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    • 专利摘要:
    C110 SOB OF THE TETE SULF OLEFINS by contacting mixtures of hydrocarbons containing them with methanol in the presence of an acidic catalyst based on ion exchange resin at 70 ° C and a pressure of 10-15 atm, separating the methyl tert-alkyl ester thus obtained from the remaining hydrocarbons, cleaving the methyl tert-alkyl ether to tert-olefin and methanol in the presence of a catalyst at 140-160 ° C and a pressure of 10 atm and separation of the tert-olefin from methanol, vc: distillation booster, characterized in that, in order to simplify the process technology, contacting is carried out in the presence of an ionorbous resin, a sulfonated copolymer of styrene and divinylbenzene containing 0.75 g / l of palladium as a catalyst, splitting is carried out in the presence of H-mordenite as a catalyst, and the tert-olefin is separated from methanol by distillation office 83,6-98,2; wt.% of methanol from (L-tert-olefins and removal of the remaining methanol by adsorption on a copolymer of styrene and divinylbenzene with dimethylbenzylamine groups or on: a methacrylic resin with dimethylbenzylamine groups at and a pressure of 1-30 atm with a mass load on the adsorbent 1-44 with desorption of absorbed methanol by the flow of a mixture of hydrocarbons containing the resulting tert-olefin at 20-65 C and a pressure of 5-30 atm, returning it to obtain the methyl tert-alkyl ester.
    公开号:SU1176825A3
    申请号:SU823452913
    申请日:1982-06-17
    公开日:1985-08-30
    发明作者:Гервиг Йенс；Шульвитц Бруно；Шлеппингхофф Бернгард；Шейф Ганс-Фаолькер；Михаэль Ланге Петер
    申请人:Эх Эрдэльхеми Гмбх (Фирма)；Байер Аг (Фирма)；
    IPC主号:
    专利说明:

    1 1 The invention relates to the production of olefins, in particular, to a method for producing pure tert-olefins. A method for producing tert-ol-fins, namely isobutylene, is known by contacting fraction C containing iso-butylene with methanol in the presence of acidic cation exchangers at elevated temperature. , the subsequent decomposition of the methyl tert-butyl ether thus obtained with the same catalyst at 80-120 ° C. The reaction products are cooled, the condensate is separated and a gas mixture containing iso-butylene ij is obtained. The disadvantage of this method is not high quality of isobutylene produced. The impurity content is 1.1%. The closest to the one proposed is a method of producing isobutylene by contacting a mixture of hydrocarbons containing methanol and a mixture in the presence of an acidic catalyst based on an ion exchange resin at a temperature of less than lOO C and pressure. sufficient to conduct contacting in the liquid phase, separating the methyl t-butyl ester thus obtained from the remaining hydrocarbons, splitting the methyl t-butyl ester to isobutylene and methanol in the presence of water and a catalyst at a temperature of less than 300 ° C and letting process in the liquid phase, the separation of tert-olefin - isobutylene - from the meta in the separator, followed by washing the isobutylene from methanol with water, drying and rectification. The methanol-water phase separated in the separator is distilled with separation of methanol and water 2j. The disadvantage of this method is the complexity of the process technology, which is associated with the multiplicity of the selection of the target product, which includes the stages of separation, drying, and rectification, 1-sh. The purity of the target product is 99%. The aim of the invention is to simplify the process technology. This goal is achieved by the method of producing tert-olefins C by contacting mixtures of hydrocarbons containing them with methaNOL in the presence of a catalyst of a sulfonated styrene copolymer and divinylbenzene containing 52 0.75 g / l palladium at 70 ° C and a pressure of 10-15 atm, separating the obtained at the same time methyl tert-alcstylether from the remaining hydrocarbons, cleavage of methyl tert-alkyl ether to tert-olefin and methanol at and 10 atm pressure in the presence of H-mordenite as catalyst, distilling tert-olefin from methanol with separating 83,698.2% by weight of methanol from t-ralphins and removing the remaining methanol by adsorbing styrene and divinylbenzene with dimethylbenzyl on the copolymer with other groups or on methacrylic resin with dimethylbenzylamine groups at 0-30 ° С: and a pressure of 1-30 atm with mass the load on the adsorbent 1-4 by desorption of absorbed methanol by a stream of a mixture of hydrocarbons containing the resulting tert-olefin at 20-65 ° C and atm pressure with returning it to produce methyl tert-alkyl ether. Tert-olefins C can be obtained by the described method from a mixture of hydrocarbons, which, in addition to at least one tert-olefin, contains other olefins or saturated hydrocarbons. In addition, the mixture may contain hydrogen, nitrogen, CO or CO2. Examples of such mixtures are the raw fraction C,}, or the raffinate C (after the extraction of butadiene) from the thermal cracking unit, the raw product stream from the unit for liquid catalytic cracking, fraction C from the catalytic cracking unit. The crude product stream from the liquid phase catalytic cracking unit can be pre-divided into stream C and stream Cj. A stream C from a thermal cracking unit is also suitable, for example, a head distillation stream in the preparation of aromatic hydrocarbons. Other mixtures may be n-butene isomerization dehydrogenation isomerization streams that contain iso-butene. Suitable starting streams for the conversion of higher tert alefins are, for example, fractions with an appropriate number of carbon atoms obtained by distillation; dehyd31 flows
    riation or skeletal isomerization of hydrocarbons with an appropriate number of carbons. In the case of mixtures of hydrocarbons containing more than one tert-olefin, several simple alkyl tert-apkyl ethers can be formed, resulting in the subsequent cleavage of the ester mixture of several tert-olefins, which can then be separated to individual components, in case mixtures of several simple al- are obtained. Kil-tert-alkyl ethers, the latter can be separated into pure products before splitting, so that after cleavage of pure ethers, pure individual tert-olefins are also obtained.
    The ratio of alkanol to tert-olefin or to tert-olefins may be, for example, 08-5 mol of methanol per mole of tert-olefin or for each mole of the molar sum of different tert-olefins. In the case of the esterification of isobutene with methanol, an excess of methanol is used, for example, in an amount of 1-4, preferably 1, 13 mol of methanol per 1 mol of iso-butene.
    The esterification is carried out at, 70 ° C and a pressure of 10-15 atm, i.e. when the reacting components are in a liquid state. The volumetric rate, expressed in liters of hydrocarbon feedstock per liter of acidic contact per hour, is, for example, 0.05-50, preferably 0.2-15.
    After the esterification process, the resulting alkyl tert-alkyl ether is separated from the non-esterified remaining mixture of hydrocarbons with non-esterifiable olefins and paraffinic hydrocarbons, and also, if necessary, from the remaining tert-olefin that is unreacted due to the unfavorable esterification,
    If necessary, the ether is subjected to a clear rectification for the purpose of separation of higher hydrocarbons and higher ethers,
    The subsequent reverse cleavage of methyl tert-alkyl ether or a mixture of such methyl tert-alkyl ethers is carried out in the liquid phase at) 40-160 ° C and a pressure of 10 atm
    68254
    on H-mordenite, which is pre-activated by treatment with hydrogen.
    Hydrogen activation can be carried out, for example, with the help of 50-500 liters of hydrogen / I l of catalyst at 100-450 s and a pressure of 1 to 50 bar for 1-60 hours.
    Cleavage of methyl tert-alkyl ether gives a mixture of the corresponding tert-olefin and methanol.
    From the mixture obtained in the cleavage of methyl tert-alkyl ether,
    5 containing methanol and the corresponding tert-olefin, are distilled off to tert-olefin with separation of 83.6-98.2 wt.% Methanol. The remaining methanol is separated by adsorption on an ion exchange resin. The methanol adsorbed on the resin is then desorbed with a stream of a mixture of hydrocarbons containing the resulting tert-olefin, which can be used as
    5 feed flow. Next to
    distilled methanol and, if necessary, fresh methanol may be added to the feed stream containing desorbed methanol,
    Q the resulting mixture is fed to the esterification.
    Thus, all the methanol used for the esterification can be completely reclaimed, with the exception of inevitable leaks and small residues of methanol contained in the pure tert-olefin and residual stream.
    Used for adsorption and
    The desorption resin is divided into two layers, one of which is mainly. free from methanol, the layer is used to adsorb the resulting by reverse cleavage of the esters
    methanol, while in another layer already loaded with methanol, a stream of raw materials is introduced in order to desorb the methanol. If necessary, you can use the -layer
    adsorbent for adsorption of excess. methanol from a tert-olefin-free residual stream, followed by desorption of methanol with the feedstock.
    The adsorption of methanol is carried out at a pressure of 1-30 atm. When adsorbed, the streams released from methanol are in a liquid state. The mass load on the adsorbent is -4 hours. The desorption of methanol is carried out with a stream of hydrocarbon mixture containing the resulting tert-olefin at 20-65 C and a pressure of 5-30 atm. As the tert-olefins increase in the desorbing flow, desorption is accelerated. Due to this, an energy-efficient mode of operation is possible, at which the desorption temperature is near the adsorption temperature. Copolymers of styrene and divinylbenzene containing dimethylbenzylamine groups are used as the adsorbent. Said adsorbent is a synthetic ion exchanger and may contain 0.3-80% by weight of divinylbenzene based on the total weight of the comonomers. Example 1. For the esterification of a partially hydrogenated mixture of hydrocarbons with 5 carbon atoms from a thermal cracking unit (craze when using aromatic hydrocarbons) with methanol, a heated flow reactor with an internal diameter of 20 mm is changed. Temperature control is carried out using instruments located at a distance of 100 mm from each other. In the 100 g / h reactor of the indicated hydrocarbon mixture with 20% by weight of isoamyl (the rest) other unsaturated hydrocarbons C and saturated hydrocarbons Co are esterified 8, 6 g / h of methanol per 110 g of acidic, macroporous cation exchanger based on styrene and divinshbenzene by sulphonic acid groups containing 0.75 g / l of elemental palladium (commercial product Levatite SPC 1 at 70 s and pressure 10. atm. At that, the mole ratio tert-olefins and ethanol is 100: 15. According to gas chromatographic analysis, the product stream has the following composition, in wt%: Isomethylenes 4,1 Methyl tertone 1 L ester (MTAE) 20.9 Methanol 1.2 Remaining hydrocarbons C, 1 Higher ethers and hydrocarbons 7 Conversion of iso-amylene to 78% by weight of the starting iso-amylene. The product stream is collected in a ripo; interstitial vessel and from there is fed to a distillation unit. A stream of hydrocarbons with the remaining amounts of isamylene and methanol is taken as the main distillation product, and quality of bottom product - MT E in a mixture with the higher ethers. In a further distillation column, this bottom product is processed into high purity MTAE (the product obtained by Golovina contains 99.9% by weight of MTAE). As a bottom product of clear distillation, undesired higher ethers are obtained. The purified MTAE is fed to a heated piston pump with an internal diameter of 25 mm, equipped with temperature measuring instruments (located at a distance of 100 mm) and a pressure regulator, where the MTAE is split to isamylene and methanol, using a membrane piston pump. Reaction conditions: Catalyst H — mordenite (commercial product), g 100 Amount of feedstock MTAE (with a purity of 99.9 wt.%), G / h100 Volumetric rate, 1 g of raw material / 1 g1 catalyst per hour Pressure, bats Temperature, C The degree of conversion of MTAE,% 96 According to gas chromatographic analysis, the cleavage product has the following composition, we, 7,: MTAE3.8 2-Methylbutylene-2 49.2 2-Methylbutylene-1 16.8 Methanol28.0 Dimethyl ether 1.6 Water0, 6 The specified cleavage product is deposited in an intermediate tank cooled to approximately 0 ° C and connected in sequence. The distillation unit is separated to the desired methyl butenes, the remaining MTAE and methanol. At the distillation stage, the top product of the following composition is obtained in wt%: H-Methylbutene-1 2-Methylbutene-2 71.1 2-Methylbutene-1 24.3 Methanol4.6 (16.4% by weight of the methanol containing the product pa. milling) MTAE 0, 1 The composition of the main product corresponds to the azeotrope of iso-amylene with methanol. The methanol content in the bottom of the column is 83.6% by weight of the methanol contained in the cleavage product. In order to remove methanol and isolate iso-amylene in pure form, the head product is passed through an adsorber. The adsorber consists of two alternately operating steel reactors with an internal diameter of 25 mm and with a total capacity of 250 ml. The reactors have a heated casing and are equipped with temperature measuring instruments. The pressure in the reactor is maintained by the regulator. The feed flow of the axle is upside down using a piston diaphragm pump. At the exit of the reactor, instant and average samples are taken, which are subjected to chromatographic analyzes. Alternately operating reactors containing 120 ml of macroporous anion exchange resin based on styrene and divinylbenzene with dimethylbenzylamine groups (Lovatit MP 62 trading product For 400 m / h of methanol adsorption, the overhead distillation product is passed through one of the adsorbers from the bottom up. The process is carried out at and pressure i At that, the load on the adsorbent is 4 g of methanol per 1 g of adsorbent per hour.The results of adsorption and their development for 4 hours are shown in Table 11. Then the product stream is fed to the second adsorption reactor, which is It is similar to the first one. The loaded adsorbent is subjected to desorption using the initial hydrocarbon mixture of the above composition fed to the esterification in an amount of 440 g / h. The desorption is carried out at 35 C and a pressure of 5 atm. The volumetric rate is 4.4 g of the hydrocarbon mixture per 1 g of adsorbent per hour. The concentration of methanol in the eluate and its change within 3 hours are presented in Table 2. After desorption, the temperature and pressure in the reactor are brought to the temperature and pressure of the adsorption process. Examples 2-5. Example 1 is repeated with the difference that the processes of adsorption and desorption are carried out under the conditions given in Table III. EXAMPLE 6 Example 1 is repeated with the difference that the head product is fed to the adsorption, which contains 0.5% by weight of methanol (1.8% of: the weight of methanol contained in the cleavage product, t. e. 98.2 wt.% i methanol is distilled off from MTAE). At the same time, the processes of adsorption and desorption are carried out under the conditions given in Table III. Example, Example 1 is repeated with the only difference that macroporous anion exchange resin based on methacrylate resin containing dimethyl benzylamine groups (Lovatit AP 246 commercial product) is used as an adsorbent. At the same time, the processes of adsorption and desorption are carried out under the conditions given in Table III. Examples 8–13, Example I is repeated, with the difference that 100 g / h of a mixture of hydrocarbons C from a thermal cracking unit are fed to the esterification (the mixture contains 40 wt.% Isobutene, 45 wt.% N -butenes and 15 wt.% saturated hydrocarbons), and the esterification is carried out at a pressure of 15 bar using 102 mol,% of methanol in terms of isobutene. Methyl tert-butyl ether (MTBE) purified by distillation with a purity of 99 , 9 wt.% Serves as a splitting at a pressure of 10 bar per 100 g of AND-mordenite. The volumetric rate is 1 g of raw material per I g of catalyst per hour.
    According to gas chromatography 1. CLAIM, the cleavage product is the following composition, wt.%: MTBE 9.2 57.8
    Iso-butene 30.5.
    Methanol
    Dimethyl
    1.8
    ether 0.7
    Water As a result of the distillation of the cleavage product, the top product of the following composition is obtained, wt.%: Iso-butene 2.5 (8.2% of the methanol weight of methanol contained in the cleavage product, i.e. 91.8 wt.% Of methanol are from MTBE) The head product is treated as described in Example 1. The processes of adsorption and desorption are carried out under the conditions listed in Table 4, and desorption is carried out using a mixture of C4 hydrocarbons consisting of 40% by weight of isobutene, 45% by weight of n-butenes and 15% by weight of saturated hydrocarbons.
    The invention makes it possible to simplify the process of producing tert-olefins, including by significantly simplifying the separation of methanol from tertolefin. You get the target product with a purity of 99.9-99.8%, i.e. more pure than in a known way.
    Table 1 Nose Pro 25 Nose
    Ta6jjHua 3 Methanol concentration in the upper adsorber, May. % Concentration of methium, thanol in the eluate, wt.%
    Process conditions
    ME 62 MP 62 MP 62 MP 62
    T a b l and c a 4
    Example
    8 1 9 I 10 Г 11 I 12 Т 13
    MR 62 AR 246 104 100 100 100 100 100
    0.1
    0.1 J.5 0.1 0.1 0.2
    5.3
    0.5 2.4 0.1 0.3 0.1
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING TRET-OLEFINS C ^ - C by contacting mixtures of hydrocarbons containing them with methanol in the presence of an acid catalyst based on an ion exchange resin at 70 ° C and a pressure of 10-15 atm, separating the methyl tert-alkyl ether obtained from the remaining hydrocarbons, and splitting the methyl tert-alkyl ether to tert -olefin and methanol in the presence of a catalyst at 140-160 ° C and a pressure of 10 atm and separating the tert-olefin from methanol, including distillation, characterized in that, with the simplification of the process technology, the contacting is carried out in the presence of stve ion exchange resin catalyst - a sulfonated copolymer of styrene and divinylbenzene, containing 0.75 g / l of palladium, the cleavage is carried out in the presence of a catalyst H + -mordenita and tert-olefin separation from methanol 'is carried out by stripping with separation 83,6-98 , 2; wt.% methanol from tert-olefins and removal of the remaining methanol by adsorption on a copolymer of styrene and divinylbenzene with dimethylbenzylamine groups or on: methacrylic resin with dimethylbenzylamine groups at 0-30 ° C and a pressure of 1-30 atm with a mass load on the adsorbent 1-4 h * -1 with the desorption of absorbed methanol by a stream of a mixture of hydrocarbons containing the obtained tert-olefin at 20-65 C and a pressure of 5-30 atm with its return to the production of methyl tert-alkyl ether.
    „” SU „„ 1176825>
    1 176825
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    同族专利:
    公开号 | 公开日
    DD202524A5|1983-09-21|
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    CS235020B2|1985-04-16|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US3409691A|1966-02-01|1968-11-05|Dow Chemical Co|Porous cation exchange resins as selective sorbents in organic systems|
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    FR2229440B1|1973-05-17|1977-07-29|Inst Francais Du Petrole|
    DE2802198A1|1978-01-19|1979-07-26|Basf Ag|PROCESS FOR THE PRODUCTION OF ISOBUTEN FROM ISOBUTEN CONTAINING C LOW 4 HYDROCARBON MIXTURES|
    DE2928509A1|1979-07-14|1981-01-29|Basf Ag|METHOD FOR THE SIMULTANEOUS PRODUCTION OF METHYL-TERT.-BUTYL ETHER AND PRODUCTION OF ISOBUTEN|
    DE2928510A1|1979-07-14|1981-01-29|Basf Ag|METHOD FOR PRODUCING ISOBUTEN FROM ISOBUTEN CONTAINING C TIEF 4-HYDROCARBON MIXTURES|
    DE2938222A1|1979-09-21|1981-04-30|Gulf Canada Ltd., Toronto, Ontario|Etherification of isobutylene in light gasoline fractions - with removal of unreacted methanol by contact with glycol|US4575567A|1982-07-06|1986-03-11|Uop Inc.|Adsorbent regeneration in etherification processes|
    US4551567A|1983-07-25|1985-11-05|Chemical Research & Licensing Company|Deetherification process|
    US4570026A|1983-08-12|1986-02-11|Petro-Tex Chemical Corporation|Production of isobutene from methyl tertiary butyl ether|
    US4558168A|1985-06-19|1985-12-10|Air Products And Chemicals, Inc.|Production of high purity butene-1 from an n-butane feedstock|
    US4748281A|1986-10-16|1988-05-31|Conoco Inc.|Recovery of methanol in an MTBE process|
    US4777310A|1987-03-02|1988-10-11|Amoco Corporation|Catalyzed olefin equlibration and separation of the equilibrated products|
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    US5030768A|1990-03-30|1991-07-09|Air Products And Chemicals, Inc.|Process for preparing alkyl tert-alkyl ethers|
    GB9117071D0|1991-08-08|1991-09-25|British Petroleum Co Plc|Chemical process|
    US5227564A|1991-12-09|1993-07-13|Dairen Chemical Corporation|Process for the preparation of tertiary olefins|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19813124294|DE3124294A1|1981-06-19|1981-06-19|METHOD FOR PRODUCING PURE TERT.-OLEFINS|
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