• 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:
    A novel process for preparing the calcium salt of alpha -hydroxy- gamma -methylmercaptobutyric acid (MHBA) by contacting solid calcium oxide or calcium hydroxide with liquid MHBA.
    公开号:SU1091854A3
    申请号:SU813332156
    申请日:1981-09-04
    公开日:1984-05-07
    发明作者:Весли Камминс Ерл；Ервин Глайч Стивн；Майкл Виджилент Роберт
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

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    This invention relates to an improved process for the preparation of the calcium salt of the s.-hydroxy | methyl mercapto-butyric acid, which is used as an additive in animal feed.
    A known method for the preparation of the calcium salt with -oxy-j-meth of shmercapto-butyric acid is that the aqueous solution of oC-hydroxy-g-meth1 mercipromatic acid is treated with calcium carbonate to pH 5.5 at a temperature of about 55 ° C; After the separation of calcium sulfate, a water solution of calcium oxide or calcium hydroxide is added, and then the mixture is heated at 95 ° C, diluted with water to keep the target product in solution about 10%, filtered, then the water is evaporated until a precipitate is formed. as an impurity, 1.5% of the ammonium salt is O1-methyl mercapto-butyric acid and about 1% of water
    The closest to the present invention is the method of obtaining the calcium salt of o-hydroxy-jp-methyl mercapto-butyric acid, which means that the aqueous solution of o-hydroxy-d-methyl mercapto-butyric acid is treated at room temperature with ammonium sulphate to saturate and release the organic layer then a suspension of calcium oxide, hydroxide or carbonate in water is added to the organic layer, filtered, the filtrate is evaporated in vacuo. The yield of the target product 90-95% C2 1
    A disadvantage of the known methods is the formation of dilute solutions, from which the desired product is isolated by evaporation of water, which requires high energy levels.
    The purpose of the invention is to reduce the cost of the process by reducing energy costs.
    This goal is achieved by the proposed method of obtaining the calcium salt of ci-hydroxy-j-methyl mercaptoacidic acid, which consists in the fact that a water solution of o - oxy-d methyl mercaptoacid acid is treated with solid oxide or calcium hydroxide at 25-100 ° C,
    The interaction of (.- hydroxy-methyl mercidobutyric acid with calcium oxide or calcium hydroxide is preferably carried out in the presence of calcium
    8 5 -42
    salts with α-oxne- {-methyl mercaptoacid acid. up to 80% of the total reaction mass, or more preferably 20-40% by weight.
    The process is preferably carried out by mixing calcium di-ox-5 methyl mercapto-butyric acid with calcium oxide or calcium hydroxide and then o (.-Hydroxy-methyl mercapto-butyric acid in contact with this mixture, which simplifies the process.
    Equivalent to silt oxide ratio
    Calcium hydroxide and c-oxy-methyl mercaptocarboxylic acid are preferably at least 1: 1.
    The process is preferably carried out with an aqueous solution of C-hydroxy-mercapto-butyric acid at 50-100 ° C, and the reaction mass is preferably stirred at 80-100 C.
    The process is preferably carried out by contacting solid oxide or calcium hydroxide with the calcium salt of α-hydroxymerc-mercaptoacidic acid, followed by treatment with a solution (U.-hydroxymethyl mercaptoacidic acid at 25-100 ° C, stirring the reaction mass at 45-100 ° C and release of the calcium salt of ci-oKCH-g-methyl mercapto-butyric acid, part of which is recycled.
    The distinguishing features of 1M The characteristics of the method are the use of solid calcium oxide or hydroxide in the process and their contacting with a solution with -oxy-- methyl mercaptoacetic acid at 25-100 C.
    o.-hydroxy-y-methylmer-butyric acid is obtained by hydrolysis of o-hydroxy methyl mercaptobutyronitrile with hydrochloric acid to obtain an aqueous suspension of ammonium chloride containing the product in the aqueous phase. This acid solution, after concentration in vacuo and filtering ammonium chloride, is used in this process. Typically, the solution contains about 75-92 wt.% Acid and about 3-20% water. The acid used in this process can also be prepared in other ways.
    To obtain a calcium salt product, at least one equivalent of calcium oxide or calcium hydroxide is used for each equivalent of acid. When it is prepared by hydrolysis in hydrochloric acid, the solution of the starting acid contains ammonium chloride, 31 which is also mutually; 1, e11 is coupled with calcium oxide or calcium hydroxide. Therefore, an additional equivalent of calcium compound for each equivalent of ammonium chloride should be used. To ensure complete interaction with α-hydroxy-methyl mercaptobutyric acid, a slight excess of the chalcium compound is preferably used. An excess of not more than 10% is preferred, otherwise the purity of the product is reduced. To obtain the calcium salt, a solution of the acid is preferably added directly to the dry oxide or calcium hydroxide in a solid mixer. If the acid is added directly to the oxide or calcium hydroxide, the resulting reaction mass becomes very viscous and difficult to mix. To avoid this, the oxide or calcium hydroxide is mixed with a portion of the dry calcium salt before adding the acid. According to such a method, which is preferred, the reaction mass is a volatile powder, and mixing is not difficult. In a continuous process, a portion of the obtained calcium salt is returned to a mixer with two rotors or a utility device. The oxide or calcium hydroxide is added to the stirred calcium salt during its passage through the system. After sufficient mixing, the acid is added, and the reaction begins with the passage of the reaction mass through the system. The superior product is dried, if necessary, and part of it is returned to the beginning of the described systems. The amount of calcium salt that is returned to the cycle varies between about 10-80% of the product produced, preferably 25-50%. The time that elapses between the addition of the acid and the output of the calcium salt is about 0.3-2 hours, preferably 0.5-1 hours. According to the batch method, the acid is preferably added to the mixture containing calcium oxide or calcium hydroxide for about 0 3-4 hours more preferably 0.5-2 hours. After the addition of the acid is complete, the reaction mixture is stirred for about 3-2 hours to complete the reaction. Example 1 The periodic reaction is carried out under laboratory conditions in a mixer with sigma-blades with two handles. The mixing chamber has an open outlet to the atmosphere, dust and steam are removed through a washing system. A powder mixture consisting of 456 parts of a wet calcium salt with α-hydroxy methyl mercaptoacid acid (12.3% water) and 126 parts of calcium hydroxide, served in a mixing chamber. Mixing is started, the chamber is heated with low pressure steam to 85-90 seconds. From the funnel, 522 parts of an acid solution (91% acid, 7% HPO, 2%) are added dropwise at 90-100 ° C over 40 minutes. The equivalent ratio of calcium hydroxide: acid to ammonium chloride is 1.01: 1. After the addition of acid is complete, the reaction mass is stirred for 85 minutes at 85-90. This additional mixing serves to partially dry the reaction mass. The resulting mixture, containing 6.1 wt.% H20, is dried in a vacuum oven at 60 ° C. The analysis shows that the dry powder contains,%: calcium salt 96.0, chloride salt 3.3; iljO 0.5; Ca (OH) 2 Oh, 1. Example 2. A periodic reaction was carried out under laboratory conditions in a mixer with sigma-blades with two handles. The mixing chamber has an open outlet to the atmosphere, dust and steam are removed through the flushing system. This example differs from example 1 in that the dry calcium salt of the acid is used as a charge, calcium oxide is used instead of calcium hydroxide and dried during mixing. 342 parts of the dry product are loaded into the mixing chamber, 97 parts of calcium oxide are added. Begin to mix, the camera is heated with low steam. From the addition funnel, 522 parts of an acid solution (89% equivalent of acid, 2% MNDS2) are added dropwise at 95 ° C over 20 minutes. The equivalent ratio of calcium hydroxide: acid to ammonium chloride is 1.05: 1.0. After addition of the acid is complete, the reaction mass is stirred for 60 min at 85-90 s.
    The composition of the product,%: Calcium salt 95, chlorchsta salt 3; Ca (OHL 1.0; H20 0.5.
    Example 3. A continuous reaction was carried out in a two-rotor mixer as described below.
    Calcium hydroxide is added to the product to reverse the cycle at a rate of 113 hours / hour. The throughput of the product for the reverse cycle is 200 hours / hour. A solution of the acid (89% acid, 2%, 9%) is added to this well-mixed mixture at a rate of 460 hours / hour. The ratio of equivalents of calcium hydroxide to total equivalents of acid and ShdC1 is 1.05: 1. The returned product is 25% by weight of the reaction mass.
    The average residence time in the mixer is about 30 minutes. The mixing chamber is heated to maintain the reaction mass
    at 85-90-. The reaction mass exits the kneader as a wet powder and is continuously dried. A portion (200 h / h) is returned to the mixer. ,
    The dried mixture consists of,% ;, calcium salt 95; chloride salt 3; Ca (OH) 1; Н20 С, 5.
    Example 4. A periodic reaction is carried out at laboratory
    conditions in a plugged mixer with two self-scraping rotors. A powder mixture consisting of 7.25 parts of calcium oxide and 15 parts of dry product is added.
    into the mixer. Then the chamber is sealed and heated to 62c. 21.14 parts of the acid solution (89% acid equivalents, 2%) are injected at 25 ° C for approximately 15 seconds.
    The reaction mixture is mixed for 5 minutes. The resulting product is a dry powder containing 93.2% calcium salt.
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING CALCIUM SALT <£ -OXY-y-METHYLMERCAPTOM
    HYDROCHLORIC ACID by the interaction of an aqueous solution containing (-oxy ~ methyl mercaptate acid) with calcium oxide or hydroxide, characterized in that, in order to reduce the cost of the process, calcium oxide or hydroxide is used in solid form and the process is carried out at 25-100 ° C.
    [2]
    2. The method according to p. ^ Characterized in that, in order to simplify the process, the latter is carried out in the presence of the target calcium salt cZ-okch - j - methyl mercaptobutyric acid in an amount of up to 80% by weight of the reaction mixture. g
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    同族专利:
    公开号 | 公开日
    DE3163511D1|1984-06-14|
    US4335257A|1982-06-15|
    ZA816163B|1983-04-27|
    IL63741D0|1981-12-31|
    EP0049057B1|1984-05-09|
    ES505229A0|1982-12-01|
    AU541915B2|1985-01-31|
    ES8301464A1|1982-12-01|
    NZ198279A|1984-03-16|
    HU190354B|1986-08-28|
    JPS5785365A|1982-05-28|
    AT7387T|1984-05-15|
    PL232880A1|1982-04-26|
    EP0049057A1|1982-04-07|
    BR8105606A|1982-05-18|
    IL63741A|1984-10-31|
    AU7482181A|1982-03-11|
    PL135443B1|1985-10-31|
    CA1182475A|1985-02-12|
    AR225363A1|1982-03-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CA694610A|1964-09-22|J. Wineman Robert|Preparation of salts of 2-hydroxy-4-alkylthiobutyric acid|
    US2745745A|1952-10-30|1956-05-15|Monsanto Chemicals|Poultry feed|
    US2946818A|1953-10-01|1960-07-26|Monsanto Chemicals|Preparation of hydroxy mercapto butyric acids and derivatives thereof|
    CH385823A|1959-09-01|1964-12-31|Inventa Ag|Process for the preparation of the calcium salt of a-oxy-y-methylthio-butyric acid|
    BE611435A|1960-12-14|1962-06-12|Stamicarbon|Process for the preparation of metal salts of alpha-hydroxy-gamma -methylmercaptobutyric acid|
    US3272860A|1964-04-02|1966-09-13|Monsanto Co|Preparation of methionine analogues|
    US4060535A|1976-08-31|1977-11-29|Tenneco Chemicals, Inc.|Process for the production of metal salts of organic acids|
    DE2838643A1|1978-09-05|1980-03-13|Metabio Joullie Meudon Fa|Magnesium and calcium salts of carboxy:alkylthio-acetic acids - with mucolytic, immuno:regulatory and antiarthritic activity|
    DE2945497C2|1979-03-06|1990-04-19|Degussa Ag, 6000 Frankfurt, De|US4388327A|1981-10-30|1983-06-14|E. I. Du Pont De Nemours & Co.|Method of increasing milk production of dairy cattle|
    US4855495A|1983-09-06|1989-08-08|Monsanto Company|Enhanced 2-hydroxy-4-methylthiobutanoic acid composition and method of preparation|
    DE3462792D1|1983-09-06|1987-04-30|Monsanto Co|Enhanced 2-hydroxy-4-methylthiobutanoic acid composition and method of preparation|
    JPH11508876A|1995-06-07|1999-08-03|ノーバスインターナショナルインコーポレイテッド|Continuous hydrolysis method for producing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof|
    US6017563A|1997-07-25|2000-01-25|Novus International, Inc.|Process for optimizing milk production|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/184,210|US4335257A|1980-09-05|1980-09-05|Preparation of the calcium salt of alpha-hydroxy-gamma-methylmercaptobutyric acid|LV920393A| LV5615A3|1980-09-05|1992-12-22|Downfall for alpha-oxy-gamma-methylcaptoswort calcium salt|
    LTRP251A| LT2075B|1980-09-05|1992-12-22|THE ALPHA-OKSI-UPSILON-METILMERKAPOSE-MIXED SUGAR CALCIUM SALT BUDGET|
    MD94-0075A| MD55C2|1980-09-05|1994-04-07|Process for obtaining calcium salt of the a-oxi-y-methyl-mercaptobutylic acid|
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