CN112759150A - Method for treating high-concentration methanol residual liquid wastewater - Google Patents

Method for treating high-concentration methanol residual liquid wastewater Download PDF

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Publication number
CN112759150A
CN112759150A CN202011638269.4A CN202011638269A CN112759150A CN 112759150 A CN112759150 A CN 112759150A CN 202011638269 A CN202011638269 A CN 202011638269A CN 112759150 A CN112759150 A CN 112759150A
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China
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wastewater
concentration methanol
iron
treating high
concentration
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CN202011638269.4A
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李锋民
董旭
储祺
郑宇�
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Ocean University of China
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Ocean University of China
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • C02F1/4678—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction of metals
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention discloses a method for treating high-concentration methanol residual liquid wastewater. Treating the high-concentration methanol residual liquid wastewater by adopting a micro-electrolysis method and Fenton oxidation method combined technology, in the micro-electrolysis reaction, adjusting the initial pH of the wastewater to 2-6, the dosage of the iron-carbon filler to 300-1700 g/L, the reaction time to 12-60 h and the like, and in the Fenton oxidation reaction, adjusting Fe2+The dosage is 0-10 g/l, H2O2The dosage is 10-50 g/l, the reaction time is 30-180 minutes, the COD in the methanol residual liquid can be removed to the maximum extent, the removal rate can reach 60% -80%, and the BOD of the wastewater can reach5/CODCrCan be improved from 0.2 to more than 0.4, the biodegradability of the wastewater can be greatly improved, and the method has the advantages of high removal efficiency, simple and convenient operation, no secondary pollution, low cost and the like.

Description

Method for treating high-concentration methanol residual liquid wastewater
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for treating high-concentration methanol residual liquid wastewater.
Background
A large amount of pharmaceutical wastewater is generated in the pharmaceutical process, and the pharmaceutical wastewater has great difference due to different pharmaceutical products and different production processes. Therefore, the treatment of pharmaceutical wastewater becomes a difficult problem, and especially the treatment of pharmaceutical wastewater becomes an important factor restricting the rapid development of pharmaceutical industry due to the continuous improvement of sewage discharge indexes in recent years.
The high-concentration methanol residual liquid wastewater is one of important sources of pharmaceutical wastewater, and mainly contains components such as methanol, dichloromethane, sodium hypochlorite, acetic acid, steroid substances and the like, so that organic matter components in the wastewater are complex and have extremely high concentration, most of the components are refractory substances, the refractory substances can inhibit microorganisms in conventional treatment, and the biochemical treatment of the wastewater is extremely difficult. The Fenton oxidation method and the iron-carbon micro-electrolysis method are two types of wastewater treatment methods which are developed relatively mature at present, in recent years, the two methods are greatly applied to pretreatment and advanced treatment of pharmaceutical and chemical engineering chemical synthesis wastewater, antibiotic pharmaceutical wastewater, pharmaceutical intermediate production wastewater and the like, the biodegradability of the treated wastewater is remarkably improved, organic matters which are difficult to degrade are well removed and degraded, and stable guarantee is provided for standard discharge of effluent water quality.
Disclosure of Invention
The invention aims to solve the technical problem that the traditional conventional water treatment process is difficult to effectively treat the high-concentration methanol residual liquid wastewater. Therefore, the invention provides a method for treating high-concentration methanol residual liquid wastewater, which can effectively remove a large amount of nonbiodegradable organic matters contained in the wastewater, improve the biodegradability of the wastewater, reduce the dosage of a medicament and improve the wastewater treatment efficiency.
In order to realize the purpose of the invention, the following technical scheme is adopted:
a method for treating high-concentration methanol residual liquid wastewater comprises the following steps:
(1) adjusting the pH value of the wastewater to 2-6, and adding an iron-carbon filler into the wastewater;
(2) carrying out aeration treatment on the wastewater added with the iron-carbon filler;
(3) standing after the reaction, and discharging supernatant after complete precipitation;
(4) adjusting the pH value of the supernatant after the iron-carbon micro-electrolysis treatment to be 8-10, standing to precipitate large-particle organic matters and impurities in the water, and facilitating the subsequent oxidation reaction;
(5) taking the wastewater after precipitation, adjusting the pH value to 2-6 according to Fe2+The dosage is 0-5 g/l, H2O2Adding a medicament into the mixture for oxidation, wherein the adding amount is 10 g/L-50 g/L;
(6) and (4) adjusting the pH of the wastewater subjected to oxidation treatment in the step (5) to 8-10, and standing to precipitate large-particle organic matters and impurities in the wastewater.
Specifically, the CODCr concentration of the wastewater in the step (1) is 70000 mg/L-110000 mg/L.
Specifically, the adding amount of the iron-carbon filler in the step (1) is 300 g/L-1700 g/L.
Specifically, the gas-water ratio in the aeration process in the step (2) is 20: 1-50: 1, the residence time is 12 to 60 hours.
Specifically, the standing time in the step (3) is 3-5 hours.
Specifically, the standing time in the step (4) is 3 to 5 hours.
Specifically, the Fenton oxidation reaction time in the step (5) is 30 to 180 minutes.
Specifically, the standing time in the step (6) is 3 to 5 hours.
The invention couples the iron-carbon micro-electrolysis and Fenton oxidation technologies. The main action mechanisms of the iron-carbon micro-electrolysis technology include reduction of iron, galvanic cell reaction, flocculation precipitation, electrochemical adsorption, physical adsorption and the like. Under acidic environment, the anode of the primary battery can generate Fe2+The cathode can generate nascent state [ H ]]The compounds have stronger activity under the combined action and can generate oxidation-reduction reaction with organic matters to destroy the molecular structure of the organic matters. Meanwhile, through electrochemical oxidation, organic matters can also generate oxidation-reduction reaction on the electrode of the primary battery. In addition, Fe is generated during the reaction2+And Fe3+The generated molten iron complex has excellent flocculation effect, and pollutants can be further removed through the net trapping and sweeping action, the hydrogen bond and the van der Waals force adsorption action. After iron-carbon micro-electrolysis treatment, a large amount of Fe exists in the wastewater2+Adding H under acidic condition2O2The reaction system forms a Fenton system, and a series of chain reactions occur rapidly to generate OH (E0 ═ 2.87V) with very strong oxidizing property, and the OH is decomposed by the strong oxidizing propertyAnd (4) organic pollutants.
The iron-carbon micro-electrolysis method and the Fenton oxidation technology are coupled to treat the methanol residual liquid in the high-concentration pharmaceutical wastewater, so that the Fe generated by the iron-carbon micro-electrolysis reaction can be fully utilized2+Reduction of Fe in advanced oxidation reactions2+The dosage is increased to reduce the treatment cost, the concentration of organic pollutants, especially toxic substances, in the high-concentration methanol residual liquid wastewater can be obviously reduced, the problems of poor effect, high cost and the like of a single treatment method can be solved, and meanwhile, the biodegradability is improved, so that the subsequent biological treatment requirement of the wastewater is met, and the standard discharge is realized.
The invention has the following beneficial effects:
the invention adjusts the pH of the wastewater, carries out iron-carbon micro-electrolysis treatment and Fe2+And H2O2The adding amount and the reaction time of the method can remove highly toxic organic matters in the methanol residual liquid wastewater to the maximum extent and improve the biodegradability of the methanol residual liquid wastewater. Fe produced during micro-electrolysis2+Can be used in the subsequent Fenton oxidation process, and is beneficial to reducing the dosage of the medicament. According to the method for treating the high-concentration methanol residual liquid wastewater, the cost for treating the high-concentration methanol residual liquid wastewater is 55-60 yuan/cubic meter, the removal rate of COD in the treated pharmaceutical wastewater is more than 60%, the content of organic pollutants in the wastewater is remarkably reduced, even part of organic matters are completely degraded, the treatment efficiency is high, and great economic benefits can be brought.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
Example 1:
100 ml of COD was takenCrHigh concentration methanol raffinate wastewater at a concentration of 82000 mg/l and an initial pH of 4.5, which was treated in sequence as follows:
(1) to this was added 133 grams of an iron carbon filler.
(2) Carrying out aeration treatment on the wastewater added with the iron-carbon filler, wherein the gas-water ratio is 20: 1-50: 1, residence time 48 hours.
(3) Standing for 4 hours after a certain reaction time, taking supernate to measure the COD concentration after complete precipitation, 33600 mg/L, adjusting the pH of the supernate after iron-carbon micro-electrolysis treatment to 10.0, standing to precipitate large-particle organic matters and impurities in water, and facilitating the subsequent oxidation reaction.
(4) Taking the effluent of the process (3), Fe2+The dosage is 0.6 g, H2O2The adding amount is 3 g, the reaction time is 120 minutes, the pH value of a water sample is adjusted to 10 after the reaction is finished, the water sample is fully stirred and stands for 4 hours, and then the water sample is discharged.
COD in the discharged waterCrThe concentration is 20000 mg/l, the COD removal rate is 75.6 percent, and BOD5/CODCrFrom 0.24 to 0.5.
Example 2:
100 ml of COD was takenCrHigh-concentration methanol raffinate wastewater with the concentration of 85000 mg/L and the initial pH of 5.0 is treated according to the following steps in sequence:
(1) 130 g of an iron carbon filler was added thereto.
(2) And (3) carrying out aeration treatment on the wastewater added with the iron-carbon filler, wherein the gas-water ratio is 40:1, and the retention time is 48 hours.
(3) Standing for 4 hours after a certain reaction time, taking supernate after complete precipitation to measure the COD concentration, 48300 mg/L, adjusting the pH of the supernate after iron-carbon micro-electrolysis treatment to 10.0, standing to precipitate large-particle organic matters and impurities in water, and facilitating the subsequent oxidation reaction.
(4) Taking the effluent in the process (3), adjusting the pH of the wastewater to 3 by using acid, and adding 4 g of H2O2Without addition of Fe2+The reaction time is 90 minutes, the pH value of a water sample is adjusted to 10.0 after the reaction is finished, and the water sample is fully stirred and stands for 4 hours before being discharged.
COD in the discharged waterCrThe concentration is 5600 mg/l, the COD removal rate is 79 percent, and BOD5/CODCrFrom 0.3 to 0.6.
Example 3:
100 ml of COD was takenCrHigh-concentration methanol raffinate wastewater with a concentration of 90000 mg/l and an initial pH of 3.0 was treated in the following order:
(2) 110 grams of an iron carbon filler was added thereto.
(2) And (3) carrying out aeration treatment on the wastewater added with the iron-carbon filler, wherein the gas-water ratio is 40:1, and the retention time is 45 hours.
(3) Standing for 4 hours after a certain reaction time, taking supernate after complete precipitation to measure the COD concentration of 55600 mg/L, adjusting the pH of the supernate after iron-carbon micro-electrolysis treatment to 10.0, standing to precipitate large-particle organic matters and impurities in water, and facilitating the subsequent oxidation reaction.
(4) Taking the effluent of the process (3), adding 2 g of Fe into the water2+4 g of H2O2The reaction time is 120 minutes, the pH value of a water sample is adjusted to 10 after the reaction is finished, and the water sample is fully stirred and stands for 4 hours before being discharged.
COD in the discharged waterCrThe concentration is 31500 mg/l, the COD removal rate is 65 percent, and BOD5/CODCrFrom 0.2 to 0.6.
The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and a person skilled in the art can modify the technical solution of the present invention or substitute the same without departing from the spirit and scope of the present invention, and the scope of the present invention should be determined by the claims.

Claims (8)

1. A method for treating high-concentration methanol residual liquid wastewater is characterized by comprising the following steps:
(1) adjusting the pH value of the wastewater to 2-6, and adding an iron-carbon filler into the wastewater;
(2) carrying out aeration treatment on the wastewater added with the iron-carbon filler;
(3) standing after the reaction, and discharging supernatant after complete precipitation;
(4) and adjusting the pH value of the supernatant after the iron-carbon micro-electrolysis treatment to be 8-10, standing to precipitate large-particle organic matters and impurities in the water, and facilitating the subsequent oxidation reaction.
(5) Taking the wastewater after precipitation, adjusting the pH value to 2-6 according to Fe2+The dosage is 0-5 g/l, H2O2Adding the medicament into the mixture for oxidation at the dosage of 10 g/L-50 g/L.
(6) And (4) adjusting the pH of the wastewater subjected to oxidation treatment in the step (5) to 8-10, and standing to precipitate large-particle organic matters and impurities in the wastewater.
2. The method for treating high-concentration methanol raffinate wastewater as claimed in claim 1, wherein the COD of the wastewater in the step (1)CrThe concentration is from 70000 mg/l to 110000 mg/l.
3. The method of claim 1, wherein the iron-carbon filler is filled in an amount of 300 g/l to 1700 g/l.
4. The method for treating high-concentration methanol raffinate wastewater as claimed in claim 1, wherein the aeration process in step (2) controls the gas-water ratio to be 20: 1-50: 1, the aeration retention time is 12 to 60 hours.
5. The method for treating high-concentration methanol raffinate wastewater as claimed in claim 1, wherein the standing time in the step (3) is 3-5 hours.
6. The method for treating high-concentration methanol raffinate wastewater as claimed in claim 1, wherein the standing time in the step (4) is 3-5 hours.
7. The method for treating high-concentration methanol raffinate wastewater as claimed in claim 1, wherein the Fenton oxidation reaction time in the step (5) is 30 to 180 minutes.
8. The method for treating high-concentration methanol raffinate wastewater as claimed in claim 1, wherein the standing time in the step (6) is 3-5 hours.
CN202011638269.4A 2020-12-31 2020-12-31 Method for treating high-concentration methanol residual liquid wastewater Pending CN112759150A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734817A (en) * 2009-12-31 2010-06-16 江苏苏净集团有限公司 Method for treating organic chemical waste water
CN103833166A (en) * 2012-11-23 2014-06-04 濮阳市德胜实业有限公司 Methyldiethanolamine (MDEA) industrial wastewater treatment method
CN204874146U (en) * 2015-06-26 2015-12-16 江西康翔环保有限公司 Pharmacy waste water integration preprocessing device
CN110921954A (en) * 2019-12-10 2020-03-27 西安华盛坤泰能源环保科技有限公司 Method and system for treating oilfield wastewater by combining iron-carbon micro-electrolysis and Fenton oxidation
CN111252973A (en) * 2018-11-30 2020-06-09 潍坊博华环境技术工程有限公司 Sewage pretreatment method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734817A (en) * 2009-12-31 2010-06-16 江苏苏净集团有限公司 Method for treating organic chemical waste water
CN103833166A (en) * 2012-11-23 2014-06-04 濮阳市德胜实业有限公司 Methyldiethanolamine (MDEA) industrial wastewater treatment method
CN204874146U (en) * 2015-06-26 2015-12-16 江西康翔环保有限公司 Pharmacy waste water integration preprocessing device
CN111252973A (en) * 2018-11-30 2020-06-09 潍坊博华环境技术工程有限公司 Sewage pretreatment method
CN110921954A (en) * 2019-12-10 2020-03-27 西安华盛坤泰能源环保科技有限公司 Method and system for treating oilfield wastewater by combining iron-carbon micro-electrolysis and Fenton oxidation

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