CN101838083A - Method for treating organic chemical wastewater having high COD and high concentration of sulfate ions - Google Patents

Method for treating organic chemical wastewater having high COD and high concentration of sulfate ions Download PDF

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CN101838083A
CN101838083A CN 201010174616 CN201010174616A CN101838083A CN 101838083 A CN101838083 A CN 101838083A CN 201010174616 CN201010174616 CN 201010174616 CN 201010174616 A CN201010174616 A CN 201010174616A CN 101838083 A CN101838083 A CN 101838083A
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treatment
cod
wastewater
anaerobic
organic chemical
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吴敏
郑刚
张勇
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a method for treating organic chemical wastewater having high COD (chemical oxygen demand) and high concentration of sulfate ions. The method mainly comprises the following steps of: Ca(OH)2 pre-treatment; anaerobic treatment; two-stage aerobic treatment and the like, wherein after the organic chemical wastewater is subjected to Ca(OH)2 pre-treatment to remove most of sulfate ions and H<+> (hydrogen ions), a method for wastewater anaerobic treatment, which takes the advantages of anaerobic bacteria, and a method for wastewater aerobic treatment, which is mainly based on halophilic aerobic microorganisms, can be formed by controlling the microorganisms as the main agent for wastewater treatment and the operating parameter factors. Therefore, the invention is particularly suitable for the treatment of organic chemical wastewater having high COD, high concentration of sulfate ions and low pH value.

Description

A kind of high COD, the acid organic chemical waste water treatment process of high concentration sulphate
Technical field
The invention belongs to environmental engineering and microbial technology field, particularly a kind of chemistry and biophase of adopting is in conjunction with the method that high COD, the acid organic chemical waste water of high concentration sulphate are handled.
Background technology
High concentration sulfate wastewater is present in the industries such as mine, metallurgy, food and medicine in a large number, and the not treated water body that directly enters of these waste water will produce a series of harm, as: 1. corrosion pipeline.In all kinds of hydraulic pipes, it will directly reduce the resistance of water and increase corrosion, the indirect circulation that has influence on sulphate reducing bacteria and the propagation of biological corrosion; 2. excessive sulfate radical can make water body produce stench, influences the sensory properties and the use thereof of water; 3. excessive sulfate radical is unfavorable for plant growth, makes the soil salinification; 4. the tap water that contains vitriol has bitter taste, and causes the effect of rushing down, and will cause symptoms such as diarrhoea and maldigestion.Therefore, the height of sulfate radical content more and more causes people's attention to the influence of its use properties in the water.
The improvement of high sulfate concentration waste water is the difficult point in water pollution control field always, need remove vitriol and organic pollutant in the waste water simultaneously.It is very high because of sulfate radical to contain high sulfate radical waste water, such waste water to be handled effectively and generally the anaerobism technology will be adopted, but when the high organic concentration waste water of the high sulfate radical of anaerobic treatment, the sulfate radical reduction generates hydrogen sulfide, is unfavorable for the removal of the organic pollutant in the waste water.Adopt at present biological process and physical chemistry treatment technology in the prior art usually, the most typical technology has following several: 1. traditional single phase anaerobic technique, under the anaerobic conditions sulfate radical is reduced to hydrogen sulfide, and realize sulfate radical is removed from waste water; Organic pollutant is by acidication and produce biogas, realizes the removal of high-enriched organics, but the hydrogen sulfide of the reductive action of sulfate radical and generation has restraining effect to the removal of organic pollutant, thereby has influenced the removal of organic pollutant.2. single-phase stripping process in the traditional single phase anaerobic technique, increases rare gas element stripping device, and the hydrogen sulfide stripping that the sulfate radical reduction is formed goes out, and alleviates the restraining effect to organic pollutant removal.3. diphasic anaerobic technique, the product acid phase and the aerogenesis stage of anaerobic treatment high concentrated organic wastewater are carried out in two reactors respectively, realized the reduction of sulfate radical and the acidifying of high concentration organic contaminant at the product acid phase, the aerogenesis stage further removes by the acidifying organic pollutant.4. traditional anaerobic technique as up-flow anaerobic sludge blanket (UASB), by add precipitation agent or other technologies removal sulfate radical and hydrogen sulfide in reactor, is eliminated removing the restraining effect of organic pollutant.Though more than these technology the method that processing contains high organic concentration waste water of high sulfate radical has been carried out valuable exploration, still can't realize promoting and widespread use because of himself technical limitation.
Summary of the invention
The objective of the invention is to overcome the defective that prior art exists, a kind of high COD, the acid organic chemical waste water treatment process of high concentration sulphate be provided:
A kind of high COD, the acid organic chemical waste water treatment process of high concentration sulphate is characterized in that may further comprise the steps:
A) in wastewater from chemical industry, add Ca (OH) 2, stirring reaction, adjust pH are removed most of sulfate radical and H to 6.7-7.5 +, going precipitation after static one hour, supernatant liquor is delivered to anaerobic reactor;
B) the controlled liq temperature is 10-30 ℃, and in COD: N: P=450: 5: 1 ratio is added nitrogen phosphorus source, and adjustings pH is 7-8, and adding sulfate reduction flora carries out anaerobic treatment, hydraulic retention 24 hours;
C) after anaerobic treatment finishes, liquid is delivered to the aeration tank, the controlled liq temperature is 20-30 ℃, in COD: N: P=250: 5: 1 ratio is added nitrogen phosphorus source, and adjustings pH is 6-7.5, and adding is had a liking for the salt-durable microbe flora and carried out one section aerobic treatment, aeration agitation, hydraulic retention enters two sections aerobic treatment after 24 hours, aeration agitation, hydraulic retention 24 hours;
D) precipitation, the supernatant water outlet.
Further, among the step a, press Ca (OH) 2: H +Mol ratio be 1-1.2: 2 ratio adds Ca (OH) in wastewater from chemical industry 2
The method that the present invention handles waste water mainly comprises Ca (OH) 2Pre-treatment, anaerobic treatment, two sections steps such as aerobic treatment.Acid organic chemical waste water is being carried out Ca (OH) 2Most of sulfate radical and H are removed in pre-treatment +After, by the wastewater treatment microbial main body and the operating parameters factor are controlled, formation is the anaerobism method of wastewater treatment of advantage with the anaerobic bacterium and is treated to main aerobic aeration treatment process to have a liking for the salt aerobic microbiological, is specially adapted to handle the organic chemical waste water of high COD, high sulfate radical, low pH.
The inventive method has overcome the drawback that traditional anaerobic and aerobic are handled high sulfate concentration waste water.Utilize Ca (OH) 2Remove most of sulfate radical and H simultaneously +, utilize the sulphate reducing bacteria flora simultaneously and have a liking for the salt-durable microbe flora and carry out anaerobic and aerobic respectively and handle to remove COD, make water outlet after the processing (former water COD 〉=20,000mg/L) reach three grades of emission standards of national sewage (≤500mg/L).
The present invention has the following advantages:
1. pre-treatment is ingenious: the present invention utilizes Ca (OH) 2,, remove sulfate radical and H in the waste water simultaneously by control adding proportion and alr mode +, simple efficient; Compared with utilizing the sheet adjusting PH with base that the advantage of cost advantage and removal sulfate radical is arranged.
2. overcome sulfate radical reduction and suppress drawback: traditional wastewater treatment for high sulfate radical and high organic contamination substrate concentration, because exist sulphate reducing bacteria (SRB) anaerobic condition under to the reduction of sulfate radical, and generation hydrogen sulfide (H 2S), produced two restraining effect so anaerobism is removed COD, showed as follows: 1. sulphate reducing bacteria (SRB) is to the acid-producing bacteria (AB) of removal COD and the substrate restraining effect of methanogen (MPB); 2. sulphate reducing bacteria (SRB) hydrogen sulfide that the reduction of sulfate radical is generated is to the acid-producing bacteria (AB) of removing COD and the poisonous restraining effect of methanogen (MPB).So only be lower than 2,000mg/L, COD/SO at sulfate concentration 4 2-, could realize that anaerobism removes the COD in the waste water effectively at 〉=10 o'clock.
The bioremediation that the present invention proposes, anaerobic stages utilizes special sulphate reducing bacteria mixed strains.10, still can carry out anaerobic treatment when 000mg/L is above at sulfate concentration, COD steady removal rate 50%.
3. processing efficiency height: the bioremediation that the present invention proposes, two sections aerobic stages utilize the special salt-durable microbe flora of having a liking for, one section aerobic back COD steady removal rate 80%, through two sections aerobic back COD reach state three grade emissioning standard (≤500mg/L).
4. it is few to move operation: chemical-biological knot and method that the present invention proposes, equipment requirements is simple, only take materialization after anaerobism add aerobic treatment, technology is simple, is easy to transform according to practical situation.
5. save cost: pretreatment stage of the present invention can reclaim gypsum (CaSO 4), reduced cost.The anaerobic and aerobic stage all adopts biological flora to handle, and takes up an area of and lacks, and operation is few, and cost is low.
Description of drawings
Fig. 1 is to use the inventive method to carry out the schematic flow sheet of wastewater treatment;
Wherein, the 1-water inlet, the 2-mechanical stirring, the 3-pretreatment pool, the 4-anaerobic reactor, the 5-aeration tank, one section of 6-is aerobic, and two sections of 7-are aerobic, the 8-water outlet.
Embodiment
Embodiment 1
The production of products such as cosmetic material, lubricating oil additive mainly is engaged in certain chemical plant, and the principal pollutant in its waste water are organism such as alcohols, fatty acid sodium salt and fatty acid ester.The factory effluent complicated component, the pollution load height is acid.Former process using sheet adjusting PH with base, the cost height, and big to the anaerobic stages inhibition, water outlet is defective.
Adopt the inventive method, press Ca (OH) 2: H +Mol ratio be that 1: 2 ratio adds Ca (OH) in wastewater from chemical industry 2, stirring reaction, adjust pH are removed most of sulfate radical and H to 6.7-7.5 +, going precipitation after static one hour, supernatant liquor is delivered to anaerobic reactor.The controlled liq temperature is 10-30 ℃, and in COD: N: P=450: 5: 1 ratio is added nitrogen phosphorus source, and adjustings pH is 7-8, and adding sulfate reduction flora carries out anaerobic treatment, hydraulic retention 24 hours; After anaerobic treatment finishes, liquid is delivered to the aeration tank, the controlled liq temperature is 20-30 ℃, and in COD: N: P=250: 5: 1 ratio is added nitrogen phosphorus source, and adjusting pH is 6-7.5, adding is had a liking for the salt-durable microbe flora and is carried out one section aerobic treatment, aeration agitation, hydraulic retention enter two sections aerobic treatment after 24 hours, do not need to add nutritive substance, aeration agitation, hydraulic retention 24 hours; Water outlet enters settling tank, the water outlet of post precipitation supernatant.
Present embodiment utilizes existing facility, through pre-treatment, anaerobic treatment, and two sections aerobic treatment, water outlet is qualified.Every index is as shown in the table:
Desired value before and after certain chemical plant wastewater of table one is handled
Figure GSA00000122688200061
The inventive method has overcome the drawback that traditional anaerobic and aerobic are handled high sulfate concentration waste water.Utilize Ca (OH) 2Remove most of sulfate radical and H simultaneously +Utilize the sulphate reducing bacteria flora simultaneously, with have a liking for the salt-durable microbe flora and carry out anaerobic and aerobic respectively and handle to remove COD, make water outlet (former water COD 〉=20 after the processing, 000mg/L) reach three grades of emission standards of national sewage (≤500mg/L), be specially adapted to handle the organic chemical waste water of high COD, high sulfate radical, low pH.

Claims (2)

1. a high COD, the acid organic chemical waste water treatment process of high concentration sulphate is characterized in that may further comprise the steps:
A) in wastewater from chemical industry, add Ca (OH) 2, stirring reaction, adjust pH are removed most of sulfate radical and H to 6.7-7.5 +, going precipitation after static one hour, supernatant liquor is delivered to anaerobic reactor;
B) the controlled liq temperature is 10-30 ℃, and in COD: N: P=450: 5: 1 ratio is added nitrogen phosphorus source, and adjustings pH is 7-8, and adding sulfate reduction flora carries out anaerobic treatment, hydraulic retention 24 hours;
C) after anaerobic treatment finishes, liquid is delivered to the aeration tank, the controlled liq temperature is 20-30 ℃, in COD: N: P=250: 5: 1 ratio is added nitrogen phosphorus source, and adjustings pH is 6-7.5, and adding is had a liking for the salt-durable microbe flora and carried out one section aerobic treatment, aeration agitation, hydraulic retention enters two sections aerobic treatment after 24 hours, aeration agitation, hydraulic retention 24 hours;
D) precipitation, the supernatant water outlet.
2. high COD as claimed in claim 1, the acid organic chemical waste water treatment process of high concentration sulphate is characterized in that, among the step a, press Ca (OH) 2: H +Mol ratio be 1-1.2: 2 ratio adds Ca (OH) in wastewater from chemical industry 2
CN 201010174616 2010-05-17 2010-05-17 Method for treating organic chemical wastewater having high COD and high concentration of sulfate ions Pending CN101838083A (en)

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CN104609541A (en) * 2013-11-05 2015-05-13 中蓝连海设计研究院 Sebacic acid wastewater direct biochemical treatment method without desalination
CN105254139A (en) * 2015-11-23 2016-01-20 刘树芹 Treating method for high-salinity pharmaceutical wastewater
CN105948255A (en) * 2016-06-23 2016-09-21 浙江微技环境修复工程有限公司 Treatment method and system for treating high-concentration polymyxin sulfate fermentation wastewater
CN105984999A (en) * 2015-03-04 2016-10-05 济南齐源环保工程有限公司 Treatment technology for biodiesel wastewater
CN106746162A (en) * 2015-11-19 2017-05-31 中国石油化工股份有限公司 A kind of processing method of cellulose ethanol production wastewater
CN107226592A (en) * 2017-07-24 2017-10-03 上海问鼎环保科技有限公司 A kind of lead salt produces the handling process of waste water
CN108918811A (en) * 2018-07-27 2018-11-30 玖龙纸业(沈阳)有限公司 A kind of test method that detection chemical industry auxiliary material influences anaerobic-aerobic
CN109354329A (en) * 2018-12-10 2019-02-19 河北旭杰环境工程有限公司 The processing method of high-sulfate, high-COD waste water
CN109425549A (en) * 2017-08-21 2019-03-05 北新集团建材股份有限公司 A method of analysis grade of gypsum
CN109694164A (en) * 2019-02-24 2019-04-30 内蒙古拜克生物有限公司 A kind of recovery and treatment method of span amino acid mother liquor
CN111606513A (en) * 2020-05-29 2020-09-01 安庆丰源化工有限公司 Method for treating high-COD high-concentration sulfate radical acidic organic chemical wastewater

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CN115594319A (en) * 2021-06-28 2023-01-13 中国石油化工股份有限公司(Cn) Treatment method of high-sulfate organic wastewater

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CN1522973A (en) * 2003-09-04 2004-08-25 哈尔滨工业大学 Alcohol type fermenting organism desulfurization method for treating sulfate organic wastewater
CN101148303A (en) * 2006-09-24 2008-03-26 江苏博大环保股份有限公司 Oil field re-injection water microbiological treatment
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104609541A (en) * 2013-11-05 2015-05-13 中蓝连海设计研究院 Sebacic acid wastewater direct biochemical treatment method without desalination
CN104609541B (en) * 2013-11-05 2016-05-25 中蓝连海设计研究院 The direct biochemical processing method of a kind of decanedioic acid not desalination of waste water
CN105984999A (en) * 2015-03-04 2016-10-05 济南齐源环保工程有限公司 Treatment technology for biodiesel wastewater
CN106746162A (en) * 2015-11-19 2017-05-31 中国石油化工股份有限公司 A kind of processing method of cellulose ethanol production wastewater
CN105254139A (en) * 2015-11-23 2016-01-20 刘树芹 Treating method for high-salinity pharmaceutical wastewater
CN105948255A (en) * 2016-06-23 2016-09-21 浙江微技环境修复工程有限公司 Treatment method and system for treating high-concentration polymyxin sulfate fermentation wastewater
CN107226592A (en) * 2017-07-24 2017-10-03 上海问鼎环保科技有限公司 A kind of lead salt produces the handling process of waste water
CN109425549A (en) * 2017-08-21 2019-03-05 北新集团建材股份有限公司 A method of analysis grade of gypsum
CN108918811A (en) * 2018-07-27 2018-11-30 玖龙纸业(沈阳)有限公司 A kind of test method that detection chemical industry auxiliary material influences anaerobic-aerobic
CN109354329A (en) * 2018-12-10 2019-02-19 河北旭杰环境工程有限公司 The processing method of high-sulfate, high-COD waste water
CN109694164A (en) * 2019-02-24 2019-04-30 内蒙古拜克生物有限公司 A kind of recovery and treatment method of span amino acid mother liquor
CN111606513A (en) * 2020-05-29 2020-09-01 安庆丰源化工有限公司 Method for treating high-COD high-concentration sulfate radical acidic organic chemical wastewater

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