• 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:
    Toluene dehydrocoupled products are produced by heating toluene in the vapor phase with an inorganic metal/oxygen composition which functions as an oxygen carrier and has the empirical formula: where M is bismuth and M2 is at least one element selected from indium, silver, Group 2a of the Periodic Table of the Elements, and mixtures thereof, and wherein a is 1, b is 0.01 to 100, and x is a number taken to satisfy the average valences of M1 and M2 in the oxidation states in which they exist in the composition. Alternatively, the same inorganic metal/oxygen composition can be employed as a catalyst or as a combination catalyst/oxygen carrier for the dehydrocoupling reaction when oxygen or an oxygen-containing gas is heated with the toluene.
    公开号:SU1095875A3
    申请号:SU803215943
    申请日:1980-12-09
    公开日:1984-05-30
    发明作者:Натан Вильямсон Алекс；Джозеф Тремонт Сэмюел
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    ; o: l x
     The invention relates to the preparation of toluene degradation products, more specifically to the oxidative synthesis of 1,2-diphenylethylene (stilbane) from toluene and to inorganic metal oxygen compositions effective for the oxidative combination of toluene to obtain stilbene.  Due to its unsaturation, sgilbene is very reactive and can be used in various organic syntheses.  Stilbene derivatives are useful for making products that can be used for dyes, dyes and resins.  It is also useful in optical body whitening, in pharmaceuticals, and as organic intermediate products.  A known method for producing stilbene by vapor-phase oxidative dehydrodimerization of toluene at 500-650 C, preferably 540-BOO in the presence of a contact, whose composition corresponds to the following empirical formula: SbqPbbSi Oq, where d 1, b 0.2-10.0 0.5, c1 c corresponds to the oxidation state of the remaining elements.  The process is carried out at the contact time Oz5-5 with in the presence of water vapor.  The conversion of toluene is 74.5%, the yield per transstllbene lj A known contact contains antimony, which is a rarely used element.  It is usually found in the form of sulfide, t. e.  antimonide SbjSj), which is converted to the corresponding oxide by burning.  Burning sulphide to produce oxide causes the conversion of sulfur compounds to produce sulfur, for example, dioxide and sulfur trioxio.  These oxides are undoubtedly refined compounds for the environment.  To eliminate this danger, further costs in order to transform the said oxides of sulfur into production.  less harmful sulfur products.  In addition, antimony and many of its compounds are toxic.  The aim of the invention is to simplify the process technology by eliminating antimony and its derivatives.  This goal is achieved in that according to the method of producing stilbene by vapor-phase oxidative dehydrodimerization of toluene in the presence of an oxide contact at 500-630 ° C, a contact of the general formula B, M Ox, kalidium, strontium, silver indium, magnesium or their mixture is used; from O, 1 to 100; the number corresponding to the valence of 6i and / V in the oxidative state, at a temperature of 500-630 C.  The process can be carried out in the presence of an oxygen-containing gas.  The inorganic metal oxygen contact acts as a catalytic, stoichiometric method as an oxidizing agent or oxygen carrier, or a combined catalytic stoichiometric method for the dehydrogenation of toluene.  In the catalytic process, oxygen or an oxygen-containing gas, such as air or oxygen-saturated air, is reacted with toluene in the presence of an inorganic metal / oxygen contact in an amount sufficient to react the dehydration combination.  In the stoichiometric method, the inorganic metal / oxygen contact is the only source of oxygen.  In the latter case, the dehydro-combination of toluene is carried out mainly in the absence of added free oxygen, as it is obtained from air. In the combined catalytic stoichiometric method, oxygen or oxygen-containing gas is added as a reagent in the same way as the catalytic method described, but the amount of added oxygen is not sufficient for the dehydrogenation reaction, and the required additional oxygen is supplied by contacting the inorganic metal / oxygen.  Of these methods, stoichiometric is usually preferred because undesirable side reactions — oxidative dealkylation, for example, with the production of benzene and oxygen dioxide — are generally reduced.  In the course of the reaction, benzene is obtained by the proposed method.  Since benzene is a valuable commercial product, it is desirable to separate it when it is obtained in a significant amount.  The separation and purification of benzene is carried out according to known methods and techniques.  By the expression dehydration combination and bonding to it by expressions is meant that the molecules of toluene combine or dimerize (and a carbon-carbon bond is formed between the carbon atoms of the methyl group) and that the bound molecules lose one or two hydrogen atoms from the methyl group of each mole. kula toluene.  If each toluene molecule loses two hydrogen atoms, then the carbon-carbon bond of the fragment to be dehydroconnected or dimerized is saturated, as in the dehydrogenation, t. e.  the product is stilbene.  On the other hand, a bibenzyl with an unsaturated carbon-carbon bond is obtained at the fragment to be combined if the toluene molecule loses only one hydrogen atom.  It is preferable to obtain stilb on as a dehydrochlorination product before bibenzyl is produced, which is due to the unsaturation of stilbene in comparison with the saturation of bibenzyl.  The presence of the unsaturated olfactory carbon – carbon double bond shows the high reactivity of stilbene, which contributes to its direct use as an organic intermediate in numerous organic syntheses.  The proposed method is easily implemented in a device suitable for carrying out chemical reactions in the vapor phase.  It is carried out in a single-stage or multi-stage reactor using a compact or fluidized bed system for contacting the reactant or reagents and contacting inorganic tal / oxygen.  Toluene is usually heated and introduced into the reactor as. vapor In addition, the reagent can be introduced into the reactor in the form of a liquid, and then evaporated.  The oxidative dehydrogenation reaction is carried out in the vapor phase and under the influence of heat.  The temperature limits at which the reaction can be carried out are about 450 to 650 ° C, preferably 500 BOO C.  In the proposed method, the pressure is not critical.  The reaction can be carried out under atmospheric pressure or below or above it, but preferably at atmospheric pressure or around atmospheric pressure.  A pressure of from about 0.25 to 4.0 atm is usually suitable.  The reaction time of contacting the reagent with an inorganic metal / oxygen contact according to the proposed method varies widely (from about 0.1 to 60 seconds).  The reaction time can be defined as the period of time (in seconds) during which the reaction gases, measured under the reaction conditions, are in contact with the inorganic metal / oxygen contact in the reactor.  The reaction time varies depending on the reaction temperature and the desired toluene conversion.  At high temperatures and lower toluene conversion, shorter contact times are required.  The contact time typically ranges from about 0.5 to 20 seconds.  For optimum conversion and selectivity in the preferred temperature range, it is advisable to use a contact time in the range of from about G to 12 s.  In addition to toluene, other inert substances, such as nitrogen, helium, etc., are present in the reactor. P.  These substances are added separately or are loaded together with other substances.  Water or steam may be introduced into the reaction zone, preferably with loading, to improve the selectivity of conversion to the desired products and especially to suppress complete oxidation to COj.  Ratios of steam to hydrocarbon in the range of 0.1-10 or higher are suitable, with the highest limit being determined by financial considerations.  Preferred ratios are from 0.5 to 3.  The inorganic metal / oxygen composition suitable for use contains oxygen in such an amount that, under the oxidative reaction conditions used, it allows the release of stoichiometric amounts of oxygen.  Oxygen in composition is associated with metals in the form of oxides, complexes consisting of at least two metals, or in the form of mixtures of oxides and complexes.  According to the proposed method, the contact inorganic metal / oxygen is used separately or together with the substrate or carrier.  Where the composition is very soft or prone to abrasion, the use of a carrier is particularly advantageous for maintaining the structural integrity of the contact during the loading of the reactor and / or under the reaction conditions during the process. Suitable carriers for contact are, for example, silica, alumina, silica-alumina, metal aluminates, for example magnesium aluminate, calcium aluminate, and the like. P.  As indicated above, the dehydro coupling reaction is carried out in the presence or absence of added free oxygen.  If no oxygen is added to the system t. e.  the reaction is carried out stoichiometrically, and the oxygen required for the reaction is obtained from an inorganic metal / oxygen mixture which reacts and as a result of the latter is reduced (in practice only partially).  This requires regeneration or re-oxidation, which is easily carried out by heating the material in air or oxygen at temperatures from about 500 to 650 ° C for about from 1 hour.  In the semi-continuous process, the regeneration is carried out periodically with the reaction stopped to re-oxidize the reduced composition, t. The reaction periods and the regeneration period alternate.  But the process can be carried out in a continuous manner, with part of the composition of the inorganic metal oxygen being continuously or intermittently re-oxidized and the repeatedly oxidized material is continuously or intermittently returned to the reaction.  The latter method is used especially where contact is made of metal / oxygen in the form of a fluidized or moving bed system. If oxygen is used as a reactant, the reaction is carried out in a catalytic or combined catalytic / stoichiometric manner depending on the amount of oxygen supplied.  According to the catalytic oxygen intake.  served in an amount sufficient to react the dehydration combination.  The specific amount of oxygen supplied is set as a function of the amount of toluene.  On this basis, the amount of oxygen supplied is usually chosen to obtain a molar ratio of hydrocarbon to oxygen from about 1 to 8, preferably from 2 to 6.  In the combined catalytic stoichiometric method, the amount of oxygen supplied as a reactant is insufficient for the dehydro-coupling reaction, and an additional source of oxygen is required, which is obtained from the inorganic metal / oxygen composition, t. e.  The composition serves as an additional source of oxygen.  As a result, the inorganic metal / oxygen contact reacts and as a result of the latter is reduced.  This requires regeneration or re-oxidation of the reduced composition, which is easily carried out, as for stoichiometric reaction, In any reception (either catalytic or combined catalytic / stoichiometric), where added oxygen is used as a reactant, free oxygen is supplied as oxygen such or in the form of oxygen-containing gas, for example in the form of air or oxygen-enriched air.  Contact inorganic metal / oxygen is obtained by various methods.  The simplest method involves carefully mixing powdered metal oxides in dry condition and burning them.  A method is known which includes the addition of metal oxides to water with stirring, filtering to remove excess water or heating to evaporate water, drying and firing, and also the method of which the crushed metal oxides are thoroughly mixed before forming a water paste. .  The paste is distributed and dried in air, after which it is burned in air. Then the calcined product is crushed and sieved to the desired value (mesh). In addition, a method is known, according to which the crushed metal oxides are mixed in a dry state together with a material that facilitates the formation of the mixture into tablets that are pressed and burned before use.  Thorough mixing of the crushed metal oxides in water and drying the resulting suspension from the sprayed solution is also used to obtain relatively free of fluids and free flowing spherical particles, which are also calcined before use. There is also a known method for producing salts (precursors of the composition of an inorganic metal / oxygen, For example, nitrates, carbonates and acetates) are thoroughly mixed or dissolved in water or nitric acid and heated to thermally decompose salts. recursors with the formation of the corresponding complexes of oxides and / or oxygen.  Before using the oxide and / or oxygen complexes, they are treated as described.  The temperatures used for baking the composition of the inorganic metal oxygen are in the range of about 400-1200 ° C.  At temperatures of about 900-1100 ° C, a higher selectivity is obtained with a slight loss of activity.  Therefore, the preferred roasting temperature is about 700-1000 ° C.  The firing time ranges from about 1 to 12 hours or more, preferably from 2 to 10 hours at higher temperatures. The inorganic metal / oxygen contact surface area suitable for use according to the invention is less than 10 m and preferred values are about 0.1-5 m / g.  As indicated, the proposed process is preferably carried out in the presence of added free oxygen, t. e.  stoichiometrically and only the inorganic metal / oxygen obtained from the contact is used.  So, generally under similar conditions (with some exceptions), the lower the toluene conversion, the higher the selectivity of the production of dehydration products.  This means that the selectivity of the production of toluene dehydrochlorination products is mainly inversely proportional to the conversion of toluene.  But for practical reasons, the dehydro-coupling reaction is usually carried out at a toluene conversion of from about 20 to 55%.  The products of toluene stilbene and bibenzyl dehydrochemicals can be regenerated and purified by any suitable known method.  The preferred product is stilbene.  In the proposed examples, preferred embodiments are given.  However, various changes and modifications are possible within the scope of the invention.  Example 1  Method A.  A series of inorganic metal / oxygen contacts with different atomic ratios Bi | M is obtained by thoroughly mixing an appropriate amount in grams of bismuth oxide (P1) (V120 h) and at least one oxide (or hydroxide) in water, filtering to remove excess water or by heating to evaporate the water and then drying.  The resulting solid is placed in an open cup. and burned in the air, first at initial temperatures, and then additionally at final temperatures.  The calcined material is removed.  from the oven, cooled, crushed in a mortar and sieved.  The parameters of the compositions, denoted by 1-A, are given in table.  one.  Method B.  A method similar to Method A is used, except that after the final calcination, the calcined material is removed from the kiln, cooled, crushed and mixed with calcium aluminate cement (AEsoa-CA-25) in an amount corresponding to 25% by weight of the dry calcined material.  The resulting solid mixture is stirred with water to form a thick paste and dried in air.  The dried paste is burned in air in an open cup for 2 hours with and then at room temperature for another 2 hours.  The resulting contact is inorganic metal / oxygen removed from the furnace, cooled, J crushed in a mortar and sieved, Parameter; compositions denoted by ;; s through f-B ,, are given in table.  one .  Method B.  Getting inorganic metal / oxygen contacts; Contains zismut and calcium on alumina.  To a solution containing 150 ,.  With i (O. AiJ MOL1)) alumina nitrate (Al (N0-5,) 91-UO) 5 dissolved in 100 ml of water, a concentrated aqueous solution of ammonia (NHTvaq), ammonium hydroxide is added to bring the pH to 8.6 (approximately 110 ml)  300 ml of water is added to facilitate mixing.  The aqueous mixture is heated with stirring to 75 ° C., and the temperature is kept for 1 hour. The gelled precipitate is hydrogenated with aluminum oxide (alumina) and filtered with suction and washed twice with water and filtered. creamy consistency. To this mixture (thoroughly mixing, slowly add a thoroughly mixed mixture of 69. 9 g (O, 15 mol) of bismuth oxide (Hi) () and 5; 6 g (O e10 mol) oxide n cal di (Ca O).  After completing the addition, the mixture is stirred for another 30 minutes.  poured into heated zmilyr kni: th vat and evaporated dosutsa at low temperature (ah. heating & g {{tile),. wen hard; 1 The calcination material in air in an open cup for 2 hours at and then at a final temperature of 1000 ° C for another 8 hours. The inorganic metal / oxygen contact is 21% by weight composed of Chlinozem (the atomic ratio of bismuth and calcium is removed from the furnace; mortar and gfoseivayut.  Parameters ohsag.  marked through 1-e5 are given in table.  1 „Method G. The method of obtaining inorganic metal / oxygen contacts containing bismuth and magnesium.  BHCf oxide. fyTa (BUT (93 ,, 2 g 0.2 (.  mol) and 48.0 g (0.40 mol) of magnesium sulfate riepe--. ieiJinti. iioT with sufficient koJIIchec-zo 1 bo, n. i, i with the receipt of 510 den of a dense iugam.  The resulting mixture is heated to dryness at lOOc and calcined in air in an open cup at 300 ° C for 8 hours.  The burned material is removed from the furnace, cooled, crushed in a mortar and sieved.  The parameters of the compositions, denoted by I-D, are given in table.  one .  Example 2, Method A.  The preparation of inorganic metal / oxygen contacts with different atomic ratios of Bi / M is obtained in the following manner.  Dissolve the appropriate amount in grams of pentahydrate nitrate of bismuth (111) nitrate (BL (NO) 5 ligO or bismuth oxide (1P) B1l0) and at least ONE m nitrate in approximately 100 ml of concentrated nitric acid (HNOo) and heated with evaporation and decomposition of nitric acid and nitrates.  The resulting solid is placed in an open cup and calcined in air for 8 hours at 850 ° C.  The calcined material is removed from the furnace, cooled, crushed in a mortar and sieved to a particle size of 14/30 mesh for the evaluation described in Example 4 in a toluene conversion reactor.  In this way, formulations denoted by 2-A are obtained with the properties of the ID useful 1 and for use in the proposed method.  Method B.  Similar to method A, but after calcination, calcined NEIus material for calcium aluminate cement (Lbsaw-Ca-25) 5 as indicated in Example 1 of Method B.  The parameters of these TaBOBJs denoted by 2-B are listed in Table.  2  I Example 3.  A series of inorganic metal / oxygen contacts5 containing two or more M elements is obtained by thoroughly mixing a suitable amount of bismuth nitrate pentahydrate (1P) (Bi (NO-) 5 H O) with at least two nitrates I. PI oxide g-shL (or by mixing a certain amount of a suitable bismuth-containing inorganic metal / oxygen dual composition with at least one nitrate or oxide M in water and heating for B1 to 1 steam of water and / and. 1; and decomposition of nitrates.  The resulting solid is placed in an open cup and fired.  They are airborne first at the initial temperature and then additionally at the final temperature.  The calcined material is removed from the furnace, cooled, crushed in a mortar and sieved to a particle size of 14/30 mesh for the evaluation described in Example 4 in a toluene conversion reactor.  The parameters of the compositions, denoted by 3-A, are given in table.  3  Example 4 BUT.  Reactor for the toluene conversion reaction.   As the reactor is used, stainless steel tubes with a length of 20.32 cm, an internal diameter of 0.95 and a capacity of 11 ml.  The reactor is installed in a vertical position and is equipped with a reagent inlet with calibrated flow controllers and evaporators at the upper end and a outlet for the reaction product of the effluent or for its direct introduction through a gas sampling valve to the gas-liquid chromatograph for analysis at the lower end.  The output is intended to introduce a diluent of an inert gas of nitrogen or helium, for example, into a stock reaction product for analysis.  A baking oven is used to maintain a constant temperature during the reaction.  The temperature is measured with a thermoelement based on the temperature at the lower outer wall of the reactor.  B.  The conversion of toluene.  The reaction is carried out in a stoichiometric manner, unless otherwise specified.  The reactor is charged with approximately 11 ml of the inorganic metal oxygen composition prepared in Examples 1-3.  Glass wool plugs are used as carriers for the composition. The loaded reactor is placed in a reflection oven and heated to maintain a constant temperature during the reaction.  Steam and toluene in a molar ratio of a research institute of 2: 1 under a pressure of 1 atm are loaded into the reactor at a rate sufficient for a residence time (contact time) in the reactor of 4 s (if not otherwise agreed) for toluene (it is assumed that reactor 50% void volume).  After 1 min, the product of the effluent reaction, diluted with helium, is subjected to gas analysis by analogous chromatography.  The results are shown in Table.  four.  P p i. meper 51 A catalytic process is used.  The reactor and method described in Example 4 are used, but air and toluene are fed to the reactor in a 2: 1 molar ratio.  The results are shown in Table.  five.  Example 6  The way v (dividing stilbene in its pure form.  Flows of products from a series of toluene dehydrogenation reactions are collected in dry ice-cooled traps.  The combined streams are rapidly heated to 200 ° C and then periodically distilled through a column with an inner diameter of 2.5 cm and a length of 90.0 cm, packed with a protruding metal.  The fraction having a boiling point at about 186 C-20 mm of mercury is collected as trans-stilbene.  Stilben is a white crystalline solid having a boiling point of 124-125 ° C and a retention time that is identical to the genuine trans-stilbene sample, as determined by gas chromatographic injection.  Molten trans-stilbene reacts rapidly with atmospheric oxygen to form numerous oxygen-rich (or polar) impurities, most of which are benzophenone.  From this it follows that the molten Transtilbene must be protected from the atmosphere.  The trans-stilbene so contaminated can be purified by recrystallization from 95% ethanol to give a pure product.
    Table 1
    Calcium aluminate cement was replaced by colloidal silica (Lugox, which is supplied by foreign company E.I. Dupont de Nemours and Company, Chemicals Dyes Pigments Dept., 1007, Market street, Wilmington, DE 19898). Bil) (a) BiCa (93.2 (U, 20)
    Table 2 CaOSr 11.2 (0.20) 20.7 (0.20) 450/1 800/8
    (a)
    1-a-1- (b)
    1-A-b (c)
    (g)
    1-a-1- (d)
    1-a-1- (e)
    1-a-1- (g)
    1-a-2- (a)
    Table 4
    nineteen
    1-a-2- (b)
    49.3
    575
    1-a-2- (c)
    1-a-2- (g)
    l-drl- (a)
    l-b-i- (a)
    1-C-1- (a)
    2-B-1- (a)
    2-B-1- (b)
    2-B-1- (c)
    1095875
    20 Continued table. four
    62.5
    2.1,1
    7.1
    69,6
    The contact time is 4 seconds, unless otherwise specified.
    23109587524 Unless otherwise specified, contact time
    Table 5 is 4 seconds.
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING STILBENE by vapor-phase oxidative dehydrodimerization of toluene in the presence of an oxide contact containing bismuth at 500-630 ° С, characterized in that, in order to simplify the process, use a contact of the general formula where M is calcium, strontium, silver, indium, magnesium or a mixture thereof; d is from 0.1 to 100;
    X is the number corresponding to the valency of Bi and M 1 in the oxidized state.
    [2]
    2. The method of pop. 1, characterized in that the process is carried out in the presence of an oxygen-containing->
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/101,942|US4247727A|1979-12-10|1979-12-10|Dehydrocoupling of toluene|
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