• 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:
    Long on-stream periods of low pressure, vapor phase isomerization of xylenes is achieved in a system having tolerance of ethyl benzene in the charge by using a zeolite catalyst such as zeolite ZSM-5 at partial pressure of eight carbon atom aromatics below 100 pounds per square inch and temperature of 500 DEG F. to 800 DEG F.
    公开号:SU893125A3
    申请号:SU782562007
    申请日:1978-01-09
    公开日:1981-12-23
    发明作者:Майкл Митчел Кеннет；Джеймс Вайз Джон
    申请人:Мобил Ойл Корпорейшн (Инофирма)；
    IPC主号:
    专利说明:

    I
    The invention relates to methods for producing p-xylene and may find application in petrochemical production.
    The known method of vapor phase isomerisation of a mixture of aromatic hydrocarbons containing ethylbenzene at low pressure using an aluminosilicate catalyst 1.
    However, this catalyst produces ethylbenzene under severe conditions, under which very significant xylene loss occurs due to disproportionation. In addition, this catalyst quickly loses its activity due to the deposition of coke, a carbon-containing layer, which closes the active points of the catalyst. Coke can be removed by burning it with air to restore the activity of the catalyst. The continuity of the operation is achieved by applying the well-known method of switching reactor, by which two or more
    reactors, one of which is in operation, and in the second, the reduction process is carried out by burning the catalyst that has lost activity due to the deposition of coke. Usually, work is carried out in one reactor for 2 days, followed by switching to the just-regenerated reactor.
    There is also known a method of isomerising a mixture of aromatic hydrocarbons under pressure sufficient to maintain the initial mixture in a liquid,
    Active zeolite catalysts under these conditions are highly efficient and have a long service life due to the fact that highly condensed compounds are dissolved with liquid reagents and washed out of the reactor before they turn into coke.
    The closest to the proposed technical essence and achievable result is a method of producing p-xylene by isomerization in the vapor phase at elevated temperature and pressure of a mixture of isomers of C / aromatic hydrocarbons containing ethyl benzene, using ZCM-5 type zeolite as a catalyst. The process is carried out at 2 bSSO C and a pressure of up to 1 atm, with a bulk feed rate of 1. The aim of the invention is to simplify the process technology. This goal is achieved by the method of p-xylene production by isomerization of the isomer mixture of CQ-aromatic hydrocarbons containing ethylbenzene in the vapor phase, at a temperature of 0-4.57 kg / cm partial pressure of the initial mixture, 2.5- 25 kg / kg zeolite h in the presence of zeolite type ZSM-5. The technology of this method is as follows. The initial mixture of aromatic hydrocarbons containing eight carbon atoms undergoes vapor phase isomerization under these conditions. Zeolite catalyst in the absence of hydrogen has the ability to accumulate coke on itself, which may lead to the need to reduce operating cycles, so the process should be carried out in compliance with the specified operating parameters. This will increase the period of catalyst operation (i.e., the catalyst will be aging at a lower rate Usually protective pads of an inert gas, such as nitrogen, are created in the storage tanks for the original alkyl aromatic fraction to prevent the development of peroxides. However, if these compounds are still formed due to contact of Cg-aromatic compounds with air, then peroxide removal can be accomplished by percolation through alumina.Preferably, the raw material is cleaned prior to contacting the isomerizing catalyst according to the proposed method. This can be done before adding aromatic compounds. into the cycle of separation and isomerization. Raw materials can be introduced into the cycle before distilling off Cd + compounds with a higher boiling point formed in the isomerizer. The proposed method allows the conversion of raw materials containing ethylbenzene, which contributes to a significant reduction in the cost of pre-purification of the raw material. The concentration of ethylbenzene in the cycle is maintained at about the same level as in the starting material, since the proposed method allows disproportionation of ethylbenzene with very insignificant x-xylene losses and remove the products of the disproportionation of ethylbenzene with the usual from the race “Ex, one raw material contains 19.0 ethylbenzene, 20.31 o-xylene, k, 3% m-xylene, 18.6% p-xylene and 0.8% Cd and heavy aromatic hydrocarbons and fed to an ethylbenzene column at a rate of 50,000 kg.h. The selection of products from the upper part of the column, predominantly consisting of ethylbenzene, is carried out at a speed of 75–5 kg, h in the usual way. The effluent from the bottom is mixed with xylenes and ethylbenzene at a rate of 37935 with kg of recycled product from the isomerization and distillation unit. A stream of kg-h mixture is fed to a p-xylene recovery unit, for example, to a fractional crystallization zone, from which 351,00 kg, p-xylene h, which is the main product, is obtained. From the regeneration zone, the flow of Cd-aromatic compounds separated from p-xylene is fed at a speed of kg / h to the isomerization zone, where it interacts in the vapor phase with the acid form of the zeolite ZSM-5 / H-ZSM-5 / at 2 б-425 ° С and pressure, which leads to the conversion of ethylbenzene partially into benzene and diethylbenzenes. The products leaving the isomerization zone are fed to a stabilizer, from where compounds with less than eight carbon atoms are taken from above, and the bottom stream in an amount of 206A60 kg-h is fed to a splitter, from which heavy fractions of compounds containing 9 or more atoms are removed. carbon. The overhead is made of a splitting agent, mainly from the aromatic compounds of Sd, in which the xylenes are represented mainly by equilibrium quantities. The stream is then recycled for mixing with a new portion of the feed from the ethylbenzene column. 5 When performing the process in the described order, the catalyst for isomerization works without replacement for many months (up to a year or more). A higher partial pressure of aromatic compounds leads to a sharp drop in the activity of the catalyst, as a result of which it begins to approach the low-cost aluminosilicate catalyst. The isomerization pressure is measured as the partial pressure of aromatic carbon, hydrogen. As the partial pressure of aromatic hydrocarbons increases, the service life of the catalyst tends to decrease. If necessary, raw materials can be supplied to the isomerizer under high total pressure by adding inert diluents such as nitrogen, hydrogen and others. However, undiluted hydrocarbons are most preferable. a pressure that is sufficient only to balance the pressure drop in the distillation device and other auxiliary units (on the order of 1.7 atm), torye substance, such as toluene and alkylated aromatic hydrocarbons containing more than eight carbon atoms may contribute to achieving equilibrium in izomerizatore. If such modifiers are used, then optional. Their partial pressure should be taken into account in the preferred mode. The catalyst used is representative of a new class of zeolites. Zeolites provide a significant conversion of aliphatic hydrocarbons to aromatics and are highly efficient in the conversion of aromatic hydrocarbons. The zeolite used in the proposed method contains an unusually small amount of alumina, and the ratio of silica to alumina is very significant. It shows high activity even if the ratio of silica to alumina exceeds 30 This is a feature of these catalysts. since the catalyst activity is usually associated with the structure of the atom of aluminumRych and related cations. These zeolites for a long time retain their crystalline state, despite the presence of high-temperature steam. ture, which causes irreversible destruction of the structure of other zeolites, such as type A and X, in addition, for the reduction of activity can be removed, if formed, by burning carbonaceous deposits at temperatures significantly higher than conventional. In many cases, non-zeolites of this class produce little coke for a long period of operation between the regeneration stages. gani. An important property of the crystalline structure of this class of zeolites is limited access to it and exit from the intercrystalline free space through pores larger than 5 L. The pores of this size are provided with 10-membered rings of oxygen atoms. It follows that these rings are formed by the correct structure of a tetrahedron that strengthens anionic structure of crystalline aluminosilicate, with the oxygen atoms themselves being attached to silicon or alumine atoms in the centers of the tetrahedron. The proposed type of zeolites is aets molar ratio of silica to alumina of at least 12, of the structure, providing poor access to the crystalline free space. The ratio of silica to alumina can be determined by routine analyzes. This ratio should reflect as accurately as possible the ratio in the rigid anionic lattice of the zeolite crystal and exclude aluminum in the binder in cationic or other form within the silicon matrix. Although zeolites with a silica-to-alumina ratio are not less than 12, it is preferable to use zeolites with higher ratios, for example, about 30 Such zeolites, after activation, have an intercrystalline sorption capacity for normal hexane, which is more than a similar capacity for water, Toe. have hydrophobic properties “The zeolite used svobodno absorbs ordinary hexane and has pores larger than 5 A, in addition, the structure of the zeolite should provide difficult access for larger molecules. Sometimes, based on the known crystal structure, it is possible to determine whether such difficult access exists . So, for example, if the pore holes in the crystal are formed by 8-membered rings of oxygen atoms, then in this case access for molecules larger than that of normal hexane is excluded and then such a zeolite is not necessary. The openings of the 10-membered rings are preferred, although in some cases merging or blocking the pores can deprive these zeolites of the effectiveness of the 12-membered rings do not, as a rule, provide the necessary obstacle for creating a satisfactory conversion. In addition, a structure can be created by blocking pores or other action. In order to determine, based on the crystal structure, whether the zeolite has the necessary obstruction, a simplest definition of the index can be made difficult by continuously passing the mixture consisting of equal parts. the weight of normal hexane and 3 methylpentane through a sample of a catalyst weighing not more than 1 g at atmospheric pressure according to the following method: A sample of zeolite in the form of granules or extrudate is crushed to grains and loaded into a glass test tube. Before starting the test, the zeolite was dusted for 15 min with a stream in spirit at 535 ° C. Then the zeolite was washed with helium and the temperature was set to 285-5 ° C with a conversion of 10 to 6Q. A mixture of hydrocarbons is passed through a zeolite at a liquid hourly space velocity of 1/1 (volume of liquid hydrocarbon per volume of zeolite per hour) with dilution of hydrocarbon with helium to a molar ratio of helium to hydrocarbon 4: 1. After 20 minutes, a liquid sample is taken for analysis. carried out in most cases by gas chromatography to determine the fraction, the remaining 6.3 changes for each of the two hydrocarbons 8. The hindrance index is determined by the formula: 1 1 1 (fraction, and the remaining n-hexane) Tog III (the fraction left 3- methyl pentane) The ndex difficulty is approximately equal to the ratio of the cracking rate constants for two hydrocarbons. The zeolite used has a difficulty index of about 1 to 12 "obstruction index (C1) for some typical zeolites: The intensity index Catalysts 8.3 ZSM-5 8.7 ZSM- 11 ZSM-12 2 2 2SM-38 ZSM-35 Off-TIT TMA n-Zeolrt R E Y Amorphous Erionite Aluminosilicate The indicated difficulty values characterize specific zeolites, but are a cumulative result of several variables used in determining and and calculating index values. Therefore, for a given zeolite, depending on the temperature condition and the conversion value from 10 to 60, the difficulty index may vary in the range from 1 to 12. Similarly, other variables may affect the difficulty index, for example, the size of zeolite crystals, the presence of occluded impurities and Binder Index The obstruction index in the form in which it is used here is a very convenient criterion for characterization (a zeolite, but rather an approximate one, taking into account the method of its determination, in which Extreme magnitudes are used in the rays.However, in all cases at a temperature of 285-510 ° C, the difficulty index for the proposed zeolite ranges from 1 to 12. The proposed zeolite can be ai; tivizirovan, for example, by heating in an inert atmosphere with 535 ° C for 1 h, followed by cation9, but exchange with ammonium salts of those zeolite species from which alkali metal cations should be removed, followed by calcination in air at. The presence of organic cations in the initial solution is not necessary for the formation of this type of zeolite, but contributes to its formation. It is desirable to activate this type of catalyst through the main exchange with ammonium salts, followed by calcination in air at about 15 minutes - 2k hours. Natural zeolites can sometimes be converted to this type of zeolite catalyst by various activation methods and other types of processing such as basal metabolism, steaming, extraction of aluminum oxide and calcination Inácio of Natural minerals which may be subjected to such processing, are ferrite, Brewster, stilbite dahiardit, epistilbit, hyulandit clinoptilolite and of zeolites selected from a crystalline lattice density in the dry hydrogen form, not much below 1.6 g / cc. The most suitable are zeolites, which meet all three criteria, i.e., those with a strength index of 1-12, a silica to alumina ratio of at least 12 and a dry crystal density of at least 1.6 r / cfi The density of a dry crystal can be calculated from the number of atoms of silicon and aluminum per 1000 A: If the crystal structure is unknown, the density of the crystal lattice can be determined by an ordinary picnometric method, or, for example, by immersing the zeolite of a dry hydrogen form in an organic plant. ry not absorbed by the crystal. It is possible that the unusual long-term activity and stability of this class of zeolites is associated with a high density of its crystalline anionic lattice of at least 1.6 g / cm, which is associated with a relatively small free space inside the crystal, which gives more stable structures . This free space plays an important role, since there are points of catalytic activity. The density of the crystalline structures of some typical zeolites can be as follows. Density Zeolite Pore volume, cm / cm of the lattice, g / cm ferierite 0.28 0.28 Mordenite ZSM-5, ZSM-11 0.29 1.61. The zeolite synthesized in the form of alkaline etalla is usually converted into the hydrogen form, as a rule, by the subsequent formation of an ammonium form as a result of the ammonium ion exchange, the calcination of the ammonium form to obtain the hydrogen form. When carrying out the conversion, it is possible to include the specified crystalline aluminosilicate zeolite in other substances resistant to the temperature and other conditions of the method used. Such matrices can be artificial or natural substances, such as inorganic substances such as clay, silica and / or metal oxides. The latter can be either of natural origin, or in the form of gelatinous precipitates, or in the form of gels, including mixtures of silica and metal oxides. Clays of natural origin, which can be included in the zeolite, are those of the kaolin and montmorillonite families, which include Sabbentonites and kaolins commonly known as Dixie, McName-Georgie and Florida clays or others, in which the main mineral components are galloisite, kaolinite, dikite, nakrit or anaouxite. Such clays can be used raw, ie that which they are delivered from the quarry, or initially subjected to calcination, and acid treatment
    for chemical conversion. Low pressure isomerizers typically operate at a WHSV / hour volume weight rate of 1.
    With the ZSM-5 type catalyst, the process can be carried out at a volumetric feed rate of the initial mixture of 2.525 kg / kg zeolite h. When operating with a zeolite catalyst, its amount is significantly reduced. However, a 3-fold decrease in the catalyst volume may cause the catalyst layers to become so thin that the distribution of the reactants will not be satisfactory. One method of correction (to obtain a length to diameter ratio L / D of 0.2 in the reactor) is to insert a sleeve to create a layer of smaller diameter. Another way is that inert granules can be introduced into the bed above the catalyst. The third method involves the preparation of a catalyst with a high content of an inert matrix, for example 70 alumina, 30% HZSM-5.
    Regardless of which of these substances can be used, the WHSV value, calculated as the supply of alkyl aromatic hydrocarbons in relation to the active component of the zeolite catalyst, should be 2.5-25 kg / kg zeolite h
    The volumetric rate considered refers to the weight of the aromatics in the feedstock. Aromatic compounds can be diluted with such inert substances as saturated low aliphatic hydrocarbons, nitrogen, hydrogen and others. Basically, such dilution is undesirable, however, if the composition should be diluted, the volumetric rate is determined by weight of alkyl aromatic hydrocarbons (mainly with 8 carbon atoms ).
    Aging of the catalyst is determined by the activity of converting ethylbenzene contained in the feedstock to isomerization. This conversion results in the production of benzene, Cr-aromatics and light hydrocarbons by disproportionating ethylbenzene to benzene and diethylbenzene and transalkylation with xylene to obtain a by-product such as methyl ethylbenzene. Despite the fact that
    xylene loss depends on ethylbenzene conversion; it is obvious that the proposed catalyst is more effective in carrying out the intermolecular displacement of the alkyl group (bimolecular transalkylation) of ethylbenzene.
    Adjusting the wear compensation process can be achieved by increasing the temperature throughout the operating cycle in order to maintain the conversion of ethylbenzene at a fairly constant level. For example, a continuous operation cycle for several months can be started at a temperature range of 260-285 ° C during the isomerization of xylene with an almost approaching equilibrium. With very insignificant xylene losses and ethylbenzene conversion at this level, it is possible to maintain the concentration of this compound in the isomerization recycle product and in the feedstock.
    I.
    It is desirable to terminate the duty cycle when the temperature condition is of the order of the order. The pressure should be maintained at a level of 0- 5 KG / CN of the partial pressure of the initial mixture. It is preferable to work with a pressure of about 1 atm.
    The process conditions, the mode parameters and the yield for the xylene isomerization process at low pressure according to the proposed method, compared with operation on a conventional aluminosilicate catalyst, are as follows:
     ZSM-5
     Alftoy
    A1
    1.76 1.76
    five
    one
    k27-f S Q
    180
    2-k
    80
    100
    2.1
    0.2
    9.8
    2.7 93.2 75.7 ne12, i
    3.9 13 The efficiency of the ZSM-5 catalyst for xylene isomerization under low pressure conditions is based on less severe conditions, significantly longer regeneration periods, improved equilibrium conditions and higher p-xylene yield, which contributes to an increase in product quality. , higher performance and lower KIM operating costs. In addition, the proposed method provides a high degree of conversion of ethylbenzene at low xylene losses due to its conversion to other substances as compared to larger losses of xylene during conversion of ethylbenzene mixed with xylenes using an aluminosilicate catalyst. The process is carried out on an experimental setup consisting of three consecutive semi-adiabatic reactors, but the catalyst (0 cm) is loaded only into one reactor. In one reactor, the process is carried out with a catalyst containing crystals (0.05 µm) ZSM-5, soda stinging 35 ppm of alumina. A catalyst with large ZSM-5 crystals is used in the second experiment. Experimental conditions are given in tabLo1. The composition of the initial mixture is shown in Table 2, Except for the first load for the first experiment, the distribution of xylene is below equilibrium for p-xylene and above equilibrium for o- and m-isomers. This distribution reproduces the industrial installation, where p-xylene is the only xylene produced by these experiments. The concentration of ethylbenzene varies from 6.9 to. 20.5% by weight. The minimum value refers to the case when a certain amount of ethylbenzene is removed by a septum before the experiment, the maximum is the case. When all the ethylbenzene in the Co-aromatic fraction from reforming enters the raw material for the cyclases. All liquid raw materials are pumped through the layers of activated alumina before being loaded into the unit. Oxidized hydrocarbons (for example, peroxides) are removed. The mixtures prepared in the laboratory contain insignificant amounts of these substances, since the mixture is prepared in contact with air. A small amount of nitrogen (equal to about 0.2 mol / mol, .HНС) is fed to the unit to maintain pressure. During the entire first experiment and during the first 8 days of the second experiment, nitrogen is mixed with the liquid feed mixture and passed through the catalyst “Thereafter, nitrogen is fed in the opposite direction of the installation (before the check valve) to remove the catalyst bed. Without such a purge, the operation of the installation is difficult. The process is carried out over 6 May, with a catalyst of the second experiment at 1.76 kg / cm, conversion of ethylbenzene 25 and WHSV, 5 in the sum of the composition, corresponding to 7.7-13 in zeolite. The loss of activity by the catalyst for the conversion of ethylbenzene is equivalent at WHSV i, per month, and at WHSV 8.51.7 ° C per month. Output at a low content of ethylenezol in the feed at a pressure of 1.76 kg / s "HSV 5, temperature 315 ° C, conversion ethylbenzene 2.6 next,%: € 50.0 C, 3 Benzene 0,7 Toluene1,6 Ethylbenzene p-Xylene 21.9 m-Xylene 3.9 o-Xylene 19.5 Cd + Aromatic Compounds 1.9 PON - paraffins, olefins , naphtheno Yield with a high content of ethylenezol in the feedstock under the specified conditions and conversion of ethylbenzene to 23.6 wt%, the following,%: Benzene Toluene Ethylbenzene p-Xylene m-Xylene O-Xylene Cd + Aro Mathematical compounds. The process is usually carried out with continuous loading of a mixture of aromatics Cg at C for at least 30 days. It is also possible to work continuously for 6 months or more. As the catalyst activity decreases, the reaction temperature increases within the indicated limits. With this asset
    15893
    The catalyst is considered from the point of view of ethylbenzene conversion, the temperature increases during the experiment to a degree that allows maintaining the conversion of ethylbenzene at a constant level. Usually, the temperature increases in steps, so that it rises at intervals of several days,
    sixteen
    On the basis of the experimental data obtained, it is possible to determine the total yield of the product during processing in the cycle. The values calculated with this are given in Table 3
    The conditions of the process and the yield of the product are presented in Table 4, the composition of the feedstock is in Table 5
    PON - paraffin, olefins, naphthenes.
    17
    Note. Boot raw materials, code: A, A, A, B, C, C
    89312518
    权利要求:
    Claims (1)
    [1]
    Table 3 PON - paraffins, olefins, naphthas. Formula of the invention. A method of producing p-xylene by vapor phase isomerization at elevated temperature is a mixture of isomers of Co-aromatic hydrocarbons containing ethylbenzene, using ZSM-5 type zeolite, as a catalyst. , in order to simplify the process technology, the latter is carried out at a partial pressure of the initial mixture
    Table 5 O-, 57 kg / cm, temperature and flow rate of the feed mixture 2.5-25 kg / kg zeolite.h. Sources of information taken into account in the examination of V. Koptyug. A. Isomerization of Aromatic Compounds. Novosibirsk, Publishing House of the Siberian Branch of the Academy of Sciences of the USSR, 1963, p. 23. 2o. U.S. Patent No. 3,578,723, Class 2BO-B72. 3. US patent No. 3856873, C. 07 C 5/2, published 197 (prototype).
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/758,214|US4101596A|1977-01-10|1977-01-10|Low pressure xylene isomerization|
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