CN112707598A - Treatment process of wastewater from steroid hormone drug synthesis - Google Patents
Treatment process of wastewater from steroid hormone drug synthesis Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003814 drug Substances 0.000 title claims abstract description 16
- 239000003270 steroid hormone Substances 0.000 title claims abstract description 16
- 229940079593 drug Drugs 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 238000003786 synthesis reaction Methods 0.000 title description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 9
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- 230000016615 flocculation Effects 0.000 claims abstract description 6
- 238000010979 pH adjustment Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical group [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 8
- 230000015271 coagulation Effects 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 20
- 239000011574 phosphorus Substances 0.000 abstract description 20
- -1 steroid compounds Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000010170 biological method Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000003431 steroids Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SCUAGCXAAJTHCE-UHFFFAOYSA-N 1,3,5-tribromoimidazolidine-2,4-dione Chemical compound C1(C(=O)N(C(=O)N1Br)Br)Br SCUAGCXAAJTHCE-UHFFFAOYSA-N 0.000 description 1
- QZLYKIGBANMMBK-UGCZWRCOSA-N 5α-Androstane Chemical compound C([C@@H]1CC2)CCC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CCC[C@@]2(C)CC1 QZLYKIGBANMMBK-UGCZWRCOSA-N 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 229930003316 Vitamin D Natural products 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001780 adrenocortical effect Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003613 bile acid Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GRXPVLPQNMUNNX-MHJRRCNVSA-N estrane Chemical compound C1CC2CCCC[C@@H]2[C@@H]2[C@@H]1[C@@H]1CCC[C@@]1(C)CC2 GRXPVLPQNMUNNX-MHJRRCNVSA-N 0.000 description 1
- 239000003163 gonadal steroid hormone Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010826 pharmaceutical waste Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229930002600 steroidal saponin Natural products 0.000 description 1
- 230000003637 steroidlike Effects 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
Abstract
The invention discloses a treatment process for wastewater generated in the production of drugs for synthesizing steroid hormones, which comprises the steps of filtering the wastewater by a plate frame, adjusting the pH value of the wastewater by sulfuric acid, enabling the wastewater after the pH adjustment to enter a low-temperature wet oxidation system, adjusting the pH value of effluent after the low-temperature wet oxidation, performing flocculation precipitation on the effluent after the pH adjustment, treating the effluent after the flocculation precipitation by using anaerobic organisms, performing aerobic organisms on the effluent after anaerobic effluent, performing Fenton advanced oxidation on the aerobic effluent, and discharging the effluent after the advanced oxidation to reach the standard; the invention adopts low-temperature wet oxidation to degrade macromolecular steroid compounds into micromolecules, thereby improving the biodegradability of the wastewater, and simultaneously, organic phosphorus compounds which are difficult to degrade by an oxidation biological method are oxidized into orthophosphate so as to improve the removal effect of phosphorus. The COD of the wastewater treated by the process is less than or equal to 120mg/L, the TP of the wastewater is less than or equal to 1.0mg/L, and other pollution factors meet the discharge requirement of pharmaceutical wastewater.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a treatment process of wastewater in steroid drug synthesis production.
Background
Steroids are widely present in the organism tissue as an important class of natural organic compounds. Sterols, vitamin D, bile acids, many sex hormones, adrenocortical hormones, certain carcinogenic hydrocarbons, steroidal saponins, and steroidal alkaloids all belong to this class. Many steroids have been found to have very important physiological effects, and steroid chemistry is naturally a very interesting area for the medical and pharmaceutical industries.
Steroid compounds are mainly extracted from organisms before, and with the rapid increase of the demand of the steroid compounds, the steroid compounds are gradually shifted to artificial synthesis production, a large amount of production wastewater is generated in the artificial synthesis production process of the steroid compounds, and the wastewater components are complex; the synthesis has the residue of raw material substances, such as dipregnane, androstane, estrane and the like, which are generally ring compounds consisting of five-membered rings and six-membered rings, have high molecular weight, stable structure and difficult biodegradation, and have the residue of chemically synthesized basic compounds, such as DHEA and tribromohydantoin allyl alcohol; meanwhile, solvent substances such as DMF (N, N dimethylformamide), HMPA (hexamethylphosphoric triamide) and tetrahydrofuran are rectified and recycled, but the residual amount in the wastewater is large, so that the wastewater produced by synthesizing steroid hormone has the characteristics of high organic matter concentration, large residual molecular weight, complex and stable structure, organic phosphorus content and the like, the conventional biochemical treatment process is difficult to treat, and a mature treatment process does not exist at home and abroad at present.
Disclosure of Invention
Aiming at the technical defects that the wastewater generated in the process of synthesizing steroid hormone medicaments is not mature and is difficult to be treated by physical and biological methods, the invention provides the process for treating the wastewater generated in the process of synthesizing steroid hormone medicaments, wherein COD (chemical oxygen demand) of the wastewater treated by the process is less than or equal to 120mg/L, TP (total phosphorus) of the wastewater is less than or equal to 1.0mg/L, and other pollution factors meet the discharge requirements of pharmaceutical wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme:
a process for treating wastewater generated in the production of drugs for synthesizing steroid hormones comprises the following steps:
(1) after the wastewater is filtered by a plate frame, adjusting the pH value of the wastewater by using sulfuric acid, and enabling the wastewater after pH adjustment to enter a low-temperature wet oxidation system;
(2) performing low-temperature wet oxidation to obtain effluent, adjusting the pH value, and performing flocculation precipitation on the effluent after the pH value is adjusted;
(3) treating the effluent after flocculation precipitation by anaerobic organisms;
(4) carrying out aerobic biological treatment on the effluent after the anaerobic biological treatment;
(5) aerobic organisms are used for treating the effluent, Fenton advanced oxidation is adopted, and the effluent after advanced oxidation is discharged after reaching the standard.
Further, in the step (1), sulfuric acid is used for adjusting the pH value of the wastewater to 3.0-5.0.
Further, the low-temperature wet oxidation system in the step (1) is divided into two sections, wherein the first section is a catalytic section, the catalyst is an iron-carbon catalyst, the ratio of iron to carbon is (4-6): 1, the filling ratio (volume ratio) of iron to carbon in the reactor is 20-50%, the reaction temperature is 120-150 ℃, and the retention time is 0.5-1.0 hour; the second section is an oxidation section, the oxidant is hydrogen peroxide, and the addition amount of the hydrogen peroxide is 5.0-20% (mass ratio) of the COD amount; the reaction time is 0.5-2.5 hours, and the reaction temperature is 120-150 ℃.
Further, the effluent is subjected to low-temperature wet oxidation in the step (2), the PH of the wastewater is adjusted to 6-9 by sodium hydroxide, the effluent after the PH is adjusted is subjected to coagulation by polyaluminium chloride, polyacrylamide is used for coagulation assistance, gravity type mud-water separation is performed, and the wastewater after separation and precipitation enters anaerobic biological treatment.
Further, in the step (3), the anaerobic biological treatment adopts a UASB mode, the anaerobic treatment is carried out at moderate temperature, and the anaerobic volume load is 1.5-3.0 kgCOD/(m)3·d)；
Further, the aerobic biological treatment in the step (4) adopts an A/O process, wherein the retention time HRT of the O section process is 120-240 hours, and the retention time of the A section is increased or decreased according to the total nitrogen amount in the wastewater.
Further, the pH value of the wastewater is adjusted to 3.0-3.5 by sulfuric acid in Fenton advanced oxidation in the step (5), and H is adjusted to be 3.0-3.52O2：FeSO4·7H2The molar ratio of O is (3-5): 1, the reaction time is 3-5 hours, after the reaction is finished, the pH value is adjusted to 6-9 by sodium hydroxide, polyacrylamide is added for coagulation assistance, then, mud-water separation is carried out, and the discharge reaching the standard is realized.
The invention has the beneficial effects that: the wastewater produced by synthesizing steroid hormone medicaments can produce a large amount of solid suspended matters insoluble in water in the synthesis process, has poor gravity settling effect, adopts a plate-frame filtration mode, can basically remove the solid suspended matters in the wastewater, and avoids the influence on each subsequent treatment unit. The catalytic section of the low-temperature wet oxidation system firstly adjusts the pH value of the wastewater to 3-5 to form a primary battery with the catalyst iron carbon of the low-temperature wet oxidation to electrolyze the wastewater, becauseThe reaction temperature is higher (120-: because the catalytic section adopts the iron carbon with high iron content (iron-carbon ratio: 4-6: 1), part of Fe can be dissolved out from the iron carbon of the catalytic section2+And the phosphorus in the organic phosphorus compound is oxidized into orthophosphate which is removed by subsequent biochemical and physicochemical treatment. The waste water after wet oxidation adopts an anaerobic + A/O aerobic treatment process, the biochemical effluent adopts a Fenton oxidation advanced treatment process, the effective degradation of the waste water is realized, the COD of the waste water treated by the process is less than or equal to 120mg/L, the TP of the waste water treated by the process is less than or equal to 1.0mg/L, and other pollution factors meet the discharge requirements of pharmaceutical waste water.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
The invention further describes the invention by combining the attached figure 1, wherein the process for treating the wastewater from the production of the steroid hormone medicament comprises the following steps:
1. after the wastewater is filtered by a plate frame, the pH value of the wastewater is adjusted to 3.1 by sulfuric acid, the COD of the wastewater is 17000mg/L, the total phosphorus is 210mg/L, and the organophosphorus is 168 mg/L.
2. The wastewater of the low-temperature wet oxidation system enters a catalytic section, the iron-carbon ratio of a catalyst iron-carbon is 5:1, the filling ratio of catalytic reaction iron-carbon is 30%, the catalytic reaction temperature is 140 ℃, the reaction time is 45min, the catalyzed wastewater enters an oxidation section of the low-temperature wet oxidation, the addition of an oxidant hydrogen peroxide is 10% of the COD (chemical oxygen demand) amount (in terms of molar ratio), the reaction temperature of the oxidation section is controlled to be 140 ℃, and the reaction time is 2.0 hours. The COD13770mg/L of the wastewater after low-temperature wet oxidation is 210mg/L of total phosphorus, wherein the removal rate of organic phosphorus is 2.2mg/L, the removal rate of COD is 19 percent, and the removal rate of the organic phosphorus is 98.69 percent.
3. The PH value of the waste water after low-temperature wet oxidation is adjusted to 7 by a sodium hydroxide solution, polyaluminium chloride is added for coagulation, polyacrylamide is used for coagulation aid, then gravity sludge-water separation is carried out, the COD of the waste water after coagulation precipitation treatment is 13500mg/L, 42mg/L of total phosphorus and 2.2mg/L of organic phosphorus, the removal rate of the COD is 2%, and the removal rate of the total phosphorus is 80%.
4. Anaerobic biological treatment is carried out on the wastewater after the coagulating sedimentation treatment, an UASB reactor is adopted for anaerobic treatment, the temperature control range of the anaerobic treatment is 30-35 ℃, and the volume load of the UASB anaerobic reactor is 1.8 kgCOD/(m)3D), after treatment, the COD of the wastewater is 4700mg/L, the total phosphorus is 32mg/L, the organic phosphorus is 1.8mg/L, the removal rate of the COD is 65%, the removal rate of the total phosphorus is 24% and the removal rate of the organic phosphorus is 18%.
5. And (3) carrying out A/O aerobic biological treatment on the wastewater after the anaerobic biological treatment, and adjusting the retention time of the tank A according to the total nitrogen index of the wastewater. The retention time of the O tank is 144 hours, the COD removal rate of the wastewater treated by the A/O aerobic organisms is 376mg/L, the COD removal rate is 92%, the total phosphorus removal rate is 12mg/L, the total phosphorus removal rate is 62%, the organic phosphorus removal rate is 0.72mg/L, and the removal rate is 60%.
6. Adjusting the pH of the wastewater after biological treatment to 3.1 and H by using sulfuric acid2O2:FeSO4·7H2The molar ratio of O to 1 is 5, the addition amount of hydrogen peroxide is equivalent to the COD amount, the stirring reaction is carried out for 4 hours, the PH value is adjusted to 7.2 by sodium hydroxide, polyacrylamide is added for coagulation assistance, gravity type mud-water separation is carried out, after Fenton advanced oxidation advanced treatment, the COD of effluent is 86mg/L, the removal rate is 77.1%, the total phosphorus is 0.8mg/L, the removal rate is 94%, and organic phosphorus is not detected.
The removal effect of each section is shown in table 1 below.
TABLE 1 removal rates for each section
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A process for treating wastewater generated in the production of drugs for synthesizing steroid hormones is characterized by comprising the following steps:
(1) after the wastewater is filtered by a plate frame, adjusting the pH value of the wastewater by using sulfuric acid, and enabling the wastewater after pH adjustment to enter a low-temperature wet oxidation system;
(2) performing low-temperature wet oxidation to obtain effluent, adjusting the pH value, and performing flocculation precipitation on the effluent after the pH value is adjusted;
(3) treating the effluent after flocculation precipitation by anaerobic organisms;
(4) carrying out aerobic biological treatment on the effluent after the anaerobic biological treatment;
(5) aerobic organisms are used for treating the effluent, Fenton advanced oxidation is adopted, and the effluent after advanced oxidation is discharged after reaching the standard.
2. The process for treating wastewater from the production of steroid hormone drugs according to claim 1, wherein: in the step (1), sulfuric acid is used for adjusting the pH value of the wastewater to be 3.0-5.0.
3. The process for treating wastewater from the production of steroid hormone drugs according to claim 1, wherein: the low-temperature wet oxidation system in the step (1) is divided into two sections, wherein the first section is a catalysis section, the catalyst is an iron-carbon catalyst, the ratio of iron to carbon is (4-6): 1, the filling ratio of iron to carbon in the reactor is 20-50%, the reaction temperature is 120-150 ℃, and the retention time is 0.5-1.0 hour; the second section is an oxidation section, the oxidant is hydrogen peroxide, and the addition amount of the hydrogen peroxide is 5.0-20% of the COD amount; the reaction time is 0.5-2.5 hours, and the reaction temperature is 120-150 ℃.
4. The process for treating wastewater from the production of steroid hormone drugs according to claim 1, wherein: and (3) performing low-temperature wet oxidation to obtain effluent, adjusting the pH of the wastewater to 6-9 by using sodium hydroxide, adjusting the pH of the effluent, coagulating by using polyaluminium chloride, coagulating by using polyacrylamide, performing gravity type mud-water separation, and treating the wastewater after separation and precipitation by using anaerobic organisms.
5. The process for treating wastewater from the production of steroid hormone drugs according to claim 1, wherein: in the step (3), the anaerobic biological treatment adopts a UASB mode, the anaerobic treatment is carried out at moderate temperature, and the anaerobic volume load is 1.5-3.0 kgCOD/(m)3·d)。
6. The process for treating wastewater from the production of steroid hormone drugs according to claim 1, wherein: the aerobic biological treatment in the step (4) adopts an A/O process, wherein the retention time HRT of the O section process is 120-240 hours, and the retention time of the A section is increased or decreased according to the total nitrogen amount in the wastewater.
7. The process for treating wastewater from the production of steroid hormone drugs according to claim 1, wherein: the pH value of the wastewater is adjusted to 3.0-3.5 by sulfuric acid in Fenton advanced oxidation in the step (5), and H2O2：FeSO4·7H2The molar ratio of O is (3-5): 1, the reaction time is 3-5 hours, after the reaction is finished, the pH value is adjusted to 6-9 by sodium hydroxide, polyacrylamide is added for coagulation assistance, then, mud-water separation is carried out, and the discharge reaching the standard is realized.
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