• 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:
    This invention relates to a method for treating cation exchangers used in organic chemistry as catalysts. The invention improves the life of the cation exchanger. The method of treating halogenated substances in dre strongly acidic cation exchangers based on copolymers of styrene and divinylbenzene consists in contacting them with demineralized water, freed from molecular oxygen dissolved in it, at a temperature of 100-150 ° C and an increased pressure to achieve a degree of removal of sulfuric acid 19- 22 mg / l cation exchanger in 1 hour and degree of hydrochloric acid cleavage 5-6 mg / l cation exchanger in 1 part 1 C. f-ly, 1 ill. W
    公开号:SU1443804A3
    申请号:SU864027193
    申请日:1986-03-28
    公开日:1988-12-07
    发明作者:Брандес Гюнтер；Нейер Вильгельм；Веберс Вернер
    申请人:Дойче Тексако Аг (Фирма)；
    IPC主号:
    专利说明:

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    This invention relates to a method for treating cation exchangers used in organic chemistry as catalysts.
    The purpose of the invention is to increase the service life of cation exchangers.
    The drawing shows a diagram of the device for the implementation of the proposed method
    PRI me R 1, the process is carried out in a device shown in the attached diagram, in which the connecting piping and the pump are made of Teflon, and a vessel equipped with a skin, executed in the form of a 3-meter enameled inside pipe, is loaded with 1000 ml of cation exchanger, containing 3.7 meq, sulphonic acids per 1 g of dry matter and 5.5 meq, chlorine per 1 g of dry matter.
    Through the pipeline, 1 liter of demineralized water, previously liberated from dissolved molecular oxygen in the apparatus by sparging with nitrogen, is hourly supplied to the lower part of the vessel. A temperature of 150 ° C is established using steam heating. At the top of the vessel, the pressure of 10 bar observed in the pipe is removed and the chloride containing as a result of cleavage by hydrolysis
    ions and ions of the sulfonic salt and


    sulfuric acid, the flow of water is cooled to a temperature of 20 ° C. The degree of cleavage of hydrochloric and sulfuric acids is constantly analyzed. After 365 hours, the degree of acid cleavage is 19 mg of sulfuric acid per 1 g of cation exchanger s for 1 h and 5 mg of hydrochloric acid per 1 l of cation exchanger per 1 hour (with 1.0 mg of organic sulfonic acid per 1 l of cation exchanger per 1 hour) and finish the process.
    The cationic resin thus treated is used as a catalyst for the synthesis of sec-butyl alcohol by direct hydration of n-butenes at a temperature of 150 ° C and a pressure of 70 atm. At the same time, after 8000 hours, a decrease in the average catalyst activity is observed 1.6 mol of sec-butyl alcohol . alcohol on 1 liter of catalyst in 1 h.
    Example 2 Example 1 is repeated, with the difference that instead of water freed from dissolved molecular oxygen, the same pretreatment solution containing 10% isopropanol alcohol is subjected to the same pretreatment. At the same time, the duration of the process until the indicated degree of acid cleavage is reduced by half, i.e. up to 180 hours without a decrease in the activity of the catalyst treated in this way compared to the catalyst treated according to Example 1.
    Example 3. Example 1 is repeated with the difference that instead of water freed from dissolved molecular oxygen, a water solution containing 1% sec-butyl alcohol is subjected to the same pre-treatment. After 180 hours, the degree of cleavage by hydrolysis of sulfuric and hydrochloric acid is 22 mg of sulfuric acid per 1 g of cation exchanger per hour and 6 mg of hydrochloric acid per 1 l of cation exchanger per 1 hour (the content of organic sulfonic acid in the medium is less than 2 mg / l cation exchanger in 1 h). The catalyst thus treated gives the same results in the synthesis of sec-butyl alcohol as the catalyst treated according to example 1.
    EXAMPLE 4 Example 1 is repeated with the difference that instead of releasing
    water extracted from molecular oxygen is subjected to the same pretreatment water solution containing 1% sec-butyl alcohol, and the contacting is carried out at a temperature. After 380 hours, the degree of cleavage of sulfuric and hydrochloric acids by splitting is 20 mg of sulfuric acid rfa 1 l of cation exchanger in 1 h and 6 mg of hydrochloric acid per 1 l of cation exchanger in 1 h (the content of organic sulfonic acid in the medium is less than 2 mg / l of cation exchanger in 1 h), the catalyst thus treated gives the same results with synthesis of sec-butyl alcohol, which is the catalyst treated according to example 1.
    Example 5 Example 1 is repeated with the difference that instead of water freed from dissolved molecular oxygen, a water solution containing 1% sec-butyl alcohol is subjected to the same pretreatment and the contacting is carried out at an increase from 100 to . After 210 hours, the degree of hydrolysis of sulfuric and hydrochloric acid is 21 mg of sulfuric acid per 1 liter of cation exchanger per hour and 6 mg of hydrochloric acid per 1 liter of cationic acid per hour (the content of organic sulfonic acid in the medium is 1 mg / liter cationite in 1 h) The catalyst thus treated gives the same results in the synthesis of sec-butyl alcohol as the catalyst treated according to example 1.
    Example 6. (comparative). Example 1 is repeated with the difference that the demineralized water supplied to the lower part of the vessel 1 is not pretreated in apparatus 2 and the liquid-phase treatment is finished after 312 hours. 26 mg of sulfuric acid per 1 liter of cationite per hour and 8 are removed. mg of hydrochloric acid per liter of cation exchanger 1 h. The average activity of the catalyst treated in this way for 6000 h is 1.6 mol of sec-butyl alcohol per liter of catalyst
    in 1 h. Then it drops sharply to
    1.2 mol.
    权利要求:
    Claims (1)
    [1]
    1. Method of processing halogen-substituted in the wood of strongly acidic cation exchangers based on copolymers of styrene and divinylbenzene by liquid-phase contact with demineralized
    water at elevated temperature and under pressure in the absence of metal ions, characterized in that, in order to increase the service life of the cation exchanger, demineralized water
    subjected to preliminary purification from molecular oxygen dissolved in it, and contacting is carried out at 100-150 ° C to the degree of removal of sulfuric acid equal to 19-22 mg / l
    cation exchanger in 1 hour and degree of hydrochloric acid cleavage equal to 5-6 mg / l cation exchanger in 1 hour.
    2, a method according to claim 1, characterized in that the demineralized water is used in the form of a 1-10% solution of a lower alcohol.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1443804A3|1988-12-07|Method of processing strong-acid cationites halogene-substituted in nucleus on the basis of copolymers of styrene or divinylbenzene
    JP2002528253A5|2006-08-17|
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    EP0764631A1|1997-03-26|Method for decolorization of alkyleneamines
    US4943360A|1990-07-24|Process for recovering nitric acid and hydrofluoric acid from waste pickle liquors
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    SU643432A1|1979-01-25|Method of demineralization of water
    JPH09308500A|1997-12-02|Production of invert type liquid sugar
    同族专利:
    公开号 | 公开日
    CA1263372A|1989-11-28|
    AT64695T|1991-07-15|
    MX168180B|1993-05-10|
    DK154886D0|1986-04-04|
    CN86102001A|1986-10-01|
    DK160915C|1991-10-21|
    BR8601564A|1986-12-09|
    TR22885A|1988-10-03|
    CS199386A2|1989-04-14|
    ZA862535B|1986-11-26|
    DD247156A5|1987-07-01|
    CS266579B2|1990-01-12|
    DE3512517A1|1986-10-09|
    JPH0425066B2|1992-04-28|
    EP0198270A3|1988-06-08|
    PL145847B1|1988-11-30|
    CH667018A5|1988-09-15|
    ES553123A0|1987-01-01|
    FI80389C|1990-06-11|
    EP0198270B1|1991-06-26|
    NO861013L|1986-10-07|
    FI80389B|1990-02-28|
    YU49586A|1988-06-30|
    DK154886A|1986-10-07|
    AU574572B2|1988-07-07|
    CN1004792B|1989-07-19|
    IN167216B|1990-09-22|
    NO167131C|1991-10-09|
    US4705808A|1987-11-10|
    DE3679930D1|1991-08-01|
    JPS61230744A|1986-10-15|
    NO167131B|1991-07-01|
    EP0198270A2|1986-10-22|
    FI861381A0|1986-04-01|
    YU44077B|1990-02-28|
    FI861381A|1986-10-07|
    AU5558186A|1986-10-09|
    ES8701522A1|1987-01-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2718489A|1951-09-19|1955-09-20|Socony Mobil Oil Co Inc|Activation of ion exchange material and process for sweetening petroleum therewith|
    BE590370A|1959-04-29|1900-01-01|
    DE1168909B|1960-01-27|1964-04-30|Rohm & Haas|Process for the production of catalysts for organic-chemical reactions which can be catalyzed by hydrogen ions|
    US3808158A|1971-07-20|1974-04-30|B Bolio|Amphoteric thermally regenerable ion exchange resins|
    US3855343A|1973-11-29|1974-12-17|Mobil Oil Corp|Isoparaffin-olefin alkylation with regeneration of resin/boron trifluoride catalyst|
    US3965039A|1974-11-19|1976-06-22|Chaplits Donat N|Ion-exchange molded catalyst and method of its preparation|
    US4298502A|1978-11-06|1981-11-03|Uop Inc.|Catalytic composite particularly useful for the oxidation of mercaptans and the removal of gums contained in a sour petroleum distillate|
    US4269943A|1979-08-23|1981-05-26|Rohm And Haas Company|Thermally stable resins prepared by bromination or chlorination of aromatic polymer beads followed by sulphonation|
    US4496667A|1983-08-15|1985-01-29|Betz Laboratories, Inc.|Method for cleaning organically fouled anion exchange resins|US5012014A|1990-04-26|1991-04-30|Mobil Oil Corporation|Catalyst pretreatment for olefin hydration|
    TW321634B|1994-07-05|1997-12-01|Mitsui Toatsu Chemicals|
    DE4425216C2|1994-07-16|2003-04-17|Sasol Germany Gmbh|Strong acid cation exchange resins, their production and application|
    CN1048921C|1995-12-02|2000-02-02|中国石化齐鲁石油化工公司|Method for prepn. of catalyst of large porous strong acid cation exchange resin|
    US20040236158A1|2003-05-20|2004-11-25|Collin Jennifer Reichi|Methods, systems and catalysts for the hydration of olefins|
    JP2005047888A|2003-07-29|2005-02-24|Rohm & Haas Co|Esterification method, system and catalyst, ester produced thereby and downstream product produced from ester|
    JP2005068126A|2003-08-20|2005-03-17|Rohm & Haas Co|Method, system and catalyst to be used in aromatic alkylation reaction|
    EP1531000A1|2003-11-13|2005-05-18|Rohm and Haas Company|Catalytic reactions using thermally stable resins|
    DE602005002663T2|2004-03-11|2008-06-26|Rohm And Haas Co.|Processes, systems and catalysts for flow-through reactors|
    CN1326820C|2005-05-31|2007-07-18|中国科学院大连化学物理研究所|Method for producing lower alcohol continuously|
    US20110136926A1|2009-12-08|2011-06-09|Jianguo Cai|Catalysts for Olefin Hydration and Method of Preparation|
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    法律状态:
    2008-07-10| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20050329 |
    优先权:
    申请号 | 申请日 | 专利标题
    DE19853512517|DE3512517A1|1985-04-06|1985-04-06|METHOD FOR THE TREATMENT OF STRONG ACID CATION EXCHANGER CATALYSTS|
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