• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    1488194 Separating butadiene SNAMPROGETTI SpA 13 May 1975 [21 May 1974] 20220/75 Heading C5E Butadiene is separated from a C 4 hydrocarbon mixture containing isobutene and at least one acetylenic compound by etherifying the isobutene in a reactor with an alcohol in the presence of an acid ion exchange resin; etherifying the acetylenic compound with an alcohol in the same or different reactor in the presence of an acid ion exchange resin containing Hg<SP>++</SP> ions in an amount less than that of the acid ions; and separating the mixture containing butadiene and ethers by distillation. C 4 linear saturated and monoolefinic hydrocarbons in the feed mixture may be separated by extractive distillation of the products of the etherification with a solvent selective towards butadiene and ethers.
    公开号:SU897107A3
    申请号:SU752134186
    申请日:1975-05-20
    公开日:1982-01-07
    发明作者:Рескалли Карло；Джиннаси Алессандро
    申请人:Снампрогетти С.П.А.(Фирма)；
    IPC主号:
    专利说明:

    I
    This invention relates to a process for separating diolefinic hydrocarbons, in particular butadiene, from hydrocarbon mixtures.
    The closest to the invention is the ryu of the technical essence and the achieved result is a method of separating butadiene from a mixture of hydrocarbons C of different degrees of saturation by extractive distillation in the presence of a selective solvent, according to which a mixture of morpholine and / or N-formylmorpholine with water is used as solvent. In the first stage, olefins and saturated hydrocarbons are isolated, in the second stage, butyl-1, vinyl acetylene, diacetylene and part of propyne are separated, propyne is removed by subsequent distillation.
    The aim of the invention is to simplify the process technology, which consists in reducing the amount of solvent used, and reducing the concentration of acetylchium compounds in
    stream directed to extractive distillation.
    The goal is achieved by the method of extracting butadiene from a mixture of hydrocarbons of varying degrees of saturation by extractive distillation in the presence of a selective solvent, and the initial mixture is pretreated with 10 aliphatic alcohol in the presence of sulfacationite, followed by methyl tert. butyl ether and distillate, which is processed by aliphatic alcohol in the presence of sulfacationite, containing 0.1–5 g of mercury ions per 1000 g of sulfate acation, followed by extractive distillation of the processed products.
    The drawing shows the implementation of the proposed method.
    Raw materials are fed via line 1 to mix with aliphatic alcohol supplied via line 2, and through line 3 to the reactor 4 to esterify most of the isobutylene (85-95) contained in the raw material. The reaction is carried out at 20-80 ° C and hourly space velocity (volumetric velocity is expressed as the volume of liquid per hour, per volume of catalyst) from 2 to 30.
    The reaction product from reactor 4 through line 5 is fed to column b at the batch. The resulting methyl tert-butyl ether from column 6 is removed via line 7. Distillate from column 6 through line 8 is mixed with aliphatic alcohol fed through line 9, and the mixture is sent via line 10 to reactor 11, where esterification occurs 20-80 0 and hourly space velocity (liquid) from 1 to 30. The reaction products are fed via line 12 to the extractive distillation column 13, where the saturated and aliphatic hydrocarbons are separated from butadiene and. output along line I, the extract containing butadiene, output along line 15 and fed to a stripping column 16, where butadiene is withdrawn along line 17, and the solvent through line 18, and recycled to column 13.
    From the vapor phase of the intermediate tray 19 of the column 16, a stream enriched with esterification products is diverted via line 20 to be recycled to column 6.
    The esterification of isobutylene can be carried out either prior to the esterification of acetylene derivatives in another reactor (only 2 reactors), or simultaneously in the same reactor.
    The resulting ethers and other compounds are then separated from the butadiene by distillation.
    The ion exchange resin (in the H-form) can be taken from any of the available, but better resin containing sulfo groups ().
    Mercury ions can be attached to the resin in the form of mercury salts, for example in the form of mercury nitrate. The content of mercury ions in the resin may also be lower than the total cationic capacity of the resin.
    For butadiene and ether, the following selective solvents are used: N-formylmorpholine, N-methylpyrrolidone, dimethylformamide, acetonitrile dimethylacetamide, N-methylimidazole, imidazolidin-1,3-one-2, ft-methoxypyropionitrile.
    Example 1. In the reactor 4, together with 16.7 kg / h of methanol (2) (isobutene / methanol 1.0 mol / mol) 100 pod / kg - feed (1), containing, wt.%:
    p-butanz 73
    ISO-Bhutan0.86
    Butene-116,44
    izo-buten29,19
    Trans-Buten-25.89
    CIS-Butene-24,29
    Butadiene-1,339,07
    Propin0.03
    Vinylacetylene0,40
    Butin-1., 0.10.
    Reactor 4 operates under the following conditions: temperature 60.80 and, pressure 10.15 and 15 atm, hourly space velocity (fluid) of 5.15 and 2, resin amberlite 15.
    The stream after leaving the reactor enters the column 6, operating under the conditions: pressure at the top of the column is 6 atm, the number of plates is 30 pcs. reflux number (4 / D) 1.
    While the bottom stream (7), containing all the methyl tert-butyl ether formed, is withdrawn from the cycle, the stream (8), discharged as the head stream, enters the reactor 11 together with 0.35 kg / h of methanol (9) . The reactor 11 operates under the following conditions: temperature 40.60 and 20 ° C, pressure 7, 15 and 15 atm, hourly volumetric velocity (fluid) 5.30 and 2, resin, amberlite 15 with ions added in such quantity that neutralize 20% of the groups - SOgH resin.
    The effluent from reactor 11 enters the extractive distillation column 13, at the top of which simultaneously a stream (14) containing 900 kg / h of extractive solvent (formylmorpholine / water in a weight ratio of 95/5) is fed. Working conditions: pressure at the top 4 atm, reflux number 1, number of plates 90 pcs. Output as head stream (T4) contains, kg / h:
    and Bhutan3,73
    ISO-Bhutan0.086
    Buten-11b, 43
    Trans-Butene-25.85
    CIS-Butene-24,14
    Butadiene-1,31,35
    Bottom or bottom stream enters column 1b, which operates
    with a pressure of 1.2 eta, a reflux ratio of 1 and the number of plates 30 pcs.
    At the same time, a stream (20) is output from the bottom of the fifth tray (vapor phase), which (after condensation) recycles to column 6 and contains, in addition to methyl waste air, all. vinyl ethers formed in the reactor and an excess of methanol (in excess of that required for the reaction) from the upper part removes a stream 17 of butadiene of a given purity (38.0 kg / h).
    The solvent coming from below (1b) (18) is used again as an extractive solvent in the column 13.
    The composition of the stream leaving the reactor k, kg / h:
    n-butane3,73
    ISO-Bhutan0.86
    Butene-1 6, k
    Methyl tert-butyl ether 5.9
    Trans-Buten-25.89
    CIS-Butene-2.09
    BZ-Butadiene39,07
    Propin0.03
    Vinylacetylene0,0
    The composition of the products leaving the reactor 11, kg / h:
    n-butane3,73
    from Bhutan0.86
    Butene-1l6, / t4
    Trans-Buten-25.89
    CIS-Butene-2.29
    1,3-Butadie39,07
    Dimethoxypropan0, 08
    Trimethoxybuten1, 1/4
    Dimethoxybutane, 0.22
    The butadiene stream leaving column 1b contains no more than 50 ppm acetylene compounds.
    (rr.m.), 1,3-butadiene concentration exceeds 90.5 wt.
    Example 2. It is carried out analogously to example 1. The temperature of the reactor is t 80 and, the pressure is 15 and 15 at, the hourly space velocity (liquids) is 15.2, the conversion of iso-butene is 95 and 90, respectively, the temperature of the reactor is 11 60 and 20 ° C , pressure 15 and 15 at, hourly space velocity (fluid) 30.2.
    Example 3. It is carried out analogously to Example 1. Ethanol, propanol, butanol are used as aliphatic alcohol. The molar ratio of iso-butene to alcohol is 1 in reactor t and 3 in reactor 11. The conversion in the reactor is 95.
    权利要求:
    Claims (1)
    [1]
    1. Patent of the USSR N 66650, cl. C 07 C 7/08, 1975 (prototype).
    类似技术:
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    同族专利:
    公开号 | 公开日
    FR2272056B1|1978-02-24|
    US4020114A|1977-04-26|
    IT1012685B|1977-03-10|
    PL102726B1|1979-04-30|
    IE41363L|1975-11-21|
    DK141286B|1980-02-18|
    DK213775A|1975-11-22|
    AT358540B|1980-09-10|
    CH605479A5|1978-09-29|
    ES438185A1|1977-05-01|
    CA1036183A|1978-08-08|
    RO72424A|1981-04-30|
    AU8125075A|1976-11-18|
    YU39210B|1984-08-31|
    SE400772B|1978-04-10|
    DE2521965C3|1979-08-09|
    MW2875A1|1976-06-09|
    DE2521965A1|1975-11-27|
    JPS50160204A|1975-12-25|
    DK141286C|1980-08-11|
    EG12588A|1979-06-30|
    PH12584A|1979-06-20|
    GB1488194A|1977-10-05|
    FR2272056A1|1975-12-19|
    NL7505997A|1975-11-25|
    NO751783L|1975-11-24|
    BG27354A3|1979-10-12|
    IN143292B|1977-10-29|
    NO144207C|1981-07-15|
    AR205569A1|1976-05-14|
    CS194225B2|1979-11-30|
    LU72538A1|1975-10-08|
    ZA752912B|1976-04-28|
    NO144207B|1981-04-06|
    JPS5635172B2|1981-08-15|
    SE7505800L|1975-11-22|
    ZM6275A1|1976-02-23|
    BR7503197A|1976-04-20|
    TR18687A|1977-06-23|
    ATA380975A|1980-02-15|
    BE829298A|1975-09-15|
    DD118057A5|1976-02-12|
    YU129075A|1982-02-28|
    DE2521965B2|1978-12-07|
    IE41363B1|1979-12-19|
    HU177136B|1981-07-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1968601A|1934-02-14|1934-07-31|Shell Dev|Preparation of olefine derivatives|
    US2480940A|1946-09-20|1949-09-06|Atlantic Refining Co|Production of aliphatic ethers|
    US3119766A|1960-10-10|1964-01-28|Sun Oil Co|Increasing antiknock value of olefinic gasoline|
    DE1224294B|1961-01-09|1966-09-08|Bayer Ag|Process for the production of tertiary butyl alkyl ethers|
    US3423385A|1964-09-18|1969-01-21|Firestone Tire & Rubber Co|Process for purifying butadiene stream|
    GB1176620A|1968-07-09|1970-01-07|Shell Int Research|Recovery of Tertiary Olefins|
    HU165735B|1970-12-29|1974-10-28|
    BE793163A|1971-12-22|1973-06-21|Sun Oil Co Pennsylvania|ETHERS DRYING PROCESS|DE2629769C3|1976-07-02|1989-03-16|Huels Ag, 4370 Marl, De|
    DE2706465C3|1977-02-16|1980-10-02|Deutsche Texaco Ag, 2000 Hamburg|Process for the production of butadiene or n-butenes from hydrocarbon mixtures containing them with separation of isobutene|
    DE2802198A1|1978-01-19|1979-07-26|Basf Ag|PROCESS FOR THE PRODUCTION OF ISOBUTEN FROM ISOBUTEN CONTAINING C LOW 4 HYDROCARBON MIXTURES|
    DE2911393C2|1979-03-23|1984-07-19|Basf Ag, 6700 Ludwigshafen|Process for the preparation of a conjugated diolefin from a C 4 or C 5 hydrocarbon mixture|
    DE3049213A1|1980-12-27|1982-07-29|Basf Ag, 6700 Ludwigshafen|METHOD FOR THE SIMULTANEOUS PRODUCTION OF ALKYL-TERT.-BUTYL ETHER AND PRODUCTION OF BUTADIENE|
    US5175363A|1991-01-28|1992-12-29|Eastman Kodak Company|Method for purification of carboxylic acids and anhydrides|
    US5763715A|1996-10-08|1998-06-09|Stone & Webster Engineering Corp.|Butadiene removal system for ethylene plants with front end hydrogenation systems|
    EP3919468A4|2020-06-03|2021-12-08|Sabic Global Technologies Bv|Systems and processes for producing methyl tertiary butyl ether|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT23008/74A|IT1012685B|1974-05-21|1974-05-21|PROCESS FOR THE SEPARATION OF BUTA DIENE FROM HYDROCARBON CURRENTS OR 4 OBTAINED BY STEAM CRACKING|
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