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    • 专利摘要:
    A METHOD FOR OBTAINING FURAN by the catalytic oxidation of 1,3-butadiene at 75104 ° C With a catalytic mixture of an aqueous copper solution with an average valence corresponding to an oxidation state between 1 and 2, and a solubilizing agent for monovalent copper at a pH less than 2, characterized in that, in order to increase the conversion of butadiene, the process is carried out in the presence of 7.5-10 - 0.5 g mol / l iodine, taken in the form of elemental iodine or in the form of an iodine-containing compound, according to the copper concentration 1 4g. mol / l with a ratio of the number of ions of divalent copper to the amount of ions of monovalent copper from 1: .1 to 4: 1 and using a solubilizing agent concentration of 0.03 - O ts 5 g-mol / l. (L
    公开号:SU1110383A3
    申请号:SU792804759
    申请日:1979-08-21
    公开日:1984-08-23
    发明作者:Ирвин Гарнетт Дональд；Лерой Петерсон Марвин
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    with
    00 00 The invention relates to a method for the production of furan, which is used in the preparation of furan resins and in the manufacture of tetrahydrofuraa.  A known method for producing furan by oxidation of 1,3-butadiene with molecular oxygen at 40-150 ° C in the vapor or in the liquid phase in the presence of a palladium salt, tali or indium 1.  The disadvantage of this method is low conversion of butadiene.  The closest to the invention by technical essence and achievable effect is the method of obtaining furan by oxidation of 1,3-butadiene when heated to 60-110 ° C with a catalytic mixture of an aqueous solution of 4.911, 6 g mol / l copper with an average valence corresponding to an average degree between 1 and 2, when the ratio of the amount of divalent honey ions to the amount of divalent copper ions is 9.6: 1 to 1: 0, and the solubilizing agent for monovalent copper ion, soluble in water and forming a soluble complex with a monovalent copper ion, for example , | lithium chloride, with a concentration of 1-7 g mol / l at a pH of 0.1-0.5 2.  The disadvantage of this method is the low conversion of 1,3-butadiene (7-9%).  The purpose of the invention is to increase the conversion of 1,3-butadiene.  The goal is achieved in that according to the method for producing furan by catalytic oxidation of 1,3-butadiene at 75-104 ° G with a catalytic, mixture of an aqueous solution of copper with an average valence, corresponding to an oxidation step between 1 and 2, and a solubilizing agent for monovalent copper ion at a pH less than 2, the process is carried out in the presence of 7.5 10 - 0.5 g mol / l iodine, taken as elementary 5 IGO iodine or as an iodine-containing compound, at a honey concentration of 1-4g-mol / l with the ratio of the number of divalent honey ions to the number one valence copper ions from 1: 1 to 4: 1, using a salt & lysing agent concentration 0.03 5g mol / L.  The aqueous medium with which the initial butadiene is in contact should have a pH less than 2.  The amount of furan produced increases when the pH is less than 0.5, it is preferable that the pH be about 0.0 or less.  However, measuring the pH value using glass electrodes in aqueous solutions of honey salts does not accurately determine the molar concentration of the hydrogen ion.  For example, the pH value of the solution, which is 0.1 n.  for hydrochloric acid and containing such concentrations of salts of honey, which are given in the examples, is less than 0 when measured with a glass electrode.  The molar concentration of IS / 1OV of hydrogen in mixtures can be determined by titrating aliquots of portions, dissolved in 10-fold amount of water, with the aid of standard solutions of bases.  A standard end point determination method can be used when titrating an acid with a base, for example using indicators (congo-red or methyl orange), or a pH meter can be used.  The molarity of hydrogen ions should be higher than 0.05, preferably 0.1-1.0.  The water used in this process contains iodine, a redox honey catalyst, for example, a mixture of monovalent honey and ions, zucvalent honey, and a solubilization agent to keep the mono-ion honey in solution.  Iodine is present in the aqueous medium in the form of iodine ion, which is typically introduced in the form of elemental iodine or in the form of an alkali metal iodide, such as sodium iodide or potassium iodide.  Since a very small amount of iodine is required, any iodine-containing compound can be used that is at least partially soluble in a water medium, for example, lithium iodide, calcium iodide, monovalent honey iodide, ferrous iron iodide, potassium iodide, acid and hydrogen iodide. organic iodides (methyl iodide and ethyl iodide).  Of these, elemental iodine iodine or alkali metal iodides are preferred.  The concentration of iodine in the aqueous medium should be in the range of 7.5 x, 5 g-mol / l (0.001 - 0.2 g mol / l).  The metal component of the catalyst is copper.  In the aquatic environment, copper oxidizes between 1 and 2, t.  e.  is a mixture of monovalent honey ion and ion dv0 (valence honey).  In a watery environment, any compound of honey can be consumed, such as honey halides (chlorides and bromides).  Advantageously, a mixture of divalent honey chloride and monovalent honey chloride is used, although any one of these chlorides can be introduced into the aqueous medium, in which case the mixture of both honey can be easily obtained either by oxidizing the unovalent honey to divalent or by reducing the divalent honey. honey to monovalent.  The total concentration of copper in the aqueous medium is in the range of 0.1-10 g mol / l, usually about 0.5-3 g mol / l.  The ratio between divalent copper ions and monovalent copper ions is 4: 1 –1: 2.  In order to keep the monovalent copper ion in solution, a solubilization agent is used - any inorganic or organic compound that is soluble in water and is capable of forming water soluble complex compound with monovalent copper ion, for example alkali metal halides, alkaline earth metal halides, ammonium halides and hydrohalic acids, as well as palladium halides and iron halides.  Especially recommended solubilization agents are sodium chloride, calcium chloride and ammonium chloride.  The concentration of the solubilization agent is typically in the range: 0.035 g mol / l, preferably 0.5-3 g mol / l.  The process is carried out at a temperature of about 50-125 ° C, the preferred ranges are 75 -105 ° C, 95-103 ° C.  The rate of furan production decreases at lower temperatures.  The process pressure is about 0.1 to 10 atm, preferably 1-3 atm (most preferably it corresponds to atmospheric pressure).  The feed rate of the source material and its passage through the aqueous medium is not critical, it should not be so high that the contact time between the source material and the aqueous medium is insufficient or so low that the time for decomposition or polymerization of the resulting product furan is created.  Due to the fact that the chloride chloride chloride has a strong corrosive effect, the reactor for carrying out the process is made of a material that does not corrode in an aqueous medium, for example, glass or ceramic lined material, titanium, metals clad with tantalum, impregnated graphite pipes and t .  P.  The oxygen-containing gas is contacted with an aqueous solution together with the starting material to oxidize the resulting copper ion to the divalent copper ion.  In a typical case, the source material and the oxygen-containing gas are shifted and then passed through an aqueous medium, although they can also be introduced in the form of separate gas flows of different streams.  The oxygen-containing gas used may be molecular oxygen as such or molecular oxygen together with a diluent that is inert with respect to the reaction (nitrogen and so on.  P. ).  Typical molecular oxygen containing gases are Bozdukh (preferred), flue gases or synthesis gases containing 11 34 residual oxygen, and any source of moles.  cular oxygen, which at least, but essentially does not contain contaminants, harmful to the desired reaction.  The amount of oxygen-containing gas should be sufficient so that approximately 1 to 2 mol of molecular oxygen is needed per I mole of the furan compound produced.  Another variant} (t of this method is a two stage method in which furan is obtained in the first stage by contacting the starting material with an aqueous solution, monovalent copper ion is oxidized to the divalent copper ion in the second stage as a result of contacting an aqueous solution containing an excess of ion monovalent copper, with the specified oxygen-containing gas.  This two-stage process can be carried out either periodically in one reaction vessel or continuously in two reaction vessels.  In a batch process, the source material is in contact with the aqueous medium until the furan yield begins to decrease, after which the supply of the source material is stopped, then the oxygen-containing gas contacts the aqueous medium until the initial bivalent copper ion is reached. monitor by controlling the acidity of the aqueous medium, or by measuring the content of the ion of disovalent copper and the ion of divalent copper.  In a continuous process, a furan compound is formed in the first reaction vessel as a result of continuous contact of the starting material with the aqueous medium.  The reaction gases, including unreacted starting material, inert gases and reaction products, in addition to the target furan, are continuously withdrawn from the reaction vessel, the furan compound is removed by marketing methods and the unreacted starting material is recovered and recycled to the first reaction vessel along with the replenishing starting material.  The aqueous medium is continuously circulated as a process solution between the first reaction vessel, in which the furan compound is formed, and the second reaction vessel, in which the oxygen-containing gas (air) co-closes with the aqueous q-rich enriched with monovalent copper ion, to oxidize single-ion copper to ion divalent copper.  The oxygen-treated aqueous medium enriched with two-copper copper ion continuously returns to the first reaction vessel.  In the examples, the degree of conversion of the starting material, e.g., butadiene, is expressed in molar percent of the Hcxoj feed, of 1HO material, which is converted into products.  When the process is carried out under optimal conditions, the degree of conversion of the starting material, for example, butadiene, is about 10-90%, the yield of furan is 70-95 mol. %  Samples for analysis by gas chromatography were taken in 1 ml Carly vessels from the stream.  Samples are injected using Carly valves for samples into 10x 1/8 columns (approximately J 3m X 3 mm) of the poropack N to determine the contents of air, carbon dioxide, butadiene and furan.  The analysis is carried out with helium as a carrier gas at a feed rate of 24 ml / min.  The peak areas on the output curve of the chromatograph are recalculated into volumetric percentages of the components using coefficients estimated during calibrations using known amounts of the components.  Example 1  A mixture of 50-06. % butadiene and 50 vol. % nitrogen was injected at a rate of 80 ml / min through a sintered glass disk into the bottom of a glass reactor in a 100 ml aqueous solution with an initial pH of 0.5, containing 2 M bivalent copper chloride, 1 M monovalent copper chloride, 1.7 M sodium chloride, 0.24 M potassium iodis and 0.06 M hydrochloric acid.  The solution is maintained at 95 ° C with ijpH using an outer napkin jacket and is moved with a disk liner agitator.  After 0.5 h of operation, the gaseous product stream containing 10.9 vol. % furan, analyzed by gas-liquid chromatography When applied at a rate of 8.7 ml / min.  The degree of conversion of butadiene into products is 20%, the yield of furan is 96 mol. %  In the control run, in the absence of added iodine, butadiene is fed at a rate of 40 ml / min to the indicated stirred reactor, in which there is 100 ml of an aqueous solution with an initial pH value equal to O or lower, containing 2 M chloride of bivalent copper, 2 M chlo; copper monovalent and 4 M lithium chloride.  The temperature is maintained at 95 ° C.  After 1 h of operation, the gaseous stream contains 3 vol. % furan, which is determined by gas liquid chromatography.  Furan is obtained at a rate of 1.2 ml / min.  Example 2  Carried out as in example 1, however, the aqueous solution contains 0.03 M iodine potassium.  Through Gh of operation, furan is obtained at a rate of 7 ml / min.  , PRI me R 3i A mixture of 50 vol. % butadiene and 50 vol. % nitrogen is fed at a rate of 120 ml / min through the cylinder from the pump. glass, placed below the disk vane mechalki in a 1-liter reactor with baffle plates.  The reactor contains 400 ml of an aqueous solution at 95 ° C with an initial pH of 2.  The solution contains 2.05 M cupric chloride, 0.5 M cupric chloride, 0.86 M sodium chloride, and 0.0075 M potassium iodide.  The production of furan in the gaseous product stream is determined by gas-liquid chromatography.  The results are shown in Table.  one.  The degree of conversion of butadiene is 22-30%, the yield of furan is 88 mol. %  Example 4  Gaseous flow of 50 vol. % butadiene in nitrogen is fed at a rate of 100 ml / min to the reactor with 100 ml of an aqueous solution containing 2 M chloride of divalent copper, 1 M chloride of monovalent copper, 2 M calcium chloride and 0.04 M of elementary diode.  The initial pH of the solution is less than 2, the solution is maintained at 95 ° C.  The gaseous product stream contains 2 vol. % furan, as determined by gas-liquid chromatography, after 0.5 h of operation.  The rate of obtaining furans.  6.2 ml / min.  Example 5  It is carried out as in Example 1, but the aqueous solution contains 2 M bivalent copper chloride, I M monovalent copper chloride, 2 M ammonium chloride and 0.12 M potassium iodide, the initial pH of the solution is about 0.0.  After 1 hour of operation, furan is obtained at a rate of 4.6 ml / min.  Example 6  Conducted in example 1,. but the aqueous solution contains 2 M of chloride, divalent copper, 0.5 M of copper monovalent chloride, 5.7 M of lithium chloride and 0.12 M of potassium iodide.  Furan is obtained at a rate of 1.7 ml / min after 0.5 h of operation.  PRI MER 7 I (illustrates the rate at which furan is produced at increasing levels of the concentration of divalent copper ion in an aqueous solution).  Gaseous flow of 50 vol. % butadiene in nitrogen is fed at a rate of 80 ml / min to the reaction vessel of example 3, containing 400 ml of an aqueous solution with an initial pH value less than 2.0.  The solution contains 5 M bivalent copper chloride, 1.5 M monovalent copper chloride, 3 M sodium chloride and 0.3 M potassium iodide.  At a reactor temperature of 100 ° C, the gaseous product stream contains 5 vol. % furan, as determined by gas-liquid chromatographic, and get it at a rate of 4 ml / min.  The conversion of furan butadiene is 85 mol. %  7111038 Re. atskyu is stopped and the concentration of bivalent copper chloride in aqueous solution is increased to 1.2 M, after which the flow of butadiene mixed with nitrogen is again started.  The aqueous solution has a pH less than 0, 5 and the reaction temperature is maintained at 103 ° C.  After 1 h of operation, the gaseous product stream is analyzed by gas liquid chromatography.  The furan content is 15.1 vol. % at the rate of production of about 12 ml / mi. The degree of conversion of butadiene to the product is 32%, the yield of furan is 87 mol. %  After this, the reaction is stopped again and the concentration of cupric chloride in the aqueous solution is increased to 1.53 M.  The gaseous flow of butadiene with nitrogen is then resumed.  At a reactor temperature of 104 ° C and a solution pH of less than 0, the gaseous product stream contains 22 vol. % of furan obtained at a rate of 17.6 ml / min after 0.5 h of operation.  Butadiene Conversion Rate 55. %, the output of furan 80 mol. %  Example 8  Gaseous flow of 46 vol. % butadena in nitrogen is fed at a rate of 65 ml / min to 250 ml of an aqueous solution in a reaction vessel equipped with a stirrer.  The pH of the aqueous solution at the beginning is less than 2, the solution is soda1, there is 2.4 M of bivalent copper chloride and 0.05 M of potassium iodide.  2 ml of tetramethylethylenediamine are added to the aqueous solution.  At a reaction temperature of 90-95 ° C, furan is obtained at a rate of 3.9-5.2 ml / min, the concentration of furan in the gaseous product stream is 6-8 vol. %, which was established by gas liquid chromatography.  Example 9  Gaseous stream with 50 vol. % butadiene in nitrogen is fed at a rate of 150 ml / min to the reactor described in example 3 with 400 ml of an aqueous solution containing 1 M bivalent copper chloride, 0.5 M calcium chloride and 0.06 M potassium iodide.  The acid content in the aqueous solution at the beginning of the experiment, as measured by titration with a standard base, corresponds to 0.1 M.  During the course of the reaction, the acidity of the solution is monitored by titrating the base of the aliquot portions and the concentration of the divalent copper ion is calculated based on the loss of one two-charge copper ion for each H ion generated.  The temperature of the solution is maintained at 75 C.  The production of furan is determined by gas chromatography.  The results are shown in Table.  2  The reaction is stopped and air is supplied to the aqueous solution for 30 minutes at a rate of 150 ml / min to oxidize the excess 15-20 monovalent copper in solution (resulting from the reduction of bivalent copper chloride during the reaction).  After; the concentration of bivalent copper chloride was restored, the flow of gaseous mixture of butadiene and nitrogen was resumed at a rate of 150 ml / min, but the temperature of the aqueous solution was maintained at 85 ° C.  The production of furan was determined by gas chromatographic method.  The dependence of the production rate on the acidity of the solution and the content of divalent copper ion is shown in Table.  3  The JPeement is again stopped to oxidize excess monovalent copper chloride to the initial chloride content of two-cup copper by introducing air into the solution at a rate of 150 ml / min.  After the concentration of bivalent copper chloride has been restored, the mixture of butadiene and nitrogen is resumed at a rate of 150 ml / min, but the temperature of the solution is maintained at 95 ° C.  The dependence of the rate of obtaining furaya on the acidity of a solution of g of the content of divalent copper ion in the table.  four.  Example 10 (shows one-step reactyl for the preparation of furaia, simultaneously with the oxidation of monovalent copper to divalent copper chloride).  400 ml of an aqueous solution containing} M chloride of divalent copper, 0.5 M of chloride of monovalent copper, 1 M of calcium chloride and 0.05 M of potassium iodide are loaded into the reactor described in example 3.  The mixture of butadiene with air is passed through the solution in the reactor at a rate of 150 ml / min.  The course of the reaction is shown in Table.  five.  Example II  Gaseous mixture of 50 vol. % butadiene in nitrogen is fed at a rate of 100 ml / min to the reactor described in example I, with 100 ml of an aqueous solution containing 1 M bromide copper, 0.5 M bromide monovalent copper, 1 M sodium bromide and 0.12 M iodide Kali.  The pH of the solution is 0.0, the temperature during the reaction is maintained at 95 C.  After 45 minutes of operation, the furan concentration in the off-gas is determined by gas-liquid chromatography, it is 3.3 vol. % at a production rate of 3.3 ml / min.  P, example 12 (illustrates the use of elemental iodine as an oxidizing agent to impart monovalent copper chloride to the activity).  Gaseous stream with 50 vol. % butadiene in nitrogen is fed at a rate of 80 ml / min to the reactor described in example 1, 100 ml of an aqueous solution with an initial pH value of 0.2, containing 1 M chloride
    monovalent copper, 2 M sodium chloride, 1 03 M potassium iodide and 0.5 M elemental iodine. During the reaction the temperature of the solution is maintained at a level. After 1 h of operation, the gaseous product stream contains 4.5 vol.% Of furan, which is established by gas-liquid chromatography, chromatography, and it is obtained at a rate of 3.6 ml / min. The degree of conversion of butadiene is 10%, the yield of furan is 90 mol%.
    Example 13 (showing the effect of iodide on the reaction rate). A mixture of 80% butadiene in a mixture of butadene and air is fed at a rate of 100 ml / min to the reactor described in example 1, which contains a solution containing 2 M bivalent copper chloride, 1 M monovalent copper chloride and 2 M calcium chloride. The pH of the reaction mixture is 0.0, the temperature is 95 C. After 45 minutes of operation, furan is obtained at a rate of 0.8 ml / min. After the addition of 0.06 mol of potassium iodide to the reaction mixture, the rate of furan production rises and after the next hour of operation reaches 5.1 ml / min. This represents a 6.3-fold increase in the rate of furan production.
    Example 14. A stream supplied at a rate of 100 ml / min, consisting of 50% butadena in air, is sent to a solution consisting of 300 g, acetonitrile, 200 g of water, 0.5 mol of divalent copper, 0, 5 mol of monovalent copper chloride, 1.0 mol of calcium chloride, 0.2 mol of HC 1 and 0.0125 mol of potassium iodide. A gaseous stream is introduced through a gas dispersion tube into a stirred solution in a 1-liter flask, which is heated at. After a flow of 2 hours, the analysis of the product flow by gas chromatography shows that it contains 0.32 mol. furan.
    Example 15. A charge from liquid crotyl chloride, fed at a rate of 0.07 ml / min, and a gaseous charge, fed at a rate of 150 ml / min, consisting of air and nitrogen, were introduced simultaneously into the reactor described in Example 3, which Soderisite 400 ml of an aqueous solution containing 1 M bivalent copper chloride, 2 M calcium chloride, 0.06 M potassium iodide and 0.50 M HCl. Reaction temperature The product stream removed from the reactor contains 3 mol% furan and 9% butadiene.
    Example 16. 1,4-Dichloro-2-butene (6.5 g, 0.05 mol) was introduced at a rate of - / 0.05 ml / min into the reactor described in Example 1, in which 100 ml of an aqueous solution were present; containing 1 M chloride of two-cuprate copper, 1 M chloride of monovalent copper, 2 M chloride grade. calcium and 6.13 M potassium iodide. The pH value of the mixture is 0.5, the temperature is 95 C.
    A stream of nitrogen is passed through the reactor at a rate of 100 ml / min. The gaseous product stream is passed through a trap cooled with a bath of dry ice and acetone. The liquid collected in the trap contains 7% butadiene and 75 mol% furan.
    This method improves the conversion of 1,3-butadiene by 21%.
    Table 1
    245
    335
    44
    53
    67
    73
    table 2
    Table 4
    9
    1.4
    4.1
    2.7
    6.5
    9.8
    9.8
    14.7
    9.0
    13.5
    9.8
    6.5
    13 After that, the experience was terminated for a day and
    14
    .1110383 Table 5 resumed the next morning.
    权利要求:
    Claims (3)
    [1]
    METHOD FOR PRODUCING FURANE by catalytic oxidation of 1,3-butadiene at 75104 ° С with a catalytic mixture of an aqueous solution of copper with an average valence corresponding to the oxidation state between 1 and 2, and a solubilizing agent for a monovalent copper ion at pH less than 2, characterized in that, with in order to increase the conversion of butadiene, the process is carried out in the presence of
    7.5 10 ~ 3 - 0.5 g mol / l of iodine taken as elemental iodine or as an iodine-containing compound, at a copper concentration of 1 -
    [2]
    4 g mol / l with a ratio of the number of ions of divalent copper to the number of ions of monovalent copper from 1: .1 to 4: 1 and use a solubilizing agent concentration of 0.03 -
    [3]
    5 g mol / L.
    >
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    引用文献:
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    FR1394382A|1963-08-27|1965-04-02|Pullman Inc|Composite catalyst for the halogenation of hydrocarbons|
    NL6409355A|1964-08-13|1966-02-14|
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    GB1541443A|1975-10-01|1979-02-28|Ici Ltd|Dicyanobutenes|
    US4096171A|1976-04-29|1978-06-20|Imperial Chemical Industries Limited|Process for the manufacture of dicyanobutene from butadiene, hydrogen cyanide and oxygen|
    SU1263566A1|1985-04-25|1986-10-15|Проектно-Конструкторско-Технологическое Бюро По Вагонам Мпс Ссср|Method of assembling oiling device|US4268421A|1979-03-26|1981-05-19|E. I. Du Pont De Nemours And Company|Preparation of furan compounds|
    US4278563A|1979-04-10|1981-07-14|E. I. Du Pont De Nemours And Company|Copper chloride containing catalysts for the preparation of furan compounds|
    US4298531A|1979-12-31|1981-11-03|E. I. Du Pont De Nemours And Company|Oxidation of butadiene to furan|
    US4257960A|1980-05-01|1981-03-24|E. I. Du Pont De Nemours And Company|Preparation of furan compounds|
    US4387236A|1982-03-03|1983-06-07|E. I. Du Pont De Nemours And Company|Liquid phase oxidation|
    US4410713A|1982-04-28|1983-10-18|E. I. Du Pont De Nemours & Co.|Preparation of furan compounds|
    US5854168A|1997-11-13|1998-12-29|Stauffer; John E.|Catalyst composition for methanol synthesis|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/935,389|US4172838A|1978-08-21|1978-08-21|Preparation of furan compounds|
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