CN101830554B - Method for improving oxygen utilization rate of supercritical water oxidation system - Google Patents
Method for improving oxygen utilization rate of supercritical water oxidation system Download PDFInfo
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- CN101830554B CN101830554B CN2010101748469A CN201010174846A CN101830554B CN 101830554 B CN101830554 B CN 101830554B CN 2010101748469 A CN2010101748469 A CN 2010101748469A CN 201010174846 A CN201010174846 A CN 201010174846A CN 101830554 B CN101830554 B CN 101830554B
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Abstract
The invention relates to a method for improving oxygen utilization rate of a supercritical water oxidation system. The method comprises the following steps of: injecting excessive oxygen and preheated organic waste liquid from the upper part of an evaporation wall reactor, mixing the oxygen and the organic waste liquid, performing supercritical water oxidation reaction on the mixture, and injecting evaporation water from the lateral surface of the evaporation wall reactor so as to form a supercritical temperature reaction area on the upper part and a sub-critical temperature salt dissolution area on the lower part in the reactor. When the reacted rest oxygen downwards flows to the sub-critical temperature salt dissolution area from the supercritical temperature reaction area, a part of oxygen is separated out and circulated to the supercritical temperature area on the upper part of the reactor to form internal circulation utilization of the oxygen; and the reacted fluid enters a high-pressure gas-liquid separator through condensation and pressure reduction, is dissolved into sub-critical water and carries the oxygen flowing out of the reactor, is separated by the high-pressure gas-liquid separator and then is re-injected to the reactor to form external circulation utilization. The method remarkably reduces the excessive oxygen amount coefficient by improving the utilization rate of the oxygen, and improves the running economy of the supercritical water oxidation system.
Description
One, technical field
The invention belongs to the organic waste process field, particularly a kind of method that improves the supercritical water oxidation system oxygen utilization rate.
Two, background technology
Supercritical water oxidation (Supercritical Water Oxidation) technology is a kind of novel processing organic waste and recovered energy and pure CO
2Technology.This technology be surpass the stagnation point of water (T=374 ℃, under high-temperature and high-pressure conditions P=22.1MPa), with oxygen or other oxygenants, the method for organism being carried out " burning " oxidation.Supercritical water has density, dissolving power and the good flowability of similar liquids, is a kind of non-polar solvent, has the spread coefficient and the low-viscosity of similar gas simultaneously again.In supercritical water, the interface of gas-liquid two-phase disappears, organism and O
2In supercritical water, dissolve each other fully, form the homogeneous phase system, speed of response is accelerated greatly.In the reaction time less than 1 minute even several seconds, the rapid burns oxygen of the organism more than 99.99% changes into CO
2, H
2The end product that O and inorganic salt etc. are nontoxic can discharge a large amount of heat energy in the simultaneous oxidation reaction process.
Special reaction condition and inorganic salt insoluble,practically characteristics in supercritical water such as the high temperature of supercritical water oxidation technology, high pressure, hyperoxia concentration make corrosion and the blockage problem of reactor drum hinder this technical development and apply.Adopt the evaporation wall reactor drum can effectively alleviate corrosion and salt sedimentation problem in the reactor drum.The evaporation wall reactor drum generally is made up of bearing shell and porous inner casing; Vaporize water injects from the reactor drum side; Penetrate in the reactor drum and form the subcritical moisture film of one deck through the porous inner casing at the porous inwall; Moisture film can stop mineral acid can be dissolved in the inorganic salt that the supercritical temperature reaction zone is separated out with contacting also of wall, thereby has solved corrosion and salt sedimentation problem in the reactor drum.
The oxygenant that is applied to supercritical water oxidation generally has air, oxygen, ydrogen peroxide 50, ozone etc., and is wherein best as the economy of oxygenant with oxygen.In the supercritical water oxidation system that utilizes the evaporation wall reactor drum, the required expense of oxygen depletion accounts for total expensive more than 70%, and along with the increase of peroxide coefficient of discharge, system operation cost also increases significantly.But in order to guarantee organic degraded fully, generally between 1.5-3, reacted fluid contains a large amount of oxygen that do not utilize to the peroxide coefficient of discharge.
Therefore, too high peroxide coefficient of discharge is the reason that causes supercritical water oxidation system running cost higher.
In present supercritical water oxidation system both domestic and external, improve the method for oxygen utilization rate and also do not appear in the newspapers.Like US4822497 " the isolating method of solid in the wet-type oxidation technology "; It sets up top supercritical temperature reaction zone and sub-critical temperature dissolved salt district, bottom in tank reactor; The inorganic salt that the supercritical temperature reaction zone is separated out on top are deposited in the dissolved discharge in sub-critical temperature district, bottom; Reacted supercutical fluid adverse current turns back to reactor drum top and discharges, but this patent does not have to propose how in reactor drum, to realize the recycle of oxygen.Relate to and only stress to solve corrosion and the salt sedimentation problem in the reactor drum in the patent of evaporation wall reactor drum; But all do not propose how inside and outside the evaporation wall reactor drum, to realize the recycle of oxygen, like US5387398 " overcritical water oxidization reactor that has wall boundary-layer flow control conduit " and US5571423 " device of supercritical water oxidation and technology " etc.In addition, because all operations under the peroxide coefficient of discharge of supercritical water oxidation system, reacted fluid must carry the oxygen of high density, and therefore, reclaiming reacted remaining oxygen is the economy inevitable choice of raising system operation.
Three, summary of the invention
A kind of method that improves the supercritical water oxidation system oxygen utilization rate; The present invention is directed to supercritical water oxidation system oxygen cost in service height and the low problem of utilization ratio; Propose through inside and outside the evaporation wall reactor drum, realizing two recycles of oxygen; Improve the supercritical water oxidation system oxygen utilization rate, and then the economy of raising system operation.The present invention realizes in the following manner:
A kind of method that improves the supercritical water oxidation system oxygen utilization rate; This system comprises oxygen canister, waste water storage tank, pure water storage tank, oxygen topping-up pump, waste liquid topping-up pump, vaporize water topping-up pump, waste water well heater, goes up branch road vaporize water well heater, oxygen mixer, evaporation wall reactor drum, oxygen recycle pump, interchanger, reducing valve, high-pressure gas-liquid separator, back pressure valve and atmospheric gas liquid/gas separator, and the step of this method is following:
(1) organic liquid waste boosts to 23-30MPa; And be preheating to 350-450 ℃, and inject from evaporation wall reactor drum top with oxygen under the uniform pressure condition and mix, carry out supercritical water oxidation; The supercritical water oxidation temperature is 400-650 ℃, and the residence time is 5-60s.
(2) vaporize water is forced into 23-30MPa; The bifurcation road is injected from the reactor drum side; Last branch road vaporize water temperature is 250-370 ℃, and the temperature remains within the normal range for following branch road vaporize water, and in reactor drum, forming top is that supercritical temperature reaction zone and bottom are sub-critical temperature dissolved salt district; React remaining oxygen and flow down to the process in sub-critical temperature dissolved salt district from the supercritical temperature reaction zone, part of oxygen separate out and be recycled to reactor drum top and and utilized again.
(3) reacted fluid gets into high-pressure gas-liquid separator after interchanger cooling and reducing valve step-down; Oxygen from high-pressure gas-liquid separator top discharge and boost through the oxygen recycle pump after refill reactor drum and and utilized again, the mixture of water and carbonic acid gas then flows out from the high-pressure gas-liquid separator bottom.
(4) mixture of water and carbonic acid gas gets into the atmospheric gas liquid/gas separator, and carbonic acid gas and water flow out from the top outlet and the lower part outlet of atmospheric gas liquid/gas separator respectively, and reclaim the carbonic acid gas of high density.
Above-mentioned a kind of method that improves the supercritical water oxidation system oxygen utilization rate, the concentration of organic liquid waste is at 3-20wt%; The mass rate of oxygen is 1-3 a times of organism complete oxidation theoretical oxygen demand in the organic liquid waste; The mass rate of vaporize water is organic liquid waste and oxygen quality flow summation 1-4 a times; The mass flux ratio of last branch road vaporize water and following branch road vaporize water is 0.3-1.5.
Pressure in the above-mentioned a kind of method that improves the supercritical water oxidation system oxygen utilization rate, high-pressure gas-liquid separator is 2-20MPa, and temperature is at 20-150 ℃.
Above-mentioned a kind of method that improves the supercritical water oxidation system oxygen utilization rate; The organic waste water of oxygen and process preheating injects mixing and carries out supercritical water oxidation from evaporation wall reactor drum top; Reaction discharges a large amount of heat energy, thereby forms the supercritical temperature reaction zone on reactor drum top.Meanwhile, inject the vaporize water of sub-critical temperature from evaporation wall reactor drum side.Vaporize water penetrates in the reactor drum through porous wall, and forms the moisture film of layer of protecting property at the porous inwall, and moisture film can be avoided the corrosion and the salt sedimentation problem of reactor drum.Vaporize water cools off the supercritical temperature fluid of reactor center, so reactor lower part forms sub-critical temperature dissolved salt district.
Simultaneously, there is 200-350 ℃ the temperature difference in last branch road vaporize water with following branch road constant-temperature evaporation water, so the supercritical temperature reaction zone on reactor drum top can carry out the transition to sub-critical temperature dissolved salt district rapidly.There is bigger density difference in the fluid in the fluid of the supercritical temperature reaction zone in reactor drum and sub-critical temperature dissolved salt district; The sub-critical temperature dissolved salt district in reactor drum simultaneously, water and oxygen also exist greater density poor.Therefore; Reacting remaining oxygen flows down to the process in sub-critical temperature dissolved salt district from the supercritical temperature reaction zone; Part of oxygen is separated out and is recycled to the supercritical temperature reaction zone on reactor drum top and forms the utilization of oxygen internal recycle, and another part oxygen then is dissolved in the subcritical water and outflow reactor.And the CO that reaction generates
2Differ less with the subcritical water density difference, and the solubleness in subcritical water compares O
2High nearly 10 times, so CO
2Carried outflow reactor by the subcritical water dissolving.
The fluid staple that flows out from reactor drum is H
2O, CO
2And O
2Because CO
2Solubleness in the high-pressure liquid water in high-pressure gas-liquid separator compares O
2High nearly 10 times, therefore in high-pressure gas-liquid separator, oxygen concentration is in gas phase and CO
2Then be dissolved in the high-pressure liquid water.
The present invention proposes through inside and outside the evaporation wall reactor drum, realizing two recycles of oxygen; Improve the method for supercritical water oxidation system oxygen utilization rate; It can effectively reduce the peroxide coefficient of discharge in the supercritical water oxidation system; Therefore the economy of raising system operation has broad application prospects.
Four, description of drawings
Fig. 1, schematic flow sheet of the present invention.
Fig. 2, evaporation wall structure of reactor figure.
Among Fig. 1: 1 is that oxygen canister, 2 is that waste water storage tank, 3 is that pure water storage tank, 4 is that oxygen topping-up pump, 5 is that waste liquid topping-up pump, 6 is that vaporize water topping-up pump, 7 is that waste water well heater, 8 is that last branch road vaporize water well heater, 9 is that oxygen mixer, 10 is that evaporation wall reactor drum, 11 is that oxygen recycle pump, 12 is that interchanger, 13 is that reducing valve, 14 is that high-pressure gas-liquid separator, 15 is that back pressure valve, 16 is the atmospheric gas liquid/gas separator.
Among Fig. 2: 17 is that oxygen intake, 18 is reactor outlet for bearing shell, 24 for drip ring, 23 for perforated tube, 22 for branch road vaporize water inlet down, 21 for last branch road vaporize water inlet, 20 for waste liquid inlet, 19.
Five, embodiment
A specific embodiment that provides below in conjunction with accompanying drawing and contriver is further described the present invention.
Concentration is that the organic liquid waste of 8wt% boosts to 25MPa through waste liquid topping-up pump 5 in the waste tank 2, and is heated to 400 ℃ through waste liquid well heater 7, injects from the waste liquid inlet 18 on evaporation wall reactor drum 10 tops.Oxygen is pressurized to 25MPa through oxygen topping-up pump 4 in the oxygen canister 1, directly injects from the oxygen intake 17 on evaporation wall reactor drum 10 tops without preheating with 2 times of oxygen requirements to the organism complete oxidation.On evaporation wall reactor drum 10 tops, oxygen and organism mixing are also carried out supercritical water oxidation.After vaporize water increased pump 6 and boosts to 25.1MPa, injected from evaporation wall reactor drum 10 sides by the bifurcation road with 3 times flow of organic liquid waste and oxygen quality flow summation for vaporize water in the pure water storage tank 3.Wherein, last branch road vaporize water is preheated to 350 ℃ from last branch road vaporize water inlet 19 injections through last branch road vaporize water well heater 8, and the branch road vaporize water directly injects from following branch road vaporize water inlet 20 without preheating down, and the mass flux ratio of two-way vaporize water is 1: 2 up and down.
Vaporize water carries out subregion through the drip ring in the annular space between bearing shell 23 and the perforated tube 21 22, and sectional vaporize water penetrates in the reactor drum and at perforated tube 21 inwalls through perforated tube 21 and forms the precritical moisture film of one deck, and perforated tube 21 is played a protective role.Forming top in the evaporation wall reactor drum 10 is that supercritical temperature reaction zone and bottom are sub-critical temperature dissolved salt district; Reacting remaining oxygen flows down to the process in sub-critical temperature dissolved salt district from the supercritical temperature reaction zone; Part of oxygen is separated out and is recycled to the supercritical temperature reaction zone on evaporation wall reactor drum 10 tops and utilized again, and another part oxygen then is dissolved in the subcritical water and outflow reactor.
Reacted fluid is discharged reactor drum through reactor outlet 24, and fluid is cooled to 50 ℃ through interchanger 12, is depressurized to 12MPa through reducing valve 13 and gets into high-pressure gas-liquid separator 14.Oxygen is discharged from high-pressure gas-liquid separator 14 tops outlets, after oxygen recycle pump 11 boosts to 25MPa, mixes in oxygen mixer 9 with former oxygen circuit and refills evaporation wall reactor drum 10.The mixture of high pressure water and carbonic acid gas is discharged from high-pressure gas-liquid separator 14 bottoms, after back pressure valve 15 is reduced to normal pressure, gets into atmospheric gas liquid/gas separator 16.Carbonic acid gas and water flow out from the top outlet and the lower part outlet of atmospheric gas liquid/gas separator 16 respectively, and reclaim the dioxide gas of high density.After the supercritical water oxidation system steady running of the present invention, can reduce oxygen flow gradually, until oxygen flow near organic liquid waste in the oxygen requirement of organism complete oxidation.
Claims (2)
1. method that improves the supercritical water oxidation system oxygen utilization rate; This system comprises oxygen canister, waste water storage tank, pure water storage tank, oxygen topping-up pump, waste liquid topping-up pump, vaporize water topping-up pump, waste water well heater, goes up branch road vaporize water well heater, oxygen mixer, evaporation wall reactor drum, oxygen recycle pump, interchanger, reducing valve, high-pressure gas-liquid separator, back pressure valve and atmospheric gas liquid/gas separator, it is characterized in that the step of this method is following:
(1) organic liquid waste boosts to 23-30MPa; And be preheating to 350-450 ℃, and inject from evaporation wall reactor drum top with oxygen under the uniform pressure condition and mix, carry out supercritical water oxidation; The supercritical water oxidation temperature is 400-650 ℃, and the residence time is 5-60s;
(2) vaporize water is forced into 23-30MPa; The bifurcation road is injected from the reactor drum side; Last branch road vaporize water temperature is 250-370 ℃, and the temperature remains within the normal range for following branch road vaporize water, and in reactor drum, forming top is that supercritical temperature reaction zone and bottom are sub-critical temperature dissolved salt district; React remaining oxygen and flow down to the process in sub-critical temperature dissolved salt district from the supercritical temperature reaction zone, part of oxygen is separated out and is recycled to the supercritical temperature reaction zone on reactor drum top and utilized again;
(3) reacted fluid gets into high-pressure gas-liquid separator after interchanger cooling and reducing valve step-down; Refill the evaporation wall reactor drum and quilt utilization again after oxygen boosts from the outflow of high-pressure gas-liquid separator top and through the oxygen recycle pump, the mixture of water and carbonic acid gas then flows out from the high-pressure gas-liquid separator bottom;
(4) mixture of water and carbonic acid gas gets into the atmospheric gas liquid/gas separator, and carbonic acid gas and water flow out from the top outlet and the lower part outlet of atmospheric gas liquid/gas separator respectively, and reclaim the carbonic acid gas of high density.
2. a kind of method that improves the supercritical water oxidation system oxygen utilization rate according to claim 1 is characterized in that the pressure in the high-pressure gas-liquid separator is 2-20MPa, and temperature is at 20-150 ℃.
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| CN2010101748469A CN101830554B (en) | 2010-05-18 | 2010-05-18 | Method for improving oxygen utilization rate of supercritical water oxidation system |
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| CN101830554B true CN101830554B (en) | 2012-03-07 |
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| CN102787830A (en) * | 2012-08-17 | 2012-11-21 | 山东大学 | Method and device for exploiting deep sea combustible ice |
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| US5387398A (en) * | 1993-12-03 | 1995-02-07 | Aerojet General Corporation | Supercritical water oxidation reactor with wall conduits for boundary flow control |
| US5571423A (en) * | 1994-10-14 | 1996-11-05 | Foster Wheeler Development Corporation | Process and apparatus for supercritical water oxidation |
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| CN1186273C (en) * | 2000-12-30 | 2005-01-26 | 深圳市宝利达实业有限公司 | Supercritical water oxiding method and device for flowing sewage treatment and power supply |
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| CN102787830A (en) * | 2012-08-17 | 2012-11-21 | 山东大学 | Method and device for exploiting deep sea combustible ice |
| CN102787830B (en) * | 2012-08-17 | 2015-01-21 | 山东大学 | Method and device for exploiting deep sea combustible ice |
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