas phase. Ammonia, primary or secondary-35. Amine containing a certain amount of methylate dissolved in methanol It is supplied with a constant flow rate through conduit 6 under the phase separation level. gas and liquid. The amine and catalyst 40 can be fed separately. , Gases (mainly inert gases containing very small amounts of carbon monoxide) leave chamber 1 through line 7. The pressure in the apparatus is maintained at a constant flow rate of reagents loaded and valve 8, which provides the desired reaction pressure. The products entrained with inert gas are retained by the condenser-50 torus 9. This condenser is useful only if very dilute carbon monoxide is used. The reaction mixture is removed from the apparatus through a valve 10 controlled depending on the level of the liquid reaction mixture 11 in the reactor chamber and the amount of the reaction mixture withdrawn from the system at any time in proportion to the amounts of reagents injected .60 To prevent the pump 2 from getting undissolved in the reaction mixture dispersed gas phase, necessary. due to the threat of cavitation damage, give the reaction chamber a height sufficiently high to 65 6 so that the undissolved gas bubbles (blatts density differences) can return to the interface between the gas and liquid phases without being caught by the pump 2 and entering the liquid phase circuit . The pump output should be high enough to ensure good heat exchange between the reaction chamber 1 and heat exchanger 3 and to ensure a constant temperature in the reaction chamber within 50-200 ° C, preferably 60-100 ° C, as well as to ensure the creation of a gas and liquid contact surface phases are on the order of preferably 1000-200Q liquid phase. In the heat exchanger, heat is exchanged between the liquid reaction mixture and the heating or cooling medium indirectly through the heat exchange surface. The pressure in the process of implementing the method is 5-110 atm, preferably 10-25 atm. The carbon monoxide used in the process of the invention may be pure carbon monoxide or a gas mixture containing inert gases, for example hydrogen, nitrogen, a hydrocarbon, etc., with the content of carbon monoxide in the gas mixture being charged being 20-100 vol. %; preferably 50-100 about. % Care must be taken to ensure that carbon monoxide or the gas mixture containing it has an extremely small amount of water, for example, less than 5 hours per million, because water destroys the catalyst to form an alkali formate precipitate. The minimum water content requirement must be observed for all substances used in the process: ammonia, monomethyl or dimethylamine. The molar ratio of the reagents in the method according to the invention — carbon monoxide and ammonia or mono- and dimethylamine — is maintained between 0.2 and 2.0, but ecjfn is only desirable to obtain formamide, preferably 0.2-1.0. In addition, it should be borne in mind that the methanol used to dissolve the alkali methylate reacts with carbon monoxide to form methyl formate. Therefore, according to one of the technological variants of the method according to the invention (it is also possible to obtain a product containing formamide (or methyl substituted formamide) and a certain amount of methyl formate. In this case, an excessive content of carbon monoxide is used in relation to the stoichiometric amount of amine. the more methyl formate, the more methanol is used. In this case, the ratio of carbon monoxide to amine is preferably 1.0-1.4. The separation of formamide (including methyl-substituted th) of methyl formate in the reaction product is carried out by virtue of
    Different boiling points of formamide, meanol and methyl formate:
    Composition
    T. Kip., ° C (mm Hg. Art.)
    Formamide 105-106 (I)
    Monomethylformamide
    180-185
    (760) Demethylform153
    (758)
    Amide Methanol (760)
    65 methyl formate
    31.5 (760)
    The sodium methoxide catalyst is used in the form of a solution in methanol with a concentration of 1-30 wt. %, preferably 1 to 5 weight. % The amount of catalyst added (E based on 100% methylate) is 0.2-4 wt. %, preferably 0.4-2.5 wt. % relative to ammonia or amine used.
    The yield obtained from the process of inventing formamides is obtained in a practically quantitative manner. In practice, it is 95-100 mol. % relative to ammonia or amine. The yield of the reaction product is a function of the carbon monoxide partial pressure in the gas mixture. With the increase in CO content, the output grows and becomes, with technically pure CO, equal to at least 95% with respect to carbon monoxide.
    Due to a very good heat exchange, high productivity is provided, a significant liquid reaction ratio is ensured by not only good stability of the reaction temperature and optimal contact of the gas and liquid phases, but also the absence of deposits (alkali metal or formate scale) on the internal surfaces of the apparatus, Particularly on heat exchange surfaces. The formation of a solid precipitate is maintained by the turbulence created by the pump, in a suspended state, i.e. the problem of the formation of solid deposits is generally eliminated. In addition, the method makes it possible to use (as applied to) various amounts of catalyst, different pressures of carbon monoxide, different temperatures, different circulation coefficients of the liquid reaction mixture, and simultaneously obtain formamide and methyl formate in one apparatus.
    In addition, a high filling ratio of the apparatus is achieved in the process, i.e., the liquid reaction mixture has a volume of at least 80% (usually not 90%) of the total volume of the apparatus. STO; It creates the possibility of a dramatic reduction in the cost of constructing and installing the apparatus for the same given hourly productivity of the product. The productivity and yield of the reaction product are increased due to the increased contact surface between the gas and the liquid.
    In the following examples illustrating the invention, an apparatus is used, the total effective volume of which is 60 liters. The pump for circulating the reaction mixture is adjusted to the flow rate, ensuring the obtaining of the contact surface of the gas and liquid phases, equal to 1200 liquid phases. The liquid phase takes up a volume of approximately 50-55 liters in the apparatus. The fill factor of the total useful volume of the apparatus is 83-91%.
    Example 1. In the apparatus serves 113.2 kg / h of a mixture containing 69.65 weight. % dimethylamine, 29,70 weight. % methanol and 0.55 weight. % sodium methoxide (0.79 wt.% relative to dimethylamine). At the same time, 59.5 kg / h of 14.5% purity carbon monoxide oxide are introduced. All reagents practically do not contain
    water i coj. The working pressure is maintained at 22 ata, and the temperature is 90 ° C using a heat exchanger through which water flows with a temperature of 60 ° C. To maintain a constant level of fluid hourly
    161.5 kg of a mixture containing 78 wt. %, i.e., productivity is equal to 126 kg / h of 100% dimethylformamide. The yield with respect to carbon monoxide is 95 mol. %, the degree of conversion of dimethylamine to 98.5%. P1-transformed dimethylamine and methanol are separated from dimethylformamide by distillation and returned to the reaction. Under the conditions described, the performance of dimethylformamide is
    2.1 kg / hl reactor capacity (126: 60).
    Comparison of these results with the results of the known 3 methods is shown in Table. 3
    Table 3
    According to the invention, at the same pressure and lower temperature, a productivity of about 5 times is achieved.
    famous.
    Example 2. Work is performed at the same pressure as in example 1 (22 atm), but at an even lower temperature of 7 ° C. Download 35.2 kg / h of a solution containing 69.61 weight. % dimethylamine, 29,86 weight. % methanol and 0.52 weight. % sodium methoxide (0.75 wt.% relative to dimethylamine), 16.3 kg / h of carbon monoxide at 99.2% frequency. The same liquid level is maintained in the reactor at the expense of extracting a 50.2 kg / h mixture containing 77.7% dimethylformamide. In this way, 39 kg / h of dimethylformamide (100%) are obtained. The productivity of dimethylformamide is 0.65 kg / h-l reactor capacity. The CO yield is 92 mol. %, the degree of conversion of dimethylamine 98%.
    This example shows that at 70 ° C (and not 120 ° C), the capacity is higher than in the known method, i.e., 0.65 versus 0.43 kg / hr of reactor capacity.
    Example 3. The process is carried out as in example 1, but with the filing of 59.5 kg / h of a mixture containing 69.3 wt. % dimethylamine 29.7% by weight of methanol and 1 weight. % sodium methoxide (1.4% by weight of dimethylamine), 26.6 kg / h of carbon oxide with 99.5% purity. The temperature is maintained at 90 ° C, the pressure is 10 atm.
    84.9 kg / h of a mixture containing 77.76 wt. % dimethylformamide, i.e., in 1 hour, 66 kg of 100% dimethylformamide is obtained. Output relative to carbon monoxide 96 mol. %, the degree of conversion of dimethylamine is 99%. The productivity of dimethylformamide is 1.1 kg / hl of the reactor capacity (66:60).
    Experience shows that at lower CO pressure and temperature with a higher catalyst amount than in the known method, higher productivity is achieved (1.1 instead of 0.43 kg / hl).
    Example 4. This example shows the effect of sodium methoxide content on the productivity of the method of the invention and by a known method.
    The results obtained are displayed in the graph shown in FIG. 2. Curve A refers to a method according to the invention, carried out at a temperature of 90 ° C and a pressure of 22 atm. Curve B refers to the software method of the present invention conducted at 70 ° C and 20 atm. Curve C refers to the process of the invention at 90 ° C and 10 atm. Point D marks the results obtained in Example 6 of a known method at 120 ° C and a pressure of 20 atm. Point E illustrates the results obtained in example 4 of a known method at 120 ° C and a pressure of 50 atm.
    As can be seen from the graphic data, at any content of the catalyst, the method according to the invention provides higher performance with a significantly more moderate temperature and lower pressure.
     To obtain the same amount of dimethylformamide of 1 kg / hl of the reactor capacity in the method according to this invention, 1.17% sodium methoxide is required at a temperature of 70 ° C and a pressure of 20 atm (according to a known method, 1.50% must be used
    sodium methylate, work carried out at 120 ° C and a pressure of 50 atm).
    Example 5. The work is carried out analogously to example 1, but in 1 h serves 31.8 kg of a mixture containing 69,76 weight. % dimethylamine, 29,79 weight. % methanol and 0.45 wt. % sodium methoxide (0.65% by weight of dimethylamine). In parallel, 17.2 kg of carbon monoxide of 99.5% purity are introduced. Temperature
    0 is equal to 70 ° C, pressure is 22 atm.
    48.2 kg / h of a mixture containing 74.68 wt. % dimethylformamide and 11.45 wt. % methyl formate. The productivity of 100% dimethyl phosphate 5 amide is 36 kg / h, 100% methyl formate 5.5 kg / h. The productivity of dimethylformamide and formate is 0.6 and 0.09 kg / hl of the reactor capacity, respectively. The yield with respect to CO is 96 mol. %, the degree of conversion of dimethylamine 100%.
    This example suggests that dimethylformamide and methylformate can be produced simultaneously. The productivity of dimethylformamide in this case decreases, exceeding the productivity by a known method (0.60 versus 0.43 kg / hl).
    Example 6. Similarly to example I in
    0 system serves per hour 32.7 kg of a mixture containing 97.56 wt. % dimethiclamine, 1.71 wt. % methanol 0.73 weight. % sodium methoxide (0.75 wt.% relative to the weight of dimethylamine). Simultaneously input
    5 31.89 kg WITH 99.5% frequency.
    52.14 kg / h of a mixture containing 97.2 wt. % dimethylformamide or 50.7 kg / h of a 100% product. The productivity of dimethylformamide is 0.84 kg / h-l reactor capacity.
    This example shows the possibility of carrying out the reaction according to the invention with a relatively very low consumption of methanol. Under these conditions may occur.
    S is the precipitation of sodium methylate, but this does not interfere with the synthesis due to the intense circulation and turbulence of the reaction mixture in the apparatus. This precipitate is not deposited on the heat exchange surface, which is confirmed by the constant reaction temperature (9 ° C).
    Example 7. The method is carried out analogously to example 1, but the feed gas mixture contains carbon monoxide and 50%
    5 hydrogen, the total pressure is maintained at a level of 100 atm (a partial pressure of carbon monoxide of about 20 atm), while taking into account the release. Performance dimethylformamide
    0 is prepared as in example 1. However, the CO yield is only 75 mol. %
    Example 8. The process is carried out as in example 1, but in 1 hour serves 107.8 kg of the mixture
    5 containing 71.58% amtskaka, 27.52% m.
    eleven
    tanol and 0.9% sodium methoxide (1.26% with respect to ammonia) and 41.3 kg / h of 99.5% carbon monoxide. The pressure is 75 atm, the temperature is 90 ° С (the partial pressure of ammonia at this temperature is about 35 atm). The output in relation to carbon monoxide 95 mol. %, the degree of conversion of ammonia to formamide about 50%. Unreacted ammonia is returned with methanol. The ammonia content in the mixture is supplemented with the addition of about 50% fresh ammonia.
    To maintain the level of fluid in the apparatus, 105.7 kg of a mixture containing 59.6% formamide is taken per hour. Productivity is equal to 63 kg / h. The specific productivity of formamide is 1.05 kg / hl of reactor capacity.
    Ex: Imer 9. The process is carried out as in Example 1, but in 1 hour, 87.05 kg of a mixture containing 69.62 wt. % monomethylamine, 29,87 weight. % methanol and 0.5 weight. % sodium methoxide (0.72 wt.% relative to monomethylamine) and 56.5 kg of carbon monoxide of 99.5% purity. The temperature is 90 ° C, the pressure is 25 atm.
    140.75 kg of a mixture containing 80.5 wt. % monomethylformamide. The throughput is 113.4 kg / h, and the specific throughput to monomethyl forms: ida 1.89 kg / hl reactor capacity.
    权利要求:
    Claims (3)
    [1]
    1. USSR author's certificate number 108803, cl. C 07 C 103/34, 1957.
    [2]
    2. Encyclopedias technical chemistry. Ed. Ullman, 3rd edition, v. 7, p. 672-678,156.
    [3]
    3. The patent of Great Britain No. 1213173, cl. In OI 3/04, pub. 1970 (prototype).
    nemufiotn sodium%
    fig.g
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    同族专利:
    公开号 | 公开日
    DD130578A5|1978-04-12|
    ES456745A1|1978-01-16|
    HU178781B|1982-06-28|
    DE2710725C2|1987-02-12|
    NL189251C|1993-02-16|
    DE2710725A1|1977-09-15|
    JPS6049626B2|1985-11-02|
    GB1568833A|1980-06-04|
    CH599128A5|1978-05-12|
    NL189251B|1992-09-16|
    CA1068300A|1979-12-18|
    JPS52131516A|1977-11-04|
    BE852300A|1977-09-12|
    NL7702420A|1977-09-14|
    FR2343719A1|1977-10-07|
    IT1083713B|1985-05-25|
    US4098820A|1978-07-04|
    BG33884A3|1983-05-16|
    BR7701471A|1978-09-19|
    FR2343719B1|1982-09-17|
    PL103044B1|1979-05-31|
    IN155954B|1985-03-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1768626C3|1967-06-08|1973-11-22|Nitto Kagaku Kogyo K.K., Tokio|Process for the production of formamides|
    US3503593A|1969-06-04|1970-03-31|Bird Machine Co|Apparatus for promoting dissolving of gas in liquid|
    US3928199A|1971-09-20|1975-12-23|Airco Inc|Gas absorption system and method|
    US4018859A|1972-12-01|1977-04-19|Mueller Hans|Arrangement for aerating of liquids|
    GB1459413A|1973-03-06|1976-12-22|Laurie A H|Aeration and mixing of liquids|
    US4017565A|1973-07-13|1977-04-12|Mueller Hans|Device for admixing a gaseous and a liquid phase|US4207180A|1979-01-11|1980-06-10|Chang Shih Chih|Gas-liquid reaction method and apparatus|
    US4302598A|1980-12-17|1981-11-24|E. I. Du Pont De Nemours And Company|Recycling catalyst in preparation of dimethylformamide from dimethylamine and carbon monoxide|
    US4510326A|1983-07-18|1985-04-09|Texaco Inc.|Process for the preparation of formylalkanolamines|
    US4565866A|1984-01-24|1986-01-21|Texaco Inc.|Method for the preparation of formamides|
    GB2177618B|1985-07-13|1989-07-19|Adrian Philip Boyes|Gas/liquid contacting|
    US4683122A|1986-04-14|1987-07-28|Herzog-Hart Corporation|Gas-liquid reactor and method for gas-liquid mixing|
    US4801742A|1987-07-17|1989-01-31|W. R. Grace & Co.-Conn.|N-formylation of amino carboxylates with alkyl formates|
    US4863643A|1988-09-13|1989-09-05|Cochran David W|Apparatus for dissolution of gas in liquid|
    US5919979A|1993-09-28|1999-07-06|Air Products And Chemicals, Inc.|Preparation of alkyl formamides|
    US5783118A|1997-07-02|1998-07-21|Kolaini; Ali R.|Method for generating microbubbles of gas in a body of liquid|
    DE19901744A1|1999-01-18|2000-07-20|Basf Ag|Process for the production of formamide|
    JP2004238358A|2003-02-07|2004-08-26|Mitsubishi Rayon Co Ltd|Method for producing dialkylformamide|
    US6723877B1|2003-06-16|2004-04-20|Air Products And Chemicals, Inc.|Dimethylformamide synthesis via reactive distillation of methyl formate and dimethylamine|
    CN102442923B|2010-10-15|2014-07-16|安徽淮化股份有限公司|Synthesis method of dimethylformamide|
    CN109553548A|2018-11-21|2019-04-02|浙江新化化工股份有限公司|A kind of production method of N- ethyl-formamide|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB10027/76A|GB1568833A|1976-03-12|1976-03-12|Process for the production of formamides|
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