CN104556529A - A treating method of nitrile-containing wastewater - Google Patents
A treating method of nitrile-containing wastewater Download PDFInfo
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- CN104556529A CN104556529A CN201310471732.4A CN201310471732A CN104556529A CN 104556529 A CN104556529 A CN 104556529A CN 201310471732 A CN201310471732 A CN 201310471732A CN 104556529 A CN104556529 A CN 104556529A
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- waste water
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Abstract
A treating method of nitrile-containing wastewater is provided. The nitrile-containing wastewater is subjected to pretreatment by adding hydrogen peroxide and a ferrous sulfate solution to oxidize and remove refractory organic compounds, wherein the reaction pH is 3-5, the mass ratio of the nitrile-containing wastewater, the hydrogen peroxide and the ferrous sulfate is 1: 0.003-0.005: 0.006-0.008, the reaction temperature is 20.0-45.0 DEG C, and the reaction time is 1.0-2.0 h. The method is capable of largely reducing the adding amount of a catalyst, largely reducing the sludge producing amount of traditional techniques, and reducing the running cost. In addition, parts of refractory macromolecule organic compounds are oxidized into organic compounds with low molecular weights, thus increasing B/C of the wastewater and improving biodegradability of the wastewater.
Description
Technical field
The present invention relates to a kind for the treatment of process containing nitrile trade effluent, particularly utilize heterocatalysis process containing the method for nitrile trade effluent.
Technical background
Nitrilon waste water process is an importance of petrochemical complex Pollution abatement and control.China has many acrylic fiber production process enterprises to adopt wet process technique, and the waste water of discharge mainly contains acidic and alkaline waste water and containing nitrile waste water two kinds, the latter contains the pollutents such as oligoacrylonitrile, is difficult point and the emphasis of process up to standard.This wastewater biodegradability is poor, and in characteristic contamination, effective removal of oligopolymer, NaSCN, total nitrogen (based on vinyl cyanide AN) has more highly difficult, and individual curing qualified discharge difficulty is large.
That produces wet spinning acrylic fiber both at home and abroad has carried out a large amount of experimental studies containing nitrile wastewater treatment, treatment process mainly contains: chemical method (chemical coagulation, chemical oxidation and Inner electrolysis), biological process (SBR method, biological contact oxidation process, pressurization aerobic biochemical process, acidization pre-treatment, biological filtering tower combined working and the special bacterial classification of interpolation), physico-chemical processes (millipore filtration and absorption), but single treatment process is difficult to effectively process waste water.At present, the development trend containing nitrile wastewater treatment is the effective pretreatment technology technology of exploitation, strengthens the removal effect of its characteristic contamination (as oligopolymer) and significantly improves B/C ratio, being conducive to the efficiency improving follow-up biochemical treatment.Existing treatment process technology be in and coagulation, biological filtering tower combined working, catalytic oxidation.Although these methods have obtained in acrylic fiber production process enterprise and applied widely, some problems also existed, have been mainly manifested in: process water outlet is difficult to up to standard, and except CODCr, in water outlet, ammonia-nitrogen content is also higher; Overstand, cause initial investment and working cost too high.
As can be seen here, the content containing the CODcr of nitrile method of wastewater treatment process water outlet and ammonia nitrogen that prior art provides is still higher, is difficult to reach pollutant emission standard requirement.
Summary of the invention
The invention provides a kind for the treatment of process containing nitrile waste water, pretreatment unit is added before wastewater treatment, the method of heterocatalysis is adopted to carry out pre-treatment to containing nitrile waste water, technical problem to be solved is efficient degradation Nitrilon waste water characteristic contamination, significantly improve biodegradability energy, and by qualified discharge after biological contact oxidization treatment.Reduce processing cost, to make up the deficiencies in the prior art.
Below technical scheme of the present invention:
1) heterogeneous catalytic reaction device is entered containing nitrile waste water, add hydrogen peroxide and copperas solution and carry out pre-treatment to containing nitrile waste water, oxidation removal hardly degraded organic substance, pH value in reaction is 3 ~ 5, be 1:0.003 ~ 0.005:0.006 ~ 0.008 containing nitrile waste water and hydrogen peroxide, ferrous sulfate mass ratio, temperature of reaction is 20.0 ~ 45.0 DEG C, and the reaction times is 1.0 ~ 2.0 hours;
2) after heterogeneous catalytic reaction outlet, waste water enters the unnecessary hydrogen peroxide of the degassed removing of medial launder, then enter neutralizing well waste water ph to control to be 6 ~ 9, enter coagulation tank again to add polymeric flocculant polyacrylamide (PAM) and carry out coagulation, the add-on of PAM is 0.5 ~ 1.5 mg/litre, then enters the pollutent that reaction removed by settling vessel;
3) settling vessel supernatant liquor enters active sludge treatment unit and carries out wastewater treatment, and water outlet reaches emission request.
Above-mentioned steps 1) described hydrogen peroxide concentration is 20% ~ 40%, ferrous sulfate concentration is 20% ~ 30%;
Above-mentioned steps 1) described pH value in reaction is preferably 3.5 ~ 4.5,1:0.0035 ~ 0.0045:0.0065 ~ 0.0075 is preferably containing nitrile waste water and hydrogen peroxide, ferrous sulfate mass ratio, temperature of reaction is preferably 25.0 ~ 40.0 DEG C, and the reaction times is preferably 1.1 ~ 1.8 hours;
Above-mentioned steps 2) described neutralizing well waste water ph controls to be preferably 7 ~ 8;
Above-mentioned steps 2) add-on of described PAM is preferably 0.6 ~ 1.2 mg/litre;
Above-mentioned steps 3) described active sludge treatment unit comprises an aeration workshop section, aeration tank F/M=0.331kg/kg, and it is 0.5 ~ 6.5mg/L that dissolved oxygen controls, and residence time control is 6 ~ 72hr, and excess sludge processes.
Contriver finds after deliberation by hydrogen peroxide and catalyst Fe
2+the oxidation system formed.Its essence is in acid condition, hydrogen peroxide is by ferrous ion catalytic decomposition thus produce the very high oxidizing species-hydroxyl radical free radical of reactive behavior, causes and propagates radical chain reaction, accelerating the oxidation Sum decomposition of organism and reducing substances.PH is regulated after oxygenizement completes, make whole solution alkaline, iron ion forms molysite flocks in the solution of alkalescence, residual organic substances in solution and heavy metal adsorption can be precipitated, and therefore heterocatalysis of the present invention is actual is oxidation and the acting in conjunction of absorption and coagulation.
In addition, except by oxygenizement organics removal in the present invention, the absorption and coagulation effect organics removal of iron ion complex compound can also be passed through.What play a major role in coagulation process is the complex compound of ferric ion.Namely in heterocatalysis, first, adding along with hydrogen peroxide in reaction, Fe
2+fe is become by rapid oxidation
3+and discharge the very strong OH of oxidation capacity, the Fe of generation
3+with aquatic products unboiled water solution-polyreaction, in its hydrolytic process, some organic pollutants is removed by absorption and coagulation.Fe
3+hydrolyzation morphology control to a great extent organic pollutant Coagulation and Adsorption mechanism.Ferric ion is progressively hydrolyzed into rudimentary polymeric form by free ion state, is hydrolyzed into the multinuclear Fe of high-polymerization degree subsequently successively
3+polymkeric substance, wherein some is separated out with precipitation forms.The hydrolytic process of this hydrolytic process and general molysite is similar.This coagulation had, precipitation function are the important component parts of organics removal.Many scholars find under study for action, coagulation process to organic clearance higher than general coagulating agent.The Fe that reaction generates
3+there is stronger hydrolysis core flocculation ability.This has two reasons: one is because the Fe of harsh product
3+not with other negatively charged ion generation complex reactions in solution and directly by hydroxyl complexing, decrease the replacement process of hydroxyl and other negatively charged ion, thus accelerate hydrolysis reaction; Two is because the hydroxyl radical free radical of heterogeneous catalytic reaction generation and Fe
3+carry out complexing by ol bridge and accelerate hydrolysis.
Compared with prior art, the invention has the advantages that:
1) heterocatalysis treating processes, significantly can reduce the chemical feeding quantity of catalyzer, also greatly reduces the mud generation of conventional art, reduces working cost.
2) larger molecular organics of part difficult degradation is oxidized to small organic molecule, thus improves the B/C of waste water, strengthens the biodegradability of waste water.
Embodiment
[embodiment 1 ~ 8, comparative example 1 ~ 2]
In each embodiment, in comparative example, each Con trolling index of waste water is taked to measure with under type:
COD
crclearance definition and NH
3-N clearance definition is respectively:
In each embodiment, containing nitrile influent waste water water quality be:
COD:800 ~ 1200 mg/litre, ammonia nitrogen: 62 ~ 76 mg/litre, pH value 3 ~ 5
Wastewater Treated by Activated Sludge Process unit, operation process condition is:
Dissolved oxygen: 0.5 ~ 6.5 mg/litre
Hydraulic detention time: 6 ~ 72 hours
Temperature: 15 ~ 35 DEG C
Adopt 30% hydrogen peroxide, 25% copperas solution, each embodiment, comparative example treatment process condition, in table 1, the results are shown in Table 2.
Table 1
Table 2
Although preferred embodiment discloses as above by the present invention; so itself and be not used to limit content of the present invention; anyly be familiar with this those skilled in the art; not departing from main spirits of the present invention and context; when doing various change and retouching, the protection domain therefore invented should be as the criterion with the basic right claimed range applied for a patent.
Claims (8)
1., containing a treatment process for nitrile waste water, it is characterized in that, the method comprises the steps:
1) heterogeneous catalytic reaction device is entered containing nitrile waste water, add hydrogen peroxide and copperas solution and carry out pre-treatment to containing nitrile waste water, oxidation removal hardly degraded organic substance, pH value in reaction is 3 ~ 5, be 1:0.003 ~ 0.005:0.006 ~ 0.008 containing nitrile waste water and hydrogen peroxide, ferrous sulfate mass ratio, temperature of reaction is 20 ~ 45 DEG C, and the reaction times is 1.0 ~ 2.0 hours;
2) after heterogeneous catalytic reaction outlet, waste water enters the unnecessary hydrogen peroxide of the degassed removing of medial launder, then enter neutralizing well waste water ph to control to be 6 ~ 9, enter coagulation tank again to add polymeric flocculant polyacrylamide (PAM) and carry out coagulation, the add-on of PAM is 0.5 ~ 1.5 mg/litre, then enters the pollutent that reaction removed by settling vessel;
3) settling vessel supernatant liquor enters active sludge treatment unit and carries out wastewater treatment, and water outlet reaches emission request.
2. a kind for the treatment of process containing nitrile waste water according to claim 1, to it is characterized in that described in step 1) containing nitrile waste water and hydrogen peroxide, ferrous sulfate mass ratio being 1:0.0035 ~ 0.0045:0.0065 ~ 0.0075, temperature of reaction is 25 ~ 40 DEG C, and the reaction times is 1.1 ~ 1.8 hours.
3. a kind for the treatment of process containing nitrile waste water according to claim 1, is characterized in that pH value in reaction described in step 1) is 3.5 ~ 4.5.
4. a kind for the treatment of process containing nitrile waste water according to claim 1, is characterized in that hydrogen peroxide concentration described in step 1) is 20% ~ 40%.
5. a kind for the treatment of process containing nitrile waste water according to claim 1, is characterized in that copperas solution concentration described in step 1) is 20% ~ 30%.
6. a kind for the treatment of process containing nitrile waste water according to claim 1, is characterized in that step 2) described neutralizing well waste water ph controls to be 7 ~ 8.
7. a kind for the treatment of process containing nitrile waste water according to claim 1, is characterized in that step 2) add-on of described PAM is 0.6 ~ 1.2 mg/litre.
8. a kind for the treatment of process containing nitrile waste water according to claim 1, it is characterized in that active sludge treatment unit described in step 3), aeration tank F/M=0.331kg/kg, it is 0.5 ~ 6.5mg/L that dissolved oxygen controls, residence time control is 6 ~ 72hr, and excess sludge processes.
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| CN201310471732.4A CN104556529A (en) | 2013-10-11 | 2013-10-11 | A treating method of nitrile-containing wastewater |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050109694A1 (en) * | 2003-11-21 | 2005-05-26 | Industrial Technology Research Institute | Method and system for treating wastewater containing organic compounds |
| CN202529945U (en) * | 2011-12-15 | 2012-11-14 | 中国石油天然气股份有限公司 | Wastewater treatment system for acrylonitrile and acrylic fiber device |
| CN103086576A (en) * | 2013-02-28 | 2013-05-08 | 北京凯易信环境科技有限公司 | Acrylonitrile/acrylon production comprehensive wastewater treatment technique |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050109694A1 (en) * | 2003-11-21 | 2005-05-26 | Industrial Technology Research Institute | Method and system for treating wastewater containing organic compounds |
| CN202529945U (en) * | 2011-12-15 | 2012-11-14 | 中国石油天然气股份有限公司 | Wastewater treatment system for acrylonitrile and acrylic fiber device |
| CN103086576A (en) * | 2013-02-28 | 2013-05-08 | 北京凯易信环境科技有限公司 | Acrylonitrile/acrylon production comprehensive wastewater treatment technique |
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Application publication date: 20150429 |