Method of continuous production of aqueous solutions of acrylamide or metacrylamide

专利摘要:
A process for the continuous production of acrylamide or methacrylamide from acrylonitrile or methacrylonitrile by use of a microorganism capable of promoting the hydration of acrylonitrile or methacrylonitrile into the corresponding amide. Said process comprising immobilizing the microorganism or enzyme extracted therefrom, continuously bringing the acrylonitrile or methacrylonitrile into contact with the immobilized microorganism or enzyme in at least one reactor containing an aqueous medium at a pH pf 6 to 10 to cause the hydration reaction, and recycling a part of the reacted solution to dilute the unreacted acrylonitrile or methacrylonitrile and water therewith.
公开号:SU1609444A3
申请号:SU802917348
申请日:1980-05-05
公开日:1990-11-23
发明作者:Ямагути Ясумаса；Ватанабе Итиро；Сато Есиаки
申请人:Нитто Кемикал Индастри Ко, Лтд (Фирма)；
IPC主号:

专利说明:

The invention relates to the field of organic chemistry, in particular to an improved method for the continuous preparation of aqueous solutions of acrylamide or methacrylamide, which can be used to prepare the corresponding polymers.
The aim of the invention is to simplify the process.
According to the proposed method, any microorganisms capable of ensuring the hydrolysis of (meth) acrylonitrile can be used to form the corresponding (meth) - acrylamide, regardless of which group a particular microorganism can be classified (classified) according to taxonomy ( systematics) of microorganisms, for example, microorganisms belonging to the genus Corynebacterium and Nocardia.
Immobilization can be carried out as follows.
The described microorganism is dispersed in an aqueous medium (for example, in water, an isotonic solution of sodium chloride or in a buffer solution) containing monomeric acrylamide and a crosslinking agent, a polymerization initiator and a polymerization accelerator are added to this system and the resulting mixture is gelled by polyO5
about
with
4 4

CM
merization at a temperature in the range of O - 30 ° C, preferably at O - 5 ° C and at pH 5 - 10, preferably less than 6 - 8.
Acrylamide monomers used for immobilization. According to the proposed method, acrylamide and methacrylamide are included. If desired, they can be used in combination with other olefin monomers capable of copolymerisation with them. Said acrylamide monomer is used in the reaction solution at such a concentration that a gel (gel system) is formed in the reaction solution as a result of the polymerization reaction.
According to the proposed method, the | -5 of the apparatus, consisting of two or more reactors connected in series. diluted with a mixture of (meth) acrylonitrile and water, used as a starting material, by means of a remobilized preparation of microorganization circulating into it a part of effluentoins or an enzyme isolated from them, can be used in the form of a fixed (fixed, fixed a) a layer or a fluidized (shyuidized) layer, although it is still preferable to have a fixed-state reactor of an immobilized preparation, in which the immobilized microorganism or an enzyme is less so There is a tendency to rupture due to mechanical friction and wear. The replacement of an immobilized microorganism enzyme is usually carried out in a Periodic manner, i.e. time τt time, and the proposed e-volume also includes a reactor with a bed of a moving type, in which loading and unloading is performed in a semi-continuous (semi-periodic) or continuous way. The contacting of the immobilized microorganism or enzyme with the reaction solution is preferably carried out using an anti-current or flow method, such as these. the methods allow for the recovery of the amount of immobilized microorganism or enzyme required for the process. .
Usually, two or more or three or more reactors are filled in series (in a row) filled with an immobilized microorganism or enzyme in which the reaction is carried out continuously after diluting the mixture of (meth) acrylonitrile and water with a part of the reaction solution that is removed from the reaction a reaction solution flowing from each reactor into which the initial mixture of (meth) acrylo-nitrile and water is introduced. To another reactor
25 (reactors), not the first, only acrylonitrile is supplied. In addition, a mixture (meth of acrylonitrile and water to be decomposed, including the unreacted (meth) acrylonitrile and water,
.JQ drank from the previous reactor, along with a freshly supplied mixture of (meth) acrylonitrile a and water.
Department of immobilized micro. an organism or an enzyme from the reaction solution is usually carried out directly in the reactor, and the solution that has slipped into the reaction solution (captured or carried away by the reaction solution) is immobilized
The microorganism or enzyme can be easily separated from it by filtration or sedimentation.
The concentration of (meth) acrylamide in the reaction solution can be personalized (up to the limit)
individual solubility. In the case of the preparation of acrylamide, its concentration is adjusted within the range of 5 to 7.5 wt.%.
35
50
55
Source materials, i.e. (meth) acrylonitrile and water are diluted with the previous (i.e., previously prepared) reaction solution, which is recycled to the start of the process. The dilution effect increases with an increase in the ratio in which the dilution is carried out, although the interval of the ratio in which the dilution is carried out is determined
the parata and is recycled to the beginning of the process, while the residual part of the reaction solution is discharged (removed) from the reaction system in the quality of the product. A part of the reaction solution was continuously withdrawn from the reaction system in the form of an aqueous solution (meth) a;
concentration approaching the concentration of (meth) acrylonitrile in the aqueous medium introduced into said reaction system.
When using the reactionary
apparatus consisting of two or more reactors connected sequentially. It is diluted with a mixture of (meth) acrylonitrile and water, used as a starting material, by means of a re-reactive solution flowing from each reactor into which the initial mixture (meth) acrylo is introduced. nitrile and water. To another reactor
5 (reactors), not the first, only acrylonitrile is supplied. In addition, a mixture of (meth) acrylonitrile and water to be diluted, including the unreacted (meth) acrylonitrile and water supplied from the previous reactor, along with the freshly supplied (meth) acrylonitrile a and water.
Department of immobilized micro. an organism or an enzyme from the reaction solution is usually carried out directly in the reactor, and the solution that has slipped into the reaction solution (captured or carried away by the reaction solution) is immobilized
0 A microorganism or enzyme can be easily separated from it by filtration or sedimentation.
The concentration of (meth) acrylamide in the reaction solution can be increased (increased) to the limit of its
individual solubility. In the case of the preparation of acrylamide, its concentration is adjusted within the range of 5 to 7.5 wt.%.
five
Source materials, i.e. (meth) acrylonitrile and water are diluted with the previous (i.e., previously prepared) reaction solution, which is recycled to the beginning of the process. The dilution effect increases with an increase in the ratio in which the dilution is carried out, although the interval of the relations in which the dilution is carried out is determined in accordance with the dilution effect and liquid resistance. The reaction rate or degree of conversion (conversion) can be controlled by changing the amount of immobilized microorganism or enzyme represented It is possible to carry out the hydration reaction of (meth) acrylonitrile with a yield reaching almost 100% for the target (meth) acrylamide. An important factor in the process is the volumetric rate (OC), which is expressed by the following formula
h
The feed rate of the feedstock to the reactor (feed volume
. „Per unit of time)
j - - ---.-.- ------.- .-.
Reactor volume
Preferably, the OC of each reactor is approximately 0.1-20 hours, 0.3 to 5 hours. Thus, the 1 / OS ratio, expressed in hours, indicates the contact time between the starting material and the immobilized microorganism or enzyme.
When unreacted (meth) acrylonitrile is present in the reaction solution, this reaction solution can be introduced into another reactor to complete the reaction, or unreacted (meth) acrylonitrile can be removed from this solution by stripping (distillation of the light fraction) or distillation. The (meth) acrylonitrile and water thus recovered can be recycled back to the process to carry out the hydration reaction. The number of additional reactors required for the hydration reaction of the residual (meth) acrylonitrile present in the reaction solution flowing out of the first reactor, in an insignificant amount, is usually small and does not exceed 1 or 2. In these reactors, since the concentration (meth) Acrylonitrile in the reaction solution entering them is rather low, there is no need to carry out further (additional) dilution of the reaction system with part of the reactionary solution resulting from them: about the solution containing the target product BCCH (meth) acrylamide. That is, in the ETI7S additional reactors, the -oceration of the dilution of the reaction solution fed to the reactor, with part of the reaction solution flowing out of the reactor, is no longer carried out.
According to the proposed method, the service life of an immobilized microorganism or enzyme can be extended many times and an aqueous solution of (meth) acrylamide can be stably obtained over a very long Q period of time. This aqueous solution of (meth) acrylamide can be used as such or after concentration by conventional methods, as a starting material for producing various polymers. Alternatively, (meth) acryl amide can be obtained as a crystalline product, based on the proposed aqueous solution, by performing such operations as concentrating the solution and cooling it. The precipitation of a crystalline precipitate can be achieved by increasing the concentration of (meth) acrylamide to a level of 5 N, which exceeds the solubility limit of this substance at a given temperature (which is achieved by evaporation or concentration of the final reaction solution) or by reducing the solubility of (meth) acrylamide, achieved by performing a high concentration aqueous solution (meth) acrylamide cooling procedure. In cases where the concentration of (meth) acrylamide in the reaction solution is quite high, this reaction solution is sometimes slightly colored, but it can be cleaned by using a porous anion exchange resin from strongly basic to weakly basic.
The concentration of the reaction product and the unreacted starting material was measured using the usual method of gas-liquid chromatography.
Example 1. 40 hours of washed biomass (water content 75%) of microorganisms of strain L-774, obtained by aerobic incubation in culture medium (pH 7.2), containing 1% glucose, 0.5% pentone, 0, 3% yeast extract, 0.3% malt extract, 4.5 parts acrylamide, 0.5 part e-methylene bisacrylamide and 40 parts physiological saline are mixed together and mixed until a uniform dispersion is formed. 5 hours is added to this dispersion.
0
15
of an aqueous solution of dimethylaminopropionitrile and 10 hours of a 2.5% aqueous solution of potassium persulfate and the mixture obtained is polymerized for 30 minutes, maintaining the temperature at 10 ° C. The gel thus obtained containing the above mentioned microorganisms in an immobilized state , crushed into particles of a small .Q; th size, and after thorough and complete washing with physiological saline, 100 parts of the immobilized microorganism are obtained in the form of gel-like particles.
A column having an internal diameter of 3 cm and a length of 25 cm, equipped with a jacket that provides for regulation of the temperature within the desired limits, is loaded with 40 g of the immobilized preparation of microorganisms. A raw mixture of 0.073 h, acrylonitrile and 0.925 parts of aqueous phosphate buffer solution (pH 8.0), premixed with 25 4 parts of effluent flowing from the -Hirac column (in the initial reaction period 0.05 M aqueous phosphate buffer solution with a pH of 8.0, which was also used in the following examples) "At the same time, the rest of the effluent is continuously removed from the reaction system: at a rate of 10 ml / h.
 The temperature in the column is maintained at a constant level of 1 ° T, equal to: by continuously passing cold water through the jacket.
After the reaction continued. e. in
in the upper part
do yourself consistently (: p d).
The initial raw material is a mixture of 0.075 acrylonitrile and 0.925 parts of a 0.05 M phosphate buffer solution (pH 3.0), premixed with 4 parts of effluent flowing from the bottom of column 1, at a flow rate of .200 ml / h (OC 2 hours in the upper part of the reaction column 1.. The rest of the effluent flowing from the bottom of column 1 is injected at an OC flow of 40 ml / h (OC 0.4 h-) column 2.
The temperature in the reaction columns. kah support at the same level. passing through a cold water shirt.
After carrying out the reaction for 1000 h in this reaction systhesis, the acrylamide and non-reactive acrylonitrile in the effluent from the bottom of column 1 is 9.5 and 0.37% respectively, and the concentration of acryl amide in the effluent is resulting from the bottom of column 2 is 10%, and this effluent does not practically contain unreacted acrylonitrile and by-products the yield of the target acrylamide is close to 100%.
Froze Columns (1 and 2) connected in series in two, removed by shirts and having an inner diameter of 3 cm and a length of 25 cm, load 40 g each of the immobilized
20
thirty
35
for 1000 hours, i.e. after 40 ° croorganism prepared by
how the column worked 100 hours; the concentration of acrylamide in the effluent (the reaction solution flowing from the column) was 10%, and in this solution it was not possible to detect (detect) any signs of unreacted acrylonitrile and no by-products, and the yield of the target acrylamide is close to 100 %
 Example 2. In Example 1, two jacketed reaction columns (1 and 2) are prepared, each of which has an internal diameter of 3 cm and a height of 25 cm, into which 40 g of the immobilized microorganism obtained in Example 1 is loaded, and these columns are are mels45
50
55
example 1.
The initial raw mixture of 0.075 hours of acrylonitrile and 0.925 parts of a 0.05 M aqueous phosphate buffer solution (pH 8.0), after mixing with a part of the effluent flowing from the bottom of column 1, is introduced into the upper part of column 1 with the OC flow 80 ml / h (OS 0.8 h). The rest of the effluent, flowing from the bottom of column 1, is introduced into the top of column 2 with a flow of 40 ml / h (OS 0.4-h).
The temperature in both reaction columns was maintained equal to that of the transmission — through the outer coat of cold water.
After carrying out the process for 1000 h, the concentration of acrylamide
15
m - .Q -
25,
. e. in
in the upper part
6094448
do yourself consistently (: p d).
The initial raw material is a mixture of 0.075 parts of acrylonitrile and 0.925 parts of 0.05 M aqueous phosphate buffer solution (pH 3.0), premixed with 4 parts of effluent flowing from the bottom of column 1, injected at a flow rate of .200 ml / h (OC 2) in the upper part of the reaction column 1. The rest of the effluent flowing from the bottom of column 1 is injected at an OC flow of 40 ml / h (OC 0.4 h-) of column 2.
The temperature in the reaction columns (k. Is maintained at the level by passing through a jacket of cold water.
After reacting for 1000 hours in this reaction system, the concentration of acrylamide and unreacted acrylonitrile in the effluent from the bottom of column 1 is 9.5 and 0.37% respectively, and the concentration of acrylamide in the effluent flowing from the bottom of column 2, is 10%, and this effluent contains almost no unreacted acrylonitrile and by-products, the yield of the target acrylamide is close to 100%.
Froze In two columns connected in series (1 and 2), equipped with jackets and having an inner diameter of 3 cm and a length of 25 cm, load 40 g of immobilized
20
thirty
35
, 40 ° croorganism prepared according to
° of the organism prepared according to
example 1.
The initial raw mixture of 0.075 parts of acrylonitrile and 0.925 parts of 0.05 M aqueous phosphate buffer solution (pH 8.0), after mixing with part of the effluent flowing from the bottom of column 1, was injected into the top of column 1 with a flow ratio 80 ml / h (fixed value 0.8 h). The rest of the effluent, flowing from the bottom of column 1, is introduced into the top of column 2 with the OC flow of 40 ml / h (OC 0.4-h-).
The temperature in both reaction columns was maintained equal by passing-through the outer jacket with cold water.
After carrying out the process for 1000 h, the concentration of acrylamide
1609444
in the effluent flowing from the bottom of column 2, it turned out to be 10%, and no unreacted acrylonitrile and by-products were detected in it.
An example. Two connected consecutive columns (I and 2), equipped with jackets and having an inner diameter of 3 cm and a length of 25 cm, are loaded. D 40 g each of the immobilized microorganism obtained in Example 1.
The initial raw mixture of 0.075 parts of acrylonitrile and 0.925 parts of 0.05 M aqueous phosphate buffer solution (pH 3.0) - after premixing with 9 parts of effluent flowing from the bottom of the reaction column I, is introduced into the upper part of the last column. OC flow of 400 ml / h (OC) The rest of the effluent flowing from column 1 is introduced into the top of column 2 with a OC flow of 40 ml / h (OC 0s 4 H-1).
The temperature in the column is maintained at a level of 10 ° C by passing cold water through the jacket.
After carrying out the process for 1000 hours, the concentration of acrylamide
ten
load 40 g of immobilized microorganism prepared according to Example 1, are connected in series. The raw mix is 0.075 hours, acrylonitrile and 0.925 parts is 0.05 M aqueous fossy buffer solution (pH 8.0) after mixing with 4 parts of effect removed from the upper part of column 2, is introduced into the lower part of column 1 (where it passes through the layer of immobilized microorganism in the direction from the bottom up) at the flow of OC 200 ml / h (OC 2 h - 1). E (bd815
The envelope withdrawn from the upper part of column 1 was then directed to the lower part of the reaction column 2 to pass through it in the bottom-up direction. The rest of the effluent withdrawn from the upper part of column 2 was introduced into the lower part of column 3 (to pass through it from the bottom to the top) at an OC flow of 40 ml / h (OC 0.4 h) and the resulting effect is continuously output from the top of this column.
The temperature in the column is maintained at 10 ° C according to Example 1. After carrying out the described process, it is in those A - - -I-1 -.V- -i. ". -one. Jiii v L. v J J., c: k. cl о i с -
in effluent resulting from the lower hour — 1000 h. acrylamide concentration
column 2, turned out to be 10%, and in this effluent no unreacted acrylonitrile and any by-products were detected,
PRI and MER 5. The procedure of example 1 is repeated with the difference that instead of the initial raw material mixture of 0.075 parts of acrylonitrile and 0.925 parts of 0.05 F aqueous phosphate buffer solution (pH 8.0), the raw material mixture is used, consisting of 0.079 parts of methacrylonitrile and 0.921 parts of 0.05 M aqueous phosphate buffer solution (pH 8.0).
After carrying out the process for 1000 h, the concentration of methacrylamide in the effluent resulting from the reaction column turned out to be 10%, and practically no signs of unreacted methacrylonitrile and by-products were found in this effluent, and the yield of the target methacrylamide was close to 100% .
Example 6. Three reaction columns 1-3, equipped with jackets for circulating thermostatic liquid, each of which has an internal diameter of 3 cm and a length of 25. cm,
35
in the fluid expelled from the top of reaction column 1, it turned out to be 10%, and this effect almost n-e contained unreacted acrylonitrile and by-products.
PRI-MER 7. The dispersion of the washed biomass (having a water content of 75%) microterganisms strain N 774, which was obtained by aerobic jQ incubation in the culture (medium pH 7.2) containing 1% glucose, 0.5% peptone, 0.3% yeast extract and 0.3% malt extract, are exposed to ultrasonic waves in order to cause cell disintegration and to ensure extraction of the enzyme from them. The dispersion is treated with ultrasonic waves by irradiating with these waves a 0.05 M aqueous 50 phosphate buffer solution containing the said microorganisms at a concentration of 5%. Irradiation (sound) is carried out with ultrasonic waves with a frequency of 20 kHz at a temperature of 20 minutes. As a generator of ultrasonic vibrations using the device Sony (}) Air-185, manufactured by the company Vranson Sonic Power Company (Branson Sonic Power
45
55
four
ten
load 40 g of immobilized microorganism prepared according to example 1, are connected in series. The initial raw mixture is 0.075 hours, acrylonitrile and 0.925 parts, 0.05 M aqueous fossian buffer solution (pH 8.0) after mixing with 4 parts of effluent discharged from the upper part of column 2, is introduced into the lower part of column 1 (where it passes through the layer of immobilized microorganism in the bottom-up direction) at the OC flow of 200 ml / h (OC 2 h - 1). E (bd
The envelope withdrawn from the top of column 1 was then directed to the bottom of the reaction column 2 to pass through it in the bottom-up direction. The rest of the effluent withdrawn from the top of column 2 was introduced into the bottom of column 3 (to pass through it from the bottom to the top) at an OC flow of 40 ml / h (OC 0.4 h) and the resulting effect is continuously output from the top of this column.
The temperature in the column is maintained at 10 ° C in example 1. After carrying out the described process in teA - - -I-1 -.V- -i. ". -one. Jiii v L. v J J., c: k. cl о i с -
cation - 1000 h acrylamide concentration
1000 hour acrylamide concentration
35
in the eluent from the upper part of the reaction column 1, it turned out to be equal to 10%, and this effect almost n-e contained unreacted acrylonitrile and by-products.
PRI-MER 7. The dispersion of the washed biomass (having a water content of 75%) microterganisms strain N 774, which was obtained by aerobic jQ incubation in the culture (medium pH 7.2) containing 1% glucose, 0.5% peptone, 0.3% yeast extract and 0.3% malt extract, are exposed to ultrasonic waves in order to cause cell disintegration and to ensure extraction of the enzyme from them. The dispersion is treated with ultrasonic waves by irradiating with these waves a 0.05 M aqueous phosphate buffer solution containing the said microorganisms at a concentration of 5%. Irradiation (sound) is carried out with ultrasonic waves with a frequency of 20 kHz at a temperature of 20 minutes. As a generator of ultrasonic vibrations using the device Sony (}) Air-185, manufactured by the company Vranson Sonic Power Company (Branson Sonic Power
five
five
1, 16
Company), the enzyme extracted in this way is mixed with Amberlite 904 porous strong-base anion exchange resin (manufactured by Rohm and Haas Company), the mixture is stirred at a temperature of about 10 ° C for 6 hours and then the enzyme is precipitated (deposited) or bound to an anion exchange resin. After this, the solution is separated from the resin and an immobilized enzyme is obtained.
Two jacketed columns 1 and 2, having an inner diameter of 3 cm and a length of 25 cm, each of which is loaded with 100 ml of immobilized enzyme, are interconnected sequentially (row). The initial raw mix .0.075 parts of acrylonitrile and 0.925 parts of pure water are introduced after mixing with 4 h of effluent flowing from the bottom of column 1 (pure water was used in the initial reaction period), in the upper part of column 1 at OS 300 ml / h stream
(OS
 3). The remainder of effluent flowing from the bottom of the reaction column 1 is introduced into the top of column 2 at an OOC stream of 60 ml / h. (OS 0.6).
The temperature in the column is maintained at 10 ° C.
After carrying out the process for 200 hours, the concentration of acrylamide in the effluent resulting from the bottom (bottom) part of column 2 was 10%, and in this effect almost no unreacted acrylonitrile and any by-products were found.
example (comparative). Two jacketed columns 1 and 2 "having an inner diameter of 3 cm. and a length of 25 cm, each of which is loaded with 40 g of the immobilized microorganism obtained in Example 1, is connected in series. The initial raw mixture of 0.075 parts of acrylonitrile and 0.925 parts of 0.05 M aqueous phosphate buffer solution (pH 3.0) is introduced in the upper part of the reaction column 1 at the OC flow of 40 ml / h (OC - 0.4 h), the effluent flowing from the lower part of the reaction column I is introduced into the upper part of the column 2 from the specified OC flow.






The temperature in the column is maintained at
10 ° C.
12
0
g n 5
0
.,.
g
five
After carrying out the reaction in these columns for 50 hours, the concentration of unreacted acrylonitrile in the effluent flowing from the bottom of the reaction column 2 increased markedly, reaching 1000 ppm. At this time, the concentration of acrylamide in the effluent was 9.9%.
As the reaction continued further for several hours, the concentration of acrylonitrile in the effluent flowing from the bottom of column 2 increased dramatically, which made it almost impossible to continue the process.
Example The procedure of Example 1 is repeated, but with the exception that the pH of the aqueous phosphate buffer solution is changed to pH 9.0 and the column is cooled with brine to a temperature of 0 ° C.
After continuing the reaction for 1000 hours, the concentration of acrylamide in the effluent was 10%, almost no unreacted acrylonitrile and by-products were detected.
PRI and MER 9. The procedure of Example 1 was repeated, with the exception that the pH of the aqueous solution from the phosphoric acid buffer was changed to pH 7.0 and the column was cooled with brine to a temperature.
After continuing the reaction for 1000 hours, the concentration of acrylamide in the effluent was 10% with virtually no unreacted acrylonitrile and side products.
Example 10. The procedure of example 1 is repeated, but with the exception that the jacketed column is loaded with immobilized microorganisms obtained by immobolizing strain L-775, which is obtained by aerobic incubation of example 1, and the column is cooled to brine to 0 ° C.
After continuing the reaction for 1000 hours, the concentration of acrylamide in the effluent stream was 10% with virtually no unreacted acrylonitrile and by-products.
A and I. 11. The procedure of example 1 is repeated, but with the exception that an immobilized microorganism is prepared in a jacketed column obtained by immobilizing strain W-771 obtained by aerobic incubation of example 1, and the column is cooled to brine P ° C.
After continuing the reaction for 1000 hours, the concentration of acrylamide in the effluent was 10% with virtually no unreacted acrylonitrile and by-products.
The proposed method is based on a combination of the facts that the enzyme activity of a microorganism capable of providing a hydration reaction of (meth) acrylonitrile to (meth) acrylamide in an aqueous solution of (meth) acrylonitrile decreases rapidly with increasing concentration of (meth) acrylonitrile, whereas in contrast. in an aqueous (meth) acrylamide solution, the enzyme activity appears to be noticeably stable over a long period of time, even in a significant concentration, and it is mainly that the hydration reaction of and periodic repetition is performed essentially using a single column.
Consequently, the number of columns used by the proposed method is significantly less than the known.
For example, in preparing a reaction solution of acrylamide with a concentration of 10 wt.%, At least 8 columns are required to adjust the concentration of the acrylonitrile solution supplied to the input of each column to 1 wt.%.
On the other hand, in preparing a 10% by weight acrylamide reaction solution, the acrylonitrile used as a starting material can be diluted at least 7 times with a reaction solution recycled to adjust the acrylonitrile solution on the column inlet to a concentration of about 1% and less with a single column. Further, the feeding of the acrylonitrile solution can be carried out in one column without the use of multiple columns.
The proposed aqueous solution of (meth) acrylamide, corresponding to

权利要求:
Claims (1)
[1]
The concentrations of the aqueous solution of (meth) acrylonitrile supplied through a single feed can be obtained continuously without using multiple columns, thereby greatly simplifying the equipment and technology required for the production of (meth) acrylamide. Q In addition, the enzyme activity in the reaction involving enzymes is usually reduced when the products are positioned; therefore, the supplied acrylonitrile solution is separately added to each 5 columns to gradually increase the acrylamide concentration. When all microorganisms are constantly in contact with a high concentration aqueous solution of (meth) acrylamide, the enzyme activity of the microorganisms used should rapidly decrease. However, the enzyme activity of microorganisms is noticeably stable when the hydration reaction is carried out for a long period of time in aqueous pacTiripe (meth) acrylamide of high concentration and, as a result, a water solution (m e) acrylic amide a high concentration. Invention Formula
0
five
The method of continuous production of aqueous solutions of acrylamide or methacrylamide in a reactor using product recovery by hydrolysis of the corresponding nitrile in an aqueous medium at pH 7.0-9.0, temperature, source rate of each reagent in the reactor, 0.4-4 hours, in the presence of strains of microorganisms H-771 or N-774 of the species Co-rnebacterium or strain C-775 of the type Nocardia deposited at the Institute of Enzyme Studies of the Agency of Industrial Science and Technology of the Ministry of World Trade and Industry of Japan, Ibaragi, which differs from h for the purpose of simplifying the process, the feed mixture pre-diluted, part of the product discharged from this reactor, at a weight ratio of 1: 1-9.

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同族专利:

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公开号 | 公开日

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DE3017005C2|1988-12-01|

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JPS55144889A|1980-11-12|

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GB2048877A|1980-12-17|

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IT1146912B|1986-11-19|

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IT8048550D0|1980-04-30|

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FR2455630A1|1980-11-28|

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JPS5835077B2|1983-07-30|

---

GB2048877B|1983-06-15|

---

US4440858A|1984-04-03|

---

FR2455630B1|1983-08-19|

---

DE3017005A1|1981-04-09|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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RU2631650C2|2012-12-10|2017-09-26|Мицубиси Кемикал Корпорейшн|Method for producing acrylamide|FR2245585B1|1973-09-19|1976-05-14|Anvar|

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FR2294999B1|1974-12-18|1977-11-10|Anvar|

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IT1162484B|1978-03-29|1987-04-01|Nitto Chemical Industry Co Ltd|PE PROCEDURE TO PRODUCE ACRYLAMIDE OR METHACRYLAMIDE USING MICROORGANISMS|DE3222912A1|1982-06-18|1983-12-22|Basf Ag, 6700 Ludwigshafen|INSOLUBLE BIO CATALYST|

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JPS6143997B2|1983-01-10|1986-09-30|Hideaki Yamada|

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JPH0235B2|1983-07-12|1990-01-05|Nitsuto Kagaku Kogyo Kk|

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JPS6143998B2|1983-10-13|1986-09-30|Hideaki Yamada|

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JPS6143999B2|1983-10-13|1986-09-30|Hideaki Yamada|

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CH664374A5|1985-02-27|1988-02-29|Lonza Ag|METHOD FOR PRODUCING L-CARNITIN BY A MICROBIOLOGICAL WAY.|

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US5863750A|1996-12-18|1999-01-26|Cytec Tech Corp|Methods for the detoxification of nitrile and/or amide compounds|

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JP4672161B2|2000-03-29|2011-04-20|三井化学株式会社|Method for producing amide compound|

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TWI296652B|2000-03-29|2008-05-11|Mitsui Chemicals Inc|Production process of amide compound|

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DE10120546A1|2001-04-26|2002-10-31|Stockhausen Chem Fab Gmbh|Process for the preparation of an aqueous acrylamide solution with a biocatalyst|

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DE10120550A1|2001-04-26|2002-10-31|Stockhausen Chem Fab Gmbh|Process for the preparation of an aqueous acrylamide solution with a biocatalyst|

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WO2010038832A1|2008-10-03|2010-04-08|ダイヤニトリックス株式会社|Method for producing acrylamide|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP54053380A|JPS5835077B2|1979-05-02|1979-05-02|

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