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    • 专利摘要:
    1528610 Isolation of an aromatic aldehyde from its -HBO 4 complex MITSUBISHI GAS CHEMICAL CO Inc 19 Dec 1975 [27 Dec 1974] 52105/75 Heading C2C An aromatic aldehyde is isolated from an aromatic aldehyde-hydrogen fluoride-boron trifluoride complex by effecting the decomposition of the complex in the presence of a compound of formula wherein n is an integer of from 1 to 6 inclusive, and m is zero or an integer of from 1 to 5, and a total of n and m is 6 or less, and mixtures of such compounds. The preferred decomposing agents are mono-fluorobenzene and monofluorotoluene.
    公开号:SU944499A3
    申请号:SU752302644
    申请日:1975-12-26
    公开日:1982-07-15
    发明作者:Фудзияма Сусуму；Такахаси Такехико；Такагава Минору；Озао Сидеки
    申请人:Мицубиси Газ Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to organic chemistry, and more specifically to a method for producing aromatic aldehydes, which are widely used in various industries. j
    A known method for producing l-toluic aldehyde in high yield and with high selectivity with minor impurities of o-toluyl aldehyde in the reaction of toluene ol with carbon monoxide in the presence of a catalyst consisting of hydrogen fluoride and boron trifluoride. This reaction is one of the two reactions that constitute the process of obtaining terephthalic acid from toluene. However, a complex of aromatic aldehyde with hydrogen fluoride and boron trifluoride is formed. When trying to decompose the complex to obtain separately aromatic aldehyde, hydrogen fluoride and boron trifluoride, the quality of the aroma often changes
    aldehyde in the presence of hydrogen fluoride and trifluoride (boron, because there are strong binding forces between the catalyst and the aromatic aldehyde. The aldehyde quality changes in the decomposition column causes the loss of aromatic aldehyde itself. In addition, a small amount of water is formed as a result of the reaction which causes a change in the quality of the aromatic aldehyde. Having formed with it, the water not only deactivates some of the catalyst, but also corrodes the apparatus, using in order to isolate the aromatic aldehyde from the complex. Consequently, the formation of water should be kept as low as possible and it is necessary to decompose the complex of aromatic aldehyde with hydrogen fluoride and boron trifluoride as quickly as possible. It is also important to choose decomposition column with efficient gas and liquid contact, it is preferable to contact the complex with the vapors of the decomposing agent when the complex is in the column while the decomposing agent is boiling under reflux. A known method for the continuous production of hydrogen fluoride, boron trifluoride and aromatic aldehyde separately by heating the complex of aromatic aldehyde with hydrogen fluoride and boron trifluoride is boiling with a refluxing diluent selected from a pile containing toluene and chlorobenzene in a decomposition system 2. However, the undecomposed trifluoride boron in the form of a complex remains in the isolated aromatic aldehyde. In addition, the reaction vessel must be made of silver in order to prevent the vessel from corroding with water that is formed as a result of the reaction. The closest in technical essence and the achieved result is a method of obtaining aromatic aldehyde by reacting an aromatic hydrocarbon with carbon monoxide in the presence of hydrogen fluoride and boron trifluoride with the subsequent decomposition of the resulting intermediate complex when heated in benzene. The decomposition of the intermediate complex is carried out in two stages, first in boiling benzene at a ratio of 15-30 mol of benzene to 1 mol of aromatic aldehyde, and then in the medium of the initial hydrocarbon at the boiling point. The method allows to achieve a sufficiently high degree of decomposition of the boron trifluoride complex with hydrogen fluoride and aromatic aldehyde (up to 90-97. 3. However, due to the incomplete decomposition of the complex, side precursors are formed, resulting in a decrease in the yield of the target aromatic aldehyde and loss of the decomposing agent. To increase the degree of decomposition of the complex, a second stage is carried out. The purpose of the invention is to increase the yield of the target product and prevent the formation of by-products. The goal is achieved in that according to the method for producing an aromatic aldehyde by reacting a corresponding aromatic hydrocarbon with carbon monoxide in the presence of hydrogen fluoride and boron trifluoride, followed by decomposing the resulting intermediate complex when heated in the presence of a decomposing agent, use a monobasil or a monoborbenzene or a network to use a decomposed intermediate complex when heated in the presence of a decomposing agent. at 100-200s and a pressure of 2-6 at. The decomposing agent is used in an amount of 15-tO mol per 1 mol of aromatic aldehyde. The type of decomposing agent has a great influence on the degree of change in the quality of the aromatic aldehyde. The reaction causing a change in the quality of the aromatic aldehyde is a condensation reaction of an aromatic aldehyde with a decomposing agent or an unreacted aromatic hydrocarbon to form, for example, triarylmethane, and undesirable water is formed during the condensation reaction. The reaction, which causes a change in the quality of the aromatic aldehyde, is accelerated by using large amounts of hydrogen fluoride and boron trifluoride, when the complex is decomposed at elevated temperatures or when the complex is decomposed for a long time. In particular, the more hydrogen fluoride is present in the decomposition system, the greater the reaction rate causing a change in the quality of the aromatic aldehyde. Therefore, the amount of hydrogen fluoride and boron trifluoride present in the decomposition system has a large effect on the temperature at which the reaction is carried out. When there is an excess amount of hydrogen fluoride in the column, the reaction is carried out at a temperature below room temperature. When there is one boron trifluoride in the system, the reaction rate causing a change in the quality of the aromatic aldehyde is slow, even at elevated temperatures. When materials other than hydrogen fluoride and boron trifluoride are present in the system, such materials usually accelerate or suppress the reaction. It is necessary that the agent for the decomposition of the aromatic aldehyde complex with hydrogen fluoride and boron trifluoride be inert to the aromatic aldehyde and substantially suppress any reaction causing any change in the quality of the aromatic aldehyde. Monofluorobenzene or monofluorotoluene satisfies the requirements for a decomposing agent: there is a slight change in the quality of aromatic aldehyde when decomposing the complex of aromatic aldehyde with hydrogen fluoride and boron trifluoride in the presence of monofluorobenzene or monofluorotoluene The nature of the subject is inhaling. boron hydrochloride and boron trifluoride as a catalyst are carried out very quickly and selectively. The reaction is highly exothermic, the temperature in the column rises. As a consequence, side reactions are observed and the yield of the target product decreases. Therefore, the reaction temperature is maintained lower, preferably from 0 to -20 ° C. The reaction pressure is kg / cm, preferably 10-30 kg / cm. The amount of carbon monoxide 0.7-1.0 mol per 1 mol of the original aromatic hydrocarbon. The amount of the catalyst is chosen such that 1-6 mol of boron trifluoride and 1-1.5 mol of boron trifluoride are present per 1 mol of the starting aromatic hydrocarbon. The molar ratio of hydrogen fluoride to boron fluoride is preferably in the range of 4: 1 to 10: 1. Source aromatic hydrocarbons include monocyclic and poly cyclic aromatic hydrocarbons, such as benzene, naphthalene, phen fen, diphenyl, diarylmethane, alkyl substituted aromatic hydrocarbons, such as toluene, ethyl benzene, propyl benzene, butyl benzene, hexyl benzene, etc. The decomposition of the complex of aromatic aldehyde with hydrogen fluoride and boron trifluoride in the presence of a decomposing agent is carried out in the range of 100-200 C. Hydrogen fluoride can be extracted from the complex at low temperatures, but usually boron trifluoride is difficult to dissociate from the complex of aromatic aldehyde with boron trifluoride at temperatures below 100 C. At that time, the deterioration in the quality of aromatic aldehyde tends to accelerate at temperatures above 200 C. Typically, the decomposition temperature is determined by the temperature to fines decomposing agent that is boiled under reflux decomposition system. The decomposition temperature depends on the type of decomposing agent and the pressure during decomposition. For example, in the case of using monofluorobenzene as a decomposing agent and decomposition pressures of 2 and 6 atm, the main part of the decomposition column is maintained at a temperature corresponding to the boiling point of monofluorobenzene, i.e. 110, and 1bO ° C, respectively, with a decomposition pressure of 2, and 6 at. But the upper part of the decomposition column is kept at a temperature below that, because the partial pressure of both hydrogen fluoride and boron trifluoride in the upper part of the column is higher than in the intermediate part of the column. The cubic part of the column, in which the aromatic aldehyde is condensed, is kept at a temperature higher than that. It is advisable to carry out the decomposition at relatively low pressure. However, it is desirable that the decomposition pressure be higher than the atmospheric pressure to allow the catalyst, consisting of hydrogen fluoride and boron trifluoride, to be recycled into the reaction system, in which the aromatic aldehyde reacts with carbon monoxide. Therefore, the decomposition is carried out at a pressure of 2-6 at. With decomposition pressure, boron trifluoride in the gaseous state released in the column can be recycled to the reaction system, in which the aromatic aldehyde reacts with carbon monoxide, for reuse without compression, so that the decomposition pressure is preferred from an economic point of view. In order to effectively carry out the decomposition of the complex, a sufficient amount of the decomposing agent is fed as reflux, which may be IS-tO mol per 1 mol of aromatic aldehyde, supplied as a synthetic solution to the decomposition column. When an amount of the decomposing agent in the form of reflux is too small in the system, the rate of heat supply required for the decomposition of the complex of aromatic aldehyde with hydrogen fluoride and boron trifluoride slows down. Supplying phlegm with too much of a decomposing agent is uneconomical.
    The drawing shows the implementation of the method.
    A decomposition solution of an aromatic aldehyde complex with hydrogen fluoride and boron trifluoride is introduced via line 1 to the top of decomposition column 2. A decomposing agent, such as monofluorobenzene or monofluorotoluene, is refluxed into the decomposition system. While the aldehyde solution is diluted with a decomposing agent and flows down the column, hydrogen fluoride and boron trifluoride dissociate from the complex.
    The mixture of aromatic aldehyde and most of the decomposing agent is removed from column 2 via line 3. After a very small amount of boron trifluoride contained in the mixture is removed from it by washing with water, the mixture is fed to a distillation column (not shown), the decomposing agent, toluene and a very small amount of a high boiling point product are removed from the aromatic aldehyde. A fresh L-decomposing agent is fed to the separator through line C to compensate for the amount of decomposing agent discharged through line 3.
    Hydrogen fluoride, boron trifluoride and a minor part of the decomposing agent are withdrawn from the head of column 2 via line 5 and sent to a partial condenser 6, in which hydrogen fluoride, boron trifluoride and the decomposing agent are cooled to a temperature at which the decomposing agent condenses. The decomposing agent thus condensed is phlegm sent to column 2 via line 7. Hydrogen fluoride and boron trifluoride are collected in line 8, condensed while cooling and then recycled to the reaction mixture.
    a system for the synthesis of aromatic aldehyde (not shown; for reuse as a catalyst for synthesis.
    The catalyst, which is deactivated with a very small amount of water, is withdrawn through line 9. The deactivated catalyst is a mixture of fluoride hydrate
    hydrogen and boron trifluoride hydrate. These hydrates regenerate to hydrogen fluoride and anhydrous boron trifluoride, which are reused as catalyst for
    synthesis of aromatic aldehyde. When decomposing an aromatic aldehyde complex with hydrogen fluoride and boron trifluoride, it is preferable to use a decomposing agent,
    boiling at a lower temperature to facilitate the distillation of the aromatic aldehyde.
    A part of the decomposing agent is removed along with the dissociated aromatic aldehyde, and some is entrained in hydrogen fluoride and boron trifluoride from the decomposition column, so that a fresh decomposing agent is required in the column
    decomposition to compensate for the release of the decomposing agent.
    In the proposed method, most of the hydrogen fluoride, containing a small amount of boron trifluoride, can be dissociated from the complex of aromatic aldehyde with hydrogen fluoride and boron trifluoride in the upper part of the decomposition column, dissociation
    Most of boron trifluoride, containing a small amount of hydrogen fluoride, occurs at the bottom of the column. In this case, the decomposing agent is not
    necessary at the bottom to avoid altering the quality of the aromatic aldehyde. However, the decomposing agent or other solvent Md is present at the bottom of the column as a solvent.
    Most of the hydrogen fluoride containing a small amount of boron trifluoride can be dissociated from the complex of aromatic aldehyde with hydrogen fluoride and
    boron trifluoride in the first decomposition column. Then, most of the boron trifluoride containing a small amount of hydrogen fluoride is dissociated in the second decomposition column. In this case, there is no need for a decomposing agent in the last decomposition column. However, a decomposing agent or other solvent may be present in the second decomposition column as a diluent. To reduce the change in the quality of the aromatic aldehyde, the gas and liquid contacting device is desired, having good efficiencies and is designed so as to shorten the residence time of the liquid. Examples of decomposition columns suitable for decomposition include spraying columns, a cascade of trays, an evaporating column in a thin film, a trash column having several trays, and an empty column. My fluoroferbenzene or monofluorotoluene used as a decomposition agent in the proposed method does not form strong bonds with hydrogen fluoride and boron trifluoride. The proposed decomposing agents do not react with the aromatic aldehyde and to a considerable degree interfere with the reaction of the aromatic aldehyde and such an aromatic hydrocarbon as toluene.
    Giving, M / h
    12,013,612,4 12,5
    o78, 5
    79,382,968,6 16,3
    15.618, A13.7
    -25 ..
    -25-25О 3,5
    3,53.52,0
    3829
    37 9 1593617
    10,811,810,7 11.0
    Table 1
    13.31,8
    80,782,3
    15.516, i
    -25О
    3,52,0
    3890 4329
    11,512.8 Feed aromatic hydrocarbon Toluene Toluene Toluene ll-xylene Toluene Toluene / l-xylene (10 which is supplied as unreacted material from the aromatic aldehyde synthesis system to the decomposition system, and does not corrode the apparatus. In addition, the change in the quality of the aromatic aldehyde is very insignificant, since decomposition is carried out in the presence of a certain decomposing agent; hydrogen fluoride, boron trifluoride and aromatic aldehyde are each obtained with a maximum yield, and the columns for The proposed process does not require expensive materials, such as silver, for its production.The starting aromatic hydrocarbon shown in Table 1, liquid hydrogen fluoride and boron gaseous fluoride are continuously fed into the displacement tank to prepare a solution of the complex hydrocarbon-hydrogen fluoride-boron trifluoride. The solution of the complex obtained in this manner is drained from the mixing tank and fed to the reactor, which is continuously fed with carbon monoxide to form a synthetic solution. The heat generated at each stage of the reaction is removed with a cooling agent and the resulting solution is sent to a decomposition column.
    88
    %
    87
    90
    The used decomposition column is made of stainless steel and has a length of 2500 ml and an inner diameter of 85 mm. Eight countercurrent plates having a ratio of holes 20 and a hole size of 3 mm are installed in the upper part of the column at regular intervals at a distance of 500 mm from the top of the column, and a 6 mm Dixon nozzle is placed in a part below the distance of 2000 mm from the bottom of the column. The first partial condenser for condensing the decomposing agent and the second partial condenser for condensing the hydrogen fluoride are located above the column head. The first condenser operates at a temperature such that hydrogen fluoride does not condense. A separator for separating hydrogen fluoride and boron trifluoride from the decomposition agent is connected to the first condenser. Hydrogen fluoride and boron trifluoride are completely withdrawn from the column head and all the decomposing agent used is supplied as reflux to the decomposition system. The boiler is connected to the cube of the column and to it is necessary.-Heat supply.
    Each of the solutions from the reaction system of an aromatic hydrocarbon with carbon monoxide, and each decomposing agent are continuously fed to a second plate on top of the column. Tse86
    89
    86
    86
    the left product in the synthetic solution is I-toluene aldehyde or 2, -dimethylbenzaldehyde, obtained from toluene or m-xylene in the presence of hydrogen fluoride and boron trifluoride as a catalyst, respectively. The decomposing agent is monofluorobenzene or I-fluorotoluene. The solution of aromatic aldehyde (3040 wt.%) In the decomposing agent is withdrawn from the bottom of the column. A low boiling material, such as a decomposing agent, and a high boiling material, such as a product obtained by changing the quality of the aromatic aldehyde, are separated by distillation, and the desired product, aromatic aldehyde, is collected. The amount of the decomposing agent in the form of reflux in the system is regulated by the supply of heat from the boiler. The pressure in the column is kept constant, and the temperature in the column is also kept constant.
     The results of decomposition are given in Table. 2
    权利要求:
    Claims (3)
    [1]
    For comparison, the proposed method is repeated using toluene and monochlorobenzene as a decomposing agent. The results of the experiments are presented in table. 2. 7 9 The claims 1. A method of producing aromatic aldehydes by reacting the corresponding aromatic carbon of hydrogen with carbon monoxide in the presence of hydrogen fluoride and boron trifluoride followed by decomposition of the resulting intermediate complex during heating in the presence of a decomposing agent, characterized in that to increase the yield of the target product and prevent the formation of by-products, monofluorobenzene or mono-fluorotoluene is used as a decomposing agent and the process out at 100-200 0 and 2-6 atm pressure. 2, the way pop. 1, in contrast to u and with the fact that the decomposing agent is used in an amount of 15 o mol per 1 mol of aromatic aldehyde. Sources of information taken by the Attention in the examination 1. Buhler. and Pearson D. Organic syntheses, M., Mir, Part 2, p. 50.
    [2]
    2. Patent of Great Britain N 713335 cl. C 2 C, pub. I960.
    [3]
    3. USSR patent K 619097, cl. C 07 C, 1973 (prototype).
    t:
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    同族专利:
    公开号 | 公开日
    DE2558164A1|1976-07-08|
    NL179274B|1986-03-17|
    GB1528610A|1978-10-18|
    US3988424A|1976-10-26|
    DE2558164C2|1983-07-07|
    FR2295941B1|1978-05-19|
    NL179274C|1986-08-18|
    FR2295941A1|1976-07-23|
    CA1055525A|1979-05-29|
    IT1051641B|1981-05-20|
    NL7515073A|1976-06-29|
    JPS5176231A|1976-07-01|
    JPS533376B2|1978-02-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2430516A|1944-08-14|1947-11-11|Standard Oil Co|Catalytic alkylation of aromatic hydrocarbons by normal paraffins|
    GB713335A|1951-07-02|1954-08-11|Ici Ltd|Catalyst recovery process|
    US3284508A|1963-02-18|1966-11-08|Du Pont|Recovery of p-tolualdehyde|
    JPS5314059B2|1973-05-25|1978-05-15|
    JPS533375B2|1973-12-21|1978-02-06|US4482433A|1982-07-30|1984-11-13|Phillips Petroleum Company|Purification|
    FR2532303B1|1982-09-01|1985-01-25|Ugine Kuhlmann|
    EP2123353B1|2002-10-28|2012-02-08|Idemitsu Kosan Co., Ltd.|Extraction of boron trifluoride or complexes thereof from a mixture of reaction products by using hydrofluorocarbon or oxygenic hydrofluorocarbon as the extraction solvent|
    WO2018193749A1|2017-04-18|2018-10-25|三菱瓦斯化学株式会社|Production method for indane carboaldehyde|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP14884074A|JPS533376B2|1974-12-27|1974-12-27|
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