• 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 process for the production of L- ascorbic acid from L-ketogulonic acid or a derivative thereof by acid- catalysed enolisation and lactonisation under pressure at a temperature of at least 80 DEG C. and with the addition of a lower alcohol after enolisation, wherein the enolisation and lactonisation are carried out continuously in a tube reactor, the flow rate of which is so adjusted that the residence time characteristic of the reacting molecules approximates to that of a plug flow, i.e. there is no back-mixing. The process may be carried out in an apparatus comprising a tube reactor having a heat exchanger and a holding tube, the inlet side of the tube reactor being connected to a metering pump and the outlet side thereof to a mixing chamber, the mixing chamber in turn being connected, on the one hand, to a second metering pump for feeding in an alcohol from a reservoir therefor and, on the other hand, to a pressure valve to which is connected a long-tube evaporator leading to a separating column, said separating column being connected to means for recovering the alcohol and means for crystallising L-ascorbic acid.
    公开号:SU1310398A1
    申请号:SU797770821
    申请日:1979-09-26
    公开日:1987-05-15
    发明作者:Йоахим Шмидт；Вольфганг Бамберг；Хартмут Груперт；Йутта Деике；Вольфганг Шлепцка；Эрхард Шорн；Хейнц Штопзак
    申请人:Феб Йенафарм (Инопредприятие)；
    IPC主号:
    专利说明:

    one
    The invention relates to a process for the preparation of L-ascorbic acid.
    . A known method of producing L-ascorbic acid by enolization and lactonic islet of L-ketogulonic acid or its diacetone derivative under the action of hydrochloric acid at 80-100 ° C and pressure of 6.4-7 atm with the addition of n-butanol (US Pat. No. 2,1989830, Cl. 260-3437, published 1940).
    The disadvantage of this method is a very long (20-40 hours) reaction time and a large amount of apparatus associated with this, due to the need to remove hydrogen chloride. In addition, the process decreases the concentration of catalysts.
    Example 1. A suspension consisting of diacetone-L-ketogulonic acid (DAHC) and a concentrated solisator due to the fact that the addition of alcohols entails the formation of an acid (10.78 kg / h DAHHL:; - 5.39 l / h of hydrochloric acid (36%), Nidy, the impregnation of which is also sent to the apparatus with a sap 1, but with additional costs. . dosing pump 2 through heated. The purpose of the invention is to intensify a tubular reactor up to 100 ° C. The supply amount of the suspension is 15.1 l / h, the extract time is 10 min. A pressure of 7 atm is set, which is stabilized by the discharge valve 5. Before the enolysate enters the long-tube evaporator 6 with the dosing pump 7 from the tank 8, 22 l / h of n-butanol is added through the mixing chamber 9 through the mixing chamber 9. Pressure on
    thirty
    35
    process.
    The invention is based on the task of developing a technically continuous process that allows obtaining L-ascorbic acid with a high yield so that the isolation of raw ascorbic acid from the mineral acid solution is accomplished by evaporating the hydrochloric acid with the participation of alcohol as an auxiliary substance.
    At the same time, the contact time between the alcohol used and the enolizing mixture containing the mineral acid should be so short that the formation of an alkyl halide can be almost completely avoided. The residual concentration of the mineral acid should be kept as low as possible, since otherwise quantitative crystallization of ac corbic acid will not occur.
    The evaporator-separation column-condenser site is 80-100 Torr, the temperature is 60-65 ° C. The volatile components — hydrochloric acid and butanol are separated in the head column 10.
    Cheese ascorbic acid is obtained in 10. Treatment and purification are carried out in a known manner. The output of 6.2 kg / h of raw vitamin C (92% of theoretical). Content of -45 96.5%.
    Example 2. Suspension, state - The flow rate of the medium through the L-ketogulonic acid tubing and the finished reactor should be adjusted with centered hydrochloric acid so that the cond. Conditions are (kg / h KGK: 5.35 l / h g reacting molecules would be close to a piston flow, i.e., they would counteract the reverse mixing.
    The duration of the mixture in the above-mentioned slurry temperature range of the suspension is 15.0 l / h, pressure is 5-15 minutes, and the pressure is kept for 10 minutes. Installed within 6.4-7 atm. The pressure in the mixer is 6.4 atm, a stable chamber located behind the pipelining by the discharge valve, holding apparatus, carried out until the enolysate is 36% long, from the apparatus with an agitator 1 is directed by a pump -dose rum 2 through heated to 100 ° C tubular reactor.p 3, 4. Served amount 103982
    is continuous dosing of n-butanol. This causes an immediate decrease in the temperature of the mixture, so that the continuation of the reaction is excluded. The butanol enolizate then passes through the injection valve and immediately evaporates under reduced pressure in the long tube apparatus in such a way that the equilibrium between the vapor and the liquid can be completely avoided.
    Thus, more than 90% hydrochloric acid is removed at an evaporation rate of less than 1 s.
    The invention is illustrated by the examples given.
    Example 1. Suspension consisting of diacetone-b-ketogulonic acid (DAHCC) and concentrated CC
    15
     lactic acid (10.78 kg / h DAKGK:; 5.39 l / h of 36% hydrochloric acid), from the apparatus with a sack 1, are sent by the dosing pump 2 through a tubular reactor heated to 100 ° C. Supplied quantity the suspension is 15.1 l / h, the duration of the extract is 10 min. A pressure of 7 atm is set, which is stabilized by the discharge valve 5. Before the enolysate enters the long-tube evaporator 6 with the dosing pump 7 from the tank 8, 22 l / h of n-butanol is added through the mixing chamber 9 through the mixing chamber 9. Pressure on
    35
    In the region of the evaporator, the separation column condenser is 80-100 Torr, the temperature is 60-65 ° C. The volatile components — hydrochloric acid and butanol are separated in the head column 10.
    Cheese ascorbic acid is obtained in 10. Treatment and purification are carried out in a known manner. The output of 6.2 kg / h of raw vitamin C (92% of theoretical). The content is 45.5%.
    Example 2. Suspension consisting of L-ketogulonic acid and concentrated hydrochloric acid (kg / h KGC: 5.35 l / h of hydrochloric acid)
     the suspension is 15.0 l / h, the delivery time is 10 minutes. The pressure is set at 6.4 atm, stabilized by the injection valve, until the enolysate is added to the long acid (36%), from the apparatus with agitator 1 it is directed by a metering pump. rum 2 through heating to 100 ° C tubular reactor.p 3, 4. Served amount313
    tube evaporator 6 with a dosing pump, 7 from the tank 8 through the mixing chamber 9 topped up with 22 l / h of n-butanol. The pressure in the section of the inflator-separator column-condenser is 80-100 mm Hg. Temperature 60-65 C. Volatile components — hydrochloric acid and butanol are separated in packed column 10. Safa ascorbic acid is obtained in 10. Processing and cleaning is carried out in a known manner. The output of 7,490 kg / h of raw ascorbic acid (87% of theoretical). Purity 96.6%.
    84
    Carrying out the process in this way allows for the first time to carry out the process of obtaining ascorbic acid continuously, ensuring a very short reaction time for enolization and lactonization, which ensures high productivity of the process. The problem of acid-catalyst removal has been solved, and this operation takes place during
    less than one second. The low thermal load of the reaction mixture hardly entails any by-products, such as a halogenated hydrocarbon and the corresponding ether.
    alcohol.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING L-ASKORBINIC ACID by enolization and lactonization of L-ketogulonic acid or its diacetone derivative under the influence of hydrochloric acid at temperature
    80-100 ° С and a pressure of 6.4-7 atm followed by the addition of n-butanol, characterized in that, in order to intensify the process, a suspension consisting of L-ketogulonic acid or its diacetone derivative. and hydrochloric acid, continuously fed under constant pressure to a tubular reactor having heat transfer and reaction zones, n-butanol is added to the enolizate and sent to a long tube evaporator, the flow rate being set so that it matches the speed of the reaction mixture throughout the installation, where there is instant evaporation of the mixture at a pressure of 80-100 mm RT.article and a temperature of 60-65 ° C, and crude ascorbic acid is isolated from the bottom of the column.
    1310398 A
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    同族专利:
    公开号 | 公开日
    FR2440366A1|1980-05-30|
    HU182734B|1984-03-28|
    GB2034315A|1980-06-04|
    DD141832A1|1980-05-21|
    DE2939052A1|1980-05-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2462251A|1945-05-16|1949-02-22|Merck & Co Inc|Process for preparing ascorbic acids|US4845246A|1987-06-15|1989-07-04|Takeda Chemical Industries, Ltd.|Ascorbic acid ester|
    ES2075148T3|1989-05-19|1995-10-01|Hayashibara Biochem Lab|ALPHA-GLYCOSYL-L-ASCORBIC ACID, AND ITS PREPARATION AND USES.|
    JPH08176133A|1994-12-26|1996-07-09|Takeda Chem Ind Ltd|Method for purifying l-ascorbic acid|
    DE19734086C1|1997-08-07|1998-08-13|Merck Patent Gmbh|L-ascorbic acid preparation|
    DE19904821C1|1999-02-05|2000-07-06|Merck Patent Gmbh|Preparation of L-ascorbic acid from 2-keto- or 2,3-4,6-diacetone-2-keto-L-gulonic acid|
    DE10022518A1|2000-05-10|2001-11-15|Basf Ag|Preparation of L-ascorbic acids by reacting 2-keto-L-gulonic acids or melt of 2-keto-L-gulonic acid alkyl esters under acid catalysis using water-miscible solvent|
    AT303373T|2000-12-22|2005-09-15|Eastman Chem Co|PROCESS FOR THE PREPARATION OF ASCORBIC ACID IN THE PRESENCE OF A SULFIT|
    DE60110932T2|2000-12-22|2006-01-19|Eastman Chemical Co., Kingsport|CONTINUOUS METHOD FOR THE PREPARATION OF L-ASCORBIC ACID|
    DE10115325A1|2001-03-28|2002-10-17|Bosch Gmbh Robert|Fuel injector, for an IC motor, has a clamp system to hold the injector housing at the base body, with a convex curvature in a ball segment shape at the clamping surface for an increased sealing action|
    US6740762B2|2001-08-24|2004-05-25|Eastman Chemical Company|Process for ascorbic acids using alkaline earth silicate catalysts|
    US6716997B1|2001-10-09|2004-04-06|Eastman Chemical Company|Systems and methods for generation of ascorbic acid with reduced color|
    CN110372649A|2019-08-08|2019-10-25|安徽丰原发酵技术工程研究有限公司|It is a kind of to prepare ascorbic method by a step acid system of raw material of 2-KLG|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DD20877378A|DD141832A1|1978-10-31|1978-10-31|METHOD AND DEVICE FOR PREPARING L-ASCORBIN ACID|
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