CN101544419B - Method and device for oxidizing and treating sewage or sludge containing organic substances by supercritical water - Google Patents
Method and device for oxidizing and treating sewage or sludge containing organic substances by supercritical water Download PDFInfo
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- CN101544419B CN101544419B CN2008100605530A CN200810060553A CN101544419B CN 101544419 B CN101544419 B CN 101544419B CN 2008100605530 A CN2008100605530 A CN 2008100605530A CN 200810060553 A CN200810060553 A CN 200810060553A CN 101544419 B CN101544419 B CN 101544419B
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Abstract
The invention relates to a method and a device for oxidizing and treating sewage or sludge containing organic substances by supercritical water. The method adopts a combustion reaction furnace, and is characterized in that substance flow of the sewage or the sludge containing the organic substances and oxidant (such as oxygen or hydrogen peroxide and the like) are preheated by a heat exchange device respectively and then enter the combustion reaction furnace, the sewage or the sludge containing the organic substances is oxidized and treated under a supercritical state, the treated substance flow is cooled by the heat exchange device again, then residual gas in the substance flow is separated by adopting a gas-liquid separator, and the lower part of the combustion reaction furnace discharges salt slag through a slag discharging hole and a valve. The method has the advantages of reasonable and practical process, energy conservation and low operation cost.
Description
Technical field
The present invention relates to method and production equipment that a kind of processing contains organism sewage or mud.
Background technology
Supercritical water oxidation (Supercritical Water Oxidation is called for short SCWO) technology is to be medium with water, (temperature＞374.3 ℃ under supercritical state; Pressure＞22.1MPa), the interface disappears between liquid phase and gas phase, oxygen can dissolve in arbitrary proportion, does not have problems such as material between the gas liquid film moves and ideal oxidizing reaction environment is provided, to suspending or being dissolved in a kind of method that the organic substance in the water carries out oxidation and removed.The SCWO method dispose of sewage have existing other sewage disposal technology incomparable advantage, the main embodiment is: the clearance rate of objectionable impurities almost reaches 100%, degradation time is in second (depending on organic kind, temperature and pressure), almost all can handle, can also realize energy-autarchic all organic objectionable impuritiess.Compare with burning, catalytic wet oxidation, SCWO has the pollutent complete oxidation at full closeding state; Final product is water, N
2, CO
2With the inorganic molecules compound, do not need to be for further processing; Advantages such as working cost is relatively low.In addition,, therefore can therefrom separate at an easy rate, handle back gained clean water and can recycle fully because inorganic salt solubleness in supercritical water is low especially.
All there are the common shortcoming both at home and abroad in present supercritical water oxidation and gasification testing apparatus:
From the type of heating of material and water, be material preheating or only pre-thermal reaction medium after reaction medium mixes earlier, and not preheating of material.The previous case, it as number of patent application 01120974.7 Chinese patent " a kind of supercritical sewage oxidizing treater ", the principle that comes to this, if preheating temperature reaches supercritical temperature, then material just begins to take place pyrolysis, scission reaction in preheating tube, can produce tar, plugged-off tubes road.If preheating temperature is low, then after entering reactor, also need to continue to be warmed to supercritical temperature, will certainly make structure of reactor more complicated.Latter event, because not preheating of material mixed before entering reactor, it is a lot of to cause whole fluidic temperature to descend, and makes total system need design more hot spots.
Current, drop into increasing man power and material in the world and be devoted to the development of SCWO technology, many scientific researches and engineering lay particular emphasis on the exploitation of the supercritical reaction device of wheels of various designs mode, to manage to solve the etching problem of equipment material under the High Temperature High Pressure, also have simultaneously many at some difficult degradations, severe toxicity, the SCWO degradation technique of volatile special organic materials exploitation, but in SCWO method sewage treatment process, nearly all prior art all will be reacted and be realized that heat is self-supporting as energy-saving and cost-reducing indispensable measure, and this becomes without thinking a kind of seemingly, the principle that must observe.Given this, must add a large amount of auxiliary fuels or sewage of low concentration is concentrated, difference according to various organism calorific values, organic content will reach more than 2%～5% at least in the sewage, just can make reaction realize the heat self-sufficiency, this COD value that is equivalent to organic sewage equals need expend a large amount of oxygen more than 80000～200000PPM (mg/l), handles oxygen-consumption at least 80～200 kilogram of one ton of such sewage.In fact most of organic sewage COD is distributed in hundreds of between several ten thousand PPM, municipal wastewater is many below 1000PPM, and the paper mill high concentration organic sewage of serious environment pollution is also only about 50000PPM, handle the sewage of most kinds with such technological thought, add auxiliary fuel and become undisputable fact.This not only can increase the processing cost of sewage, has also brought other a series of problems simultaneously, as: add auxiliary fuels such as oil, alcohol, processing cost is improved, incident high oxygen-consumption has increased cost of investment and running cost undoubtedly simultaneously; If as oxygen source, with the big free air delivery air compressor of needs costliness, conversion oxygen amount must be excessive 100% with air, and 78% nitrogen not only can hinder normally carrying out of oxidizing reaction in the supercritical water in the air, and can consume part energy; To need to invest expensive air separation plant and a series of equipment such as expensive liquid oxygen storage tank, liquid oxygen pump, vaporizer with liquid oxygen with good lagging facility; Use hydrogen peroxide or nitric acid not only can promote cost greatly, also can strengthen corrosion equipment material; Use pure oxygen, can require oxygen container to have comparatively large vol, in the high pressure vessel as large volume, its manufacturing cost is higher.Even more serious is under the envrionment conditions of High Temperature High Pressure, and too high oxygen concn will add the severity of large equipment oxygen corrosion.This also is all technical schemes of the why relevant this respect of current report owing to adopted above-mentioned technology, causes investment or running cost higher and really do not obtain the reason in market.
Mud output in sewage treatment process is very huge, and according to incompletely statistics, based on the sewage treatment process of activated sludge process, its mud generation is 0.3%～0.5% (in a water ratio 97%) of sewage load, and quantity is very surprising.The mud of discharging from sewage work generally is a kind of loose, water content is at the glue-dissolving shape lotion thing of 95%-99%, have light specific gravity, bulky (be contained solids volume tens of times), thixotropy strong (being difficult for dehydration), have outside the very easily corrupt malodorous physics and chemistry characteristics, all kinds of sewage are through handling, pollutants in sewage is almost all transferred in the mud, also enrichment pathogenic agent and a large amount of high densitys, persistence organic toxic noxious pollutant.The landfill that adopts and agricultural has had a strong impact on the face of land, groundwater environment at present, causes serious secondary pollution.At following 50 years, on the Chinese side, most of population will focus on the above cities and towns of ten thousand people, and the sewage that is produced is all handled, and will produce mud every year more than 200,000,000 tons.This numeral also is the mud of municipal sewage plant.Remove in addition, the sewage-farm (station) of providing for oneself of factory and enterprise also produces the bigger industrial sludge of environmental hazard.Thereby the processing of mud has become an instant public works difficult problem.
To reach mud decrement be way the most completely by burning, and the advantage of dehydrated incineration method is that to burn the residuum that produces few, and the lime-ash free from extraneous odour after burning; But the investment of the dedicated treatment facility of anhydration and incineration is huge, energy-output ratio is big (even the mud that sewage work produces passes through mechanical dehydration, water ratio is also between 75%～85%, show that according to experiment and calculating the external energy that the mud of water ratio 75%～85% will be needed by mummification is much larger than energy that sludge incineration produced).Running expense is high, and the expense of sludge anhydration burning is more than 400 yuan/ton.And have toxic and harmfuls such as Dioxins in the burning process and escape into atmosphere.
In sum, the SCWO technology proposed so far for two more than ten years first at 20th century the mid-80 American scholar M.Modell and can not come into the market, its major cause is the too complexity of getting in touch that is confined to material pre-heating system, supercritical water medium heating system, oxygenant (oxygen) heating system and reactor, equipment material requires very high, not only equipment construction and production run cost are very high, and cause the total system operation very unreliable.
Summary of the invention
Primary technical problem to be solved by this invention provides a kind of reasonable and practical process, supercritical water oxidation energy-conservation, that reduce running cost is handled the method that contains organism sewage or mud.
Another technical problem to be solved by this invention provides a kind of practicality rational in infrastructure, supercritical water oxidation energy-conservation, that reduce running cost is handled the device that contains organism sewage or mud.
The present invention solves the technical scheme that above-mentioned primary technical problem adopts: a kind of supercritical water oxidation is handled the method that contains organism sewage or mud, it adopts the combustion reactions stove, it is characterized in that containing the logistics of organism sewage or mud and oxygenant (as oxygen, oxygen-rich air or hydrogen peroxide etc.) air-flow is preheated by heat-exchanger rig respectively and enters into the combustion reactions stove, under supercritical state, oxide treatment contains organism sewage or mud, logistics after the processing is cooled by heat-exchanger rig once more, adopt gas-liquid separation device to isolate gas remaining in the logistics then, and the bottom of combustion reactions stove is by slag-drip opening and Valved discharge salt slag.
Described heat-exchanger rig adopts placed in-line interchanger and heat transfer reactor, makes the logistics that contains organism sewage or mud through the interchanger heating, mixes with oxidizer flow, further oxidizing reaction in heat transfer reactor.Like this, material and oxygen are in admixture in heat transfer reactor, make material begin in heat transfer reactor (the super and non-critical zone of transition of system), supercritical water oxidation to take place before the pyrolysis coking, just coal dust cheaply can be mixed and help heat in the material and be not easy material coking, blocking pipeline problem, device is simplified greatly thus, build with running cost and reduce significantly, and the operation of entire treatment system also becomes very reliable.
Described gas-liquid separation device adopts placed in-line first step gas-liquid separator and second stage gas-liquid separator, by first step gas-liquid separator, tell gas and enter atmosphere through reducing valve or through miniature steam turbine, the liquid of telling is the mixed solution of carbonic acid gas and water, mixed solution reduce pressure again or through small hydraulic turbine to second stage gas-liquid separator, isolated carbon dioxide, compressed again one-tenth commodity Liquid carbon dioxide, the liquid of telling is clean water, can do industrial water of productive use or directly discharging.Can fully utilize resource like this, increase economic efficiency, reduce the production operation cost, and can utilize the power that small hydraulic turbine provided that clean water is configured after the system handles to make auxiliarypower (drive material as small hydraulic turbine distribution transforming electric motor cooperation frequently and feed high-pressure pump), make production system can reach good energy-saving effect.
Described combustion reactions stove is arranged on the Reaktionsofen outside with pulse flame ignition system, the all available a kind of material of Reaktionsofen and heat transfer reactor (structure and common interchanger are basic identical) (high temperature high voltage resistant, wear-resisting and oxidation-resistant alloy) is made, and the equipment that has solved unlike material combination making is because of the different security seal difficult problems that cause of the coefficient of expansion.And come total system is heated up, boosts by Reaktionsofen burning combustible gas.Save indirect heating, the insulation measure obtains bigger energy-saving effect thereby can take better, simultaneously can make abundantly as far as possible with Reaktionsofen and heat transfer reactor (system super with non-critical zone of transition) and significantly prolongs their work-ing life.By time variable control combustible gas delivery system transponder pulse combustible gas stream, in the oxygen atmosphere, ignite and the pulse flame that generates temperature＞2000 ℃ is injected Reaktionsofen through the fire tube road, meet with the combustible gas of combustible gas nozzle ejection in the Reaktionsofen and light Reaktionsofen through high-voltage spark.In the Reaktionsofen ignition process, by there being the cooling effect of continuous Oxygen Flow between setup parameter (pressure, flow, recurrence interval etc.) and pulse flame, overdo pipe temperature＜500 ℃ of control, valve has lasting good seal performance on the pipeline of guaranteeing to overdo.
Described oxygenant adopts oxygen, and the oxygen that obtains by space division system boosts to the about 25Mpa of the required operating pressure of production system through increasing apparatus again after oxygen compressor is compressed to 15MPa.This booster system mainly constitutes the oxygen that about 25MPa is provided continuously to production system by four oxygen storage tanks and two high pressure plunger pumps.
Described organism sewage or mud mix and go up coal dust, coal powder density is implemented the production system temperature controlling in the control logistics, because material feeds high-pressure pump to there not being valve to hinder between first step gas-liquid separator, make total system unobstructed fast, material and oxygen are in admixture in heat transfer reactor, and supercritical water oxidation has taken place in heat transfer reactor before material begins the pyrolysis coking; Also owing to feed high-pressure pump to entering in the Reaktionsofen process from material, pulverized coal particle also has the cleaning effect to pipeline in flowing fast, be not easy to stop up before organism sewage enters Reaktionsofen thereby make more to contain, basically do not have the material coking, the blocking pipeline problem, a large amount of coal ash powder particles behind the supercritical water oxidation generate the crystallization of a large amount of small-particle salt as nucleus, just can not form bulk salt crystalline substance in the Reaktionsofen bottom, can not stop up interchanger yet, simplification device so greatly, reduce significantly and build and running cost, and the operation of entire treatment system also becomes very reliable.
The present invention solves the technical scheme that above-mentioned another technical problem adopts: a kind of supercritical water oxidation is handled the device that contains organism sewage or mud, it adopts the combustion reactions stove, it is characterized in that the logistics and the oxidizer flow that contain organism sewage or mud are connected to the combustion reactions stove by heat-exchanger rig respectively, under supercritical state, oxide treatment contains organism sewage or mud, logistics after the processing is cooled by heat-exchanger rig once more, be connected to gas-liquid separation device, isolate gas remaining in the logistics, the lower disposed of combustion reactions stove has slag-drip opening and Valved discharge salt slag.
Described heat-exchanger rig adopts placed in-line interchanger and heat transfer reactor, makes the logistics that contains organism sewage or mud through the interchanger heating, mixes with oxygenant, just begins oxidizing reaction in heat transfer reactor.
When described oxygenant is oxygen, the booster system that adopts is to boost to the about 25MPa of the required operating pressure of production system through increasing apparatus by the oxygen that space division system obtains again after oxygen compressor is compressed to 15MPa to advance heat transfer reactor, this booster system mainly is made of four oxygen storage tanks and two high pressure plunger pumps, its structure mainly is that the oxygen inlet pipe is divided into three the tunnel, through separately non-return control valve with valve is connected respectively to oxygen storage tank top, the left and right sides and cleaning water is replenished a jar top, cleaning water is replenished jar lower part outlet and is divided into three the tunnel through behind the valve, one the tunnel connects right oxygen storage tank bottom, two-way connects the import and the outlet of high-pressure pump respectively through valve in addition, and the import of high-pressure pump and outlet are respectively through separately valve, converge again and connect left oxygen storage tank bottom, oxygen storage tank top, the left and right sides is respectively through separately pressure limiting vacuum breaker, converge connection oxygen again and go out pipe, the oxygen of about 25MPa can be provided continuously to production system, be controlled at work under the supercritical state just passable.
Compared with prior art, the invention has the advantages that: its core is that material pre-heating system, supercritical water medium heating system, oxygenant (air or oxygen) heating system and reactor combine, make technology realize that necessary energy all produces in internal system, can take easily effectively to be incubated measure and more energy-conservation, and be easy to reach realization condition (temperature＞374.3 ℃ of the required fullest of SCWO method; Pressure＞22.1MPa), simultaneously, because material feeds high-pressure pump to there not being valve to hinder between first step gas-liquid separator, make total system unobstructed fast, material and oxygen are in admixture in heat transfer reactor, before beginning the pyrolysis coking, material in heat transfer reactor (the super and non-critical zone of transition of system) supercritical water oxidation takes place, just coal dust cheaply can be mixed and help heat in the material and do not have the material coking, the blocking pipeline problem, device is simplified greatly thus, build with running cost and reduce significantly, and the operation of entire treatment system also becomes very reliable.Whole process structure is reasonable and practical, energy saving economy, the few advantage of process cost.
So not only make organic toxic sewage in supercritical water environment, efficiently, apace oxidizing reaction take place and thoroughly degraded, also can dispose a large amount of mud that the Sewage Plant biochemical treatment is produced as the support equipment of municipal sewage plant.Mud is moisture more than 97%, and organic objectionable impurities is very high, and is flowing material, is solving under coking, the blockage problem prerequisite, carries out harmlessness disposing with regard to adopting the present invention fully.If adopt the equipment of technical solution of the present invention can maximize, can obtain high pressure steam driving turbine driven set production electric power by interchanger, perhaps just can replace municipal sewage plant's daily handling ability in ten thousand tons biochemical process.Can reclaim simultaneously the gas fertilizer of a large amount of Liquid carbon dioxides, and the sulfur in the coal all is oxidized to vitriol and dissolves in the clean water, do not discharge any pollutent (zero release) to atmosphere and water body in whole process of production as agriculture production.
The present invention also utmost point is applicable to the burning city domestic garbage power station, and the domestic waste water ratio has had the technical program supporting up to more than 50%, can extrude most of moisture, thereby improve the generating efficiency of domestic refuse greatly earlier with the rubbish squeezing.
Description of drawings
Fig. 1 is that supercritical water oxidation of the present invention is handled method and the production system schema thereof that contains organism sewage or mud;
Label is wherein represented respectively:
1, Reaktionsofen; 2, heat transfer reactor; 3, interchanger; 4, material feeds high-pressure pump; 5, oxygenant (oxygen) supply system; 6, first step gas-liquid separator; 7, second stage gas-liquid separator; 8 co 2 liquefaction systems; , 9, the combustible gas delivery system; 10, pulse flame ignition system; 11, miniature steam turbine; 12, small-sized water turbine unit; 13, material feeds the high-pressure pump outlet valve; 14, oxygenant (oxygen) supply system outlet valve; 15, the combustible gas delivery system is to the Reaktionsofen delivery valve; 16, pulse flame ignition system and Reaktionsofen connecting pipeline valve; 17, Reaktionsofen bottom salt discharge, residual cake valve; 18, first step gas-liquid separator vent valve; 19, first step gas-liquid separator water discharge valve; 20, second stage gas-liquid separator vent valve; 21, second stage gas-liquid separator water discharge valve; 22, operation automation control system.
Fig. 2 is a supercritical water oxidation furnace structure synoptic diagram of the present invention;
Label is wherein represented respectively:
1a, Reaktionsofen material inlet; 1b, Reaktionsofen material outlet; 1c, Reaktionsofen salt discharge, slag outlet; 1e, pulse flame entry portal; 1d, Reaktionsofen combustible gas input aperture.
10a, pulse flame ignition system oxygen spout; 10b, pulse flame ignition system combustible gas nozzle; 10c, vibration high-voltage generating device electrode.
Fig. 3 is an oxygen supply of the present invention system increasing apparatus synoptic diagram
Label is wherein represented respectively:
5.1, high-pressure pump; 5.2.1,5.2.2, oxygen storage tank; 5.3, cleaning water replenishes jar; 5.4,5.5,5.6,5.7,5.8,5.9, valve; 5.10,5.11, the non-return control valve; 5.12,5.13, the pressure limiting vacuum breaker.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
As Fig. 1-3, a kind of supercritical water oxidation is handled the device that contains organism sewage or mud, it includes combustion reactions stove 1, wherein the material import that feeds high-pressure pump 4 can be connected with running water pipe with sewage lagoon with valve by pipeline in switching, material feeds the import of the outlet of high-pressure pump 4 by outlet valve 13 connection interchanger 3,5, oxygenant (oxygen) supply system 5 is connected between heat transfer reactor 2 and the interchanger 3 by its outlet valve 14, the outlet of heat transfer reactor 2 is connected to the material inlet 1a at combustion reactions stove 1 top, the material outlet 1b of Reaktionsofen 1 bottom returns another import that is connected to heat transfer reactor 2, the correspondence outlet of heat transfer reactor 2 is by pipe connection another import to interchanger 3, the correspondence outlet of interchanger 3 is arrived first step gas-liquid separator 6 by pipe connection, first step gas-liquid separator 6 is a nitrogen, gas-liquid separators such as oxygen, vent valve 18 is arranged at the top, connect miniature steam turbine 11, make and tell gas and enter atmosphere through reducing valve or through miniature steam turbine 11, water discharge valve 19 is arranged at the bottom, connect small hydraulic turbine 12, the liquid of telling is the mixed solution of carbonic acid gas and water, mixed solution reduce pressure again or through small hydraulic turbine 12 to second stage gas-liquid separator 7, second stage gas-liquid separator 7 is the carbonic acid gas gas-liquid separator, the top has vent valve 20 to meet co 2 liquefaction system 8, make the compressed again one-tenth commodity of isolated carbon dioxide Liquid carbon dioxide, water discharge valve 21 is arranged at the bottom, and the liquid of telling is clean water can do industrial water of productive use or directly discharging.Combustible gas delivery system 9 is divided into two-way, one the tunnel meets pulse flame ignition system 10, the pulse flame entry portal 1e that connects combustion reactions stove 1 through connecting pipeline valve 16, another road meets Reaktionsofen combustible gas input aperture 1d, combustion reactions stove 1 lower disposed has salt discharge slag outlet 1c, connects salt discharge residual cake valve 17.Operation automation control system 22 connects each controlled part.Pulse flame ignition system includes oxygen spout 10a and combustible gas nozzle 10b and is arranged on vibration high-voltage generating device electrode 10c in the ignition system.
Oxygen supply system increasing apparatus principle of work is described, as shown in Figure 3: the oxygen that oxygenant obtains by space division system boosts to the about 25MPa of the required operating pressure of production system through increasing apparatus again and advances heat transfer reactor after oxygen compressor is compressed to 15MPa, its structure mainly is that the oxygen inlet pipe is divided into three the tunnel, through non-return control valve 5.11 separately, 5.10 and valve 5.9 is connected respectively to left and right sides oxygen storage tank 5.2.1,5.2.2 top and cleaning water are replenished jar 5.3 tops, cleaning water is replenished jar 5.3 lower part outlets and is divided into three the tunnel through behind the valve 5.8, one the tunnel connects right oxygen storage tank 5.2.2 bottom, two-way passes through valve 5.7 respectively in addition, 5.4 connect the import and the outlet of high-pressure pump 5.1, and the import of high-pressure pump 5.1 and outlet are respectively through separately valve 5.6,5.5, converge again and connect left oxygen storage tank 5.2.1 bottom, left and right sides oxygen storage tank 5.2.1,5.2.2 top is respectively through separately pressure limiting vacuum breaker 5.12,5.13, converge connection oxygen again and go out pipe, thereby the oxygen of about 25MPa is provided continuously to production system.The oxygen that boosts to 15MPa through space division system and oxygen compressor enters the oxygen storage tank of having adorned half cleaning water like this, Open valve 5.4,5.6 and high-pressure pump 5.1, the oxygen of 15MPa continues to enter oxygen storage tank 5.2.1, clear water is pressed into oxygen storage tank 5.2.2 from oxygen storage tank 5.2.1, oxygen in the oxygen storage tank 5.2.2 just is compressed, when pressure reaches 25MPa, pressure limiting vacuum breaker 5.13 is opened the oxygen that 25MPa is provided to production system automatically, when almost being full of the oxygen of 15MPa in the oxygen storage tank 5.2.1, close high-pressure pump 5.1 and valve 5.4 when almost being full of cleaning water in the oxygen storage tank 5.2.2,5.6; Subsequent Open valve 5.5,5.7 and high-pressure pump 5.1, the oxygen of 15MPa begins to enter oxygen storage tank 5.2.2, clear water then is pressed into oxygen storage tank 5.2.1 from oxygen storage tank 5.2.2, oxygen in the oxygen storage tank 5.2.1 just is compressed, when pressure reaches 25MPa, pressure limiting vacuum breaker 5.12 is opened the oxygen that 25MPa is provided to production system automatically, and the collaborative formation of such two covering devices booster system just can provide the oxygen of 25MPa continuously to production system.
The evaporation of cleaning water in the device reduces in process of production, can be replenished to device by additional jar 5.3 of cleaning water or high pressure fresh water pump.
Set up procedure before first step starts, as shown in Figure 1: Open valve outlet valve 13, water discharge valve 19, water discharge valve 21, feed high-pressure pump 4 by material and begin to inject clean water or tap water to total system, the flow process of clean water is: through interchanger 3 → heat transfer reactor 2 → Reaktionsofen 1 → heat transfer reactor 2 → interchanger 3 → first step gas-liquid separator 6 → valve 19 → small-sized water turbine unit 12 → second stage gas-liquid separator 7 → water discharge valve 21.When water discharge valve 21 has clear water to flow out, to close material and feed high-pressure pump 4, the while is valve-off outlet valve 13, water discharge valve 19, water discharge valve 21 also, and this moment, total system nearly all was full of clean water or tap water.
The second step reaction furnace igniting program, as shown in Figure 2: adjust earlier the oxygen delivery device of pulse flame ignition system 10 and combustible gas delivery system to pulse flame ignition system output pressure (as＞0.2MPa), valve 16 on complete opening pulse flame ignition system and Reaktionsofen 1 connecting pipeline, preestablishing the ratio of combustion that flow makes oxygen and combustible gas makes oxygen excessive a little, the 1 bottom salt discharge of complete opening Reaktionsofen, residual cake valve 17 makes system be in emptying state, the outlet valve 14 of open system, start oxygenant (oxygen) supply system 5 and regulate oxygen to suitable output flow, clean water in the Reaktionsofen 1 will be by salt discharge, residual cake valve 17 flows out, after clean current in the Reaktionsofen 1 are intact, unbalanced pulse flame ignition system oxygen delivery device, provide continuous Oxygen Flow by spout 10a, unbalanced pulse flame ignition system oscillation high-voltage generating device makes electrode 10c and combustible gas nozzle 10b form continual electrical spark, the pulse sequence of control transport pulse combustible gas stream of starting impulse flame ignition system combustible gas e Foerderanlage, just produce temperature and inject Reaktionsofen 1 up to the pulse flame more than 2000 ℃, and then open the delivery valve 15 of combustible gas delivery system 9 and carry combustible gas to Reaktionsofen 1, Reaktionsofen 1 is promptly lighted.When operation automation control system 22 is confirmed Reaktionsofens 1 temperature＞600 ℃ (combustible gas ℃ air of temperature＞550 with regard to automatic combustion, also can carry fuel oil or industrial spirit to substitute combustible gas simultaneously) to Reaktionsofen, close pulse flame ignition system, valve-off 16, residual cake valve 17, total system is with regard to the temperature control that begins to enter next step program of boosting.
The third step temperature control program of boosting, as shown in Figure 1: adjust combustible gas delivery system 9 and oxygenant (oxygen) supply system and make oxygen excessive slightly (preestablishing ordering parameter), when operation automation control system 22 shows that temperature is higher than 700 ℃ in the Reaktionsofen 1, and pressure is not when also arriving 25MPa, can open outlet valve 13 and material and feed high-pressure pump 4 and inject in a small amount sewage and adjust.Temperature until Reaktionsofen 1 is adjusted to 700 ℃, and whole production system pressure is to 25MPa, closure systems combustible gas delivery valve 15, and total system just will enter normal operating condition.
The normal working procedure of the 4th step, as shown in Figure 1: open material and feed high-pressure pump 4, be adjusted to normal operation flow, (as: pump 4.1 is introduced and is contained 20% coal dust sewage with the sewage that adds coal dust in proportion, pump 4.2 is introduced sewage, regulate the temperature of their throughput ratio may command Reaktionsofen 1) the introducing production system, adjust oxygenant (oxygen) supply system 5 simultaneously and advance production system to suitable flow (oxygen can be inexcessive), open and regulate vent valve 18, water discharge valve 19, vent valve 20, it is 25MPa that water discharge valve 21 makes production system keep pressure, through the unnecessary oxygen of production system oxygen depleted and miscellaneous nitrogen or a spot of nitrogen in producing and carbon monoxide and hydrogen (in temperature＜374.3 ℃, pressure is to be gaseous state under the 25MPa environment, and the CO that production system produced
2Being in liquefaction is miscible in water) drive miniature steam turbine 11 back emptyings, clean water and liquid CO at first step gas-liquid separator 6 by valve 18
2Mixed solution enters second stage gas-liquid separator 7, CO after valve 19 drives small-sized water turbine unit 12
2Gas enters co 2 liquefaction system 8 by valve 20 and makes commodity liquid CO
2, clean water is by water discharge valve 21 dischargings.
Parameter under the running status:
Production system operating pressure: 25MPa;
Contain the residence time of organism sewage in Reaktionsofen 1: 60 seconds.
Oxygen (25MPa), coal dust (particle diameter＜0.3 millimeter) and sewage are mixed in proportion and reach temperature＞600 through high efficiency interchanger and heat transfer reactor and ℃ advance Reaktionsofen 1, ratio by coal dust and sewage allocates controlled temperature, Reaktionsofen 1 essence is playing the temperature regulation effect to a greater extent, is started and the urgent temperature regulation of implementing Reaktionsofen 1 that heats by 9 pairs of Reaktionsofens 1 of combustible gas delivery system.
The 5th step production system bolt down procedure, as shown in Figure 1: just feed high-pressure pump 4 and change into clean water or tap water into by advancing sewage and coal dust mixed solution at operating material, close oxygenant (oxygen) supply system 5 simultaneously and advance the flow of production system, system i.e. cooling rapidly, when Reaktionsofen 1 temperature is reduced to below 200 ℃, to close material and feed high-pressure pump 4, system's rapid depressurization is also discharged clean water in the Reaktionsofen 1, when water discharge valve 21 anhydrous rows, can close all valves and device power supply (DPS).
Above-mentioned steps is realized by the operation automation control system.
Application Example
1, insecticide factory's sewage: water inlet COD:80000～15000mg/L
Water outlet COD:13.8mg/L
2, petrochemical plant sewage: water inlet COD:110000～230000mg/L
Water outlet COD:17.6mg/L
3, papermaking sewage: water inlet COD:46000～87000mg/L
Water outlet COD:9.3mg/L
Claims (8)
1. a supercritical water oxidation is handled the method that contains organism sewage or mud, it adopts the combustion reactions stove, it is characterized in that containing the logistics of organism sewage or mud and oxygenant is preheated by heat-exchanger rig respectively and enters into the combustion reactions stove, under supercritical state, oxide treatment contains organism sewage or mud, logistics after the processing is cooled by heat-exchanger rig once more, adopt gas-liquid separation device to isolate gas remaining in the logistics then, and the bottom of combustion reactions stove is by slag-drip opening and Valved discharge salt slag;
Described heat-exchanger rig adopts placed in-line interchanger and heat transfer reactor, makes the logistics that contains organism sewage or mud through the interchanger heating, mixes with oxygenant, further carries out oxidizing reaction in heat transfer reactor and Reaktionsofen.
2. method according to claim 1, it is characterized in that described gas-liquid separation device adopts placed in-line first step gas-liquid separator and second stage gas-liquid separator, by first step gas-liquid separator, tell gas and enter atmosphere through reducing valve or through miniature steam turbine, the liquid of telling is the mixed solution of carbonic acid gas and water, mixed solution reduce pressure again or through small hydraulic turbine to second stage gas-liquid separator, isolated carbon dioxide, compressed again one-tenth commodity Liquid carbon dioxide, the liquid of telling is clean water, does industrial water of productive use or directly discharging.
3. method according to claim 1 is characterized in that described combustion reactions stove is arranged on the body of heater outside with pulse flame ignition system, is come total system is heated up, boosts by Reaktionsofen burning combustible gas.
4. method according to claim 1, when it is characterized in that described oxygenant adopts oxygen, the oxygen that obtains by space division system boosts to the required operating pressure 25MPa of production system through increasing apparatus again after oxygen compressor is compressed to 15MPa.
5. method according to claim 1 is characterized in that upward coal dust of described organism sewage or mud doping, implements the production system temperature controlling by the control coal powder density.
6. a supercritical water oxidation is handled the device that contains organism sewage or mud, it adopts the combustion reactions stove, it is characterized in that the logistics and the oxygenant that contain organism sewage or mud are connected to the combustion reactions stove by heat-exchanger rig respectively, under supercritical state, oxide treatment contains organism sewage or mud, logistics after the processing is cooled by heat-exchanger rig once more, be connected to gas-liquid separation device, isolate gas remaining in the logistics, the lower disposed of combustion reactions stove has slag-drip opening and Valved discharge salt slag;
Described heat-exchanger rig adopts placed in-line interchanger and heat transfer reactor, makes the logistics that contains organism sewage or mud through the interchanger heating, mixes with oxygenant, further carries out oxidizing reaction in heat transfer reactor.
7. device according to claim 6, it is characterized in that described gas-liquid separation device adopts placed in-line first step gas-liquid separator and second stage gas-liquid separator, by first step gas-liquid separator, tell gas and enter atmosphere through reducing valve or through miniature steam turbine, the liquid of telling is the mixed solution of carbonic acid gas and water, mixed solution reduce pressure again or through small hydraulic turbine to second stage gas-liquid separator, isolated carbon dioxide, compressed again one-tenth commodity Liquid carbon dioxide, the liquid of telling is clean water, does industrial water of productive use or directly discharging.
8. device according to claim 6, when it is characterized in that described oxygenant is oxygen, the oxygen that obtains by space division system boosts to the required operating pressure 25MPa of production system through increasing apparatus again and advances heat transfer reactor after oxygen compressor is compressed to 15MPa, its structure mainly is that the oxygen inlet pipe is divided into three the tunnel, through separately non-return control valve with valve is connected respectively to oxygen storage tank top, the left and right sides and cleaning water is replenished a jar top, cleaning water is replenished jar lower part outlet and is divided into three the tunnel through behind the valve, one the tunnel connects right oxygen storage tank bottom, two-way connects the import and the outlet of high-pressure pump respectively through valve in addition, and the import of high-pressure pump and outlet are respectively through separately valve, converge again and connect left oxygen storage tank bottom, oxygen storage tank top, the left and right sides is respectively through separately pressure limiting vacuum breaker, converge connection oxygen again and go out pipe, thereby the oxygen of 25MPa is provided continuously to production system.
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