CN103771656A - Reusing treatment method of refinery waste water - Google Patents
Reusing treatment method of refinery waste water Download PDFInfo
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- CN103771656A CN103771656A CN201210415018.9A CN201210415018A CN103771656A CN 103771656 A CN103771656 A CN 103771656A CN 201210415018 A CN201210415018 A CN 201210415018A CN 103771656 A CN103771656 A CN 103771656A
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Abstract
The invention discloses a reusing treatment method of refinery waste water. Oil removing and suspended matter treatment, sequencing bath reactor (SBR) treatment and osmotic membrane bioreactor (OMBR) treatment are performed in sequence on the refinery waste water. The reusing treatment method is suitable for deep purification and reusing treatment of various types of waste water in an oil refinery, and the water quality of treated water is similar to that of reverse osmosis outlet water.
Description
Technical field
The invention belongs to technical field of waste water processing, relate in particular to a kind of process for reclaiming of refinery water.
Background technology
China's oil refinery effluent treatment scheme is generally oil removal-flotation-biochemical treatment-clarification, biochemical treatment is generally traditional activated sludge process, A/O method, biological activated carbon method etc., although this class biochemical processing process is ripe, but exist floor space larger, the deficiencies such as processing efficiency is lower, and effluent quality is not high and unstable.Along with China drug in some provinces (Beijing, Tianjin, Jiangsu, Shandong, Liaoning etc.) carry out stricter local wastewater discharge standard (COD≤60 mg/L or 50 mg/L), the existing treatment process of refinery faces a qualified discharge difficult problem.
Many refinerys of China are in water-deficient area; face day by day serious shortage of water resources crisis; and still there are gap in wastewater discharge and the developed country of the fresh water unit consumption of refinery and processing ton crude oil, water saving, reduction of discharging and waste water recycling become the only way of Sustainable Development of Enterprises.
The necessary means of Save Water In Refineries and reduction of discharging by reuse after bio-chemical effluent appropriateness or advanced treatment.Appropriateness treatment technology mainly comprises charcoal absorption, biological activated carbon, running sand filtration, membrane filtration (micro-filtration, ultrafiltration and nanofiltration), advanced oxidation (as ozone oxidation), membrane bioreactor etc.Charcoal absorption and biological activated carbon produce a large amount of secondary pollutant waste active carbons; Running sand filtration only can be removed suspended substance, and solvability COD is not had to removal effect substantially; Membrane filtration technique drives by transmembrane pressure, and film easily stops up; High-level oxidation technology is not mature enough, and cost is higher; Membrane bioreactor is very fast in development at present, but also exists film to stop up and the higher difficult problem of energy consumption.Appropriateness is processed water outlet and is generally back to recirculated cooling water make up water, and because this type of quality of reused water is not high, the cycles of concentration of recirculated water is lower.Advanced treatment water outlet can reuse be made de-salted water, and treatment technology is mainly reverse osmosis and electrodialysis.Due to remaining a certain amount of solvability microbial product (as polysaccharide, humic acid class etc.) and calcium magnesium in biochemical treatment water outlet, the reverse osmosis membrane driving by transmembrane pressure also easily occurs to stop up and flux declines.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of process for reclaiming of refinery water, be mainly used in the Treatment for Reuse of all kinds of waste water of refinery.
The process for reclaiming of refinery water of the present invention is as follows: refinery water carries out successively oil removing and oil removal processing, sequencing batch activated sludge (being SBR) are processed and forward osmosis membrane bioreactor (being OMBR) is processed; Wherein oil removing and oil removal are processed main petroleum-type and the suspended substance removed, and SBR processes and removes most COD and ammonia nitrogen, and OMBR removes remaining COD, and holds back suspended substance and inorganic salt.
In the present invention, oil removing and oil removal processing can be conventional methods, as one or more in oil removal, breakdown of emulsion, flocculation, flotation etc., are generally oil removal and flotation.
In the present invention, oil removing and suspended substance are processed water outlet and are processed with SBR.The operational condition of SBR is: 20～40 ℃ of wastewater temperatures, pH 6.0～8.0, sludge concentration (MLSS) 2000～6000 mg/L, hydraulic detention time (HRT) 10～40 h, sludge retention time (SRT) 15～45 d, volumetric loading (organic loading) 0.30～0.60 kg COD/ (m
3d), aerobic processes dissolved oxygen 2.0～5.0 mg/L, anaerobic process dissolved oxygen are no more than 0.5 mg/L, the SBR cycle of operation is 12～24 h, mode is water inlet-aeration-stirring (anaerobism)-precipitate-strain water, wherein each cycle water inlet 0.5～2.0 h, aeration (aerobic)/stirrings (anaerobism) 8.0～20.0 h, precipitation 1.0 ~ 4.0 h, strain water 0.5～2.0 h, the time of aeration and stirring is than being 1:1～2:1.Aeration-stirring can repeat 2～5 times.
In the present invention, SBR processes water outlet and carries out OMBR processing, OMBR by forward osmosis membrane biological reaction tank, draw liquid basin and transferpump and draw the reverse osmosis concentrated compression system of liquid and form.OMBR is immersion, operates in continuous aerobic treatment pattern.OMBR membrane module is flat, tubular fibre formula, tubular type or spiral forward osmosis membrane, and material is triacetate fiber (CTA) or thin layer polymeric amide, and aerating system is installed on the bottom of membrane module.Aerating system comprises air pocket gas distributor and microbubble gas sparger, and air pocket gas distributor adopts conventional aeration structure, as coil tube type aeration structure, and branch pipe type aeration structure etc., the diameter of air pocket is generally 5～50mm, is preferably 10～30mm.Microbubble gas sparger is by film aeration structure etc., and microvesicle diameter is less than 1mm.Two kinds of aerating systems are evenly arranged on the bottom of membrane module.Aeration rate for air pocket is generally 5～30L/m
3water is 1～10 L/m for the tolerance of microvesicle
3water.Air pocket and microvesicle are provided respectively, and air pocket mixes for mud and prevents that film from stopping up, and microvesicle is mainly used in microorganism oxygen supply.OMBR operating parameter is as follows: diafiltration flux 5～20 L/ (m
2h), hydraulic detention time (HRT) 3～18 h, sludge retention time (SRT) 15～45 d, mixed liquor suspended solid, MLSS concentration (MLSS) 3000～8000 mg/L, organic loading (OLR) 0.5～3.5 kg COD/ (m
3d).Draw the sodium chloride solution that liquid is 0.5～1.5 mol/L, the dense forward osmosis membrane assembly that draws liquid and flow through by pump delivery biological reaction tank, draw purifying waste water in biological reaction tank by positive osmosis, and be diluted, rare liquid that draws concentrates by conventional reverse osmosis system, dope returns and draws liquid basin, and water from diffusion is purification water outlet.
The present invention's application two-stage efficient biochemical treatment process, wherein SBR can process COD and ammonia nitrogen simultaneously, OMBR can effectively process COD, suspended substance and inorganic salt, can effectively substitute the two waste water advanced treatment and reuse treatment process of film of traditional Two-Stage Biochemical processing+clarification or sand filtration processing+ultrafiltration and reverse osmosis, structures and floor space are less, are easy to realize efficient deviceization operation and management.Residual sludge in SBR water outlet can be used for OMBR, saves traditional clarification or sand filtration processing, and OMBR membrane filtration is that chemical concentration difference drives, and coordinates suitable working method, has solved the film blockage problem that conventional pressure differential causes.Utilization is drawn liquid by the forward osmosis membrane water intaking that circulates, with the concentrated liquid that draws of reverse-osmosis circulating, and discharge and purify waste water, eliminate routine biochemistry and processed the reverse osmosis membrane blockage problem that in water outlet, microbial product (as polysaccharide and humic acid class material etc.) and calcium magnesium cause.OMBR water outlet can reach reverse osmosis water outlet water quality, has realized efficient advanced treatment and the reuse of refinery water.In the present invention, suitable OMBR and SBR combination, realize advanced treatment and reclaim oil refining sewerage, and running is simultaneously stable, simple to operate, can long period steady running.
Embodiment
Further illustrate the solution of the present invention and effect below by embodiment.
Embodiment 1
Adopt refinery water process for reclaiming of the present invention, technical process is oil removal-flotation-SBR-OMBR, and concrete test conditions is as follows:
Get sewage from oil refinery and process the 10 L SBR small testing device processing for water outlet of an oil removal and flotation, main operational condition is: 25 ℃ of wastewater temperatures, pH 7.0, sludge concentration (MLSS) 3500 mg/L, hydraulic detention time 15 h, sludge retention time 25 d, the SBR cycle of operation is 12 h, mode for water inlet-(aeration-stirring) repeat 3 times-precipitate-strain water, wherein each cycle intake 1.0 h, aeration (aerobic)/stirring (anaerobism) 8.0 h, precipitation 2.0 h, strain water 1.0 h, time of aeration and stirring is than being 1:1.
10 L OMBR small testing device processing for SBR water outlet, OMBR film is 0.1 m × 0.5 m triacetate fiber forward osmosis membrane (Hydration Technologies company provides), draw the sodium chloride solution that liquid is 1.0 mol/L, circulation velocity is 3.0 L/min, and membrane permeation flow velocity is 3～7 L/m
2/ h, hydraulic detention time 10 h, sludge retention time 20 d, sludge concentration 6500 mg/L.
Under the processing condition of optimizing, process above-mentioned waste water, the leading indicator of water inlet and processing water outlet is in table 1.
Table 1 embodiment 1 is intake and is processed water outlet leading indicator.
| Project | Water inlet, mg/L | Purify water outlet, mg/L | Clearance, % |
| COD | 4000～6000 | ≤10 | ≥99.7％ |
| NH 3-N | 10～45 | ≤0.5 | ≥95.0％ |
| Petroleum-type | 10～35 | ≤0.1 | ≥99.9％ |
| Turbidity | － | ≤0.3 NTU | － |
Embodiment 2
Adopt refinery water treatment process of the present invention, technical process is oil removal-flotation-SBR-OMBR, under the processing condition of optimizing, processes above-mentioned waste water, and the leading indicator of water inlet and processing water outlet is in table 2.
In the present invention, oil removing and suspended substance are processed water outlet and are processed with SBR.The operational condition of SBR is: 30 ℃ of wastewater temperatures, pH 7.0, sludge concentration (MLSS) 5000 mg/L, hydraulic detention time (HRT) 20 h, sludge retention time (SRT) 20 d, volumetric loading (organic loading) 0.40 kg COD/ (m
3d), aerobic processes dissolved oxygen 2.0 mg/L, anaerobic process dissolved oxygen are no more than 0.4 mg/L, the SBR cycle of operation is 20 h, mode is water inlet-aeration-stirring (anaerobism)-precipitate-strain water, wherein each cycle intake 1.0 h, aeration (aerobic)/stirring (anaerobism) 17.0 h, precipitation 1.0 h, strain water 1.0 h, time of aeration and stirring is than being 2:1.Aeration-stirring can repeat 4 times.
In the present invention, SBR processes water outlet and carries out OMBR processing, OMBR by forward osmosis membrane biological reaction tank, draw liquid basin and transferpump and draw the reverse osmosis concentrated compression system of liquid and form.OMBR is immersion, operates in continuous aerobic treatment pattern.OMBR membrane module is flat forward osmosis membrane, material is triacetate fiber (CTA) or thin layer polymeric amide, aerating system is installed on the bottom of membrane module, air pocket and microvesicle are provided respectively, air pocket mixes for mud and prevents that film from stopping up, and air pocket mean diameter is 20mm, and microvesicle is mainly used in microorganism oxygen supply, microvesicle mean diameter is 0.7mm, and the tolerance of air pocket is 14L/m
3water, the tolerance of microvesicle is 5 L/m
3water.OMBR operating parameter is as follows: diafiltration flux 14 L/ (m
2h), hydraulic detention time (HRT) 15h, sludge retention time (SRT) 20 d, mixed liquor suspended solid, MLSS concentration (MLSS) 4500 mg/L, organic loading (OLR) 2.5 kg COD/ (m
3d).Draw the sodium chloride solution that liquid is 1.2 mol/L, the dense forward osmosis membrane assembly that draws liquid and flow through by pump delivery biological reaction tank, draw purifying waste water in biological reaction tank by positive osmosis, and be diluted, rare liquid that draws concentrates by conventional reverse osmosis system, dope returns and draws liquid basin, and water from diffusion is purification water outlet.
Table 2 embodiment 2 is intake and is processed water outlet leading indicator.
| Project | Water inlet, mg/L | Purify water outlet, mg/L | Clearance, % |
| COD | 3500～5000 | ≤10 | ≥99.7％ |
| NH 3-N | 15～60 | ≤0.5 | ≥95.0％ |
| Petroleum-type | 5～20 | ≤0.1 | ≥99.9％ |
| Turbidity | － | ≤0.3 NTU | － |
Embodiment 3
Adopt refinery water treatment process of the present invention, technical process is oil removal-flotation-SBR-OMBR, under the processing condition of optimizing, processes above-mentioned waste water, and the leading indicator of water inlet and processing water outlet is in table 3.
In the present invention, oil removing and suspended substance are processed water outlet and are processed with SBR.The operational condition of SBR is: 40 ℃ of wastewater temperatures, pH 6.5, sludge concentration (MLSS) 3000 mg/L, hydraulic detention time (HRT) 15 h, sludge retention time (SRT) 15 d, volumetric loading (organic loading) 0.30 kg COD/ (m
3d), aerobic processes dissolved oxygen 4.0 mg/L, anaerobic process dissolved oxygen are no more than 0.3 mg/L, the SBR cycle of operation is 12 h, mode is water inlet-aeration-stirring (anaerobism)-precipitate-strain water, wherein each cycle intake 1.0 h, aeration (aerobic)/stirring (anaerobism) 10.0 h, precipitation 0.5 h, strain water 0.5 h, time of aeration and stirring is than being 1:1.Aeration-stirring can repeat 6 times.
In the present invention, SBR processes water outlet and carries out OMBR processing, OMBR by forward osmosis membrane biological reaction tank, draw liquid basin and transferpump and draw the reverse osmosis concentrated compression system of liquid and form.OMBR is immersion, operates in continuous aerobic treatment pattern.OMBR membrane module is flat, tubular fibre formula, tubular type or spiral forward osmosis membrane, material is triacetate fiber (CTA) or thin layer polymeric amide, aerating system is installed on the bottom of membrane module, air pocket and microvesicle are provided respectively, air pocket mixes for mud and prevents that film from stopping up, and microvesicle is mainly used in microorganism oxygen supply.OMBR operating parameter is as follows: diafiltration flux 13 L/ (m
2h), hydraulic detention time (HRT) 10 h, sludge retention time (SRT) 20 d, mixed liquor suspended solid, MLSS concentration (MLSS) 4200 mg/L, organic loading (OLR) 2.5 kg COD/ (m
3d).Draw the sodium chloride solution that liquid is 1.3 mol/L, the dense forward osmosis membrane assembly that draws liquid and flow through by pump delivery biological reaction tank, draw purifying waste water in biological reaction tank by positive osmosis, and be diluted, rare liquid that draws concentrates by conventional reverse osmosis system, dope returns and draws liquid basin, and water from diffusion is purification water outlet.
Table 3 embodiment 3 is intake and is processed water outlet leading indicator.
| Project | Water inlet, mg/L | Purify water outlet, mg/L | Clearance, % |
| COD | 5000～7500 | ≤10 | ≥99.7％ |
| NH 3-N | 15～65 | ≤0.5 | ≥95.0％ |
| Petroleum-type | 20～50 | ≤0.1 | ≥99.9％ |
| Turbidity | － | ≤0.3 NTU | － |
Embodiment 4
Option A: press the working method of embodiment 2, long-term operation 3000 hours, treatment effect is stable, and degradation problem under film obstruction and effluent quality does not occur.
Option b: press the working method of embodiment 2, just cancel the air pocket aeration of OMBR, turn round after 800 hours, have obvious film latch up phenomenon, need to carry out film cleaning.
Claims (10)
1. a process for reclaiming for refinery water, is characterized in that comprising following process: refinery water carries out successively oil removing and oil removal processing, sequencing batch activated sludge are processed and forward osmosis membrane bioreactor processing; Wherein oil removing and oil removal are processed main petroleum-type and the suspended substance removed, and SBR processes and removes most COD and ammonia nitrogen, and OMBR removes remaining COD, and holds back suspended substance and inorganic salt; Sequencing batch activated sludge is SBR, and forward osmosis membrane bioreactor is OMBR.
2. method according to claim 1, is characterized in that: oil removing and oil removal are processed one or more that adopt in oil removal, breakdown of emulsion, flocculation, flotation.
3. method according to claim 1, it is characterized in that: oil removing and oil removal are processed water outlet SBR and processed, and the operational condition of SBR is: wastewater temperature is that 20～40 ℃, pH 6.0～8.0, sludge concentration are that 2000～6000 mg/L, hydraulic detention time are that 10～40 h, sludge retention time are that 15～45 d, volumetric loading are 0.30～0.60 kg COD/ (m
3d), aerobic processes dissolved oxygen 2.0～5.0 mg/L, anaerobic process dissolved oxygen are no more than 0.5 mg/L.
4. according to the method described in claim 1 or 3, it is characterized in that: the SBR cycle of operation is 12～24 h, mode is water inlet-aeration-stir-precipitate-strain water, wherein each cycle water inlet 0.5～2.0 h, aeration/stirring 8.0～20.0 h, precipitation 1.0 ~ 4.0 h, strain water 0.5～2.0 h, the time of aeration and stirring, aeration-stirring repeated 2～5 times than being 1:1～2:1.
5. method according to claim 1, is characterized in that: SBR processes water outlet and carries out OMBR processing, OMBR by forward osmosis membrane biological reaction tank, draw liquid basin and transferpump and draw the reverse osmosis concentrated compression system of liquid and form.
6. method according to claim 1 or 5, is characterized in that: OMBR is immersion, operates in continuous aerobic treatment pattern.
7. method according to claim 1 or 5, is characterized in that: OMBR membrane module is flat, tubular fibre formula, tubular type or spiral forward osmosis membrane, and material is triacetate fiber or thin layer polymeric amide, and aerating system is installed on the bottom of membrane module.
8. method according to claim 1 or 5, is characterized in that OMBR operating parameter is as follows: diafiltration flux 5～20 L/ (m
2h), hydraulic detention time 3～18 h, sludge retention time 15～45 d, mixed liquor suspended solid, MLSS concentration 3000～8000 mg/L, organic loading 0.5～3.5 kg COD/ (m
3d).
9. method according to claim 5, it is characterized in that: draw the sodium chloride solution that liquid is 0.5～1.5 mol/L, the dense forward osmosis membrane assembly that draws liquid and flow through by pump delivery biological reaction tank, draw purifying waste water in biological reaction tank by positive osmosis, and be diluted, rare liquid that draws concentrates by conventional reverse osmosis system, and dope returns and draws liquid basin, and water from diffusion is purification water outlet.
10. method according to claim 7, it is characterized in that: aerating system comprises air pocket gas distributor and microbubble gas sparger, air pocket gas distributor adopts conventional aeration structure, comprise coil tube type aeration structure or branch pipe type aeration structure, the diameter of air pocket is 5～50mm, is preferably 10～30mm; Microbubble gas sparger comprises film aeration structure, and microvesicle diameter is less than 1mm.
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