CN116177805B - Advanced treatment method for biochemical effluent of traditional Chinese medicine extraction wastewater - Google Patents
Advanced treatment method for biochemical effluent of traditional Chinese medicine extraction wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 128
- 238000011282 treatment Methods 0.000 title claims abstract description 104
- 239000003814 drug Substances 0.000 title claims abstract description 56
- 238000000605 extraction Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000003647 oxidation Effects 0.000 claims abstract description 134
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 134
- 241001522129 Pinellia Species 0.000 claims abstract description 73
- 238000004140 cleaning Methods 0.000 claims abstract description 57
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000006228 supernatant Substances 0.000 claims abstract description 29
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 28
- 238000001556 precipitation Methods 0.000 claims abstract description 26
- 238000002791 soaking Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 239000012530 fluid Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 15
- 239000004343 Calcium peroxide Substances 0.000 claims description 12
- 235000019402 calcium peroxide Nutrition 0.000 claims description 12
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005273 aeration Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 22
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 238000006065 biodegradation reaction Methods 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000001976 improved effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229940037003 alum Drugs 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 241000205585 Aquilegia canadensis Species 0.000 description 2
- 241000334154 Isatis tinctoria Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241001061264 Astragalus Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 235000006533 astragalus Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 210000004233 talus Anatomy 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a deep treatment method of biochemical effluent of Chinese medicine extraction wastewater, which comprises the following steps: adjusting biochemical effluent of the traditional Chinese medicine extraction wastewater to be slightly acidic, adding commercial aluminum sulfate and pinellia tuber clean soaking wastewater for reaction, and then adding a first organic flocculant for primary blending precipitation to obtain a first supernatant; the first supernatant fluid sequentially passes through a primary oxidation system, a secondary oxidation system and a tertiary oxidation system, and three-stage oxidation treatment effluent is obtained after treatment; adding commercial aluminum sulfate and pinellia tuber cleaning and washing wastewater into the effluent of the three-stage oxidation treatment for reaction, and then adding a second organic flocculant for secondary blending precipitation to obtain a second supernatant; and regulating the second supernatant to be slightly alkaline, and discharging after being treated by the aeration biological filter. The invention recovers the aluminum sulfate resource in the pinellia tuber cleaning wastewater, solves the difficult problem of treating the pinellia tuber cleaning wastewater, reduces the advanced treatment cost of biochemical effluent of the traditional Chinese medicine extraction wastewater, and achieves remarkable economic benefit and environmental benefit.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a method for deeply treating biochemical effluent of traditional Chinese medicine extraction wastewater, in particular to a method for deeply treating biochemical effluent of traditional Chinese medicine extraction wastewater based on pinellia tuber cleaning wastewater recovery.
Background
Pinellia ternate is a toxic traditional Chinese medicine, and cleaning is one of means for preparing pinellia ternate decoction pieces, and wastewater generated in the production process of the pinellia ternate is pinellia ternate cleaning wastewater. According to the production process of pinellia tuber cleaning, the pinellia tuber cleaning wastewater can be divided into pinellia tuber cleaning soaking wastewater and pinellia tuber cleaning washing wastewater. The pinellia tuber clean wastewater belongs to typical organic industrial wastewater with difficult biodegradation and high concentration, and the organic matter component characteristics of the wastewater are similar to those of the traditional Chinese medicine extraction wastewater. However, compared with the traditional Chinese medicine extraction wastewater, the pinellia tuber cleaning wastewater has the characteristics of less water quantity, high alum residue and high biological toxicity. If the pinellia tuber clean wastewater is directly discharged, not only is the environment polluted, but also abundant aluminum sulfate resources in the pinellia tuber clean wastewater are wasted.
At present, pinellia tuber clean wastewater is mainly treated by a biological method, but the biological toxicity is high, so that the rapid starting and stable operation of a biological treatment system are greatly hindered, and the treatment method is always a technical problem in the pinellia tuber decoction piece wastewater treatment industry. The advanced treatment of biochemical effluent of the traditional Chinese medicine extraction wastewater is usually carried out in an oxidation treatment mode, but the advanced treatment adopts single oxidation treatment, so that the problems of high treatment cost and incomplete treatment exist.
Disclosure of Invention
In view of the above technical problems, the present invention provides a method for advanced treatment of biochemical effluent of Chinese medicine extraction wastewater, so as to at least solve some of the above mentioned technical problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for advanced treatment of biochemical effluent of Chinese medicine extraction wastewater comprises the following steps: adjusting the pH value of biochemical effluent of the traditional Chinese medicine extraction wastewater to be slightly acidic, adding commercial aluminum sulfate and pinellia ternate for cleaning and soaking wastewater for reaction, and then adding a first organic flocculant for primary blending precipitation to obtain a first supernatant;
the first supernatant fluid sequentially passes through a primary oxidation system, a secondary oxidation system and a tertiary oxidation system, and three-stage oxidation treatment effluent is obtained after treatment;
adding commercial aluminum sulfate and pinellia tuber cleaning and washing wastewater into the effluent of the three-stage oxidation treatment to react, and then adding a second organic flocculant to perform secondary blending precipitation to obtain a second supernatant;
regulating the pH value of the second supernatant to be slightly alkaline, and then discharging the second supernatant after being treated by the biological aerated filter;
wherein the primary oxidation system comprises O 3 /Fe 2+ Calcium peroxide/Oxone (i.e. potassium hydrogen peroxymonosulfate), the secondary oxidation system comprising O 3 Activated Carbon (AC)/H 2 O 2 The tertiary oxidation system comprises UV (ultraviolet)/O 3 Peroxodisulfate (PDS)/Oxone.
According to the technical scheme, the advanced treatment method for biochemical effluent of the traditional Chinese medicine extraction wastewater has at least one or a part of the following beneficial effects:
the alum residue in the pinellia tuber cleaning wastewater is high, the pinellia tuber cleaning wastewater can be used as a source of aluminum sulfate, and the water quantity of the pinellia tuber cleaning wastewater is very small compared with that of the traditional Chinese medicine extraction wastewater. Based on the two characteristics of the pinellia tuber cleaning wastewater, the pinellia tuber cleaning soaking wastewater and the pinellia tuber cleaning washing wastewater are respectively applied to primary blending precipitation and secondary blending precipitation of biochemical effluent of the traditional Chinese medicine extraction wastewater, thereby providing a place for the digestion of the pinellia tuber cleaning wastewater without affecting the stability of the treatment process of the biochemical effluent of the traditional Chinese medicine extraction wastewater, and simultaneously realizing the removal of organic matters in the biochemical effluent of the traditional Chinese medicine extraction wastewater and the pinellia tuber cleaning wastewater and the recycling of aluminum sulfate in the pinellia tuber cleaning wastewater.
Meanwhile, a multistage oxidation treatment system is adopted, and in each stage of oxidation treatment system, the generation of free radicals is promoted by adopting the combination of various oxidants and various activation means, so that the problem that the generation amount and the consumption amount of the free radicals are not matched can be effectively solved, the utilization efficiency of the free radicals is improved, further, organic matters are efficiently degraded, and the biodegradability of the organic matters, particularly the biodegradation rate of the organic matters, is obviously improved. On the basis, the aerobic biological treatment of the aeration biological filter tank is combined, so that the degradation-resistant organic matters in the biochemical effluent of the traditional Chinese medicine extracted wastewater and the pinellia tuber purified wastewater are further removed with high efficiency.
The invention not only thoroughly solves the treatment problem of pinellia tuber clean wastewater, but also recovers aluminum sulfate resources therein, reduces the cost of advanced treatment of biochemical effluent of traditional Chinese medicine extraction wastewater, and achieves remarkable economic benefit and environmental benefit.
Drawings
Fig. 1 is a schematic flow chart of a method for advanced treatment of biochemical effluent of Chinese medicine extraction wastewater in an embodiment of the invention.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
Aiming at the problems of large biotoxicity, high alum residue and more barriers in biological treatment of pinellia tuber clean wastewater and the problems of large biochemical effluent amount and high treatment cost of traditional Chinese medicine extraction wastewater, the invention provides a method for deeply treating biochemical effluent of traditional Chinese medicine extraction wastewater. Based on the characteristics that the organic matter component characteristics in the pinellia tuber cleaning wastewater are similar to those of the traditional Chinese medicine extraction wastewater, but alum residue is high and water quantity is small, the pinellia tuber cleaning wastewater is recycled and applied to the advanced treatment of biochemical effluent of the traditional Chinese medicine extraction wastewater, and aluminum sulfate resources which are rich in the pinellia tuber cleaning wastewater are utilized for coagulating sedimentation, so that effluent water meeting requirements can be realized, aluminum sulfate resources in the pinellia tuber cleaning wastewater are recycled, and the problems that the treatment of the pinellia tuber cleaning wastewater is difficult, the treatment cost of the biochemical effluent of the traditional Chinese medicine extraction wastewater is high, and the deep degradation of refractory organic matters in the pinellia tuber cleaning wastewater and the biochemical effluent of the traditional Chinese medicine extraction wastewater are difficult are solved.
Fig. 1 is a schematic flow chart of a method for advanced treatment of biochemical effluent of Chinese medicine extraction wastewater in an embodiment of the invention.
Specifically, as shown in fig. 1, the advanced treatment method of biochemical effluent of traditional Chinese medicine extraction wastewater mainly comprises the following steps: the method comprises the steps of primary blending sedimentation treatment, multistage oxidation treatment, secondary blending sedimentation treatment, pH adjustment and aeration biological filter treatment, wherein the primary blending sedimentation treatment and the secondary blending sedimentation treatment produce sludge to be subjected to uniform recovery treatment, and the following parts are described in detail:
according to an embodiment of the present invention, the primary blending precipitation process includes:
adjusting the pH value of biochemical effluent of the traditional Chinese medicine extraction wastewater to be slightly acidic, adding commercial aluminum sulfate and pinellia tuber clean soaking wastewater for reaction, and then adding a first organic flocculant for primary blending precipitation to obtain a first supernatant and primary coagulating sedimentation sludge. The traditional Chinese medicine extraction wastewater in the embodiment of the invention can be, for example, traditional Chinese medicine extraction wastewater of honeysuckle, astragalus, dyers woad leaf and the like.
Specifically, dilute sulfuric acid is utilized to adjust the pH of biochemical effluent of traditional Chinese medicine extraction wastewater to a weak acid environment of 6.0-6.2, then 240-260mg/L of commercial aluminum sulfate and pinellia tuber cleaning soaking wastewater are added into the biochemical effluent of the weak acid traditional Chinese medicine extraction wastewater under a rapid stirring state of 300-350r/min for reaction for 0.5-1min, wherein the added pinellia tuber cleaning soaking wastewater is filtrate obtained by filtering the wastewater in a soaking section of a pinellia tuber cleaning process through a sulfuric acid acidification and a 100-120-mesh filter screen, the pH value is 3.2-3.4, and the adding amount is 2-3 per mill of the water inflow of primary blending precipitation. Then adding 1.2-1.4mg/L of first organic flocculant under a slow stirring state of 40-60r/min, stopping stirring after slow stirring reaction for 10-15min, and standing for precipitation for 30-40min to obtain a first supernatant, wherein the first organic flocculant is at least one selected from polyacrylamide and polydimethyl diallyl ammonium chloride.
In the embodiment of the invention, commercial aluminum sulfate, pinellia tuber cleaning and soaking wastewater and a first organic flocculant are added into biochemical effluent of the acidified traditional Chinese medicine extraction wastewater for blending precipitation, so that part of organic pollutants in the pinellia tuber cleaning and soaking wastewater and the traditional Chinese medicine extraction wastewater effluent can be coagulated and precipitated, and preliminary removal of the organic pollutants is realized. In addition, the pinellia tuber clean soaking wastewater contains abundant aluminum sulfate resources to replace part of commercial aluminum sulfate, so that the treatment cost of biochemical effluent of the traditional Chinese medicine extraction wastewater is reduced, and the resource utilization of the pinellia tuber clean soaking wastewater is realized.
According to an embodiment of the present invention, a multi-stage oxidation process includes:
and the first supernatant sequentially passes through a primary oxidation system, a secondary oxidation system and a tertiary oxidation system, and the tertiary oxidation treated effluent is obtained after treatment.
Wherein the primary oxidation system comprises O 3 /Fe 2+ Calcium peroxide/Oxone comprising in particular 4-6mg/L O 3 Fe at 19-21mg/L 2+ 24-26mg/L of calcium peroxide and 16-18mg/L of Oxone (namely potassium hydrogen peroxymonosulfate).
The secondary oxidation system comprises O 3 Activated carbon/H 2 O 2 O-zone, in particular comprising 5-7mg/L O 3 12-14mg/L Activated Carbon (AC), 0.12-0.13 ml/L30 wt% H 2 O 2 And 15-17mg/L of Oxone.
The tertiary oxidation system comprises UV/O 3 Perdisulfate/Oxone, specifically 240-260nm UV 5-8W, 6-8mg/L O 3 16-18mg/L of peroxodisulfate and 14-16mg/L of Oxone. More specifically, the Peroxodisulfate (PDS) may be sodium peroxodisulfate used in the embodiment of the present invention, but is not limited thereto.
More specifically, 4-6mg/L of O is added to the obtained first supernatant 3 Fe at 19-21mg/L 2+ The method comprises the steps of carrying out primary oxidation treatment for 38-42min at a stirring speed of 90-110r/min by using 24-26mg/L of calcium peroxide and 16-18mg/L of Oxone, controlling the pH value of biochemical effluent of traditional Chinese medicine extraction wastewater to enable the calcium peroxide in a primary oxidation system to release hydrogen peroxide more slowly, overcoming the defect of too fast decomposition of liquid hydrogen peroxide, improving the activation efficiency and utilization rate of the primary oxidation system, solving the problem that free radicals are generated in a large amount in a short time and cannot be effectively utilized, and realizing the preliminary treatment of organic matters in the biochemical effluent of pinellia tuber cleaning soaking wastewater and traditional Chinese medicine extraction wastewaterOxidative degradation.
Then, 5-7mg/L O is added into the water after the primary oxidation treatment 3 12-14mg/L active carbon, 0.12-0.13 ml/L30 wt% H 2 O 2 And 15-17mg/L of Oxone, and carrying out secondary oxidation treatment for 26-32min at a stirring speed of 90-110r/min, wherein Active Carbon (AC) and the like are utilized to promote the generation of free radicals in a secondary oxidation system, so that degradation of refractory organic matters in the effluent of the primary oxidation treatment is further carried out, and meanwhile, the COD and chromaticity of the effluent of the secondary oxidation treatment are further obviously reduced.
Along with the reduction of the concentration and chromaticity of the organic matters in the water system of the secondary oxidation treatment, in order to further effectively degrade the residual organic matters, under the irradiation of ultraviolet light (UV) with the wavelength of 240-260nm and 5-8W, adding 6-8mg/L of O into the water of the secondary oxidation treatment 3 The method comprises the steps of performing three-stage oxidation treatment for 30-32min at a stirring speed of 90-110r/min by using 16-18mg/L of peroxodisulfate and 14-16mg/L of Oxone, and inducing further generation of free radicals by using an ultraviolet light and other activation modes, so that the concentration and chromaticity of organic matters in water produced by the three-stage oxidation treatment can be further reduced.
In the embodiment of the invention, compared with the traditional single-oxidant and single-stage oxidant adding mode, the method adopts multiple oxidants and activating means and a multi-stage oxidant adding mode to realize multi-stage oxidation, thereby effectively promoting the generation and effective utilization of free radicals, enabling each stage of oxidation treatment system to be matched with the wastewater quality in the corresponding stage of oxidation treatment area, effectively improving the degradation effect of organic pollutants in each stage of oxidation treatment area, remarkably improving the biological degradation performance of the organic matters, particularly the biological degradation rate of the organic matters, and improving the oxidation treatment efficiency of the wastewater.
According to an embodiment of the present invention, the secondary blending precipitation treatment is performed on the tertiary oxidation treatment effluent obtained after the multistage oxidation treatment, including:
adding commercial aluminum sulfate and pinellia tuber cleaning and washing wastewater into the effluent of the three-stage oxidation treatment to react, and then adding a second organic flocculant to perform secondary blending precipitation to obtain a second supernatant.
Specifically: adding 48-52mg/L of commercial aluminum sulfate and pinellia tuber cleaning and washing wastewater into the three-stage oxidation treatment effluent under the rapid stirring state of 300-350r/min, and rapidly stirring for 0.5-1min, wherein the added pinellia tuber cleaning and washing wastewater is filtrate obtained by filtering the washing section wastewater of the pinellia tuber cleaning process through a sulfuric acid acidification and a 100-120 mesh filter screen, the pH value is 3.2-3.4, and the adding amount is 3.5-4% of the water inflow of the secondary blending precipitation o . Then adding 0.35-0.45mg/L of a second organic flocculant under a slow stirring state of 40-60r/min, stopping stirring after the slow stirring reaction is carried out for 10-15min, and standing and precipitating for 30-40min to obtain a second supernatant, wherein the second organic flocculant is at least one selected from polyacrylamide and polydimethyl diallyl ammonium chloride.
In the embodiment of the invention, the commercial aluminum sulfate, the pinellia tuber cleaning and washing wastewater and the second organic flocculant are added into the tertiary oxidation treatment effluent for blending precipitation, so that partial organic matters remained in the tertiary oxidation treatment effluent can be removed, a proper place is found for the digestion of the pinellia tuber cleaning and washing wastewater while the pinellia tuber cleaning and washing wastewater is utilized to assist the traditional Chinese medicine extraction wastewater biochemical effluent for advanced treatment, the problem that the pinellia tuber cleaning and washing wastewater is difficult to treat is solved, the recycling utilization of aluminum sulfate in the pinellia tuber cleaning and washing wastewater is realized, and the treatment cost of the traditional Chinese medicine extraction wastewater biochemical effluent is also reduced.
According to the embodiment of the invention, the pH value of the supernatant liquid of the secondary blending precipitation is regulated to 7.2-7.4, and the supernatant liquid is discharged after being treated by the biological aerated filter, so that the deep purification of the pinellia tuber clean wastewater and the biochemical effluent of the traditional Chinese medicine extraction wastewater is realized, wherein the hydraulic retention time of the biological aerated filter is 2.8-2.9h, and the gas-water ratio is 3.0:1-3.5:1.
according to the embodiment of the invention, the coagulating sedimentation sludge generated in the primary blending sedimentation unit and the secondary blending sedimentation unit is discharged to the sludge treatment unit.
According to the embodiment of the invention, the advanced treatment method of the biochemical effluent of the traditional Chinese medicine extraction wastewater is suitable for treating the biochemical effluent of the traditional Chinese medicine extraction wastewater with COD of 540-560mg/L, chromaticity of 120-130 times and pH of 6-9.
The technical scheme of the invention is further described by the following specific examples. It should be noted that the following specific examples are given by way of illustration only and are not intended to limit the present invention. The experimental methods used in the following examples are conventional methods unless otherwise specified; the wastewater to be treated is biochemical effluent (honeysuckle and dyers woad leaf) of Chinese medicine extraction wastewater obtained from a certain Chinese medicine enterprise and pinellia tuber cleaning wastewater obtained from a certain toxic Chinese medicine decoction piece enterprise, and the materials, reagents, instruments and the like used are all commercially available unless specified.
Example 1: establishment of oxidation system type
Example 1-1:
adopting the advanced treatment method of the biochemical effluent of the traditional Chinese medicine extraction wastewater shown in the figure 1, firstly adjusting the pH value of the biochemical effluent of the traditional Chinese medicine extraction wastewater to 6.0 by sulfuric acid, then simultaneously adding commercial aluminum sulfate (the adding amount is 250 mg/L) and pinellia ternate clean soaking wastewater (the adding amount is 2.5 per mill of the water inflow of primary blending precipitation) into the biochemical effluent of the slightly acidic traditional Chinese medicine extraction wastewater under the rapid stirring state of 320r/min, and stirring for 0.5 min; adding polyacrylamide (PAM dosage 1.3 mg/L) under slow stirring at 50r/min, stirring for 10 min, standing for 30 min to obtain first supernatant, wherein the COD of biochemical effluent of the traditional Chinese medicine extraction wastewater is 545mg/L, chromaticity is 124 times, and pH value is 6-9.
Then, 4mg/L O was added to the first supernatant 3 Fe at 19mg/L 2+ 24mg/L of calcium peroxide and 17mg/L of Oxone are subjected to primary oxidation treatment for 40 minutes, and the stirring speed in the reaction process is 100r/min.
Subsequently, 7mg/L O was added simultaneously to the effluent of the primary oxidation treatment 3 13mg/L AC, 0.12 ml/L30 wt% H 2 O 2 Carrying out secondary oxidation treatment for 28 minutes on 15mg/L Oxone, wherein the stirring speed in the reaction process is 100r/min;
then, a UV lamp tube (250 nm, 5W) is started, and then 6mg/L O is added into the water of the secondary oxidation treatment 3 18mg/L PDS (sodium peroxodisulfate) and 15mg/L Oxone were subjected to a 30-minute tertiary oxidation treatmentThe stirring speed during the reaction was 100r/min.
Then, adding commercial aluminum sulfate (the adding amount is 50 mg/L) and pinellia tuber cleaning and washing wastewater (the adding amount is 4.0 per mill of the water inflow of the secondary blending precipitation) into the water discharged from the tertiary oxidation treatment under the rapid stirring state of 320r/min, and stirring for 0.5 min; PAM (0.4 mg/L) was added to the wastewater under slow stirring at 50r/min, stirred for 10 minutes, and then allowed to stand still for 30 minutes to obtain a second supernatant.
Finally, regulating the pH value of the second supernatant to 7.2, and discharging after the treatment of a Biological Aerated Filter (BAF), wherein the hydraulic retention time in the treatment process of the biological aerated filter is 2.9 hours, and the air-water ratio is 3.3:1.
respectively taking water samples of primary blending precipitation effluent, primary oxidation treatment effluent, secondary oxidation treatment effluent and tertiary oxidation treatment effluent, respectively standing for 30 minutes, and taking supernatant fluid for effluent quality analysis, wherein specific test results are shown in table 1:
TABLE 1
| Water sample | COD(mg/L) | Chromaticity (times) | BOD5/COD | Biodegradation rate constant (d) -1 ) |
| Inflow of water | 545 | 124 | 0.13 | 0.12 |
| First-stage blending precipitation effluent | 370 | 105 | 0.13 | 0.14 |
| Effluent from primary oxidation treatment | 324 | 92 | 0.18 | 0.21 |
| Effluent from secondary oxidation treatment | 262 | 64 | 0.25 | 0.26 |
| Three-stage oxidation treatment effluent | 146 | 26 | 0.37 | 0.53 |
As can be seen from Table 1, COD and chromaticity are remarkably reduced in the effluent after the primary oxidation treatment, the secondary oxidation treatment and the tertiary oxidation treatment, and a high organic matter degradation effect is obtained, and BOD 5 The COD and the biodegradation rate constant are obviously improved, which means that the biodegradation performance of the organic matters is obviously improved. In particular, after the three-stage oxidation treatment, the biodegradation rate constant of the effluent is increased by 104% relative to that of the effluent in the secondary oxidation zone, and the three-stage oxidation treatment is particularly remarkable in improving the biodegradation rate of the organic matters.
Further, the BAF effluent in the embodiment 1-1 is analyzed and tested, and the COD (chemical oxygen demand) of the water quality of the effluent is 26mg/L, the chromaticity is 14 times and the pH is 6-9, so that the effluent completely and stably meets the standard of the table 3 in the discharge standard of water pollutants in the pharmaceutical industry of traditional Chinese medicine (GB 21906-2008); compared with the whole method using the commercial aluminum sulfate, the blending method of the commercial aluminum sulfate and the pinellia tuber cleaning wastewater saves the cost by 1/10 to 1/8, and thoroughly solves the problem of treating the pinellia tuber cleaning wastewater.
Examples 1-2:
the operation in example 1-2 was similar to that in example 1-1, the main difference being the type of oxidizing agent in the primary oxidation system, and the water sample of the water inlet and the water after the primary oxidation treatment was allowed to stand for 30 minutes and then was examined, and the specific test results are shown in Table 2:
TABLE 2
As is clear from Table 2, during the primary oxidation treatment, O 3 Calcium peroxide, fe 2+ And the addition of the Oxone is favorable for improving the degradation effect and the biodegradability of the organic matters, and the synergistic effect of the medicaments is obvious.
Examples 1-3:
the operation in example 1-3 is similar to that in example 1-1, with the main difference being the type of oxidant in the secondary oxidation system. The water sample of the water inlet and the water treated by the secondary oxidation treatment is kept stand for 30 minutes and then is detected, and the specific test results are shown in the table 3:
TABLE 3 Table 3
As can be seen from Table 3, the secondary oxidation treatment realizes the efficient oxidation treatment of the wastewater, and the biodegradability of the organic matters is improved to a certain extent.
Examples 1 to 4:
the operation in examples 1-4 is similar to that in example 1-1, with the main difference being the type of oxidant in the tertiary oxidation system. The water sample of the water inlet and the water after the three-stage oxidation treatment is stood for 30 minutes for detection, and the specific test results are shown in table 4:
TABLE 4 Table 4
As can be seen from Table 4, the activation means such as UV and the like contribute to the mass production of free radicals, thereby improving the oxidation treatment effect of the wastewater in the tertiary oxidation zone, PDS and Oxone are two different oxidants, and are used in UV/O 3 The simultaneous addition of the two components in the/PDS/Oxone can obviously improve the degradation effect of the organic matters, and simultaneously, the biodegradation rate of the organic matters is also obviously improved.
Example 2: establishment of tertiary oxidation system
Example 2-1:
the operation in example 2-1 is similar to that in example 1-1, the main difference being in adjusting the order of the oxidation systems of the stages, wherein O 3 /Fe 2+ The primary oxidation system consisting of calcium peroxide and Oxone is named A, O 3 /AC/H2O 2 The secondary oxidation system consisting of/Oxone is named B and O 3 The three-stage oxidation system consisting of UV/PDS/Oxone is named as C, water samples of the water inflow water and the water discharged from the three-stage oxidation treatment are respectively kept stand for 30 minutes, and then supernatant liquid is taken for detection and analysis, and specific test results are shown in the following table 5:
TABLE 5
| Water sample | COD(mg/L) | Chromaticity (times) | BOD 5 /COD | Biodegradation rate constant (d) -1 ) |
| First-stage blending precipitation effluent | 370 | 105 | 0.13 | 0.14 |
| A, B and C water outlet | 146 | 26 | 0.37 | 0.53 |
| A, C and B effluent | 157 | 33 | 0.31 | 0.42 |
| C- & gt B- & gt A effluent | 198 | 52 | 0.22 | 0.16 |
| C, A and B effluent | 188 | 48 | 0.21 | 0.17 |
| B-C-A effluent | 172 | 43 | 0.23 | 0.28 |
| B- & gt A- & gt C effluent | 169 | 38 | 0.22 | 0.32 |
As is clear from Table 5, the combination order of the oxidation systems has a large influence on the organic matter removal effect, in particular, O 3 When the UV/PDS/Oxone is used as a primary oxidation system, the removal of organic matters is not facilitated, and the main reason is that the color degree of the organic matters in the water is higher, so that the working performance of ultraviolet light is influenced.
Example 2-2
The operation in example 2-2 was similar to that in example 1-1, with the main difference that the oxidation system of each stage was modified to be identical or partially identical, as follows: A-A and (2) A. Wherein O is as follows 3 /Fe 2+ The primary oxidation system consisting of calcium peroxide and Oxone is named A, O 3 /AC/H 2 O 2 The secondary oxidation system consisting of/Oxone is named B and O 3 The three-stage oxidation system consisting of UV/PDS/Oxone is named as C, water samples of the water inflow water and the water discharged from the three-stage oxidation treatment are respectively kept stand for 30 minutes, and then supernatant liquid is taken for detection and analysis, and specific test results are shown in the following table 6:
TABLE 6
As can be seen from Table 6, the use of three identical oxidation systems and two of the same oxidation systems was less efficient at removing organics than the use of three different oxidation systems.
Examples 2 to 3
The operation in example 2-3 is similar to that in example 1-1, the main difference being that the same oxidation system in each stage of oxidation system is entirely fed in the primary oxidation zone in the total of the three or two stages, wherein O is fed 3 /Fe 2+ The primary oxidation system consisting of calcium peroxide and Oxone is named A, O 3 /AC/H 2 O 2 The secondary oxidation system consisting of/Oxone is named B and O 3 The tertiary oxidation system consisting of UV/PDS/Oxone is named C, such as A+A +A or A+A the form of → B is added. Respectively standing water samples of water inlet, water outlet of primary oxidation treatment, water outlet of secondary oxidation treatment and water outlet of tertiary oxidation treatment for 30 minutes, and taking supernatant for detection and analysis, wherein specific test results are shown in the following table 7:
TABLE 7
| Water sample | COD(mg/L) | Chromaticity (times) | BOD 5 /COD | Biodegradation rate constant (d) -1 ) |
| First-stage blending precipitation effluent | 370 | 105 | 0.13 | 0.14 |
| A, B and C three-stage oxidation effluent | 146 | 26 | 0.37 | 0.53 |
| A+A.fwdarw.B two-stage oxidation system | 158 | 35 | 0.29 | 0.31 |
| A+A.fwdarw.C two-stage oxidation system | 162 | 36 | 0.26 | 0.28 |
| B+B.fwdarw.A two-stage oxidation system | 168 | 37 | 0.26 | 0.32 |
| B+B.fwdarw.C two-stage oxidation system | 179 | 41 | 0.29 | 0.30 |
| C+C.fwdarw.A two-stage oxidation system | 208 | 72 | 0.19 | 0.16 |
| C+C.fwdarw.B two-stage oxidation system | 209 | 68 | 0.21 | 0.15 |
| a+A+A stage Oxidation system | 181 | 43 | 0.25 | 0.27 |
| B+B +B first level Oxidation system | 193 | 52 | 0.22 | 0.27 |
| C+C +C first level Oxidation system | 217 | 82 | 0.20 | 0.17 |
As can be seen from Table 7, the use of the multi-point addition method of the oxidation system is more advantageous for improving the oxidation effect of wastewater than the method of adding the same total amount of the oxidation system at a single point (e.g., a two-stage oxidation system or a one-stage oxidation system, table 7). Different oxidants are adopted in each level of oxidation system, and compared with a single oxidation system, the oxidation system is more beneficial to the improvement of the oxidation effect of the wastewater and the improvement of the biological degradation performance of the organic matters.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (9)
1. A method for advanced treatment of biochemical effluent of Chinese medicine extraction wastewater comprises the following steps:
adjusting the pH value of biochemical effluent of traditional Chinese medicine extraction wastewater to be slightly acidic, adding commercial aluminum sulfate and pinellia ternate cleaning and soaking wastewater to react, and then adding a first organic flocculant to perform primary blending precipitation to obtain a first supernatant, wherein the pinellia ternate cleaning and soaking wastewater is filtrate obtained by acidifying and filtering the pinellia ternate cleaning and soaking section wastewater with sulfuric acid, and the addition amount of the commercial aluminum sulfate is 240-260mg/L;
the first supernatant fluid sequentially passes through a primary oxidation system, a secondary oxidation system and a tertiary oxidation system, and three-stage oxidation treatment effluent is obtained after treatment;
adding commercial aluminum sulfate and pinellia tuber cleaning and washing wastewater into the effluent of the three-stage oxidation treatment to react, and then adding a second organic flocculant to carry out secondary blending precipitation to obtain a second supernatant, wherein the pinellia tuber cleaning and washing wastewater is filtrate obtained by acidifying and filtering the wastewater in the washing section of the pinellia tuber cleaning process, and the adding amount of the commercial aluminum sulfate is 48-52mg/L;
regulating the pH value of the second supernatant to be slightly alkaline, and discharging after being treated by a biological aerated filter;
wherein the primary oxidation system comprises O 3 /Fe 2+ Calcium peroxide/Oxone, said secondary oxidation system comprising O 3 Activated carbon/H 2 O 2 An oxidation system comprising UV/O 3 peroxodisulfate/Oxone.
2. The method according to claim 1, wherein:
the pH value of the pinellia tuber cleaning and soaking wastewater is 3.2-3.4;
the adding amount of the pinellia tuber cleaning and soaking wastewater is 2-3 per mill of the water inflow of the primary blending precipitation.
3. The method according to claim 1, wherein:
the adding amount of the first organic flocculant is 1.2-1.4mg/L.
4. The method according to claim 1, wherein:
the primary oxidation system comprises:
4-6mg/L O 3 Fe at 19-21mg/L 2+ 24-26mg/L of calcium peroxide and 16-18mg/L of Oxone;
the secondary oxidation system comprises:
5-7mg/L O 3 12-14mg/L active carbon, 0.12-0.13 ml/L30 wt% H 2 O 2 And 15-17mg/L of Oxone;
the tertiary oxidation system comprises:
UV of 240-260nm and 5-8W, O of 6-8mg/L 3 16-18mg/L of peroxodisulfate and 14-16mg/L of Oxone.
5. The method according to claim 1, wherein:
the pH of the pinellia tuber cleaning and washing wastewater is 3.2-3.4;
the adding amount of the pinellia tuber cleaning and washing wastewater is 3.5-4 per mill of the water inflow of the secondary blending precipitation.
6. The method according to claim 1, wherein:
the adding amount of the second organic flocculant is 0.35-0.45mg/L.
7. The method according to claim 1, wherein:
the weak acidity has a pH of 6.0-6.2;
the pH of the weak alkalinity is 7.2-7.4.
8. The method according to claim 1, wherein:
the hydraulic retention time of the biological aerated filter is 2.8-2.9 hours, and the air-water ratio is 3:1-3.5:1.
9. the method according to claim 1, wherein:
the first organic flocculant and the second organic flocculant are each independently selected from at least one of the following:
polyacrylamide, polydimethyldiallyl ammonium chloride.
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