CN102190363B - Supercritical water oxidation reactor by using auxiliary fuel for supplying heat - Google Patents
Supercritical water oxidation reactor by using auxiliary fuel for supplying heat Download PDFInfo
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- CN102190363B CN102190363B CN201110121463XA CN201110121463A CN102190363B CN 102190363 B CN102190363 B CN 102190363B CN 201110121463X A CN201110121463X A CN 201110121463XA CN 201110121463 A CN201110121463 A CN 201110121463A CN 102190363 B CN102190363 B CN 102190363B
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- end cap
- reactor
- salt
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
- C02F11/08—Wet air oxidation
- C02F11/086—Wet air oxidation in the supercritical state
Abstract
The invention discloses a supercritical water oxidation reactor by using an auxiliary fuel for supplying heat, the heat required for a reaction can be supplied by using the auxiliary fuel, Material, fuel and an oxidizing agent (air or oxygen) are mixed with a high efficiency through the different directional jets for raising oxidation efficiency. According to the invention, the reactor employs a combination structure of evaporation wall and pot type backflow, the reaction vessel volume is effectively used and the reaction time is increased, the blockage problem generated by salt deposition can be also prevented, the corrosion problem of the reactor is effectively reduced. The temperature of the reactor bottom can be preciously controlled through a cooling water pipeline at the reactor bottom, thereby the safe operation of equipment is guaranteed. The reactor effectively solves the economic problem of a supercritical water reaction system by using the auxiliary fuel for supplying, the invention has the advantage of easy industrial amplification, and is widely applied to organic liquid such as high density and difficult biodegradation organic waste water/garbage leachate and the like for a harmlessness processing.
Description
Affiliated field
The invention belongs to environmental protection and chemical field, particularly utilize supercritical water the useless organic liquids such as organic wastewater/percolate of high concentration bio-refractory to be carried out a kind of super-critical water treatment reactor of innocent treatment procedure as reaction medium.
Background technology
Supercritical water be meant temperature and pressure all be higher than its critical point (T=374.2 ℃, the water of special state P=22.1MPa).Supercritical water has the character of liquid and vaporous water concurrently, and dielectric constant is similar to non-polar organic solvent, has high diffusion coefficient and low viscosity.Under this state, organic matter, oxygen can dissolve each other by maximum ratio and supercritical water, thereby make heterogeneous reaction become homogeneous reaction, have reduced the resistance of mass transfer, heat transfer greatly.And the solubility of inorganic salts in supercritical water is extremely low, easily it is separated.Therefore but the characteristic of this continually varying density of supercritical water, low electrostatic media constant, low viscosity makes it become a kind of ideal response medium with high diffusivity, highly dissoluble.Can utilize the variation of its temperature and pressure to control reaction environment, concerted reaction speed and chemical balance, regulate selection of catalysts property etc.
Supercritical water oxidation technology (Supercritical Water Oxidation; Be called for short SCWO) be the special nature of utilizing water under supercriticality, to be had; Make organic matter and oxidant that oxidation reaction take place rapidly in supercritical water and come thorough decomposing organic matter, it is changed into harmless CO fully
2, H
2And H
2Micromolecular compounds such as O.The SCWO technology is for handling poisonous and harmful substance (like dyestuff refuse, pharmacy refuse, lubricant refuse, the insulating oil that contains PCBs, radioactivity mixed waste, Polychlorinated biphenyls, effumability acid etc.), the debirs (mud, paper mill slip etc.) of high-concentration hardly-degradable, the military harmful toxic matter (chemical weapons that those difficulties disappear and ruin; Propellant, explosive etc.) has unique effect.
Though the supercritical water treatment technology has obtained very much progress; About using the experimental rig and the commercial apparatus of supercritical water technology; Have relevant report at present both at home and abroad; But still have problems such as the blockage problem that mineralization causes in the reactor to be solved, high corrosion rate problem and performance driving economy, be in particular in:
1) material corrosion problem.Because supercritical water reaction apparatus is under high temperature, the condition of high voltage, especially contains halogen, sulphur or phosphorus etc. in the organic matter, can produce acid after in supercritical water, decomposing, cause the strong corrosion of equipment; Even have better corrosion proof nickel-base material, in supercritical water, particularly in subcritical water, still suffer serious corrosion easily.
2) mineralization problem.Water at normal temperature is a kind of fine solvents to most of salt, and solubility is bigger.On the contrary, most of salt solubility in low-density supercritical water is minimum.When subcritical solution is heated to supercritical temperature rapidly; Because the solubility of salt reduces significantly, has a large amount of depositions to separate out, the salt of the deposition device that can induce reaction is imported and exported pipeline blockage; The normal operation that this has not only influenced reactor also can bring potential hidden trouble of equipment.
3) economy problems.Though the SCWO process is an exothermic reaction, when organic mass fraction reaches 2～3%, just can realize self-heating, in the device start process, still need external heat source that it is carried out concurrent heating.The mode of heating overwhelming majority of at present external supercritical water oxidation plants adopts the electrical heating form, and this not only causes the equipment investment expense huge, and the heavy industrialization application of this technology has been caused huge obstacle.
Summary of the invention
The purpose of this invention is to provide a kind of auxiliary fuel that utilizes as the method for anaplerotic reaction heat new construction overcritical water oxidization reactor, and then improve the economy of device running with the problem that solves the supply of supercritical water oxidation process energy.In addition, require this reactor easy disassembly, load easily and catalyst changeout more, be easy to maintenance and safeguard, can safe and reliable operation, have multifunctionality.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of overcritical water oxidization reactor that utilizes auxiliary fuel supply heat; Comprise kettle and catalyst tank wherein, it is characterized in that the kettle upper end is fixedly connected with end cap; Space between end cap and the top, catalyst tank case top is a high temperature combustion zone, and the catalyst tank below is the salt Disengagement zone; The autoclave body bottom center is provided with the solid salt outlet, and solid salt outlet top is subcritical dissolved salt district; Coolant outlet and liquid salt outlet that autoclave body bottom is provided with the product outlet, is communicated with subcritical dissolved salt district; Cool air inlet and material inlet are set on the end cap, and are communicated with high temperature combustion zone through axial channel; The end cap center is provided with fuel core tubular axis to putting in end cap in the high temperature combustion zone top; Between fuel core pipe periphery and the end cap annular space is arranged, the end cap side has hot air inlet through horizontal hole and annular space UNICOM; Fuel core pipe puts in end cap portions and divides the tube wall outside to be provided with helical fin; First temperature-measuring casing that has armoured thermocouple on the end cap axially puts in the end cap; Catalyst tank is fixed on around the vertical section of central tube, and the tilting section of central tube is communicated with the outlet of the product of autoclave body bottom; Be provided with the tubular porous evaporator wall near inner wall of kettle, the kettle arranged outside has second temperature-measuring casing of evaporation wall water inlet and armoured thermocouple to be communicated in porous evaporator wall and the formed ring cavity of inner wall of kettle.
In the such scheme, end cap cooling annular groove is set below end cap, comprises being used for air cooled inner groove and the outer groove that is used for the material cooling, there are two circle holes the inner groove bottom surface, and the downward oblique fuel core tube side of inner ring hole is to, the oblique porous evaporator wall direction of cycle hole; The outer groove bottom surface have the downward oblique fuel core tube side in a circle hole to.
Described fuel core pipe lower end outlet is blind hole structure, when fuel flows out blind hole through around the tube wall tiltedly 4 perforates of lower direction to around form jet.
Said catalyst tank is a cylindrical shell, and this cylindrical shell bottom inlet and cylindrical shell top exit are the porous plectane, its top porous plectane top be provided with can be for convenience detach spherical case lid.
Be provided with the 3rd temperature-measuring casing of built-in armoured thermocouple near said autoclave body bottom subcritical dissolved salt district and the salt Disengagement zone.
Compare with existing overcritical water oxidization reactor, the invention has the advantages that:
1, the present invention is directed to issuable high temperature after the fuel combustion, the reactor end cap that multithread is threaded a pipe is set.Cold conditions oxidant and material can both be built cooling effect to reactor end.Further, the cooling annular groove is set below the reactor end cap, can high temperature combustion zone and end cap lower plane be effectively kept apart.And be furnished with the pod apertures of different directions below the annular groove in cooling; Make fuel, oxidant and material realize sufficient jets collision from different perspectives in the combustion zone; Promote the high efficient mixed and the burning of fuel; The high temperature of emitting during the effectively required heat of anaplerotic reaction, and burning can thoroughly decompose hard-degraded substances such as ammonia nitrogens effectively.
2, end cap of the present invention week side have hot air inlet through outside horizontal direction duct and the fuel core pipe and the annular space between the end cap be communicated with, as high-temperature oxydation agent transfer pipeline.Core pipe bottom is provided with helical fin, and outlet at bottom is a blind hole structure, and the oblique bottom of fuel is sprayed all around, enlarges burning area, the jets collision of efficient realization and oxidant fluid.
3, at reactor bottom the cooling water inlet is set,, can accurately controls salt discharge district temperature through regulating the cooling water flow size.Work as reactor bottom desalination pipeline simultaneously and stop up, can be through regulating cooling water flow to improve the dissolubility of bottom salt; When reacting device overtemperature, super high pressure accident, can feed cooling water and reduce the inside reactor temperature and pressure fast, guarantee the safe operation of equipment.
4, inside reactor catalyst tank and spherical case lid are set and by the form fix of welding on central tube, the catalyst tank entrance and exit is porous plate.The reactor end cap with in the seal cavity that the kettle of catalyst tank combines the back to form is set, form many deflector types structure, can overcome the long shortcoming of tubular reactor size, effectively utilize the reaction kettle body internal volume, increase the reaction time.
The overcritical water oxidization reactor of fuel make up heat disclosed by the invention can be widely used in the harmless treatment and the recycling process of the useless organic liquids such as organic wastewater/percolate of high concentration, bio-refractory.
Description of drawings
Fig. 1 utilizes the structural representation of the super-critical water treatment reactor of auxiliary fuel supply heat for the present invention.Wherein 1, fastening bolt; 2, catalyst tank; 3, kettle; 4, porous evaporator wall; 5, liquid salt outlet; 6, solid salt outlet; 7, product outlet; 8, cooling water inlet; 9, evaporation wall water inlet; 10, end cap cooling annular groove; 11, hot air inlet; 12, fuel core pipe; 13, cool air inlet; 14, material inlet; 15, end cap; 16, high temperature combustion zone; 17, subcritical dissolved salt district; 18, desalination district temperature-measuring casing; 19, evaporation wall ring cavity temperature-measuring casing; 20, reactor end cap temperature-measuring casing; 21, salt Disengagement zone; 22, central tube.
The specific embodiment
As shown in Figure 1, a kind of overcritical water oxidization reactor that utilizes auxiliary fuel supply heat combines to form the confined reaction space by end cap 15 and kettle 3 through fastening bolt 1.Space between end cap 15 and the catalyst tank dome top is a high temperature combustion zone 16, and the catalyst tank lower zone is salt Disengagement zone 21, and the autoclave body bottom center is provided with solid salt outlet 6, and its upper area is subcritical dissolved salt district 17.
Fuel core pipe adopts corrosion-resistant, high-temperature alloy material; Fuel core pipe puts in end cap portions and divides the tube wall outside to be provided with helical fin (not drawing among the figure); Make oxidant (air or oxygen) fluid produce eddy flow to promote itself and the high efficient mixed of fuel, the while can make things convenient for the installation and the location of core pipe.Cool air inlet 13 (around end cap central bore, being uniformly distributed with four), material inlet 14 (being uniformly distributed with four along the end cap central bore periphery) also are set on the end cap; Be communicated with high temperature combustion zone 16 through axial channel, low-temperature oxidation agent (cold air or oxygen) is through cool air inlet 13 inflow reactors.The cold conditions material is got in the reactor by material inlet 14.Cold conditions material and low-temperature oxidation agent can both be played the effect of end cap cooling.The end cap temperature-measuring casing 20 that has armoured thermocouple on the end cap axially puts in the end cap, to measure the conversion zone temperature.
Cause the potential safety hazard of end cap overtemperature in order to prevent high temperature combustion zone 16 from possibly emit too high heat, end cap cooling annular groove 10 is set below reactor end cap 15.Annular groove is welded on the end cap below; Inner groove is air cooling annular groove (a cool air inlet passage relatively), and two circle ducts are arranged at the annular groove bottom, the downward oblique fuel core tube side of inner ring hole to; The oblique porous evaporator wall direction of cycle hole; The former offers the fuel secondary wind, guarantees full combustion of fuel, and the latter offers material and carries out oxidation wholly or in part; Outer groove is material cooling annular groove (a material inlet passage relatively); The bottom surface have the downward oblique fuel core tube side in a circle hole to; Low-temperature material is effectively wrapped up flame zone, reduce high temperature fluid, also can effectively cool off end cap to the influence that evaporation wall caused.The reactor end cap is provided with temperature-measuring casing 20 and built-in armoured thermocouple carries out temperature survey.This structure can make material, cold conditions oxidant, high-temperature oxydation agent and fuel fluid form jets collision from different directions, carries out efficiently mixed and forms the high-temperature region, helps the removal of difficult oxidation material (for example ammonia nitrogen etc.).
Be provided with tubular porous evaporator wall 4 near kettle 3 inwalls, the kettle arranged outside has evaporation wall water inlet 9 and temperature-measuring casing 19 to be communicated in porous evaporator wall and the formed ring cavity of inner wall of kettle.Behind evaporation wall water inlet 9 entering evaporation wall ring cavities, pass porous evaporator wall and form even moisture film after the clean water preheating, can effectively prevent mineralization and corrosion in the inboard.Temperature-measuring casing 19 built-in armoured thermocouples are measured the Temperature Distribution with monitoring reaction device kettle wall temperature, evaporation wall wall temperature and inside reactor reacting fluid, with the adjusting that realizes the subsequent reactions condition, the Gradient distribution and the security control of temperature.
The concrete course of work of the present invention is that fuel and oxidant are through getting into inside reactor through fuel core pipe 12 and core pipe outside annular space respectively behind the high temperature preheating.When temperature reached the fuel firing point, fuel and oxidant burning were rapidly emitted big calorimetric.Material through low-temperature prewarming gets in the reactor end cap air ring groove 10 through material inlet 14 and cool air inlet 13 respectively with the oxidant of a part without preheating.Material, oxidant and fuel carry out jet, head-on collision from different directions, carry out the high efficient mixed heat release in the combustion zone.Reacting fluid flows to the reactor below through behind the high temperature combustion zone from the annular space between the catalyst tank outside and the evaporation wall, and solid salt separates in desalination district 21 with reacting fluid under the gravity effect.After carrying out the gravity desalting process, fluid flows to beds top after getting into catalyst tank by catalyst tank lower end porous plectane, after the catalytic oxidation process, gets into central tube 22, exports 7 outflow reactors through product from top to bottom.Solid salt after the separation gets into dissolved salt district 17, and discharges through the solid salt outlet 6 of bottom, and dissolubility salt is discharged reactor through liquid salt outlet 5.
Claims (5)
1. overcritical water oxidization reactor that utilizes auxiliary fuel supply heat; Comprise kettle and catalyst tank wherein, it is characterized in that the kettle upper end is fixedly connected with end cap; Space between end cap and the top, catalyst tank case top is a high temperature combustion zone, and the catalyst tank below is the salt Disengagement zone; The autoclave body bottom center is provided with the solid salt outlet, and solid salt outlet top is subcritical dissolved salt district; Cooling water inlet and liquid salt outlet that autoclave body bottom is provided with the product outlet, is communicated with subcritical dissolved salt district; Cool air inlet and material inlet are set on the end cap all to be communicated with high temperature combustion zone through axial channel; The end cap center is provided with fuel core pipe, and this fuel core tubular axis is to putting in end cap in the high temperature combustion zone top; Between fuel core pipe periphery and the end cap annular space is arranged, the end cap side has hot air inlet, and this hot air inlet is through horizontal hole and annular space UNICOM; The tube wall outside that fuel core pipe puts in the end cap part is provided with helical fin; Have first temperature-measuring casing of built-in armoured thermocouple on the end cap, this first temperature-measuring casing axially puts in the end cap; Catalyst tank is fixed on around the vertical section of a central tube, and the tilting section of central tube is communicated with the outlet of the product of autoclave body bottom; Be provided with the tubular porous evaporator wall near inner wall of kettle, the kettle arranged outside has second temperature-measuring casing of evaporation wall water inlet and built-in armoured thermocouple all to be communicated in porous evaporator wall and the formed ring cavity of inner wall of kettle.
2. the overcritical water oxidization reactor that utilizes auxiliary fuel supply heat as claimed in claim 1; It is characterized in that; End cap cooling annular groove is set below end cap, comprises being used for air cooled inner groove and the outer groove that is used for the material cooling, there are two circle holes the inner groove bottom surface; The downward oblique fuel core tube side of inner ring hole is to, the downward oblique porous evaporator wall direction of cycle hole; The outer groove bottom surface have the downward oblique fuel core tube side in a circle hole to.
3. the overcritical water oxidization reactor that utilizes auxiliary fuel supply heat as claimed in claim 1; It is characterized in that; Described fuel core pipe lower end outlet is blind hole structure, when fuel flows out blind hole through around the tube wall tiltedly 4 perforates of lower direction to around form jet.
4. the overcritical water oxidization reactor that utilizes auxiliary fuel supply heat as claimed in claim 1; It is characterized in that; Said catalyst tank is a cylindrical shell, and this cylindrical shell bottom inlet and cylindrical shell top exit are the porous plectane, establishes dismountable spherical case lid on its top porous plectane.
5. the overcritical water oxidization reactor that utilizes auxiliary fuel supply heat as claimed in claim 1 is characterized in that, is provided with the 3rd temperature-measuring casing of built-in armoured thermocouple near autoclave body bottom subcritical dissolved salt district and the salt Disengagement zone.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110121463XA CN102190363B (en) | 2011-05-12 | 2011-05-12 | Supercritical water oxidation reactor by using auxiliary fuel for supplying heat |
| PCT/CN2011/078050 WO2012151794A1 (en) | 2011-05-12 | 2011-08-05 | Supercritical water oxidation reactor using auxiliary fuel to supply heat |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110121463XA CN102190363B (en) | 2011-05-12 | 2011-05-12 | Supercritical water oxidation reactor by using auxiliary fuel for supplying heat |
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| CN102190363A CN102190363A (en) | 2011-09-21 |
| CN102190363B true CN102190363B (en) | 2012-11-28 |
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| WO (1) | WO2012151794A1 (en) |
Cited By (2)
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|---|---|---|---|---|
| US11780753B2 (en) | 2019-06-28 | 2023-10-10 | Revive Environmental Technology, Llc | Destruction of PFAS via an oxidation process and apparatus suitable for transportation to contaminated sites |
| US11970409B2 (en) | 2022-11-21 | 2024-04-30 | Revive Environmental Technology, Llc | Destruction of PFAS via an oxidation process and apparatus suitable for transportation to contaminated sites |
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| CN103193309B (en) * | 2012-01-04 | 2014-09-17 | 新奥科技发展有限公司 | Mixed desalination method and device for wastewater |
| CN102910690B (en) * | 2012-08-29 | 2014-05-07 | 新奥科技发展有限公司 | Method and equipment for wastewater temperature increasing and desalting |
| CN105408017B (en) * | 2013-08-01 | 2018-10-26 | 英派尔科技开发有限公司 | Corrosion-resistant surface for reactor |
| CN103776038B (en) * | 2014-01-25 | 2016-01-06 | 陕西万丰能源环保科技有限公司 | Multi-functional overcritical hydro-thermal burner |
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| CN104907002A (en) * | 2015-06-09 | 2015-09-16 | 王冰 | Supercritical reaction kettle capable of sorting and discharging products automatically and method |
| CN105782995A (en) * | 2016-05-17 | 2016-07-20 | 山东大学 | Jet combustion device and method for super-critical water oxidization of organic matter |
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| CN109574194A (en) * | 2019-01-23 | 2019-04-05 | 南京新奥环保技术有限公司 | Supercritical water oxidation treatment system |
| CN110124584A (en) * | 2019-06-19 | 2019-08-16 | 广西大学 | A kind of tubular type evaporation wall reactor for supercritical water oxidation processing |
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| US11970409B2 (en) | 2022-11-21 | 2024-04-30 | Revive Environmental Technology, Llc | Destruction of PFAS via an oxidation process and apparatus suitable for transportation to contaminated sites |
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| Publication number | Publication date |
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| WO2012151794A1 (en) | 2012-11-15 |
| CN102190363A (en) | 2011-09-21 |
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