CN102515397B - Waste water treatment process and system - Google Patents
Waste water treatment process and system Download PDFInfo
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- CN102515397B CN102515397B CN201210007181.1A CN201210007181A CN102515397B CN 102515397 B CN102515397 B CN 102515397B CN 201210007181 A CN201210007181 A CN 201210007181A CN 102515397 B CN102515397 B CN 102515397B
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Abstract
The invention provides a kind of waste water treatment process, comprising: step a: make waste water enter concentration device and carry out concentration, by the part water in waste water with water vapor isolated in form go out to obtain concentrated after waste water; Step b: supercritical water oxidation process is carried out, fluid after forming reactions to the waste water after concentrated; Step c: after making reaction, part or all of fluid produces pressure by Pressure generator, obtains pressure release fluid, and the pressure produced with Pressure generator provides pressure condition for concentration.On the other hand, the present invention also provides a kind of Waste Water Treatment for waste water treatment process of the present invention, comprising: Waste water concentrating treatment unit; Supercritical water reaction device; Pressure generator; Concentration device also has to realize the higher chamber of the relative pressure of processed and the lower chamber of relative pressure, and the lower chamber of relative pressure is communicated with pressure chamber.Capacity usage ratio of the present invention is high.
Description
Technical field
The present invention relates to a kind of waste water treatment process and Waste Water Treatment.
Background technology
The high-concentration hardly-degradable waste waters such as pharmaceutical factory waste water, military project waste water are owing to mostly having toxicity, and usually adopt biology aerobic technology or anaerobic technology to be difficult to process, microorganism can kill by toxic substance.So, still adopt dilution to fall dense mode traditionally, waste water COD is diluted to discharging standards, inherently will successfully not process the organic matter in the middle of waste water.This not only can cause the secondary pollution of environment, wastes a large amount of water resourcess simultaneously.Indivedual waste water is by incineration oxidation or mix the processing mode of burning oxidation, and because waste water has very high water-content, result causes treating processes energy consumption greatly to improve, and heat not easily reclaims.Meanwhile, organic liquid waste is insufficient owing to burning, and with in the middle of fume emission to air, can create and again pollute.Some multiring aromatic hydrocarbon substance due to temperature lower (general 600-800 DEG C), creates the hypertoxic pollutents such as dioxin in combustion, has very serious murder by poisoning to environment and human body, animal.
Generally speaking, fall by dilution the process problem that mode that is dense or that burn fails fundamentally to solve high-concentration hardly-degradable waste water, remain the focus of countries nowadays government and research institution's concern and research.
As everyone knows, material can the state such as solid-state, liquid, gaseous state and supercritical state exist, and the state residing for material depends on its state parameter such as temperature, pressure, density, composition.When the temperature and pressure of material is simultaneously higher than its critical temperature and emergent pressure, then it is claimed to be in supercritical state.Supercritical state is different from gaseous state and liquid state, and it has special physicochemical property.Overcritical is the one of supercutical fluid.When temperature is higher than 374.1 DEG C, pressure is higher than (pressure described herein is absolute pressure, lower same) during 22.12MPa, and water is in supercritical state, and its character there occurs very large change.Such as, under non-supercritical state, basic metal or alkaline earth metal hydroxides or basic metal or alkaline earth metal carbonate usually have good solubility in water, but in the water close to above-critical state and supercritical state, their solubleness will sharply reduce, so that can separate out from its aqueous solution, the solubleness of salt in overcritical reduces greatly.In addition, under supercritical state, the specific inductivity of water reduces, and polarity weakens, and this makes it closer to organism, therefore has good solvency action to organic matter, and it also has excellent mass transfer ability simultaneously, is a kind of desirable reaction medium.
Membrane distillation (MD) is the membrane separating process that membrane technique combines with still-process, and it is with special mould material for medium, and under the effect of film both sides vapour pressure deficit, in feed liquid, volatile constituent is in vapour form through fenestra, thus realizes the object of separation.Usually, membrane distillation temperature approximately controls at 65-95 DEG C, and the both sides of film exist certain pressure reduction, and charging side is generally normal pressure, and discharging side is negative pressure, and vacuum tightness is generally 25-90kPa.Membrane distillation has that separation efficiency is high, operational condition is gentle, mechanical property requirements not high to film and stock liquid interphase interaction and film.
Reverse osmosis (RO) is also known as reverse osmosis, and a kind of is impellent with pressure difference, isolates the membrane sepn operation of solvent from solution.Apply pressure to the feed liquid of film side, when pressure exceedes its osmotic pressure, solvent can make inverse osmosis against the direction of naturally osmotic, thus the low-tension side of film obtain through solvent, i.e. penetrating fluid; High-tension side obtains the solution concentrated, i.e. concentrated solution.
Jet vacuum pump principle: utilize fluid to carry out the vacuum acquirement device of transferring energy and quality, is adopted and has the medium of certain pressure to be sprayed by the nozzle of the certain skew back degree of symmetrical uniform one-tenth, be aggregated in a focus.Because injection water flow velocity is high especially, be kinetic energy by pressure energy, make the low generation vacuum of air-breathing district Pressure Drop.Vacuum tightness is by regulating the aperture of nozzle, and exit velocity or jetting stream vacuum pump structure regulate.Article " design-chemical engineering design-Wei Tongcheng of spray tube and Venturi tube, 6 phase 21-27 in 1993 " describes the design of a kind of spray tube and Venturi tube, describes the principle of work of jet vacuum pump in detail.The people such as Ma Shengjun " application of jet vacuum pump in underpressure distillation " (Zhejiang chemical industry 33 phases in 2002), all contribute to the summary of the invention understanding this patent.High velocity flow fully mixes compression through Venturi meter contraction section with larynx footpath, carries out molecular diffusion energy exchange, and speed is balanced.Increasing through expansion segment speed reduction pressure, be generally greater than barometric point.
Traditional supercritical gasification or oxidizing process, do not carry out concentrated and desalting treatment, directly enter supercritical reaction system, result causes the device unit time to process organic inferior capabilities, too much moisture enters reactive system and then flows out reactive system again, this not only adds the energy expenditure of power-equipment, and creates more energy expenditure.
1. membrane distillation method needs to maintain certain temperature and vacuum tightness, and utilize merely, running cost is high, energy recovery difficulty, and concentrated after product salts contg improves simultaneously, can cause the corrosion of equipment, reduce service life of equipment during actual treatment;
The oxidation of 2.SCWO (supercritical water oxidation) oxidation technology is organic, has heat-transfer effect good, organic matter transformation rate high.But when processing lower concentration waste liquid, unit time treatment capacity is low, and energy consumption is high, cost increases.
Summary of the invention
For Problems existing in correlation technique, the object of the present invention is to provide a kind of waste water treatment process and Waste Water Treatment, to solve the low technical problem of capacity usage ratio in prior art.
For achieving the above object, the invention provides a kind of waste water treatment process, comprising: step a: make waste water enter concentration device and carry out concentration, by the part water in waste water with water vapor isolated in form go out to obtain concentrated after waste water; Step b: supercritical water oxidation process is carried out, fluid after forming reactions to the waste water after concentrated; Also comprise: step c: after making reaction, part or all of fluid produces pressure by Pressure generator, obtains pressure release fluid, and the pressure produced with Pressure generator provides pressure condition for concentration.
Preferably, present invention process also comprises steps d: isolated water when pressure release fluid and concentration is carried out heat exchange, thinks that concentration provides temperature condition, and then isolated water is evaporated.
Preferably, fluid after reaction is divided into two strands, wherein one produces pressure by Pressure generator, obtain pressure release fluid, and the pressure produced with Pressure generator provides pressure condition for concentration, be separated water outlet when another stock and concentration and carry out heat exchange, think that concentration device provides temperature condition, and then isolated water is evaporated.
Preferably, between step b and c, also comprise step b2: after making partly or entirely reaction, the waste water of fluid and process to be concentrated carries out heat exchange, after wherein passing into the reaction of Pressure generator in step c, fluid is fluid after reaction in step b2 after heat exchange.
Preferably, present invention process also comprises: step e: make the waste water of the pressure release fluid in steps d after heat exchange and process to be concentrated carry out heat exchange.
Preferably, waste water treatment process of the present invention is for the treatment of process pharmaceutical factory waste water and/or military project waste water.
On the other hand, the present invention also provides a kind of Waste Water Treatment for the aforementioned arbitrary waste water treatment process of the present invention, comprising: Waste water concentrating treatment unit, for carrying out concentration to waste water, there is waterwater entrance and the concentrated outlet for discharging the waste water after concentrating; Supercritical water reaction device, carries out supercritical water oxidation process to the waste water after concentrated, has and the reactor inlet of concentrated outlet, reactor outlet for fluid expulsion after the reaction after supercritical water reaction process; Pressure generator, has opening for feed, discharge gate, pressure chamber between opening for feed and discharge gate, and after reaction, fluid produces pressure when flowing to discharge gate from opening for feed in pressure chamber; Concentration device also has to realize the higher chamber of the relative pressure of processed and the lower chamber of relative pressure, and these two chambers are located between waterwater entrance and concentrated outlet, and the lower chamber of relative pressure is communicated with pressure chamber.
Preferably, in the chamber that relative pressure is lower, be provided with the heat transfer tube flowed through for fluid after the reaction of discharging from discharge gate, heat transfer tube is communicated with the discharge gate of Pressure generator.
Preferably, present system also comprises: the waste water treating concentration carries out the First Heat Exchanger heated, First Heat Exchanger have for process to be concentrated wastewater streams through the first heat exchanger channels, for the second heat exchanger channels of flowing through of fluid after the reaction of flowing out from heat transfer tube, wherein, the outlet of the first heat exchanger channels is communicated with the waterwater entrance of concentration device, and the entrance of the second heat exchanger channels is communicated with the exit end of heat transfer tube.
Preferably, present system also comprises: the waste water treating concentration carries out the second interchanger heated, second interchanger have for process to be concentrated wastewater streams through the 3rd heat exchanger channels, for the 4th heat exchanger channels that flows through of fluid after the reaction of discharging from reactor outlet, wherein, the outlet of the 3rd heat exchanger channels is communicated with the waterwater entrance of concentration device, the entrance of the 4th heat exchanger channels is communicated with reactor outlet, and the outlet of the 4th heat exchanger channels is communicated with the opening for feed of Pressure generator.
Preferably, Waste water concentrating treatment unit is membrane separation unit, and membrane separation unit tunicle is divided into the higher chamber of relative pressure and the lower chamber of relative pressure.
Preferably, Pressure generator is jet vacuum pump.
Preferably, membrane separation unit is distillation device, micro-filtration, ultra-filtration equipment, electrodialysis apparatus, electrodialysis unit, nanofiltration device or reverse osmosis unit.
Advantageous Effects of the present invention is:
Waste water after concentration is carried out supercritical water oxidation by the present invention, with fluid after forming reactions (High Temperature High Pressure product); Then part or all of fluid after reaction is produced pressure (negative pressure) by Pressure generator, and the pressure produced with Pressure generator provides pressure condition for concentration, thus the negative pressure that fluid after reaction is produced by Pressure generator by the present invention, carry out be coupled (coupling) with the negative pressure needed for concentration; Further, when the pressure release fluid that the present invention obtains after rear for reaction fluid is flowed through Pressure generator and concentration, isolated water carries out heat exchange, think that concentration provides temperature condition, thus the low-grade energy of fluid after reaction carries out be coupled (coupling) with temperature required during concentration by the present invention, meeting of pressure condition and temperature condition, isolated water is evaporated, and discharges from Pressure generator in the lump with pressure release fluid.Present invention utilizes low grade heat energy and the partial pressure energy of the rear fluid of reaction, and after not affecting reaction, the higher-grade energy (kinetic energy etc. that the release of heat energy, pressure energy and pressure energy produces) of fluid can be used for generating electricity or producing high pressure steam; Thus, the present invention has higher energy efficiency, and reduces cost.
Further again, the concentration that the present invention carries out in concentration device, except comprising processed, also desalting treatment can be comprised, salinity after concentration, can utilize the salinity feature that solubleness reduces greatly under overcritical situation, centralized recovery salinity, both effectively prevent salt sedimentation and blocked pipeline, also can realize the recycling of salinity.
Accompanying drawing explanation
Fig. 1 shows a schematic flow sheet in waste water treatment process of the present invention;
Fig. 2 shows another schematic flow sheet of waste water treatment process of the present invention;
Fig. 3 is the schematic diagram of an embodiment of Waste Water Treatment of the present invention, wherein also shows wastewater treatment process with arrow;
Fig. 4 is the schematic diagram of another embodiment of Waste Water Treatment of the present invention, wherein also shows wastewater treatment process with arrow.
Embodiment
See accompanying drawing, specific embodiments of the invention are described below.
See Fig. 1-Fig. 4, waste water treatment process of the present invention is described, it comprises: step a: make waste water enter concentration device and carry out concentration, by the part water in waste water with water vapor isolated in form go out to obtain concentrated after waste water, wherein concentration comprises dehydration and desalting treatment, also can only have processed and not have desalting treatment; Step b: the waste water feeding supercritical water reaction device 1 after concentrated is carried out supercritical water oxidation process, fluid after forming reactions; Step c: after making described reaction, part or all of fluid produces pressure by Pressure generator, obtains pressure release fluid, and the pressure produced at Pressure generator with fluid after reaction provides pressure condition for concentration.
In the present invention, the concentration in step a comprises dehydration and desalting treatment, and also can only have processed and not have desalting treatment, correspondingly concentration device can only include dewatering unit, also can comprise dewatering unit and desalting plant simultaneously.About step c, see Fig. 3-4, be described as follows when Pressure generator is jet vacuum pump: wherein jet vacuum pump has opening for feed, discharge gate, pressure chamber between opening for feed and discharge gate, and concentration device has and carries out the lower chamber of the relative pressure of processed and the higher chamber of relative pressure to waste water (concentration device is distillation device 2 in figure 3, the chamber that correspondingly relative pressure is lower is exactly the negative pressure cavity 21 of distillation device 2), and the chamber that this relative pressure is lower is communicated with pressure chamber, thus when fluid after reaction is when flowing to discharge gate from opening for feed, it flows through pressure chamber and in pressure chamber, produces pressure (negative pressure), thus achieve as concentration provides pressure condition, further, present invention process also comprises steps d: isolated water when pressure release fluid and concentration is carried out heat exchange, thinks that concentration provides temperature condition, meeting of pressure condition and temperature condition, isolated water is evaporated, and discharges from Pressure generator in the lump with pressure release fluid.This can be described in detail as follows see Fig. 3: in the negative pressure cavity 21 of distillation device 2, be provided with heat transfer tube 8, to the water heat release in negative pressure cavity 21 when the pressure release fluid of discharging for jet vacuum pump flows through heat transfer tube 8.Thus can be implemented as concentration temperature condition is provided.Obviously, now the present invention is that after the reaction of being discharged by supercritical water reaction device 1, fluid is divided into two strands, wherein one produces pressure by Pressure generator, obtain pressure release fluid, and the pressure produced with Pressure generator provides pressure condition for concentration, when another stock and concentration, isolated water carries out heat exchange, thinks that concentration device provides temperature condition.
Continue see Fig. 3, present invention process also comprises step e: make the waste water of the pressure release fluid in steps d after heat exchange and process to be concentrated carry out heat exchange.In figure 3, pressure release fluid is first to negative pressure cavity 21 heat release of distillation device 2, and then to the waste water heat release of process to be concentrated, to preheat waste water before concentration, the heat exchange wherein and between waste water is carried out in First Heat Exchanger 6.
See Fig. 4, between step b and step c, also step b2 can be comprised: after making partly or entirely reaction, the waste water of fluid and process to be concentrated carries out heat exchange, and this carries out in the second interchanger 3.Now, passing into fluid after the reaction of Pressure generator in step c, is fluid after the reaction in step b2 after heat exchange.Particularly, be presented as in the diagram: after reaction, fluid is after the waste water preheating treating concentration, just flows to the opening for feed of jet vacuum pump.
On the other hand, the present invention also provides a kind of Waste Water Treatment in order to waste water treatment process of the present invention, and see Fig. 3-4, it comprises: Waste water concentrating treatment unit, supercritical water reaction device 1, Pressure generator.Waste water concentrating treatment unit is used for carrying out concentration to waste water, and it has waterwater entrance and the concentrated outlet for discharging the waste water after concentrating; Supercritical water reaction device carries out supercritical water oxidation process to the waste water after concentrated, and it has and the reactor inlet of concentrated outlet, reactor outlet for fluid expulsion after the reaction after supercritical water reaction process; Pressure generator has opening for feed, discharge gate, pressure chamber between opening for feed and discharge gate, and after reaction, fluid produces pressure when flowing to discharge gate from opening for feed in pressure chamber; Wherein, concentration device comprises dewatering unit, this dewatering unit has the higher chamber of pressure and the lower chamber of relative pressure, these two chambers are located between waterwater entrance and concentrated outlet, and the chamber that relative pressure is lower is communicated with the pressure chamber of Pressure generator, thus after reaction, the concentration of fluid when flowing through pressure chamber for water provides pressure condition.Wherein Pressure generator is jet vacuum pump 4 in the embodiment illustrated in figs. 3 and 4, but the present invention is not limited to this, but can be that any can making reacts the device that can produce pressure when rear fluid flows through.
See shown in Fig. 3, Waste Water Treatment of the present invention also comprises heat transfer tube 8, heat transfer tube 8 is located in the lower chamber (negative pressure cavity) of jet vacuum pump 4 relative pressure, and be communicated with the discharge gate of jet vacuum pump, for when after the reaction of discharging from discharge gate, fluid flows through to negative pressure cavity release of heat.The First Heat Exchanger 6 that the waste water treating concentration carries out heating is also show in Fig. 3, this First Heat Exchanger 6 have for process to be concentrated wastewater streams through the first heat exchanger channels, for fluid after the reaction of flowing out from heat transfer tube 8 (namely from the pressure release fluid that heat transfer tube 8 flows out) the second heat exchanger channels of flowing through, the outlet of the first heat exchanger channels is communicated with the waterwater entrance of concentration device, and the entrance of the second heat exchanger channels is communicated with the exit end of heat transfer tube 8.After reaction wherein in the second heat exchanger channels, fluid is to waste water heat release in the first heat exchanger channels, to realize before concentration waste water preheating.
See Fig. 4, different from situation shown in Fig. 3, Waste Water Treatment of the present invention can adopt the second interchanger 3, make to react rear fluid before flowing through jet vacuum pump, first carry out heat exchange with waste water, to realize to waste water preheating before concentration, be not namely utilize pressure release fluid institute heat content to carry out preheating to waste water.Particularly, second interchanger 3 have for process to be concentrated wastewater streams through the 3rd heat exchanger channels, for the 4th heat exchanger channels that flows through of fluid (not being pressure release fluid) after the reaction of discharging from reactor outlet, the outlet of the 3rd heat exchanger channels is communicated with waterwater entrance, the entrance of the 4th heat exchanger channels is communicated with reactor outlet, and the outlet of the 4th heat exchanger channels is communicated with the opening for feed of jet vacuum pump.
It may be noted that the concentration device that the present invention relates to is preferably membrane separation unit, this membrane separation unit tunicle is divided into the higher chamber of described relative pressure and the lower chamber of described relative pressure.Membrane separation unit can be distillation device, micro-filtration, ultra-filtration equipment, electrodialysis apparatus, electrodialysis unit, nanofiltration device or reverse osmosis unit.Although Fig. 3 and 4 is for distillation device 2, distillation device 2 tunicle 10 is divided into the higher chamber of described relative pressure and the lower chamber of described relative pressure, can membrane separation unit can be in fact any one in above-mentioned membrane separation unit.Waste water of the present invention is the high-concentration hardly-degradable waste water such as pharmaceutical factory waste water, military project waste water.The concentration related in the present invention is when comprising desalting treatment process, and this desalting treatment can adopt any one in the modes such as gravity settling, distillation, electrodialysis, and the salinity removed can be processed further for industry or food service industry.
For further understanding the present invention, further illustrate 5 embodiments of waste water treatment process of the present invention below see Fig. 3-4.
[embodiment 1 of waste water treatment process]
See Fig. 3, in distillation device 2, carry out processed to waste water, the temperature in distillation device 2 controls at 65-80 DEG C, vacuum tightness (vacuum tightness of the negative pressure cavity 21 of distillation device) 25-47.5Kpa, wherein.Waste water concentrates 7 times after processed, and the waste water of concentrated 7 times is sent in desalting plant 5 by high-pressure pump and carried out desalting treatment.In the process of carrying out desalting treatment, wastewater pressure is at 22-25MPa, and waste water is heated to 360-380 DEG C, and now more than 95% salinity is separated out from water, removes system remove salinity through gravity settling.Remove the waste water after salinity and enter supercritical water reaction device 1, in supercritical water reaction device 1, organic matter in oxygen and waste water reacts fluid (oxidation reactant gas) after formation reaction and releases heat, supercritical water reaction device discharge gate temperature controls at 500-650 DEG C, pressure 22-25MPa (that is, temperature when oxidation reactant is discharged from supercritical water reaction device 1 control 500-650 DEG C, pressure is at 22-25MPa).Partial heat in aforesaid releases heat enters distillation device 2 and provides heat for membrane distillation process, maintains the technological temperature of membrane distillation process at 65-80 DEG C.Meanwhile, the reactor outlet of supercritical water reaction device 1 is connected with jet vacuum pump 4, and jet vacuum pump 4 has pressure chamber, and wherein the negative pressure cavity 21 of distillation device is communicated with the pressure chamber of jet vacuum pump 4.Thus the oxidation reactant gas of the high pressure of discharging from supercritical water reaction device 1 is that membrane distillation provides subnormal ambient when step-down, decreases the consumption of energy.In the present embodiment, jet vacuum pump temperature out controls at 110-130 DEG C, the negative pressure cavity 21 internal pressure 25-47.5kpa of distillation device 2, in addition in order to utilize from the heat energy contained by the oxidation reactant of supercritical water reaction device 1, the oxidation reactant of discharge jet vacuum pump 4 and membrane distillation negative pressure cavity carry out heat exchange, for the water vapor in negative pressure cavity provides heat, oxidation reactant after heat exchange can again with the wastewater heat exchange (after heat exchange, the temperature of medium maintains 100-120 DEG C) of process to be concentrated to improve the temperature that waste water enters distillation device 2, namely realize carrying out thermal pretreatment to waste water before processed, after preheating, the temperature of waste water is 65-80 DEG C, pressure is normal pressure.
[embodiment 2 of waste water treatment process]
Difference from Example 1 is: the oxidation products ejected from jet vacuum pump 4, in direct introducing First Heat Exchanger 6, the waste water of delivery film water distilling apparatus is wanted in heating, and in the oxidation products introducing distillation device do not ejected by jet vacuum pump 4, negative pressure cavity 21 carries out heat release; All the other steps are identical with embodiment 1 step.
[embodiment 3 of waste water treatment process]
See Fig. 4, waste water enters in dewatering unit through pumping and carries out processed, and dewatering unit is distillation device 2, and in distillation device 2, temperature controls at 80-95 DEG C, vacuum tightness 47.5-84.5KPa (the negative pressure cavity vacuum tightness of distillation device).Waste water concentrating 7 times after processed, waste water after concentrated 7 times is fed into desalting plant 5 by high-pressure pump and carries out desalting treatment, in desalting treatment, maintain wastewater pressure at 22-25MPa, waste water is heated to 360-380 DEG C, now most of salinity is separated out from water, system is removed through gravity settling, rest materials enters supercritical water reaction device 1, in supercritical water reaction device 1, organic matter in oxygen and waste water reacts and generates oxidation reactant (after reacting fluid) and releases heat, supercritical water reaction device temperature out controls at 500-650 DEG C, (waste water have passed through two step heat exchange altogether can first to carry out heat exchange with waste water from the oxidation reactant of supercritical water reaction device 1 discharge, one is First Heat Exchanger, two is heat transfer tube, the heat exchange effect of the two can keep temperature in distillation device 2 to control at 80-95 DEG C), oxidation reactant after heat exchange enters jet vacuum pump 4.Wherein the negative pressure cavity 21 of distillation device is communicated with the pressure chamber of jet vacuum pump 4, thus high-pressure oxidation reactant gas is membrane distillation workshop section when step-down provides subnormal ambient, which reduce the consumption of energy, namely, high-pressure oxidation reactant gas from the process entering into discharging jet vacuum pump 4, for the negative pressure cavity 21 of distillation device provides subnormal ambient.The high-pressure oxidation reactant gas (being also referred to as mixing prod Fig. 4) of wherein discharging from jet vacuum pump 4 is described pressure release fluid.
The present embodiment make use of the oxidation reactant gas institute heat content of discharging from supercritical water reaction device 1, to heat the waste water that will carry out processed (can 140-160 DEG C be heated to), wherein oxidation reactant gas temperature after heated waste water is 400-550 DEG C, and pressure still maintains 22-25MPa.
[embodiment 4 of waste water treatment process]
This embodiment is mainly and adopts mode of reverse osmosis to carry out the concentrated of waste water.
Waste water (normal temperature and pressure) enters dewatering unit through pumping and carries out processed, dewatering unit is adopt the mode of reverse osmosis to carry out the reverse osmosis unit dewatered, working pressure is 0.75MPa, pH value is 7.5-8.5, be fed into desalting plant by high-pressure pump after Waste water concentrating 5 times and carry out desalting treatment, in desalting plant, maintain pressure at 22-25MPa, waste water is heated to 360-380 DEG C, now more than 95% salinity is separated out from water, system is removed through centrifugation, rest materials enters supercritical water reaction device, in supercritical water reaction device, organic matter in oxygen and waste water reacts and generates oxidation reactant, and releases heat, maintain the supercritical state of water, supercritical water reaction device temperature out controls at 500-650 DEG C, high pressure steam can be produced after heat exchange, heat exchange after product is isolated to energy product.
Similar to embodiment 1-3, the present embodiment can be connected with jet vacuum pump at the reactor outlet of supercritical water reaction device, jet vacuum pump has pressure chamber, wherein reverse osmosis unit has the higher chamber of relative pressure and the lower chamber of relative pressure, and the chamber that this relative pressure is lower is communicated with the pressure chamber of jet vacuum pump.Thus the oxidation reactant gas of the high pressure of discharging from supercritical water reaction device is that concentration provides pressure environment when step-down, decreases the consumption of energy.In addition, in order to utilize from the heat energy contained by the oxidation reactant of supercritical water reaction device, the chamber that the oxidation reactant of being discharged by jet vacuum pump introduces relative pressure lower carries out heat release, for concentration provides temperature condition, the temperature that oxidation reactant after heat exchange can enter to improve waste water with the wastewater heat exchange of process to be concentrated again, namely realizes carrying out thermal pretreatment to waste water before processed.
[embodiment 5 of waste water treatment process]
This embodiment is mainly and adopts semi-permeable membranes mode to carry out the concentrated of waste water.
Waste water (normal temperature and pressure) enters in concentration device through pumping and carries out concentration, in the present embodiment, concentrating unit is the semipermeable membrane device adopting Immunohistochemistry mode, working pressure is 0.55MPa, and after semi-permeable membranes process, salt can be separated further with water.By high-pressure pump and through preheater preheats to 380-400 DEG C after Waste water concentrating 5 times, enter supercritical water reaction device, maintain pressure at 22-25MPa.In overcritical water oxidization reactor, organic matter in oxygen and waste water reacts and generates oxide products, and releases heat, supercritical water reaction device temperature out controls at 500-650 DEG C, can produce high pressure steam after heat exchange, heat exchange after product is isolated to energy product.
Similar to embodiment 1-3, the present embodiment can be connected with jet vacuum pump at the reactor outlet of supercritical water reaction device, jet vacuum pump has pressure chamber, wherein semipermeable membrane device has the higher chamber of relative pressure and the lower chamber of relative pressure, and the chamber that this relative pressure is lower is communicated with the pressure chamber of jet vacuum pump.Thus the oxidation reactant gas of the high pressure of discharging from supercritical water reaction device is that concentration provides pressure environment when step-down, decreases the consumption of energy.In addition, in order to utilize from the heat energy contained by the oxidation reactant of supercritical water reaction device, the chamber that the oxidation reactant of being discharged by jet vacuum pump introduces relative pressure lower carries out heat release, for concentration provides temperature condition, oxidation reactant after heat exchange can again with the wastewater heat exchange of process to be concentrated to improve the temperature that waste water enters semipermeable membrane device, namely realize carrying out thermal pretreatment to waste water before processed.
It may be noted that, the desalting treatment related in above 5 embodiments is preferred processing mode, in other words, as long as adopt concentration device can realize concentrated technique effect by dehydration, those skilled in the art can adopt or not adopt desalting treatment according to the difference of the kind of waste water and moiety, and it is omissible step.Correspondingly, the desalting plant for desalting treatment is also preferred.
Waste water after concentration is carried out supercritical water oxidation by the present invention, with fluid after forming reactions (High Temperature High Pressure product); Then part or all of fluid after reaction is produced pressure (negative pressure) by Pressure generator, and the pressure produced with Pressure generator provides pressure condition for concentration, thus the negative pressure that fluid after reaction is produced by Pressure generator by the present invention, carry out be coupled (coupling) with the negative pressure needed for concentration; Further, when the pressure release fluid that the present invention obtains after rear for reaction fluid is flowed through Pressure generator and concentration, isolated water carries out heat exchange, thinks that concentration provides temperature condition; Meeting of pressure condition and temperature condition, isolated water is evaporated, and discharge from Pressure generator in the lump with pressure release fluid, thus the low-grade energy of fluid after reaction carries out be coupled (coupling) with temperature required during concentration by the present invention, make use of low grade heat energy and the partial pressure energy of the rear fluid of reaction, and after not affecting reaction, the higher-grade energy (kinetic energy etc. that the release of heat energy, pressure energy and pressure energy produces) of fluid can be used for generating electricity or producing high pressure steam; Thus, the present invention has higher energy efficiency, and reduces cost.Further again, the concentration that the present invention carries out in concentration device, except comprising processed, also desalting treatment can be comprised, salinity after concentration, can utilize the salinity feature that solubleness reduces greatly under overcritical situation, centralized recovery salinity, both effectively prevent salt sedimentation and blocked pipeline, also can realize the recycling of salinity.The present invention can realize pollutent and process completely, and inorganics can realize reclaiming, and supercritical oxidation process is discarded organic, and organic matter transformation rate can reach more than 99.99%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. a waste water treatment process, comprising:
Step a: make waste water enter concentration device and carry out concentration, by the part water in waste water with water vapor isolated in form go out to obtain concentrated after waste water, described concentration device has and carries out the lower chamber of the relative pressure of processed and the higher chamber of relative pressure to waste water;
Step b: supercritical water oxidation process is carried out, fluid after forming reactions to the waste water after concentrated;
It is characterized in that: also comprise:
Step c: after making described reaction, part or all of fluid produces pressure by Pressure generator in its pressure chamber, obtain pressure release fluid, the chamber that described relative pressure is lower is communicated with described pressure chamber, and the pressure produced with described Pressure generator provides pressure condition for described concentration; Described Pressure generator is jet vacuum pump, and described jet vacuum pump carries out step-down to fluid after described reaction, thus the described pressure condition provided for described concentration is subnormal ambient.
2. waste water treatment process according to claim 1, is characterized in that, also comprises:
Steps d: isolated water when described pressure release fluid and described concentration is carried out heat exchange, thinks that described concentration provides temperature condition.
3. waste water treatment process according to claim 1, is characterized in that,
Fluid after described reaction is divided into two strands, wherein one produces pressure by described Pressure generator, obtain pressure release fluid, and the pressure produced with described Pressure generator provides pressure condition for described concentration, be separated water outlet when another stock and described concentration and carry out heat exchange, think that described concentration device provides temperature condition.
4. waste water treatment process according to claim 1, is characterized in that,
Also step b2 is comprised: after making partly or entirely reaction, the waste water of fluid and process to be concentrated carries out heat exchange between described step b and c,
Passing into fluid after the reaction of described Pressure generator in wherein said step c, is fluid after the reaction in described step b2 after heat exchange.
5. waste water treatment process according to claim 2, is characterized in that, also comprises:
Step e: make the waste water of the pressure release fluid in described steps d after heat exchange and process to be concentrated carry out heat exchange.
6. the waste water treatment process according to any one of claim 1-5, is characterized in that, described waste water treatment process is for the treatment of pharmaceutical factory waste water and/or military project waste water.
7., for a Waste Water Treatment for waste water treatment process according to any one of claim 1-6, it is characterized in that, comprising:
Waste water concentrating treatment unit, for carrying out concentration to waste water, has waterwater entrance and the concentrated outlet for discharging the waste water after concentrating;
Supercritical water reaction device, carries out supercritical water oxidation process to the waste water after concentrated, has and the reactor inlet of described concentrated outlet, reactor outlet for fluid expulsion after the reaction after supercritical water reaction process; And
Pressure generator, have opening for feed, discharge gate, pressure chamber between described opening for feed and discharge gate, after described reaction, fluid produces pressure when flowing to described discharge gate from described opening for feed in described pressure chamber;
Wherein, described concentration device also has to realize the higher chamber of the relative pressure of processed and the lower chamber of relative pressure, these two chambers are located between described waterwater entrance and concentrated outlet, and the lower chamber of described relative pressure is communicated with described pressure chamber; Described Pressure generator is jet vacuum pump, and described jet vacuum pump carries out step-down to fluid after described reaction, thus the described pressure condition provided for described concentration is subnormal ambient.
8. Waste Water Treatment according to claim 7, is characterized in that,
In the chamber that described relative pressure is lower, be provided with the heat transfer tube flowed through for fluid after the reaction of discharging from described discharge gate, described heat transfer tube is communicated with the discharge gate of described Pressure generator.
9. Waste Water Treatment according to claim 8, is characterized in that,
Also comprise: the waste water treating concentration carries out the First Heat Exchanger heated, described First Heat Exchanger have for process to be concentrated wastewater streams through the first heat exchanger channels, the second heat exchanger channels of flowing through for fluid after the reaction of flowing out from described heat transfer tube,
Wherein, the outlet of described first heat exchanger channels is communicated with the waterwater entrance of described concentration device, and the entrance of described second heat exchanger channels is communicated with the exit end of described heat transfer tube.
10. Waste Water Treatment according to claim 7, is characterized in that,
Also comprise: the waste water treating concentration carries out the second interchanger heated, described second interchanger have for process to be concentrated wastewater streams through the 3rd heat exchanger channels, the 4th heat exchanger channels that flows through for fluid after the reaction of discharging from described reactor outlet,
Wherein, the outlet of described 3rd heat exchanger channels is communicated with the waterwater entrance of described concentration device, and the entrance of described 4th heat exchanger channels is communicated with described reactor outlet, and the outlet of described 4th heat exchanger channels is communicated with the opening for feed of described Pressure generator.
11. according to described Waste Water Treatment arbitrary in claim 7-10, it is characterized in that, described Waste water concentrating treatment unit is membrane separation unit, and described membrane separation unit tunicle is divided into the higher chamber of described relative pressure and the lower chamber of described relative pressure.
12. Waste Water Treatments according to claim 11, is characterized in that, described membrane separation unit is distillation device, micro-filtration, ultra-filtration equipment, electrodialysis apparatus, nanofiltration device or reverse osmosis unit.
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| CN104478135A (en) * | 2014-12-15 | 2015-04-01 | 新奥科技发展有限公司 | Treatment method of salt-containing wastewater |
| CN105858944A (en) * | 2015-01-19 | 2016-08-17 | 王冰 | Novel comprehensive treatment system and method for sewage with zero-pollution discharge |
| CN104710045B (en) * | 2015-03-23 | 2017-05-31 | 王冰 | A kind of new dyeing waste water total system and method |
| CN104710046B (en) * | 2015-03-23 | 2017-11-14 | 王冰 | A kind of novel rare-earth wastewater comprehensive treatment system and method |
| CN104787982B (en) * | 2015-04-22 | 2016-07-13 | 江苏省环境科学研究院 | A kind of processing method of percolate |
| CN105130080B (en) * | 2015-09-08 | 2017-07-14 | 广州中国科学院先进技术研究所 | A kind of supercritical water oxidation handles the System and method for of high volatile organic wastewater |
| CN105130081B (en) * | 2015-09-08 | 2017-11-10 | 广州中国科学院先进技术研究所 | A kind of System and method for of supercritical water oxidation processing low volatility organic wastewater |
| CN106564994A (en) * | 2015-10-13 | 2017-04-19 | 内蒙古天环境技术有限公司 | Flat sheet membrane pool using novel DEP electrode and membrane concentration system |
| CN105923927A (en) * | 2016-06-30 | 2016-09-07 | 无锡龙盈环保科技有限公司 | Treatment process and device for soybean protein wastewater |
| CN108911107A (en) * | 2018-08-10 | 2018-11-30 | 大连亿斯德制冷设备有限公司 | A kind of organic wastewater Supercritical water oxidation treatment device and method |
| CN112321051A (en) * | 2020-11-01 | 2021-02-05 | 自然资源部天津海水淡化与综合利用研究所 | Multi-membrane coupling process and device for space station wastewater treatment |
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