CN101618901A - Preprocessing method of neopentyl glycol production wastewater - Google Patents
Preprocessing method of neopentyl glycol production wastewater Download PDFInfo
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Abstract
A preprocessing method of neopentyl glycol production wastewater belongs to the technical field of environment governance wastewater processing. In the processing method, preprocessing is carried out on the neopentyl glycol production wastewater by utilizing calcium oxide alkaline catalysis polymerization method, so that the inhibiting effect of formaldehyde on the microorganism can be effectively removed, meanwhile, the effect of flocculating setting is given play to, biodegradability of the neopentyl glycol production wastewater can be effectively improved. The preprocessing method can be applicable to disproporation for synthesizing the wastewater generated in the production of neopentyl glycol, and can remove methanal in the wastewater on the condition that lower temperature is 40 DEG C or 50 DEG C and molar ratio of calcium oxide to methanal is 1:1, and can exert flocculating setting effect at the same time, the removal rate of methanal can reach more than 95%, the removal rate of suspended particles can reach more than 90%; the reaction time is shorter, the process effect can be reached after reacting for 60 minutes; the neopentyl glycol production wastewater after being preprocessed can be thoroughly governed by common biological method.
Description
Technical field
The invention belongs to the environmental improvement technical field of sewage, relate to the pretreatment process of neopentyl glycol industrial wastewater, be specifically related to the method for a kind of calcium oxide base catalysis polymerization pre-treatment by the synthetic neopentyl glycol industrial wastewater of discrimination method technology.
Background technology
Neopentyl glycol (neo-pentyl ethylene glycol, NPG) be white crystals, be mainly used in and produce the used ester class of saturated polyester resin, unsaturated polyester resin, polyester polyol and synthetic lubricant (Neol of BASF AG brand neopentyl glycol is used for making the dibasic acid esters that ucon oil production is used), polymeric plasticizer and Synolac etc.The neopentyl glycol derivative is widely used in fields such as automobile, weaving, medicine, coating, agricultural chemicals, plastics and oil.States such as U.S., day all are being devoted to the new Application Areas exploitation of neopentyl glycol.It with the neopentyl glycol resin that the saturated polyester resin performance of raw material production is better than spent glycol (having the crystal problem) and propylene glycol (having hydrolysis problem) preparation.It is that the powder coating of feedstock production, high solid component coating have performances such as excellent flowability, snappiness, chemical stability (especially resistance to hydrolysis), weathering resistance, chlorine resistance, thermostability and UV resistant irradiation that neopentyl structure makes with this resinoid.
The industrial production neopentyl glycol all adopts the isobutyric aldehyde route both at home and abroad at present, be starting raw material with isobutyric aldehyde, formaldehyde promptly, generate intermediate 2 through the basic catalyst catalyzing and condensing, 2-dimethyl-3 hydroxy propanal (is commonly called as hydroxy pivalin aldehyde, be called for short HPA), restore and be neopentyl glycol.The method that is reduced because of HPA has formaldehyde disproportionation and shortening, so divide 2 kinds of discrimination method, hydrogenation methods on the technology again.Discrimination method claims one kettle way, sodium formate method again, refer to that isobutyric aldehyde, formaldehyde are under liquid caustic soda (30%～40%NaOH solution) katalysis, elder generation's condensation generates HPA, again under strong alkaline condition, HPA and formaldehyde generation Connizzaro (Cannizzaro) disproportionation reaction, HPA is generated neopentyl glycol by formaldehyde reduction, and formaldehyde then is oxidized to formic acid, in liquid caustic soda and generate sodium formiate.The processing condition gentleness of discrimination method, simple to operate.After 1980, introduction along with domestic a few cover fourth octanol large-scale plants, the isobutyric aldehyde amount of by-product is inexpensive greatly, Zibo City enterprise such as fluidisation worker company limited, east, Shandong occasion Group Co.,Ltd forever successively adopts this technology to set up production equipment, make this technology further perfect, product purity after refining can reach more than 99.5%, and the technology total recovery reaches 72%～74% (in isobutyric aldehyde).At present, it is hydrogenation method that Sino-German BASF Jiization neopentyl glycol company limited is only arranged in the domestic neopentyl glycol manufacturer, and all the other all adopt discrimination method.
As raw material and reductive agent, one consumes more formaldehyde and liquid caustic soda to discrimination method with formaldehyde, and production cost is raise; The sodium formiate of a large amount of low values of its two by-product, and the sodium formiate of trace has a significant impact the quality of product in the product; The synthetic neopentyl glycol of its three discrimination method produces the factory effluent that contains formaldehyde in a large number in producing.Formaldehyde is very strong to the toxicity of people and warm-blooded animal, skin irritation, easily cause dermatitis, the people there is carcinogenesis, if the water source that human long-term drinking is polluted by formaldehyde, can cause giddy, anaemia and various nervous system disorders, formaldehyde can directly react with the intravital protein of microorganism, DNA, RNA, cause microbial death or suppress its biological activity, maximum permissible concentration in Drinking Water and the domestic water is 0.01mg/L, and the highest permission emission concentration of " urban wastewater treatment firm pollutant emission standard " regulation formaldehyde must not be higher than 1.0mg/L.The formaldehyde solution form is a true solution, and conventional treatment processes such as coagulation, biological process are difficult to prove effective.
Zijin Lu and W.Hegenann (Water Research, 1998,32 (1): 209～215) report concentration of formaldehyde when being higher than 100mg/L, the exclusive bacterium activity of formaldehyde only be former activated 10%, almost completely are suppressed above microorganism active behind the 200mg/L.Be not suitable for directly handling because formaldehyde, contains the neopentyl glycol industrial wastewater of higher concentration formaldehyde to the restraining effect of microorganism, and still do not have cost-effective treatment process at present with biological process.
Summary of the invention
The objective of the invention is to: remedy the deficiency of art methods, the pretreatment process of the waste water that a kind of low cost, the synthetic neopentyl glycol of high efficiency, discrimination method produce in producing is provided.The present invention is reduced to below the 20mg/L concentration of formaldehyde in the synthetic neopentyl glycol industrial wastewater of discrimination method, with the formaldehyde of removing the waste water middle and high concentration restraining effect to microorganism, improve the biodegradability of waste water, pretreated neopentyl glycol industrial wastewater can adopt common biological process to handle.
The pretreatment process of the factory effluent of neopentyl glycol of the present invention comprises the following steps:
1) getting the factory effluent water sample that contains formaldehyde, is 1: 1～10: 1 adding calcium oxide by calcium oxide/formaldehyde mole ratio;
2) under the vibration condition of 150r/min, 70～40 ℃ of reactions of control reaction temperature, 50～70min;
3) measure pre-treatment front and back concentration of formaldehyde, chemical oxygen demand (COD) (CODcr) and suspended particulate matter concentration (SS).
Preferably, every index of the factory effluent water sample monitoring of described neopentyl glycol containing is respectively: 45～50 ℃ of water temperatures, colourity is 15～20, the pH value is 5.5～6.5, concentration of suspension is 80～100mg/L, ammonia nitrogen is 60～75mg/L, and concentration of formaldehyde is 300～500mg/L, and CODcr is 2600～3500mg/L.The monitoring method of the every index of above neopentyl glycol industrial wastewater is respectively: colourity is the extension rate method, concentration of suspension is a weighting method, and ammonia nitrogen is the nessler reagent spectrophotometry, and concentration of formaldehyde is the methyl ethyl diketone spectrophotometry, CODcr is a potassium dichromate process, and the pH value adopts pH meter to measure.
The preparation of above-described simulation formaldehyde waste water is to utilize 37% formaldehyde solution (analytical pure) dilution to obtain the simulation formaldehyde waste water of close concentration, and the concrete concentration of formaldehyde adopts the methyl ethyl diketone spectrophotometry.
Preferably, the reaction times step 2) is 60min.
Above-mentioned steps 2) finishes by the control of constant temperature vibration case.
The application of the pretreatment process of the factory effluent of neopentyl glycol of the present invention is used to handle the factory effluent that contains formaldehyde.
Neopentyl glycol industrial wastewater is the multicomponent system of a complexity, the neopentyl glycol industrial wastewater pretreatment process calcium oxide base catalysis polymerization of present invention, calcium oxide base catalysis polymerization ratio juris is under the situation that calcium oxide exists, oxymethylene polymerization generates the glucide that can be used as microbe carbon source, this method is that a kind of processing cost is low, the treatment process that pretreating effect is good.In the processing research of simulation formaldehyde waste water, under the felicity condition, the formaldehyde clearance reaches more than 99%; This technical scheme is applied to the synthetic neopentyl glycol industrial wastewater of discrimination method, experiment shows the formaldehyde that can remove in the waste water under lower temperature (40 ℃ or 50 ℃) and calcium oxide/formaldehyde mole ratio (2: 1 or higher) condition, play the effect of flocculating settling simultaneously, the formaldehyde clearance can reach more than 95%, and the suspended particulate clearance reaches more than 90%; The pretreatment process reaction times of present invention is shorter, and 60min can reach treatment effect; Can thoroughly be administered through common biological process by the pretreated neopentyl glycol industrial wastewater of this method, this method has higher society and economic benefit, has wide application prospect.
The application of calcium oxide base catalysis polymerization method for pretreating
The application of calcium oxide base catalysis polymerization method for pretreating mainly is to be used for the pre-treatment that contains Formaldehyde Production waste water that the synthetic neopentyl glycol of discrimination method technology is produced, and can be applied to the pre-treatment that other contain the formaldehyde organic chemical waste water simultaneously.Along with the reinforcement of people's environmental consciousness, environmental protection coating materials such as powder coating, high solid component coating develop rapidly, and it is extensive day by day to cause neopentyl glycol to be used, and market enlarges day by day.In addition, neopentyl glycol also has application in fields such as unsaturated polyester resin, medicine, tackiness agent, and market potential is very big.In the neopentyl glycol manufacturing enterprise there be main production firm: BASF Jiization neopentyl glycol company limited, device capability is 1.5 ten thousand ta
-1, go into operation in May, 1998, expanded to 2.5 ten thousand ta in 2005
-1, production technique advanced person, product price is higher than other manufacturers of a few family; The Linzi, Shandong device capability of fluidisation worker limited-liability company forever is 0.8 ten thousand ta
-1, 2 newly-increased production lines will be constructed and put into operation the end of the year 2004, and total capacity reaches 20,000 ta
-1Dongying east, Shandong occasion group company builds up 1 cover, 0.3 ten thousand ta in October, 2003
-1Device, expansion in the end of the year 2004 can be to 0.7 ten thousand ta
-1China in 2008 is about 10.2 ten thousand t to the demand of neopentyl glycol.Though China's output is brought up to 6～70,000 ta
-1, full production can not be met the need of market, 30,000～40,000 t market has openings of still having an appointment.It is hydrogenation method that Sino-German BASF Jiization neopentyl glycol company limited is only arranged in the present domestic neopentyl glycol manufacturer, and all the other all are discrimination methods, and the synthetic neopentyl glycol of discrimination method produces the factory effluent that contains formaldehyde in a large number.To containing the factory effluent of formaldehyde neopentyl glycol, the present domestic cost-effective treatment process of still not having.Therefore, the present invention contains at the synthetic neopentyl glycol industrial wastewater of discrimination method and other that tool has a extensive future aspect improvement of formaldehyde organic chemical waste water.
Description of drawings
Fig. 1 for 300mg/L simulation formaldehyde waste water under calcium oxide/formaldehyde mole ratio is 5: 1 conditions, formaldehyde clearance behind the reaction 60min under the differing temps.Wherein, X-coordinate is a temperature, unit ℃, and ordinate zou is formaldehyde clearance (%).
Fig. 2 for 500mg/L simulation formaldehyde waste water under calcium oxide/formaldehyde mole ratio is 2: 1 and 70 ℃ of conditions, the clearance that formaldehyde changed with the reaction times.Wherein, X-coordinate is the time, and the min of unit, ordinate zou are formaldehyde clearance (%).
Fig. 3 reacts 60min, formaldehyde and CODcr clearance under different calcium oxide/formaldehyde mole ratio condition under 70 ℃ of conditions of neopentyl glycol industrial wastewater.Wherein, X-coordinate is calcium oxide and formaldehyde mole ratio, and ordinate zou is formaldehyde clearance (%).
Fig. 4 reacts 60min, formaldehyde and CODcr clearance under different calcium oxide/formaldehyde mole ratio condition under 50 ℃ of conditions of neopentyl glycol industrial wastewater.Wherein, X-coordinate is calcium oxide and formaldehyde mole ratio, and ordinate zou is formaldehyde clearance (%).
Fig. 5 reacts 60min, formaldehyde and CODcr clearance under different calcium oxide/formaldehyde mole ratio condition under 40 ℃ of conditions of neopentyl glycol industrial wastewater.Wherein, X-coordinate is calcium oxide and formaldehyde mole ratio, and ordinate zou is formaldehyde clearance (%).
Embodiment
Realize purpose of the present invention, experimental technique of the present invention is:
1. investigating waste water produces link and monitor leading indicator: investigate the neopentyl glycol production technique, the link that clear and definite waste water produces is determined the kind of principal pollutant in the waste water, and every index of monitoring waste water is for the pre-treatment of neopentyl glycol industrial wastewater is prepared;
2. simulate the preparation of formaldehyde waste water: according to 1. monitoring result, obtain in one period concentration of formaldehyde scope in the neopentyl glycol industrial wastewater, preparation obtains the simulation formaldehyde waste water of similar concentration;
3. simulate the processing of formaldehyde waste water: get 100mL simulation formaldehyde waste water, do not wait by calcium oxide/formaldehyde mole ratio to add calcium oxide respectively, under the vibration condition of 150r/min, control certain reaction thermotonus;
4. simulate the result analysis of formaldehyde waste water: the monitoring concentration of formaldehyde obtains the optimal conditions of formaldehyde with the clearance and the treatment of simulated formaldehyde waste water in reaction times with the variation in reaction times;
5. the pre-treatment of neopentyl glycol industrial wastewater: get representative 100mL neopentyl glycol industrial wastewater water sample, do not wait by calcium oxide/formaldehyde mole ratio and to add calcium oxide respectively, under the vibration condition of 150r/min, control certain reaction thermotonus 60min, measure pre-treatment front and back concentration of formaldehyde, chemical oxygen demand (COD) (CODcr) and suspended particulate matter concentration (SS);
6. pre-treatment interpretation of result: analyze experimental data, obtain most economical rational pretreatment condition.
According to above-mentioned experimental technique,, found most economical rational pretreatment condition through experiment in a large number.
Below in conjunction with drawings and Examples the present invention is further described, but protection scope of the present invention not only is confined to embodiment, the change that this field professional does technical solution of the present invention all should belong in protection scope of the present invention.
Fig. 1 for 300mg/L simulation formaldehyde waste water under calcium oxide/formaldehyde mole ratio is 5: 1 conditions, formaldehyde clearance behind the reaction 60min under the differing temps.Fig. 1 can obtain under 50 ℃ and the 60 ℃ of conditions, and the formaldehyde clearance is lower, and under 70 ℃ and the 80 ℃ of conditions, the formaldehyde clearance is comparatively obvious, all near 100%.Illustrate that temperature is the major influence factors of this method, under the mol ratio condition of certain concentration of formaldehyde and CaO/HCHO, the high more formaldehyde clearance of temperature is high more;
Fig. 2 is under 2: 1 and 50 ℃, 60 ℃, 70 ℃ and the 80 ℃ of conditions for 500mg/L simulation formaldehyde waste water in calcium oxide/formaldehyde mole ratio, the clearance that formaldehyde changed with the reaction times.Fig. 2 can obtain under 50 ℃ of conditions, and concentration of formaldehyde does not have considerable change in the 400min, and under 60 ℃ of conditions, the clearance of formaldehyde rises rapidly near 100% near 350min; Illustrate that the calcium oxide catalytic polymerization carries out at short notice, under 70 ℃ and the 80 ℃ of conditions, the clearance of formaldehyde illustrates equally that promptly near 100% temperature is the major influence factors of this method in the shorter reaction time (40min and 26min);
Fig. 3 reacts 60min, formaldehyde and CODcr clearance under different calcium oxide/formaldehyde mole ratio condition under 70 ℃ of conditions of neopentyl glycol industrial wastewater.Fig. 3 can obtain under 70 ℃ temperature of reaction, and the mol ratio of CaO/HCHO is 1: 1 o'clock, and the formaldehyde clearance is all near 90% in the 60min, and the interior formaldehyde clearance of mol ratio 60min that increases CaO/HCHO is all near 100%; CODcr does not have considerable change in entire reaction course, illustrate that calcium oxide base catalysis polymerization preprocessing neopentyl glycol just makes the form of formaldehyde that variation has taken place, do not remove fully, but neopentyl glycol industrial wastewater can be removed the toxicity restraining effect of formaldehyde to microorganism after the pre-treatment;
Fig. 4 reacts 60min, formaldehyde and CODcr clearance under different calcium oxide/formaldehyde mole ratio condition under 50 ℃ of conditions of neopentyl glycol industrial wastewater.The same Fig. 3 of Fig. 4 gained conclusion;
Fig. 5 reacts 60min, formaldehyde and CODcr clearance under different calcium oxide/formaldehyde mole ratio condition under 40 ℃ of conditions of neopentyl glycol industrial wastewater.Fig. 5 can obtain under 40 ℃ temperature of reaction, calcium oxide/formaldehyde mole ratio is 1: 1 and 2: 1 o'clock, the formaldehyde clearance is near 90% and 96% in the 60min, the interior formaldehyde clearance of mol ratio 60min that increases CaO/HCHO is all near 100%, illustrate that this treatment process is under the wastewater effluent temperature condition, can carry out pre-treatment to it, and pretreating effect to obviously be better than simulating the treatment effect of formaldehyde waste water;
The processing experimental result of simulation formaldehyde waste water shows under 50 ℃ and the 60 ℃ of conditions, formaldehyde clearance lower (shown in Figure 1), and the raising temperature of reaction can effectively improve reaction efficiency; Neopentyl glycol industrial wastewater is the multicomponent system of a complexity, calcium oxide base catalysis pre-treatment experimental result is presented under lower calcium oxide/formaldehyde mole ratio (1: 1) and temperature (40 ℃ and the 50 ℃) condition and can PARA FORMALDEHYDE PRILLS(91,95) effectively handles, and this is the feature part of this pretreatment process just.
Embodiment 1:
Getting 300mg/L simulation formaldehyde waste water 100mL in Erlenmeyer flask, is 5: 1 adding calcium oxide 0.28g by calcium oxide/formaldehyde mole ratio, is under the vibration condition of 150r/min at rotating speed, and control reaction temperature is 70 ℃, and the monitoring concentration of formaldehyde changes.
Current treatment effect is: under 70 ℃ of conditions, the reaction times, the formaldehyde clearance was 99.8% when being 60min, and handling the back concentration of formaldehyde is 0.65mg/L, was lower than the highest permission emission concentration of " urban wastewater treatment firm pollutant emission standard " regulation formaldehyde limit value.
Embodiment 2:
Getting 500mg/L simulation formaldehyde waste water 100mL in Erlenmeyer flask, is 2: 1 adding calcium oxide 0.187g by calcium oxide/formaldehyde mole ratio, is under the vibration condition of 150r/min at rotating speed, and control reaction temperature is 70 ℃, and the monitoring concentration of formaldehyde changes in time.
Current treatment effect is: under 70 ℃ of conditions, the clearance of formaldehyde rises near 90% rapidly near 40min, and the reaction times, concentration of formaldehyde was 0.73mg/L when being 50min, promptly can reach pretreating effect in the short period.
Embodiment 3:
Get representative neopentyl glycol industrial wastewater 100mL (the about 310mg/L of concentration of formaldehyde) in Erlenmeyer flask, at rotating speed is under the vibration condition of 150r/min, control reaction temperature is 70 ℃, by calcium oxide/formaldehyde mole ratio is 5: 1 adding calcium oxide 0.158g, measure concentration of formaldehyde behind the reaction times 60min, CODcr and SS.
Current treatment effect is: under 70 ℃ temperature of reaction, the mol ratio of calcium oxide/formaldehyde is 5: 1 o'clock, and the formaldehyde clearance is near 99.9% in the 60min, and concentration of formaldehyde is 0.37mg/L after the pre-treatment; CODcr does not have considerable change in entire reaction course, calcium oxide base catalysis polymerization preprocessing neopentyl glycol just makes the form of formaldehyde that variation has taken place, do not remove fully, but neopentyl glycol industrial wastewater can be removed the toxicity restraining effect of formaldehyde to microorganism after the pre-treatment; The SS clearance reaches 90%.
Embodiment 4:
Treatment process is identical with embodiment 3, and difference is that calcium oxide/formaldehyde mole ratio is 2: 1, and the amount that adds calcium oxide is 0.063g.
Current treatment effect is: under 70 ℃ temperature of reaction, the mol ratio of calcium oxide/formaldehyde is 2: 1 o'clock, the formaldehyde clearance is 98.5% in the 60min, concentration of formaldehyde is 4.5mg/L after the pre-treatment, the SS clearance reaches 90%, CODcr does not have considerable change in entire reaction course, but the BOD of pretreated waste water
5/ COD value can reach 0.56, can be handled by common biological process.
Embodiment 5:
Treatment process is identical with embodiment 4, and difference is that temperature of reaction is controlled at 50 ℃, and resulting pretreating effect is similar to embodiment 4.
Embodiment 6:
Treatment process is identical with embodiment 4, and difference is that temperature of reaction is controlled at 40 ℃.Treatment effect is: under 40 ℃ temperature of reaction, calcium oxide/formaldehyde mole ratio is 2: 1 o'clock, and the formaldehyde clearance is 95.6% in the 60min, and concentration of formaldehyde is 13.2mg/L after the pre-treatment, also can be handled by common biological process.This pretreatment process is 2: 1 adding calcium oxide by calcium oxide/formaldehyde mole ratio under the wastewater effluent temperature condition, stirs, and can carry out pre-treatment to it.
Claims (5)
1. the pretreatment process of the factory effluent of a neopentyl glycol comprises the following steps:
1) getting the factory effluent water sample that contains formaldehyde, is 1: 1～10: 1 adding calcium oxide by calcium oxide/formaldehyde mole ratio;
2) under the vibration condition of 150r/min, 70～40 ℃ of reactions of control reaction temperature, 50～70min;
3) measure pre-treatment front and back concentration of formaldehyde, chemical oxygen demand (COD) (CODcr) and suspended particulate matter concentration (SS).
2. the pretreatment process of the factory effluent of neopentyl glycol as claimed in claim 1, it is characterized in that, every index of the factory effluent water sample monitoring of described neopentyl glycol containing is respectively: 45～50 ℃ of water temperatures, colourity is 15～20, the pH value is 5.5～6.5, and concentration of suspension is 80～100mg/L, and ammonia nitrogen is 60～75mg/L, concentration of formaldehyde is 300～500mg/L, and CODcr is 2600～3500mg/L.
3. the pretreatment process of the factory effluent of neopentyl glycol as claimed in claim 1 is characterized in that step 2) in reaction times be 60min.
4. the pretreatment process of the factory effluent of neopentyl glycol as claimed in claim 1 is characterized in that step 2) finish by the control of constant temperature vibration case.
5. the application of the pretreatment process of the factory effluent of neopentyl glycol as claimed in claim 1 is used to handle the factory effluent that contains formaldehyde.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774739A (en) * | 2010-03-15 | 2010-07-14 | 核工业北京化工冶金研究院 | Treatment technology for wastewater from production of neopentyl glycol |
| CN101774675B (en) * | 2010-01-15 | 2011-07-20 | 济南大学 | Method for preprocessing neopentyl glycol industrial wastewater by catalytic oxidation |
| CN104108827A (en) * | 2014-06-27 | 2014-10-22 | 李开明 | Processing method for high concentration organic acid wastewater containing formaldehyde |
| CN111718035A (en) * | 2020-07-07 | 2020-09-29 | 湖北凌晟药业有限公司 | Method for removing aldehydes in cephalosporin wastewater |
-
2009
- 2009-08-11 CN CN200910017599A patent/CN101618901A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774675B (en) * | 2010-01-15 | 2011-07-20 | 济南大学 | Method for preprocessing neopentyl glycol industrial wastewater by catalytic oxidation |
| CN101774739A (en) * | 2010-03-15 | 2010-07-14 | 核工业北京化工冶金研究院 | Treatment technology for wastewater from production of neopentyl glycol |
| CN104108827A (en) * | 2014-06-27 | 2014-10-22 | 李开明 | Processing method for high concentration organic acid wastewater containing formaldehyde |
| CN104108827B (en) * | 2014-06-27 | 2016-07-06 | 李开明 | A kind of processing method containing formaldehyde high concentration organic acidity waste water |
| CN111718035A (en) * | 2020-07-07 | 2020-09-29 | 湖北凌晟药业有限公司 | Method for removing aldehydes in cephalosporin wastewater |
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