CN101580320B - Method for operating a supercritical water treatment system of waste organic substances - Google Patents
Method for operating a supercritical water treatment system of waste organic substances Download PDFInfo
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- CN101580320B CN101580320B CN2009100228498A CN200910022849A CN101580320B CN 101580320 B CN101580320 B CN 101580320B CN 2009100228498 A CN2009100228498 A CN 2009100228498A CN 200910022849 A CN200910022849 A CN 200910022849A CN 101580320 B CN101580320 B CN 101580320B
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Abstract
The invention belongs to the field of environmental protection, relates to a method for performing innocent treatment and resource utilization on waste organic substance liquid of high concentration and difficult biochemical degradation such as organic wastewater/municipal sludge by utilizing supercritical water as reaction medium, and discloses a method for operating a supercritical water treatment system of waste organic substances. The operation method comprises the steps of preparation, pre-heating, operation and a shutdown, quickly and smoothly realizes the commissioning and the shutdown of the supercritical water treatment system of the waste organic substances through the heating, spontaneous heating and stimulation operation, is energy-saving and high-efficiency, and avoids the problems of the blocking and corrosion of the system.
Description
Technical field
The invention belongs to field of environment protection; Relate to and utilize supercritical water the waste organic matter liquid such as organic waste water/municipal sludge of high density bio-refractory to be carried out harmless treatment and recycling, particularly a kind of working method of super critical water treatment system of waste organic matter 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).Supercritical water has the character of liquid and vaporous water concurrently, has only a spot of hydrogen bond to exist under this state, and specific inductivity is similar to organic solvent, has high spread coefficient and low viscosity.Under sufficiently high pressure; 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 particularly the solubleness of salt in SCW is extremely low for inorganics, easily it is separated.
The organic compound supercritical water treatment technology comprises supercritical water oxidation technology (being called for short SCWO), supercritical water partial oxidation technology (being called for short SCWPO) and supercritical water gasification technology (being called for short SCWG); SCWO is a special property of utilizing water under supercritical state, to be had; Make organism and oxygenant that oxidizing reaction take place rapidly in supercritical water and come thorough decomposing organic matter, SCWO is to be ultimate aim with the organism harmless treatment.SCWPO is a unique physical chemical property of utilizing supercritical water, and under the prerequisite that the partially oxidation agent is provided, organism being decomposed generate with hydrogen is main a kind of inflammable gas.SCWG is physicochemical property of utilizing supercritical water unique, and under the condition of oxidizer not, reactions such as hydrolysis, pyrolysis take place in supercritical water organism, and generating with hydrogen is main a kind of inflammable gas.SCWPO and SCWG are that transform to produce hydrogen with organism be ultimate aim.In a word; The supercritical water treatment technology is that to utilize supercritical water all be the special property of good solvent to organism and oxygenant; Organism carries out homogeneous reaction in supercritical water environment under the prerequisite that the different quantities oxygenant is provided; Rapidly, fully, up hill and dale the organic constitution degree of depth is destroyed, change into harmless CO
2, H
2(SCWPO and SCWG) and H
2The micromolecular compound that O etc. are innoxious.
But the operational conditions of HTHP has proposed strict requirement to the working method of super critical water treatment system, and the main at present problem that exists has: it is big to start energy consumption, and toggle speed is slow; Salinity during startup in the charging is difficult to be removed, and stops up easily; And there is acid to generate in the start-up course, causes equipment corrosion easily.
Summary of the invention
The object of the present invention is to provide a kind of working method of super critical water treatment system of waste organic matter, can reduce salt sedimentation, obstruction, the corrosion of reactor drum and pipeline, and startup is fast, energy consumption is low.
In order to achieve the above object, the present invention adopts following technical scheme to be achieved.
A kind of working method of super critical water treatment system of waste organic matter, the super critical water treatment system of said waste organic matter comprises:
Reaction member; The reactor drum, desalting and deslagging device, the storage salt pond that comprise the countercurrent pot-type of vertically arranged mixing tank, built-in evaporation wall; The material outlet end of said mixing tank is communicated with the material inlet end of reactor drum; The salt discharge exit end of reactor bottom is communicated with the inlet end of desalting and deslagging device, and the outlet at bottom end of desalting and deslagging device is communicated with the inlet end in storage salt pond; Be provided with heat exchange coil in the said reactor drum;
Oxygen comprises liquid oxygen storage tank, liquid oxygen pump, liquid oxygen carburetor, is used for first interchanger of preheated oxygen, and is composed in series the oxygen supply path successively, to mixing tank oxygen intake end oxygen is provided;
Feed unit comprises materials-stored box, first high-pressure metering pump, first electric heater, and is composed in series the material path successively, to the material inlet end of mixing tank material is provided;
Gas collection unit; Comprise the high pressure vapour liquid separator; First back pressure valve and the hydrogen cylinder that are communicated with the top exit end of high pressure vapour liquid separator successively; The first low pressure vapour liquid separator is arranged on second back pressure valve between the high pressure vapour liquid separator outlet at bottom end and the first low pressure vapour liquid separator top inlet end, the second low pressure vapour liquid separator; The dry device of carbonic acid gas that is communicated with first, second low pressure vapour liquid separator top exit end respectively is communicated with the carbonic acid gas topping-up pump and the dioxide bottle of the dry device of carbonic acid gas successively;
The first evaporation wall water feeding unit; The 3rd interchanger, second electric heater that comprise the evaporation wall water that first liquid-collecting box, second high-pressure metering pump, preheating first liquid-collecting box that are communicated with the first low pressure vapour liquid separator outlet at bottom end successively provided; The exit end of second electric heater is divided into three the tunnel; One the tunnel is communicated with the inlet end of the evaporation wall water of mixing tank, and another road is communicated with the evaporation wall water inlet end of reactor head, and Third Road is communicated with the evaporation wall water inlet end at reactor drum middle part;
The second evaporation wall water feeding unit comprises second interchanger that second liquid-collecting box, the 3rd high-pressure metering pump, preheating second liquid-collecting box that are communicated with the second low pressure vapour liquid separator outlet at bottom end successively provide evaporation wall water; The evaporation wall water out end of second interchanger is communicated with the bottom evaporation wall water inlet end of reactor drum;
The reaction exit end of said reactor drum is communicated with the thermal source inlet end of the 3rd interchanger, and the thermal source exit end of said the 3rd interchanger is communicated with the inlet end of high pressure vapour liquid separator; The fluid of the top exit end of said desalting and deslagging device is as thermal source flow through successively first interchanger, second interchanger, and flows into the second low pressure vapour liquid separator through the 3rd back pressure valve;
It is characterized in that said working method may further comprise the steps:
(1) auxiliary line is set, between the outlet at bottom end of the thermal source inlet end of the 3rd interchanger and desalting and deslagging device, is provided with first auxiliary line that is communicated with; Between the first high pressure measurement pump intake and first liquid-collecting box, be provided with second auxiliary line of connection;
(2) preparatory stage fills clean water to first liquid-collecting box, opens second auxiliary line, starts first high-pressure metering pump, first electric heater successively, charges into clean water to reactor drum and salt discharge deslagging device; Restart second high-pressure metering pump, second electric heater, in reactor drum, inject evaporation wall water; At first carry out system evacuation, after the system evacuation, the top exit end of off-response device; Open first auxiliary line; Constitute clean water circulation preheating path, and regulate first back pressure valve, second back pressure valve, make the supercritical water pressure of the pressure-stabilisation of reactor drum and salt discharge deslagging device in setting; Clean water preheating temperature in question response device and the desalting and deslagging device is opened the top exit end of reactor drum after the supercritical water temperature, close first auxiliary line and second auxiliary line;
(3) temperature rise period at first starts liquid oxygen pump, liquid oxygen carburetor and first interchanger, is oxygen through liquid oxygen carburetor vaporization liquid oxygen, gets into mixing tank again after feeding the first interchanger preheating; Simultaneously, in materials-stored box, add organic solution, organic solution is provided to the material inlet end of mixing tank; Drop into gas collection unit, the second evaporation wall water feeding unit and second interchanger then successively; Organic solution is decomposed at the reactor drum internal reaction, emits the fluid that heat comes the reactor heating top, and controls first electric heater and second electric heater, makes the reactor head fluid be heated to the setting temperature of reaction;
(4) operation phase adds materials-stored box with treating material, normally moves the super critical water treatment system of waste organic matter;
(5) shutdown phase after treating material is finished dealing with, is opened second auxiliary line, and off-response device exit end continues the aerating oxygen oxidation and is trapped in the organism in the reactor drum; 0.2 after～0.8 hour, close liquid oxygen pump, stop supplies oxygen is closed first electric heater, second electric heater, and regulates second back pressure valve, progressively step-down cooling.
Further improvement of the present invention is: said organic solution is ethanol or aqueous propanol solution.
In the working method of the present invention; At first be open at first subsidiary conduit that is provided with between the first high pressure measurement pump intake and first liquid-collecting box; Constitute the clean water circulation path, feed clean water, the supercritical pressure the when pipeline of assurance system reaches reactor drum work in advance safely; Opening first electric heater, second electric heater reaches fluid temperature (F.T.) in reactor drum and the desalting and deslagging device to set the supercritical water temperature; The obstruction and the etching problem of reactor drum and pipeline have been prevented; Secondly, feed organic solution, its calorific value equals pending true material, and through the decomposition fully of organic solution, the core flow of autothermic reactor satisfies true waste organic matter reaction conditions, makes system start energy consumption and is reduced to minimum; The 3rd, drop into true waste organic matter material, make system smoothly get into normal operating phase; At last; In shutdown phase; Be open at second subsidiary conduit that is provided with between the first high pressure measurement pump intake and first liquid-collecting box, and lasting aerating oxygen oxidation is trapped in the organism in the reactor drum, reaches cleaning system, make things convenient for the purpose that repeats to open, reduce system's operation troubles rate of system.
Working method of the present invention makes full use of heat energy in the preparatory stage, and energy consumption is low; In the temperature rise period, utilize organic solution to strengthen heating up, cheap, quick heating does not contain not block system of salinity, does not produce not etching system of acidic substance, and has simulated reaction process, has checked the security of reactive system.In sum, working method of the present invention has outstanding characteristics and significant effect.
Description of drawings
Below in conjunction with description of drawings and embodiment the present invention is explained further details.
Fig. 1 is the structural representation of the super critical water treatment system of waste organic matter of the present invention;
Among the figure: 1 is the liquid oxygen storage tank, and 2 is liquid oxygen pump, and 3 is liquid oxygen carburetor, and 4 is first interchanger, and 5 is mixing tank, and 6 is materials-stored box; 7 is first high-pressure metering pump, and 8 is heat exchanger package, and 8a is the first step interchanger of heat exchanger package, and 8b is the second stage interchanger of heat exchanger package, and 8c is the third stage interchanger of heat exchanger package, and 9 is first electric heater; 10 is reactor drum, and 11 is desalting and deslagging device, and 12 are the storage salt pond, and 13 is line strainer, and 14 is the 3rd back pressure valve; 15 is the second low pressure vapour liquid separator, and 16 is second liquid-collecting box, and 17 are storage alkali case, and 18 is the 3rd high-pressure metering pump, and 19 is second interchanger; 20 is second high-pressure metering pump, and 21 is the 3rd interchanger, and 22 is second electric heater, and 23 is the 4th interchanger, and 24 is the 5th interchanger; 25 is cooling-water pump, and 26 is the high pressure vapour liquid separator, and 27 is second back pressure valve, and 28 is the first low pressure vapour liquid separator, and 29 is first liquid-collecting box; 30 is hydrogen flowmeter, and 31 is hydrogen cylinder, and 32 is the dry device of carbonic acid gas, and 33 is the carbon dioxide flow meter, and 34 is snubber; 35 is the carbonic acid gas topping-up pump, and 36 is dioxide bottle, and 37 is the 3rd liquid-collecting box, and 38 is first back pressure valve, and V1～V52 is the first to the 52 valve.
Embodiment
With reference to Fig. 1, equipment connection mode is following in the super critical water treatment system of a kind of waste organic matter of the present invention:
1) exit end of cryogenic liquid oxygen storage tank 1 is communicated with the inlet end of cryogenic liquid oxygen pump 2; The exit end of liquid oxygen pump 2 is communicated with the oxygen intake end of hot water bath formula liquid oxygen carburetor 3; The oxygen outlet end of hot water bath formula liquid oxygen carburetor 3 is communicated with the oxygen intake end of positive displacement first interchanger 4, and the oxygen outlet end of first interchanger 4 is communicated with the material inlet end of the second stage interchanger 8b of the oxygen intake end of mixing tank 5 and heat exchanger package 8 respectively.
2) the material outlet end of materials-stored box 6 is communicated with the material inlet end of first high-pressure metering pump 7; The material outlet end of first high-pressure metering pump 7 is communicated with the material inlet end of heat exchanger package 8; The material outlet end of heat exchanger package 8 is communicated with the material inlet end of first electric heater 9, and first electric heater, 9 material outlet ends are communicated with the material inlet end of mixing tank 5.Heat exchanger package 8 comprises three grades of interchanger of placed in-line telescoping, is respectively first step interchanger 8a, second stage interchanger 8b, second stage interchanger 8c; The material inlet end input of second stage interchanger 8b has the preheated oxygen from first interchanger 4; The diameter of pipe enlarges step by step in the material of first, second and third grade of telescoping interchanger 8a, 8b, 8c, is convenient to the transmission of material.
3) mixing tank 5, reactor drum 10, desalting and deslagging device 11 and storage salt pond 12 vertical layouts.The material outlet end of mixing tank 5 is communicated with the material inlet end of reactor drum 10; To pass through the material entering reactor drum 10 that mixing tank 5 is handled; Reactor drum 10 is the reactor drum of the countercurrent pot-type of built-in evaporation wall; The salt discharge exit end of its bottom is communicated with the inlet end of desalting and deslagging device 11; The outlet at bottom end of desalting and deslagging device 11 is communicated with the inlet end in storage salt pond 12; The inlet end in storage salt pond 12 is communicated with the inlet end of heating coil in the desalting and deslagging device 11 simultaneously and constitutes first auxiliary line (see dotted line pipeline among Fig. 1, promptly first auxiliary line is arranged between the outlet at bottom end of thermal source inlet end and desalting and deslagging device of the 3rd interchanger), stores the exit end and the salt discharge pipeline connection in salt pond 12.
The countercurrent pot-type reactor drum 10 of built-in evaporation wall comprises staving, top cover, heat exchange coil and is arranged on the evaporation wall in the staving.Feed evaporation wall water between the evaporation wall staving inwall; Internal surface in evaporation wall forms a kind of protectiveness moisture film; The evaporation wall inboard is a reaction compartment, and material flows into through material inlet end that is arranged on top cover and the centre pipe that stretches into the reaction compartment middle part, and reacted hot-fluid flows out through the reaction exit end that is arranged on the top cover; Reactor bottom space deposition strong brine and waste residue flow out from the salt discharge exit end that is arranged on the staving bottom then; Heat exchange coil is arranged on the reaction compartment middle part, and its exit end and inlet end stretch out top cover.Desalting and deslagging device 11 comprises tank body and is arranged on a jar intravital heating coil, and heating coil is positioned at the zone, middle and upper part of tank body; Make this regional hot-fluid be in supercritical region; Separate out salinity, discharge clean hot-fluid, discharge dense salt and waste residue from the bottom of tank body from the top of tank body; The inlet end and the exit end in storage salt pond 12 are provided with inlet valve and discharge control valve, and the system of being convenient to realizes intermittent salt discharge slagging-off.
The reaction exit end at reactor drum 10 tops is divided into three the tunnel, the one tunnel and is communicated with the thermal source inlet end of positive displacement the 5th interchanger 24, and its thermal source exit end is communicated with the thermal source inlet end of telescoping the 4th interchanger 23; Another road is communicated with the thermal source inlet end of positive displacement the 3rd interchanger 21, and the exit end of its thermal source is communicated with the thermal source inlet end of the 4th interchanger 23; Third Road is communicated with the inlet end of spiral type heated coil pipe in the desalting and deslagging device 11; The thermal source inlet end of third stage interchanger 8c in the exit end of this heating coil and the heat exchanger package 8 is communicated with; The thermal source exit end of third stage interchanger 8c is communicated with the thermal source inlet end of second stage interchanger 8b; The thermal source exit end of second stage interchanger 8b is communicated with the thermal source inlet end of first step interchanger 8a, and the thermal source exit end of first step interchanger 8a is communicated with the thermal source inlet end of the 4th interchanger 23.
4) the thermal source exit end of the 4th interchanger 23 is communicated with the inlet end of high pressure vapour liquid separator 26.The top exit end of high pressure vapour liquid separator 26 is communicated with the inlet end of first back pressure valve 38, and the exit end of first back pressure valve 38 is communicated with the inlet end of hydrogen flowmeter 30, and the exit end of hydrogen flowmeter 30 is communicated with the inlet end of hydrogen cylinder 31.
The outlet at bottom end of high pressure vapour liquid separator 26 is communicated with the inlet end of second back pressure valve 27; The exit end of second back pressure valve 27 is communicated with the inlet end of the first low pressure vapour liquid separator 28; The exit end one tunnel of the first low pressure vapour liquid separator, 28 bottoms is communicated with formation the 3rd auxiliary line with storage salt pond 12 top inlet ends and (sees dotted line pipeline among Fig. 1; Promptly the 3rd auxiliary line is arranged between the first low pressure vapour liquid separator outlet at bottom and storage top, the salt pond inlet); Another road is communicated with the thermal source inlet end of hot water bath formula liquid oxygen carburetor 3; The thermal source exit end of hot water bath formula liquid oxygen carburetor 3 is communicated with the inlet end of first liquid-collecting box 29; First liquid-collecting box 29 has three way outlet ends, and one of which way outlet end is communicated with the inlet end of second liquid-collecting box 16, and a way outlet end is communicated with formation second auxiliary line (seeing dotted line pipeline among Fig. 1) with the inlet end of first high-pressure metering pump 7;
The top exit end of the first low pressure vapour liquid separator 28 is communicated with the inlet end of moisture eliminator 32; The exit end of moisture eliminator 32 is communicated with the inlet end of carbon dioxide flow meter 33; The exit end of carbon dioxide flow meter 33 is communicated with the inlet end of snubber 34; The exit end of snubber 34 is communicated with the inlet end of carbonic acid gas topping-up pump 35, and the exit end of carbonic acid gas topping-up pump 35 is communicated with the inlet end of dioxide bottle 36.
Another way outlet end of first liquid-collecting box 29 is communicated with the inlet end of second high-pressure metering pump 20; The exit end of second high-pressure metering pump 20 is communicated with the evaporation wall water inlet end of positive displacement the 3rd interchanger 21; The evaporation wall water out end of the 3rd interchanger 21 is communicated with the inlet end of second electric heater 22; The exit end of second electric heater 22 divides three the tunnel; One the tunnel is communicated with the evaporation wall water inlet end of mixing tank 5, and one the tunnel is communicated with the evaporation wall water inlet at reactor drum 10 tops, also has one the tunnel to be communicated with the evaporation wall water main entrance at reactor drum 10 middle parts.
5) the top exit end of desalting and deslagging device 11 is communicated with the thermal source inlet end of positive displacement first interchanger 4; The thermal source exit end of first interchanger 4 is communicated with the thermal source inlet end of telescoping second interchanger 19; The thermal source exit end of second interchanger 19 is communicated with the inlet end of line strainer 13; The exit end of line strainer 13 is communicated with the inlet end of the 3rd back pressure valve 14, and the exit end of the 3rd back pressure valve 14 is communicated with the inlet end of the second low pressure vapour liquid separator 15.
The top exit end of the second low pressure vapour liquid separator 15 is communicated with the inlet end of moisture eliminator 32; The exit end of moisture eliminator 32 is communicated with the inlet end of carbon dioxide flow meter 33; The exit end of carbon dioxide flow meter 33 is communicated with the inlet end of snubber 34; The exit end of snubber 34 is communicated with the inlet end of topping-up pump 35, and the exit end of topping-up pump 35 is communicated with the inlet end of dioxide bottle 36.
The outlet at bottom end of the second low pressure vapour liquid separator 15 is communicated with the inlet end of second liquid-collecting box 16; The exit end of second liquid-collecting box 16 is communicated with the exit end of storage alkali case 17 and the inlet end of the 3rd high-pressure metering pump 18 respectively; The exit end of the 3rd high-pressure metering pump 18 is communicated with the evaporation wall water inlet end of telescoping second interchanger 19, and the evaporation wall water out end of second interchanger 19 is communicated with the bottom evaporation wall water inlet end of reactor drum 10.
6) the 3rd liquid-collecting box 37 stores water coolant; Its exit end is communicated with the inlet end of highly compressed cooling-water pump 25; The outlet of cooling-water pump 25 is divided into two-way; One the tunnel with reactor drum 10 in the inlet end of spiral heat exchange coil be communicated with, the pipeline connection that the exit end of this heat exchange coil is outer with being arranged in reactor drum 10 is used for externally providing steam or hot water; Another road is communicated with the cooling water inlet end of telescoping the 4th interchanger 23; The cooling water outlet end of the 4th interchanger 23 is communicated with the cooling water inlet end of the 5th interchanger 24; The cooling water outlet end of the 5th interchanger 24 is communicated with outside connecting pipeline, is used for externally providing hot water.
The principle of work of the super critical water treatment system of above-mentioned waste organic matter is following:
1) the liquid oxygen in the liquid oxygen storage tank 1 get into liquid oxygen pump 2 pressurized with regulating after; Get in the hot water bath formula liquid oxygen carburetor 3; Utilize the liquid heat in the first low pressure vapour liquid separator 28 to make it be vaporized into gas oxygen; Gas oxygen gets into the pipe layer of positive displacement first interchanger 4, and after the hot-fluid preheating from desalting and deslagging device 11 tops in the shell, one road oxygen directly gets into mixing tank 5 to be mixed and pre-reaction with material; The first step interchanger 8a of another road oxygen in double-pipe exchanger group 8 manages the material outlet end and the mixing of materials of layer, gets into the material inlet end of second stage interchanger 8b then.
2) whisking appliance that is provided with in the materials-stored box 6 stirs with homogenizing material to be handled; At the exit end of materials-stored box 6 filtering net being set filters out big solid particulate; Get into then first high-pressure metering pump 7 pressurized with regulating after; Successively during the pipe layer of first, second, third grade of interchanger 8a through heat exchanger package 8,8b, 8c,, get into first electric heater 9 then again by the hot-fluid preheating of the reaction exit end in the shell; Material is entered into mixing tank 5 at last and mixes and pre-reaction by 9 heating of first electric heater when system's startup or shortage of heat.
3) oxygen, material and evaporation wall water are in mixing tank 5 after thorough mixing and the pre-reaction; Get into reactor drum 10; Rely on salt in supercritical water, to have the characteristic of utmost point low solubility, the close-to-critical range of salt being separated and is deposited to reactor drum 10 bottoms under condition of supercritical water dissolves it again, and the reacting fluid adverse currents of a large amount of cleanings upwards flow; Through behind the catalyst bed reaction, from the reaction exit end outflow at reactor drum 10 tops.When system can just self-heating; Be divided into two-way from the effusive hot-fluid of reactor drum 10 top exit ends: the one tunnel gets into the spiral type heated coil pipe the desalting and deslagging device 11; The fluid that is used for heating desalting and deslagging device 11 makes it reach the supercritical water temperature; The effusive hot-fluid of spiral type heated coil pipe from desalting and deslagging device 11; Get into successively again heat exchanger package 8 the 3rd, second, the shell of first step interchanger 8c, 8b, 8a removes the preheating material, and the thermal source exit end temperature of the first interchanger 8a shell is reduced to about 50 ℃.The pipe layer that another road gets into positive displacement the 3rd interchanger 21 removes the evaporation wall water of preheating shell, and the temperature of the thermal source exit end of displacement heat exchanger 21 pipe layers is reduced to about 50 ℃.When system thermal has when more than needed, be divided into three the tunnel from the effusive hot-fluid of reactor drum 10 top exit ends, except that above-mentioned two-way, Third Road gets into the pipe layer of the 5th interchanger 24, by the water quench of shell.Three tunnel reacted hot-fluids finally mix at the thermal source inlet end of telescoping the 4th interchanger 23 pipe layers, after being further cooled through the 4th interchanger 23, get into high pressure vapour liquid separator 26.
4) hydrogen is insoluble to cryogenic high pressure water; But carbonic acid gas is dissolved in cryogenic high pressure water; Therefore the hydrogen that utilizes high pressure vapour liquid separator 26 to separate flows out from the top through after 38 step-downs of first back pressure valve, measures its productive rate through hydrogen flowmeter 30, gets into hydrogen cylinder 31 then and is collected.
The cryogenic high pressure liquid that high pressure vapour liquid separator 26 is separated flows out from the bottom through getting into the first low pressure vapour liquid separator 28 after 27 step-downs of second back pressure valve, is dissolved in the CO in the cryogenic high pressure liquid
2Be separated, flow out the inlet end that enters into moisture eliminator 32 from the first low pressure vapour liquid separator, 28 tops, remove the water vapor that contains, pass through CO then through moisture eliminator 32
2Flowmeter survey CO
2Productive rate again through behind the snubber 34, after 35 superchargings of entering carbonic acid gas topping-up pump, is stored in CO
2In the gas cylinder 36.The cryogenic liquid oxygen that the shell of the first low pressure vapour liquid separator, 28 isolated liquid entering hot water bath formula liquid oxygen carburetors 3 is managed layer is cooled to about 20 ℃, gets into first liquid-collecting box 29 again.According to what of charging saltiness, every operation for some time of system, the first low pressure vapour liquid separator, 28 isolated liquid get into through part and store salt pond 12 and carry out system's salt discharge.
5) shell of hot-fluid entering positive displacement first interchanger 4 of desalting and deslagging device 11 tops cleaning is managed the cryogenic oxygen cooling of layer; The shell that gets into telescoping second interchanger 19 is then managed about the low-temperature evaporation wall water cooling to 40 ℃ of layer; Get into the 3rd back pressure valve 14 by after the step-down through line strainer 13 then; Get into the second low pressure vapour liquid separator 15 again and carry out gas-liquid separation, isolated CO
2Flow out from the top exit end of the second low pressure vapour liquid separator 15, get into the inlet end of moisture eliminator 32.
The isolated liquid water in the second low pressure vapour liquid separator, 15 bottoms gets into second liquid-collecting box 16; As reactor bottom evaporation wall water; And with after alkali lye from storage alkali case 17 mixes, get into the 3rd high-pressure metering pump 18 pressurized with regulating after, the pipe layer of entering telescoping second interchanger 19; After the hot-fluid preheating of shell, the awl section evaporation wall water interlayer space that gets into reactor drum 10 bottoms again is as evaporation wall water and water coolant.
6) when the heat of reaction part is unnecessary; Start cooling-water pump 25; Water coolant starts telescoping the 4th interchanger 23 and positive displacement the 5th interchanger 24 from the 3rd liquid-collecting box 37, and the water coolant that pumps with cooling-water pump 25 removes to cool off reacted hot-fluid in the 4th interchanger 23 and the 5th interchanger 24 pipe layers; It is cooled to about 50 ℃, and the hot water that water coolant forms is collected the back and is used as the domestic hot-water or is used for refrigeration.
When great amount of heat was had more than needed, the spiral heat exchange coil that starts in the reactor drum 10 was used for forming high-temperature steam or hot water, collected the back as living with heat or being used for refrigeration and generating.
When system started or can not self-heating, the heat exchange coil in cooling-water pump 25, the 4th interchanger 23, the 5th interchanger 24 and the reactor drum 10 did not all start.
The working method of the super critical water treatment system of above-mentioned waste organic matter is divided into setting on the basis of auxiliary line: preparatory stage, temperature rise period, operation phase and shutdown phase, and its concrete steps are following:
(1) preparatory stage:
1) the inspection oxygen pipeline has or not oil stain, guarantees that oxygen safety puts into operation;
2) whether the inspection oxygen pipeline leaks gas.Promptly close V4 and V5 on the oxygen pipeline, open V2 then, whether the pressure on the inspection oxygen pipeline descends, and guarantees that the oxygen pipeline no oxygen is to external leakage.
3) whether the lubricated oil level of check system mesohigh volume pump is normal, guarantees that each pump its lubricating oil before operation is in normal oil level, and periodic replacement lubricating oil.
4) upper limit pointer with the electro connecting pressure gauge of first high-pressure metering pump 7, second high-pressure metering pump 20 and the 3rd high-pressure metering pump 18 transfers to 30MPa, and the lower limit pointer transfers to normal pressure; The upper limit pointer of the electro connecting pressure gauge of cooling-water pump 25 is transferred to 25MPa, and the lower limit pointer transfers to normal pressure; The upper limit pointer of the electro connecting pressure gauge of liquid oxygen pump 2 is transferred to 35MPa, and the lower limit pointer transfers to 25MPa;
5) earth leakage circuit-breaker in the loop system and all air switches start power supply;
6) close V50, open V41, first liquid-collecting box 29 and second liquid-collecting box 16 are full of clean water, close V41 then through external water source.Simultaneously the 3rd liquid-collecting box 37 is full of clean water coolant.
7) close V6, in materials-stored box 6, fill aqueous ethanolic solution, its calorific value equals true material, opens simultaneously to be arranged on the V7 on the subsidiary conduit (seeing dotted line pipeline among Fig. 1) between first high-pressure metering pump, 7 inlets and first liquid-collecting box 29.
8) inspection and assurance V1, V3, V7～V21, V25～V37, V39, V40, V42, V44～V47, V49, V51, V52 are in opened condition; Inspection also guarantees that V22～V24, V38, V43, V48, V50 are in closing condition;
9) heating parameters of setting first electric heater 9 and second electric heater 22 is set reactor drum 10 top fluidic working temperatures, starts first electrically heated 9 and second electric heater 22;
10) frequency converter frequency with first high-pressure metering pump 7 and second high-pressure metering pump 20 is set to peak, starts first high-pressure metering pump 7 and second high-pressure metering pump 20 then, fills clean water, the air that accumulates in the system of draining to system.Observe valve export and whether there are flowing out system, then close this valve, close V21, V16, V27, V14, V3, V37, V42 that exhaust is used successively if there are flowing out;
11) start cooling-water pump 25 to systems pumps water, get rid of telescoping the 4th interchanger 23 and the interior air of positive displacement the 5th interchanger 24 shells, discharge the air in the heat exchange coil in the reactor drum 10, close cooling-water pump 25 then, close V13, V31;
12) through regulating the aperture of V17, the assignment of traffic of carrying out two outlets in reactor drum 10 tops and bottom;
13) through regulating the aperture of second back pressure valve 27 and the 3rd back pressure valve 14, the supercritical water pressure that the pressure-stabilisation in the reactor drum 10 is being set;
14) open the V24 on the auxiliary line between desalting and deslagging device internal heating coil pipe inlet end and storage top, the salt pond inlet end is set, close V29, make that fluidic only flows out through its outlet at bottom in the reactor drum 10;
15) reach the supercritical water temperature when above when the temperature of desalting and deslagging device 11 internal flows, open V29, close V24, system gets into the temperature rise period;
(2) temperature rise period:
1) opens V6, V50, close V7, make charging into calorific value and the true identical aqueous ethanolic solution of material, open V4, V5, open liquid oxygen pump 2, regulate its flow to set(ting)value;
2) regulate the aperture of V47, V51 and V52, the level stability that makes high-pressure gas-liquid separator 26, the first low-pressure gas-liquid separator 28, the second low-pressure gas-liquid separator 15 is in set(ting)value;
3) open V37, regulate the aperture of first back pressure valve 38 of high-low pressure vapour liquid separator 26 top exits, and make system pressure be stabilized in the supercritical water pressure of setting through the aperture of finely tuning second back pressure valve 27; Slowly open V43, make the first low-pressure gas-liquid separator 28 separate 15 pressure-stabilisation with second low-pressure gas-liquid about 0.5MPa;
4) open the 3rd high-pressure metering pump 18,, the fluid temperature (F.T.) of reactor drum 10 bottoms is stabilized in the subcritical water TR of setting through regulating its flow;
5) through regulating the flow of second high-pressure metering pump 20, regulate the power of second electric heater 22, and regulate the temperature that the aperture of V25, V26, V28 is come conditioned reaction device 10 and mixing tank 5 pressure-bearing walls;
6) carry out the assignment of traffic of reactor drum 10 top exits three tunnel through the aperture of regulating V9, V32, V36, the fluid stable that makes desalting and deslagging device 11 inside is about the supercritical water temperature of setting;
7) have when a small amount of more than needed when system thermal, open V31, start cooling-water pump 25, open telescoping the 4th interchanger 23 and positive displacement the 5th interchanger 24, the flow of regulating cooling-water pump 25 makes that pipe outlet fluid temperature (F.T.)s are stabilized in about 50 ℃ in the 4th interchanger 23;
8) when system thermal has a large amount of having more than needed, open V13 to certain aperture, start cooling-water pump 25, open the heat exchange coil in the reactor drum 10, make reactor drum 10 top fluidic temperature-stables about design temperature through the flow of regulating cooling-water pump 25;
9) when reactor drum 10 overhead stream temperature reached the setting temperature of reaction, system got into the operation phase;
(3) operation phase:
1) makes the material in the materials-stored box 6 into true material, open valve V28, regulate its aperture, in the pipeline of the second evaporation wall water feeding unit, add alkali, to guarantee that this road evaporation wall water ph value is in neutral range to set(ting)value;
2) open V38, close V37, collect hydrogen in hydrogen cylinder 31; Open V46, close V44, start carbonic acid gas topping-up pump 35, with carbon dioxide collection in carbonic acid cylinder 36;
3) according to saltiness in the material what, system is carried out intermittent type salt discharge operation.Valve-off V20 during salt discharge opens V22 to certain aperture, slowly discharges the saliferous fluid in the storage salt pond 12, after the pressure in storage salt pond 12 is reduced to normal pressure, slowly opens V23 again to certain aperture, continues to get rid of the saliferous fluid in the storage salt pond 12.After waiting to store the relative cleaning of salt pond 12 outlet at bottom fluids, close V23, V22, open V20;
(4) shutdown phase:
1) V7 is opened, close V6, V50, the clean water after system feeding is made into to handle in first liquid-collecting box 29; System continues normal operation 30min;
2) close V2, V4, V5 on the oxygen pipeline, stop liquid oxygen pump 2, close V1; Stop first electric heater 9 and second electric heater 22;
3) start cooling-water pump 25, open V30, reactor drum 10 overhead stream temperature are reduced to below 50 ℃, stop cooling-water pump 25 then, close V30;
4) carry out step-down through 27 pairs of systems of second back pressure valve, the pressure in the reactor drum in the system is reduced to about 1Mpa; Open V22, discharge the saliferous fluid in the storage salt pond 12,12 outlet at bottom fluids are closed V22 after the cleaning relatively up to the storage salt pond;
5) close the first high-pressure metering pump pump 7, the second high-pressure metering pump pump 20, the 3rd high-pressure metering pump pump 18 successively, close general supply again;
6) system is carried out wet preservation, require in the system in the water chloride ion content less than 10mg/L.
Claims (2)
1. the working method of the super critical water treatment system of a waste organic matter, the super critical water treatment system of said waste organic matter comprises:
Reaction member; The reactor drum, desalting and deslagging device, the storage salt pond that comprise the countercurrent pot-type of vertically arranged mixing tank, built-in evaporation wall; The material outlet end of said mixing tank is communicated with the material inlet end of reactor drum; The salt discharge exit end of reactor bottom is communicated with the inlet end of desalting and deslagging device, and the outlet at bottom end of desalting and deslagging device is communicated with the inlet end in storage salt pond; Be provided with heat exchange coil in the said reactor drum;
Oxygen comprises liquid oxygen storage tank, liquid oxygen pump, liquid oxygen carburetor, is used for first interchanger of preheated oxygen, and is composed in series the oxygen supply path successively, to mixing tank oxygen intake end oxygen is provided;
Feed unit comprises materials-stored box, first high-pressure metering pump, first electric heater, and is composed in series the material path successively, to the material inlet end of mixing tank material is provided;
Gas collection unit; Comprise the high pressure vapour liquid separator; First back pressure valve and the hydrogen cylinder that are communicated with the top exit end of high pressure vapour liquid separator successively; The first low pressure vapour liquid separator is arranged on second back pressure valve between the high pressure vapour liquid separator outlet at bottom end and the first low pressure vapour liquid separator top inlet end, the second low pressure vapour liquid separator; The dry device of carbonic acid gas that is communicated with first, second low pressure vapour liquid separator top exit end respectively is communicated with the carbonic acid gas topping-up pump and the dioxide bottle of the dry device of carbonic acid gas successively;
The first evaporation wall water feeding unit; The 3rd interchanger, second electric heater that comprise the evaporation wall water that first liquid-collecting box, second high-pressure metering pump, preheating first liquid-collecting box that are communicated with the first low pressure vapour liquid separator outlet at bottom end successively provided; The exit end of second electric heater is divided into three the tunnel; One the tunnel is communicated with the inlet end of the evaporation wall water of mixing tank, and another road is communicated with the evaporation wall water inlet end of reactor head, and Third Road is communicated with the evaporation wall water inlet end at reactor drum middle part;
The second evaporation wall water feeding unit comprises second interchanger that second liquid-collecting box, the 3rd high-pressure metering pump, preheating second liquid-collecting box that are communicated with the second low pressure vapour liquid separator outlet at bottom end successively provide evaporation wall water; The evaporation wall water out end of second interchanger is communicated with the bottom evaporation wall water inlet end of reactor drum;
The reaction exit end of said reactor drum is communicated with the thermal source inlet end of the 3rd interchanger, and the thermal source exit end of said the 3rd interchanger is communicated with the inlet end of high pressure vapour liquid separator; The fluid of the top exit end of said desalting and deslagging device is as thermal source flow through successively first interchanger, second interchanger, and flows into the second low pressure vapour liquid separator through the 3rd back pressure valve;
It is characterized in that said working method may further comprise the steps:
(1) auxiliary line is set, between the outlet at bottom end of the thermal source inlet end of the 3rd interchanger and desalting and deslagging device, is provided with first auxiliary line that is communicated with; Between the first high pressure measurement pump intake and first liquid-collecting box, be provided with second auxiliary line of connection;
(2) preparatory stage fills clean water to first liquid-collecting box, opens second auxiliary line, starts first high-pressure metering pump, first electric heater successively, charges into clean water to reactor drum and salt discharge deslagging device; Restart second high-pressure metering pump, second electric heater, in reactor drum, inject evaporation wall water; At first carry out system evacuation, after the system evacuation, the top exit end of off-response device; Open first auxiliary line; Constitute clean water circulation preheating path, and regulate first back pressure valve, second back pressure valve, make the supercritical water pressure of the pressure-stabilisation of reactor drum and salt discharge deslagging device in setting; Clean water preheating temperature in question response device and the desalting and deslagging device is opened the top exit end of reactor drum after the supercritical water temperature, close first auxiliary line and second auxiliary line;
(3) temperature rise period at first starts liquid oxygen pump, liquid oxygen carburetor and first interchanger, is oxygen through liquid oxygen carburetor vaporization liquid oxygen, gets into mixing tank again after feeding the first interchanger preheating; Simultaneously, in materials-stored box, add organic solution, organic solution is provided to the material inlet end of mixing tank; Drop into gas collection unit, the second evaporation wall water feeding unit and second interchanger then successively; Organic solution is decomposed at the reactor drum internal reaction, emits the fluid that heat comes the reactor heating top, and controls first electric heater and second electric heater, makes the reactor head fluid be heated to the setting temperature of reaction;
(4) operation phase adds materials-stored box with treating material, normally moves the super critical water treatment system of waste organic matter;
(5) shutdown phase after treating material is finished dealing with, is opened second auxiliary line, and off-response device exit end continues the aerating oxygen oxidation and is trapped in the organism in the reactor drum; 0.2 after～0.8 hour, close liquid oxygen pump, stop supplies oxygen is closed first electric heater, second electric heater, and regulates second back pressure valve, progressively step-down cooling.
2. the working method of the super critical water treatment system of a kind of waste organic matter according to claim 1 is characterized in that, said organic solution is ethanol or aqueous propanol solution.
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| CN102213954B (en) * | 2010-04-09 | 2014-04-02 | 大连森和节能环保科技有限公司 | Supercritical water processing control system and control method thereof |
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| CN102633351B (en) * | 2012-04-23 | 2013-07-10 | 西安交通大学 | Desalting and salt discharging control method for supercritical water oxidation systems |
| CN102642965B (en) * | 2012-04-23 | 2013-07-10 | 西安交通大学 | Supercritical water oxidization treatment device for organic waste water and temperature control method |
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| CN114772775B (en) * | 2022-03-31 | 2024-02-09 | 深圳市华尔信环保科技有限公司 | Heat self-supply supercritical water hydrogen production system |
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Assignee: ECOWA ENVIRONMENTAL AND ENERGY TECHNOLOGIES (ZHANGJIAGANG) CO., LTD. Assignor: Xi'an Jiaotong University Contract record no.: 2011610000009 Denomination of invention: Method for operating a supercritical water treatment system of waste organic substances License type: Exclusive License Open date: 20091118 Record date: 20110309 |
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