CN102659260B - Advanced treatment method for effluent of vinasse wastewater or starchiness raw material biochemical engineering wastewater subjected to biochemical treatment - Google Patents
Advanced treatment method for effluent of vinasse wastewater or starchiness raw material biochemical engineering wastewater subjected to biochemical treatment Download PDFInfo
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Abstract
The invention discloses an advanced treatment method for effluent of vinasse wastewater or starchiness raw material biochemical engineering wastewater subjected to biochemical treatment, and relates to the technical field of wastewater treatment. The advanced treatment method comprises the following steps of: adding biochemical effluent into a pH adjusting tank, and adding acid to adjust the pH value to 5 to 6, and adding a catalyst and a strong oxidant; performing air aeration oxidation treatment on the wastewater in an oxidation tank by using an aeration device, and performing the air aeration oxidation treatment continuously for 0.5 to 6 hours; adding effluent of the oxidation tank into the pH adjusting tank, and adding alkali to adjust the pH value of the wastewater to 6 to 9; adding the wastewater of which the pH value is adjusted to be 6 to 9 into a flocculation reaction tank, and adding a flocculant simultaneously; and precipitating the wastewater for 4 to 6 hours. Chemical xygen demand (COD) of a liter of wastewater treated by the advanced treatment method is less than 50 mg, the chroma removal rate of the wastewater is more than or equal to 99 percent, and a chroma index of water quality is less than 10 times. The advanced treatment method is low in treatment cost, high in treatment efficiency, low in investment and convenient to popularize and use, runs stably and can be used in large scale.
Description
Technical field
The present invention relates to technical field of waste water processing, particularly relate to a kind for the treatment of process of the water outlet behind biochemistry to distillery waste water or starchy material biochemical industry waste water.
Background technology
Starchy material comprises farm crop and the cash crop of rich in starch such as corn, Ipomoea batatas, cassava, potato.
China is the biochemical industry industry process long-run development of main raw material(s) with starch, existing certain basis.Particularly after the reform and opening-up, the development of biochemical industry has entered a brand-new stage.At present, the biochemical industry product has related to several aspects such as food, medicine, health care, feed and organic acid.But along with the development of biochemical industry, its problem of environmental pollution also is on the rise, and it has become the environmental pollution rich and influential family of China.In the industry-by-industry of biochemical industry, because starch, beer, alcohol, monosodium glutamate, citric acid, the antibiotic output value are bigger, environmental pollution is serious, causes that especially people pay attention to.Wherein the quantity discharged of wastewater from starch industry accounts for the first place.China's starch industry has 600 many enterprises.At home, 1 ton of starch of every production will produce 10-20m
3Waste water is that have even more.Mainly contain pollutents such as starch, carbohydrate, protein, spent acid and salkali waste in the waste water, with the difference of production technique, the COD concentration in the waste water is between 2000-20000mg/l.Be the biological fermentation product of main raw material(s) with starch particularly, produce high density degradation of organic substances waste water in process of production, be mainly the material that produces some ring-types, larger molecular weight in the further chiral process of biological fermentation and leavened prod.
The starch processing waste water is mainly derived from raw-material soaking and washing, pulverizes operations such as separation, fiber cleaning, dehydration; Waste water in the Alcohol Production process is mainly poor from the alcohol of discharging after the distillation fermenting-ripening wine with dregs, the washing water of production unit, wash-down water, and the water coolant of boiling, saccharification, fermentation, distil process etc.Starch biochemical industry waste water is mainly derived from the waste water that produces in starch biological fermentation product separation, purification, the chemical reaction process.The concentration of such waste water is higher, colourity is high, suspension object height, good biodegradability.At present, the main treatment process of such waste water is: anaerobism+aerobic+materialization advanced treatment, but the effluent COD concentration after biochemical treatment reduces significantly, but water quality biochemical variation, contain a large amount of hardly degraded organic substances, the water yield is bigger simultaneously, and COD and chromaticity index all can not reach existing emission standard requirement.The existing advanced treatment of this class waste water adopts the materialization adding method thereof more, exists the poor stability of investment, running cost height or system always, can not stably reaching standard etc. problem.Therefore, how effectively removing residual hardly degraded organic substance, reach the emission request of new standard, is the problem that presses for solution.
Domestic publish can following report once be arranged at the document of distillery waste water or the wastewater treatment of starchy material biochemical industry.Gansu Province environmental science design and research institute adopts Fenton reagent oxidation method to handle yam starch waste water (environmental science and technology, 2011 the 24th volume A01 phases), this technology is to be applied in the preprocessing process of yam starch waste water, uses the starch processing of Fenton reagent oxidation method advanced treatment and starch deep processed product processing wastewater and does not see relevant report through bio-chemical effluent.
Domestic and foreign literature has in a large number about improving the report of Fenton method, the method of the plural serial stage reactor of for example mentioning among the CN200810119444.1 or single-stage flow reactor multi-point adding medicament, this method is still undesirable to the clearance of COD and colourity, particularly be applied to distillery waste water or starchy material biochemical industry waste water on the advanced treatment of water outlet behind the biochemistry, can't reach COD less than 50mg/L, colourity is less than 10 times requirement.And exist the defective of the poor stability of investment, running cost height or system.
In sum, no matter be that the Fenton oxidizing process is used or the improvement technology of Fenton method in the pre-treatment of yam starch, all exist in the advanced treatment process of water outlet behind biochemistry at distillery waste water or starchy material biochemical industry waste water and can not satisfy the environmental protection new-standard requirement that improves day by day, and have problems such as running cost height or fluctuation of service.
Summary of the invention
The objective of the invention is to solve distillery waste water or the water outlet behind biochemistry of starchy material biochemical industry waste water, COD concentration is at 100-400mg/L, colourity is not up to standard, water outlet is difficult to further degraded if carry out biochemical treatment again, present method reaches COD less than the 50mg/L emission request after by one or more levels oxide treatment, and chroma removal rate reaches 99%, and effluent color dilution is lower than 10 times, and stable effluent quality, running cost is low.
The present invention is used for the treatment process of distillery waste water and the water outlet behind biochemistry of biochemical industry waste water thereof, comprises following processing step:
(1) bio-chemical effluent enters the PH equalizing tank and adds acid and adjust PH to 5-6, adds catalyzer and strong oxidizer simultaneously;
(2) with aerating apparatus the waste water of oxidation pond is carried out the air aeration oxide treatment, continue air aeration oxide treatment 0.5-6 hour;
(3) the oxidation pond water outlet enters the PH equalizing tank and adds alkali and adjust the waste water pH value to 6-9;
(4) the adjustment pH value enters flocculation tank to the waste water of 6-9, adds flocculation agent simultaneously;
(5) wastewater sedimentation 2-6 hour.
Described waste water comprises that to cassava, Ipomoea batatas, corn, potato be the waste water of raw material starch producing, and be that starch material carries out the waste water that produces in biological fermentation and the fermentation deep processing technology process with it, comprise with cassava, Ipomoea batatas, corn, potato being that starch material matter prepares microbiotic such as alcohol, Avrmectin, terramycin, Streptomycin sulphate, the waste water that needs advanced treatment process to handle after the waste water process routine biochemistry system handles that produces in the process for organic acid processes such as L-glutamic acid citric acid.
Describedly add acid to adjust PH used acid in the 5-6 technology be a kind of in hydrochloric acid, sulfuric acid, phosphoric acid, organic acid, the sulfur waste acid that contains iron ion or the abraum salt acid solution, or two or more mixtures; Preferably contain sulfur waste acid or the abraum salt acid of iron ion.
Described catalyzer is the salt of iron content or the spent acid of iron content, namely contains ferrous iron or ferric iron molysite and polymeric ferric salt, polymeric aluminum molysite, pipe mill's pickle solution etc.
Described oxygenant is hydrogen peroxide.
Describedly add alkali to adjust waste water pH value used alkali in the 6-9 technology be white lime, caustic soda or soda ash.
Described flocculation agent is cationic, non-ionic type or anion-polyacrylamide, or other macromolecule organic flocculating agent.
Described air aeration oxidation processing technique contains secondary and multi-stage oxidizing mode, preferably adopts the multi-stage oxidizing mode.
Technology of the present invention can be added and a kind of mud that advanced treatment process produces be carried out the method for recycling treatment, and it comprises following processing step:
(1) get after the advanced treatment of the present invention chemical sludge and enter the PH equalizing tank and add acid and adjust PH to 1-2, stirring is simultaneously fully dissolved chemical sludge;
(2) the chemical sludge acid solution after the dissolving enters oxidation pond after adding oxygenant;
(3) with aerating apparatus the chemical sludge acid solution in the oxidation pond is carried out the air aeration oxide treatment, continue air aeration oxide treatment 0.5-6 hour, organic clearance can reach more than 90%;
(4) after the chemical sludge acid solution of oxidation pond outflow removes by filter insolubles, be back to use in the wastewater oxidation treatment system, use as the catalyst recirculation of wastewater oxidation treatment system.
Describedly add acid to adjust PH used acid in the 1-2 technology be hydrochloric acid, sulfuric acid, sulfur waste acid or abraum salt acid; Described oxygenant is hydrogen peroxide.
Concrete technology controlling and process of the present invention is:
Acid adjustment pH value control is at 5-6, thus greatly reduce the consumption (or replace with industrial waste acid) of acid thus reduced running cost.
Catalyzer uses salt or the spent acid of iron content, namely contain ferrous iron or ferric iron molysite and polymeric ferric salt, polymeric aluminum molysite, take full advantage of the spent acid of iron content, realized refuse reclamation, also greatly reduce simultaneously consumption and (2) the middle ferrous consumption of catalyst sulfuric acid of acid in (1), thereby significantly reduced running cost.
When adopting the reaction of secondary or multi-stage oxidizing, the pH value of stair oxidation water outlet can be controlled at 4-6, behind flocculation sediment, waste water can directly enter secondary or multi-stage oxidizing reaction, needn't add acid again and adjust pH value, thereby secondary or multi-stage oxidizing reaction have reduced the usage quantity to soda acid, thereby have significantly reduced running cost.
When carrying out one or more levels oxidizing reaction, the usage quantity of oxygenant can be added under the condition that does not increase consumption several times, thereby improved the utilization ratio of oxygenant, improve the removal efficient of Fenton oxidation, thereby also reduced running cost.
Last step water outlet in the multi-stage oxidizing reaction controls pH value at 6-9, behind flocculation sediment, and discharged wastewater met the national standard, water outlet COD is stable less than 50mg/L, and colourity is lower than 10 times.Namely the waste water of handling through the present invention can satisfy among fermentation alcohol and liquor emission of industrial pollutants standard " fermentation alcohol and liquor emission of industrial pollutants standard " the GB 27631-2011, " urban wastewater treatment firm pollutant emission standard " be middle primary standard requirement (GB18918-2002), starch industry new standard " starch industry pollution discharge standard " GB 25461-2010 requirement, the waste water specific targets are: COD is less than 50mg/L, and colourity is less than 30 times.
The present invention compares with traditional treatment process method, and the waste water quality after the processing is stable, chroma removal rate is high, running cost is low.The invention solves distillery waste water or target advanced treatment technical barrier is further carried in the water outlet behind biochemistry of starchy material biochemical industry waste water, also allow simultaneously the Fenton method veritably low cost stably move and become reality.Present device less investment, low, the stable effluent quality of running cost satisfy the requirement of through engineering approaches, are convenient to large-scale promotion application.
Description of drawings
Fig. 1 is that the embodiment of the invention 1 is handled water outlet COD removal running condition figure;
Fig. 2 is that the embodiment of the invention 1 is handled effluent color dilution removal running condition figure;
Fig. 3 is that the embodiment of the invention 2 is handled water outlet COD removal running condition figure;
Fig. 4 is that the embodiment of the invention 2 is handled effluent color dilution removal running condition figure;
Fig. 5 is that the embodiment of the invention 3 is handled water outlet COD removal running condition figure;
Fig. 6 is that the embodiment of the invention 3 is handled effluent color dilution removal running condition figure;
Fig. 7 is that the embodiment of the invention 4 is handled water outlet COD removal running condition figure;
Fig. 8 is that the embodiment of the invention 4 is handled effluent color dilution removal running condition figure;
Fig. 9 is that the embodiment of the invention 5 is handled water outlet COD removal running condition figure;
Figure 10 is that the embodiment of the invention 5 is handled effluent color dilution removal running condition figure;
Figure 11 is that the embodiment of the invention 6 is handled water outlet COD removal running condition figure;
Figure 12 is that the embodiment of the invention 6 is handled effluent color dilution removal running condition figure;
Figure 13 is the process flow sheet that the present invention is used for distillery waste water or starchy material biochemical industry waste water deep treatment method of water outlet behind biochemistry.
Embodiment
The invention will be further described below in conjunction with embodiment, but the protection domain that the present invention requires is not limited to the scope that embodiment explains.
Example 1: with cassava alcohol fermentation and series of biologic Chemicals (acetic acid, ethyl acetate, butylacetate, tetramethylolmethane, oxalic dialdehyde, phenylglycine, synthetic ammonia) waste water through biochemical system (a2/o, various forms of aerobic) water outlet after handling, COD is about 400mg/L.
The employing hydrogen peroxide is oxygenant, and catalyzer is selected pipe mill's spent acid for use, and used soda acid is the vitriol oil and sodium hydroxide.Concrete operations: (1) bio-chemical effluent enters the PH equalizing tank and adds molysite or spent acid 1000-3000ppm, add a spot of acid then and adjust PH to 5-6, add hydrogen peroxide 300-400 ppm again, oxidizing reaction 1 hour, add alkali and adjust PH to 5-6, flocculation sediment enters the secondary oxidation operation then with (1), the water outlet qualified discharge of handling.
Continuously more than the operation two weeks, stablely reach emission request, COD is lower than 50mg/L, and colourity is lower than 10 times.
Operation result as shown in Figure 1 and Figure 2.
Experiment two: with the water outlet after the processing of W-Gum fermentative production Avermectin Wastewater process biochemical system, COD=300-500mg/L.
The employing hydrogen peroxide is oxygenant, and catalyzer is selected pipe mill's spent acid for use, and used soda acid is the vitriol oil and sodium hydroxide.Concrete operations: (1) bio-chemical effluent enters the PH equalizing tank and adds molysite or spent acid 1000-3000ppm, add a spot of acid then and adjust PH to 5-6, add hydrogen peroxide 200-400 ppm again, oxidizing reaction 1 hour, add alkali and adjust PH to 5-6, flocculation sediment enters the secondary oxidation operation then with (1), and the water outlet result of handling as shown in Figure 3, Figure 4.
Experiment three: produce the water outlet of waste water after biochemical treatment that the terramycin technological process produces with W-Gum, COD is about 300mg/L, and colourity at 80-120 doubly.
It is oxygenant that present method adopts hydrogen peroxide, and catalyzer is selected pipe mill's spent acid for use, and used soda acid is the vitriol oil and sodium hydroxide.Concrete operations: (1) bio-chemical effluent water yield is 10m3/h, enter the PH equalizing tank and add molysite or spent acid 1000-3000ppm, add a spot of acid then and adjust PH to 5-6, add hydrogen peroxide 200-400 ppm again, oxidizing reaction 1 hour adds alkali and adjusts PH to 5-6, flocculation sediment, enter the secondary oxidation operation then with (1), the water outlet qualified discharge of handling.
Result such as Fig. 5, shown in Figure 6 move more than the two weeks continuously, and water outlet COD is stable to be lower than 50mg/L, and colourity is lower than 10 times.
Experiment four: produce the water outlet of waste water after biochemical treatment that produces in the Streptomycin sulphate technological process, COD=200 mg/L with W-Gum.
The employing hydrogen peroxide is oxygenant, and catalyzer is selected pipe mill's spent acid for use, and used soda acid is the vitriol oil and sodium hydroxide.Concrete operations: (1) bio-chemical effluent water yield is 20m3/h, enter the PH equalizing tank and add molysite or spent acid 1000-3000ppm, add a spot of acid then and adjust PH to 5-6, add hydrogen peroxide 200-400 ppm again, oxidizing reaction 1 hour adds alkali and adjusts PH to 5-6, flocculation sediment, enter the secondary oxidation operation then with (1), the water outlet qualified discharge of handling.
Result such as Fig. 7, shown in Figure 8: move continuously more than the two weeks, water outlet COD is stable to be lower than 50mg/L, and colourity is lower than 10 times.
Experiment five: with the water outlet of waste water after biochemical treatment that sweet potato starch and distortion starch producing technology produce, COD=100 mg/L.
The employing hydrogen peroxide is oxygenant, and catalyzer is selected pipe mill's spent acid for use, and used soda acid is the vitriol oil and sodium hydroxide.Concrete operations: (1) bio-chemical effluent water yield is 20m3/h, enter the PH equalizing tank and add molysite or spent acid 1000-3000ppm, add a spot of acid then and adjust PH to 5-6, add hydrogen peroxide 200-400 ppm again, oxidizing reaction 1 hour, add alkali and adjust PH to 5-6, flocculation sediment, the water outlet qualified discharge of handling.
Result such as Fig. 9, shown in Figure 10: move continuously more than the two weeks, water outlet COD is stable to be lower than 50mg/L, and colourity is lower than 10 times.
Experiment six: with yam starch and deep processed product processing wastewater bio-chemical effluent, COD is about 150 mg/L.
The employing hydrogen peroxide is oxygenant, and catalyzer is selected pipe mill's spent acid for use, and used soda acid is the vitriol oil and sodium hydroxide.Concrete operations: (1) bio-chemical effluent water yield is 30m3/h, enter the PH equalizing tank and add molysite or spent acid 1000-3000ppm, add a spot of acid then and adjust PH to 5-6, add hydrogen peroxide 200-400 ppm again, oxidizing reaction 1 hour adds alkali and adjusts PH to 5-6, flocculation sediment, enter the secondary oxidation operation then with (1), the water outlet qualified discharge of handling.
Result such as Figure 11, shown in Figure 12: move continuously more than the two weeks, water outlet COD is stable to be lower than 50mg/L, and colourity is lower than 10 times.
Claims (8)
1. deep treatment method that is used for distillery waste water or the water outlet behind biochemistry of starchy material biochemical industry waste water is characterized in that comprising following processing step:
(1) bio-chemical effluent enters the pH regulator pond and adds acid and adjust pH to 5-6, adds catalyzer and strong oxidizer simultaneously;
(2) with aerating apparatus the waste water of oxidation pond is carried out the air aeration oxide treatment, continue air aeration oxide treatment 0.5-6 hour;
(3) the oxidation pond water outlet enters the pH regulator pond and adds alkali and adjust waste water ph to 6-9;
(4) adjustment pH value enters flocculation tank to the waste water of 6-9, adds flocculation agent simultaneously;
(5) wastewater sedimentation 4-6 hour;
(6) get after the advanced treatment chemical sludge and enter the pH regulator pond and add acid and adjust pH to 1-2, stirring is simultaneously fully dissolved chemical sludge;
(7) the chemical sludge acid solution after the dissolving enters oxidation pond after adding oxygenant;
(8) with aerating apparatus the chemical sludge acid solution in the oxidation pond is carried out the air aeration oxide treatment, continue air aeration oxide treatment 0.5-6 hour; Organic clearance can reach more than 90%;
(9) be back to use in the in-depth treatment process system of waste water after the chemical sludge acid solution of oxidation pond outflow removes by filter insolubles, continue to use as catalyzer.
2. the deep treatment method of the water outlet behind biochemistry for distillery waste water or starchy material biochemical industry waste water as claimed in claim 1, it is characterized in that: described waste water comprises cassava, Ipomoea batatas, corn, potato is the waste water of raw material starch producing, and be that starch material carries out the waste water that produces in biological fermentation and the fermentation deep processing technology process with it, comprise with cassava, Ipomoea batatas, corn, potato is that starchy material prepares alcohol, Avrmectin, terramycin, produce in the Streptomycin sulphate technological process, through the waste water that needs advanced treatment process to handle after the routine biochemistry system handles.
3. the deep treatment method of the water outlet behind biochemistry for distillery waste water or starchy material biochemical industry waste water as claimed in claim 1 is characterized in that: describedly add acid to adjust pH used acid in the 5-6 technology be hydrochloric acid, sulfuric acid, phosphoric acid, organic acid, the sulfur waste acid that contains iron ion or abraum salt acid solution.
4. the deep treatment method of the water outlet behind biochemistry for distillery waste water or starchy material biochemical industry waste water as claimed in claim 1, it is characterized in that: described catalyzer is salt or the spent acid of iron content, namely contains ferrous iron or ferric molysite and polymeric ferric salt, polymeric aluminum molysite.
5. the deep treatment method of the water outlet behind biochemistry for distillery waste water or starchy material biochemical industry waste water as claimed in claim 1, it is characterized in that: described oxygenant is hydrogen peroxide.
6. the deep treatment method of the water outlet behind biochemistry for distillery waste water or starchy material biochemical industry waste water as claimed in claim 1 is characterized in that: describedly add alkali to adjust waste water ph used alkali in the 6-9 technology be white lime, caustic soda or soda ash.
7. the deep treatment method of the water outlet behind biochemistry for distillery waste water or starchy material biochemical industry waste water as claimed in claim 1 is characterized in that: described flocculation agent is cationic, non-ionic type or anion-polyacrylamide.
8. the deep treatment method of the water outlet behind biochemistry for distillery waste water or starchy material biochemical industry waste water as claimed in claim 1 or 2, it is characterized in that: described air aeration oxidation processing technique contains secondary and multi-stage oxidizing mode.
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| CN103663668B (en) * | 2013-11-26 | 2015-01-21 | 上海交通大学 | Chemical oxidation wastewater treatment system utilizing solar heating and treatment method |
| CN104925983B (en) * | 2014-03-20 | 2017-09-05 | 天津大学 | A kind of advanced treatment device for industrial wastewater and its method |
| CN104591440A (en) * | 2015-01-20 | 2015-05-06 | 广西中粮生物质能源有限公司 | Method for treating wastewater generated after preparing alcohol from cassavas as raw material |
| CN105565615B (en) * | 2016-03-04 | 2018-05-15 | 苏州苏沃特环境科技有限公司 | A kind of technique of pentaerythrite wastewater to reach standard processing |
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| CN101092262A (en) * | 2006-06-23 | 2007-12-26 | 哈尔滨工业大学 | Preparation method of treating wastewater from middle stage of straw pulp papermaking |
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| CN101092262A (en) * | 2006-06-23 | 2007-12-26 | 哈尔滨工业大学 | Preparation method of treating wastewater from middle stage of straw pulp papermaking |
| CN101392463A (en) * | 2008-11-07 | 2009-03-25 | 东华大学 | Soaping processing and dyeing waste water decoloring after instead of reactive dyes dyeing by using Fenton method |
| CN101525190A (en) * | 2009-02-26 | 2009-09-09 | 江苏艾特克环境工程设计研究院有限公司 | Efficient wastewater treating process based on Fenton reaction |
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