CN110642363A - Multifunctional supercritical water reactor for graded reinforcement of degradation of organic pollutants - Google Patents
Multifunctional supercritical water reactor for graded reinforcement of degradation of organic pollutants Download PDFInfo
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- CN110642363A CN110642363A CN201911007894.6A CN201911007894A CN110642363A CN 110642363 A CN110642363 A CN 110642363A CN 201911007894 A CN201911007894 A CN 201911007894A CN 110642363 A CN110642363 A CN 110642363A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 20
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 20
- 230000015556 catabolic process Effects 0.000 title claims abstract description 19
- 230000002787 reinforcement Effects 0.000 title description 2
- 239000000446 fuel Substances 0.000 claims abstract description 74
- 239000000498 cooling water Substances 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000002347 injection Methods 0.000 claims description 81
- 239000007924 injection Substances 0.000 claims description 81
- 239000007800 oxidant agent Substances 0.000 claims description 36
- 230000001590 oxidative effect Effects 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 230000002708 enhancing effect Effects 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- 239000007921 spray Substances 0.000 abstract description 2
- 238000009529 body temperature measurement Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000009284 supercritical water oxidation Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229910052698 phosphorus Chemical group 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The utility model provides a hierarchical super critical water reactor who strengthens organic pollutant degradation, includes the reactor head, reactor middle part and reactor bottom, and the reactor head includes oxygen cooling channel, nozzle opening, supercritical water filling opening, temperature measurement mouth, cooling water export and nozzle platform. Wherein, a flame detector is arranged on the oxygen cooling channel through threads, a material nozzle is arranged at the nozzle opening through threads, and a temperature thermocouple is arranged at the temperature measuring opening through threads. The middle part of the reactor comprises an upper reactor section, a middle reactor section and a lower reactor section. The upper section of the reactor is installed with the head of the reactor by bolts. The upper section of the reactor, the middle section of the reactor and the lower section of the reactor are respectively provided with a secondary oxidation port, a tertiary oxidation port and a quaternary oxidation port through bolt connection. The middle section of the reactor is respectively provided with the inside of the reactor, a catalyst inner liner, an auxiliary fuel spiral sleeve and a cooling water jacket from inside to outside. The bottom of the reactor is welded with the lower section of the reactor, and a tapered spray head is arranged in the middle of the reactor.
Description
Technical Field
The invention belongs to the technical field of supercritical water oxidation, and particularly relates to a multifunctional supercritical water reactor for stepwise enhancing degradation of organic pollutants.
Background
Research on supercritical water oxidation technology was initiated in the early 1980 s and was first proposed by professor Modell. Supercritical Water Oxidation (SCWO) is a Water treatment technology that can safely, cleanly and effectively degrade organic waste liquid with an organic matter content of less than 20 wt% at a temperature above the critical point of Water (Tc 647K, Pc 221 bar).
Near or above the critical point of pure water, the thermophysical properties of water are significantly changed from those of water at normal temperature. The apparent decrease in dielectric constant results in a significant increase in solubility of hydrocarbons and gases such as oxygen, nitrogen and carbon dioxide in supercritical water, and the oxidation reaction proceeds in a homogeneous environment, thereby avoiding interphase resistance of the phase interface to mass and heat transfer. Conversely, the solubility of inorganic salts in supercritical water decreases dramatically. In addition, the low viscosity of supercritical water ensures high diffusivity of many substances in the supercritical water, thereby promoting rapid and effective reaction. Therefore, the supercritical water provides an ideal reaction medium for the oxidative degradation of organic matters. However, even though the supercritical water treatment technology has various advantages, the problems of strong corrosivity, high material requirement and salt deposition during operation caused by the harsh reaction conditions of SCWO become the biggest obstacles to the commercialization of SCWO at present. The specific surface is as follows:
(1) supercritical water oxidation reaction conditions are severe, and higher temperature and pressure are required. For the conventional tubular reactor, the tube wall of the reactor needs to withstand the high temperature of 600-.
(2) The energy requirement of the device is large, and the economical efficiency of the reaction system is not high. Although the SCWO process is an exothermic reaction, when the mass fraction of organic matters reaches 2-3%, self-heating can be realized, but an external heat source is still required for supplementing heat to the organic matters in the starting process of the equipment. In addition, during the operation of the apparatus, the current reactor mostly mixes the preheated material with the oxidant at the inlet of the reactor, so that the material can rapidly reach the supercritical state in the reactor to complete the degradation of the organic matter. At present, most of the heating modes of supercritical water oxidation equipment at home and abroad adopt an electric heating mode, which not only causes huge equipment investment cost, but also causes huge obstacles to large-scale industrial application of the technology.
(3) And the corrosion of materials. In a supercritical water environment, the corrosion rate of the corrosion-resistant material is accelerated by high temperature, high pressure, dissolved oxygen and some free radicals and ions generated in the reaction. Furthermore, heteroatoms such as halogens, sulfur, and phosphorus contained in the organic matter decompose in supercritical water to generate acids, which further cause strong corrosion of equipment.
(4) The problem of salt deposition. Water is an excellent solvent for most of salts at normal temperature, and has high solubility. In contrast, most salts are extremely poorly soluble in supercritical water at low densities. When the subcritical solution is rapidly heated to the supercritical temperature, a large amount of precipitates are separated out due to the great reduction of the solubility of the salt, and deposited salt can cause the blockage of inlet and outlet pipelines of the reactor, so that the normal operation of the reactor is influenced, and potential equipment hidden troubles are also brought.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a multifunctional supercritical water reactor for graded enhancement of organic pollutant degradation, which utilizes auxiliary fuel to supply reaction heat and promotes the oxidation reaction by the initiation of active free radicals generated by the auxiliary fuel. At the reactor top, through rationally setting up nozzle platform structure, cold material, alcohols, supercritical water and oxygen can be at same reaction plane in the homogeneous mixing, effectively prevented because of the material preheats corrosion, salt deposit phenomenon in heating system and pipeline. In addition, the reactor also has the characteristics of convenient disassembly and assembly, easy loading and catalyst replacement, easy maintenance, and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
the utility model provides a multi-functional supercritical water reactor of organic matter pollutant degradation is reinforceed in grades, is including connecting gradually reactor head 5, reactor middle part and reactor bottom 28 of assembly, its characterized in that, reactor head 5 is the end cover structure, and its bottom sets up nozzle platform 33, forms isolated oxidant space and supercritical water space between nozzle platform 33 and the reactor head 5, and oxidant space and supercritical water space communicate with reactor inner space 34 through independent pore respectively, reactor head 5 opens there are supercritical water injection mouth 30 and nozzle opening 2, and supercritical water injection mouth 30 and supercritical water space communicate, are equipped with nozzle 1 in the nozzle opening 2, and 1 ring chamber of nozzle communicates with oxidant space, and 1 inner tube of nozzle is organic pollutant aqueous solution passageway, runs through nozzle platform 33 and stretches into reactor inner space 34.
The reactor head 5 is provided with an oxygen cooling channel 4 directly communicated with the inner space 34 of the reactor, and the flame detector 3 is inserted into the oxygen cooling channel 4.
The middle part of the reactor is of a cylinder structure, and a catalyst inner bushing 9, an auxiliary fuel spiral sleeve and a cooling water jacket are arranged from inside to outside.
The cooling water jacket and the auxiliary fuel spiral sleeve are respectively provided with a single spiral channel inclining downwards, and the direction of the single spiral channel and the horizontal plane form a 10-45 degree angle.
The reactor middle part includes reactor upper segment 6, reactor middle section A15, reactor middle section B18 and reactor lower section 23 that connect the assembly in proper order, wherein be equipped with second grade injection device 11 between reactor upper segment 6 and reactor middle section A15, be equipped with tertiary injection device 16 between reactor middle section A15 and reactor middle section B18, be equipped with level four injection device 21 between reactor middle section B18 and reactor lower section 23, auxiliary fuel spiral shell and the cooling water jacket between the adjacent section communicate from top to bottom through the injection device of corresponding level respectively, the cooling water jacket the top communicates with the cooling water outlet 32 of reactor head 5.
The reactor head part 5 is provided with a first temperature measuring port 31 directly communicated with the inner space 34 of the reactor, the side wall of the upper section 6 of the reactor is provided with a second temperature measuring port 10, the second-stage injection device 11 is provided with a third temperature measuring port 12, the third-stage injection device 16 is provided with a fourth temperature measuring port 17, the fourth-stage injection device 21 is provided with a fifth temperature measuring port 22, the side wall of the lower section 23 of the reactor is provided with a seventh temperature measuring port 26, and each temperature measuring port is provided with a temperature measuring thermocouple 29.
The upper section 6 of the reactor is provided with a catalyst inner bushing 9, an auxiliary fuel spiral sleeve I8 and a cooling water jacket I7 from inside to outside, and the secondary injection device 11 is provided with a secondary fuel injection port 35 communicated with the auxiliary fuel spiral sleeve I8 and a secondary oxidant injection port 36 communicated with the cooling water jacket I7; the middle section A15 of the reactor is provided with a catalyst inner bushing 9, an auxiliary fuel spiral sleeve II 14 and a cooling water jacket II 13 from inside to outside, and the third-stage injection device 16 is provided with a third-stage fuel injection port 37 communicated with the auxiliary fuel spiral sleeve II 14 and a third-stage oxidant injection port 38 communicated with the cooling water jacket II 13; the middle section B18 of the reactor is provided with a catalyst inner bushing 9, an auxiliary fuel spiral sleeve three 20 and a cooling water jacket three 19 from inside to outside, and the fourth-stage injection device 21 is provided with a fourth-stage fuel injection port 39 communicated with the auxiliary fuel spiral sleeve three 20 and a fourth-stage oxidant injection port 40 communicated with the cooling water jacket three 19; the lower section 23 of the reactor is provided with a catalyst inner bushing 9, an auxiliary fuel spiral sleeve four 25 and a cooling water jacket four 24 from inside to outside, and the side surface of the bottom of the lower section 23 of the reactor is provided with a methanol injection port 27 communicated with the auxiliary fuel spiral sleeve four 25 and a cooling water inlet 41 communicated with the cooling water jacket four 24.
The catalyst inner liner 9 is provided with a plurality of downward inclined annular holes at the positions of each stage of fuel injection port and each stage of oxidant injection port, and the angle is 45-80 degrees with the horizontal plane.
The auxiliary fuel spiral sleeve I8 penetrates through the catalyst inner lining 9 inwards at the top end of the spiral channel and is provided with a plurality of downward inclined annular holes, and the plane of the channel and the horizontal plane form an angle of 45-80 degrees.
The reactor bottom 28 is of a tapered configuration.
Compared with the prior art, the invention has the beneficial effects that:
1. the method aims at the problems that the energy demand of the current supercritical water oxidation reaction device is large and the system economy is not high. According to the invention, by reasonably arranging the nozzle platform, a large amount of heat is released through the reaction of clean auxiliary fuel and oxygen, and then the clean auxiliary fuel and the oxygen are mixed with materials. When the waste material enters the reactor through the spiral atomizing nozzle, the waste material can be uniformly mixed with the auxiliary fuel, so that low-temperature incidence of the waste material can be realized, the energy consumption is greatly reduced, and the problems of corrosion and salt deposition of the waste material in the preheater are fundamentally solved.
2. The reactor is wide in feeding concentration application range, supercritical water heat combustion is adopted for high-concentration organic pollutants, and enhanced measures such as segmented oxygen injection and auxiliary fuel injection are matched, so that the organic matters can be efficiently degraded at the reaction temperature of 600-1100 ℃ in a short retention time. To low concentration organic pollutant, through pouring into with the auxiliary fuel cooperation, effectively improved the calorific value of feeding, the reactor head has the supercritical water filling mouth in addition, can improve the temperature of material fast through the homogeneous mixing with the material.
3. The inside real-time supervision of reactor has been realized, and the reactor is inside to be provided with the flame detector to let in oxygen in the annular gap between flame detector and reactor head and realize the cooling of flame detector, effectively solved the unable problem that bears the high temperature of high-pressure glass, and the oxygen that lets in will further promote going on of reaction in the reactor.
4. The temperature of the fluid inside the supercritical water reactor is much higher than that of the conventional SCWO reactor, and therefore cooling protection is required to the walls. The device is innovatively provided with the auxiliary fuel spiral sleeve and the cooling water jacket, and can preheat the methanol which is injected in a grading and strengthening way, and can ensure that high-temperature fluid in the reactor is not directly contacted with the external pressure-bearing wall, so that the material selection requirement of the external pressure-bearing wall is effectively reduced, and the processing cost is further reduced. In addition, the inner wall of the reactor is a replaceable catalyst inner bushing which can be replaced according to the material type and the operation duration, so that the degradation of organic matters is efficiently carried out.
Drawings
FIG. 1 is a sectional view showing the structure of a reactor of the present invention.
FIG. 2 is an enlarged view of a portion of the upper part of the reactor of the present invention.
FIG. 3 is a partial enlarged view of the secondary injection device of the multi-functional supercritical water reactor of the present invention.
Wherein, 1 is a nozzle, 2 is a nozzle opening, 3 is a flame detector, 4 is an oxygen cooling channel, 5 is a reactor head, 6 is a reactor upper section, 7 is a cooling water jacket, 8 is an auxiliary fuel screw sleeve, 9 is a catalyst inner sleeve, 10 is a temperature measuring opening, 11 is a two-stage injection device, 12 is a temperature measuring opening, 13 is a cooling water jacket, 14 is an auxiliary fuel screw sleeve, 15 is a reactor middle section, 16 is a three-stage injection device, 17 is a temperature measuring opening, 18 is a reactor middle section, 19 is a cooling water jacket, 20 is an auxiliary fuel screw sleeve, 21 is a four-stage injection device, 22 is a temperature measuring opening, 23 is a reactor lower section, 24 is a cooling water jacket, 25 is an auxiliary fuel screw sleeve, 26 is a temperature measuring opening, 27 is a methanol injection opening, 28 is a reactor bottom, 29 is a temperature measuring thermocouple, 30 is a supercritical water injection opening, 31 is a temperature measuring opening, 32 is a cooling water outlet, 33 is a nozzle platform, reference numeral 34 denotes a reactor interior, 35 denotes a secondary fuel inlet, 36 denotes a secondary oxidant inlet, 37 denotes a tertiary fuel inlet, 38 denotes a tertiary oxidant inlet, 39 denotes a quaternary fuel inlet, 40 denotes a quaternary oxidant inlet, and 41 denotes a cooling water inlet.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
As shown in fig. 1, a multi-functional supercritical water reactor for enhancing degradation of organic pollutants in a graded manner mainly comprises three major parts, namely a reactor head part 5, a reactor middle part and a reactor bottom part 28 which are sequentially connected and assembled.
The reactor head 5 is an important part of the present invention, and as shown in fig. 2, the reactor head is of an end cover structure, a nozzle platform 33 is disposed at a bottom end, an oxidant space and a supercritical water space which are isolated from each other are formed between the nozzle platform 33 and the reactor head 5, specifically, the oxidant space and the supercritical water space are both annular spaces, which are isolated from each other by an annular zone, and the oxidant space is located inside the supercritical water space.
Oxidant space and supercritical water space communicate with reactor inner space 34 through independent pore respectively, reactor head 5 opens there are supercritical water injection mouth 30 and nozzle opening 2, wherein nozzle opening 2 can open the central authorities of locating reactor head 5, supercritical water injection mouth 30 and supercritical water space communicate, threaded connection has nozzle 1 in nozzle opening 2, the ring chamber and the oxidant space intercommunication of nozzle 1, and 1 inner tube of nozzle runs through reactor head 5 and nozzle platform 33 and stretches into to reactor inner space 34, as organic pollutant aqueous solution passageway, nozzle 1 can adopt the spiral nozzle mouth.
Meanwhile, an oxygen cooling channel 4 directly communicated with the inner space 34 of the reactor can be arranged on the head part 5 of the reactor, and a flame detector 3 is inserted into the oxygen cooling channel 4.
The middle part of the reactor comprises an upper reactor section 6, a middle reactor section A15, a middle reactor section B18 and a lower reactor section 23 which are sequentially connected and assembled, the whole reactor is of a cylinder structure, a catalyst inner bushing 9, an auxiliary fuel spiral sleeve and a cooling water jacket are arranged from inside to outside, the cooling water jacket and the auxiliary fuel spiral sleeve are respectively provided with a single spiral channel inclining downwards, and the direction of the channels and the horizontal plane form a 10-45 degree angle.
Specifically, the upper section 6 of the reactor is provided with a catalyst inner bushing 9, an auxiliary fuel spiral bushing one 8 and a cooling water jacket one 7 from inside to outside, the middle section a15 of the reactor is provided with the catalyst inner bushing 9, the auxiliary fuel spiral bushing two 14 and the cooling water jacket two 13 from inside to outside, the middle section B18 of the reactor is provided with the catalyst inner bushing 9, the auxiliary fuel spiral bushing three 20 and the cooling water jacket three 19 from inside to outside, and the lower section 23 of the reactor is provided with the catalyst inner bushing 9, the auxiliary fuel spiral bushing four 25 and the cooling water jacket four 24 from inside to outside.
A second-stage injection device 11 is arranged between the upper section 6 of the reactor and the middle section A15 of the reactor, a third-stage injection device 16 is arranged between the middle section A15 of the reactor and the middle section B18 of the reactor, a fourth-stage injection device 21 is arranged between the middle section B18 of the reactor and the lower section 23 of the reactor, an auxiliary fuel screw sleeve and a cooling water jacket between adjacent sections are respectively communicated up and down through the injection devices of corresponding stages, the uppermost part of the cooling water jacket is communicated with a cooling water outlet 32 on the head part 5 of the reactor, a plurality of downward inclined annular holes are formed in the positions of each stage of fuel injection opening and each stage of oxidant injection opening of the catalyst inner liner 9, the angle is 45-80 degrees with the horizontal plane, the auxiliary fuel screw sleeve 8 penetrates through the catalyst inner liner 9 inwards at the top end of the screw channel and is provided with a plurality of downward inclined annular holes, the plane of the channel is 45-80 degrees with. The side surface of the bottom of the lower reactor section 23 is provided with a methanol injection port 27 communicated with an auxiliary fuel spiral sleeve four 25 and a cooling water inlet 41 communicated with a cooling water jacket four 24.
Further, as shown in fig. 3, a secondary fuel injection port 35 communicating with the auxiliary fuel screw sleeve one 8 and a secondary oxidant injection port 36 communicating with the cooling water jacket one 7 may be provided in the secondary injection device 11; the third-stage injection device 16 is provided with a third-stage fuel injection port 37 communicated with the auxiliary fuel spiral sleeve II 14 and a third-stage oxidant injection port 38 communicated with the cooling water jacket II 13; the fourth-stage injection device 21 is provided with a fourth-stage fuel injection port 39 communicated with the auxiliary fuel spiral sleeve three 20 and a fourth-stage oxidant injection port 40 communicated with the cooling water jacket three 19 for grading and enhancing the degradation of organic matters.
In order to monitor the reaction effect conveniently, the head part 5 of the reactor is provided with a first temperature measuring port 31 which is directly communicated with the inner space 34 of the reactor, the side wall of the upper section 6 of the reactor is provided with a second temperature measuring port 10, the second-stage injection device 11 is provided with a third temperature measuring port 12, the third-stage injection device 16 is provided with a fourth temperature measuring port 17, the fourth-stage injection device 21 is provided with a fifth temperature measuring port 22, the side wall of the lower section 23 of the reactor is provided with a seventh temperature measuring port 26, and each temperature measuring port is provided with.
The bottom 28 of the reactor is of a tapered structure and is connected with the middle part of the reactor by welding.
According to the structure, the process flow of the invention is as follows:
organic pollutant aqueous solution of certain concentration under supercritical pressure gets into the nozzle inner tube through 1 top entry of nozzle, spiral nozzle mouth through 1 below of nozzle starts to revolve and gets into reactor inner space 34, oxidant gets into nozzle ring chamber through 1 upper end side entry of nozzle under supercritical pressure, reach the oxidant space between nozzle platform 33 and the reactor head 5, spout downwards through the orifice of nozzle platform 33 and get into reactor inner space 34 and contact with organic matter aqueous solution, high-temperature high-pressure supercritical water gets into the supercritical water space through supercritical water entry 30, get into reactor inner space 34 and contact with organic matter aqueous solution and oxidant through the orifice of nozzle platform 33 again, produce supercritical hydrothermal flame afterwards, another share of oxidant gets into reactor inner space 34 through oxygen cooling channel 4.
A stream of alcohol fuel solution under supercritical pressure is injected into the reactor inner space 34 through the methanol injection port 27 and the single spiral channel upwards to enter the auxiliary fuel spiral casings 25, 20, 14 and 8 respectively to reach the inclined holes at the top end for fuel supplement.
And three groups, wherein each group comprises two groups of oxidant and alcohol fuel solutions under supercritical pressure, and the oxidant and alcohol fuel solutions are obliquely and inwards sprayed into the inner space 34 of the reactor through a secondary fuel injection port 35, a secondary oxidant injection port 36, a tertiary fuel injection port 37, a tertiary oxidant injection port 38, a quaternary fuel injection port 39 and a quaternary oxidant injection port 40 to carry out graded enhanced organic pollutant degradation reaction.
A stream of supercritical pressure cooling water enters through cooling water inlet 41, rises through the single spiral channels of cooling water jackets 24, 19, 13, 7 respectively to cool the reactor and exits through cooling water outlet 32 at the top.
In summary, the present invention discloses a supercritical water reactor for staged enhancement of degradation of organic pollutants, which comprises three main parts, namely a reactor head part, a reactor middle part (an upper reactor section, a middle reactor section and a lower reactor section) and a reactor bottom part. The reactor head comprises an oxygen cooling channel, a nozzle opening, a supercritical water injection opening, a temperature measuring opening, a cooling water outlet and a nozzle platform. Wherein, a flame detector is arranged on the oxygen cooling channel through threads, a material nozzle is arranged at the nozzle opening through threads, and a temperature thermocouple is arranged at the temperature measuring opening through threads. The middle part of the reactor comprises an upper reactor section, a middle reactor section and a lower reactor section. The upper section of the reactor is installed with the head of the reactor by bolts. The upper section of the reactor, the middle section of the reactor and the lower section of the reactor are respectively provided with a secondary oxidation port, a tertiary oxidation port and a quaternary oxidation port through bolt connection. The middle section of the reactor is respectively provided with the inside of the reactor, a catalyst inner liner, an auxiliary fuel spiral sleeve and a cooling water jacket from inside to outside. The bottom of the reactor is welded with the lower section of the reactor, and a tapered spray head is arranged in the middle of the reactor.
The device can realize the incidence of the cold materials of the organic wastes and has wide application range to the incident concentration of the materials. The method is matched with strengthening measures such as segmented oxygen injection and auxiliary fuel injection, and can realize the efficient degradation of organic matters in a short retention time at a reaction temperature of 600-1100 ℃.
The above is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A multi-functional supercritical water reactor for enhancing degradation of organic pollutants in a graded manner comprises a reactor head (5), a reactor middle part and a reactor bottom (28) which are sequentially connected and assembled, and is characterized in that the reactor head (5) is of an end cover structure, a nozzle platform (33) is arranged at the bottom end of the reactor head, an oxidant space and a supercritical water space which are separated from each other are formed between the nozzle platform (33) and the reactor head (5), the oxidant space and the supercritical water space are respectively communicated with a reactor inner space (34) through independent pore channels, the reactor head (5) is provided with a supercritical water injection port (30) and a nozzle opening (2), the supercritical water injection port (30) is communicated with the supercritical water space, a nozzle (1) is arranged in the nozzle opening (2), an annular cavity of the nozzle (1) is communicated with the oxidant space, and an inner pipe of the nozzle (1) is an organic pollutant water, the nozzle platform (33) extends into the reactor interior (34).
2. The multifunctional supercritical water reactor for staged enhancement of organic pollutant degradation according to claim 1 is characterized in that the reactor head (5) is opened with an oxygen cooling channel (4) directly communicating with the reactor inner space (34), and a flame detector (3) is inserted into the oxygen cooling channel (4).
3. The multifunctional supercritical water reactor for graded enhancement of organic pollutant degradation according to claim 1 is characterized in that the middle part of the reactor is of a cylindrical structure, and a catalyst inner bushing (9), an auxiliary fuel spiral bushing and a cooling water jacket are arranged from inside to outside.
4. The multifunctional supercritical water reactor according to claim 3 is characterized by that the cooling water jacket and the auxiliary fuel screw sleeve are both provided with single screw channel inclined downwards, and the channel direction is 10-45 ° to the horizontal plane.
5. The multifunctional supercritical water reactor according to claim 3 or 4, it is characterized in that the middle part of the reactor comprises a reactor upper section (6), a reactor middle section A (15), a reactor middle section B (18) and a reactor lower section (23) which are sequentially connected and assembled, wherein, a second-stage injection device (11) is arranged between the upper section (6) of the reactor and the middle section A (15) of the reactor, a third-stage injection device (16) is arranged between the middle section A (15) of the reactor and the middle section B (18) of the reactor, a fourth-stage injection device (21) is arranged between the middle section B (18) of the reactor and the lower section (23) of the reactor, the auxiliary fuel screw sleeve and the cooling water jacket between the adjacent sections are respectively communicated up and down through the injection devices of the corresponding stages, and the uppermost part of the cooling water jacket is communicated with a cooling water outlet (32) of the head part (5) of the reactor.
6. The multifunctional supercritical water reactor for graded enhancement of degradation of organic pollutants according to claim 5, wherein the reactor head (5) is provided with a first temperature measuring port (31) directly communicated with the reactor inner space (34), the side wall of the reactor upper section (6) is provided with a second temperature measuring port (10), the secondary injection device (11) is provided with a third temperature measuring port (12), the tertiary injection device (16) is provided with a fourth temperature measuring port (17), the quaternary injection device (21) is provided with a fifth temperature measuring port (22), the side wall of the reactor lower section (23) is provided with a seventh temperature measuring port (26), and each temperature measuring port is provided with a temperature measuring thermocouple (29).
7. The multifunctional supercritical water reactor for graded enhancement of organic pollutant degradation according to claim 5 is characterized in that the upper section (6) of the reactor is provided with a catalyst inner bushing (9), an auxiliary fuel screw bushing I (8) and a cooling water jacket I (7) from inside to outside, and the secondary injection device (11) is provided with a secondary fuel injection port (35) communicated with the auxiliary fuel screw bushing I (8) and a secondary oxidant injection port (36) communicated with the cooling water jacket I (7); the middle section A (15) of the reactor is provided with a catalyst inner bushing (9), an auxiliary fuel spiral sleeve II (14) and a cooling water jacket II (13) from inside to outside, and a tertiary injection device (16) is provided with a tertiary fuel injection port (37) communicated with the auxiliary fuel spiral sleeve II (14) and a tertiary oxidant injection port (38) communicated with the cooling water jacket II (13); the middle section B (18) of the reactor is provided with a catalyst inner bushing (9), an auxiliary fuel spiral sleeve III (20) and a cooling water jacket III (19) from inside to outside, and a four-stage injection device (21) is provided with a four-stage fuel injection port (39) communicated with the auxiliary fuel spiral sleeve III (20) and a four-stage oxidant injection port (40) communicated with the cooling water jacket III (19); the reactor lower section (23) is provided with a catalyst inner bushing (9), an auxiliary fuel spiral sleeve four (25) and a cooling water jacket four (24) from inside to outside, and the side surface of the bottom of the reactor lower section (23) is provided with a methanol injection port (27) communicated with the auxiliary fuel spiral sleeve four (25) and a cooling water inlet (41) communicated with the cooling water jacket four (24).
8. The multifunctional supercritical water reactor for staged enhancement of degradation of organic contaminants as claimed in claim 7, wherein the catalyst inner liner (9) has several rings at the positions of each stage of fuel injection port and each stage of oxidant injection port, and the angle is 45-80 ° from the horizontal plane.
9. The multifunctional supercritical water reactor for staged enhancement of organic pollutant degradation according to claim 7 wherein the first auxiliary fuel screw sleeve (8) is perforated with several downward inclined annular holes at the top end of the screw channel inwardly through the catalyst inner liner (9), the plane of the channel forming 45-80 ° with the horizontal plane.
10. The multifunctional supercritical water reactor according to claim 1 is characterized by the reactor bottom (28) is tapered.
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