CN103508589B - Reactor for supercritical water oxidation or gasification treatment of high-salt organic waste water - Google Patents
Reactor for supercritical water oxidation or gasification treatment of high-salt organic waste water Download PDFInfo
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- CN103508589B CN103508589B CN201310467265.8A CN201310467265A CN103508589B CN 103508589 B CN103508589 B CN 103508589B CN 201310467265 A CN201310467265 A CN 201310467265A CN 103508589 B CN103508589 B CN 103508589B
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Abstract
The invention discloses a reactor for supercritical water oxidation or gasification treatment of high-salt organic waste water. The reactor comprises a cylinder, and a top cover connected with the upper end of the cylinder in a sealing manner, wherein a closed space between the cylinder and the top cover forms a reaction chamber; anti-corrosion linings are arranged on the inner wall of the cylinder and the lower surface of the top cover; the top cover is provided with a reaction fluid inlet, a reaction fluid outlet, a pressure gauge and a safety value interface communicated with the reaction chamber in the cylinder, and is provided with a plurality of temperature measuring bushings extending into different height positions of the reaction chamber, wherein the reaction fluid inlet extends to the middle of the reaction chamber through a center pipe; a filter is suspended at the upper part of the reaction chamber; a narrow gap is reserved between the filter and the inner wall of the cylinder; a conical shield surrounding the center pipe is arranged under the filter; a strong brine outlet and a cooling water inlet communicated with the lower part of the reaction chamber are formed in the bottom of the cylinder; a heating furnace is arranged on the outer wall of the cylinder.
Description
Technical field
Waste water innoxious process for treating of the present invention, the particularly reactor of the high saliferous of one (Inorganic salt 5 ~ 10wt%) organic waste water supercritical water oxidation or gasification process.
Background technology
Supercritical Water Oxidation Technology (being called for short SCWO) is the special property utilizing water had in the supercritical state, makes organism and oxygenant that oxidizing reaction occur rapidly in supercritical water and carrys out thorough decomposing organic matter.Supercritical water (T>374.15 DEG C, P>22.12MPa) is equivalent to non-polar solvent, can be miscible with arbitrary proportion with air, oxygen and organism, thus forms homogeneous phase.The disappearance of gas liquid film, also just eliminates alternate resistance to mass transfer, and speed of response is no longer by the mass transport limitation of oxygen.Meanwhile, high temperature of reaction also makes speed of response accelerate, and even within a few second, just can reach high destructive rate to organism.SCWO reacts completely, thoroughly, final product is water, N
2, CO
2with inorganic molecules compound, there is no the problem of secondary pollution, compared with other treatment technology, there is significant superiority.SCWO has unique effect for those organic waste waters that are poisonous, difficult degradation of process, therefore, has a good application prospect at the reluctant organic pollutant of process ordinary method and replacing in traditional burning method etc. in some occasion.
In recent years, each state has all dropped into a large amount of manpower and materials and has studied SCWO.The current U.S. has applied the harmless treatment that this technology has carried out the pollutents such as rocket fuel residue, nuke rubbish, chemical weapons residue, explosive substance, volatile acid, industrial slip, physiology rubbish, municipal sludge.Germany, France, Sweden, Spain and Japan and other countries also achieve important achievement in effective process of indusrial toxic waste liquid, the dregs of fat and municipal wastes.Just point out in one of listed by American National gordian technique six large fields " energy and environment ", one of the most promising organic waste treatment technology is supercritical Water Oxidation Technology.
In addition, supercritical water gasification technology (being called for short SCWG) is the physicochemical property utilizing supercritical water uniqueness, under the condition do not added or add small amounts agent, the reaction process such as organism is hydrolyzed in supercritical water, pyrolysis, partial oxidation, generate the flammable gaseous product based on hydrogen.This technology has the advantages such as gasification efficiency is high, hydrogen yield is high, tar yield is low.Therefore, SCWO and SCWG has the Technology Potential realizing organic waste water harmless treatment and recycling.
Highly salt containing organic waste water results from the industries such as chemical industry, agricultural chemicals and medicine usually, and generation is large, organism kinds is many, complicated component, even can reach 10% containing Inorganic salt.The blockage problem that emphasis solution salt sedimentation causes is needed in this kind of organic waste water supercritical water oxidation/gasification.In highly salt containing organic waste water supercritical water oxidation/gasification; because the solubleness of inorganic salt in supercritical water is extremely low; these inorganic salt can be separated out; the inorganic salt that some viscosity is larger can deposit on reactor internal surface; and then the blocking of induce reaction device or its export pipeline; cause reaction unit disorderly closedown, had a strong impact on complete assembly reliability of operation and economy, constrain the development of supercritical water oxidation/gasification technology.In addition, under condition of supercritical water, the reaction conditions of High Temperature High Pressure and the reaction environment of high density dissolved oxygen can aggravate reactor corrosion.Reactor corrosion not only can induce reaction device safety problem, reduce reactor work-ing life, and corrosion product also can affect treatment effect.Therefore, the etching problem effectively overcoming reactor is needed.In view of highly salt containing organic waste water organism kinds is various and change in concentration is larger, supercritical water oxidation/gasification reaction conditions difference is larger, in order to make reactor feed, there is the larger scope of application, meeting the functional requirement that can carry out highly salt containing organic waste water supercritical water oxidation and gasification process on same reactor simultaneously, just requiring to realize stable reaction conditions when carrying out highly salt containing organic waste water supercritical water oxidation/gasifying reactor development and Design.Therefore, need to develop a kind of novel reactor to go to solve the problem.
Summary of the invention
The blocking caused at anti-salt sedimentation for existing highly salt containing organic waste water supercritical water oxidation/gasifying reactor, protection against corrosion, meet the defect that exists in oxidation and gasification service requirements or deficiency simultaneously, the object of the present invention is to provide a kind of highly salt containing organic waste water supercritical water oxidation/gasifying reactor.
In order to reach above object, the present invention takes following technical scheme to be achieved;
The reactor of a kind of supercritical water oxidation or gasification treatment of high-salt organic waste water, comprise cylindrical shell, the top cover be tightly connected with this cylindrical shell upper end, enclosed space between cylindrical shell and top cover is reaction chamber, it is characterized in that, described cylinder inboard wall, top cover lower surface is provided with anti-corrosion liner, top cover is provided with the reacting fluid import be communicated with reaction chamber in cylindrical shell, reacting fluid exports, tensimeter and relief valve connection, and be provided with some temperature-measuring casings and put in reaction chamber different heights position, wherein, reacting fluid import extends to the middle part of reaction chamber by a pipe core, the top of reaction chamber is unsettled arranges a strainer, small gaps is left between this strainer and cylinder inboard wall, be provided with a cone-shaped hood surrounded by pipe core below strainer, cylinder body bottom is provided with the strong brine be communicated with reaction chamber bottom and exports and entrance of cooling water, and cylinder body outer wall is provided with process furnace.
In such scheme, described strainer is made up of sintering metal, porous ceramics or multiple layer metal net; By the bracing frame carried that is connected unsettled with top cover lower surface.Described cone-shaped hood is fixed by the some ribs be connected on bracing frame.Described process furnace is electrical heater, and its periphery arranges lagging casing and insulated roof.Described entrance of cooling water is by the watercooling jacket seal of tube through cylindrical shell bottom lagging casing.It stretches into after bottom reaction chamber has an elbow, the central shaft of orientating reaction room.The described temperature-measuring casing putting in reaction chamber has two, and one is positioned at pipe core exit, and another is positioned at reaction chamber bottom.
Advantage of the present invention is, reacting fluid utilizes the method for inertia and gravity separation that the inorganic salt of precipitation are deposited to reactor bottom in the reactor, then by pumping into water coolant formation close-to-critical range, the inorganic salt of precipitation are dissolved again, take reactor out of again, reacting fluid adverse current after desalination upwards flows, by cone-shaped hood and the further desalination of strainer, and then from reactor head reacting fluid outlet outflow reactor, and then effectively overcome the blockage problem that salt precipitates reactor and the export pipeline thereof caused.By arranging protection against corrosion liner at reactor shell internal surface, effectively reducing the erosion rate of reactor, ensureing the operation that reactor is safe and reliable.In addition, by reactor shell outer setting electrical heater, can require to carry out additional heat according to temperature of reactor, same reactor realizes supercritical water oxidation process or the gasification process of highly salt containing organic waste water.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
Fig. 1 is the structural representation of reactor of the present invention.
Fig. 2 is the A direction view of Fig. 1.
In figure: 1, nut; 2, bolt; 3, pad; 4, reactor head; 5, graphite grazing pad; 6, filter support; 7, nut pull bar; 8, ribs; 9, pipe core; 10, temperature-measuring casing; 11, electrical heater; 12, reactor lagging casing; 13, sleeve pipe; 14, lagging material; 15, nameplate; 16, reactor shell; 17, anti-corrosion liner; 18, screw; 19, reactor lagging casing top cover; 20, temperature-measuring casing; 21: cone-shaped hood; 22: strainer; 23: tensimeter and safety valve skirt; 24, anti-corrosion liner; 25, nut.N1: reacting fluid import; N2, N3: thermopair interface; N4: tensimeter and relief valve connection; N5: reacting fluid exports; N6, strong brine export; N7: entrance of cooling water.
Embodiment
See figures.1.and.2, highly salt containing organic waste water supercritical water oxidation/gasifying reactor, comprise the reactor head 4 for pressure-bearing and reactor shell 16, for sealed reactor top cover 4 and reactor shell 16 be tightly connected nut 1, bolt 2, pad 3 and graphite grazing pad 4, for supporting the filter support 6 with Fixed-Filter 22, for the nut pull bar 7 of Fixed-Filter bracing frame 6, for supporting the ribs 8 of cone-shaped hood 21, nut 25 is utilized to be fixed on the pipe core 9 of bottom, reactor head 4 central position, for thermometric temperature-measuring casing 20(pipe core 9 outlet position) and 10(reactor bottom), for the electrical heater 11 heated to reactor, reactor lagging casing 12, reactor lagging casing top cover 19, for the screw 18 that reactor lagging casing 12 and reactor lagging casing top cover 19 are connected and fixed, for sealing the sleeve pipe 13 of tubular stinger interface, for the lagging material 14 of reactor insulation, reactor nameplate 15, for the protection of the etch-proof anti-corrosion liner 17 of reactor, for the cone-shaped hood 21 that inorganic salt are separated, for the strainer 22 that inorganic salt remove, the skirt 23 of tensimeter and safety valve, a reacting fluid import N1 on reactor head 4, two thermopair interface N2 and N3 on reactor head 4, a shared tensimeter and relief valve connection N4 on reactor head 4, reactor bottom strong brine outlet N6, reactor top covers a reacting fluid outlet N5, reactor bottom entrance of cooling water N7.
Wherein, when carrying out highly salt containing organic waste water supercritical water oxidation, be preheated the reacting fluid import N1 inflow reactor that rear highly salt containing organic waste water and oxygenant cover from reactor top, enter pipe core 9, partial oxidation reaction is carried out, simultaneously by the pyroreaction fluid heating of pipe core 9 outside at pipe core 9.When carrying out highly salt containing organic waste water SCWG or carry out the highly salt containing organic waste water SCWO containing organic concentrations is lower, start electrical heater 11 for the heat needed for supplementary maintenance temperature of reaction.Reacting fluid reaches supercritical temperature state in pipe core 9 exit, because inorganic salt solubleness is at supercritical conditions extremely low, therefore can separate out from reacting fluid, form tiny inorganic salt xln, rely on inertia and action of gravity can fall into reactor bottom region.Arrange entrance of cooling water N7 at reactor bottom, form little close-to-critical range by pumping into low-temperature cooling water at reactor bottom, inorganic salt fall into close-to-critical range and can again dissolve, then from the strong brine outlet N6 outflow reactor of reactor bottom.In order to reduce the disadvantageous effect of water coolant to reaction zone, reactor top, the water-cooled tube going deep into reactor bottom has an elbow, the central shaft of orientating reaction device.In reactor head, another reacting fluid outlet N5 is set, cover the fluid flow rate of reacting fluid outlet N5 by controlling to flow through reactor bottom strong brine outlet N6 and reactor top, and then control reactor main fluid by the reacting fluid outlet N5 outflow reactor on reactor head 4.Export from reactor central tube 9 and flow out the reacting fluid adverse current after carrying out desalination to the flowing of reactor top, in flow process, carry out supercritical water oxidation/gasification reaction process simultaneously.First the bottom of cone-shaped hood 21 is entered, because cone-shaped hood 21 provides a large deposition plane, inorganic salt deposit in cone-shaped hood 21 base plane, carry out inorganic salt separation further, reacting fluid then by close gap between cone-shaped hood 21 and anti-corrosion liner 17 towards reactor ionized motion, carry out reaction process in flow process simultaneously, the inorganic salt particle of separating out when entering strainer 22 is retained down further, then by the reacting fluid outlet N5 outflow reactor on reactor head 4.The materials such as the above-mentioned strainer 22 mentioned can be sintering metal, porous ceramics, multiple layer metal net are made, and strainer 22 is fixed by filter support 6 frame, then utilizes four groups of nut pull bars 7 to be fixedly carried on reactor head 4.Can realize avoiding the inorganic salt in highly salt containing organic waste water supercritical water oxidation/gasification to deposit the blockage problem of reactor and the export pipeline thereof caused by above-mentioned desalination scheme, the operation that reactor is safe and reliable can be ensured.Introduce the disadvantageous effect of low-temperature cooling water to reactor pressure cylinder 16 base material generation thermal stresses to reduce, water coolant water pipe runs through bottom reactor shell, is sealed by sleeve pipe 13.
In order to reduce the erosion rate of highly salt containing organic waste water supercritical water oxidation/gasifying reactor, anti-corrosion liner 24 is set at reactor head 4 lower surface, anti-corrosion liner 17 is also set at the internal surface of reactor shell 16.Anti-corrosion liner 17 and 24 all adopts built-up welding form; the material of corrosion resistance and good can be selected; such as Hastelloy etc.; thus effectively avoid the corrosion of pressure-bearing wall; available protecting reactor head 4 and reactor shell 16; reaction top cover 4 and reactor shell 16 can select common corrosion resistant material as austenitic stainless steel 304,316 etc., thus effectively reduce the cost of reactor.In addition, by at reactor shell 16 outer setting electrical heater 11, can require to carry out additional heat according to temperature of reactor, the heat maintained needed for temperature of reaction can be supplemented when carrying out the highly salt containing organic waste water SCWO containing low-concentration organic, can be used for additional heat when carrying out highly salt containing organic waste water SCWG, thus supercritical water oxidation process or the gasification process of highly salt containing organic waste water can be realized on same reactor.Reactor head 4 is provided with two thermopair interfaces N2, N3, can be used for measuring and control the temperature of reactor central tube 9 outlet position and reactor bottom close-to-critical range.Reactor head 4 is provided with tensimeter and relief valve connection N4, for pressure monitor and the safety control of reactor.
The workflow of reactor of the present invention is as described below: the reacting fluid after preheating (is the mixture of organic waste water and oxygenant during SCWO, organic waste water is only during SCWG) enter reactor by reacting fluid import N1 on reactor head 4, supercritical state is reached in pipe core 9 outlet, the inorganic salt of separating out rely on inertia and gravity to fall into reactor bottom, close-to-critical range is formed at reactor bottom by pumping into water coolant to reactor bottom, the inorganic salt of precipitation are dissolved again, again with the strong brine outlet N6 outflow reactor of the form of strong brine from reactor bottom, reacting fluid adverse current after desalination upwards flows, and carry out supercritical water oxidation/gasification reaction simultaneously, inorganic salt particle is removed further successively by cone-shaped hood 21 and strainer 22, reacted fluid is again from reactor head fluid outlet N5 outflow reactor, thus effectively overcome the problem that salt in highly salt containing organic waste water supercritical water oxidation/gasification precipitates reactor or the export pipeline blocking caused.By at reactor shell 16 outer setting electrical heater 11, if in organic waste water, organic concentration is lower or when carrying out supercritical water gasification process when carrying out supercritical water oxidation, can require to carry out heat supplement according to temperature of reaction, thus the supercritical water oxidation/gasification process of highly salt containing organic waste water can be realized on same reactor.By arranging anti-corrosion liner 24 and 17 at reactor head 4 and reactor shell 16 internal surface, the erosion rate of reactor effectively can be reduced.In addition, by arranging the temperature of thermopair measuring point monitoring reactor central tube 9 outlet and reactor bottom close-to-critical range, thus the temperature control of realization response device needs.By arranging the pressure of tensimeter monitoring reactor, ensure the trouble-free service of reactor by arranging safety valve.
Claims (2)
1. the reactor of a supercritical water oxidation or gasification treatment of high-salt organic waste water, comprise cylindrical shell, the top cover be tightly connected with this cylindrical shell upper end, enclosed space between cylindrical shell and top cover is reaction chamber, it is characterized in that, described cylinder inboard wall, top cover lower surface is provided with anti-corrosion liner, top cover is provided with the reacting fluid import be communicated with reaction chamber in cylindrical shell, reacting fluid exports, tensimeter and relief valve connection, and be provided with some temperature-measuring casings and put in reaction chamber different heights position, wherein, reacting fluid import extends to the middle part of reaction chamber by a pipe core, the top of reaction chamber is unsettled arranges a strainer, small gaps is left between this strainer and cylinder inboard wall, be provided with a cone-shaped hood surrounded by pipe core below strainer, cylinder body bottom is provided with the strong brine be communicated with reaction chamber bottom and exports and entrance of cooling water, and cylinder body outer wall is provided with process furnace, described strainer is made up of sintering metal, porous ceramics or multiple layer metal net, by the bracing frame carried that is connected unsettled with top cover lower surface, described cone-shaped hood is fixed by the some ribs be connected on bracing frame, described entrance of cooling water is by the watercooling jacket seal of tube through cylindrical shell bottom lagging casing, and this cooling water pipe stretches into after bottom reaction chamber has an elbow, the central shaft of orientating reaction room.
2. the reactor of supercritical water oxidation as claimed in claim 1 or gasification treatment of high-salt organic waste water, it is characterized in that, described process furnace is electrical heater, and its periphery arranges lagging casing and insulated roof.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310467265.8A CN103508589B (en) | 2013-09-30 | 2013-09-30 | Reactor for supercritical water oxidation or gasification treatment of high-salt organic waste water |
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| CN201310467265.8A CN103508589B (en) | 2013-09-30 | 2013-09-30 | Reactor for supercritical water oxidation or gasification treatment of high-salt organic waste water |
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| CN103508589A CN103508589A (en) | 2014-01-15 |
| CN103508589B true CN103508589B (en) | 2015-05-27 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104628062B (en) * | 2015-02-04 | 2017-04-26 | 西安交通大学 | Method for gasifying unsymmetrical dimethylhydrazine waste liquor through supercritical water |
| WO2017198275A1 (en) * | 2016-05-19 | 2017-11-23 | Aquarden Technologies Aps | A supercritical water oxidation reactor and process |
| CN107790067A (en) * | 2017-10-27 | 2018-03-13 | 三门峡化工机械有限公司 | A kind of supercritical reaction kettle |
| CN108823866A (en) * | 2018-07-13 | 2018-11-16 | 青岛即发集团股份有限公司 | A kind of supercritical dyeing dyeing caldron and dyeing installation |
| CN108751383B (en) * | 2018-08-16 | 2023-11-21 | 成都九翼环保科技有限公司 | Countercurrent supercritical water oxidation kettle type reactor and preparation method and application thereof |
| CN109851130B (en) * | 2019-02-03 | 2020-10-09 | 中国原子能科学研究院 | Supercritical water oxidation system and organic wastewater treatment method |
| CN110038504A (en) * | 2019-04-23 | 2019-07-23 | 中海油能源发展股份有限公司 | A kind of reaction system suitable for supercritical water oxidation intermittent duty |
| CN111056616B (en) * | 2019-12-26 | 2022-07-22 | 一重集团大连工程技术有限公司 | Supercritical water oxidation system with air as oxidant and starting method |
| CN111638239B (en) * | 2020-05-24 | 2022-04-05 | 西安交通大学 | Supercritical water device capable of observing inorganic salt crystal evolution process in situ |
| CN111781229B (en) * | 2020-07-06 | 2021-05-28 | 西安交通大学 | Multifunctional inorganic salt crystallization-deposition comprehensive testing device |
| CN111781108B (en) * | 2020-07-06 | 2021-07-27 | 西安交通大学 | System and method for testing crystallization-deposition of inorganic salt in subcritical/supercritical water |
| CN112811568A (en) * | 2021-02-07 | 2021-05-18 | 江苏省环境科学研究院 | Heterogeneous catalysis supercritical water oxidation reactor |
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| DE4244482A1 (en) * | 1992-12-30 | 1994-07-07 | Solvay Deutschland | Wastewater treatment process |
| CN102515295B (en) * | 2011-12-13 | 2013-07-10 | 西安交通大学 | Scraper demineralizer for supercritical water treatment of waste organic matters |
| CN102659232A (en) * | 2012-04-23 | 2012-09-12 | 西安交通大学 | Supercritical salting and desalting device for treating brine waste |
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