CN110157751A - A kind of synthetic method of low conductivity aqueous amide compound solution - Google Patents
A kind of synthetic method of low conductivity aqueous amide compound solution Download PDFInfo
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- CN110157751A CN110157751A CN201910486958.9A CN201910486958A CN110157751A CN 110157751 A CN110157751 A CN 110157751A CN 201910486958 A CN201910486958 A CN 201910486958A CN 110157751 A CN110157751 A CN 110157751A
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
Abstract
The invention discloses a kind of synthetic methods of low conductivity aqueous amide compound solution, the synthetic method is the following steps are included: under solution system existing for the biocatalyst with nitrile hydratase activity, corresponding amide compound is synthesized by nitrile compound, and the temperature in synthesis process is 9-14 DEG C.This method uses microbial method synthesis of acrylamide under cryogenic, and by taking 42% acrylamide product as an example, by-product acrylic acid content is low (0.0846%), the 400 μ Scm of conductivity of product‑1。
Description
Technical field
The present invention relates to the technical fields of the manufacture of acrylamide aqueous solution, and in particular to a kind of low conductivity amidation
Close the synthetic method of object aqueous solution.
Background technique
The main substrate of production acrylamide is acrylonitrile at present, for severe toxicity, there is volatility, sucking human body mainly causes
Nerve injury, is carcinogen.The method of acrylonitrile process acrylamide is hydration reaction, using water and acrylonitrile as reactant
Hydration occurs to generate product propylene amide.Catalyst is an important factor for influencing hydration reaction.The mainstream of acrylamide is urged
Agent experienced since occurring from acrylamide to be changed three times, is that sulfuric acid is used to carry out hydration preparation as catalyst first；Later
Occur preparing by the hydration method of catalyst of copper by improvement；The current highest method of newest and efficiency is microorganism conversion
Method, using biological inoculum as catalyst acrylonitrile process acrylamide.
It mainly uses microbial method synthesis of acrylamide in industry under the reaction condition of normal temperature and pressure at present, there is reaction
The disadvantages of consuming time is long, strain dosage is high, product conductivity is high, product post processing cost is high.
Accordingly, it is desirable to provide a kind of method for the synthesis quality for effectively improving aqueous amide compound solution.
Summary of the invention
The purpose of the present invention is to provide a kind of synthetic methods of low conductivity aqueous amide compound solution, in order to overcome system
Disadvantages mentioned above during standby, the present invention will be by low ambient temperatures, the amide compound of low conductivity being synthesized with microbial method
Object aqueous solution.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention provides a kind of synthetic method of low conductivity aqueous amide compound solution, includes the following steps:
Under solution system existing for the biocatalyst with nitrile hydratase activity, corresponding acyl is synthesized by nitrile compound
Amine compounds, and the temperature in synthesis process is 9-14 DEG C.
The beneficial effects of the present invention are:
Amide compound the present invention provides a kind of synthetic method of low conductivity aqueous amide compound solution, in the present invention
Object aqueous solution is by synthesizing the aqueous amide compound solution of low conductivity, acyl with microbial method under 9-14 DEG C of low temperature environment
Impurity content in amine compound aqueous solution is low, and conductivity is significantly lower than the conductivity value of similar product in the market
Market provides high-purity high-quality product, meets high-end customer demand.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the gas chromatogram that 42%AM is synthesized at 9-10 DEG C；
Fig. 2 is the gas chromatogram that 42%AM is synthesized at 11-12 DEG C；
Fig. 3 is the gas chromatogram that 42%AM is synthesized at 13-14 DEG C；
Fig. 4 is the gas chromatogram that 50%AM is synthesized at 9-10 DEG C；
Fig. 5 is the gas chromatogram that 50%AM is synthesized at 11-12 DEG C；
Fig. 6 is the gas chromatogram that 50%AM is synthesized at 13-15 DEG C；
Fig. 7 is the gas chromatogram that AN is added dropwise that duration 6h synthesizes 42%AM；
Fig. 8 is the gas chromatogram that AN is added dropwise that duration 7h synthesizes 42%AM；
Fig. 9 is the gas chromatogram that AN is added dropwise that duration 8h synthesizes 42%AM；
Figure 10 is the gas chromatogram that AN is added dropwise that duration 6h synthesizes 50%AM；
Figure 11 is the gas chromatogram that AN is added dropwise that duration 6.5h synthesizes 50%AM；
Figure 12 is the gas chromatogram that AN is added dropwise that duration 7h synthesizes 50%AM；
Figure 13 is the gas chromatogram that strain dosage 1.25g synthesizes AM；
Figure 14 is the gas chromatogram that strain dosage 1.5g synthesizes AM；
Figure 15 is the gas chromatogram that strain dosage 2g synthesizes AM.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Have below to a kind of synthetic method of low conductivity aqueous amide compound solution provided in an embodiment of the present invention
Body explanation.
The embodiment of the present invention provides a kind of synthetic method of low conductivity aqueous amide compound solution, includes the following steps:
Under solution system existing for the biocatalyst with nitrile hydratase activity, corresponding acyl is synthesized by nitrile compound
Amine compounds, and the temperature in synthesis process is 9-14 DEG C.
The embodiment of the invention provides a kind of synthetic methods of low conductivity aqueous amide compound solution, are hydrated with nitrile
Corresponding amide compound is synthesized by nitrile compound in the presence of the biocatalyst of enzymatic activity, controls the temperature in the reaction process
It is 9-14 DEG C, inventor's discovery: when temperature is lower than 9-14 DEG C, so that having the enzyme in the biocatalyst of nitrile hydratase activity
Activity is lower, and the yield of obtained aqueous amide compound solution is smaller, when temperature is higher than 9-14 DEG C, synthesizing amide compound water-soluble
Liquid starts to be declined, while being found out by gas-chromatography map analysis, in reaction system the content of amide compound with temperature liter
High and increases, reason may be that temperature increases, the propylene phytase activity raising in Nocard's bacillus cell, by catalysed partial amidation
It closes object and the corresponding acid of oxidation reaction generation occurs.
Therefore low conductivity amide is catalyzed and synthesized using the biocatalyst with nitrile hydratase activity at low ambient temperatures
Compound, reaction temperature should be avoided too low or excessively high, and temperature is too low may to make catalysis reaction insufficient, and product assay is caused to drop
Low, temperature is excessively high may to promote amide compound to be oxidized to corresponding acid, and product assay is caused to reduce, therefore control synthesized
Temperature in journey is 9-14 DEG C, and in this temperature range, raw material nitrile compound residual quantity can be less, synthesizing amide compound water-soluble
The content of amide compound in liquid is higher.
In some embodiments, temperature is 11-12 DEG C.
In some embodiments, biocatalyst is selected from Nocardia.
In some embodiments, processing of the biocatalyst through following steps: opening stirring, and the pH for adjusting water is 7.5-
8.0, biocatalyst is added, while reducing bath temperature, the pH for adjusting solution again is 7.0-7.5, and biocatalyst is made
Aqueous solution.
In some embodiments, biocatalyst is specifically through the processing of following steps: mixing speed 60-80r/min,
The pH of water is adjusted to 7.5-8.0 using 8-12%NaOH, biocatalyst is added, while reducing bath temperature to 9-14 DEG C,
The pH for adjusting solution again is 7.0-7.5, and the aqueous solution of biocatalyst is made,
Preferably, the weight ratio of biocatalyst and water is 0.15-0.4:62-68.
In some embodiments, by the way of dropwise addition by nitrile compound instill have biocatalyst solution in into
Row reaction,
Preferably, nitrile compound is selected from acrylonitrile.
In some embodiments, the rate of addition of nitrile compound is 3-5 drops/sec, time for adding 6-6.5h,
Preferably, the weight ratio of water is 31-37:62-68 in the aqueous solution of nitrile compound and biocatalyst.
In some embodiments, further includes: after acrylonitrile is added dropwise, 0.1-0.3 parts of diatomite and 0.01- is added
0.03 part of active carbon stirs, and aqueous amide compound solution is made in filtering.
In some embodiments, aqueous amide compound solution is acrylamide aqueous solution.
In some embodiments, the mass concentration of acrylamide is 38%-50% in aqueous amide compound solution.
Feature and performance of the invention are described in further detail with reference to embodiments.
AM below represents acrylamide；AN represents acrylonitrile.
Embodiment 1
42% acrylamide aqueous solution, plan synthesis 500g.Need raw material propylene nitrile 156.8g, pure water 343.2g, PH control
System is within the scope of 7.0-7.5.
(1) water of 62-68 parts by weight is poured into 500ml four-hole boiling flask.Use the third of electronic balance weighing intended use
Alkene nitrile pours into spare in 100ml cartridge type separatory funnel.Install experimental facilities；
(2) electric blender is opened, revolving speed is set as 60-80r/min；
(3) pure water pH is measured using pH meter, 8%-12%NaOH solution is added dropwise and adjusts pH to 7.5-8.0；
(4) Nocard's bacillus of 0.15-0.4 parts by weight is added into 500ml volumetric flask；
(5) ice cube is added into water-bath, cools to 10-12 DEG C of experiment；
(6) thallus measures pH after stirring being added 8-12 minutes, and pH is controlled in 7.0-7.5, is not added dropwise then in right amount in this range
NaOH solution is adjusted；
(7) start that acrylonitrile is added dropwise.Controlling rate of addition is 3-5 drops/sec.Pay attention to controlling the temperature of reaction system；
(8) the reaction was continued 20min after the acrylonitrile of 31-37 parts by weight being added dropwise, takes 100ml sample to be analyzed；
(9) 0.2 parts by weight diatomite is added in sample, 0.02 parts by weight of activated carbon stirs 8-12 minutes；
(10) filter device filtered sample is built；
After collecting filtrate, acrylonitrile content is detected using bromination method, gas chromatograph；Measure conductivity, pH.
42% acrylamide aqueous solution prepared in the embodiment, acrylonitrile residue is low (0.0117%), and the third of synthesis
Acrylamide content is high (41.8%), and by-product acrylic acid content is low (0.0846%), the 400 μ Scm of conductivity of product-1, and it is current
The product synthesized in industry before refining conductivity value in 600-1200 μ Scm-1Between.Therefore it is provided in the embodiment of the present invention above-mentioned
The residual quantity of acrylonitrile in acrylamide aqueous solution can be effectively reduced in synthetic method, and the acrylamide content of synthesis is high, by-product
Object acrylic acid content is low, and the conductivity value of product is the later period significantly lower than synthesis of acrylamide aqueous solution conductivity value in industry
Purification alleviates burden.
Embodiment 2
50% acrylamide aqueous solution, plan synthesis 500g.Need raw material propylene nitrile 187.0g, pure water 313.0g, pH control
System is within the scope of 7.0-7.5.
(1) water of 62-68 parts by weight is poured into 500ml four-hole boiling flask.Use the third of electronic balance weighing intended use
Alkene nitrile pours into spare in 100ml cartridge type separatory funnel.Install experimental facilities；
(2) electric blender is opened, revolving speed is set as 60-80r/min；
(3) pure water pH is measured using pH meter, 8%-12%NaOH solution is added dropwise and adjusts pH to 7.5-8.0；
(4) Nocard's bacillus of 0.15-0.4 parts by weight is added into 500ml volumetric flask；
(5) ice cube is added into water-bath, cools to 10-12 DEG C of experiment；
(6) thallus measures pH after stirring being added 8-12 minutes, and pH is controlled in 7.0-7.5, is not added dropwise then in right amount in this range
NaOH solution is adjusted；
(7) start that acrylonitrile is added dropwise.Controlling rate of addition is 3-5 drops/sec.Pay attention to controlling the temperature of reaction system；
(8) 20min is reacted after the acrylonitrile of 31-37 parts by weight being added dropwise, 100ml sample is taken to be analyzed；
(9) 0.2 parts by weight diatomite is added in sample, 0.02 parts by weight of activated carbon stirs 8-12 minutes；
(10) filter device filtered sample is built；
After collecting filtrate, acrylonitrile content is detected using bromination method, gas chromatograph；Measure conductivity, PH.
Embodiment 3
3.1 predominantly detect method
Experiment will survey the content of acrylamide using three kinds of saccharometer method, gas chromatography, bromination rule methods
It is fixed.
3.1.1 saccharometer method
Saccharometer is mainly used for quickly measuring the content of soluble solid in solution.It can be fast using saccharometer in experiment
The content of acrylamide in reaction solution is detected fastly.
Detecting step: saccharometer first is corrected with deionized water.About 0.3ml reaction solution is drawn using rubber head dropper and is dripped in sugar
On degree meter prism, START key is pressed, is read after waiting 3s, repeated this operation three times, recorded after being averaged.
3.1.2 gas chromatography
Gas chromatography is using gas as mobile phase, and sample, by capillary chromatographic column, makes in sample through overflash
Each component separation, is detected, a kind of detection means of inner mark method ration with flame ionization ditector (FID).This paper is real
It tests by GB/T 24769-2009[22]Use the content of gas chromatograph GC-9790II detection acrylamide.
3.1.3 bromination method
This detection method is tested by company standard Q/YDYC 003-2017, concrete operation step are as follows: accurate (accurate
Sample 2.2-2.5g is weighed to 0.0002g), is placed in 100ml volumetric flask, deionized water is added and is diluted to scale (solution I).Make
5.0ml solution I is accurately pipetted with 5ml pipette, is placed in 250ml iodine flask, the 0.1mol/L bromine titer of 20.0ml is added
With the 1mol/L sulfuric acid of 30ml, bottle stopper is covered tightly immediately, with the sealing of 5% liquor kalii iodide of about 2-3ml (in order to avoid the bromine in bottle escapes
Out), be placed in dark place reaction 40min, into iodine flask plus 25ml 5% liquor kalii iodide (be added by bottle stopper, so as not to bromine ease
Out), it after reacting 5min, is titrated with the sodium thiosulfate standard solution of 0.1mol/L, until 1ml is added when nearly terminal 0.5% forms sediment
Powder solution indicator, dropping to blue just disappeared is terminal, parallel three groups of above-mentioned experiment, while doing blank test.
The content of acrylamide is according to the following formula:
In formula:
X1-- the percentage composition of acrylamide, %；
V0-- the volume of the hypo solution of blank test consumption, ml；
The volume of V-laboratory sample consumption hypo solution, ml；
The molar concentration of sodium thiosulfate standard solution used in C--；
Every mM of titration solution of 0.0355-- quite sample quality；
M---- sample quality, g.
3.2 experimental results and discussion
3.2.1 influence of the temperature to acrylamide concentration
Using temperature as variable, acrylonitrile is added dropwise duration and Nocard's bacillus strain dosage and remains unchanged, and is respectively synthesized 42% the third
Acrylamide solution and each 3 groups of 50% acrylamide solution study influence of the temperature to acrylamide concentration.
The condition of 42% acrylamide synthetic reaction are as follows: duration 5.5h, anti-is added dropwise in Nocard's bacillus strain dosage 2g, acrylonitrile
System pH7.0-7.5 is answered, following table 1 is influence of the temperature to 42% acrylamide content.
Influence of 1 temperature of table to 42% acrylamide content
Meanwhile referring to attached drawing 1-3, Fig. 1 is the gas chromatogram that 42%AM is synthesized at 9-10 DEG C；Fig. 2 is to close at 11-12 DEG C
At the gas chromatogram of 42%AM；Fig. 3 is the gas chromatogram that 42%AM is synthesized at 13-14 DEG C；
As shown in the gas chromatogram of attached drawing 1, there are two peaks in figure, first peak is acrylonitrile, removes 58% and does not examine
The H measured2O, content 0.1550%, second peak are acrylamide, content 41.8450%.
As shown in the gas chromatogram of attached drawing 2, there are 4 peaks in figure, first is unknown peak, and content is extremely low, it may be possible to
The impurity brought into when sample introduction；Second peak is acrylonitrile, content 0.0097%；Third peak is acrylic acid, and content is
0.2484%；4th peak is acrylamide, content 41.7387%.
As shown in the gas chromatogram of attached drawing 3, there are 5 peaks in figure, and first peak is acrylonitrile, and content is
0.0112%；Second peak is acrylic acid, content 0.2607%；Third peak is acrylamide, and the 4th peak is one and drags
End peak, misoperation when producing cause may be sample introduction, but it is similarly acrylamide, therefore the content of acrylamide is
41.7141%；5th is unknown peak, it may be possible to contain trace impurity in sample.
The condition of 50% acrylamide synthetic reaction are as follows: duration 6h, reaction is added dropwise in Nocard's bacillus strain dosage 3g, acrylonitrile
System pH7.0-7.5, following table 2 are influence of the temperature to 50% acrylamide content.
Influence of 2 temperature of table to 50% acrylamide content
Meanwhile referring to attached drawing 4-6, Fig. 4 is the gas chromatogram that 50%AM is synthesized at 9-10 DEG C；Fig. 5 is to close at 11-12 DEG C
At the gas chromatogram of 50%AM；Fig. 6 is the gas chromatogram that 50%AM is synthesized at 13-15 DEG C.
4 peaks are co-existed in as shown in the gas chromatogram of attached drawing 4, in figure, first peak is remaining acrylonitrile, and content is
0.0056%；Second peak is acrylic acid, content 0.3588%；Third peak is acrylamide, content 49.6329%；
The last one peak is unknown peak, it may be possible to the impurity contained in sample.
4 peaks are co-existed in as shown in the gas chromatogram of attached drawing 5, in figure, first peak is remaining acrylonitrile, and content is
0.0075%；Second peak is acrylic acid, content 0.3099%；Third peak is acrylamide, and the 4th peak is tailing peak,
When may be sample introduction caused by misoperation, acrylamide is represented, so the content of acrylamide is 49.6827%.
4 peaks are co-existed in as shown in the gas chromatogram of attached drawing 6, in figure, first peak is remaining acrylonitrile, and content is
0.0095%；Second peak is acrylic acid, content 0.4535%；Third peak is acrylamide, and the 4th peak is tailing peak,
When may be sample introduction caused by misoperation, acrylamide is represented, so the content of acrylamide is 49.5371%.
Comprehensive analysis data are it is found that at low ambient temperatures, using microbial method synthesis of acrylamide, raw material propylene nitrile turns
Rate can achieve 99% or more, and the acrylamide concentration of synthesis is also close to the concentration for reaching theoretical calculation.9-12 DEG C this
In temperature range, the concentration of acrylamide is increased with the raising of temperature, in 11-12 DEG C or so acrylonitrile conversion at acrylamide
Concentration reach highest, 13-15 DEG C is that the concentration of synthesis of acrylamide starts to be declined.Simultaneously in terms of gas-chromatography map analysis
Out, the content of acrylic acid is increased with the raising of temperature in reaction system, and reason may be that temperature increases, in Nocard's bacillus cell
Propylene phytase activity increase, by catalysed partial acrylamide occur oxidation reaction generate acrylic acid.
Therefore acrylamide is catalyzed and synthesized using Nocard's bacillus at low ambient temperatures, excessively high, temperature should be avoided in reaction temperature
It is excessively high acrylamide to be promoted to be oxidized to acrylic acid, cause product assay to reduce, therefore reaction temperature should control as far as possible
At 11-12 DEG C, in this temperature range, raw material propylene nitrile less residue, the content of synthesis of acrylamide is higher.
3.2.2 influence of the duration to acrylamide concentration is added dropwise in acrylonitrile
A length of variable when with the dropwise addition of acrylonitrile, reaction temperature and Nocard's bacillus strain dosage are remained unchanged, are respectively synthesized
Duration is added dropwise to the shadow of acrylamide concentration in 42% acrylamide solution and each 3 groups of 50% acrylamide solution, research acrylonitrile
It rings.
The condition of 42% acrylamide synthetic reaction are as follows: Nocard's bacillus strain dosage 1.5g, reaction temperature be 11-12 DEG C,
Reaction system pH7.0-7.5, table 3 are that influence of the duration to 42% acrylamide content is added dropwise in AN.
Influence of the duration to 42% acrylamide content is added dropwise in 3 AN of table
Meanwhile the gas chromatogram that duration 6h synthesizes 42%AM being added dropwise for AN referring to attached drawing 7-9, Fig. 7；Fig. 8 is AN dropwise addition
The gas chromatogram of duration 7h synthesis 42%AM；Fig. 9 is the gas chromatogram that AN is added dropwise that duration 8h synthesizes 42%AM.
3 peaks are co-existed in as shown in the gas chromatogram of attached drawing 7, in figure, first peak is remaining acrylonitrile, and content is
0.0377%；Second peak is acrylic acid, content 0.0897%；Third peak is acrylamide, content 41.8726%.
3 peaks are co-existed in as shown in the gas chromatogram of attached drawing 8, in figure, first peak is remaining acrylonitrile, and content is
0.0962%；Second peak is acrylic acid, content 0.2390%；Third peak is acrylamide, content 41.6648%.
3 peaks are co-existed in as shown in the gas chromatogram of attached drawing 9, in figure, first peak is remaining acrylonitrile, and content is
0.0597%；Second peak is acrylic acid, content 0.1856%；Third peak be acrylamide, content 41.7521%,
Following table 4 is that influence of the duration to 50% acrylamide content is added dropwise in AN.
Influence of the duration to 50% acrylamide content is added dropwise in 4 AN of table
Meanwhile the gas chromatogram that duration 6h synthesizes 50%AM being added dropwise for AN referring to attached drawing 10-12, Figure 10；Figure 11 is AN
The gas chromatogram of duration 6.5h synthesis 50%AM is added dropwise；Figure 12 is the gas chromatogram that AN is added dropwise that duration 7h synthesizes 50%AM.
4 peaks are co-existed in as shown in the gas chromatogram of Figure 10, in figure, first peak is remaining acrylonitrile, and content is
0.0075%；Second peak is acrylic acid, content 0.3099%；Third peak is acrylamide, and the 4th peak is tailing peak,
It is equally acrylamide, the content of acrylamide is 49.6827%.
4 peaks are co-existed in as shown in the gas chromatogram of Figure 11, in figure, first peak is remaining acrylonitrile, and content is
0.0058%；Second peak is acrylic acid, content 0.2993%；Third peak be acrylamide, content 49.6926%,
4th peak is unknown peak, it may be possible to the impurity contained in sample.
3 peaks are co-existed in as shown in the gas chromatogram of Figure 12, in figure, first peak is remaining acrylonitrile, and content is
0.0081%；Second peak is acrylic acid, content 0.3021%；Third peak is that acrylamide content is 49.6899%.
3.2.3 influence of the Nocard's bacillus strain dosage to acrylamide concentration
Using Nocard's bacillus strain dosage as variable, reaction temperature and acrylonitrile are added dropwise duration and remain unchanged, and plan 42% the third
3 groups of acrylamide solution, study influence of the Nocard's bacillus strain dosage to acrylamide concentration.Reaction condition are as follows: acrylonitrile is added dropwise
Duration 6h, 11-12 DEG C of reaction temperature, reaction system pH7.0-7.5, following table 5 is shadow of the strain dosage to acrylamide content
It rings.
Influence of the 5 strain dosage of table to acrylamide content
Meanwhile the gas chromatogram of AM is synthesized for strain dosage 1.25g referring to attached drawing 13-15, Figure 13；Figure 14 is strain use
Measure the gas chromatogram of 1.5g synthesis AM；Figure 15 is the gas chromatogram that strain dosage 2g synthesizes AM.
6 peaks are co-existed in as shown in Figure 13 gas chromatogram, in figure, first peak is remaining acrylonitrile, and content is
4.6453%；Second peak is acrylic acid, content 0.0555%；5th peak is acrylamide, content 37.2929%；
Third, the 4th and the 6th peak are unknown peak, it may be possible to the impurity contained in sample.
3 peaks are co-existed in as shown in Figure 14 gas chromatogram, in figure, first peak is remaining acrylonitrile, and content is
0.0081%；Second peak is acrylic acid, content 0.1045%；Third peak is acrylamide, content 41.8874%.
5 peaks are co-existed in as shown in the gas chromatogram of Figure 15, in figure, first peak is unknown peak, it may be possible in sample
The impurity contained；Second peak is acrylonitrile, content 0.0117%；Third peak is acrylic acid, content 0.0846%；The
Four peaks are acrylamide, and the 5th peak is a tailing peak, is similarly acrylamide, therefore the total content of acrylamide is
41.8880%.
For the above-mentioned data of comprehensive analysis it is found that when too low strain dosage, acrylonitrile residue is higher, while acrylamide contains
Amount is far below calculated value, and reason may be Nocard's bacillus catalysis acrylonitrile reactor, and acrylamide is relative to strain concentration mistake
It is high, it is suppressed that the activity of nitrile hydratase in strain causes reaction not exclusively and acrylonitrile residue.It can be summarized from above-mentioned data
Nocard's bacillus strain dosage and the content of generation acrylamide are positively correlated out, and Nocard's bacillus strain dosage is more, generates propylene
The content of amide is closer to calculated value.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of low conductivity aqueous amide compound solution, which comprises the steps of:
Under solution system existing for the biocatalyst with nitrile hydratase activity, corresponding amidation is synthesized by nitrile compound
Object is closed, and the temperature in synthesis process is 9-14 DEG C.
2. synthetic method according to claim 1, which is characterized in that the temperature is 10-12 DEG C.
3. synthetic method according to claim 1, which is characterized in that the biocatalyst is selected from Nocardia.
4. synthetic method according to claim 3, which is characterized in that processing of the biocatalyst through following steps:
Stirring is opened, the pH for adjusting water is 7.5-8.0, biocatalyst is added, while reducing bath temperature, adjusts the pH of solution again
For 7.0-7.5, the aqueous solution containing the biocatalyst is made.
5. synthetic method according to claim 4, which is characterized in that the biocatalyst is specifically through the place of following steps
Reason: the pH of water is adjusted to 7.5-8.0 using 8-12%NaOH, biocatalyst is added, together by mixing speed 60-80r/min
When reduce bath temperature to 9-14 DEG C, again adjust solution pH be 7.0-7.5, be made biocatalyst aqueous solution,
Preferably, the weight ratio of the biocatalyst and the water is 0.15-0.4:62-68.
6. synthetic method according to claim 1, which is characterized in that instilled the nitrile compound by the way of being added dropwise
It is reacted in solution with the biocatalyst,
Preferably, the nitrile compound is selected from acrylonitrile.
7. synthetic method according to claim 6, which is characterized in that the rate of addition of the nitrile compound be 3-5 drop/
Second, time for adding 6-6.5h,
Preferably, the weight ratio of water is 31-37:62-68 in the aqueous solution of the nitrile compound and the biocatalyst.
8. synthetic method according to claim 6, which is characterized in that further include: the acrylonitrile is added dropwise and reacts
After the completion, 0.1-0.3 parts of diatomite and 0.01-0.03 parts of active carbons are added, after stirring, filtering.
9. synthetic method according to claim 1, which is characterized in that the aqueous amide compound solution is acryloyl aqueous amine
Solution.
10. synthetic method according to claim 9, which is characterized in that acrylamide in the aqueous amide compound solution
Mass concentration be 38%-50%.
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Citations (4)
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|---|---|---|---|---|
| CN1218834A (en) * | 1997-10-23 | 1999-06-09 | 三菱人造丝株式会社 | Process for preparing amide compounds |
| CN1486370A (en) * | 2000-12-20 | 2004-03-31 | 大野绿水株式会社 | Process for producing amide compound using microbial catalyst |
| CN1612933A (en) * | 2001-04-26 | 2005-05-04 | 施托克豪森公司 | Method for the production of an aqueous acrylamide solution with a bio-catalyst |
| CN105008545A (en) * | 2013-02-19 | 2015-10-28 | 三菱丽阳株式会社 | Method for producing amide compound |
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218834A (en) * | 1997-10-23 | 1999-06-09 | 三菱人造丝株式会社 | Process for preparing amide compounds |
| CN1486370A (en) * | 2000-12-20 | 2004-03-31 | 大野绿水株式会社 | Process for producing amide compound using microbial catalyst |
| CN1612933A (en) * | 2001-04-26 | 2005-05-04 | 施托克豪森公司 | Method for the production of an aqueous acrylamide solution with a bio-catalyst |
| CN105008545A (en) * | 2013-02-19 | 2015-10-28 | 三菱丽阳株式会社 | Method for producing amide compound |
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