• 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:
    1518338 Recovering metal catalyst components; Heating fluidised bed DEUTSCHE GOLD - UND SILBER - SCHEIDEANSTALT 29 Sept 1975 [18 Nov 1974 (2)] 39738/75 Headings B1E and B1F [Also in Divisions Cl and C2] Epoxidation and hydroxylation catalysts are separated from a distillation residue resulting from use of the catalyst by introducing the residue into a fluidised bed of inert solid material and burning off organic material from the residue with a free oxygencontaining gas, metal compounds originating from the catalyst being deposited onto the inert material in the reactor or onto the fines of the inert material or as the solid compounds themselves in the exhaust gas from the reactor for collection by a solidsseparator following the reactor. The catalyst may comprise compounds of Zr, V, Nb, Ta, Cr, Mo, W, Re or U as salts or organometallic compounds or in the presence of basic components, e.g. Li, Na, K, Rb, Cs, Mg, Ca, Sr or Ba. The inert material may be silicon carbide, quartz, sand, corundum or calcined clay. The metal compounds recovered may be directly dissolved in water or other solvent or otherwise treated for recycle to the epoxidation or hydroxylation process. The Examples describe the recovery of catalysts comprising (i) sodium tungstate; (ii) sodium molybdate; (iii) sodium vanadate; (iv) vanadyl acetyl acetonate (deposited as vanadium pentoxide and dissolved in an alcohol for recovery as a vanadic acid ester); and (v) niobium naphthalate (deposited as niobium pentoxide and recovered by dissolution in alkali solution). Apparatus suitable for effecting the separation is shown in Fig. 1. The fluidised bed reactor 6 is heated by a salt bath 5 and has inlet connections for the distillation residue 1, for fluidising air 3 and for the inert material 7. The inert material with metal compound deposits is removed by line 4 and, after being combined with fines recovered in separator 9, is passed to vessel 14 where the metal compounds are extracted with water. The inert material is then recycled by line 14 to inlet 7.
    公开号:SU727115A3
    申请号:SU752188261
    申请日:1975-11-11
    公开日:1980-04-05
    发明作者:Фридрих Хайнц；Хайм Вольфганг；Клееманн Аксель；Колб Хайнц；Шрайер Герд
    申请人:Дегусса (Фирма)；
    IPC主号:
    专利说明:

    3 At the same time as an inert ma ““. material can be used quartz. sand, silicon carbide, calcined silica, or calcined clay. The method according to the invention is carried out as follows. The distillation residue containing the cat (and the Lysator is heated or diluted with water so that it can be transported by a pump. The reactor is heated to a temperature of minus 500 C. After the start of the combustion reaction in the fluidized bed reactor, the excess heat is removed through the system "Or. The organic components contained in the distillation residue are burned in a stream of air, while the metallic compounds of the catalyst are precipitated on an inert fluidized material. The particle size of the latter is 0,, 0, preferably 0.5.1.5 mm. Combustion the organic components of the distillation residue in a fluidized bed reactor must be complete in order to protect the environment. The reaction temperature is maintained equal to C. The temperature. The reactor is controlled by cooling with conventional cooling agents, for example, nitri-nitrite melts. the reactor is fluidized, the material is treated with water.The resulting catalyst solution can be fed back into the process, the fluidized material, O-separated from the solution, dried and re-introduced into the ps9 reactor p ,. coats . Example 1. When epoxylated or hydroxylated allyl alcohol with aqueous hydrogen peroxide to glycide or glycerin in the presence of sodium tungsten, a distillation residue is formed, which is 2% by weight consists of a catalyst, while the rest is glycerol or polyglyceric, This residue is mixed with water and on. heat up to OO-80 C. The mixture in the amount of 2 kg / h is fed to the bottom of the reactor and at the same time 8 MV4 air is blown in there: a. The inflow 16 MV4 of the heated to 3SO C Bowadha is fed through the base through the inflow. The fluidized bed reactor (24OO mm height, 15O mm diameter, from nickel-chromium steel) is wrapped in a salt bath (nitrite nitrous alloy), which first serves as a heater, and after entering the ex-melter reactor, it is cooled, Ieby, warm. This is used by a heat exchanger placed in a salt bath. As. Pseudo-fluidized material uses silica sand with a particle size of 0.5 ™ 1.5 mm. I heat the reactor with a salt bath to 540 ° C. Due to the combustion of the organic part of the residue, the temperature in the reactor rises to 5OO-650 ° C. Combustion proceeds completely (the content of monoxide in the exhaust gas is 0.1 vol%). Every hour, a liter of sand is removed and replaced with fresh. The tungstate-containing sand withdrawn from the reactor is washed with water to obtain 4. a solution of waaframate. The washed sand is separated, dried and re-introduced into the reactor as an inert resin. teriala. An aqueous solution of tungstate is used to epoxidize or hydroxylate allyl alcohol with hydrogen peroxide. Sand and tungstate carried out with exhaust gas are separated in a cyclone and washed. Hot exhaust air is used to heat the fresh air needed for combustion in the heat exchanger. The cooled exhaust gases are passed through a washing device for further purification. The resulting wash water containing a minor amount of tungstate is used to dilute the distillation residue. 158 g (2.73 mol) of ally alcohol, 20O g of water, and 33 g of an aqueous regenerated solution of sodium tungstate (from 4.9% of tungstic acid) are placed in a round-bottomed co-buccane and heated to. Then, with stirring over 100 minutes, 97 g (1 mol) 35, hydrogen peroxide is added dropwise. The yield of glycide is 85% (counting on hydrogen peroxide). Pr and mr 2. When epoxidation ™ scientific research institute. Diclohexane using hydroperoxide cumene in the presence of vanadyl acetylacetonate to obtain 1,2-α-epoxycyclohexane, a distillation residue is obtained which contains a vanadium compound. This residue is processed in the same manner as in Example 1. The resulting vanadium pentoxide is precipitated on a fluidized bed. From the latter, vanadium pentoxide is separated by dissolving in alkalis. From these 57 aqueous solutions of vanadate, vanadium or an EPP compound is prepared in a known manner. Example 3. A comparative example with a fresh solution of sodium tungstate. In a three-liter flask with a capacity of 1 l with a stirrer, an addition funnel, a thermometer, and a reflux condenser, 158 g of allyl alcohol and 200 m of water are placed. 1.5 g of sodium tungstate are dissolved in 33 ml of water and added to mode6-CI. The solution is heated to. Then, while stirring for 10 minutes, 97 g of .35.6% hydrogen peroxide is added dropwise. The output of fencing 86% (counting on hydrogen peroxide). Example 4 The table below shows the data on the reaction with these alcohols. The reaction conditions are the same as in examples 1 and 2.
    Crotyl
    83.2
    Metallic
    55.5
    Example 5. In a three-neck flask with a stirrer, an internal thermometer, a cooler and a dropping funnel, 58 g (1 mol) of allyl alcohol and 3 g of sodium molybdate dissolved in 74 ml of water are placed and heated to 6 6 C. Then for 1 h, 102 g (1.1 mol) of 36.7% " - hydrogen peroxide are added dropwise. The output of glycerin 7O wt.%. The catalyst is regenerated as described in Example 1, except that instead of silica sand, silicon carbide with a grain size of 0.1-1.0 mm is used. When using regenerated Mo ««: a talizator analogously to example 1, the yield of glycerol is 67 wt.%.
    Example 6 Instead of tungstate, sodium vanadate is used under the conditions of examples 1 and 2. The yield of glycerol in the case of using a freshly prepared catalyst is 2% by weight, and in the case of regenerated using. the use of baked clay (chamotte) as an inert material is 22 wt.%. The regeneration process is carried out as in Example 1, only fireclay with a grain size of 1-3 mm is used, and burning is carried out.
    2,3-Epoxy butanol
    lf2--3noKcn.
    -2 methyl-
    propanal-3
    the atmosphere of air heated to 35 ° C with its supply of 9O nm / h.
    权利要求:
    Claims (2)
    [1]
    Invention Formula
    1 A method for regenerating an epoxidation catalyst or hydroxylation of water-soluble olefinic compounds with hydrogen peroxide containing volforate, vanadate or potassium or sodium molybdate, by separating the catalyst from epoxidation products or hydroxylation by distillation followed by precipitation of the catalyst from the resulting distillation residue an inert material, characterized in that, in order to simplify the method of regeneration, the deposition of the catalyst is carried out on an inert material that is in a pseudo in a liquefied state with simultaneous burning out of the organic part of the bottom residue in a stream of air at a temperature of 500-900 ° C, followed by washing out the catalyst from the inert material with water.
    [2]
    2. A method according to claim 1, characterized in that a quartz material is used as an inert material.
    juice, silicon carbide, burnt K1em-1. German Patent No. 12,30000
    Nezem OR burnt clay.kl 12 o 5/03, published 1969.
    The sources of information ,. 2, US Patent No. 2869986,
    taken into account in the examination of the. 23-140, published. 1964 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
    KR920010470B1|1992-11-28|Process for production of acrylic acid
    RU2384365C2|2010-03-20|Catalyst for oxidising methanol to formaldehyde
    US3435069A|1969-03-25|Oxidation of acrolein and methacrolein with a molybdenum polyvalent metaloxygen catalyst
    JPH06262081A|1994-09-20|Regeneration of catalyst
    SU727115A3|1980-04-05|Method of regenerating epoxydation or hydroxylation catalyst
    US20080081008A1|2008-04-03|Oxide catalyst and phosphoric oxide catalyst for hydrocarbon steam cracking, method for preparing the same and method for preparing olefin by using the same
    JP4166334B2|2008-10-15|Method for preparing oxidation catalyst
    US5095125A|1992-03-10|Maleic anhydride production
    US3065264A|1962-11-20|Vapor phase oxidation of propylene acrylic acid
    US4632915A|1986-12-30|Iron/lithium--promoted catalysts for the production of maleic anhydride
    EP0087118B1|1986-12-03|Vapor phase oxidation of n-butane to maleic anhydride and catalyst therefor
    US4933312A|1990-06-12|Maleic anhydride catalysts and process for their manufacture
    JP2002518172A|2002-06-25|Preparation of improved vanadium-phosphoric acid catalyst and method for producing maleic anhydride using the same
    US3173957A|1965-03-16|Process for the preparation of acrolein
    JPH0686399B2|1994-11-02|Method for producing acrylic acid
    JP2005526597A|2005-09-08|Catalyst precursor for the production of maleic anhydride and process for its production
    CN101087648A|2007-12-12|Method of preparing acrylic acid from propane in the absence of water vapor
    GB2055829A|1981-03-11|Preparation of carboxylic acids from aldehydes
    CA1045106A|1978-12-26|Catalyst with mo, v, ti and process for preparing unsaturated acids
    KR0174273B1|1999-02-18|Improved phosphorous/vanadium/zinc/lithium mixed oxides for oxidation catalyst
    US4996179A|1991-02-26|Maleic anhydride catalysts and process for their manufacture
    US4085122A|1978-04-18|Production of maleic anhydride using a mixed-oxide oxidation catalyst containing vanadium and pentavalent phosphorus
    EP0146099A2|1985-06-26|A process for producing acrylic acid by oxidation of acrolein and a novel catalyst useful thereof
    US4416803A|1983-11-22|Process for the manufacture of catalysts useful for the oxidation of butane to malelic anhydride
    US4670415A|1987-06-02|Process for the preparation of iron/lithium -promoted catalysts for the production of maleic anhydride
    同族专利:
    公开号 | 公开日
    GB1518338A|1978-07-19|
    US4197161A|1980-04-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2484900C2|2007-12-13|2013-06-20|Бп П.Л.К.|Method of extracting catalyst|
    RU2673798C2|2013-07-24|2018-11-30|Басф Се|Regeneration of titanium-containing zeolite|US3172913A|1965-03-09|Pgocess for oxidizing olefins |
    US2164826A|1937-05-07|1939-07-04|Langwell Herbert|Purification of impure noble metals|
    US2649463A|1949-09-30|1953-08-18|Kellogg M W Co|Preparation of olefin oxides|
    US2758073A|1952-09-04|1956-08-07|Exxon Research Engineering Co|Fluidized solids distillation process|
    US2838575A|1956-05-03|1958-06-10|Shell Dev|Production of glycerine by hydroxylation of allyl alcohol|
    US3240718A|1963-11-13|1966-03-15|Universal Oil Prod Co|Regeneration and recovery of catalyst from sludge|
    US3410761A|1966-04-28|1968-11-12|Fmc Corp|Recovery of epoxy polybutadiene by plural stage flash distillation|
    US3562150A|1967-06-16|1971-02-09|Gulf Research Development Co|Removal of metal contaminants from catalysts with hydrogen peroxide|
    CH585155A5|1973-04-19|1977-02-28|Lonza Ag|
    JPS535879B2|1973-08-14|1978-03-02|
    US3926129A|1975-01-03|1975-12-16|Dorr Oliver Inc|Evaporative concentration of waste sludges with incinerator exhaust gases|JPH0525813B2|1984-07-18|1993-04-14|Daiseru Kagaku Kogyo Kk|
    US5147619A|1986-02-19|1992-09-15|Camlaw Limited|Nickel recovery using a fluidized bed process|
    US5081267A|1989-10-05|1992-01-14|Arco Chemical Technology, Inc.|Epoxidation process|
    US6414168B1|1998-12-28|2002-07-02|Caschem, Inc.|Epoxidation of ricinic compounds using a phase-transfer catalyst|
    US6051725A|1998-12-28|2000-04-18|Caschem, Inc.|Epoxidation of ricinic compounds using a phase-transfer catalyst|
    US6933397B2|2003-09-22|2005-08-23|Council Of Scientific And Industrial Research|Process for epoxidation of a liquid olefinic organic compound using a supported nano-gold catalyst|
    EP3263557A1|2016-06-30|2018-01-03|Evonik Degussa GmbH|Method for reactivation of a homogeneous oxidation catalyst|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19742454630|DE2454630C3|1974-11-18|Process for the recovery of catalysts in the epoxidation and hydroxylation of olefinic compounds with hydrogen peroxide|
    DE19742454572|DE2454572C3|1974-11-18|1974-11-18|Process for the separation of epoxidation and hydroxylation catalysts from distillation residues|
    [返回顶部]