CN115536548B - Environment-friendly synthesis method of intermediate - Google Patents
Environment-friendly synthesis method of intermediate Download PDFInfo
- Publication number
- CN115536548B CN115536548B CN202211234159.0A CN202211234159A CN115536548B CN 115536548 B CN115536548 B CN 115536548B CN 202211234159 A CN202211234159 A CN 202211234159A CN 115536548 B CN115536548 B CN 115536548B
- Authority
- CN
- China
- Prior art keywords
- aniline
- benzyl
- magnesium chloride
- water
- mother liquor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an environment-friendly synthesis method of an intermediate, which comprises the steps of standing and layering after a condensation reaction reaches a terminal, recycling a lower layer solution, condensing an upper layer solution and benzyl chloride, continuing to react, standing and layering after the reaction reaches the terminal, wherein the upper layer is a product, cooling and crystallizing the lower layer after the lower layer is decolorized by active carbon to separate out 6-water magnesium chloride crystals, and a small amount of filtrate is used as bottom water. The invention effectively separates the mother liquor and the gas generated in the dye production process, separates valuable components from the mother liquor and the gas, and is used as raw materials for producing other products, thereby reducing carbon emission and reducing environmental pollution. The mother liquor generated in the invention is concentrated and crystallized to recycle magnesium chloride for resource utilization, and the purified magnesium chloride crystal can be sold out, thereby increasing economic benefit; the water produced by concentration can be used as dilution water and washing water in the reaction process for recycling, so that zero emission of wastewater is realized, and the aims of clean production, energy conservation and emission reduction are achieved.
Description
Technical Field
The invention belongs to the technical field of dye production, relates to an intermediate of disperse orange 288, and particularly relates to an environment-friendly synthesis method of the intermediate.
Background
The disperse orange 288 product is the product with the largest disperse dye productivity,
n, N-cyanoethylbenzylaniline is white powder with a melting point of 97.2-102.3 ℃. N, N-cyanoethylbenzyl aniline is an important organic intermediate and is widely applied to the synthesis of pesticides, dyes and the like. The manufacturers in China are few, mainly depend on import from countries such as the United states, japan and the like, and the N, N-cyanoethylbenzyl aniline has good prospect and huge economic benefit in China.
Wang Qi (dye & stain, process research on N-cyanoethyl-N-benzylaniline, 1992 (4): 20-21) discloses a process for the preparation of N, N-cyanoethylbenzylaniline comprising: to a 250ml three-necked flask equipped with a reflux condenser, 40ml of water and 74.8. 74.8g N-cyanoethylaniline were added, and the temperature was raised to 90 to 100℃while 67.8g of benzyl chloride and a 20% sodium carbonate solution were added dropwise. After the dripping is finished, the mixture is reacted for 3 hours at the temperature of 90 to 100 ℃, glacial acetic acid is added, the mixture is stirred and is slowly cooled to 30 ℃, white solid is separated out at the moment, and the finished product is obtained after filtering and water washing. In the method, glacial acetic acid is added in post-treatment, so that the mother solution water contains various substances such as sodium acetate, sodium chloride and the like, the post-treatment difficulty is increased, and besides, waste gas carbon dioxide can be generated in the reaction process. In the above method, once sodium carbonate is excessively added, a part of benzyl chloride and N-cyanoethylaniline may be lost in the reaction.
The Chinese patent publication No. CN1036974A discloses a method for producing N, N-cyanoethylbenzyl aniline dye, which relates to a method for producing N, N-cyanoethylbenzyl aniline, comprising the following steps: in a non-organic solvent medium, N-cyanoethylaniline and benzyl chloride are subjected to a melting reaction at 80-130 ℃, water is added for pulping, sodium hydroxide is added after cooling, and then the N, N-cyanoethylbenzylaniline is obtained through filtering, water washing and drying, wherein the yield is about 85-92%. In the reaction process of the method, the product hydrochloric acid is continuously enriched, and the pH of the system is strong acid, so that the reaction is incomplete, and the yield is relatively low.
The intermediate N-cyanoethyl N-benzyl aniline (benzyl for short) is synthesized by excessive proportion of benzyl chloride and N-cyanoethyl, and the benzyl contains residual benzyl chloride. The method has relatively bad benzyl chloride smell in the processes of beating benzyl substances and synthesizing 288 orange, and not only is VOC easily exceeded during exhaust emission, but also has potential carcinogenicity to human bodies. To allow for proper production of the product, the problem of benzyl chloride in the benzyl must be eliminated.
The above patent documents do not mention the post-treatment of the mother liquor generated by the reaction, and if the mother liquor is directly discharged, the purification effect of a biological treatment system in sewage treatment can be seriously affected due to the high salt content in the mother liquor and the toxic action of chloride ions on bacteria; there is no mention of how to eliminate the problem of benzyl chloride in the benzyl.
Disclosure of Invention
In order to solve the problems, the invention provides an environment-friendly synthesis method of an intermediate of disperse orange 288, which effectively separates mother liquor and gas generated in the dye production process, and separates valuable components from the mother liquor and gas to be used as raw materials for producing other products. Reduce carbon emission and reduce environmental pollution.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an environment-friendly synthesis method of an intermediate comprises the following steps:
1) Adding N-cyanoethylaniline, benzyl chloride, hydroquinone, water and an acid-binding agent into a reaction kettle under the control of a DCS system, feeding back according to the change of pH in a reaction system after heating, automatically controlling the addition amount of the acid-binding agent, and controlling the pH of the reaction system to be 7-9 until the reaction of detecting N-cyanoethylaniline to be less than 2.5% by HPLC is finished, so as to obtain a material I;
2) Cooling the temperature jacket of the material I obtained in the step 1) to 90-105 ℃ in a water bath, adding aniline, aniline recovery water and magnesium chloride solution, reacting until the reaction is finished when the benzyl chloride is less than 0.05% detected by a gas chromatography, separating steam, recovering aniline, and detecting no benzyl chloride and the HPLC aniline is less than 0.05% detected by the gas chromatography in slurry to obtain a material II;
3) Standing and layering the material II obtained in the step 2), wherein the lower layer is magnesium chloride mother liquor, and the upper layer is the product N-cyanoethyl N-benzyl aniline;
4) Decolorizing the magnesium chloride mother liquor obtained in the step 3) by using active carbon, cooling and crystallizing to obtain 6 magnesium chloride hydrate crystals, and applying part of magnesium chloride solution; the upper layer of N-cyanoethyl N-benzyl aniline liquid is diluted into 288 washing water to synthesize 288 orange through weighing and metering.
In the invention, the condensation reaction is carried out to the end point, then the mixture is stood for layering, the lower layer solution is recycled and reused, the upper layer solution and benzyl chloride are condensed for continuous reaction, the upper layer is a product after the reaction is carried out to the end point, the lower layer is decolorized by active carbon and then cooled for crystallization to separate out 10-water magnesium chloride crystals, and a small amount of filtrate is used as bottom water for reuse.
As a preferred embodiment of the present invention, in step 1), the temperature of the reaction system is 80 to 115 ℃.
As a preferred embodiment of the present invention, in step 1), the temperature of the reaction system is 85 to 110 ℃.
As a preferable scheme of the invention, the molar ratio of the N-cyanoethylaniline, benzyl chloride, hydroquinone, water and the acid binding agent is 1:1.0 to 1.05:0.0015 to 0.005: 8-12:0.5-1.1.
As a preferred embodiment of the invention, in step 2), the molar ratio of aniline to benzyl chloride remaining in step 1) is 1:0.05 to 0.6.
As a preferred embodiment of the invention, in step 2), the molar ratio of aniline to benzyl chloride remaining in step 1) is 1:0.1 to 0.4.
As a preferred embodiment of the invention, in step 3), the temperature of the stationary delamination separation is 90-105 ℃.
As a preferred embodiment of the present invention, the acid-binding agent is a combination of magnesium carbonate and magnesium hydroxide.
As a preferable scheme of the invention, the treatment steps of the lower magnesium chloride mother solution are as follows: decolorizing with active carbon, filtering, crystallizing the filtrate, filtering, and filtering to obtain filtrate.
As a preferable scheme of the invention, the upper layer N-cyanoethyl N-benzyl aniline liquid can be salted out by sodium chloride solution with the mass fraction of 10-18%, press-filtered, the obtained filtrate is used mechanically, and the filter cake is sold.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention effectively separates the mother liquor and the gas generated in the dye production process, separates valuable components from the mother liquor and the gas, and is used as raw materials for producing other products, thereby reducing carbon emission and reducing environmental pollution.
2) The invention simplifies the production process and improves the production efficiency.
3) The mother liquor generated in the invention is concentrated and crystallized to recycle magnesium chloride for resource utilization, and the purified magnesium chloride crystal can be sold out, thereby increasing economic benefit; the water produced by concentration can be used as dilution water and washing water in the reaction process for recycling, so that zero emission of wastewater is realized, and the aims of clean production, energy conservation and emission reduction are achieved.
Drawings
Fig. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present invention, unless otherwise specified, the process, equipment or raw materials used are all existing.
Referring to fig. 1, the environment-friendly synthesis method of the intermediate provided by the invention effectively separates mother liquor and gas generated in the dye production process, separates valuable components from the mother liquor and gas, and reduces carbon emission and environmental pollution as raw materials for producing other products.
The reaction equation of the invention is:
main reaction
Or is:
side reactions
Or is:
example 1
The embodiment provides an environment-friendly synthesis method of an intermediate, which comprises the following steps:
1) Under the control of a DCS system, adding N-cyanoethylaniline, benzyl chloride, hydroquinone, water and an acid binding agent (the acid binding agent is: magnesium carbonate, magnesium hydroxide) in a molar ratio of 1:1.0:0.0015:8:0.5, automatically controlling the addition amount of the acid binding agent according to the change feedback of pH in the reaction system after the temperature is raised to 110 ℃, and controlling the pH of the reaction system to be 7-9 until the reaction of N-cyanoethylaniline which is detected by HPLC is less than 2.5 percent is finished, thus obtaining a material I.
2) The temperature of the material I obtained in the step (1) is adjusted to 100 ℃, aniline recovery water and a small amount of magnesium chloride solution (molar ratio of aniline to residual benzyl chloride in the step 1) are added as follows: 0.1 And (3) after the reaction is finished until the detection of benzyl chloride in the distilled liquid is less than 0.05 percent, (otherwise, aniline is supplemented), then steam separation is carried out to recover aniline, until the detection of benzyl chloride in the distilled liquid is no, the detection of aniline in the distilled liquid is less than 0.05 percent, and (distilled aniline water is recovered and used for synthesizing N-cyanoethylaniline) to obtain a material II.
3) Standing and layering and separating the material II at 100 ℃, wherein the lower layer is magnesium chloride mother liquor, and the upper layer is the product N-cyanoethyl N-benzyl aniline.
4) Decolorizing the magnesium chloride mother liquor with active carbon, cooling and crystallizing to obtain 10 water magnesium chloride crystals, and mechanically using the rest magnesium chloride after filtration; the upper layer N-cyanoethyl N-benzyl aniline liquid (100 ℃) is metered and diluted into dispersed 288 washing water (or mother liquor water) through a weighing module to synthesize 288 orange (diluted into diluted 10-18% sodium chloride normal-temperature brine for filtration if takeaway, the filtrate is applied for application, and the filter cake is taken away).
Example 2
The embodiment provides an environment-friendly synthesis method of an intermediate, which comprises the following steps:
1) Under the control of a DCS system, adding N-cyanoethylaniline, benzyl chloride, hydroquinone, water and an acid binding agent (the acid binding agent is: magnesium carbonate, magnesium hydroxide) in a molar ratio of 1:1.02:0.003: and 9:1, automatically controlling the addition amount of the acid binding agent according to the change feedback of the pH value in the reaction system after the temperature is raised by 100 ℃, and controlling the pH value of the reaction system to be 7-9 until the reaction of the N-cyanoethylaniline which is detected by HPLC is less than 2.5 percent is finished, thus obtaining a material I.
2) The temperature of the material I obtained in the step (1) was adjusted to 105℃and aniline, aniline recovery water and a small amount of magnesium chloride solution (molar ratio of aniline to residual benzyl chloride of the step 1) were added as 1:0.3 And (3) after the reaction is finished until the detection of benzyl chloride in the distilled liquid is less than 0.05 percent, (otherwise, aniline is supplemented), then steam separation is carried out to recover aniline, until the detection of benzyl chloride in the distilled liquid is no, the detection of aniline in the distilled liquid is less than 0.05 percent, and (distilled aniline water is recovered and used for synthesizing N-cyanoethylaniline) to obtain a material II.
3) Standing and layering and separating the material II at 105 ℃, wherein the lower layer is magnesium chloride mother liquor, and the upper layer is the product N-cyanoethyl N-benzyl aniline.
4) Decolorizing the magnesium chloride mother liquor with active carbon, cooling and crystallizing to obtain 6-hydrate magnesium chloride crystals, and mechanically using the residual magnesium chloride mother liquor after filtration; the upper layer N-cyanoethyl N-benzyl aniline liquid (105 ℃) is diluted into dispersed 288 washing water (or mother liquor water) by a weighing module to synthesize 288 orange (diluted into diluted 10-18% sodium chloride normal temperature brine for filtration if takeaway, the filtrate is used for application, and the filter cake is taken away).
Example 3
The embodiment provides an environment-friendly synthesis method of an intermediate, which comprises the following steps:
1) Under the control of a DCS system, adding N-cyanoethylaniline, benzyl chloride, hydroquinone, water and an acid binding agent (the acid binding agent is: magnesium carbonate, magnesium hydroxide) in a molar ratio of 1:1.05:0.005: and (12) 1.1, automatically controlling the addition amount of the acid binding agent according to the change feedback of the pH value in the reaction system after the temperature is increased to 85 ℃, and controlling the pH value of the reaction system to be 7-9 until the reaction of the N-cyanoethylaniline which is detected by HPLC is less than 2.5% is finished, so as to obtain a material I.
2) The temperature of the material I obtained in the step (1) is adjusted to 90 ℃, aniline recovery water and a small amount of magnesium chloride solution (molar ratio of aniline to residual benzyl chloride in the step 1) are added as follows: 0.4 And (3) after the reaction is finished until the detection of benzyl chloride in the distilled liquid is less than 0.05 percent, (otherwise, aniline is supplemented), then steam separation is carried out to recover aniline, until the detection of benzyl chloride in the distilled liquid is no, the detection of aniline in the distilled liquid is less than 0.05 percent, and (distilled aniline water is recovered and used for synthesizing N-cyanoethylaniline) to obtain a material II.
3) Standing and layering and separating the material II at 90 ℃, wherein the lower layer is magnesium chloride mother liquor, and the upper layer is the product N-cyanoethyl N-benzyl aniline.
4) Decolorizing the magnesium chloride mother liquor with active carbon, cooling and crystallizing to obtain 6-hydrate magnesium chloride crystals, and mechanically using the residual magnesium chloride mother liquor after filtration; the upper layer N-cyanoethyl N-benzyl aniline liquid (103 ℃) is metered and diluted into dispersed 288 washing water (or mother liquor water) through a weighing module to synthesize 288 orange (diluted into diluted 10-18% sodium chloride normal-temperature brine for filtration if takeaway, the filtrate is applied for application, and the filter cake is taken away).
Comparative example 1N-cyanoethyl N-benzylaniline, a conventional process for the production of N-cyanoethyl N-benzylaniline.
The VOC index of the tail gas of the N-cyanoethyl N-benzylaniline prepared in examples 1 to 3 and the N-cyanoethyl N-benzylaniline prepared in comparative example 1 were measured at 30℃for coupling with p-nitroaniline diazonium salt or N-cyanoethyl N-benzylaniline alone for beating, and the results are shown in Table 1.
TABLE 1 detection results
| Exhaust VOC index | National standard | |
| Example 1 | 30 | ≤60 |
| Example 2 | 25 | ≤60 |
| Example 3 | 20 | ≤60 |
| Comparative example 1 | 500 | ≤60 |
As can be seen from Table 1, the problem of benzyl chloride is eliminated in the intermediate obtained by the synthesis method of the invention, and the mother liquor and gas generated in the dye production process are effectively separated, so that valuable components in the mother liquor and gas are separated, and the mother liquor and gas are used as raw materials for producing other products, thereby reducing carbon emission and reducing environmental pollution.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The environment-friendly synthesis method is characterized by comprising the following steps of:
1) Adding N-cyanoethylaniline, benzyl chloride, hydroquinone, water and an acid-binding agent into a reaction kettle under the control of a DCS system, feeding back according to the change of pH in a reaction system after heating, automatically controlling the addition amount of the acid-binding agent, and controlling the pH of the reaction system to be 7-9 until the reaction of detecting N-cyanoethylaniline to be less than 2.5% by HPLC is finished, so as to obtain a material I;
2) Adjusting the temperature of the material I obtained in the step 1) to 90-105 ℃, adding aniline, aniline recovery water and magnesium chloride solution, reacting until the reaction is finished when the benzyl chloride is detected to be less than 0.05% by gas chromatography, separating and recovering aniline by steam, and obtaining a material II when the benzyl chloride is detected to be free by gas chromatography in slurry and the aniline is detected to be less than 0.05% by HPLC;
3) Standing and layering the material II obtained in the step 2), wherein the lower layer is magnesium chloride mother liquor, and the upper layer is the product N-cyanoethyl N-benzyl aniline;
4) Decolorizing the magnesium chloride mother liquor obtained in the step 3) by using active carbon, cooling and crystallizing to obtain magnesium chloride hexahydrate crystals, and applying part of magnesium chloride solution; the upper layer of N-cyanoethyl N-benzyl aniline liquid is diluted into 288 washing water to synthesize 288 orange through weighing and metering.
2. The method according to claim 1, wherein in the step 1), the temperature of the reaction system is 80-115 ℃.
3. The method according to claim 2, wherein in step 1), the temperature of the reaction system is 85-110 ℃.
4. The environment-friendly synthesis method according to claim 1, wherein the molar ratio of the N-cyanoethylaniline, the benzyl chloride, the hydroquinone, the water and the acid binding agent is 1:1.0 to 1.05:0.0015 to 0.005: 8-12:0.5-1.1.
5. The method according to claim 1, wherein in step 2), the molar ratio of aniline to benzyl chloride is 1:0.05 to 0.6.
6. The method according to claim 5, wherein in the step 2), the molar ratio of aniline to benzyl chloride is 1:0.1 to 0.4.
7. The method according to claim 1, wherein in the step 3), the temperature of the static delamination separation is 90-105 ℃.
8. The method of any one of claims 1-7, wherein the acid binding agent is a combination of magnesium carbonate and magnesium hydroxide.
9. The method for synthesizing the magnesium chloride as defined in claim 1, wherein the lower magnesium chloride mother liquor is treated by the steps of: decolorizing with active carbon, filtering, crystallizing the filtrate, filtering, and filtering to obtain filtrate.
10. The environment-friendly synthesis method according to claim 1, wherein the upper layer of N-cyanoethyl N-benzyl aniline liquid can be salted out by 10-18% sodium chloride solution by mass fraction, and the obtained filtrate is reused by pressure filtration, and the filter cake is sold.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211234159.0A CN115536548B (en) | 2022-10-10 | 2022-10-10 | Environment-friendly synthesis method of intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211234159.0A CN115536548B (en) | 2022-10-10 | 2022-10-10 | Environment-friendly synthesis method of intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115536548A CN115536548A (en) | 2022-12-30 |
| CN115536548B true CN115536548B (en) | 2023-09-12 |
Family
ID=84733823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211234159.0A Active CN115536548B (en) | 2022-10-10 | 2022-10-10 | Environment-friendly synthesis method of intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536548B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391804A (en) * | 1993-02-04 | 1995-02-21 | Bayer Aktiengesellschaft | Process for the preparation of mono-N-β-cyanoethylanilines |
| CN102604413A (en) * | 2011-12-26 | 2012-07-25 | 浙江吉华集团有限公司 | Middle-temperature type disperse dye compound and preparation method and application thereof |
| CN107793328A (en) * | 2016-08-30 | 2018-03-13 | 浙江迪邦化工有限公司 | A kind of production method of N, N cyanoethyl benzylaniline |
| CN109503424A (en) * | 2018-12-10 | 2019-03-22 | 杭州申航新材料有限公司 | N- cyanoethyl-Phenhenzamine production equipment and method |
| CN110872236A (en) * | 2018-08-30 | 2020-03-10 | 浙江闰土研究院有限公司 | N-cyanoethyl-N-benzylaniline and preparation method and application thereof |
| CN112479927A (en) * | 2020-11-03 | 2021-03-12 | 浙江汇翔新材料科技股份有限公司 | Production process of N-cyanoethyl-N-benzylaniline |
-
2022
- 2022-10-10 CN CN202211234159.0A patent/CN115536548B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391804A (en) * | 1993-02-04 | 1995-02-21 | Bayer Aktiengesellschaft | Process for the preparation of mono-N-β-cyanoethylanilines |
| CN102604413A (en) * | 2011-12-26 | 2012-07-25 | 浙江吉华集团有限公司 | Middle-temperature type disperse dye compound and preparation method and application thereof |
| CN107793328A (en) * | 2016-08-30 | 2018-03-13 | 浙江迪邦化工有限公司 | A kind of production method of N, N cyanoethyl benzylaniline |
| CN110872236A (en) * | 2018-08-30 | 2020-03-10 | 浙江闰土研究院有限公司 | N-cyanoethyl-N-benzylaniline and preparation method and application thereof |
| CN109503424A (en) * | 2018-12-10 | 2019-03-22 | 杭州申航新材料有限公司 | N- cyanoethyl-Phenhenzamine production equipment and method |
| CN112479927A (en) * | 2020-11-03 | 2021-03-12 | 浙江汇翔新材料科技股份有限公司 | Production process of N-cyanoethyl-N-benzylaniline |
Non-Patent Citations (1)
| Title |
|---|
| Investigation from Synthesis to Crystal Structure to Application of Ecofriendly Disperse Dyes on One-Step Dyeing of PET Fabric;Min Li等;《ACS Sustainable Chem. Eng.》;第5卷;758-766 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115536548A (en) | 2022-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102344220B (en) | Method for treating metronidazole waste water | |
| CN102010310B (en) | Productive technology of vanlillin by glyoxylic acid method | |
| CN102241606B (en) | Clean production method of N-cyanoethylaniline | |
| CN108530278A (en) | A kind of preparation method of D, L- naproxen | |
| CN101492399B (en) | Method for preparing methylpropene sodium sulfonate | |
| CN112979561B (en) | Post-treatment method for synthesizing 4, 6-dihydroxypyrimidine | |
| CN115536548B (en) | Environment-friendly synthesis method of intermediate | |
| CN109970543B (en) | Method for recycling acyclovir condensation by-product and solvent | |
| CN110818573B (en) | Preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane | |
| CN102503810B (en) | Method for recovering and recycling L-tartaric acid | |
| CN107056646A (en) | A kind of synthetic method of adipic dihydrazide | |
| CN101508678B (en) | Process for preparing 2-methyl-4-amino-5-acetyl aminomethyl pyrimidine | |
| CN109134215B (en) | Production method for preparing trimethyl orthoformate by liquid metal sodium slag method | |
| CN216303678U (en) | Recovery processing device for waste liquid generated in acetochlor production | |
| CN115417786A (en) | Method for purifying and recovering DMF (dimethyl formamide) waste solvent | |
| CN113004168A (en) | Production process of methoxyamine for synthesizing furan ammonium salt | |
| CN110922320B (en) | Method for extracting methyl isobutyl ketone and sodium p-toluenesulfonate | |
| CN113860995A (en) | Recovery treatment process and treatment device for waste liquid generated in acetochlor production | |
| CN107915343B (en) | Process wastewater treatment process in production process of pyrazolone series products | |
| CN107778160B (en) | Preparation method of 3,4,5, 6-tetrafluorophthalic acid | |
| CN111848459A (en) | Clean and efficient preparation method of 1,6 and 1, 7-clevuric acid | |
| CN108546232A (en) | A kind of monosubstituted or disubstituted benzene formic ether compounds preparation methods | |
| CN110540505B (en) | Green and clean production process of isooctyl p-methoxycinnamate | |
| CN113493400B (en) | Method for producing bisphenol S and co-producing sodium lignin sulfonate | |
| CN211445568U (en) | Production device of malonic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |