CN101987755A - Supercritical water treatment system of organic wastewater with low salt content - Google Patents
Supercritical water treatment system of organic wastewater with low salt content Download PDFInfo
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Abstract
The invention discloses a supercritical water treatment system and method of organic wastewater with low salt content. In the system, the heat after reaction is fully recycled by a heat exchanger to generate hot water; liquid and gas after reaction are separated and recycled by a gas-liquid separator; according to the characteristics of different materials, an optimal supercritical water treatment mode is flexibly selected by controlling the air flow; on the basis of reserving a tubular reactor, a tank reactor is connected in parallel; the treatment effect of ammonia nitrogen and the like is improved and the conditions required for the supercritical reaction are reduced by adding catalysts; a desalting buffer tank is provided for realizing the desalting operation in a supercritical state; and the clogging problem of a feeding pipeline caused by preheating can be effectively avoided by controlling the preheating temperature of the wastes. The system of the invention integrates removal of COD, inorganic salt and ammonia nitrogen, integrates the pretreatment, mixing, reaction, product separation and product collection of materials, and is widely applied to the harmless treatment processes of pollutants such as high-concentration organic waste which can not be biochemically degraded easily and the like.
Description
Technical field
The present invention relates to a kind of system that utilizes supercritical water bio-refractory organic waste water to be carried out harmless treatment, the super critical water treatment system of particularly a kind of low saline salinity (1-2%) organic waste water as reaction medium.
Background technology
Supercritical water (Supercritical Water, be called for short SCW) be meant temperature and pressure all be higher than its stagnation point (T=374.15 ℃, the water of special state P=22.12MPa).Have only a spot of hydrogen bond to exist under this state, specific inductivity is similar to organic solvent, has high spread coefficient and low viscosity.Organism, oxygen can dissolve each other by arbitrary proportion and SCW, thereby make inhomogeneous reaction become homogeneous reaction, have reduced the resistance of mass transfer, heat transfer greatly.And inorganics particularly the solubleness of salt in SCW is extremely low, easily it is separated.
The supercritical water treatment technology of organic waste water comprises supercritical water oxidation technology (Supercritical Water Oxidation, abbreviation SCWO), supercritical water gasification technology (Supercritical Water Gasification, be called for short SCWG) and supercritical water partial oxidation technology (Supercritical Water Partial Oxidation is called for short SCWPO).
SCWO is a special property of utilizing water to be had under supercritical state, makes organism and oxygenant that oxidizing reaction take place rapidly in supercritical water and comes thorough decomposing organic matter, realizes organic harmless treatment.
SCWG is a special property of utilizing water to be had under supercritical state, and under the condition of oxidizer not, reactions such as hydrolysis, pyrolysis take place in supercritical water organism, generates the flammable gonosome based on hydrogen.
SCWPO is a special property of utilizing water to be had under supercritical state, under the prerequisite that the partial oxidation agent is provided, makes organism decompose the inflammable gas that generates based on hydrogen.The adding of oxygenant makes the material that originally is difficult to decompose in gasification to decompose, and improves vaporization rate, and simultaneously, oxygenant also can make the generation of tar be inhibited, and reduces the latch up phenomenon of reactor.
Though the supercritical water treatment technology has obtained very much progress, still have some problems that need solution, show:
1) the SCWO process is a thermopositive reaction, and just can realize self-heating when organic massfraction reaches 1～2%.But because the recovery and the optimization problem of supercritical water oxidation treatment system energy do not have fine solution, so the running cost of supercritical water treatment process is still higher.
2) in the lower supercritical water of density, the solubleness of inorganic salt in water significantly reduces.Therefore the salt that generates in material and the reaction process is easy to separate out the formation salt sedimentation from supercritical water.Salt sedimentation can cause the pipeline and the reactor plugs of system, can make the heat transfer deterioration of equipment such as interchanger simultaneously, finally causes system normally to move.And existing demineralization plant or system are limited by operational condition, are not suitable under the supercritical state, safety, desalination easily.
3) reactor that is used for supercritical water treatment at present mainly is a tubular reactor.The structure of tubular reactor is simple relatively, be widely used, but has that the salt precipitation is easily stifled, uncontrollable exothermic heat of reaction, be difficult to distinguish shortcomings such as pressure influence and temperature effect.Though and existing evaporation wall type reactor can effectively be avoided problems such as salt sedimentation, corrosion, has the low problem of energy utilization efficiency also.
4) during supercritical water oxidation was handled, the oxidation of ammonia nitrogen is difficulty comparatively.There are some researches show: when catalyst-free, when temperature was lower than 640 ℃, any degraded did not take place in ammonia; And reach 680 ℃, 24.8MPa when reaction conditions, the residence time is when being 10s, has only 10% ammonia oxidized.Other there are some researches show: promptly use MnO
2/ CeO
2As catalyzer, when reaction conditions is 450 ℃, 27.6MPa, the residence time, the degradation rate of ammonia also had only 40% when being 0.8s.
Summary of the invention
The objective of the invention is to overcome the existing existing deficiency of super critical water treatment system, a kind of novel super critical water treatment system is provided, can be widely used in the harmless treatment and the recycling process of low saline salinity organic waste water.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of super critical water treatment system of low saline salinity organic waste water, it is characterized in that, comprise air preheater, the inlet end of described air preheater shell-side connects high-pressure air, the exit end of air preheater shell-side is communicated with a mixer entrance end, another inlet end of this mixing tank is communicated with the outlet of waste water preheater shell-side, and waste water preheater shell-side inlet is communicated with the waste water storage device; The outlet of described mixing tank links to each other with the inlet of first tubular reactor, the outlet of first tubular reactor links to each other with the inlet of second tubular reactor, the outlet of second tubular reactor is divided into two-way, one the tunnel links to each other with the inlet end of three-tube type reactor, and another road links to each other with the inlet end of tank reactor; It is to be communicated with the inlet end of preheating of air organ pipe side after one the tunnel that the exit end of three-tube type reactor and the water side of tank reactor are converged, the outlet of preheating of air organ pipe side is communicated with the entrance and exit of waste water preheater tube side respectively, by the distribution between the realization of the variable valve on the pipeline two-way flow; The outlet of waste water preheater tube side is communicated with the inlet of hot water generator pipe side, and the outlet of hot water generator pipe side is communicated with a gas-liquid separator by back pressure valve; The shell-side of hot water generator is communicated with the thermal water utilization device; Be equipped with well heater on described first tubular reactor and second tubular reactor.
In the such scheme, described tank reactor is the baffling tank reactor, and its bottom salt outlet is communicated with blow-off line by a desalination surge tank.
Described thermal water utilization device comprises the clear water storage tank that connects tap water, its outlet is communicated with a fresh water pump, this clear water pump outlet is divided into two-way by threeway, and one the tunnel is communicated with the inlet end of hot water generator shell-side, and another road is communicated with the outlet at bottom end of desalination surge tank; The exit end of hot water generator shell-side is communicated with a hot water storage tank's inlet end.
Described waste water storage device comprises and has the storage tank that adds the alkali jar that its inlet end connects raw material waste water by valve; Exit end is communicated with the inlet end of waste water preheater shell-side by a product pump.Be provided with agitator in the storage tank.
Be provided with line strainer between the outlet of described hot water generator pipe side and the back pressure valve.
The major advantage of system of the present invention is:
1, by air preheater, the pre-thermal material of waste water preheater, produce life by hot water generator and use hot water, make full use of fluidic heat after the reaction.Electric heater starts or reacts and can not come into operation during self-heating in system, and replenishment system normally moves institute's heat requirement.By to the reacted heat of abundant recycling, effectively reduce the running cost of the super critical water treatment system of low saline salinity organic waste water.
2, on the basis of tubular reactor, increased the baffling tank reactor, can be by increasing the speed that catalyzer improves supercritical water reaction.
3, owing to adopted the baffling tank reactor, utilize inorganic salt to carry out the first step salt at the low dissolution characteristics of overcritical water electrode in reactor and separate, the salt sedimentation after the separation is at reactor bottom.The tank reactor lower end connects the desalination surge tank, close desalination surge tank outlet at bottom valve, open the valve between tank reactor and the desalination surge tank, the inorganic salt that are deposited on reactor bottom by pressure reduction and action of gravity are brought in the desalination surge tank, intermittent type ground opens and closes desalination surge tank two ends valve up and down, realize the intermittent type removal of inorganic salt, avoided because of the caused blockage problem of salt sedimentation, liquid after having guaranteed to handle is saliferous or contain the salt of minute quantity not, has satisfied the desalination requirement.
Pre-treatment, mixing, reaction, the gas-liquid separation of system of the present invention collection charging are collected in one, and the integrated performance of system is good.Can choose suitable supercritical water treatment mode flexibly at different feeds, under the prerequisite that guarantees charging harmless treatment (COD reduction of discharging, desalination), realize the purpose of its recycling (product hydrogen).
Description of drawings
The present invention is described in further detail below in conjunction with the drawings and the specific embodiments.
Fig. 1 is the structural representation of system of the present invention.
Among the figure: 1 is High-Pressure Compressor, 2 is surge tank, 3 is air preheater, 4 for adding the alkali jar, 5 is storage tank, 6 is product pump, 7 is the waste water preheater, 8 is mixing tank, 9 is first tubular reactor, 10 is second tubular reactor, 11 is the three-tube type reactor, 12 is tank reactor, 13 is the desalination surge tank, 14 is the clear water storage tank, 15 is fresh water pump, 16 is hot water generator, 17 is the hot water storage tank, 18 is line strainer, 19 is back pressure valve, 20 is gas-liquid separator.
Legend implication among Fig. 1 sees Table 1
Instrument code implication among Fig. 1 sees Table 2.
Table 1
Table 2
| Code | The code meaning | Code | The code meaning |
| FIC | Flow shows control | TIC | Temperature shows control |
| PIC | Pressure shows control | LIC | Liquid level shows control |
| ELEC1 | Electric heater 1 | ELEC2 | |
Embodiment
With reference to shown in Figure 1, equipment connection mode is as follows in the super critical water treatment system of low saline salinity organic waste water:
High-Pressure Compressor 1 is communicated with the inlet end of surge tank 2, and the exit end of surge tank 2 is communicated with the inlet end of air preheater 3 shells, and the exit end of air heat exchanger 3 shell-sides is communicated with mixing tank 8 inlet ends.
The outlet that adds alkali jar 4 links to each other with the inlet of storage tank 5, the exit end of storage tank 5 is communicated with the inlet end of product pump 6, the exit end of product pump 6 is communicated with the inlet end of waste water preheater 7 shell-sides, the outlet of waste water preheater 7 shell-sides be communicated with another inlet end of mixing tank 8.
The outlet of mixing tank 8 links to each other with the inlet of first tubular reactor 9, and the outlet of first tubular reactor 9 links to each other with the inlet of second tubular reactor 10.Arrange first step electric heater (ELEC1) on first tubular reactor 9, arrange second stage electric heater (ELEC2) on second tubular reactor 10.The outlet of second tubular reactor 10 is divided into two-way, and one the tunnel is communicated with the inlet end of three-tube type reactor 11, and another road links to each other with the inlet end of tank reactor 12.During normal the operation, having only wherein one tunnel work, does not work in another road.It is one the tunnel that the water side of the exit end of three-tube type reactor 11 and tank reactor 12 is converged, and is communicated with the inlet end of air preheater 3 pipe sides.The pipe side outlet of air preheater 3 is divided into two-way, and one the tunnel is communicated with the inlet end of waste water preheater 7 pipe sides, and one the tunnel is communicated with exit end that waste water preheater 7 is managed sides, by the distribution between the realization of the variable valve on the pipeline two-way flow.The outlet of waste water preheater 7 pipe sides is communicated with the inlet of hot water generator 16 pipe sides, the outlet of hot water generator 16 pipe sides links to each other with the inlet of line strainer 18, the outlet of line strainer 18 is communicated with the inlet of back pressure valve 19, and the outlet of back pressure valve 19 is communicated with the inlet of gas-liquid separator 20.
The bottom salt outlet of tank reactor 12 is communicated with the inlet end of desalination surge tank 13, and the exit end of desalination surge tank 13 connects blow-off line.
The outlet of clear water storage tank 14 is communicated with the inlet of fresh water pump 15, and the exit end of fresh water pump 15 is divided into two-way by threeway, and one the tunnel is communicated with the inlet end of the shell-side of hot water generator 16, and another road is communicated with the outlet at bottom end of desalination surge tank 13.The exit end of hot water generator 16 shell-sides is communicated with hot water storage tank 17 inlet end.
The super critical water treatment system principle of work of low saline salinity organic waste water shown in Figure 1 is as follows:
1) air is after High-Pressure Compressor 1 pressurization and Flow-rate adjustment, enter surge tank 2 and reduce flow rate fluctuation, enter the shell-side of airheater 3 then, be heated to about 300 ℃ by the outlet fluid of reactor 11 or 12 and directly enter mixing tank 8 and mix with charging (organic liquid waste).
2) according to the physicochemical property of charging, select suitable alkali and add alkali number, alkaline solution is stored in adds in the alkali jar 4, unlatching adds alkali jar 4 and is exported to valve between storage tank 5 inlet, start the agitator be arranged in the storage tank 5 mixed and monitored parallel feeding to charging pH, after charging enters the pressurized and Flow-rate adjustment of product pump 6, enter the shell-side of waste water preheater 7 again, reacted hot-fluid by the pipe side is preheated to about 200 ℃, then enters mixing tank 8.
3) high-pressure air (what participate in reaction mainly is oxygen), organism charging enter first tubular reactor 9 behind the thorough mixing in mixing tank 8, then second enter tubular reactor 10.By managing outer the heating the tube fluid heat temperature raising to more than the supercritical temperature of water.If the ammonia nitrogen of organic liquid waste and inorganic salt content is lower, supercutical fluid optionally enters three-tube type reactor 11, does not carry out the desalination operation; If the higher (NH of the ammonia nitrogen of organic liquid waste and inorganic salt content
3-N＞50mg/L), supercutical fluid optionally enters tank reactor 12, and wherein tank reactor 12 inside have catalyst tank can lay pellet type catalyst.In tank reactor 12, rely on the characteristic of salt utmost point low solubility in supercritical water, to reactor bottom, the reacting fluid adverse current of a large amount of cleanings upwards flows and flows out through the water side from tank reactor 12 bottoms behind the catalyst bed reaction inorganic salt through gravity settling.
4) the pipe side that enters air preheater 3, waste water preheater 7, hot water generator 16 successively from reactor 11 or 12 effusive hot-fluids is removed preheated air, waste water, and obtains hot water.Wherein the pipe side outlet of air preheater 3 is divided into two-way, one the tunnel is communicated with the inlet end of waste water preheater 7 pipe sides, one the tunnel is communicated with the exit end of waste water preheater 7 pipe sides, by the distribution between the realization of the variable valve on the pipeline two-way flow, guarantee that the temperature after the waste water preheating is about 200 ℃, is lower than the temperature of waste water generation pyrolysis and coking.Hot water generator 16 pipe side outlet place fluid temperature (F.T.)s are reduced to about 80 ℃.Cooled fluid is decompressed to normal atmosphere through line strainer 18 through back pressure valve 19, enters gas-liquid separator 20 then and carries out gas-liquid separation.
5) tap water is stored in the clear water storage tank 14 in advance, and tap water is divided into two-way after fresh water pump 15 pressurizations, and one the road flows into the shell-side of hot water generator 16, obtains life through heat exchange and uses hot water, and be stored among the hot water storage tank 17; Another road clear water flows into the salt discharge outlet conduit of desalination surge tank 13, is used for the desalination operation.
System of the present invention has carried out optimization process to energy-recuperation system, has utilized reaction back fluidic heat.By air preheater 3, waste water preheater 7 pre-thermal materials heat is brought in the system again, produces life by hot water generator 16 and use hot water, make full use of reaction back fluidic heat.Start or reaction can not self-heating the time in system, electrically heated ELEC1, ELEC2 come into operation, and replenishment system normally moves institute's heat requirement.When reaction can self-heating, then close electrically heated ELEC1, ELEC2.By to the reacted heat of abundant recycling, reduced the running cost of the super critical water treatment system of low saline salinity organic waste water.
The pipe side outlet of air preheater 3 is divided into two-way in the system of the present invention, and one the tunnel is communicated with the inlet end of waste water preheater 7 pipe sides, and one the tunnel is communicated with exit end that waste water preheater 7 is managed sides.Exit end at waste water preheater 7 shell-sides is provided with thermopair, according to the preheating temperature of waste water, regulates automatically by the distribution between the realization of the variable valve on the pipeline two-way flow, and the temperature after the assurance wastewater heat exchange is lower than the temperature of waste water generation pyrolysis and coking.Air mixes with charging in mixing tank 8, can increase the flow velocity of charging, carries out initial reaction with charging simultaneously, reduces the easily generations of obstruction material such as tar.The blockage problem that these measures have effectively avoided feeding preheating to be easy to generate in the pyroprocess.
The supply of the air in the system of the present invention can be regulated by bypass emptying, at different chargings, by the add-on of adjusting air and the start and stop of electrically heated ELEC1, ELEC2, can select different supercritical water treatment modes flexibly, the easy to handle organism is preferentially selected SCWG, more unmanageable organism can be selected SCWPO, and the organism of intractable is selected SCWO.System of the present invention can guarantee to realize as much as possible under the prerequisite of charging harmless treatment the purpose of its recycling, has multifunctionality.The pre-treatment, mixing, reaction, the gas-liquid separation that collect charging simultaneously are collected in one, and the integrated performance of system is good.
Claims (5)
1. the super critical water treatment system of a low saline salinity organic waste water, it is characterized in that, comprise air preheater, the inlet end of described air preheater shell-side connects high-pressure air, the exit end of air preheater shell-side is communicated with a mixer entrance end, another inlet end of this mixing tank is communicated with the outlet of waste water preheater shell-side, and waste water preheater shell-side inlet is communicated with the waste water storage device; The outlet of described mixing tank links to each other with the inlet of first tubular reactor, the outlet of first tubular reactor links to each other with the inlet of second tubular reactor, the outlet of second tubular reactor is divided into two-way, one the tunnel links to each other with the inlet end of three-tube type reactor, and another road links to each other with the inlet end of tank reactor; It is to be communicated with the inlet end of preheating of air organ pipe side after one the tunnel that the exit end of three-tube type reactor and the water side of tank reactor are converged, the outlet of preheating of air organ pipe side is communicated with the entrance and exit of waste water preheater tube side respectively, by the distribution between the realization of the variable valve on the pipeline two-way flow; The outlet of waste water preheater tube side is communicated with the inlet of hot water generator pipe side, and the outlet of hot water generator pipe side is communicated with a gas-liquid separator by back pressure valve; The shell-side of hot water generator is communicated with the thermal water utilization device; Be equipped with well heater on described first tubular reactor and second tubular reactor.
2. the super critical water treatment system of low saline salinity organic waste water as claimed in claim 1 is characterized in that, described tank reactor is the baffling tank reactor, and its bottom salt outlet is communicated with blow-off line by a desalination surge tank.
3. the super critical water treatment system of low saline salinity organic waste water as claimed in claim 2, it is characterized in that, described thermal water utilization device comprises the clear water storage tank that connects tap water, its outlet is communicated with a fresh water pump, this clear water pump outlet is divided into two-way by threeway, one the tunnel is communicated with the inlet end of hot water generator shell-side, and another road is communicated with the outlet at bottom end of desalination surge tank; The exit end of hot water generator shell-side is communicated with a hot water storage tank's inlet end.
4. the super critical water treatment system of low saline salinity organic waste water as claimed in claim 1 is characterized in that, described waste water storage device comprises and have the storage tank that adds the alkali jar that its inlet end connects raw material waste water by valve; Exit end is communicated with the inlet end of waste water preheater shell-side by a product pump, is provided with agitator in the storage tank.
5. the super critical water treatment system of low saline salinity organic waste water as claimed in claim 1 is characterized in that, is provided with line strainer between the outlet of described hot water generator pipe side and the back pressure valve.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190362A (en) * | 2011-05-12 | 2011-09-21 | 西安交通大学 | Supercritical water oxidation reaction system for obtaining heat supplemented by auxiliary fuel |
| CN104628059A (en) * | 2015-02-04 | 2015-05-20 | 总装备部工程设计研究总院 | Continuous device for gasifying unsymmetrical dimethylhydrazine waste liquid with supercritical water |
| CN108751384A (en) * | 2018-06-13 | 2018-11-06 | 西安交通大学 | For the inner circulation fluidized bed-type supercritical water oxidation system of organic wastewater with difficult degradation thereby |
| CN108862698A (en) * | 2018-06-13 | 2018-11-23 | 西安交通大学 | For highly concentrated high salt organic waste water supercritical water oxidation fluidized bed type reaction system |
| CN110015747A (en) * | 2019-05-24 | 2019-07-16 | 山东豪迈化工技术有限公司 | Supercritical water oxidation apparatus and wastewater treatment method |
| CN110542346A (en) * | 2019-10-22 | 2019-12-06 | 开封龙宇化工有限公司 | device for removing scale of trioxymethylene heat exchanger |
| CN111056616A (en) * | 2019-12-26 | 2020-04-24 | 一重集团大连工程技术有限公司 | Supercritical water oxidation system with air as oxidant and starting method |
| CN111760517A (en) * | 2020-07-01 | 2020-10-13 | 西安交通大学 | Supercritical hydrothermal synthesis system and method capable of switching multi-material mixing mode and sequence |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190362A (en) * | 2011-05-12 | 2011-09-21 | 西安交通大学 | Supercritical water oxidation reaction system for obtaining heat supplemented by auxiliary fuel |
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| CN104628059A (en) * | 2015-02-04 | 2015-05-20 | 总装备部工程设计研究总院 | Continuous device for gasifying unsymmetrical dimethylhydrazine waste liquid with supercritical water |
| CN108751384A (en) * | 2018-06-13 | 2018-11-06 | 西安交通大学 | For the inner circulation fluidized bed-type supercritical water oxidation system of organic wastewater with difficult degradation thereby |
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| CN110015747A (en) * | 2019-05-24 | 2019-07-16 | 山东豪迈化工技术有限公司 | Supercritical water oxidation apparatus and wastewater treatment method |
| CN110542346A (en) * | 2019-10-22 | 2019-12-06 | 开封龙宇化工有限公司 | device for removing scale of trioxymethylene heat exchanger |
| CN111056616A (en) * | 2019-12-26 | 2020-04-24 | 一重集团大连工程技术有限公司 | Supercritical water oxidation system with air as oxidant and starting method |
| CN111056616B (en) * | 2019-12-26 | 2022-07-22 | 一重集团大连工程技术有限公司 | Supercritical water oxidation system with air as oxidant and starting method |
| CN111760517A (en) * | 2020-07-01 | 2020-10-13 | 西安交通大学 | Supercritical hydrothermal synthesis system and method capable of switching multi-material mixing mode and sequence |
| CN114790026A (en) * | 2022-04-29 | 2022-07-26 | 西安交通大学 | Supercritical water oxidation treatment method and system |
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