CN102153230B - Method and device for treating salt-containing wastewater produced during producing epoxy chloropropane by using glycerol as raw material - Google Patents
Method and device for treating salt-containing wastewater produced during producing epoxy chloropropane by using glycerol as raw material Download PDFInfo
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Abstract
The invention relates to the technical field of industrial wastewater treatment, in particular to a method and a device for treating salt-containing wastewater produced during producing epoxy chloropropane by using glycerol as a raw material. The treatment method comprises the following steps of: (1) mixing the salt-containing wastewater and other wastewater with low pollution, adding nitrogen and phosphorus nutrients, and discharging the mixed wastewater after the salt content of the wastewater is less than 5 percent; (2) introducing the wastewater treated in the step (1) into a moving bed film biological reactor, and further treating the wastewater by using active sludge; and (3) introducing the wastewater treated in the step (2) into an ozone reaction unit to perform ozone oxidation treatment, and then discharging the treated wastewater. The invention also provides the wastewater treatment device adopted by the method. The device mainly comprises a regulating tank, the moving bed film biological reactor and the ozone reaction unit. The treatment process is simple, the operation is stable, the cost is low, the water quality of the discharged water can be ensured, and the method and the device are suitable for treating the organic wastewater with high salt content and high chemical oxygen demand (COD).
Description
Technical field
The present invention relates to the technology for treating industrial waste water field, relate to the processing of industrial brine waste, specifically, be a kind of be the treatment process and the device of the brine waste of raw material production epoxy chloropropane with glycerine and sodium-chlor.
Background technology
Epoxy chloropropane is a kind of important Organic Chemicals and fine chemical product, has widely in industries such as coating, tackiness agent, strongthener, cast material and electronic shell stampings and uses.The working method of traditional epoxy chloropropane has based on two kinds of the propylene high-temperature chlorination of petroleum and propylene acetate methods.In recent years, because skyrocketing of oil price makes the epoxy chloropropane of above-mentioned explained hereafter hold at high price.In this case, people have developed the glycerine that the utilizes biodiesel byproduct novel process for the raw material production epoxy chloropropane.This process free to the dependence of petroleum resources, also reduced pollution simultaneously to environment, with respect to the technology of producing epoxy chloropropane with petroleum, its input on equipment also significantly reduces.But; In the process that with glycerine is the raw material production epoxy chloropropane, can produce a kind of high salinity (sodium-chlor), high chemical oxygen demand (COD; With glycerine is main) organic waste water, therefore, this waste water effectively is treated as one of key that can this production technique successful Application.
At present, the treatment process to salt-containing organic wastewater mainly contains physico-chemical process, oxidation style and biological process etc.Chinese patent CN1004695B discloses " a kind of method that from brine waste, reclaims glycerine ", and its step mainly comprises: evaporation, with the amylalcohol contact, separate and separate out salt, flash distillation and go out amylalcohol, rectification under vacuum; This technology relatively is suitable for the brine waste that the process for producing epichlorohydrin resin produces; Simultaneously can obtain refining glycerine and solid sodium chloride, still, this method complex process; Energy consumption is high, and processing costs is than higher.Patent CN 101066819 discloses " a kind of high density saliferous bio-refractory organic industrial sewage combined treatment process " one by one; It comprises: freezing pre-treatment; Said waste water is placed freezing freezing, temperature is 0～30 ℃, treats that waste water is freezing after certain solid-to-liquid ratio, to take out ice sample; Melt with water purification flushing back, treat that follow-up catalytic treatment is subsequent use; The ice sample thawing water is carried out photocatalytic degradation, control light-catalysed dosage, light application time, system pH parameter and control the treatment process operation.The advantage of this treatment process is to handle high density salt-containing organic wastewater such as the reluctant waste water of biological processes such as percolate, dye intermediate wastewater; Remove most salinity and organism in the waste water; Reduce the photocatalysis treatment load; Improve photocatalysis efficiency, the COD clearance can be improved more than 30%.But the processing power of this method is low, and energy consumption is high, is not suitable for the big said waste water of day output.Chinese patent CN101531442A discloses " it is the wastewater treatment method and the device of raw material production epoxy chloropropane that a kind of absorbing process is handled with glycerine "; It adopts the glycerine in the sorbing material absorption waste water similar with the Oils,glyceridic,cod-liver molecular diameter; Wash out the glycerine in the adsorption column with rinse water then; Absorption effluent contains sodium-chlor, can be used for the change salt solution of chlorine industry, contains rinse water discharging after biological process is handled of lower concentration glycerine.The advantage of this treatment process is that technology is simple.But, this treatment process to sorbing material have relatively high expectations and adsorption treatment after water outlet in remaining glycerol concentration still higher, the cost of waste water reuse is higher.
Adopting biological process (activated sludge process) to handle to salt-containing organic wastewater is the method for present the most a kind of processing of using.But the high salt in the waste water can produce the biology of treatment system and poison, suppresses, or destroys sludge settling property, thereby causes ordinary activated sludge to be difficult to realize the effective processing to high-salt wastewater.Chinese patent CN 101054232A discloses " a kind of highly efficient treatment process for waster water with high content of salt "; It is through forming aerobic particle mud and adopting certain startup operation method and sludge acclimatization mode in sequencing batch reactor; Thereby under the condition that does not add halophilic bacterium, make the mud in the reactor drum realize assembling growth and form the anti-salt impact capacity that little ecology is improved system, realize efficient processing high slat-containing wastewater.But its main deficiency is that the cultivation of aerobic particle mud is difficulty very.Chinese patent CN 101723539A discloses " a kind of treatment process of brine waste ", and it adopts BAF as the agent set of handling, and has good salt tolerance; The characteristics that capacity of resisting impact load is strong, still, because the processing of BAF load is not high; And need to adopt special suspending carrier and engineering bacteria; Therefore, be difficult to handle the higher waste water of organic pollutant load, processing cost is higher simultaneously.In addition, the treatment process of above-mentioned two patents is relatively more difficult to the processing that salt concn surpasses 30g/L waste water.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, providing a kind of is the treatment process of the brine waste of raw material production epoxy chloropropane with glycerine; A purpose more of the present invention is the wastewater treatment equipment that provides said method to adopt.
Described brine waste is for being the high content of salt that produces in the process of raw material production epoxy chloropropane, the organic waste water of high chemical oxygen demand (COD) with glycerine; Its sodium chloride content is 200～260g/L; COD content is 2000～3000mg/L; Most COD are made up of glycerine and verivate thereof in the waste water, and the content of amounting to into glycerine is about 2.0～3.5g/L.Hence one can see that, though be that the waste water salinity that produces in the production process of raw material production epoxy chloropropane is high, COD is high with glycerine, its component is simple, mainly is made up of sodium-chlor, water and glycerine, is a kind of more special waste water.Because main organic pollutant (glycerine) has good biodegradability in the waste water, therefore, can adopt biological treatment that it is handled.Simultaneously, the processing of this waste water must solve three problems: (1) high density salinity in biological treatment process to the inhibition of microbial cells; (2) settling property of mud is poor in the biological treatment process of high slat-containing wastewater, and water quality instability of (3) water outlet and COD concentration maybe be higher.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
A kind of is the treatment process of the brine waste of raw material production epoxy chloropropane with glycerine, it is characterized in that, may further comprise the steps:
(1) described brine waste being introduced equalizing tank with other salt concentrations and the lower waste water of Pollutant levels mixes; Make the sodium-chlor saltiness of mixing back waste water at 20～60 g/L; In waste water, add an amount of nitrogen, phosphorus nutrition thing simultaneously, guarantee organic pollutant needed nutrient concentrations in degradation process in the waste water, the mass ratio of COD, nitrogen and phosphorus is 85:5:1 in the waste water; Regulate the water quality of waste water, make the saltiness of waste water be lower than 5% back discharge equalizing tank;
The waste water of (2) step (1) equalizing tank being discharged is introduced the moving-bed membrane bioreactor and is handled; Concentration of activated sludge is 2500～10000mg/L in it, and the admission space ratio of floating stuffing is 40～80%, utilizes the active sludge in the reactor drum to further process;
The waste water of (3) step (2) moving-bed membrane bioreactor being discharged is introduced the ozone reaction unit, in waste water, charges into ozone 5～30 minutes with ozone reactor, with further removal COD, and the water outlet after output is handled then;
The tail gas that this treatment step produces is removed ozone with the ozone layer destroying device, and remaining gas returns the moving-bed membrane bioreactor and does the aeration use.
The described nitrogen of step (1), phosphorus nutrition thing are ammonium chloride and sodium phosphate.
The described moving-bed membrane bioreactor of step (2) is made up of Moveable packings bio-reactor and mud-water separation film unit, the filler employing lightweight in the Moveable packings bio-reactor, thread, the cylindric or globular floating stuffing that specific surface area is bigger; Mud-water separation film unit or be immersed in the type that the vacuumizes membrane module in the moving-bed membrane bioreactor; Or be independent of the malleation filtering type membrane module of moving-bed membrane bioreactor; Aperture in the said membrane module is 0.05～1 micron; Filtering waste water is discharged reactor drum, active sludge is trapped in the reactor drum.
The described ozone reaction of step (3) unit comprises ozone oxidation pond, ozone reactor and ozone layer destroying device.
Described ozone oxidation pond is made up of the ozonizer outside pond body, pond inner bottom part ozone gas distribution system, ozone transport pipe and the pond, obtains after the required ozone in ozone oxidation pond is handled pure oxygen or air by ozonizer.When adopting pure oxygen as ozone gas source, the tail gas after the ozone reactor utilization will be collected and feed in the moving-bed bed membrane bioreactor, for the mikrobe in it provides oxygen.
A kind of is the treatment unit of the brine waste of raw material production epoxy chloropropane with glycerine; Contain equalizing tank, moving-bed membrane bioreactor, ozone reaction unit; Between equalizing tank and the moving-bed membrane bioreactor, use pipe connection between moving-bed membrane bioreactor and the ozone reaction unit; It is characterized in that; Described moving-bed membrane bioreactor is made up of Moveable packings bio-reactor and mud-water separation film unit: the floating stuffing employing lightweight in the Moveable packings bio-reactor, thread, the cylindric or globular floating stuffing that specific surface area is bigger; Mud-water separation film unit or be immersed in the type that the vacuumizes membrane module in the moving-bed membrane bioreactor, or be independent of the malleation filtering type membrane module of moving-bed membrane bioreactor; Described ozone reaction unit comprises ozone oxidation pond, ozone reactor and ozone layer destroying device.
Described have vacuumize the type membrane module the moving-bed membrane bioreactor by the moving-bed membrane bioreactor, vacuumize type membrane module, blast aeration pipe, tail gas aeration tube, floating stuffing, water inlet pipe, rising pipe and rising pipe suction pump and constitute, the aperture that vacuumizes in the type membrane module is 0.05～1 micron.
The described moving-bed membrane bioreactor that has malleation filtering type membrane module is made up of moving-bed membrane bioreactor, malleation filtering type membrane module, blast aeration pipe, tail gas aeration tube, floating stuffing, water inlet pipe, rising pipe, rising pipe topping-up pump and mud return line, and the aperture in the malleation filtering type membrane module is 0.05～1 micron.
Described ozone oxidation pond is made up of gas communication, effluent weir, tail gas escape pipe, water outlet buffer zone and the rising pipe of pond body, water inlet pipe, water inlet buffer zone, influent weir, reaction zone, ozone inlet pipe, ozone gas distribution system, reaction zone and exhalant region, obtains after the required ozone in ozone oxidation pond is handled pure oxygen or air by the ozonizer outside the pond.
Positively effect of the present invention is:
(1) described treatment process adopts other waste water to being that the waste water of raw material production epoxy chloropropane mixes and dilutes with glycerine; Reclaim and utilize the tail gas of ozone oxidation reaction; Realized effective processing, resources effective has been reclaimed and utilization waste water and waste gas;
(2) wastewater treatment process is simple, and is stable and cost is low, and effluent quality can be able to guarantee;
(3) described treatment unit is rational in infrastructure, preferably the treatment process of embodiment of the present invention;
(4) not only to be suitable for handling with glycerine be the high content of salt that produces in the process of raw material production epoxy chloropropane, the organic waste water of high COD to technical scheme of the present invention, and be applicable to and handle brine waste (salt concn 1～5%, the COD concentration 200～1000mg/L) that oil, petrochemical industry, Coal Chemical Industry and pharmaceutical industry etc. produce.
Description of drawings
Fig. 1 is the FB(flow block) of treatment process of the brine waste of raw material production epoxy chloropropane with glycerine for the present invention;
Fig. 2 is the structural representation that has the moving-bed membrane bioreactor that vacuumizes the type membrane module;
Fig. 3 is the structural representation that has the moving-bed membrane bioreactor of malleation filtering type membrane module;
Fig. 4 is the structural representation in ozone oxidation pond;
Fig. 5 is the detected result figure of moving-bed membrane bioreactor small testing device water outlet COD and chlorine ion concentration;
Fig. 6 is the detected result figure of useful volume 400L moving-bed membrane bioreactor water outlet COD and chlorine ion concentration;
Label among the figure is respectively:
1, moving-bed membrane bioreactor; 2, vacuumize the type membrane module; 3, blast aeration pipe;
4, tail gas aeration tube; 5, floating stuffing; 6, water inlet pipe;
7, rising pipe; 8, rising pipe suction pump;
21, moving-bed membrane bioreactor; 22, malleation filtering type membrane module; 23, blast aeration pipe;
24, tail gas aeration tube; 25, floating stuffing; 26, water inlet pipe;
27, rising pipe; 28, rising pipe topping-up pump; 29, mud return line;
31, pond body; 32, water inlet pipe; 33, water inlet buffer zone;
34, influent weir; 35, reaction zone; 36, ozone inlet pipe;
37, ozone gas distribution system; 38, the gas communication of reaction zone and exhalant region; 39, effluent weir;
310, tail gas escape pipe; 311, water outlet buffer zone; 312, rising pipe.
Embodiment
Provide embodiment of the present invention below in conjunction with accompanying drawing, but be noted that enforcement of the present invention is not limited to following embodiment.
Referring to accompanying drawing 1, a kind of is the treatment process of the brine waste of raw material production epoxy chloropropane with glycerine, may further comprise the steps:
(1) described brine waste being introduced equalizing tank with other salt concentrations and the lower waste water of Pollutant levels mixes; Said other waste water comprise the water outlet of sewage work and/or the waste water that other salt concn are lower, Pollutant levels are lower; Make the sodium-chlor saltiness of mixing back waste water at 20～60 g/L; In waste water, add an amount of ammonium chloride and sodium phosphate simultaneously, guarantee organic pollutant needed nutrient concentrations in degradation process in the waste water, the mass ratio of COD, nitrogen and phosphorus is 85:5:1 in the waste water; Regulate the water quality of waste water, make the saltiness of waste water be lower than 5% back discharge equalizing tank;
The waste water of (2) step (1) equalizing tank being discharged is introduced the moving-bed membrane bioreactor and is handled; Described moving-bed membrane bioreactor is made up of Moveable packings bio-reactor and mud-water separation film unit; Filler employing lightweight in the Moveable packings bio-reactor, thread, the cylindric or globular floating stuffing that specific surface area is bigger; The admission space ratio of floating stuffing is 40～80%, and concentration of activated sludge is 5000mg/L in it;
Described mud-water separation film unit or be immersed in the type that the vacuumizes membrane module in the moving-bed membrane bioreactor; Or be independent of the malleation filtering type membrane module of moving-bed membrane bioreactor; Aperture in the said membrane module is 0.05～1 micron; Can filtering waste water be discharged reactor drum, active sludge is trapped in the reactor drum;
The waste water of (3) step (2) moving-bed membrane bioreactor being discharged is introduced the ozone reaction unit; Described ozone reaction unit comprises ozone oxidation pond, ozone reactor and ozone layer destroying device, obtains after the required ozone in ozone oxidation pond is handled pure oxygen or air by ozonizer; Described ozone oxidation pond is made up of the ozonizer outside pond body, pond inner bottom part ozone gas distribution system, ozone transport pipe and the pond;
With charging into ozone 5 minutes in the waste water of ozone reactor in the ozone oxidation pond, with further removal COD; When adopting pure oxygen as ozone gas source, the tail gas after ozone reactor utilizes is removed ozone with the ozone layer destroying device, and remaining gas will be collected and feed the moving-bed membrane bioreactor, for the mikrobe in it provides oxygen;
Water outlet after output is handled after handle in the ozone oxidation pond, its water outlet COD can reach below the 100mg/L.
Referring to accompanying drawing 2～4.A kind of is the treatment unit of the brine waste of raw material production epoxy chloropropane with glycerine; Contain equalizing tank, moving-bed membrane bioreactor, ozone reaction unit, between equalizing tank and the moving-bed membrane bioreactor, use pipe connection between moving-bed membrane bioreactor and the ozone reaction unit; Described moving-bed membrane bioreactor is made up of Moveable packings bio-reactor and mud-water separation film unit, the floating stuffing employing lightweight in the Moveable packings bio-reactor, thread, the cylindric or globular floating stuffing that specific surface area is bigger.Described mud-water separation film unit or be immersed in the type that the vacuumizes membrane module in the moving-bed membrane bioreactor, or be independent of the malleation filtering type membrane module of moving-bed membrane bioreactor.
Referring to accompanying drawing 2; Have vacuumize the type membrane module the moving-bed membrane bioreactor by moving-bed membrane bioreactor 1, vacuumize type membrane module 2, blast aeration pipe 3, tail gas aeration tube 4, floating stuffing 5, water inlet pipe 6, rising pipe 7 and rising pipe suction pump 8 and constitute; Wherein, Floating stuffing 5 is housed in the Moveable packings bio-reactor 1; Floating stuffing 5 employing lightweights, thread, the cylindric or globular floating stuffing that specific surface area is bigger, the admission space ratio is 60%, concentration of activated sludge is 5000mg/L in it; Be arranged on the side in the moving-bed membrane bioreactor 1 with vacuumizing type membrane module 2, the aperture that vacuumizes in the type membrane module 2 is 0.05～1 micron; Blast aeration pipe 3 feeds in the moving-bed membrane bioreactor 1 from the bottom with tail gas aeration tube 4; Water inlet pipe 6 feeds in the moving-bed membrane bioreactor 1 from the top that vacuumizes type membrane module 2 opposite sides; Rising pipe 7 is derived outside the moving-bed membrane bioreactor 1 by the top that vacuumizes type membrane module 2, and rising pipe 7 is provided with rising pipe suction pump 8.
Referring to accompanying drawing 3; The described moving-bed membrane bioreactor that has malleation filtering type membrane module is made up of moving-bed membrane bioreactor 21, malleation filtering type membrane module 22, blast aeration pipe 23, tail gas aeration tube 24, floating stuffing 25, water inlet pipe 26, rising pipe 27, rising pipe topping-up pump 28 and mud return line 29; Wherein, Floating stuffing 25 is housed in the Moveable packings bio-reactor 21; Floating stuffing 25 employing lightweights, thread, the cylindric or globular floating stuffing that specific surface area is bigger, the admission space ratio is 60%, concentration of activated sludge is 5000mg/L in it; Malleation filtering type membrane module 22 is arranged on a side of moving-bed membrane bioreactor 21 outsides, and the aperture in the malleation filtering type membrane module 22 is 0.05～1 micron; Blast aeration pipe 23 feeds in the moving-bed membrane bioreactor 21 from the bottom with tail gas aeration tube 24; Water inlet pipe 26 feeds in the moving-bed membrane bioreactor 21 from the top of malleation filtering type membrane module 22 opposite sides; Between moving-bed membrane bioreactor 21 and malleation filtering type membrane module 22, set out water pipe 27 and rising pipe topping-up pump 28, rising pipe 27 is derived from the opposite side of malleation filtering type membrane module 22;
Derive a mud return line 29 from the top of malleation filtering type membrane module 22, mud return line 29 imports moving-bed membrane bioreactor 21 in the upper end at nearly water inlet pipe 26 places.
Referring to accompanying drawing 4, described ozone reaction unit comprises ozone oxidation pond, ozone reactor and ozone layer destroying device.Described ozone oxidation pond is made up of gas communication 38, effluent weir 39, tail gas escape pipe 310, water outlet buffer zone 311 and the rising pipe 312 of pond body 31, water inlet pipe 32, water inlet buffer zone 33, influent weir 34, reaction zone 35, ozone inlet pipe 36, ozone gas distribution system 37, reaction zone and exhalant region; Pond body 31 is darker reaction zone 35 at the bottom of constituting a pond between influent weir 34 to the effluent weir 39; Pond body 31 is water inlet buffer zone 33 in the front of influent weir 34, and the lower end of water inlet buffer zone 33 is provided with water inlet pipe 32; The lower end of darker reaction zone 35 is provided with ozone gas distribution system 37 between influent weir 34 and effluent weir 39; Connect an ozone inlet pipe 36 of stretching out pond body 31 in the middle of the ozone gas distribution system 37, make the required ozone in ozone oxidation pond can be by supplying with behind processing pure oxygen of the ozonizer the pond outside or the air; A dividing plate is set, the space that the lower end of dividing plate and ozone gas distribution system 37 remain with in the rear section of reaction zone 35; The pond body 31 of effluent weir 39 back is water outlet buffer zone 311, and the lower end of water outlet buffer zone 311 is provided with rising pipe 312.
After the waste water of discharging from the moving-bed membrane bioreactor gets into pond, ozone oxidation pond bodies 31 from water inlet pipe 31; At first get into water inlet buffer zone 33; Carry out the water yield and water quality homogenizing, cover influent weir 34 then and get into reaction zone 35, ozone gas distribution system 37 makes ozone and waste water thorough mixing and reaction; Reaction back water outlet covers effluent weir 39 and gets into water outlet buffer zone 311, discharges via rising pipe 312 again.Tail gas behind the ozone oxidation reaction is then discharged from tail gas escape pipe 310 via the gas communication 38 of reaction zone and exhalant region.The gas that contains residual ozone of discharging feeds the moving-bed membrane bioreactor again after ozone layer destroying device (seeing accompanying drawing 1) is handled, thereby the oxygen that contains in the gas is effectively utilized again.
3 EXPERIMENTAL EXAMPLE of the present invention below are provided:
Embodiment 1
Adopting moving-bed membrane bioreactor small testing device to handle with glycerine is the brine waste of raw material production epoxy chloropropane, and the content of glycerine is 2500mg/L in the waste water, and NaCl content is 208000 mg/L; Water outlet after employing sewage work handles and described waste water are by the mixed of 6～8:1; The COD of sewage disposal plant effluent is 70～90mg/L; Chlorine ion concentration is 3000～5000mg/L, and the COD that mixes back waste water is 500～700mg/L, and chlorine ion concentration is about 20000～25000mg/L;
The useful volume 7.5L of moving-bed membrane bioreactor small testing device; In PVC material column protruded packing that to adorn 60 diameters be 4cm, high 4cm; The filler of filling accounts for 50% of reactor drum useful volume; Adorn 2 board-like microfiltration membrane of PVDF in the reactor drum, 0.1～1 micron of membrane pore size, the useful area 0.08m of film
2The hydraulic detention time of composite waste in reactor drum is 1 day, and activated sludge concentration is 4000～6000mg/L in the reactor drum, and organic pollution load is about 0.15kgCOD/ (kgMLSS days); Experimental result is shown in accompanying drawing 5 water outlet COD and chlorine ion concentration monitoring result figure, and through 40 days domestication, the COD of reactor drum water outlet can reduce to 120～130 mg/L.
Embodiment 2
The employing useful volume is that the Membrane Bioreactor for Wastewater Treatment of 400L is the brine waste of raw material production epoxy chloropropane with glycerine, and pretreatment mode is identical with instance 1, and the COD that mixes back waste water is 600～700mg/L, and chlorine ion concentration is about 17000～20000mg/L;
Plate type membrane component is housed in the reactor drum, and membrane material is identical with instance 1, and the useful area of film is 1.3m
2, sludge concentration is 5000～6000mg/L, organic pollution load is 0.1 kgCOD/ (kgMLSS days); Through 60 days steady running, the COD of reactor drum water outlet can be controlled in 80～130 mg/L, saw shown in Fig. 6 water outlet COD and the chlorine ion concentration monitoring result figure.
Embodiment 3
Adopt the water outlet after the ozone oxidation step is handled instance 2 to carry out advanced treatment, the ozone oxidation reaction device that experiment is used is internal diameter 10cm, the highly glass scrubbing bottle of 4 liters of 55cm, useful volume.The oxygen and the ozone mixed gas that are produced by ozonizer feed in the ozone oxidation reaction device continuously; Air-flow velocity is 1L/min; Ozone concn is 60mg/L; Through 20 minutes ozone oxidation reaction, the COD of waste water reduced to 90 mg/L by initial 130mg/L, and the clearance of total organic carbon can reach 45% after 60 minutes.Water quality after the ozone oxidation step process reaches the requirement of " Shanghai City provincial standard integrated wastewater discharge standard DB31/199-2009 " secondary discharge standard.
Claims (9)
1. one kind is the treatment process of the brine waste of raw material production epoxy chloropropane with glycerine, it is characterized in that, may further comprise the steps:
(1) described brine waste being introduced equalizing tank with other salt concentrations and the lower waste water of Pollutant levels mixes; Make the sodium-chlor saltiness of mixing back waste water at 20～60 g/L; In waste water, add an amount of nitrogen, phosphorus nutrition thing simultaneously, guarantee organic pollutant needed nutrient concentrations in degradation process in the waste water, the mass ratio of COD, nitrogen and phosphorus is 85:5:1 in the waste water; Regulate the water quality of waste water, make the saltiness of waste water be lower than 5% back discharge equalizing tank;
The waste water of (2) step (1) equalizing tank being discharged is introduced the moving-bed membrane bioreactor and is handled; Concentration of activated sludge is 2500～10000mg/L in it, and the admission space ratio of floating stuffing is 40～80%, utilizes the active sludge in the reactor drum to further process;
Said moving-bed membrane bioreactor is made up of Moveable packings bio-reactor and mud-water separation film unit, the filler employing lightweight in the Moveable packings bio-reactor, thread, the cylindric or globular floating stuffing that specific surface area is bigger; Mud-water separation film unit or be immersed in the type that the vacuumizes membrane module in the moving-bed membrane bioreactor; Or be independent of the malleation filtering type membrane module of moving-bed membrane bioreactor; Aperture in the said membrane module is 0.05～1 micron; Filtering waste water is discharged reactor drum, active sludge is trapped in the reactor drum;
The waste water of (3) step (2) moving-bed membrane bioreactor being discharged is introduced the ozone reaction unit, in waste water, charges into ozone 5～30 minutes with ozone reactor, with further removal COD, and the water outlet after output is handled then;
The tail gas of this generating step is removed ozone with the ozone layer destroying device, and remaining gas returns the moving-bed membrane bioreactor and does the aeration use.
2. according to claim 1 is the treatment process of the brine waste of raw material production epoxy chloropropane with glycerine, it is characterized in that, the described nitrogen of step (1), phosphorus nutrition thing are ammonium chloride and sodium phosphate.
3. according to claim 1 is the treatment process of the brine waste of raw material production epoxy chloropropane with glycerine, it is characterized in that, the described ozone reaction of step (3) unit comprises ozone oxidation pond, ozone reactor and ozone layer destroying device.
4. according to claim 3 is the treatment process of the brine waste of raw material production epoxy chloropropane with glycerine; It is characterized in that; Described ozone oxidation pond is made up of the ozonizer outside pond body, pond inner bottom part ozone gas distribution system, ozone transport pipe and the pond, obtains after the required ozone in ozone oxidation pond is handled pure oxygen or air by ozonizer.
5. according to claim 3 is the treatment process of the brine waste of raw material production epoxy chloropropane with glycerine; It is characterized in that; When adopting pure oxygen as ozone gas source; Tail gas after the ozone reactor utilization will be collected and feed in the moving-bed membrane bioreactor, for the mikrobe in it provides oxygen.
6. one kind is the treatment unit of the brine waste of raw material production epoxy chloropropane with glycerine; Contain equalizing tank, moving-bed membrane bioreactor, ozone reaction unit; Between equalizing tank and the moving-bed membrane bioreactor, use pipe connection between moving-bed membrane bioreactor and the ozone reaction unit; It is characterized in that; Described moving-bed membrane bioreactor is made up of Moveable packings bio-reactor and mud-water separation film unit: the floating stuffing employing lightweight in the Moveable packings bio-reactor, thread, the cylindric or globular floating stuffing that specific surface area is bigger; Mud-water separation film unit or be immersed in the type that the vacuumizes membrane module in the moving-bed membrane bioreactor, or be independent of the malleation filtering type membrane module of moving-bed membrane bioreactor; Described ozone reaction unit comprises ozone oxidation pond, ozone reactor and ozone layer destroying device.
7. according to claim 6 is the treatment unit of the brine waste of raw material production epoxy chloropropane with glycerine; It is characterized in that; Described have the moving-bed membrane bioreactor that vacuumizes the type membrane module by moving-bed membrane bioreactor (1), vacuumize type membrane module (2), blast aeration pipe (3), tail gas aeration tube (4), floating stuffing (5), water inlet pipe (6), rising pipe (7) and rising pipe suction pump (8) and constitute, the aperture that vacuumizes in the type membrane module (2) is 0.05～1 micron.
8. according to claim 6 is the treatment unit of the brine waste of raw material production epoxy chloropropane with glycerine; It is characterized in that; The described moving-bed membrane bioreactor that has malleation filtering type membrane module is made up of moving-bed membrane bioreactor (21), malleation filtering type membrane module (22), blast aeration pipe (23), tail gas aeration tube (24), floating stuffing (25), water inlet pipe (26), rising pipe (27), rising pipe topping-up pump (28) and mud return line (29), and the aperture in the malleation filtering type membrane module (22) is 0.05～1 micron.
9. according to claim 6 is the treatment unit of the brine waste of raw material production epoxy chloropropane with glycerine; It is characterized in that; Described ozone oxidation pond is made up of gas communication (38), effluent weir (39), tail gas escape pipe (310), water outlet buffer zone (311) and the rising pipe (312) of pond body (31), water inlet pipe (32), water inlet buffer zone (33), influent weir (34), reaction zone (35), ozone inlet pipe (36), ozone gas distribution system (37), reaction zone and exhalant region, obtains after the required ozone in ozone oxidation pond is handled pure oxygen or air by the ozonizer outside the pond.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100470412A CN102153230B (en) | 2011-02-28 | 2011-02-28 | Method and device for treating salt-containing wastewater produced during producing epoxy chloropropane by using glycerol as raw material |
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| CN106745927A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of epoxychloropropane produces the integrated conduct method of waste water |
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| CN103073086B (en) * | 2013-01-18 | 2013-12-11 | 上海化学工业区中法水务发展有限公司 | Method for adsorbing glycerol contained in wastewater by using resin treated by boric acid |
| CN104140179B (en) * | 2013-05-07 | 2016-02-10 | 中国石化工程建设有限公司 | A kind of Waste Water Treatment and method |
| CN104291523A (en) * | 2014-09-18 | 2015-01-21 | 波鹰(厦门)科技有限公司 | Method for recovering sodium chloride and glycerin from glycerin-containing high-salinity organic wastewater |
| CN104445600A (en) * | 2014-11-28 | 2015-03-25 | 深圳中清环境科技有限公司 | Membrane pollution in-situ control based membrane bioreactor and technology thereof |
| CN104609629B (en) * | 2014-12-30 | 2017-02-22 | 中国天辰工程有限公司 | Method for treating glycerin-based epoxy chloropropane saponification wastewater |
| JPWO2018051630A1 (en) * | 2016-09-15 | 2019-06-27 | 住友電気工業株式会社 | Membrane separation activated sludge treatment system |
| CN107555715A (en) * | 2017-09-20 | 2018-01-09 | 上海市政工程设计研究总院（集团）有限公司 | A kind of wastewater treatment equipment and its application method |
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