• 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 producing acrylamide from acrylonitrile by utilizing a microorganism or enzyme capable of hydrating acrylonitrile into acrylamide in the form of a highly concentrated aqueous solution of acrylamide which comprises bringing acrylonitrile in contact with the microorganism or enzyme in an aqueous medium at a pH of from 6 to 10, at a temperature of from the freezing point to 50 DEG C., and under such conditions that the concentration of acrylamide in the reaction solution after the completion of the reaction is from 5% by weight to less than 20% by weight, and concentrating the resulting reaction solution; this invention further includes an embodiment wherein the reaction solution is concentrated by cooling the reaction solution after the reaction to from -4 DEG C. to -9 DEG C. to crystallize ice, separating the ice, and using the ice so separated for cooling during the hydration reaction. In addition, this invention includes an embodiment wherein the concentrated solution obtained by the above embodiment is further concentrated by evaporating the water contained in the concentrated solution.
    公开号:SU1694061A3
    申请号:SU802937825
    申请日:1980-06-18
    公开日:1991-11-23
    发明作者:Ямагути Ясумаса；Ватанабе Итиро；Сатох Есиаки
    申请人:Нитто Кемикал Индастри Ко., Лтд. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to organic chemistry, namely to the improvement of the bath method for the preparation of acrylamide, which can be used to obtain polymers
    The purpose of the invention is to increase the quality of the target product.
    Example 1 Strain N-774 is incubated aerobically on a medium (pH 7.2) containing 1% glucose, 0.5% peptone, 0.3% yeast extract and 0.3% wheat extract. An washed-washed strain N-774 (containing 75% water) in an amount of 40 hours is mixed with 4.5 parts of acyl amide, 0.5 parts of N, NT / - methylene bisac; And tamid and 40 hours isoto
    no sodium chloride solution until a homogeneous suspension is obtained. To this suspension is added 5 h-5% aqueous solution of dimethylaminopropionitrile and 10 h of an aqueous solution of potassium persulfate and the resulting mixture is polymerized, maintaining the temperature at 10 ° C for 10 minutes. The array of strain containing gel thus prepared is sprayed into fine particles and washed thoroughly with an isotonic solution of sodium chloride to obtain 100 parts of immobilized strain.
    Using the strain immobilized by such a sebraz, the reaction is carried out
    about
    4 o o o

    s
    3
    ratation and concentration in two reactors. First, the first and the second reactors are loaded with 40 parts of the immobilized strain obtained by the method described. Water with a pH of 8 is poured into the refrigerator and the crystallizer, and water with a pH of 8 is poured into the first and second reactors. Then the aqueous solution of acrylonitrile at pH 8, in which 4.5 hours / h A 0.1% aqueous solution of acrylic acid is neutralized with an aqueous solution of sodium carbonate and 16 hours / hour of ice. The resulting cooled solution in the refrigerator is sent to the first reactor at a rate of 200 hours / hour using a circulation pump "From the stream withdrawn from the first reactor, 160 h „/ h are returned to the refrigerator, and the remaining 40 h / h are served in the second reactor. The stream withdrawn from the second reactor, served in the mold, where it is cooled with brine. A slurry of ice thus obtained is recovered in a centrifugal separator and 21 hours / hour of the liquid thus obtained is withdrawn, and the remainder is returned to the crystallizer. Formed in the amount of 16 h / h the ice is fed into the refrigerator.
    When the reaction is almost established,
    ten
    15
    ,
    in 10 ml of water at 25 ° C. After a period of time of about 15 minutes, the polymerization goes sharply and in 90 minutes reaches the maximum reaction temperature. After / further incubation at 90 (I for 16 hours, the gel-like hydroxymer is sprayed and dried with hot air at 60 ° C for 16 hours, resulting in a dry product.
    The viscosity of a 0.1% aqueous polymer solution (determined by a Brookfield viscometer with a rotor No. 1, (6 rpm) is about 700 cP, the degree of hydrolysis is 13 mol, and the degree of polymerization is about 100%
    When the polymer obtained was added in an amount of 0.5-1 parts per million, to the waste waters of the paper industry, the pH of which was set at 6.5-7, was from 30 to 50 hours. per million of sulfate, it demonstrates a noticeably high ability to form aggregates
    Example 2 “According to the procedure of Example 1, strain N-774 is inoculated and immobilized. This immobilized strain in an amount of 100 hr was introduced into the stirred reactor and 900 parts of an aqueous solution with a pH of 8 was added thereto, which was obtained by neutralizing a 0.1% aqueous solution of acrylic acid with an aqueous solution of sodium carbonate. Then, with external cooling at 5 ° C with stirring for 2 hours into the reactor
    20
    25
    thirty
    the temperature in the refrigerator is -4 ° C, the temperature at the outlet is ,,. 80 parts of acrylonitrile are added. After
    The temperature in the crystallizer is -8 ° C. The concentration of acrylamide in the stream withdrawn from the second reactor is 15%, and the concentration of acrylamide in the concentrated solution discharged through the pipeline is 28% o.
    To characterize the quality of the aqueous solution of acrylamide thus obtained, the following esters are carried out.
    57 g of the obtained concentrated acrylamide solution (concentration 28%) and 119 g of water passed through an ion exchange, 4.8 g of boric acid, and 3.2 g of sodium hydroxide are added to the polymerization reactor, as hydrolyzing agents. The air in the polymerization reactor is then completely replaced with gaseous nitrogen and 32 mg of potassium persulfate and 32 mg of dimethylaminopropio-1-nitrile, each of which is dissolved, are added.
    40
    45
    50
    55
    completion of the reaction, the immobilized strain is filtered. The aqueous solution of acrylics obtained in this way is 950 hours (and the concentration of acrylamide in it is 10%.
    This solution is cooled in the specified reactor, and then re-subjected to freeze concentration consisting of ice crystallization and centrifugation. “Thus, a 20% aqueous solution of acrylamide is obtained. This aqueous solution in the amount of 920 g is loaded into a polymerization reactor and in the same way as in Example 1, a dry polymer is obtained.
    EXAMPLE 3 The reaction was carried out and the solution was concentrated by the method of Example 2, except that the amount of acrylonitrile introduced into the reaction was 125 hours, a 20% aqueous solution of acrylamide and a dry polymer of acrylamide were obtained.
    PRI me R 4 (comparative), Conducting a hydration reaction with such
    e, 10
    15
    %
    694061
    in 10 ml of water at 25 ° C. After a period of time of about 15 minutes, the polymerization goes sharply and in 90 minutes reaches the maximum reaction temperature. After / further incubation at 90 (I for 16 hours, the gel-like hydrogypolymer is sprayed and dried with hot air at 60 ° C for 16 hours, resulting in a dry product.
    The viscosity of a 0.1% aqueous polymer solution (determined by a Brookfield viscometer with a rotor No. 1, (6 rpm) is about 700 cP, the degree of hydrolysis is 13 mol, and the degree of polymerization is about 100%
    When the polymer obtained is added in the amount of 0.5-1 parts per million to the waste waters of the paper industry, the pH of which is set at 6.5-7 and added from 30 to 50 hours. per million of sulfate, it demonstrates a noticeably high ability to form aggregates
    Example 2 “According to the procedure of Example 1, strain N-774 is inoculated and immobilized. This immobilized strain in an amount of 100 hr was introduced into the stirred reactor and 900 parts of an aqueous solution with a pH of 8 was added thereto, which was obtained by neutralizing a 0.1% aqueous solution of acrylic acid with an aqueous solution of sodium carbonate. Then, with external cooling at 5 ° С, with stirring for 2 hours into the reactor
    20
    25
    thirty
    - ,,. 80 parts of acrylonitrile are added. After
    0
    five
    0
    five
    completion of the reaction, the immobilized strain is filtered. The aqueous solution of acrylamide thus obtained is 950 hours (and the concentration of acrylamide in it is 10%.
    This solution is cooled in the specified reactor, and then re-subjected to freeze-concentration, consisting of crystallization of ice and centrifugation. “Thus, a 20% aqueous solution of acrylamide is obtained. This aqueous solution in the amount of 920 g is loaded into a polymerization reactor and in the same way as in Example 1, a dry polymer is obtained.
    EXAMPLE 3 The reaction was carried out and the solution was concentrated by the method of Example 2, except that the amount of acrylonitrile introduced into the reaction was 125 hours, a 20% aqueous solution of acrylamide and a dry polymer were obtained. acrylamide
    PRI me R 4 (comparative), Conducting a hydration reaction with such
    51
    in the same way as in example 2, except that the amount of acrylonitrile used is increased to 173 hours, and thus a 2PX aqueous solution of acrylamide is obtained. / (more recently. this aqueous solution is treated according to the method of Example 2 and a dry polymer is obtained.
    PRI me R 5 (comparative). The hydration reaction is carried out in the same manner as in Example 2, except that the amount of acrylonitrile used is increased to 226 hours, and thus a 25% aqueous solution of acrylamide is obtained. Next, this aqueous solution is treated according to the method of example 2 and get a dry polymer. The results are shown in table 1 and 2,
    Example 6 o Into two fixed bed reactors equipped with a jacket are loaded (each) with 40 parts of immobilized strain N-774, half
    according to the method of Example 1, with
    five
    0
    five
    this peai-horn Gchch -scheny consistently. In the first reactor in its lower part serves an aqueous solution with pH And, obtained by neutralizing the 0.1% aqueous solution of acrylic acid with sodium carbonate, in an amount of 200 hours / h From the stream withdrawn from the upper part of the first reactor, part of the stream in the amount 160 h / h call into the first reactor, and the remaining 40 h, / h are fed into the second reactor through its upper part. After cooling to bc using brine flowing through the crates of each reactor, 35.5 hours / hour of aqueous solution, instead of 40 hours / hour of aqueous solution, and 4.5 hours / hour of acrylonitrile are mixed with 160 hours / h of the stream withdrawn from the upper part of the first reactor, and a semilk, thus the mixture is fed into the first reactor through its lower part in an amount of 200 h „/ h. Volume to speed 2 hours. Volume velocity is determined by the equation
    C -% Raw material feed volume} in e c | N1Schu v2meni Reactor volume
    The concentration of acrylamide in the stream withdrawn from the second reactor after the p-reaction has been established is 15%.
    The 15% aqueous solution of acrylamide thus obtained is heated to 40 ° C, blowing air through it, and then sent to an evaporator of an instant effect, where it is evaporated and concentrated. To obtain a concentrated solution,
    thirty
    100 h, acrylonitrile and 792 parts of water
    load into the reactor and carry out the hydration reaction in a nitrogen atmosphere at about 100 ° C for 8 hours. After the reaction is completed, the catalyst is removed. In the solution thus obtained, the end of the 35 tract of acrylamide is 15%, and the amount of unreacted acrylonitrile is 0.01%.
    The reaction solution is introduced into the crystallizer,
    where is he gradually
     which would be lower, the same procedure with the refrigerant up to -Ü ° С in 4 hours (the DURU is repeated and a 30% yield is obtained
     The resulting suspension of ice is filtered on a centrifuge, resulting in 647 parts of a 20% aqueous solution of acrylamide.
    acrylamide aqueous solution
    The solution thus obtained is treated as in Example 1, whereby a dry polymer is obtained. Polymerization proceeds calmly. For the obtained dry polymer, the viscosity of its 0.1% aqueous solution is about 700 cP, and the degree of hydrolysis is 13 mol%. When this polymer is added in an amount of from 0.5 to 1 ppm in the wastewater of the paper industry, the pH of which is set at 6.5-7, adding from 30 to 50 ppm of aluminum sulphate, it shows a good to education. cue aggregates
    Example 7 (comparative). A mixture of 10 hours of copper catalyst
    100 h, acrylonitrile and 792 parts of water
    loaded into the reactor and carried out the hydration reaction in a nitrogen atmosphere at 100 ° C for 8 hours. After completion of the reaction, the catalyst is removed. In the solution thus obtained, the concentration of acrylamide is 15%, and the amount of unreacted acrylonitrile is 0.01%.
    The reaction solution is introduced into the crystallizer,
    where is he gradually
    lag coolant to -b ° C for 4 h
    lag coolant to -b ° C for 4 h
    The resulting suspension of ice is filtered on a centrifuge, resulting in 647 parts of a 20% aqueous solution of acrylamide.
    This concentrated solution
    loaded into a polymerization reactor, where it is polymerized by the method of Example 2, but even after 4 hours, no polymer is formed.
    This measuring cylinder is turned upside down 10 times and then set. The time required to lower the boundary between the phases by 12.5 cm compared to the initial position is measured.
    Lower values indicate greater ability to form aggregates.
    In the example, the hydration reaction and the concentration are carried out.
    In the same manner as in Example 1, and except that strain N-774 was used in place of strain N-771, a 28% aqueous solution of acrylamide was prepared. This solution is polymerized and dried in the same manner as in Example 1, the dry polymer. For a dry olimer, the viscosity of a 0.1% aqueous solution is approximately d 700 centipoise, the degree of hydrolysis is 13 mol.%, The degree of polymerization is almost 100%. When this polymer is added to the wastewater of the pulp industry in an amount of 0.5–1 ppm, the pH of the waste water is adjusted to a value of 6.5–7 by adding 30–50 ppm aluminum sulphate, from - his ability to form aggregates is good.
    Example 9 By carrying out the hydration reaction and concentration in accordance with the method of Example 2 and Ig, using instead of strain N-774 strain N-775, a 20% aqueous solution of acrylamide is obtained. 920 g of this obtained solution is loaded into a liquefaction reactor and polymerization is carried out in accordance with the procedure of Example 1 to obtain a dry polymer. .%, the degree of polymerization is almost 100%. Adding 0, parts per million of polymer to wastewater from the pulp industry, whose pH has been adjusted to 6.5-7.0 by adding 30-50 parts per million of aluminum sulloate, its good ability to form aggregates dd is established,
    In comparative example 4, the hydration reaction of acrylonitrile is carried out without a concentration step to obtain a 20% acrylamide solution. When the concentration of acrylamide exceeds 20% by mass during the hydration reaction, the quality of acrylamide suddenly deteriorates and, as a result, it is necessary to control the reaction conditions so that the concentration of acrylamide after the reaction is less than 20% by mass. In accordance with this, as shown in Table 1, it can be concluded from the results of Example 4 that the physical properties of the anhydrous α-polymer obtained solely by the hydratapy reaction
    35

    0 d
    five
    without a stage of concentration. are better than the physical properties of the polymer in examples 2 and 3, obtained using a 20% aqueous solution of acrylamide with a combination of hydration reaction and concentration stage, In comparative example 5, the aqueous solution of acrylamide obtained by the hydration reaction rises to 25%.
    Example 10. When carrying out the hydration and freeze-concentration reaction to the following; as described in Example 1, a 28% acrylamide solution is obtained. The resulting concentrated acrylamide solution is heated to 40 ° C while air is blown through it and sent to an evaporative evaporator under reduced pressure, where it is evaporated by means of instantaneous evaporation and concentrated. In order to obtain a concentrated solution, its temperature is swept and the same operations are repeated to obtain a LBH acrylamide aqueous solution.
    The solution obtained in this way. treated as described in example 1 to obtain an anhydrous polymer
    The polymerization process proceeds smoothly. For the anhydrous polymer obtained, the viscosity in a 0.1% aqueous solution is about 700 sec. 10 When this polymer is added in an amount of from 0.5 to 1 ppm to the wastewater from paper mills whose pH is set to by 6.5-7 by adding 30-50 ppm of aluminum sulphate, it shows a good ability to aggregate
    Example 8: When carrying out the hydration and concentration reaction as described in Example 2, except that the hydration reaction is carried out at 25 ° C, an aqueous solution of acrylamide and anhydrous acrylamide polymer are obtained. The polymerization reaction proceeds smoothly. For the anhydrous polymer obtained, the viscosity of a 0.1% aqueous solution is about 670 cP. When this polymer is added in an amount of 0.5-1 ppm, the effluent from paper industry enterprises whose pH has been set to level 6.5-7 by adding from 30
    )
    up to 50 ppm of aluminum sulphate, the polymer showed good aggregability.
    Example 9. Conducting the hydration reaction and concentration as in Example 2, except that the pH hydration reaction was adjusted to 7 B, a 20% aqueous solution of acrylamide was obtained. Thus, the resulting solution was treated as in Example 1 and a dry polymer was obtained. The polymerization is smoothly carried out. For the dry polymer obtained, the shchkost of its polymer is 0;
    Example 10 A hydration reaction and concentration was carried out as in Example 9, except that the pH in the hydration reaction was adjusted to 9, a 20% aqueous solution of acrylamide was obtained. The solution thus obtained is treated as in Example 1 and is dried. polymer Polymerization is smoothly carried out. For the polymer obtained (the dry viscosity of its 0.1% aqueous solution is 700 ell.
    According to the proposed method, it is possible to obtain an aqueous solution of acrylamide with high quality.
    In the proposed method, which includes a combination of hydration reaction using microorganisms and concentrating by freezing, since the hydration reaction is performed at a temperature of from -4 to 25 C3 and then the concentration by freezing is carried out at a temperature of from -4 to -9 ° C, energy, required for cooling the reaction solution can be significantly reduced. In particular, when the hydration reaction is carried out at a temperature close to the freezing point, it is strictly necessary to cool the reaction solution while concentrating by freezing and, as a result, only heat removal is required, which is
    necessary for the crystallization of ice.
    The proposed method has a distinct advantage over the known freezing concentration method in that the cooling energy obtained by the chiller is used for both stages — cooling while concentrating by freezing and removing the heat of the hydration reaction.
    561
    AND)
    about
    0
    -
    five
    five
    0
    five
    0
    0
    five
    by using i-tick organisms at a temperature of about
    Since the ice separated in the freeze-concentrating step and the water obtained by disengaging the ice can be added to the hydration reaction solution, the washing and collecting steps of the solute (acrylamide) adhering to the ice are not necessary, resulting the loss of the obtained acrylamide is reduced. In addition, a heat exchange machine is not required for cooling the reaction solution, which results in a highly efficient cooling process.
    Thus, the concentration of the obtained acrylamide in the reaction solution after completion of the reaction is from 10 to less than 20% by weight. In the case where the target product, having a high concentration, is obtained by a concentration step, the concentration of the reaction solution is usually increased before concentration. However, it has been found that by controlling the concentration of acrylamide after completing the reaction in a range of a certain concentration, the quality of the acrylamide aqueous solution, which is obtained by concentrating this reaction solution, becomes excellent, and this acrylamide aqueous solution can be used as a starting material for polymerization without additional body cleaning.
    The resulting acrylamide aqueous solution can be used as a starting material to obtain various polymers without further purification, and as a result, polymers with high molecular weights and good performance that cannot be obtained by known methods can be obtained.
    Thus, as shown in Examples 2 and 3, when such reaction solutions, the concentration of acrylamide in which after completion of the reaction is 10 and 15 wt.%, Are concentrated to 20 wt.%, The polymers obtained using such acrylamide aqueous The solutions are characterized by a viscosity of 700 cP in a 0.1% aqueous solution and an aggregation capacity of 50-60 s and this data is good. Sledova-
    Generally, such polymers have sufficient efficacy and can be used as aggregating agents.
    On the other hand, when the concentration of acrylamide is brought to 20 wt0% by reaction only, the polymer obtained using such acrylamide has a viscosity of 600 ell in its 0.1% aqueous solution and an aggregation capacity of 80-90 s and therefore, it is difficult to use as an aggregating agent. When the concentration of acrylamide is increased to 25% by weight only by means of a reaction obtained using such acrylamide, the polymer has a viscosity of 500 ell in a 0.1% aqueous solution and an aggregation capacity of 100 seconds or higher and this polymer has a quality that allows its as an aggregating substance.
    The quality of acrylamide, which is obtained by hydration reaction using a microorganism or enzyme, suddenly deteriorates when the concentration of acrylamide in the reaction solution exceeds 20% by weight. For this reason, it is necessary to
    Initial amount of acrylonitrile, h0 Acrylate concentration after reaction,% Concentration Acrylamide concentration after concentration,
    Reactions

    Reactions
     h
    The time required for the polymerization temperature
    reached the maximum.
    A Brookfield viscometer (rotor P 1, 6 rpm) is measured.
    Calculated from the data obtained by potentiometric titration with the use of 0.1 n sodium hydroxide.
    H
    Slurries of clay (Tstichiya Kaolin) and 1.4 ml of a 0.1 liter aqueous dry polymer are loaded into a measuring cylinder with a ground glass stopper with a height of 25 gm and a volume of 100 m.
    0
    five
    0
    five
    the stocks are chosen so that the acrylamide concentration after completion of the reaction is less than 20 wt.%.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining acrylamide in aqueous medium by hydrolysis of acrylonitrile at pH 7-9, temperature (-4) - (25) ° C in the presence of itm immobilized microorganism N-771 or N-774 Corynebacterium, or N-775 Kocardia, deposited with the Scientific Researcher The Institute of Industrial Science and Technology of Japan, at an acrylamide concentration in the reaction mixture from 10 to 15 wt0%, is characterized by the fact that, in order to improve the quality of the product, the resulting acrylamide solution is concentrated to 20-28 wt. % by cooling to a temperature of () - (- 9) ° C until crystallization l and which was then separated and used for cooling in the hydration reaction, and the resulting solution, if necessary, heated to 40 ° C and concentrated to 55 wt% by removing water by evaporation at atmospheric or reduced pressure.
    Table 1
    173 20
    226 25
    20
    13
    Note. In examples 1, 6 and 8, the output of acrylic
    amide is measured in an effluent-1-thief effluent from the second reactor.
    Editor N. Yatsola Tehred M. Morgental
    Zaka 4085 Circulation: Subscription
    VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, 4/5 Raushsk nab.
    Production and publishing plant Patent, Uzhgorod, st. Gagarin, 101
    16940Ы
    U b l and c a 2
    Proofreader O. Kravtsov
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1694061A3|1991-11-23|Method of acrylamide preparation
    SU1299501A3|1987-03-23|Method for producing solutions of acrylamide or methacrylamide
    US4041135A|1977-08-09|Production of high capacity inorganic crystalline base exchange materials
    JP2664648B2|1997-10-15|Method for producing L-aspartic acid
    CN100562493C|2009-11-25|Hot method is handled alkali-making mother solution, is produced the ammonium chloride industrialization technology
    KR20040007475A|2004-01-24|Process for Producing Acrylamide Using Microbial Catalyst Having Been Washed with Aqueous Acrylic Acid Solution
    WO1996017950A1|1996-06-13|Process for the production of l-aspartic acid
    US4851342A|1989-07-25|Method for producing acrylamide using a microorganism
    GB2152030A|1985-07-31|Isolating L-amino acids by ion exchange
    CN110373440B|2022-03-01|Method for preparing DL-serine by one-pot enzyme method
    JPH07308195A|1995-11-28|Production of l-aspartic acid
    JP2004143078A|2004-05-20|Method for producing solution of acrylamidealkanesulfonic acid
    CN108285427A|2018-07-17|A kind of method of phosphoric acid by wet process round-robin method continuous production big particle industrial grade urea phosphate
    CN211689011U|2020-10-16|Acrylamide production system
    CN1218005A|1999-06-02|Method for preparation of potassium sulfate
    JP2804005B2|1998-09-24|Method for producing L-aspartic acid
    LU500313B1|2021-12-22|Process for clean extraction of l-aspartic acid
    JP3704769B2|2005-10-12|Method for producing L-aspartic acid
    JP2872178B2|1999-03-17|Method for producing L-aspartic acid
    JP3704770B2|2005-10-12|Method for producing L-aspartic acid
    CN112626141A|2021-04-09|Production method of acrylamide solution
    CN112522337A|2021-03-19|Continuous production method of acrylamide solution
    JPH09322791A|1997-12-16|Production of l-aspartic acid
    JPH09149792A|1997-06-10|Production of l-aspartic acid
    CN1153767A|1997-07-09|Formic acid and sodium sulfate producing method
    同族专利:
    公开号 | 公开日
    JPS6231913B2|1987-07-10|
    IT8048990D0|1980-06-17|
    DE3022912C2|1990-06-07|
    IT1143920B|1986-10-29|
    DE3022912A1|1981-04-02|
    JPS561888A|1981-01-10|
    GB2054563B|1983-07-13|
    FR2459285A1|1981-01-09|
    FR2459285B1|1984-04-06|
    US4414331A|1983-11-08|
    GB2054563A|1981-02-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3389567A|1961-04-03|1968-06-25|Chemetron Corp|Method of crystallizing fluids|
    US3624154A|1970-03-26|1971-11-30|Dow Chemical Co|Concentration of aqueous acrylamide|
    US4032572A|1971-12-06|1977-06-28|Mitsui Toatsu Chemicals, Incorporated|Method for concentrating an acrylamide aqueous solution|
    FR2245585B1|1973-09-19|1976-05-14|Anvar|
    US3887425A|1973-10-01|1975-06-03|American Cyanamid Co|Concentrating acrylamide solutions|
    FR2294999B1|1974-12-18|1977-11-10|Anvar|
    IT1162484B|1978-03-29|1987-04-01|Nitto Chemical Industry Co Ltd|PE PROCEDURE TO PRODUCE ACRYLAMIDE OR METHACRYLAMIDE USING MICROORGANISMS|JPS5835078B2|1980-08-19|1983-07-30|Nitto Chemical Industry Co Ltd|
    JPH0549273B2|1984-11-16|1993-07-23|Nitto Chemical Industry Co Ltd|
    TW422882B|1994-02-01|2001-02-21|Sumitomo Chemical Co|Process for production of amide compounds using microorganism|
    US5863750A|1996-12-18|1999-01-26|Cytec Tech Corp|Methods for the detoxification of nitrile and/or amide compounds|
    DE10120550A1|2001-04-26|2002-10-31|Stockhausen Chem Fab Gmbh|Process for the preparation of an aqueous acrylamide solution with a biocatalyst|
    JP2003277416A|2002-03-22|2003-10-02|Daiyanitorikkusu Kk|Aqueous acrylamide solution containing saccharides|
    US8361763B2|2006-12-06|2013-01-29|Bunge Oils, Inc.|Continuous process and apparatus for enzymatic treatment of lipids|
    US20130059349A1|2010-05-06|2013-03-07|Dia-Nitrix Co., Ltd.|Method for producing acrylamide using microbial catalyst|
    CN103687956A|2011-05-31|2014-03-26|三菱丽阳株式会社|Method for producing acrylamide|
    EP2783006A2|2011-11-22|2014-10-01|BP Corporation North America Inc.|Purification methods and systems related to renewable materials and biofuels production|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP54076351A|JPS6231913B2|1979-06-19|1979-06-19|
    [返回顶部]