CN108940369A - A kind of preparation method and applications of salen Cu (II) catalyst - Google Patents
A kind of preparation method and applications of salen Cu (II) catalyst Download PDFInfo
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- CN108940369A CN108940369A CN201810780038.3A CN201810780038A CN108940369A CN 108940369 A CN108940369 A CN 108940369A CN 201810780038 A CN201810780038 A CN 201810780038A CN 108940369 A CN108940369 A CN 108940369A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The present invention provides a kind of preparation method of salen Cu (II) catalyst, specifically utilize (S, S) intermediate (the S of-salen catalyst ligand, S the filtrate that)-mono-salt is synthetically produced extracts the cyclohexanediamine tosilate of racemization, one pot reaction obtains salen Cu (II) catalyst of racemization in single solvent with 3,5- di-tert-butyl salicylaldehyde and copper acetate again.The present invention synthesizes salen Cu (II) catalyst by waste liquid produced by utilizing intermediate (S, the S)-mono-salt of (S, S)-salen catalyst ligand to synthesize, and turns waste into wealth, can reduce environmental pressure and widen purposes.Invention additionally discloses a kind of applications of above-mentioned catalyst, are specifically used for cyanide wastwater degradation, and cyanogen breaking process is simple, and broken cyanide effect is good, and salen Cu (II) catalyst is easily recycled, at low cost, are easy to large-scale production, have and value is widely applied.
Description
Technical field
The present invention relates to catalyst and technical field of waste water processing, particularly, are related to a kind of salen Cu (II) catalyst
Preparation method and applications.
Background technique
It is to contain cyanic acid after cyanogenation occurs for raw material that cyanide wastewater, which refers to using hydrocyanic acid salt (Cymag or potassium cyanide),
The waste water of radical ion.Because cyanic acid ion is hypertoxic, it is necessary to which carrying out broken cyanide processing to it makes cyanic acid ion reach state's domestic discipline and family rules
Fixed discharge standard (1mg/L) can just discharge.
There are several types of (1) hypochlorite oxidation methods for the method for broken cyanide, this method is using hypochlorite under the weak basic condition
It is aoxidized, cyanic acid ion is oxidized to nitrogen, the gases such as carbon dioxide, and advantage is that reaction is fast, and reaction is thorough, but cost
Height, and waste water contains the complete hypochlorite of unreacted, will lead to secondary pollution；(2) hydrogen peroxide oxidation method, this method use dioxygen
It is aoxidized under the same weak basic condition of water, cyanic acid ion can equally be oxidized to nitrogen and carbon dioxide gas, advantage
That reaction is fast, cost is medium, the disadvantage is that hydrogen peroxide be it is explosive, misoperation is easy to happen explosion, danger close；(3) highly pressured hydrolysis
Method, this method make cyanate radical itself decompose to become ammonium carbonate salts using high temperature and pressure, and advantage is not need to add other chemistry
Substance, the disadvantage is that energy consumption height causes at high cost, and high temperature and pressure needs special equipment；(4) electrolysis method, this method utilize electrochemistry
It is special that redox reaction destroys the cyaniding in waste water.Advantage is that new noxious material is not added into waste water, and processing high concentration contains
Processing cost is low when cyanogen waste water, but equipment is once put into greatly, and cleaning difficulty is big in operational process, and with cyanogen in operational process
Acid ion concentration reduces and power consumption is significantly increased, and final processing cost is higher than other methods；(5) biochemical process, this method
Treatment of Cyanide-containing Wastewater is to carry out resolving into carbonate and nitrate, advantage to cyanate radical in two stages using targetedly strain
Be processing waste water removal cyanate radical it is high-efficient, drain nontoxic, the disadvantage is that bad adaptability, be only capable of processing extremely low concentration and concentration becomes
Change range and fluctuates small cyanide wastewater；(6) it is acidified absorption method, this method is adjusted with acid the pH value of cyanide wastewater, is allowed in acidity, cyanogen
Acid group is changed into hydrocyanic acid gas, and when being filled with inert gas into waste water, the gas and sodium hydroxide solution for being loaded with hydrocyanic acid are connect
Touching, hydrocyanic acid become hydrocyanic acid sodium salt benefit again and have recycled recovery.The advantages of the method is the medicament salt acid value of processing
Lattice are low, and processing cost is small by waste water composition, the disadvantage is that safety coefficient is low when processing, once there is gas to escape from the device,
The hydrocyanic acid gas of severe toxicity will cause the fatal risk of moment to operator；(7) sulfur dioxide-air oxidation process, this method
Specifically: within the scope of certain pH, under the catalytic action of the copper salts, containing cyanogen using the oxidation of the synergistic effect of sulfur dioxide and air
Cyanate radical in waste water, according to reaction mechanism, sulfur dioxide gas is actually converted into sulphite and oxygen in mantoquita
Catalytic reaction gives birth to radical reaction, generates sulfate and active oxygen, active oxygen carry out cyanate radical to be oxidized to ammonium carbonate salts.This method work
Skill is simple, and equipment is simple, and treatment effect is better than hypochlorite oxidation method, and reagent cost is low, small investment, the disadvantage is that because using mantoquita
Copper ion after as catalyst treatment in waste water can be exceeded, and organic impurities and inorganic impurity in waste water, wastewater pH
Value etc. is very big on the catalytic action of mantoquita influence, therefore applies and be very restricted.Other processing methods there are also natural purification method,
Supercritical water oxidation method, membrane separation process, wet oxidation process, ion-exchange, activated carbon oxidation process etc., but level of application be not so good as with
Upper method is wide.
Salen [derives from N, two (salicylidene of N-bis (salicylidine) ethylene-diamine, N, N'- ethylene
Imines)], refer to the general designation of diimine class compound, is important in asymmetric catalysis and asymmetric syntheses in recent years match
One of body.The synthesis step of the chiral salen complex of Jacobsen group report: splitting trans- 1 by chiral tartaric acid,
2- cyclohexanediamine, obtaining chiral 1,2- cyclohexanediamine-tartrate is chiral mono-salt；By chiral 1,2- cyclohexanediamine-wine
Stone hydrochlorate and potassium carbonate react in water, obtain chiral 1,2- cyclohexanediamine aqueous solution；Again with the tertiary fourth of the 3,5- of two molecules bis-
Base salicylide methanol solution reacts to obtain ligand.In the first step using in tartaric acid resolution reaction, contain another in filtrate
Enantiomer, and in trans- 1, the 2- cyclohexanediamine because using containing 30~40% cis- body, in addition synthesize (S, S)-salen urge
The chiral value for the D- tartaric acid that intermediate (S, S)-mono-salt of agent ligand uses leads to the hexamethylene two in its mother liquor less than 98%
Amine is almost racemization, and many producers are all that this filtrate is worked as liquid waste processing at present, increases environmental protection pressure.
Therefore, a kind of filtrate progress that (S, S)-salen catalyst intermediate (S, S)-mono-salt is synthetically produced by energy is developed
The method rationally utilized is of great significance.
Summary of the invention
The present invention provides a kind of preparation method of salen Cu (II) catalyst, and specific technical solution is as follows:
A kind of preparation method of salen Cu (II) catalyst, utilize (S, S)-salen catalyst ligand intermediate (S,
S the filtrate that)-mono-salt is synthetically produced extracts the cyclohexanediamine tosilate of racemization, then with 3,5- di-tert-butyl salicylaldehyde
One pot reaction obtains salen Cu (II) catalyst of racemization in single solvent with copper acetate.
It is preferred in above technical scheme, comprising the following steps:
The first step splits trans- 1,2- cyclohexanediamine after obtaining the filtrate dehydration of (S, S)-cyclohexanediamine mono-salt, is added
With the organic solvent of trans- 1,2- cyclohexanediamine equal weight, it is warming up to reflux, p-methyl benzenesulfonic acid is added and is adjusted to pH=7, heat preservation 2
~3 hours, it is cooled to 0~5 DEG C, centrifugation obtains cyclohexanediamine tosilate；
Second step, the alkali and 5~6 times of quality that 0.7~0.75 times of mass ratio is added in cyclohexanediamine tosilate
The organic solvent of ratio reacts at room temperature 5~6 hours, the organic solvent solution of cyclohexanediamine is obtained after filtering, after being heated to reflux, drop
Add the copper acetate and 14~15 of 3,5- di-tert-butyl salicylaldehyde by 1.2~1.4 times of weight ratios, 0.7~0.75 times of mass ratio
The mixed liquor that the organic solvent of times mass ratio is formed, insulation reaction 8~10 hours, is cooled to room temperature, is centrifuged, and obtains after dry
Salen Cu (II) catalyst.
It is preferred in above technical scheme, the structural formula of salen Cu (II) catalyst are as follows:
Preferred in above technical scheme, organic solvent is methanol, ethyl alcohol, positive third in the first step and second step
At least one of alcohol, isopropanol and tetrahydrofuran.
Preferred in above technical scheme, alkali is in sodium carbonate, potassium carbonate, lithium carbonate and potassium phosphate in the second step
At least one.
It is preferred in above technical scheme, comprising the following steps:
The first step will be split to obtain the filtrate of (S, S)-cyclohexanediamine mono-salt by trans- 1, the 2- cyclohexanediamine of 200kg, dense
After contracting, 200kg methanol is added, after being heated to reflux, 100kg p-methyl benzenesulfonic acid and 100kg methanol solution is added dropwise, with to toluene
The instillation of sulfonic acid has a large amount of solid to be precipitated, and keeps the temperature 2~3 hours, is cooled to 0~5 DEG C, centrifugation obtains 135kg ring after dry
Hexamethylene diamine tosilate；
Second step puts into 35kg cyclohexanediamine tosilate and 25kg sodium carbonate in reaction kettle, and 200kg first is added
Alcohol is stirred at room temperature 5~6 hours, the organic solvent solution of cyclohexanediamine is obtained by filtration；
After the organic solvent solution of cyclohexanediamine is heated to reflux, atropurpureus solution is instilled, with the drop of atropurpureus solution
Enter, there is red solid precipitation, keep the temperature 8~10 hours, be cooled to room temperature, be centrifuged, elute, centrifugation obtains 50kgsalen after dry
Cu (II) catalyst, in which: atropurpureus solution is by 45kg3,5- di-tert-butyl salicylaldehyde, 25kg copper acetate and 500kg first
Alcohol obtains after dissolving by heating.
The present invention utilizes intermediate (S, S)-mono-salt of (S, S)-salen catalyst ligand to synthesize produced waste liquid to synthesize
SalenCu (II) catalyst, concrete principle route are as follows:
(1) cyclohexanediamine tosilate is extracted from (S, S)-mono-salt filtrate:
(2) one-pot synthesis salen Cu (II) catalyst:
The present invention is come by waste liquid produced by utilizing intermediate (S, the S)-mono-salt of (S, S)-salen catalyst ligand to synthesize
Salen Cu (II) catalyst is synthesized, turns waste into wealth, environmental pressure can be reduced and widen purposes.
The present invention also provides a kind of applications of above-mentioned salen Cu (II) catalyst, specifically: using above-mentioned salen
Cu (II) catalyst is used for Treatment of Cyanide-containing Wastewater.
Preferred in above technical scheme, the detailed process of Treatment of Cyanide-containing Wastewater is: will add in mass ratio in cyanide wastewater
Enter the sulphite of 2%-5% and salen Cu (II) catalyst of 0.05%-0.01%, compressed air 2-5 is passed through under stirring
Hour, the water that obtains that treated, in which: cyanic acid ion concentration is greater than 2000mg/L in cyanide wastewater；Cyanogen in treated water
Acid ion is less than 1mg/L.
Preferred in above technical scheme, the sulphite is in sodium sulfite, potassium sulfite and sodium pyrosulfite
At least one.
For salen Cu (II) catalyst of the invention applied to cyanide wastewater processing, particular technique principle is as follows:
Cyanic acid ion is abolished using salen Cu (II) catalyst:
CN-+[O]+2H2O=CO3 2--+NH4 +。
Under salen Cu (II) catalyst existence condition, the oxygen in sulfite ion and air reacts to be produced the present invention
Liveliness proof oxygen, active oxygen is reacted with cyanic acid ion generates carbanion and ammonium ion, and cyanogen breaking process is simple, broken cyanide effect
Good, salen Cu (II) catalyst is easily recycled, at low cost；Because salen Cu (II) catalyst structure is stable and not soluble in water,
This broken cyanide method is no longer influenced by the influence of organic impurities in waste water, inorganic impurity, pH value of waste water, is easy to large-scale production, has
Value is widely applied.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
Below with reference to embodiment, the present invention is described in further detail.
Specific embodiment
The solution of the present invention is described in detail with reference to embodiments, but the present invention can be limited according to claim
Fixed and covering multitude of different ways is implemented.
Embodiment 1:
A kind of preparation method of salen Cu (II) catalyst, specifically includes the following steps:
The first step will be split to obtain the filtrate of (S, S)-cyclohexanediamine mono-salt by trans- 1, the 2- cyclohexanediamine of 200kg, dense
After contracting, 200kg methanol is added, after being heated to methanol eddy, 100kg p-methyl benzenesulfonic acid and 100kg methanol solution 1.8-2.2 is added dropwise
Hour, as the instillation of p-methyl benzenesulfonic acid has a large amount of solid to be precipitated, 2~3 hours are kept the temperature, is cooled to 0~5 DEG C, centrifugation, 60
Under the conditions of DEG C -70 DEG C it is dry after, obtain 135kg cyclohexanediamine tosilate；
Second step puts into 35kg cyclohexanediamine tosilate and 25kg sodium carbonate in reaction kettle, and 200kg first is added
Alcohol is stirred at room temperature 5~6 hours, the organic solvent solution of cyclohexanediamine is obtained by filtration；
After the organic solvent solution of cyclohexanediamine is heated to methanol eddy, instill atropurpureus solution 1.8-2.2 hours, with
The instillation of atropurpureus solution, have a red solid precipitation, keep the temperature 8~10 hours, be cooled to room temperature, be centrifuged, elute, centrifugation,
50kgsalen Cu (II) catalyst is obtained after drying under the conditions of 60 DEG C -70 DEG C, in which: atropurpureus solution is by 45kg3,5- bis-
Tert-butyl salicylide, 25kg copper acetate and 500kg methanol obtain after being heated to 60 DEG C of -70 DEG C of dissolutions.
Salen Cu (II) catalyst obtained by the present embodiment is used for the processing of cyanide wastewater, specific as follows:
2% sodium sulfite and 0.05% salen Cu (II) catalyst will be added in mass ratio in cyanide wastewater, stirs
It mixes down and is passed through compressed air 2 hours, the water that obtains that treated (is discharged into dirt after treated water recycling salen Cu (II) catalyst
Water treatment station carries out subsequent biochemical processing).
See Table 1 for details for waste water situation before and after treatment.
Embodiment 2-5
2 difference from Example 1 of embodiment is: by be added in mass ratio in cyanide wastewater 2% sodium sulfite and
0.08% salen Cu (II) catalyst, is passed through compressed air 2 hours under stirring, the water that obtains that treated.
3 difference from Example 1 of embodiment is: by be added in mass ratio in cyanide wastewater 2% sodium sulfite and
0.1% salen Cu (II) catalyst, is passed through compressed air 2 hours under stirring, the water that obtains that treated.
4 difference from Example 1 of embodiment is: by be added in mass ratio in cyanide wastewater 4% sodium sulfite and
0.05% salen Cu (II) catalyst, is passed through compressed air 2 hours under stirring, the water that obtains that treated.
5 difference from Example 1 of embodiment is: by be added in mass ratio in cyanide wastewater 5% sodium sulfite and
0.05% salen Cu (II) catalyst, is passed through compressed air 2 hours under stirring, the water that obtains that treated.
The waste water situation statistical form of 1 embodiment 1- embodiment 5 of table before and after treatment
As can be seen from Table 1:
Known to embodiment 1-3 comparison: can be incited somebody to action using the catalyst of 0.05% mass ratio and the sodium sulfite of 2% mass ratio
Cyanic acid ion in waste water is degraded by 2500ml/L to 0.09mg/L, and waste water meets discharge standard；When the use for increasing catalyst
When amount is to 0.1%, less, but cost has raising for the degradation effect variation of cyanic acid ion.
Embodiment 1 and embodiment 4-5 are relatively known: can be by the cyanic acid in waste water using the sodium sulfite of 2% mass ratio
Radical ion is degraded to 0.09mg/L, and waste water meets discharge standard；When the dosage of sodium sulfite increases to 5%, cyanic acid ion
More adequately it is degraded, but degradation effect increase rate very little.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of salen Cu (II) catalyst, it is characterised in that: utilize (S, S)-salen catalyst ligand
The filtrate that intermediate (S, S)-mono-salt is synthetically produced extracts the cyclohexanediamine tosilate of racemization, then with the tertiary fourth of 3,5- bis-
Base salicylide and the copper acetate one pot reaction in single solvent obtain salen Cu (II) catalyst of racemization.
2. the preparation method of salen Cu (II) catalyst according to claim 2, it is characterised in that: including following step
It is rapid:
The first step splits trans- 1,2- cyclohexanediamine after obtaining the filtrate dehydration of (S, S)-cyclohexanediamine mono-salt, is added and anti-
Formula 1, the organic solvent of 2- cyclohexanediamine equal weight are warming up to reflux, and p-methyl benzenesulfonic acid is added and is adjusted to pH=7, heat preservation 2~3
Hour, it is cooled to 0~5 DEG C, centrifugation obtains cyclohexanediamine tosilate；
Second step, the alkali that 0.7~0.75 times of mass ratio is added in cyclohexanediamine tosilate and 5~6 times of mass ratioes
Organic solvent, react at room temperature 5~6 hours, the organic solvent solution of cyclohexanediamine is obtained after filtering, after being heated to reflux, be added dropwise by
The copper acetate and 14~15 times of matter of the 3,5- di-tert-butyl salicylaldehyde of 1.2~1.4 times of weight ratios, 0.7~0.75 times of mass ratio
The mixed liquor that the organic solvent of ratio is formed is measured, insulation reaction 8~10 hours, room temperature is cooled to, is centrifuged, obtain salen after dry
Cu (II) catalyst.
3. the preparation method of salen Cu (II) catalyst according to claim 2, it is characterised in that: the salen Cu
(II) structural formula of catalyst are as follows:
4. the preparation method of salen Cu (II) catalyst according to claim 3, it is characterised in that: the first step and
Organic solvent is at least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol and tetrahydrofuran in second step.
5. the preparation method of salen Cu (II) catalyst according to claim 4, it is characterised in that: in the second step
Alkali is at least one of sodium carbonate, potassium carbonate, lithium carbonate and potassium phosphate.
6. the preparation method of salen Cu (II) catalyst according to claim 5, it is characterised in that: including following step
It is rapid:
The first step will be split to obtain the filtrate of (S, S)-cyclohexanediamine mono-salt by trans- 1, the 2- cyclohexanediamine of 200kg, concentration
Afterwards, 200kg methanol is added, after being heated to reflux, 100kg p-methyl benzenesulfonic acid and 100kg methanol solution is added dropwise, with to toluene sulphur
The instillation of acid has a large amount of solid to be precipitated, and keeps the temperature 2~3 hours, is cooled to 0~5 DEG C, centrifugation obtains 135kg hexamethylene after dry
Diamines tosilate；
Second step puts into 35kg cyclohexanediamine tosilate and 25kg sodium carbonate in reaction kettle, and 200kg methanol is added,
It is stirred at room temperature 5~6 hours, the organic solvent solution of cyclohexanediamine is obtained by filtration；
After the organic solvent solution of cyclohexanediamine is heated to reflux, instill atropurpureus solution has with the instillation of atropurpureus solution
Red solid is precipitated, and keeps the temperature 8~10 hours, is cooled to room temperature, is centrifuged, and elutes, and centrifugation obtains 50kgsalen Cu after dry
(II) catalyst, in which: atropurpureus solution is by 45kg3,5- di-tert-butyl salicylaldehyde, 25kg copper acetate and 500kg methanol
It is obtained after heating for dissolving.
7. a kind of application of salen Cu (II) catalyst, it is characterised in that: use as claimed in any one of claims 1 to 6
Salen Cu (II) catalyst is used for Treatment of Cyanide-containing Wastewater.
8. the application of salen Cu (II) catalyst according to claim 7, it is characterised in that: the tool of Treatment of Cyanide-containing Wastewater
Body process is: the salen Cu of the sulphite and 0.05%-0.1% of 2%-5% will be added in mass ratio in cyanide wastewater
(II) catalyst is passed through compressed air 2-5 hours under stirring, the water that obtains that treated, in which: cyanic acid ion in cyanide wastewater
Concentration is greater than 2000mg/L；Cyanic acid ion is less than 1mg/L in treated water.
9. the application of salen Cu (II) catalyst according to claim 8, it is characterised in that: the sulphite is Asia
At least one of sodium sulphate, potassium sulfite and sodium pyrosulfite.
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| CN110467303A (en) * | 2019-08-20 | 2019-11-19 | 湖南亚王医药科技有限公司 | A kind of processing method of benzene acetonitrile class production waste water |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467303A (en) * | 2019-08-20 | 2019-11-19 | 湖南亚王医药科技有限公司 | A kind of processing method of benzene acetonitrile class production waste water |
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