• 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:
    The components of aqueous ammonium fluoride solutions are recovered as ammonia and potassium fluoride by adding potassium hydroxide, di stilling to remove and secure the ammonia, concentrating the remaining solution and combining it with a water soluble, dipolar, aprotic solvent, such as N-methylpyrrolidone, and distilling to remove the remaining water to obtain the potassium fluoride as a slurry in the solvent. Slurries of potassium fluoride are useful in the replacement of chloride in heterocyclyl and aryl chlorides by fluoride.
    公开号:SU1727530A3
    申请号:SU874202932
    申请日:1987-07-20
    公开日:1992-04-15
    发明作者:Д.Кэмпвелл Кент；Б.Крэмптон Ли；Дж.Дайтчи Лаура；Д.Ховда Кейт；К.Тайсон Джордж；А.Вильсон Чарльз
    申请人:Дзе Дау Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    A suspension consisting of potassium fluoride in a water-soluble, dipolar, aprotic solvent-M-methylpyrrolidone in the process, which consists of mixing the solution with the solvent and distilling water. Potassium hydroxide is mixed with an aqueous solution of ammonium fluoride, ammonia is removed by heating and in some cases the resulting aqueous solution of potassium fluoride is concentrated by removing water.
    Ammonia and fluoride from aqueous solutions containing ammonium fluoride as the main solute can be recovered using the proposed method, regardless of the source of the solution. High concentrations of ammonia in solutions do not interfere with the process. Such solutions are usually in the form of streams of by-products in ammonia reactions of organic fluorine-containing compounds and in glass grinding and metal etching. A suitable solution is obtained as a by-product in the conversion of 3,5-dichloro-2,4,6-trifluoropyridine to 4-amino-3,5-dichloro-2,6-difluorpyridine when treated with aqueous ammonia.
    Potassium hydroxide can be used either as a solid or as an aqueous solution and can be mixed with aqueous solutions of ammonium fluoride, which must be reprocessed by any known method. For example, it may be added to an ammonium fluoride solution or an ammonium fluoride solution may be added to it. Mixing can be carried out at any temperature and pressure and is usually carried out at room temperature and pressure. Mixing can be carried out gradually or all at once, with or without mixing. It is preferable to mix these agents gradually with stirring. In addition, it is preferable to carry out addition in a vessel with controlled openings to prevent the formation of ammonia into the atmosphere.
    The purity of the potassium fluoride extracted during the process depends in part on the amount of potassium hydroxide used. It is preferable to use an almost equimolar amount of fluoride ion containing ammonium fluoride in an aqueous solution, but useful products obtained with other amounts and in some cases an excess or deficiency may even be preferable.
    Ammonia formed by the addition of potassium hydroxide is partially soluble.
    in water. What is excessive with respect to solubility quickly disappears when potassium hydroxide is added. Essentially all remaining ammonia can
    to be distilled off by heating the solution at the boiling point or by heating near the boiling point and passing steam through the solution. The volatilized ammonia is then distilled to produce anhydrous ammonia, or else it is absorbed in water to produce aqueous ammonia. Other traditional ammonia collection methods may also be used. In some cases, it may not be necessary to remove organic compounds that are present in the stock solution and are distilled off with steam from the ammonia collected before it can be reused. This can be done by conventional methods such as decantation or extraction.
    Ammonia is usually continuously removed until the remaining solution is freed from ammonia, or until
    5, the ammonia concentration in the stripping fraction will not be too low to allow economical recovery.
    The solution remaining after removal
    0 ammonia, in some cases concentrated to remove water. This is done for convenience and to minimize the cost of raw materials and energy. The removal of water is carried out by distillation at atmospheric or reduced pressure using conventional equipment and methods. However, it can also be carried out by other means, such as evaporation, when using semi-permeable
    0 membranes or selective absorbents.
    Water removal is continued until the concentration of potassium fluoride in the remaining solution reaches at least 20%. It is preferable to concentrate to a solution containing at least 30% potassium fluoride, and it is especially preferable to concentrate to at least 40%. The concentration step is not carried out if an already prepared potassium fluoride solution is obtained.
    The water-soluble, dipolar, aprotic solvent is combined with the potassium fluoride concentrate in the next process step. The result is a solution
    5 or two-phase system depending on the amount of water present, temperature and water-solvent ratio. Sufficient solvent is used so that the final product of the process is a mobile suspension of potassium fluoride in
    solvent. Such amount of solvent is usually used in order to obtain a prepared suspension containing 3-35% potassium fluoride. It is preferable to use such an amount in order to obtain a paste containing 5-25% potassium fluoride, and it is preferable to use such an amount in order to obtain a paste containing 8-2 0%.
    The potassium fluoride solvent and concentrate can be mixed at any convenient temperature or pressure and in any way. It is often more convenient to add the solvent to the concentrated solution. The addition is usually carried out while the concentrated solution is still hot from the previous operation and it is better to do this with good stirring. It is also often convenient to add the concentrated solution to the solvent. In a preferred embodiment of the method, the concentrated solution is added to the hot solvent by spraying. This procedure facilitates the precipitation of small particles of potassium fluoride, which easily form mobile pastes.
    In this process, a water-soluble dipolar, aprotic solvent that is distilled above the boiling point of water, such as N-methylpyrrolidone, can be used.
    The residual water is then removed as a distillate by fractionating the aqueous potassium fluoride-solvent slurry. Any conventional batch or continuous distillation equipment and any technology can be used, but it is preferable to use apparatus equipped with means for mixing in a vessel. Depending on the efficiency of the column and the solvent used, it may be necessary to remove a certain amount of the solvent in the form of a distillate, respectively. to get the finished product, c. sufficiently freed from water. Typically, the water content in the final product is reduced to less than 1%. Preferably, it is reduced to less than 0.1%, and more preferably to less than 0.01%.
    Individual operations of the proposed method can be carried out in separate equipment or multiple individual operations can be carried out in the same equipment. It is often convenient to carry out all operations sequentially in one unit. Thus, an aqueous solution of ammonium fluoride is placed in a periodic distillation apparatus.
    preferably equipped with means for mixing and at least one group of fractionation columns. The solution is heated with stirring, potassium hydroxide is added, and the ammonia is removed by distillation and collected. Distillation is carried out to remove water and concentrate the solution. A water-soluble, dipolar aprotic solution is then added.
    0 solvent to the stirred, hot, concentrated solution and continue distillation until water is completely removed.
    A suspension of potassium fluoride in a dipole p5, aprotic solvent is effective for converting aryl and heterocyclyl chlorides to aryl and heterocyclyl fluorides. For example, pentachloropyridine is a known product to react with potassium fluoride in a dipolar aprotic solvent, including N-methylpyrrolidone and sulfolane to obtain 3,5-dichloro-2,4,6-trifluoropyridine. Aryl and heterocyclyl fluorides are useful.
    5 as chemical intermediates, as dye-binding agents, and in a variety of other applications.
    For example 1. Combine 24 g (0.36 mol)
    0 85% potassium hydroxide tablets with 24 g of ice and the resulting solution are placed in a 500 ml round-bottomed flask equipped with a mechanical stirrer and a distant tube, the outlet of which is connected to a condenser and a dry ice trap in series. Under stirring at a rate of about 10 ml / min, add 100 ml (101.2 g) of an aqueous solution containing 4.7 mol / l of ammonium fluoride (as determined by a specific fluoride ion electrode) and some amount of ammonia, this solution was obtained as a by-product in the interaction of aqueous ammonia and 3,5-dichloro-2,4,6-trifluoropyridi5. The resulting mixture, which has a pH of 12-13, is allowed to stand overnight. The residual ammonia and some excess water are distilled off from the resulting solution at 70-100 ° C and
    0 atmospheric pressure to extract 69.1 g of aqueous ammonia. Carefully lower the pressure and the remaining hot solution, which contains about 30-40% potassium fluoride, is slowly diluted with 150 ml.
    5 N-methylpyrrolidone, maintaining the temperature above 80 ° C. Another 59.3 g of water is distilled off at 60-65 ° C and a pressure of 60 mm Hg. and condense. A dry ice trap contains about 6g at this point. The stripping tube is again connected to a 10-column column,
    50 ml of N-methylpyrrolidone are added and the remaining mixture is distilled at 100 mm Hg. and to about 120 ° C to obtain 11.4 g of distillate. Continue the distillation at 25 mm Hg. and 90-100 ° C to get another 12.4 g of distillate. The water content of the remaining potassium fluoride suspension in N-methylpyrrolidone was determined by Karl Fischer titration and was approximately 219 ppm (parts per million). This suspension is successfully used to convert pentachloropyridine to 3,5-dichloro-2,4,6-trifluoropyridine.
    EXAMPLE 2. With vigorous stirring, 100 ml of an aqueous ammonia solution of ammonium fluoride, obtained as a by-product by the reaction of aqueous ammonia with 3,5-dichloro-2.4, b-trifluoropyridine, containing 0.31 mol of fluoride ion and 0.59 mol of ammonia (as determined by ion-specific electrode analysis) to 25.4 g of an aqueous solution containing 0.26 mol of potassium hydroxide in a 2 l flask equipped with a mechanical stirrer, a heating jacket and a by-pass tube with a condenser and a trap cooled by dry ice but. Gas evolution begins immediately. The mixture was heated under reflux with stirring to distill off the ammonia. About 53 g of distillate consisting of ammonia and water are collected in a condenser. 250 ml of N-methylpyrrolidone are added with stirring and the remaining approximately 60 ml of hot aqueous solution at such a rate that the bottom temperature remains above 95 ° C. Distillation continues. Another 250 ml of N-methylpyrrolidone is added as previously and distillation is continued until the head fraction reaches about 200 ° C. The total amount of distillate obtained after adding the solvent is about 76 g, part of which is N-methylpyrrolidone. The remaining potassium fluoride suspension contains some potassium bifluoride. It is used to convert pentachloropyridine to 3,5-dichloro-2,4,6-trifluorpyridine.
    Froze 100 g of 85% tablets (1.5 mol) of potassium hydroxide and 80 g of ice in a 2-liter round-bottom flask of stainless steel equipped with an inlet, a mechanical stirrer, a thermometer and a 5-plate column and a condenser, along with a tap, and a scrubber containing 250 ml of water attached to a tap hole. With stirring over a period of 15 min, 500 ml of an aqueous ammonia solution of fluoride are added dropwise with stirring.
    ammonium, obtained by dissolving 55.6 g (1.5 mol) of ammonium fluoride and 88.4 g of 29% aqueous ammonia (1.5 mol) in water. Then the flask is heated for 2 hours to
    temperature of the head fraction of 100 ° C to drive off ammonia. Heating is continued until about 100 ml of water is distilled off as distillate. The distillate and scrubber are combined for
    0 obtain 395 ml of aqueous ammonia. Another 94 ml of water is removed by distillation. Analysis of the remaining solution by ion-specific electrode analysis indicates that the pH is 13.9, 3.83 molar in potassium ion,
    5 3.89 molarity of fluoride ion and 3.65 10 molar ratio of ammonia. The scrubber gives 5.72 molar ammonia (2.25 mol, 75% recovery) and the second water fraction is 0.11 molar in ammonia (0.01 mol, 0.3%
    0 of the amount of the possible). 1.5 L of N-methylpyrrolidone is added and the mixture is distilled under stirring until the head fraction reaches 200-205 ° C to obtain approximately 450 ml
    5 distillate. The residual suspension contains about 0.13% water during Karl Fischer titration. Stripping is continued at a pressure of 100 mm Hg. and removing another 50 ml of solvent to obtain approximately
    0 6.2% suspension of potassium fluoride in N-methylpyrrolidone, containing about 0.03% water.
    The method allows the processing of an aqueous solution of ammonium fluoride and the effective use of potassium fluoride in the processes of replacing chlorine in organic compounds with fluorine.
    权利要求:
    Claims (4)
    [1]
    1. A method of treating an aqueous solution containing ammonium fluoride to ammonia and metal fluoride, including treating the solution with a compound of the corresponding metal and distilling ammonia, which is so as to ensure the effective use of metal fluoride in the chlorine replacement processes in organic compounds to fluorine, the initial solution is treated with potassium hydroxide with stirring, the reaction
    0 The mixture is heated at 70-100 ° C with ammonia distillation to obtain a potassium fluoride solution of 30-40%, the potassium fluoride solution is mixed with M-methylpyrrolidone and water is distilled from the reaction mixture to obtain a suspension of potassium fluoride in a solvent.
    [2]
    2. A method according to claim 1, characterized in that the mixing of the solvent and the potassium fluoride solution is carried out by adding the solvent to the potassium fluoride solution while stirring the reaction medium.
    [3]
    3. A method according to claim 1, characterized in that the mixing of the solvent and the potassium fluoride solution is carried out by spraying the solution into the solvent.
    dingy
    [4]
    4. The method according to claim 1, characterized in that the by-product from the reaction of ammonia with organofluorine is used as an initial solution
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    同族专利:
    公开号 | 公开日
    DE3772656D1|1991-10-10|
    JPS6335415A|1988-02-16|
    AU7502787A|1988-01-28|
    IL83191A|1990-11-05|
    CA1288212C|1991-09-03|
    CN1012567B|1991-05-08|
    EP0254063A2|1988-01-27|
    CN87104895A|1988-02-03|
    KR900006903B1|1990-09-24|
    HU201497B|1990-11-28|
    AU587706B2|1989-08-24|
    JP2516637B2|1996-07-24|
    HUT45947A|1988-09-28|
    IL83191D0|1987-12-31|
    BR8703760A|1988-03-29|
    EP0254063B1|1991-09-04|
    EP0254063A3|1988-04-20|
    ES2024457B3|1992-03-01|
    KR880001527A|1988-04-23|
    US4713231A|1987-12-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1581819A|1925-05-09|1926-04-20|Siegel Wilhelm|Process of manufacturing sodium fluoride from silicofluorine compounds|
    US1928510A|1930-11-14|1933-09-26|Koppers Co Inc|Production of pure ammonia|
    GB529852A|1939-06-03|1940-11-29|Bataafsche Petroleum|A process for the removal of water by distillation or rectification|
    US2285093A|1939-10-28|1942-06-02|Vaman R Kokatnur|Mixture of materials and method of making|
    US2339160A|1940-08-02|1944-01-11|Shell Dev|Distillation process|
    US2527320A|1944-10-14|1950-10-24|Robert C Mcharness|Dehydration of alkali-metal acid fluorides|
    US2781244A|1952-09-18|1957-02-12|Allied Chem & Dye Corp|Controlled recovery of ammonia from liquors containing fixed ammonia values|
    US3359076A|1964-01-31|1967-12-19|Dow Chemical Co|Precipitation of potassium halides from mixed brines using organic solvents|
    GB1306517A|1970-06-08|1973-02-14|Ici Ltd|Manufacture of halogenated pyridine derivatives|
    GB1306596A|1970-07-21|1973-02-14|Ici Ltd|Manufacture of hydroxy-halogenopyridines or salts thereof|
    GB1340421A|1971-01-14|1973-12-12|Ici Ltd|Manufacture of chlorofluoropyridines|
    FI47081C|1971-12-13|1973-09-10|Kemira Oy|Process for refining as a by-product in the fertilizer industry fluorine is obtained.|
    US3920419A|1974-04-10|1975-11-18|Republic Steel Corp|Method of removing ammonia from ammonia containing liquor|
    US4542221A|1981-05-18|1985-09-17|The Dow Chemical Company|Exchanging fluorine for chlorine in a chlorinated pyridine with an alkali metal fluoride|US4994252A|1990-02-09|1991-02-19|Dowelanco|Removal of potassium chloride from solvents|
    US4976946A|1990-02-09|1990-12-11|The Dow Chemical Company|Separation of potassium salts|
    JPH0533169A|1991-07-26|1993-02-09|Toomen Constr Kk|Method for treating and recovering waste etchant containing fluorine and ammonia compound|
    DE59203900D1|1991-12-16|1995-11-09|Neumann & Stallherm Gmbh|Process for the extraction of fluorsparand ammonia or ammonia water from an aqueous ammonium fluoride solution as a waste material from fuel element production.|
    WO1996008445A2|1994-09-15|1996-03-21|Alliedsignal Inc.|Process for treating an aqueous kf waste stream and for converting kf into hf and koh|
    US7033562B2|2002-10-16|2006-04-25|Kion Corporation|Ammonia recovery in the preparation of silazanes and polysilazanes|
    US7229601B2|2004-02-06|2007-06-12|Seh-America, Inc.|Ammonia reclamation system|
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    CN101376509B|2007-08-31|2010-11-17|多氟多化工股份有限公司|Method for preparing potassium fluoride|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/887,587|US4713231A|1986-07-21|1986-07-21|Process for the recovery of ammonia and fluoride values from ammonium fluoride solutions|
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