• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    Alkylidene diesters such as ethylidene diacetate are selectively produced in high yields by reacting an ether and/or an ester under substantially anhydrous conditions with carbon monoxide and hydrogen in contact with a catalyst system comprising a rhodium compound, a halogen component, a palladium cocatalyst and a promoter component which is an agent for liberation of carboxylic acid anions. The process is carried out in the liquid phase in a solvent comprising a carboxylic acid at a temperature in the range of 150 to 190 DEG C. and at a carbon monoxide partial pressure in the range from about 1.0 to 1100 kg/cm<2> and a carbon monoxide/hydrogen mole ratio of 6:1 to 1:2 for the ester reaction and 10:1 to 1:2 for the ether reaction. When ethylidene diacetate is the product, it can then be decomposed to produce vinyl acetate and acetic acid by well-known techniques. Since one mole of acetic acid is also produced in the synthesis of the diacetate, the invention makes possible an overall process or the production of vinyl acetate which produces acetic acid rather than consumes it.
    公开号:SU1225480A3
    申请号:SU823459996
    申请日:1982-07-05
    公开日:1986-04-15
    发明作者:Эдвард Паулик Фрэнк；Джордж Шульц Роберт
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of ethylidene diacetate used in a fine organic synthesis of 3a,
    The purpose of the invention is to increase the yield of the target product.
    The invention is illustrated by the following examples.
    Etc. and meper 1. A 300 ml autoclave built into the system is used as a reactor, the reaction is allowed to be performed at constant pressure and temperature, and the pressure drop is measured on the basis of a pressure air reservoir with the system. that it is possible to inject liquid into an autoclave pressurized. The pressure in the tank, the temperature of the autoclave or the pressure drop is recorded automatically. In order to conduct reactions requiring large quantities of CO and H, it is possible to restore the pressure in the tank during this reaction. The reactor is first loaded with weighed amounts of solid materials, for example, rhodium salt and palladium salt, and then with the desired amounts of liquid components, i.e., methyl acetate reagent, acetic acid, and promoter. The autoclave is then sealed and checked for pressure. In the case of using dimethyl ether as a reagent, the latter, in the form of a solution of acetic acid from a flask under pressure, is introduced into the autoclave through a side opening equipped with a valve at a pressure of 3.2 kg / cm, then the pressure in the autoclave is increased with a mixture of CO / H2 to AjS-Sjl kg / cm and heated to the temperature of the reaction. Then, in order to initiate the reaction, a promoter catalyst, methyl iodide, is added from the reservoir of liquid under a pressure of 35.2-42.2 kg / cm. Then the pressure in the autoclave is increased to the desired level with a mixture of CO / Hj and the reaction is carried out with mixing with the number. 750 rpm for the desired reaction period. At the end of the reaction, the autoclave is cooled. Then, when the pressure in the autoclave is removed from the pressure and the resulting liquid product is analyzed by gas chromatography (GC).
    Similarly to the above, the reception of the reactor load, mol: 0,001
    five
    0
    five
    0
    Mol % 4.32
    Moth
    9.98 0.0698
    0.77 0.92 0,0123
    88.60 85.91 1.4318
    6.31
    14.89 0.1020
    X HjO; 0.313 methyl acetate (MeOLS); 1,203 acetic acid (AcOH), 0.0015 PdCB and 0.006 triphenylphosphine (OjP), Q contains 10 mol of methyl iodide (Mel) in the liquid reservoir. The reaction is carried out for 6 h at 175 ° C using the analyzed mixture (mol% : CO / H CO 65.8; H 34.1; CO ,, 0.1) under pressure of 35.2 kg / cm; Below are the data obtained as a result of GC product
    g
    Methyl iodide
    5 Methyl acetate (MeOAc) Acetic acid
    0 CNLOTS
    (AcOH)
    ETILIDB Ndiacetate
    OH YEAH)
    5 In order to isolate the EDA from the reaction mixture, the latter is distributed between 200 ml of water and 200 ml of benzene in a 1 l separating funnel. Then the benzene solution is extracted with 200-250 ml portions of water, diluted with aqueous sodium carbonate. (until the aqueous extracts are alkaline, usually in three portions) and water (twice) in order to hydrolyze any amount of acetic anhydride to acetic acid and then extract the acetic acid into the aqueous sodium carbonate extracts as sodium acetate. The benzene solution is dried with anhydrous sodium sulfate and concentrated by evaporation in a rotary evaporator. The resulting residue is distilled in vacuum, collecting the fraction boiling at 65-67 ° C / 1.33 kPa (100 mmHg, stm).
    Using this method, it is possible to achieve an output of ED at least 70% of the amount of EDA contained in the reaction mixture, usually 90-95%,
    Calculations showed that 96 mol,% MeOAc was converted to EDA without inducible education, which corresponds to selectivity relative to EDA in 100% and yield in 96%. 55 Examples 2-13 (comparative), In order to prove the decisive value of the introduction of the proposed palladium cocatalyst for higher
    Selectivity with respect to EDA against acetic anhydride in carbonylation was performed using a reactor of Example 1. In this series of experiments, either the cocatalyst is generally excluded or the palladium cocatalyst is replaced by other metals of the VIII group of the periodic system of elements. Although it is known that some of the Group VIII metals, with which the palladium cocatalyst was replaced, possess catalytic properties similar to palladium, it suddenly turned out that the palladium cocatalyst has a decisive
    In Example 8, with FeCt as a cocatalyst in the reactor, a heavy white precipitate was deposited, which possibly reduced the selectivity relative to the ED to a specified value of 10.5%.
    2254804
    value for the proposed catalytic system (see Table 1).
    For each experiment, the reactor is loaded, mol: 0.001 RhCfj - x 0.315 MeOAc; 1.20 AcOH; 0.012 and 0.0015 PdCtj or another metallic compound to replace the palladium cocatalyst. 0.100 moles of Mel are added in each case from the liquid reservoir. In each experiment, a mixture of 90 Co and 10% Hj is used. The pressure in the system in each case is 35.2 kg / cm, and the temperature is 175 ° C.
    Table 1
    From tab. 1 that only the palladium cocatalyst provides
    significant improvement over
     -about
    with the system of Example J, which does not contain cocatalyst. This is quite unexpected due to the well-known factor. Such metals as nickel, cobalt, iron, platinum and ruthenium are quite similar in their action to palladium in the catalyzing of such reactions as hydrogenation.
    Example 14 This example should illustrate the effect of lithium acetate (LiOAc) as a reagent, releasing acetate ions and replacing in this respect the triphenylphosphine of Example 1,
    The reactor of example 1 is loaded, mol: RhCe, X HjO; 0.938 MeOA
    0.164 AcOH, 0.100 Ac, jO "0.0015 PdCtj and 0.010 LiOAc. The liquid reservoir contains 0.10 mol Mel. The temperature, pressure and the ratio of CO / H are the same as in Example 1. The results of the analysis of the reaction product show selectivity relative to EDA 99 ,, 2% with the conversion of MeOAc 74.7%
    to and yield 74.1%.
    Examples 15-19 (comparative). To illustrate the effect of the proposed reaction system in the absence of one or more of its
    15 components carried out a series of experiments with the use of a reactor similarly to an example 1. The temperature, pressure and CO / H ratio are the same as in Example 1. The results of the experiments are shown in Table. 2
    table 2
    From tab. 2, it follows that the exclusion of one or several of the essential components of the proposed system, i.e. palladium cocatalyst, acetic acid and the promoter causes a decrease in the selectivity of the reaction relative to the ED and / or conversion of the starting ester.
    Example 20. To illustrate the carbonylation of ether as the starting material according to the proposed method, the following experiment was carried out using the reactor of Example 1.
    Loaded into the reactor, mol: 0.001 RhCEj X HjO; 0.309 dimethyl ester (MegO), 0.978 acetic acid (AcOH); 0.190 acetic anhydride; 0.0015 PdCjj and 0.010 lithium acetate. As a result, 0.10 mol of methyl iodide (Mel) is kept in the liquid; the reaction is carried out for 6 hours at 175 ° C using the analyzed CO / H mixture, (mol%: CO 79;
    10.2 6.1
    9.32 5.61
    The reaction mixture is distributed between 200 ml of water and 200 ml of benzene in a separating funnel with a capacity of 1. The benzene solution is extracted twice with water in 200-250 ml portions, diluted with sodium carbonate (bringing the aqueous extracts to alkaline in three portions) and twice water to hydrolyze the total amount of acetic anhydride to acetic acid and extract the acetic acid into aqueous sodium carbonate extracts as sodium acetate. The benzene solution is dried with sodium sulfate and concentrated by evaporation in


    Hj 21) under pressure of 42, 2 kg / cm. The GC data of the product show 100% selectivity of the reaction of dimethyl ether relative to EDA with the conversion of the ester to more than 99%.
    Example 21 (comparative). Using the reactor system described in Example 1, the following process is carried out in order to demonstrate the effect of having a low hydrogen content and omitting the necessary critical palladium catalyst.
    Charged to the reactor, mol: 0,691 g (0,0010) КЬ (С, Н,) зР / 2 (СО) С1; 23.3 g (0.315) MeAc; 20.0 g (0.333) HOAc and 51.0 g (0.50). The liquid reservoir contains 14.3 g (0.10 mol) Mel. The reaction is carried out for about 16 hours at 175 ° C using a CO / Hj mixture analyzed (molar ratio 95/5 at a pressure of 35.2 kg / cm) . The reaction mixture was analyzed by GC.
    5.78 6.68
    74.0
    rotary evaporator apparatus. The resulting residue is distilled into va-. cuome. A fraction boiling at 65 - 67 ° C / 1.33 kPa (10 mmHg) is collected to give 2.5 g and identified as pure EDA NMR spectroscopy at 60 KHz; NMR (,, TMS) S 1.35 (d, 3), 1.90 (S 6), 6.80 (q, t).
    Examples 22-105. In order to demonstrate the limits of the carbonylation volume according to the invention, a series of runs was performed using the reactor and method of Example 1. The parameters and results are summarized in tab. 3
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    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING EPIPIDENDIACETATE by reacting dimethyl ether or methyl acetate with carbon monoxide and hydrogen at 160-190 ° C, at a partial pressure of carbon monoxide of 35.2-42.2 atm and a hydrogen content in the gas mixture of 10-34.7 mol. %, in the liquid phase in the environment of acetic acid under anhydrous conditions with the content of acetic acid in the reaction mixture of 13-70 mol. % in the presence of a catalyst containing rhodium trichloride, methyl iodide, cocatalyst and promoter, with a molar ratio of rhodium trichloride and promoter 1: 2.5-48 and rhodium trichloride and cocatalyst 1: 1.5-3.75, characterized in that, in order to increase the yield of the target product, palladium chloride is used as a cocatalyst, and a substance selected from the group: triphenylphosphine, lithium acetate is used as a promoter.
    SU „„ 1225480
    I 1225480
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    同族专利:
    公开号 | 公开日
    EP0077116B1|1984-09-12|
    JPS5867645A|1983-04-22|
    EP0077116A1|1983-04-20|
    YU144782A|1985-03-20|
    JPH0210135B2|1990-03-06|
    CA1185987A|1985-04-23|
    YU43520B|1989-08-31|
    DE3260724D1|1984-10-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    SE426583B|1975-03-10|1983-01-31|Halcon Res & Dev|SET TO MAKE ETHYLIDEN ACETATE|
    EP0028515B1|1979-11-02|1984-03-21|Mitsubishi Gas Chemical Company, Inc.|Process for producing ethylidenediacetate|NL7908980A|1978-12-29|1980-07-01|Halcon Res & Dev|PROCESS FOR PREPARING ACETEALDEHYDE.|
    CA2093747C|1992-04-15|1999-06-15|Francis J. Waller|Process for converting dimethyl ether to ethylidene diacetate|
    US5502243A|1992-04-15|1996-03-26|Air Products And Chemicals, Inc.|Hydrocarbonylation of dimethyl ether|
    CA2093752C|1992-04-15|1999-06-15|David W. Studer|Integrated process for oxygenated acetyl compounds from synthesis gas via dimethyl ether|
    US5744637A|1996-12-13|1998-04-28|Eastman Chemical Company|Carboxylic acid accelerated formation of diesters|
    CN103553913B|2013-10-28|2015-05-13|中国石油化工股份有限公司|Synthetic method of ethylidene diacetate|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US30994981A| true| 1981-10-09|1981-10-09|
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