CN101898844A - Method for treating salt-containing sewage - Google Patents
Method for treating salt-containing sewage Download PDFInfo
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- CN101898844A CN101898844A CN2009100117692A CN200910011769A CN101898844A CN 101898844 A CN101898844 A CN 101898844A CN 2009100117692 A CN2009100117692 A CN 2009100117692A CN 200910011769 A CN200910011769 A CN 200910011769A CN 101898844 A CN101898844 A CN 101898844A
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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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention relates to a method for treating salt-containing sewage. The pH value of the salt-containing sewage is adjusted to between 8 and 12, the salt-containing sewage is biochemically treated by an activated sludge process, the effluent after the activated sludge process treatment is treated by an ozone-catalytic oxidation process adopting a solid catalyst, and the effluent after the ozone-catalytic oxidation process treatment is discharged through a biofilter; and in the ozone-catalytic oxidation process adopting the solid catalyst, the solid catalyst is granular activated carbon loaded with an active component which is one or more of tin, copper, manganese, titanium, cobalt, vanadium and nickel. The method can effectively purify the sewage which has high salt content and is refractory to biodegrade, and the effluent after treatment has the COD of less than or equal to 50 mg/L and the NH3-N of less than or equal to 8 mg/L, so that the strict sewage discharge standard of developed regions is met. The method has the advantages of simple treatment process, no need of sewage dilution, clean and clear effluent after treatment and realization of direct standard discharge.
Description
Technical field
The present invention relates to a kind of treatment process of oil refining sewerage, be specially adapted to the qualified discharge treatment process of refinery high density saline sewage.
Background technology
The combination treatment mode is concentrated in the general employing of oil refining sewerage at present, be about to purify waste water and sanitary sewage mixes the back and handles the back discharging by oil removal-flotation-biochemical combination process from oily(waste)water, saline sewage, sour water stripping that each production equipment is discharged, water outlet still can be satisfied COD≤100mg/L, NH
3The discharging standards of-N≤15mg/L.Yet along with the Petrochemical Enterprises processing butyrous variation day by day of crude oil with because of the increasingly stringent of shortage of water resources to the reusing sewage requirement, this sewage concentrates the mode and the treatment scheme of combination treatment more and more to expose bigger problem.At first, the exploitation of high-sulfur/high-acid crude oil and processing ratio cumulative year after year, oil product needs to add chemical agents such as a large amount of emulsion splitters, inhibiter and polymer coagulant in the course of processing, cause that the emulsification of waste water oil-containing is serious, the concentration of difficult for biological degradation organic pollutant, sulfide, ammonia nitrogen and inorganic salt and other material constantly increases, and shows that especially the higher oil product tank field of electric desalting draining, gasoline alkaline residue, diesel alkaline residue, liquid hydrocarbon alkaline residue and petroleum-type and organic pollutant content cuts water etc.Because sewage character is relatively poor, often wastewater treatment field oil removal, floatation system or biochemical system is impacted, and influences the stably reaching standard of wastewater treatment field draining.Though can realize the purpose of organism and desalination in the degradation of sewage by adopting senior method for oxidation+two embrane methods such as ozone oxidation or electrodialytic technology, circulating cooling make-up water or oiler feed are done in reuse after treatment, but the supersalinity in the composite waste increases initial cost greatly, and enterprise is difficult to bear.Therefore, each oil refining enterprise takes the principle of " dirty shunting " and " dirty dividing and ruling " with oil-containing and saline sewage separate treatment one after another.Oily(waste)water is owing to low salinity, and biodegradability is good, has the potentiality of reusing sewage, adopts present technique means, can accomplish qualified discharge fully, can satisfy reuse standard after appropriateness is handled.But saline sewage has been concentrated various unmanageable waste water in the oil refining process, comprise that various alkaline residues or alkaline water, electric desalting draining, oil product tank field cut water etc., characteristics with salts contg height, biodegradability difference, refractory organic accounts for 8%～20% of total organic loading, causes the stably reaching standard discharging of saline sewage to become the problem of needing solution badly.Secondly, along with the increasingly stringent of environmental protection standard, especially in the area that are fairly developed economically, the water emission standard is strict more, requires COD≤60mg/L or COD≤50mg/L, and this handling problem to saline sewage is more outstanding.
For the present adoptable main method of saliferous high density difficult for biological degradation organic waste water is the combination process of wet oxidation, advanced oxidation or catalyzed oxidation, anaerobism or acidification hydrolization etc. or these technology and aerobic biochemical technology formation.
CN98121081.3 proposes a kind of method of handling oil products in petroleum refining industry soda finishing waste lye, at first at 100～190 ℃ and waste lye is remained under the pressure of liquid phase, with air or oxygen-rich air is oxidizing medium, high density sulfide oxidation in the waste lye is become thiosulfate anion or sulfate radical, remove stench, and make organic pollutant generation partial oxidation, promptly relax wet oxidation and handle; Treat effluent adopts the vitriol oil to regulate the pH value again, reclaims the valuables such as volatile phenol in the waste water; Water outlet after the recovery is sent into the intermittent activated sludge process treatment unit after by suitable dilution, and promptly SBR carries out pre-treatment, handles the back water outlet and finally sends into the sewage-farm and focus on qualified discharge.This method has solved the odor pollution of high-concentration waste water preferably, and can be to the volatile phenol efficient recovery in the waste water, but after this method was handled, waste water is qualified discharge directly, and the processing of the organic composite waste of high density particularly complicated for forming, that recovery value is little is not suitable for adopting.
US6576144 proposes a kind of chemical oxidization method and handles waste lye and other wastewater treatment method, with iron, copper, nickel, titanium, vanadium, molybdenum, metal ion catalyst and hydrogen peroxide such as cobalt, potassium permanganate, ozone, dioxide peroxide, oxygenants such as clorox are added to respectively in waste lye and other waste water continuously, catalytic oxidation takes place in plug flow reactor, by controlling dosage and pH regulator to reach the sulfide that removes in waste lye and other waste water, ammonia, the processing intent of volatile phenol and other organic pollutant, but this method is owing to need add catalytic metal ion continuously, there is the water outlet heavy metal pollution problem, and high-concentration waste water is difficult to obtain treatment effect preferably.
CN03133960.3 proposes a kind of treatment process and device of heterogeneous multiple catalyzing electrolysis oxidation sewage, do solid adsorption material with particles such as gacs, with graphite, noble metal or plain carbon stool are electrode, with water-soluble iron, aluminium, magnesium or manganese metal-salt are catalyzer, with the air is oxidizing medium, by applying the electrolysis voltage below the 36v, make solid adsorption material, electrode materials, support of the catalyst, liquid-phase catalyst, gaseous oxidizing agent combines with processes such as electrolysis, form a sewage physical-chemical-electrolytic processing apparatus, be used for biochemical preceding pre-treatment and the advanced treatment of wastewater behind the biochemistry with comprehensive subtractive process.This method can reach the purpose effect of degree of depth degradable organic pollutant, raising wastewater biodegradability by the catalysed oxidn of electrolysis generation free radical and metal-salt, but owing to need the continuous supplementation metal salt catalyst, cause the consumption of metal-salt on the one hand, make the metal content in the water outlet increase on the other hand, heavy metal contamination easily takes place, be unfavorable for subsequent disposal, particularly be unfavorable for follow-up biochemical treatment.
CN02147755.8 proposes a kind of treatment process and equipment of high concentrated organic wastewater, high concentrated organic wastewater and divalent iron salt reagent are placed electrolyzer, by regulating control pH 1.5～2.5, continue to add hydrogen peroxide high concentrated organic wastewater is carried out the advanced oxidation processing, and, reach the purpose that reduces sludge yield by the reduction utilization that ferrous iron and ferric conversion and ferric iron reflux.But this method is owing to consume a large amount of hydrogen peroxide, and lacks the bigger catalytic carrier of surface-area and cause the residence time longer, and organic matter removal efficient is limited, has water outlet generation metal secondary pollution problem equally.
CN01120210.6 proposes a kind of method of handling industrial waste water with high sulfur content, with at first carrying out the wet oxidation pre-treatment behind the wastewater dilution, and under conditions such as 255～260 ℃ of high temperature, 6.6～7.0MPa pressure, 74%～76% COD in the removal waste water; The catalytic oxidation processing is carried out in water outlet again, and the operational condition of control current 1.0～2.5A, voltage 6～12V, the residence time 1～7h finally makes the total clearance of COD of waste water reach 89.2%～92.3%, thereby reaches the purpose of waste water advanced processing respectively.But because process relates to the High Temperature High Pressure operation, construction investment and working cost are very high, are unsuitable for the processing of big wastewater flow rate.
At present, the quantity that becomes the various synthetic additives of interpolation in bad and the oil production owing to crude quality is increasing, makes that the not bio-degradable composition in the saline sewage is more and more.Experiment shows, contains 8%～20% the not biodegradable material of having an appointment in the oil refining high density brine waste, and common biochemical treatment or combination biochemical treatment are difficult to satisfy strict emission control standards and require (as COD≤60mg/L or COD≤50mg/L).
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of treatment process of high density saline sewage, the inventive method can be handled high density saline sewage deep purifying, does not increase new pollutent simultaneously, can reach the requirement of strict environmental protection standard.
The treatment process of saline sewage of the present invention comprises following process, saline sewage is regulated pH value to 8～12, adopt activated sludge process to carry out biochemical treatment then, the catalytic ozonation method of Wastewater Treated by Activated Sludge Process effluent adopting solid catalyst is handled, and ozone catalytic oxygen treat effluent is discharged after through the biological filter.Adopt in the catalytic ozonation method of solid catalyst; solid catalyst is the granulated active carbon of load active component; active ingredient is one or more in tin, copper, manganese, titanium, cobalt, vanadium and the nickel; ozone dosage 20～800mg/L; best 20～100mg/L; the residence time of waste water in the catalytic ozonation reactor is 5～120min, is preferably 10～60min.
In the saline sewage treatment process of the present invention, saline sewage comes from generally that water is cut in electric desalting apparatus draining, liquid hydrocarbon alkaline residue sewage, gasoline alkaline residue sewage, diesel alkaline residue sewage, crude oil tank farm, one or more combined sewages in the contour concentration saline sewage of water, recirculated water blowdown and reverse osmosis concentrated shrink are cut in the oil product tank field.Contain 8%～20% the not biodegradable organism of having an appointment in the above-mentioned saline sewage, salts contg is at 5g/L～15g/L; TKN70mg/L～130mg/L; PH 〉=12.
In the saline sewage treatment process of the present invention, the Wastewater Treated by Activated Sludge Process that saline sewage is regulated after the pH value can adopt the existing activated sludge process in this area, as intermittent activated sludge process (SBR), circulating active sludge method (CASS) or loop cycle aerating activated sludge process (CAST) etc., specifically as the described method of CN98121082.1 etc.In order to reach the ideal treatment effect, the preferred employing intake at a slow speed and unrestricted aeration operating method, and keeps aeration process to guarantee dissolved oxygen concentration 〉=2mg/L in the waste water all the time.
In the saline sewage treatment process of the present invention; ozone is produced by high frequency ozone generator in the catalytic ozonation reactor; solid catalyst is carrier with the granulated active carbon; the carrier particle diameter is 6～100 orders; preferable particle size is 8～24 orders; gac can be the gac in various sources, preferred active fruit shell carbon or coal mass active carbon.Active ingredient generally by the pickling process load of this area routine, also can be introduced required active ingredient in process for preparing active carbon, the weight content of active ingredient is generally 0.5%～15% of final solid catalyst weight, is preferably 2%～10%.
In the saline sewage treatment process of the present invention, the biological filter technology of this area routine is adopted in the biological filter, and the present invention adopts the aerobic biofilter of aeration operation.The used filler in biological filter is haydite, zeolite or gac etc., preferably the spherical haydite of the lightweight of particle diameter 3～6mm.Biological filter volumetric loading 0.3kgCOD/ (m
3* d)～3.0kgCOD/ (m
3* best 0.3kgCOD/ (m d),
3* d)～1.0kgCOD/ (m
3* d).
In the saline sewage treatment process of the present invention, adopt suitable microbiological treatment unit, unique catalytic treatment unit, and suitable array mode and the operational condition of employing, the high density saline sewage that conventional treatment method or conventional combination treatment method can be difficult to effectively handle is effectively handled, reach the effect of advanced treatment, meet strict environmental emission standard.
In the catalytic treatment unit that the present invention adopts,, avoided heavy metal ion to enter and caused secondary pollution in the waste water, avoided the consumption of active ingredient simultaneously, reduced operating cost owing to adopt solid catalyst.And the carrier of solid catalyst has stronger adsorption to the organic pollutant in the sewage, helps improving the catalyzed reaction effect.Exist at solid catalyst, decomposition reaction takes place in the organic pollutant part in the sewage, the more important thing is, though it is limited that the effect that reduces pollutant load is thoroughly decomposed in organic contamination, but under the effect of catalyzer, the oxidation products of the organic pollutant of difficult for biological degradation has better biodegradability, can the degree of depth transform in biological filter thereafter, has realized outstanding comprehensive treatment effect.
After the inventive method is handled, make the high density brine waste satisfy the purpose of direct qualified discharge, avoided impact, and helped the advanced treatment and reclamation of oily(waste)water general sewage-farm.Advantages such as the method that the present invention proposes has that high-concentration sewage can realize that disposable processing qualified discharge, waste water do not need to dilute, the secondary pollution of treat effluent non-metallic ion, investment and working cost are lower.
Embodiment
A kind of concrete saline sewage treatment process process of the present invention is: 1. use the vitriol oil that the draining of refinery electric desalting apparatus, liquid hydrocarbon alkaline residue sewage, gasoline alkaline residue sewage, diesel alkaline residue sewage, the alkali cleaning waste lye of dry gas, crude oil tank farm are cut water, oil product tank field and cut the composite waste of water, recirculated water blowdown and the contour concentration brine waste of reverse osmosis concentrated shrink and neutralize, make its pH value 9.2～10.6; 2. adopt water inlet at a slow speed and unrestricted aeration mode that waste water is pumped in the SBR aeration tank, under action of microorganisms, thiosulphate in the waste water, organonitrogen and ammonia nitrogen etc. are converted into vitriol and nitric nitrogen respectively, and the basicity in the consumption waste water, and reason waste water alkalescence is not crossed strong and microbiostatic activity; 3. the SBR water outlet enters the catalytic ozonation reactor, and under the effect of catalyzer, ozone generates the hydroxyl radical free radical with strong oxidation capacity, thus with refractory organic in the waste water upright connect mineralising or be converted into be easy to the biological degradation organism; 4. utilize the biological filter to the catalytic ozonation reactor water outlet carry out advanced treatment, can guarantee the stably reaching standard discharging of high density saline sewage.
Use the present invention and handle the mixed waste water of high density saliferous, can adopt traditional SBR, also can adopt the modified version of SBR such as CASS or CAST.Because thiosulphate is converted into vitriol very soon in the waste water under microbial process, and compete basicity in order to make thiosulphate unlikely nitrifying process in conversion process with ammonia nitrogen or organonitrogen, preferably adopt water inlet and unrestricted aeration mode at a slow speed in the SBR operational process, and keep aeration process to guarantee dissolved oxygen concentration 〉=2mg/L in the waste water all the time.Water inlet in the SBR cycleoperation, reaction, precipitation, draining and step such as idle are controlled automatically by the PLC system, and the SBR device is mainly used in bio-degradable material and the kjeldahl nitrogen of removing in the high-concentration sewage.The SBR process using is water intake mode and unrestricted aeration at a slow speed, and the basicity that microorganism can make full use of in the waste water is converted into vitriol with sulfide in the waste water or thiosulphate, and inorganic nitrogen or organonitrogen are converted into nitric nitrogen.SBR operation week issue 1～4 cycle/day, best 2～3 the cycle/day, flooding time accounts for 20%～90% of the periodic duty time, best 50%～80%.Activated sludge process (as SBR) water inlet volumetric loading is at 0.3kgCOD/ (m
3* d)～1.7kgCOD/ (m
3* d), be preferably in 0.3kgCOD/ (m
3* d)～1.3kgCOD/ (m
3* d), sewage is after Wastewater Treated by Activated Sludge Process, and water outlet COD is at 200～500mg/L, waste water BOD
5/ COD is 0.
Ozone used in the present invention is produced by high frequency ozone generator; the catalyst activity component is one or more in tin, copper, manganese, titanium, cobalt, vanadium, the nickel; carrier is particle diameter 6～100 purpose granulated active carbons; preferably particle diameter 8～24 purpose fruit shell carbons or ature of coal charcoal can directly be catalyzer with the gac also.Reactor bottom adopts common micro porous aeration head or other any effective aeration mode, ozone dosage 20～800mg/L, best 20～100mg/L.The void tower residence time 5～120min of composite waste in the catalytic ozonation reactor is preferably 10～60min, and service temperature is pressed the self-temperature of sewage.The catalytic ozonation associated plant is the bottom aeration, bottom water inlet or top water inlet, bottom aeration preferably, bottom water inlet.Because catalyzed oxidation can transform the organism of difficult for biological degradation biodegradable organism, the water outlet of catalytic ozonation reactor enters in the biological filter, can utilize the organic substance in the further degrading waste water of microbial film in the biological filter, waste water be played the effect of advanced treatment.
Adopt the inventive method to the draining of present refinery electric desalting apparatus, crude oil tank farm is cut water, water is cut in other oil product tank field, liquid hydrocarbon alkaline residue sewage, gasoline alkaline residue sewage, diesel alkaline residue sewage, the composite waste of recirculated water blowdown and the contour concentration saline sewage of reverse osmosis concentrated shrink is handled, can make the COD1500～4000mg/L in the composite waste, ammonia nitrogen 30～80mg/L, kjeldahl nitrogen 80～140mg/L, volatile phenol 200～700mg/L handles COD≤50mg/L respectively, volatile phenol＜0.5mg/L, ammonia nitrogen≤8mg/L, satisfy the water disposal of pollutants new standard of developed regions COD≤60mg/L, eliminate impact simultaneously, and make the oily(waste)water system because the reduction of water outlet salts contg and pollution concentration brings good effect to reusing sewage to oil-containing sewage treatment system.
Embodiment
The composite waste that adopts treatment process of the present invention that water etc. is cut in domestic certain refinery electric desalting apparatus draining, liquid hydrocarbon alkaline residue sewage, gasoline alkaline residue (at first carrying out deodorization through the wet oxidation device handles), diesel alkaline residue sewage and oil product tank field is handled.Composite waste COD 3000mg/L, BOD5 1200mg/L, petroleum-type 20mg/L, ammonia nitrogen 50mg/L, kjeldahl nitrogen 120mg/L, pH value 12.38, salts contg 12.3g/L, volatile phenol 400mg/L, thiosulphate 1000mg/L.Adopt SBR+ catalytic ozonation of the present invention+biological filter combination process to handle mixed waste water, at first need waste water to be carried out neutralizing treatment, make about composite waste pH10, handle then with the vitriol oil.
The used SBR of present embodiment aeration tank useful volume is 10L, and the bottom is provided with boring aeration pipe, and operations such as water inlet, reaction, precipitation, draining are controlled automatically by the PLC system.Because the thiosulphate in the waste water is oxidized prior to ammonia nitrogen at microbial process, and the basicity in the consumption waste water, therefore SBR adopts water intake mode and unrestricted aeration at a slow speed, on the one hand can effectively utilize the basicity in the waste water that thiosulphate is converted into vitriol, the reason waste water ph is too high and make that microorganism active is suppressed in the SBR aeration tank on the other hand.Used catalytic ozonation reactor diameter 6cm, high 23cm, the filling load has the about 290g of cupric oxide (containing cupric oxide 6wt%) activity of such catalysts charcoal.Device is the bottom water inlet, the bottom aeration, and be provided with micro porous aeration head.Adopt the high frequency ozone generator ozone supply.The used biological filter of the present invention size is with the catalytic ozonation reactor, and the bottom water inlet is also adopted the micro porous aeration head aeration, inner filling light ceramic filtrate, the about 0.80kg of loadings.SBR water inlet flow velocity 5ml/min in the present embodiment, cycle water inlet 6 hours 40 minutes, 2 the cycle/day, gas-water ratio 40: 1, cycle sedimentation 1 hour.Catalytic ozonation reactor flooding velocity 10ml/min, ozonize airshed 0.01m
3/ h, water outlet directly enters the biological filter.Biological filter aeration rate 0.03m
3/ h.
After SBR+ catalytic ozonation of the present invention+biological filter combination process is handled, water outlet COD40mg/L, TOC 10mg/L, ammonia nitrogen 3.5mg/L, pH 7.4, and treat effluent is as clear as crystal, satisfies the primary standard in the sewage drainage standard of implementing developed regions.
Claims (10)
1. the treatment process of a saline sewage, comprise following process, saline sewage is regulated pH value to 8～12, adopt activated sludge process to carry out biochemical treatment then, the catalytic ozonation method of Wastewater Treated by Activated Sludge Process effluent adopting solid catalyst is handled, and ozone catalytic oxygen treat effluent is discharged after through the biological filter; Adopt in the catalytic ozonation method of solid catalyst; solid catalyst is the granulated active carbon of load active component; active ingredient is one or more in tin, copper, manganese, titanium, cobalt, vanadium and the nickel; ozone dosage 20～800mg/L, the residence time of waste water in the catalytic ozonation reactor is 5～120min.
2. in accordance with the method for claim 1, it is characterized in that: in the catalytic ozonation method of solid catalyst, the ozone dosage is 20～100mg/L, and the residence time of waste water in the catalytic ozonation reactor is 10～60min.
3. in accordance with the method for claim 1, it is characterized in that: described saline sewage comes from that water is cut in electric desalting apparatus draining, liquid hydrocarbon alkaline residue sewage, gasoline alkaline residue sewage, diesel alkaline residue sewage, crude oil tank farm, one or more combined sewages in water, recirculated water sewer and the reverse osmosis concentrated shrink are cut in the oil product tank field, contain 8%～20% not biodegradable organism in the saline sewage.
4. it is characterized in that in accordance with the method for claim 1: described activated sludge process is intermittent activated sludge process, circulating active sludge method or loop cycle aerating activated sludge process.
5. according to claim 1 or 4 described methods, it is characterized in that: activated sludge process adopts water inlet and unrestricted aeration operating method at a slow speed, and keeps aeration process to guarantee dissolved oxygen concentration 〉=2mg/L in the waste water all the time.
6. in accordance with the method for claim 1; it is characterized in that: ozone is produced by high frequency ozone generator in the catalytic ozonation reactor; solid catalyst is carrier with the granulated active carbon; the carrier particle diameter is 6～100 orders, and the weight content of active ingredient is 0.5%～15% of a final solid catalyst weight.
7. in accordance with the method for claim 1, it is characterized in that: the aerobic biofilter of aeration operation is adopted in described biological filter, and the used filler in biological filter is haydite, zeolite or gac.
8. it is characterized in that in accordance with the method for claim 5: the activated sludge process flooding time accounts for 20%～90% of the periodic duty time.
9. it is characterized in that in accordance with the method for claim 1: the water inlet volumetric loading of activated sludge process is at 0.3kgCOD/ (m
3* d)～1.7kgCOD/ (m
3* d), biological filter volumetric loading 0.3kgCOD/ (m
3* d)～3.0kgCOD/ (m
3* d).
10. it is characterized in that in accordance with the method for claim 1: the water inlet volumetric loading of activated sludge process is at 0.3kgCOD/ (m
3* d)～1.3kgCOD/ (m
3* d), biological filter volumetric loading 0.3kgCOD/ (m
3* d)～1.0kgCOD/ (m
3* d).
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