CN111909042A - Resource utilization method of pendimethalin waste residue - Google Patents
Resource utilization method of pendimethalin waste residue Download PDFInfo
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Abstract
The invention provides a method for recycling pendimethalin waste residue, which is used for obtaining pendimethalin products from pendimethalin waste residue. The method uses sulfamic acid as a reducing agent under an acidic condition to recycle pendimethalin residues, so that N-nitrosopendimethalin is converted into pendimethalin. The invention comprises the following steps: carrying out mass ratio of pendimethalin waste residue, sulfamic acid, solvent and SBA-15 molecular sieve to 1: 0.6-0.9: 7-10: 0-1, putting into a container and mixing; and adding an acid solution into the container, wherein the mass ratio of the pendimethalin waste residue to the acid solution is 1: 3-5; stirring and reacting for 5-7 hours at the temperature of 50-60 ℃, cooling to room temperature after reaction, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin; the filtrate was subjected to distillation treatment to recover the solvent.
Description
The technical field is as follows:
the invention belongs to the field of waste residue resource utilization, and particularly relates to recovery of pendimethalin and conversion and recovery of nitrosopendimethalin solid in pendimethalin waste residue. The nitration process for producing pendimethalin has large heat release amount and is easy to be over-oxidized to generate tar, after the product is separated, a large amount of tar is enriched into solid waste residue, called waste residue for short, and the main components of the waste residue are the tar, the pendimethalin and the nitroso pendimethalin.
Background art:
pendimethalin (pendimethalin), the chemical name of which is N- (3-pentyl) -3, 4-dimethyl-2, 6-dinitroaniline, is a dinitroaniline herbicide and is a selective preemergence herbicide developed and popularized by American Cyanamid Company; has good effect on most annual gramineous weeds and certain broad-leaved weeds. The herbicide has good effect, low toxicity and good safety, is widely popularized and applied, is a selective herbicide with the largest dosage in the world at present, and has large internal and external demands and wide market.
The production process of pendimethalin uses 3, 4-dimethyl nitroaniline as raw material, and the raw material is alkylated with 3-pentone, and then the product pendimethalin is obtained through nitration and post-treatment. Because the nitration process has large heat release amount and is easy to generate tar through over oxidation, a large amount of tar is enriched to be treated as solid waste residue after the product is separated. Currently about 1 ton of residue is present per 10 tons of pendimethalin produced. Because the tar component in the residue is complex, qualitative analysis is difficult to carry out, and the residue contains products and nitrosation compounds thereof.
In CN 101070287 a, the crude product of pendimethalin was purified using thiocyanate and hydrochloric acid; in CN 109867607 a, a solvent (methanol, ethanol, isopropanol, n-butanol, etc.) and pendimethalin waste residue are heated to dissolve, filtered, and then distilled and purified. The product content in the residue is low, the nitration reaction usually contains a large amount of polynitro compounds, and the high temperature has the risk of explosion, so that the product cannot be carried out by means of high-temperature distillation. Therefore, the residue is mainly used as solid waste for incineration treatment at present. So a method for reasonably designing the resource of pendimethalin waste residue is needed.
The invention content is as follows:
aiming at the state of the prior art, the invention provides a method for recycling pendimethalin waste residue, and a pendimethalin product is obtained from pendimethalin waste residue.
The specific technical scheme of the invention is as follows:
a method for recycling pendimethalin waste residue comprises the following steps:
carrying out mass ratio on pendimethalin waste residue, sulfamic acid, solvent and SBA-15 molecular sieve to obtain a mixture, wherein the mass ratio of the pendimethalin waste residue to the sulfamic acid to the solvent is 1: 0.6-0.9: 7-10: 0-1, putting into a container and mixing; and adding an acid solution into the container, wherein the mass ratio of the pendimethalin waste residue to the acid solution is 1: 3-5; stirring and reacting for 5-7 hours at the temperature of 50-60 ℃, cooling to room temperature after reaction, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin; the filtrate was subjected to distillation treatment to recover the solvent.
Further, the solvent is one or more than two mixed solvents of chloroform, 1, 2-dichloroethane, dichloromethane, triethylamine, diethylamine, ethylenediamine or acetone;
further, the acid solution is one or more than two mixed acids of sulfuric acid, phosphoric acid or hydrochloric acid;
further, the mass concentration of the sulfuric acid is 25-90%;
further, the mass concentration of the phosphoric acid is 25-80%;
further, the mass concentration of the hydrochloric acid is 5-30%;
further, preferably, the mass ratio of the pendimethalin waste residue to the sulfamic acid, the chloroform and the SBA-15 molecular sieve is as follows: 1: 0.7: 9: the best is 0.1;
further, the acid solution is a sulfuric acid solution with the mass concentration of 50%, and the mass ratio of the pendimethalin waste residue to the sulfuric acid solution is 1: 4 is best;
further, the reaction temperature was 58 deg.CoC; the reaction time is optimal when 5 hours;
further, when the reaction is finished, filtering while the reaction is hot, filtering out residual solid impurities, and collecting solid waste; the filtrate was cooled to room temperature and filtered.
The principle of the invention is as follows:
under the acidic condition, sulfamic acid is used as a reducing agent, and the sulfamic acid and the nitroso-pendimethalin react to generate pendimethalin and nitrogen, so that a pendimethalin product is obtained, other components are not added, and organic impurities are not introduced. The SBA-15 molecular sieve is a polyhydroxy molecular sieve, can fix nitroso and can greatly shorten the reaction time. As can be seen from the reaction equation of fig. 1, no other contaminants are generated during the process. And in the reaction process, the hot filter is used for removing impurities such as tar and the like in the product.
Compared with the prior art, the invention has the following advantages:
1. under the acidic condition (wherein, the sulfuric acid solution with the mass concentration of 50% is the best, the invention provides the acidic environment, which is beneficial to the reduction of nitroso), in the solvent with low boiling point, the sulfamic acid can reduce the nitroso-pendimethalin at lower temperature. The SBA-15 molecular sieve is added in the method, so that the reaction time is shortened (from 7 h to 5 h). According to the invention, the nitroso is easily fixed by a sulfuric acid solution with the mass concentration of 50% and Van der Waals force between the SBA-15 molecular sieve and the nitroso-pendimethalin, so that the nitroso is favorably reduced. The whole reaction is easy to operate, the steps are simple, pendimethalin is separated from impurities by a thermal filtration method, the safety is high, industrialization is easy to realize, and the solvent recovered by distillation is repeatedly used in the reaction process, so that the recycling of the solvent is realized.
2. The invention recycles the toxic, harmful and uneconomic residues to obtain the pendimethalin product, realizes the recycling of the residues, has obvious economic benefit, and achieves the aims of reducing the production cost and improving the ecological environment.
3. The invention reduces the pollution of pendimethalin waste residue to the environment through recovery treatment and improves the production benefit. In the whole recycling treatment process, the reaction operation is simple, the condition is mild, the control is easy, the safety is high, the requirement on equipment is low, and the large-scale production is easy.
4. The method comprises the following steps of mixing pendimethalin waste residue, sulfamic acid, a solvent, an SBA-15 molecular sieve and an acidic solution according to a mass ratio of 1: 0.6-0.9: 7-10: 0-1: 3-5, carrying out reaction; and stirring and reacting for 5-7 hours at the temperature of 50-60 ℃. By comparison of examples, the mass ratio of pendimethalin waste residue to sulfamic acid, chloroform and SBA-15 molecular sieve is as follows: 1: 0.7: 9: 0.1, wherein the acid solution is a sulfuric acid solution with the mass concentration of 50%, and the mass ratio of the pendimethalin waste residue to the sulfuric acid solution is 1: 4, at 58oWhen C reacts for 5 hours, the reaction effect is best, the recovery rate is 64 percent, and the obtained pendimethalin is infraredThe spectrogram is good, and the peak of the nitroso is very small, which indicates that the nitroso is reduced; and an N-H stretching vibration peak appears, which indicates that the nitroso-pendimethalin is converted into pendimethalin.
Description of the drawings:
FIG. 1 is a diagram of the equation for the reaction of nitrosopendimethalin with urea (also abstract);
FIG. 2 is an IR spectrum of the product obtained in example 1; wherein (A) is pendimethalin pure sample, and (B) is the obtained product;
FIG. 3 is an IR spectrum of the product obtained in example 2; wherein (A) is pendimethalin pure sample, and (B) is the obtained product;
FIG. 4 is an IR spectrum of the product obtained in example 3; wherein (A) is pendimethalin pure sample, and (B) is the obtained product;
FIG. 5 is an IR spectrum of the product obtained in example 5; wherein (A) is pendimethalin pure sample, and (B) is the obtained product;
FIG. 6 is an IR spectrum of the product of example 28; wherein (A) is pendimethalin pure sample, and (B) is the obtained product;
FIG. 7 is an IR spectrum of the product obtained in example 31; wherein (A) is pendimethalin pure sample, and (B) is the obtained product;
FIG. 8 is an IR spectrum of the product of example 42; wherein (A) is pendimethalin pure sample, and (B) is the obtained product;
FIG. 9 is an IR spectrum of the product of example 44; wherein (A) is pendimethalin pure sample, and (B) is the obtained product;
note: the FT-IR plots of the products obtained in the other examples are similar to the FT-IR plots and are not listed here.
Detailed Description
The invention provides a method for recycling pendimethalin waste residues, which is further illustrated by the following embodiments: the SBA-15 molecular sieve used in the examples below was mesoporous silica, purchased from south beige, gambogic instruments ltd).
Example 1:
the invention relates to a method for recycling pendimethalin waste residue, wherein the equation of the reaction of nitrosopendimethalin and urea is shown in figure 1 (the equations of other embodiments are the same), and the method comprises the following specific steps:
putting pendimethalin waste residue (10 g), sulfamic acid (6 g) and chloroform (70 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.7 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.2 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
The pendimethalin obtained in this example was tested and the IR spectrum is shown in FIG. 2, which is 3437 cm-1Is the-OH stretching vibration peak of water; 2970, 2921, 2877 cm-1Is the stretching vibration peak of alkane (C-H), 1621, 1571 and 1484 cm-1Is the stretching vibration peak of the benzene ring, 1527 cm-1Is aromatic NO2Antisymmetric stretching vibration peak of 1335 cm-1Is aromatic NO2Symmetrical telescopic vibration peak of 1254 cm-1Is the C-N stretching vibration peak, 925 cm-1Is the bending vibration peak of C-H, 757 cm-1Is the out-of-plane stretching vibration peak of C-H on the benzene ring. Stretching vibration of aromatic nitroso (-N = O) is 1422 cm-1The peak of nitroso is small and is substantially reduced when viewed from the infrared spectrum.
Example 2:
putting pendimethalin waste residue (10 g), sulfamic acid (9 g) and chloroform (70 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.8 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.4 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
The infrared spectrum is shown in figure 3, and the stretching vibration of aromatic nitroso (-N = O) in the figure is 1424 cm-1The smaller peak of the nitroso group in the IR spectrum indicates that it is reduced.
Example 3:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and chloroform (70 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.7 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.7 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
The infrared spectrum is shown in figure 4, and the stretching vibration of aromatic nitroso (-N = O) in the figure is 1424 cm-1The smaller peak of the nitroso group in the IR spectrum indicates that it is reduced.
And conclusion one: it can be seen from the above examples that the best reaction results were obtained when the mass ratio of pendimethalin waste residue to sulfamic acid was 10:7 without changing other conditions (example 3) (higher recovery of pendimethalin and better infrared spectrum of pendimethalin product, lower peak of nitroso group indicating reduction), so sulfamic acid in example continued to react at 7 g.
Example 4:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and chloroform (100 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.1 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 5:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and chloroform (90 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.9 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
The infrared spectrum is shown in figure 5, and the stretching vibration of aromatic nitroso (-N = O) in the figure is 1428 cm-1The smaller peak of the nitroso group in the IR spectrum indicates that it is reduced.
Example 6:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and 1, 2-dichloroethane (70 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 7:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and 1, 2-dichloroethane (100 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.8 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.5 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 8:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and 1, 2-dichloroethane (90 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.3 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 9:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and dichloromethane (70 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25% is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.3 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 10:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and dichloromethane (100 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25% is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.7 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 11:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and dichloromethane (90 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25% is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.2 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.7 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 12:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and triethylamine (70 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25% is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.4 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.4 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 13:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and triethylamine (100 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25% is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.2 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.2 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 14:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and triethylamine (90 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25% is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.3 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.5 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 15:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and diethylamine (70 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25 percent is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 16:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and diethylamine (100 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25 percent is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.4 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.3 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 17:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and diethylamine (90 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25 percent is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 18:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and ethylenediamine (70 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.4 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.7 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 19:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and ethylenediamine (100 g) are put into a container, and a sulfuric acid solution (30 g) with the mass concentration of 25% is added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.4 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 20:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and ethylenediamine (90 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.4 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.5 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 21:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and acetone (70 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 22:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and acetone (100 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.2 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 23:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g) and acetone (90 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.4 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 24:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and a mixed solvent (chloroform (35 g) and 1, 2-dichloroethane (35 g)) were put into a container, and a sulfuric acid solution (30 g) having a mass concentration of 25% was added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.4 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.7 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 25:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and a mixed solvent (chloroform (50 g) and 1, 2-dichloroethane (50 g)) were put into a container, and a sulfuric acid solution (30 g) having a mass concentration of 25% was added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.5 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 26:
pendimethalin waste residue (10 g), sulfamic acid (7 g) and a mixed solvent (chloroform (45 g) and 1, 2-dichloroethane (45 g)) were put into a container, and a sulfuric acid solution (30 g) having a mass concentration of 25% was added into the container. Stirring was carried out at 50 ℃ for 7 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.4 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
And a second conclusion: as can be seen from the above examples, under otherwise unchanged conditions, when the solvent is chloroform, the mass ratio of pendimethalin waste residue to chloroform is 1: the best reaction results were obtained in example 5 (the recovery rate was relatively high, and the IR spectrum of pendimethalin in example 5 was relatively good, and the peak of nitroso was relatively small, indicating that it was reduced), so that chloroform was used as the solvent in the example and the mass was 90 g.
Example 27:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (10 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.7 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 28:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (6.0 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
The infrared spectrum is shown in figure 6, and the stretching vibration of aromatic nitroso (-N = O) is 1426 cm-1The peak of nitroso is smaller from the infrared spectrogram, which indicates that the nitroso is reduced; and 3315 cm-1Is the stretching vibration peak of N-H, which indicates that the nitroso group in nitrosopendimethalin is reduced.
Example 29:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (5 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.8 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
And conclusion three: it can be seen from the above examples that, under the condition of no change of other conditions, when the mass ratio of pendimethalin waste residue to SBA-15 molecular sieve is 1: at 0.1, the reaction was most effective (example 28) (pendimethalin recovery was relatively high, pendimethalin of example 28 had a relatively good IR spectrum, the peak for nitroso was relatively small, indicating that it was reduced, and the stretching peak of N-H appeared, indicating that nitroso of nitrosopendimethalin was reduced and the reaction rate was increased by adding SBA-15 molecular sieve), so the mass of SBA-15 in example was 1 g.
Example 30:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 90% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 31:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a sulfuric acid solution (30 g) with the mass concentration of 50% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (6.1 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
The infrared spectrum is shown in figure 7, and the stretching vibration of aromatic nitroso (-N = O) is 1422 cm-1The peak of nitroso is smaller from the infrared spectrogram, which indicates that the nitroso is reduced; and 3325 cm-1Is a stretching vibration of N-HA peak indicating that the nitroso group in nitrosopendimethalin is reduced.
Example 32:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding phosphoric acid solution (30 g) with the mass concentration of 25% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.7 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 33:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding phosphoric acid solution (30 g) with the mass concentration of 80% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.4 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 34:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding phosphoric acid solution (30 g) with the mass concentration of 50% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.7 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.7 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 35:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a hydrochloric acid solution (30 g) with the mass concentration of 5% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 36:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a hydrochloric acid solution (30 g) with the mass concentration of 30% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.4 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 37:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a hydrochloric acid solution (30 g) with the mass concentration of 20% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.7 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 38:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a mixed acidic solution (a phosphoric acid solution with the mass concentration of 25 percent (15 g) and a sulfuric acid solution with the mass concentration of 25 percent (15 g)) into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the remaining solid impurities were filtered off as a solid waste (1.4 g). Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.5 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 39:
pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) were put into a container, and a mixed acidic solution (80% phosphoric acid solution (15 g) and 90% sulfuric acid solution (15 g)) was added to the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.4 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 40:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a mixed acidic solution (a phosphoric acid solution (15 g) with the mass concentration of 50% and a sulfuric acid solution (15 g) with the mass concentration of 50%) into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.8 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.6 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
And conclusion four: as is apparent from the above description, when the acidic solution is a sulfuric acid solution having a mass concentration of 50% without changing other conditions, the reaction effect is the best (example 31) (the recovery rate is relatively high, and the ir spectrum of pendimethalin of example 31 is relatively good, the peak of nitroso is relatively small, indicating that it is reduced, and the stretching vibration peak of N — H appears, indicating that the nitroso of nitrosopendimethalin is reduced), so the acidic solution is a sulfuric acid solution having a mass concentration of 50% in the examples.
Example 41:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding 50% sulfuric acid solution (50 g) into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.4 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.8 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 42:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a sulfuric acid solution (40 g) with the mass concentration of 50% into the container. Stirring was carried out at 50 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.6 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the filtered crystal to obtain pendimethalin (6.2 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
The infrared spectrum is shown in figure 8, and the stretching vibration of aromatic nitroso (-N = O) is 1427 cm-1The peak of nitroso is smaller from the infrared spectrogram, which indicates that the nitroso is reduced; and 3328 cm-1Is the stretching vibration peak of N-H, which indicates that the nitroso group in nitrosopendimethalin is reduced.
And a fifth conclusion: from the above, it is understood that, under otherwise unchanged conditions, when the mass of the acidic solution is 40 g, the reaction effect is the best (example 42) (the recovery rate is relatively high, and the ir spectrum of pendimethalin of example 42 is relatively good, the peak of nitroso is small, indicating that it is reduced, and the stretching vibration peak of N — H appears, indicating that nitroso in nitrosopendimethalin is reduced), so that the mass of the acidic solution is 40 g in the examples.
Example 43:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a sulfuric acid solution (40 g) with the mass concentration of 50% into the container. Stirring was carried out at 60 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.4 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (5.8 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
Example 44:
putting pendimethalin waste residue (10 g), sulfamic acid (7 g), chloroform (90 g) and SBA-15 molecular sieve (1 g) into a container, and adding a sulfuric acid solution (40 g) with the mass concentration of 50% into the container. Stirring was carried out at 58 ℃ for 5 hours. At the end of the reaction, the reaction mixture was filtered while hot, and the residual solid impurity (1.5 g) was filtered off as a solid waste. Then cooling the filtrate to room temperature, filtering, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin (6.4 g); distilling the filtrate to recover the solvent; and adding sodium bicarbonate into the acidic filtrate after the solvent is recovered until the acidic filtrate is neutral, and discharging.
The infrared spectrum is shown in FIG. 9, and the stretching vibration of aromatic nitroso (-N = O) is 1420 cm-1The peak of nitroso is smaller from the infrared spectrogram, which indicates that the nitroso is reduced; and 3318 cm-1Is the stretching vibration peak of N-H, which indicates that the nitroso group in nitrosopendimethalin is reduced.
And conclusion six: as can be seen from the above, the reaction temperature was 58 ℃ under otherwise unchanged conditionsoC, the reaction effect is the bestGood (example 44) (high recovery of 64% and good IR spectrum of pendimethalin of example 44, small nitroso indicating reduction and appearance of a stretching vibration peak of N-H indicating reduction of nitroso in nitrosopendimethalin), so the reaction temperature in the example is 58 deg.CoC。
And (4) summarizing conclusion: by comparison of the above examples, 7 g of sulfamic acid as a reducing agent and 90 g of chloroform as a solvent can be obtained, namely the mass ratio of pendimethalin waste residue to sulfamic acid, chloroform and SBA-15 molecular sieve is as follows: 1: 0.7: 9: preferably, when the concentration is 0.1, the acid solution is a sulfuric acid solution (40 g) with the mass concentration of 50%, and the mass ratio of the pendimethalin waste residue to the sulfuric acid solution is 1: optimum at 4, 58oThe reaction effect was best when C was reacted for 5 hours (example 44, recovery 64%).
Claims (10)
1. A resource utilization method of pendimethalin waste residue comprises the following steps:
carrying out mass ratio on pendimethalin waste residue, sulfamic acid, solvent and SBA-15 molecular sieve to obtain a mixture, wherein the mass ratio of the pendimethalin waste residue to the sulfamic acid to the solvent is 1: 0.6-0.9: 7-10: 0-1, putting into a container and mixing; and adding an acid solution into the container, wherein the mass ratio of the pendimethalin waste residue to the acid solution is 1: 3-5; stirring and reacting for 5-7 hours at the temperature of 50-60 ℃, cooling to room temperature after reaction, and carrying out vacuum drying on the crystal obtained by filtering to obtain pendimethalin; the filtrate was subjected to distillation treatment to recover the solvent.
2. The method for recycling pendimethalin waste residue as claimed in claim 1, wherein the solvent is one or more of chloroform, 1, 2-dichloroethane, dichloromethane, triethylamine, diethylamine, ethylenediamine and acetone.
3. The method for recycling pendimethalin waste residue according to claim 2, wherein the acidic solution is one or more of sulfuric acid, phosphoric acid and hydrochloric acid.
4. A recycling method of pendimethalin waste residue as claimed in claim 3, wherein the mass concentration of the sulfuric acid is 25-90%.
5. A recycling method of pendimethalin waste residue as claimed in claim 3, wherein the mass concentration of the phosphoric acid is 25-80%.
6. A recycling method of pendimethalin waste residue as claimed in claim 3, wherein the mass concentration of the hydrochloric acid is 5-30%.
7. A resource utilization method of pendimethalin waste residue as claimed in any one of claims 1-6, wherein the mass ratio of pendimethalin waste residue to sulfamic acid, chloroform and SBA-15 molecular sieve is 1: 0.7: 9: 0.1.
8. a resource utilization method of pendimethalin waste residue as claimed in claim 7, wherein the acidic solution is a sulfuric acid solution with a mass concentration of 50%, and the mass ratio of the pendimethalin waste residue to the sulfuric acid solution is 1: 4.
9. the method for recycling pendimethalin waste residue as claimed in claim 8, wherein the reaction temperature is 58%oC; the reaction time was 5 h.
10. A resource utilization method of pendimethalin waste residue as claimed in claim 1, wherein after the reaction is finished, the hot residue is filtered, the residual solid impurities are filtered out, and solid waste is collected; the filtrate was cooled to room temperature and filtered.
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Citations (3)
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|---|---|---|---|---|
| US4134917A (en) * | 1977-04-25 | 1979-01-16 | American Cyanamid Company | Method for the denitrosation of organic nitrosamines |
| US5922915A (en) * | 1998-05-11 | 1999-07-13 | Srm Chemical, Ltd., Co. | Process for removing N-nitroso compounds from organo-amine compositions including dinitroaniline herbicides |
| CN109970573A (en) * | 2019-05-17 | 2019-07-05 | 江苏永安化工有限公司 | The method of N- nitroso compound is sloughed from pendimethalin |
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2020
- 2020-08-17 CN CN202010823754.2A patent/CN111909042A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4134917A (en) * | 1977-04-25 | 1979-01-16 | American Cyanamid Company | Method for the denitrosation of organic nitrosamines |
| US5922915A (en) * | 1998-05-11 | 1999-07-13 | Srm Chemical, Ltd., Co. | Process for removing N-nitroso compounds from organo-amine compositions including dinitroaniline herbicides |
| CN109970573A (en) * | 2019-05-17 | 2019-07-05 | 江苏永安化工有限公司 | The method of N- nitroso compound is sloughed from pendimethalin |
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| 郭劲等编: "《放电引发非链式脉冲氟化氘激光器》", 31 July 2017, 国防工业出版社第1版 * |
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