CN100443426C - Treatment method for waste water containing high content calcium and organic matter - Google Patents
Treatment method for waste water containing high content calcium and organic matter Download PDFInfo
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- CN100443426C CN100443426C CNB2005100709555A CN200510070955A CN100443426C CN 100443426 C CN100443426 C CN 100443426C CN B2005100709555 A CNB2005100709555 A CN B2005100709555A CN 200510070955 A CN200510070955 A CN 200510070955A CN 100443426 C CN100443426 C CN 100443426C
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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
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Abstract
The present invention provides a method for treating waste water having high content of calcium and organic matter. The present invention comprises the steps that the waste water to be treated passes through a regulating pool and an oil separator to remove floating oil and then enters an anaerobic reactor for processing; the pH value of anaerobic yielding water is regulated to 6 to 9, a decalcifying and iron-removing softening agent is added into the anaerobic yielding water, and then the anaerobic yielding water is deposited and separated; the softened yielding water is injected into a secondary aeration biological filtering pool to reduce COD until the yielding water meets requirements. The present invention has the characteristics of high organic matter loads, high efficiency of decalcification and iron removal, little area occupation, etc. The COD<cr> concentration of raw water which can be treated is from 10000 mg/L to 20000 mg/L, the content of calcium is from 500 mg/L to 6000 mg/L, and the content of iron is from 0 to 500 mg/L; the COD<cr> concentration of treated waste water can be reduced below 800 mg/L, the content of the calcium is reduced below 200 mg/L, and the content of iron is reduced below 10 mg/L.
Description
Technical field
The present invention relates to the method for wastewater treatment of a kind of high calcium, high organic content, particularly refinery high density electric desalting wastewater treatment method.
Background technology
The salt and the impurity that contain different quantities in the crude oil, this quality to the deep processing of crude oil and product has influence in various degree, therefore must carry out the desalination decalcification to crude oil and handle.Present crude oil desalting decalcification method is to inject water, decalcifying agent and the crude oil of crude oil through the mixing tank thorough mixing, under the effect of temperature, electric field and emulsion splitter, destroys water solution of oil then, makes water coalescent, realizes oily water separation, removes the salt in the water.The important feature of this electric desalting waste water is that the water yield is little, accounts for 2%～3% of the total wastewater flow rate in refinery; Organic calcium salt content is higher, if the crude oil calcium content is 1250 μ g/g (one of crude oil that world today's processing calcic is the highest), then the calcium content in the decalcification waste water is about 4100mg/L; Organic concentration is higher, and the CODcr value of waste water can reach mg/L up to ten thousand; The iron level height.If this high-concentration waste water directly enters the sewage-farm, a large amount of calcium iron can cause biochemical treatment system calcium deposition of iron phenomenon, causes that inorganic components raises in the active sludge, the mud mis-behave; The deposition of calcium salt and molysite pipeline, equipment surface in bio-aeration pool can be quickened the corrosion of pipe-line equipment in the pond, can make the bio-reactor volume reducing when serious.By 1,000,000 tons of/year crude capacities, the electric desalting water displacement is 50m
3/ h, the about 5000mg/L of calcium content in the water if waste water directly enters sewage work, is deposited on the CaCO in the biological tank every year
3Near 5000 tons.Therefore, be necessary the effective novel process flow process of exploiting economy, this high density electric desalting waste water carried out pre-treatment, thereby effectively reduce the content of calcium iron in the waste water, avoid the deposition of calcium iron in water processing establishment, the organic content in the waste water is reduced greatly.Waste water is mixed into the Sewage treatment systems of refinery's routine with other waste water after pre-treatment, for the steady running that guarantees refinery's Sewage treatment systems, the operation and the overhead charges that reduce Sewage treatment systems have important practical significance.
Consulted the U.S. chemical abstract database at interior domestic and international 10 patents, bibliographic data base,, do not seen relevant direct research report and patented technology as yet at refinery's high density electric desalting wastewater treatment from the information that obtains.Similar wastewater treatment method about high calcium, high ferro, high organic content has much both at home and abroad, for example:
US 6858147B2 proposes a kind of method that removes metal in the waste water, adopts hollow-fibre membrane to handle.Colloidal silica dispersion flows through from the inboard or the outside of fiber, and the waste water that contains heavy metal flows through from opposition side.Though this method can effectively be removed the metal ion in the waste water, in actual applications, there is the investment height in membrane separation technique, working cost is high, operational conditions is harsh, pre-treatment requires high shortcoming to water quality.Therefore this technology can't satisfy the requirement of high density electric desalting wastewater treatment.
CN 1295034A has reported a kind of recovery and treatment method of waste water containing high-concentration benzene dicarboxylic acid, and its COD value of waste water is up to 10000mg/L.This method is with hydrochloric acid soln the pH value of waste water to be transferred to about 3.3, adds the flocculation agent flocculating settling under stirring fast, and after the plate-and-frame filter press press filtration, liquor C OD can reduce to below the 2000mg/L.This technology is only applicable to the processing of phthalic acid waste water, and calcium, iron and organism in the high density electric desalting waste water are not had effective clearance.
CN 1358673A proposes the separation method and the device of calcium, magnesium ion in a kind of oil extraction waste water.The oil extraction waste water that will contain calcium, magnesium ion flows through a magnetic field, flows through an electrostatic field then, by effect of electric field, ion is concentrated collection, and the waste water after the purification is used for the oil field re-injection.Ion more than 90% all is removed.It is oil extraction waste water about 70mg/L that this technology is only applicable to calcium ions and magnesium ions concentration, be not suitable for the removal of calcium ion in the high density electric desalting waste water, and facility investment is big, working cost height, poor practicability.
Summary of the invention
The present invention is directed to the above problem that prior art exists, the method of wastewater treatment of a kind of high calcium, high organic content is provided, particularly refinery high density (high organic content, high calcium and high Fe content) electric desalting wastewater treatment method solves the impact of this high-concentration waste water to Sewage treatment systems.
The method of wastewater treatment of high calcium provided by the present invention, high organic content consists of the following components: anaerobic reactor, decalcification, the softening pond of deferrization, secondary BAF.
Specifically, method provided by the invention may further comprise the steps:
1) pending waste water is sent into anaerobic reactor and is handled after equalizing tank, oil trap remove oil slick.The organic loading of anaerobic reactor is 4～25kgCOD/m
3.d, preferred 6～20kgCOD/m
3.d, hydraulic detention time 3～48
H, preferred 6～32h, service temperature is 20～60 ℃, is preferably 25～40 ℃.
Described anaerobic reactor is a prior art, but reference CN1009485, CN1002811, ZL02282322.0, ZL02282323.9, ZL 03227936.1 etc., the characteristics of this reactor are the processing efficiency height, reactor volume is little, and cost is low, and processing cost is low, the anti impulsion load ability is strong, mud discharging is few, the characteristics but the production methane gas acts as a fuel etc., and the organism in the water inlet more than 80% can remove at this.
2) decalcification, the softening processing of deferrization.The pH of anaerobism water outlet is transferred to 6～9, add decalcification, deferrization tenderizer 2～50mg/L, preferred 5～30mg/L, the calcium in the water, iron are separated out with the form of solid salt, and discharge settlement separate back.
The decalcification of being adopted, deferrization tenderizer are made up of organic tenderizer, inorganic tenderizer and coagulant aids three parts.With the tenderizer gross weight is benchmark, and wherein the weight content of organic tenderizer is 5～99%, preferred 10～90%; The weight content of inorganic tenderizer is 1～95%, preferred 10～90%; The weight content of coagulant aids is 0～20%.Organic tenderizer can be one or several the compound in polyacrylamide and derivative, poly dimethyl allyl ammonia chloride, diallyl ammonia chloride/acrylamide copolymer, acrylic acid multipolymer, acrylamide/dimethylaminoethyl acrylate methyl ammonia ethyl ester multipolymer, sodium polyacrylate and derivative thereof, polyvinyl alcohol, polyoxyethylene, the poly-sulfo group vinylbenzene, preferred diallyl ammonia chloride/acrylamide copolymer, poly dimethyl allyl ammonia chloride, sodium polyacrylate and derivative thereof; Inorganic tenderizer can be one or several a compound of polymerize aluminum chloride, bodied ferric sulfate, poly-ferric sulfate chloride, aluminium iron polychloride, Tai-Ace S 150, ferrous sulfate, iron(ic) chloride, and preferably sulfuric acid is ferrous, Tai-Ace S 150, iron(ic) chloride; Coagulant aids can be potassium permanganate, liquid chlorine, hydrogen peroxide, Losantin, potassium bichromate etc.
3) the secondary BAF is sent in the water outlet of step 2, further COD is reduced to meet the requirements.Wherein one-level BAF hydraulic detention time is 1～10h, preferred 3～6h, COD volumetric loading 2～15KgCOD/m
3.d, preferred 4～12KgCOD/m
3.d.Secondary BAF hydraulic detention time is 1～10h,, preferred 3～6h, COD volumetric loading 2～15KgCOD/m
3.d, preferred 4～12KgCOD/m
3.d.
Step 1 and 2 order also can be exchanged, and promptly high-concentration waste water can carry out decalcification earlier, deferrization is softening handles, and then carries out anaerobic and aerobic and handle.
Technical process provided by the invention has the characteristics such as organic loading height, decalcification deferrization efficient height, floor space are little of handling.Can handle the waste water of industry high calciums such as petrochemical complex, wine brewing, food, medicine, high ferro, high organic concentration, former water COD
CrConcentration is 10000～20000mg/L, and calcium contents is 500～6000mg/L, and iron level is 0～500mg/L, the waste water COD after the processing
CrConcentration can reach 800mg/L, and calcium contents is reduced to 200mg/L, and iron level is reduced to below the 10mG/L.
Description of drawings
Fig. 1 has described technical process of the present invention.
Embodiment
Embodiment 1
High-concentration waste water (COD
CrValue is that 12000mg/L, calcium contents are that 5000mg/L, iron level are 250mg/L), oil removal is handled after be pumped in the anaerobic reactor (EIC), and service temperature is 30 ℃, hydraulic detention time 32h, COD volumetric loading 7.2KgCOD/m
3.d, the pH of anaerobism water outlet is transferred to 7, add 25mg/L decalcification deferrization tenderizer then and soften processing (tenderizer consists of 5 heavy % sodium polyacrylates, 85 heavy % Tai-Ace S 150,10 heavy % hydrogen peroxide), the sedimentation water outlet is sent into BAF and is carried out aerobic treatment, one-level BAF hydraulic detention time 6.5h wherein, COD volumetric loading 4.8KgCOD/m
3.d, secondary BAF hydraulic detention time 6.5h, COD volumetric loading 2.9KgCOD/m
3.d.Final outflow water water quality: COD
CrBe 650mg/L, calcium contents is that 200mg/L, iron level are 10mg/L.
Embodiment 2
High-concentration waste water (the COD value is that 20000mg/L, calcium contents are that 4000mg/L, iron level are 100mg/L), oil removal is handled after be pumped into the softening pond of decalcification deferrization and is softened processing, the pH of water outlet is transferred to 8, add 15mg/L decalcification deferrization tenderizer (tenderizer consists of 50 heavy % diallyl ammonia chloride/acrylamide copolymers, 50 heavy % iron(ic) chloride), after the sedimentation supernatant liquor is sent in the anaerobic reactor (EIC), service temperature is 35 ℃, hydraulic detention time 20h, COD volumetric loading 12KgCOD/m
3.d, the anaerobism water outlet is sent into BAF and is carried out aerobic treatment, one-level BAF hydraulic detention time 6.5h wherein, COD volumetric loading 8KgCOD/m
3.d, secondary BAF hydraulic detention time 6.5h, COD volumetric loading 4.8KgCOD/m
3.d final outflow water water quality: COD
CrBe 800mg/L, calcium contents is that 100mg/L, iron level are 5mg/L.
Embodiment 3
High-concentration waste water (the COD value is that 20000mg/L, calcium contents are that 4000mg/L, iron level are 150mg/L), oil removal is handled after be pumped into the softening pond of decalcification deferrization and is softened processing, the pH of water outlet is transferred to 8, add 5mG/L decalcification deferrization tenderizer (tenderizer is formed 90 heavy % poly dimethyl allyl ammonia chlorides, 5 heavy % iron(ic) chloride, 5 heavy % potassium permanganate), after the sedimentation supernatant liquor is sent in the anaerobic reactor (EIC), service temperature is 40 ℃, hydraulic detention time 32h, COD volumetric loading 18KgCOD/m
3.d, the anaerobism water outlet is sent into BAF and is carried out aerobic treatment, one-level BAF hydraulic detention time 4h wherein, COD volumetric loading 6KgCOD/m
3.d, secondary BAF hydraulic detention time 4h, COD volumetric loading 4KgCOD/m
3.d.Final outflow water water quality: COD
CrBe 700mg/L, calcium contents is that 200mg/L, iron level are 4mg/L.
Claims (12)
1. the method for wastewater treatment of a high calcium, high organic content may further comprise the steps in order:
1) pending waste water is sent into anaerobic reactor and is handled after equalizing tank, oil trap remove oil slick, and the organic loading of anaerobic reactor is 4～25kgCOD/m
3.d, hydraulic detention time 3～48h, service temperature is 20～60 ℃;
2) pH with the anaerobism water outlet transfers to 6～9, adds decalcification, deferrization tenderizer, and is settlement separate;
3) the secondary BAF is sent in the water outlet after will softening, and reduces COD to meeting the requirements; Pending waste water COD
CrConcentration is 10000～20000mg/L, and calcium contents is 500～6000mg/L.
2. according to the described treatment process of claim 1, it is characterized in that the organic loading of anaerobic reactor is 6～20kgCOD/m
3.d, hydraulic detention time 6～32h, service temperature is 25～40 ℃.
3. according to the described treatment process of claim 1, it is characterized in that decalcification, deferrization tenderizer add-on 2～50mg/L.
4. according to right 3 described treatment processs, it is characterized in that the add-on of decalcification, deferrization tenderizer is 5～30mg/L.
5. according to the described treatment process of claim 1, it is characterized in that, decalcification, deferrization tenderizer are made up of organic tenderizer, inorganic tenderizer and coagulant aids three parts, with the tenderizer gross weight is benchmark, the weight content of organic tenderizer is 5～99%, the weight content of inorganic tenderizer is 1～95%, and the weight content of coagulant aids is 0～20%.
6. according to the described treatment process of claim 5, it is characterized in that the weight content of organic tenderizer is 10～90%, the weight content of inorganic tenderizer is 10～90%.
7. according to the described treatment process of claim 5, it is characterized in that organic tenderizer is selected from one or several the compound in polyacrylamide and derivative, poly dimethyl allyl ammonia chloride, diallyl ammonia chloride/acrylamide copolymer, acrylic acid multipolymer, acrylamide/dimethylaminoethyl acrylate methyl ammonia ethyl ester multipolymer, sodium polyacrylate and derivative thereof, polyvinyl alcohol, polyoxyethylene, the poly-sulfo group vinylbenzene.
8. according to the described treatment process of claim 5, it is characterized in that inorganic tenderizer is selected from one or several the compound in polymerize aluminum chloride, bodied ferric sulfate, poly-ferric sulfate chloride, aluminium iron polychloride, Tai-Ace S 150, ferrous sulfate, the iron(ic) chloride,
9. according to the described treatment process of claim 5, it is characterized in that coagulant aids is selected from potassium permanganate, liquid chlorine, hydrogen peroxide, Losantin.
10. according to the described treatment process of claim 5, it is characterized in that, organic tenderizer is diallyl ammonia chloride/acrylamide copolymer, poly dimethyl allyl ammonia chloride or sodium polyacrylate and derivative thereof, and inorganic tenderizer is ferrous sulfate, Tai-Ace S 150 or iron(ic) chloride.
11., it is characterized in that first step BAF hydraulic detention time is 1～10h according to the described treatment process of claim 1, COD volumetric loading 2～15KgCOD/m
3.d; Second stage BAF hydraulic detention time is 1～10h, COD volumetric loading 2～15KgCOD/m
3.d.
12., it is characterized in that first step BAF hydraulic detention time is 3～6h according to the described treatment process of claim 11, COD volumetric loading 4～12KgCOD/m
3.d; Second stage BAF hydraulic detention time is 3～6h, COD volumetric loading 4～12KgCOD/m
3.d.
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| WO2018189563A1 (en) * | 2017-04-14 | 2018-10-18 | Total Sa | Method for purifying produced water from a subterranean hydrocarbon formation |
| CN108373234A (en) * | 2018-01-30 | 2018-08-07 | 浙江工业大学 | A kind of processing method of biodiesel sulfur acid waste water |
| CN108862938A (en) * | 2018-08-17 | 2018-11-23 | 江苏泰利达新材料股份有限公司 | The method for treating waste liquid of CMC or ammonia creatine sodium or liquid detergent |
| CN110228902A (en) * | 2019-06-05 | 2019-09-13 | 南京化工园博瑞德水务有限公司 | A kind of wastewater treatment method of high calcium, high content of organics |
| CN114804503A (en) * | 2021-01-22 | 2022-07-29 | 中石油克拉玛依石化有限责任公司 | Method for treating crude oil electric desalting wastewater |
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