CN101591110B - Oil refining sewage treatment technology - Google Patents
Oil refining sewage treatment technology Download PDFInfo
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- CN101591110B CN101591110B CN2008101133946A CN200810113394A CN101591110B CN 101591110 B CN101591110 B CN 101591110B CN 2008101133946 A CN2008101133946 A CN 2008101133946A CN 200810113394 A CN200810113394 A CN 200810113394A CN 101591110 B CN101591110 B CN 101591110B
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Abstract
The invention relates to an oil refining sewage treatment technology. Oil refining mixed sewage is sequentially treated by oil removal, air flotation, magnetic separation and biochemical treatment, and then is discharged. On the basis of the original oil refining mixed sewage treatment process flow, the invention adds the step of magnetic separation, which can lighten the load of a secondary bio-chemical treatment device, avoids shock to a biochemical system and greatly improves effluent quality in biochemical treatment. The technology of the invention has the advantages of good treatment effect, wide application range of water quality, stable operation, strong operability, simple flow, small investment, low operation cost, etc.
Description
Technical field
The invention belongs to the multiple-stage treatment of water, waste water or sewage, particularly a kind of oil refining combined sewage treatment process that comprises the magnetic separating step.
Background technology
Along with rapid economy development and population sharply increase, shortage of water resources and environmental pollution are on the rise becomes undisputable fact, and the cry that requires industrial enterprise to carry out reusing sewage and raising sewage drainage standard grows to even greater heights.Simultaneously, along with the crude oil poor qualityization and the crude resources trend of globalization increase, petroleum chemical enterprise's processing crude oil with poor quality is fast rise trend, further increased sewage biochemical treatment difficulty, cause biochemical treatment apparatus efficient to reduce, water outlet even not up to standard for a long time also brings bigger difficulty to reusing sewage.According to statistics, adopt the petroleum chemical enterprise of " oil removal-flotation-biochemistry " " old three covers " art breading oil refining sewerage, only account for the national grade one discharge standard that reaches that the externally discharged waste water Pollutant levels of total release 30% can be more stable, other sewage of 70% do not reach national grade one discharge standard.For this reason, some newly-built or reorganization and expansion enterprises, sewage disposal take to remove contamination shunting, the dirty measure of dividing and ruling make high-concentration and low-concentration waste water obtain respectively handling, and the overall process effect is better; Some enterprises increase one-level biochemistry again after " old three covers " technology or materialization is handled, and effluent quality is further improved, and guarantee the sewage stably reaching standard, also create conditions for reusing sewage.Yet the shunting of taking to remove contamination, the dirty technology of dividing and ruling are not suitable for " long-established enterprise ", handle and have problems such as facility investment is big, running cost height and increase one-level biochemistry or materialization again after " old three cover " technology.How to make the externally discharged waste water stably reaching standard of oil refining enterprise or reach the requirement of reuse, do not increase too much cost again simultaneously, become long-term puzzlement people's a great problem.
Magnetic separation method is applied to the processing of steel iron wastewater the earliest, removes magnetic suspension thing in the water, and it is big to have treatment capacity, solid-liquid separation efficiency height, the advantage that floor space is little.Magnetic separation technique is the effect by magnetic field force, the material of different magnetic is separated existing application the in recirculated water, boiler feed water and process water and sewage disposal.Sewage passes through magnetic field with certain flow rate, cutting magnetic line, and the magnetic substance in the sewage under the effect in magnetic field, is attracted to around the magnet, and separate the back of leaving the water, and sewage is purified.Common and the flocculence logotype of magnetic separation method is by adding magnetic species such as magnetite or ferrite powder etc. to strengthen separating effect in sewage.Research thinks that magnetic field effect can promote the relevant chemical reaction in the sewage treatment process and the activity of material, improves coagulation effect, and the suspended substance touch opportunity under the action of a magnetic field in the water body is increased, and increases flocculating rate thereby improve coalescent speed.
Consulted the U.S. chemical abstract database at interior domestic and international 10 patents, bibliographic data base, from the information that obtains, the technology about disposing of sewage by magnetism separate method of bibliographical information has a lot, but all concentrate on the processing of industry sewage such as metallurgy, iron and steel, do not relate to the processing of oil refining sewerage.
CN1911823A has reported a kind of magnetic flocculation separation waste water treatment technology.The factory effluent of enterprises such as metallurgy, mine, before magnetic separating apparatus, add flocculation agent and coagulant aids, and adopt static line mixer to mix, make dispersed oil, oil in water emulsion breakdown of emulsion in the waste water, oil, fine non-magnetic particle and magnetic flocculation are combined, again by the magnetic separating apparatus isolation of purified, there is not follow-up filterer's preface, effluent quality reaches SS＜20mg/L, and the clearance of dispersed oil and oil in water emulsion is up to 95%, but direct reuse.This waste water treatment process is fit to metallurgical, mine factory effluent, and refinery water pollutant component complexity, this short flow processing can not reach and efflux or the purpose of reuse.
CN 1276881C has reported membrane-flocculation sediment sewage treatment systems, at first adopts membrane bioreactor sewage treatment, handles through flocculation sediment technology again, reaches emission request thereby make general technology be difficult to handle sewage up to standard.Adopt the shortcoming of membrane technique processing petroleum refining industry sewage to be that this technology is domestic at the early-stage, there is not long playing experience many places in test or small-scale operation phase, and advance film pretreatment technology long flow path, the investment height of sewage before.Therefore adopt membrane process to handle sewage from oil refinery and also need to do further experimental study.
" petrochemical complex environment protection " the 2nd phase in 2003 discloses " application of BAF technology in oil refining sewerage is handled "; data analysis wherein shows; BAF (BAF) is good to the removal effect of ammonia nitrogen; COD also there is certain removal effect; it is feasible technically to be applied to advanced Treatment for Refinery Waste Water, can further improve the water quality of externally discharged waste water.But the stable water outlet of BAF is subjected to the influence of influent quality bigger.To guarantee in this technology actual motion that the second pond water outlet meets the water inlet requirement in BAF pond, just can make the BAF maximum possible bring into play its effect, reduce follow-up unitary processing pressure.
In sum,, press for the novel method that exploitation improves oil refining sewerage treatment system effluent quality, to guarantee sewage qualified discharge and normal reuse in view of the increasingly stringent of environmental regulation.
Summary of the invention
Problem at prior art exists the present invention proposes a kind of oil refining sewage treatment technology, particularly a kind of oil refining sewage treatment technology that comprises the magnetic separating step.
A kind of oil refining sewage treatment technology comprises: the oil refining combined sewage is successively through effluxing after oil removal, air supporting, magnetic separation and the biochemical treatment.
Find that by further investigation the operating performance of oil removal and air supporting facility is directly connected to the normal operation and the effluent quality of follow-up biochemical processing unit to oil refining sewerage treatment system operating performance quality.Owing to process the continuous variation of oil quality in recent years, the emulsification of sink drainage influent quality increased the weight of, existing oil removal, air supporting mode and medicament majority can not be brought into play useful effect, sewage is through oil removal, air supporting bi-level treatment, still have the fine suspended substance of a great deal of or oils such as suspension oil, dispersed oil and the oil in water emulsion of non-solubility effectively not to be removed, this part material belongs to the COD of non-solubility.When treatment effect is better, contain the COD of 5%～30% left and right sides non-solubility of having an appointment in the water outlet usually, during poor processing effect, the COD of non-solubility can reach 20%～50% in the water outlet.The COD of this part non-solubility has increased the load of follow-up biochemical treatment facility, has influenced the qualified discharge of sewage.Most enterprises increase new waste-oil scavenger and medicament by transforming, and improve pneumatically supported treatment effect as new type flotation machine, various demulsifying flocculants etc., but result and not fully up to expectations.
The present invention compared with prior art possesses following outstanding advantage.
1. on the basis of " old three covers " technology, the present invention is by increasing the magnetic separating step, can alleviate the load of secondary biochemical treatment facility, avoid impact to a certain extent to biochemical system, and significantly improved externally discharged waste water water quality, guarantee the stably reaching standard of externally discharged waste water, for reusing sewage is laid good basis.
2. technical process of the present invention is simple, less investment, and working cost is low, and can reduce the consumption of coagulated agent, and the magnetic kind can be used repeatedly, does not increase the mud discharge capacity of Sewage treatment systems, is a kind of treatment process of saving the medicament and the energy.
3. technical process treatment effect of the present invention is good, wide, stable to the water quality scope of application, workable, not only is fit to long-established enterprise, also is fit to newly-built or reforming enterprise.
Description of drawings
Accompanying drawing is a process flow diagram of the present invention.
Embodiment
Further set forth the present invention below in conjunction with accompanying drawing.
The combined sewage of at first refining oil enters oil trap, handles by oil removal, and the oil-contg of oil removal water outlet is controlled at below the 400mg/L; Sewage is pumped into air flotation pool then, adds coagulating agent, handles by one-level, two-stage or three grades of air supportings, and the oil-contg in the sewage is reduced to below the 100mg/L, and COD reduces to below the 800mg/L, and suspended substance is reduced to below the 80mg/L; The air supporting water outlet is pumped into magnetic separating apparatus again, adds coagulating agent and magnetic kind, removes the coagulation body that forms by magnetic separating apparatus, and the water-quality COD clearance of handling through magnetic separating apparatus is 20～50%, suspended substance≤20mg/L, oil-contg≤5mg/L; Then the magnetic separation system water outlet is pumped into biochemical treatment system, through after the biochemical treatment, COD≤60mg/L, water outlet can directly efflux.Processing such as sterilization, filtration, water conditioning can be further carried out in the biochemical treatment water outlet, make the microorganism of handling in the water of back, suspended substance etc. meet the reuse requirement, and making the peculiar smell in the sewage obtain more thoroughly removing, the externally discharged waste water after the processing directly enters circulating water system and uses.
Said oil removal is the relative density difference that utilizes between oil and the water, floats to the water surface by on the elaioleucite nature, the method that oil is removed then, and oil trap commonly used has parallel flow intercepter and tilted plate intercepter etc.But the oil removal operation is mainly used to remove the bigger thick dispersiveness oil slick grain of diameter in the sewage.
Said air supporting is to utilize the micro-bubble of high dispersing to go to stick pollutants in waste water as carrier, and it is removed to the water surface with air bubble buoyancy.Air-float method commonly used has electrolytic gas float glass process and dissolved air flotation.Air supporting is mainly used in oil in water emulsion and the trickle suspended solid of hydrophobicity that separates in the waste water.
Said magnetic separate be branch dried up in nonmagnetic impurity, comprise the oil and the fine suspended substance of a small amount of non-solubility need in water, adding an amount of magnetic kind such as Fe
3O
4, magnetic materials such as iron ore, a small amount of iron powder of blast furnace disintegrating slag, fusion that contains magnetic substance or placer iron cement, lime carbonate etc., carry out chemical coagulation to generate the coagulation body that comprises the magnetic kind, can realize sharp separation after the magnetic kind is magnetized.Magnetic separator commonly used has high gradient magnetic separator, magnetic disk separator and magnetic knockouts.
High gradient magnetic separator is to use magnetizing coil and magnetic loop to cause high high-intensity magnetic field in equipment, utilize stainless steel wool to improve field gradient as filter substrate, by adding magnetic-particle, add an amount of coagulating agent simultaneously, carry out chemical coagulation and generate the coagulation body that comprises magnetic-particle, can realize sharp separation behind the granulated magnetic.
Magnetic disk separator is the magnetic force by disk, the magnetic suspension particulate matter in the sewage is adsorbed on the disk of slow rotation, along with the rotation of disk, take body refuse out of the water surface, remove through cleaning shoe, the disk card enters in the water again, again the particle in the planar water so goes round and begins again.
The magnetic knockouts is to make sewage pass through uniform magnetic field, because field gradient is zero, the magnetic-particle thing can not captured by magnetic field in the water, but is gathered into macrobead mutually between the particle, thereby improves settling rate, and common and coagulating agent is used.
The said coagulating agent of the present invention is meant the medicament with cohesion and/or throwing out.In air supporting step and the magnetic separating step, used coagulating agent is selected from one or more in inorganic polymer coagulant, organic polymer coagulating agent and the compound coagulant of the two.
Anaerobic treatment can adopt flow lifting type anaerobic sludge layer reactor (UASB), internal-circulation anaerobic reactor (IC), anaerobic filter, anaerobic fluidized bed reactor (AFBR), membrane bioreactor etc.; Aerobic treatment can adopt activated sludge process, BAF (BAF), bio-contact oxidation, membrane bioreactor, blodisc, trickling filter, fluidized-bed reactor etc.
Processing such as sterilization, filtration, water conditioning also can be further passed through in the water outlet of biochemical treatment makes water quality reach the requirement of reuse circulating water system, and treatment system comprises devices such as sterilization pond, strainer, chemical treatment medicine system.Above-mentioned Stability Technique of Water Quality is to wait the requirement of satisfying the reuse circulating water system by adding alkaline matter and/or inhibiter, Scale inhibitors and/or biocide.Alkaline matter can be lithium, sodium and potassium oxide compound, oxyhydroxide, carbonate or supercarbonate with and composition thereof; Inhibiter can be organophosphate and metal oxide, organophosphate such as 1-hydroxyethyl-1,1-bisphosphate, Amino Trimethylene Phosphonic Acid, ethylene diamine tetramethylene phosphonic acid, 2-hydroxyl phosphino-acetate etc. and composition thereof, metal oxide such as zinc chloride, zinc sulfate, zinc oxide, molybdate, tungstate, silicate etc. and composition thereof; Dirt dispersion agent can be the sodium polyacrylate that is applicable to water treatment, acrylic acid/esters multipolymer, sodium acrylate/2-methyl-2 '-acrylamido-propene sulfonic acid multipolymer, poly-epoxy succinic acid, the acid of poly-asparagus fern peace etc. and composition thereof; Biocide can be the compound that discharges hypochlorite in chlorine, hypochlorite and the use thereof, smell oxygen, dioxide peroxide, quaternary ammonium salt, quaternary alkylphosphonium salt, glutaraldehyde, isothiazolinone, dibromo Malonamide nitrile etc. and composition thereof.
Embodiment 1
Certain refinery composite wastewater water yield is about 500t/h, COD is about 3000mg/L, be pumped into two-stage inclined plate grease pond, but remove the bigger thick dispersiveness oil slick grain of diameter in the sewage, but because of having relative density difference between oil slick grain and the water, floating to the water surface by floating naturally upward method can be removed, and the oil-contg of oil removal water outlet is reduced to below the 400mg/L.
The oil removal water outlet is pumped into three grades of air-dissolving air-float ponds, add 100mg/L polymerize aluminum chloride and 12mg/L cationic polyacrylamide for every grade by chemicals dosing plant, utilize the micro-bubble of high dispersing to go to stick pollutants in waste water as carrier, it is removed to the water surface with air bubble buoyancy, separate oil in water emulsion and the trickle suspended solid of hydrophobicity in the waste water.Handle by three grades of air supportings, the oil-contg in the sewage is reduced to below about 100mg/L, and COD reduces to about 750mg/L, and suspended substance is reduced to about 80mg/L.
The air supporting water outlet is pumped into magnetic disk separator again, this equipment field intensity is 1kGs, be provided with chemicals dosing plant and static mixer before the pump, add dosage and be about 3mg/L poly dimethyl allyl ammonia chloride, trickle suspended substance and a small amount of suspension oil, dispersed oil and emulsification wet goods non-magnetic substance are in the same place the about 3h of design hydraulic detention time with magnetic species iron ore coagulation in pipeline that particle diameter is about 1-3mm.After the magnetic separating treatment, the waste water COD clearance is 40%, suspended substance≤20mg/L, oil-contg≤5mg/L.
Magnetic is isolated water and is pumped into biochemical treatment system, carries out a biological disposal upon through anaerobic fluidized bed reactor, BAF.The about 24h of anaerobic reactor hydraulic detention time wherein, the about 4h of BAF hydraulic detention time, the about 5-10 of gas-water ratio: 1, bio-chemical effluent COD＜60mg/L.
Bio-chemical effluent is by adding water stabilizers such as quaternary amine biocide, organophosphate inhibiter and sodium polyacrylate Scale inhibitors, make the microorganism of handling in the water of back, suspended substance etc. meet the reuse requirement, and making the peculiar smell in the sewage obtain more thoroughly removing, the externally discharged waste water after the processing directly enters circulating water system and uses.Under this condition of water quality, erosion rate≤0.10mm/a, adhesion speed≤15mg/ (cm
2.month), total plate count≤1 * 10
5Individual/mL, and cycles of concentration reaches about 6, satisfied the water quality requirement of recirculated water.
Comparative Examples 1
Certain refinery composite wastewater water yield is about 500t/h, COD is about 3000mg/L, be pumped into two-stage inclined plate grease pond, but remove the bigger thick dispersiveness oil slick grain of diameter in the sewage, but because of having relative density difference between oil slick grain and the water, floating to the water surface by floating naturally upward method can be removed, and the oil-contg of oil removal water outlet is reduced to below the 400mg/L.
The oil removal water outlet is pumped into three grades of air-dissolving air-float ponds, add 100mg/L polymerize aluminum chloride and 12mg/L cationic polyacrylamide for every grade by chemicals dosing plant, utilize the micro-bubble of high dispersing to go to stick pollutants in waste water as carrier, it is removed to the water surface with air bubble buoyancy, separate oil in water emulsion and the trickle suspended solid of hydrophobicity in the waste water.Handle by three grades of air supportings, the oil-contg in the sewage is reduced to below about 100mg/L, and COD reduces to about 750mg/L, and suspended substance is reduced to about 80mg/L.
The air supporting water outlet is pumped into biochemical treatment system, carries out a biological disposal upon through anaerobic fluidized bed reactor, BAF.The about 24h of anaerobic reactor hydraulic detention time wherein, the about 4h of BAF hydraulic detention time, the about 5-10 of gas-water ratio: 1, the about 150-250mg/L of bio-chemical effluent COD.Externally discharged waste water after the processing can not directly enter circulating water system and use, and further advanced treatment makes microorganism in the water, suspended substance, COD etc. meet the reuse requirement.
Claims (8)
1. an oil refining sewage treatment technology comprises: efflux after the process oil removal successively of oil refining combined sewage, air supporting, magnetic separation and the biochemical treatment.
2. according to the described technology of claim 1, it is characterized in that the oil-contg of oil removal water outlet is controlled at below the 400mg/L.
3. according to the described technology of claim 1, it is characterized in that the oil-contg of air supporting water outlet is controlled at below the 100mg/L, COD is controlled at below the 750mg/L, and suspended substance is controlled at below the 80mg/L.
4. according to the described technology of claim 1, it is characterized in that used magnetic separator was selected from one or more in high gradient magnetic separator, magnetic disk separator and the magnetic knockouts during magnetic separated.
5. according to claim 1 or 4 described technologies, it is characterized in that magnetic separates the suspended substance≤20mg/L of water outlet, oil-contg≤5mg/L.
6. according to the described technology of claim 1, it is characterized in that said biochemical treatment is anaerobic treatment and/or aerobic treatment.
7. according to claim 1,2,3,4 or 6 described technologies, it is characterized in that, sterilization, filtration, Handling of Stabilizing Water Quality are carried out in the water outlet of biochemical treatment after, with its reuse circulating water system.
8. according to the described technology of claim 5, it is characterized in that, sterilization, filtration, Handling of Stabilizing Water Quality are carried out in the water outlet of biochemical treatment after, with its reuse circulating water system.
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| CN103204606B (en) * | 2013-03-25 | 2014-03-12 | 中国石油天然气集团公司 | Advanced treatment process for treating complex waste water of super-heavy oil |
| CN103359861B (en) * | 2013-07-31 | 2015-05-27 | 庆华集团新疆和丰能源化工有限公司 | Treating technology and treating system for oil sand oil exploitation sewage |
| CN103373796A (en) * | 2013-08-14 | 2013-10-30 | 中国科学院成都生物研究所 | Method for treating oil refining wastewater |
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| CN105016432A (en) * | 2015-08-07 | 2015-11-04 | 中国海洋石油总公司 | Oil refining reclaimed water reuse high-concentration-ratio circulating water treatment method and device |
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| CN111511473B (en) * | 2017-07-28 | 2023-06-13 | 营养与生物科技美国第一有限公司 | Use of non-oxidizing biocides for selective recovery of valuable metals in froth flotation processes |
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