CN110802077A - Online cleaning system and method based on supercritical water oxidation technology - Google Patents
Online cleaning system and method based on supercritical water oxidation technology Download PDFInfo
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- CN110802077A CN110802077A CN201910969322.XA CN201910969322A CN110802077A CN 110802077 A CN110802077 A CN 110802077A CN 201910969322 A CN201910969322 A CN 201910969322A CN 110802077 A CN110802077 A CN 110802077A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/007—Heating the liquid
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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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
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Abstract
The invention discloses an on-line cleaning system and method based on supercritical water oxidation technology. The method is characterized in that an auxiliary alcohol solution with the same concentration as a material to be treated and large-flow subcritical water are adopted to regularly clean a supercritical water oxidation system for treating high-concentration high-salt organic wastewater, industrial sludge or municipal sludge and the like on line, the cleaning process is mainly divided into normal-flow alcohol solution cleaning, medium-flow alcohol solution cleaning, large-flow alcohol solution cleaning and large-flow subcritical water cleaning, electric heaters with different powers are used in parallel or in series, normal and stable operation of the system is maintained, and meanwhile, inorganic salts and insoluble solid particles in a heat exchanger, a reactor and a conveying pipeline in the system are dissolved and taken away, so that the problems of system blockage and shutdown caused by continuous accumulation of the inorganic salts or the insoluble solids are avoided.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of chemical industry and environmental protection, and relates to an online cleaning system and method based on a supercritical water oxidation technology.
[ background of the invention ]
With the continuous development of industry, organic wastewater and industrial sludge generated in the industrial process increase year by year, especially from the industries of pesticide, pharmacy, textile printing and dyeing, coal chemical industry and the like, the generated wastewater has complex organic matter components, high concentration, high content of inorganic salt, strong toxicity and poor biodegradability, and the conventional treatment method is difficult to degrade. If the wastewater or sludge which does not reach the standard is directly discharged, harmful substances in the wastewater or sludge cause serious pollution to the land and water environment and harm to human health.
At present, the treatment methods of high-concentration high-salt organic wastewater and sludge mainly comprise a biochemical method and an incineration method. But the biochemical properties of most of high-concentration high-salt organic wastewater and sludge are extremely poor, and the effluent cannot be discharged after reaching the standard by the conventional biochemical method; while the incineration method is used as a main method for treating industrial sludge, although organic pollutants can be degraded to a certain extent, secondary pollution and poor economy are main defects of the technology, on one hand, secondary pollutants such as NOx, SOx, dioxin and the like are inevitably generated by high-temperature incineration and seriously pollute the atmosphere, heavy metal substances are contained in generated fly ash and residues, the generated fly ash and the generated residues belong to dangerous wastes and need secondary treatment, on the other hand, the incineration method cannot self-sustained combustion, high running cost is brought by adding auxiliary fuel and secondary treatment of subsequent products, and in addition, because industrial wastewater or sludge is generally high in concentration and salt, the high-temperature corrosion of equipment is aggravated in the incineration process, the requirement on equipment materials is high, and the investment is huge.
Supercritical water oxidation technologyProfessor Modell of national institute of science and technology of Massachusetts proposes that organic pollutants can be degraded rapidly and thoroughly, and elements such as C, H and N in organic matters can be converted into harmless CO2、H2O and N2When small molecular compounds, heterocyclic atoms Cl, S and P are converted into corresponding acids or salts, the heavy metals are mineralized and deposited stably in solid phase residues, no secondary pollution is generated, and harmless treatment of gas, liquid and solid three-phase products is thoroughly realized. Compared with the conventional technology, the supercritical water oxidation technology has the following technical advantages:
(1) the organic matter which is difficult to degrade can be quickly and thoroughly oxidized into small molecular compounds within extremely short reaction time (less than 2min), and the removal rate of the substances which are difficult to degrade by the conventional technology such as dioxin, polychlorinated biphenyl and the like which are extremely toxic is as high as 99.99 percent;
(2) compared with the burning method, can thoroughly convert refractory substances into harmless CO2、N2、H2Small molecular compound such as O, etc., without generating NOx、SOxSecondary pollution such as dioxin and the like, closed reaction system, no peculiar smell in the treatment process and no need of a subsequent gas treatment device;
(3) when the mass concentration of the organic matter reaches 3%, the reaction can reach a supercritical state by means of self heat release, no additional auxiliary fuel is needed, the surplus heat can be further recycled, and the system operation cost is greatly reduced.
However, when supercritical water oxidation technology is used for treating high-salinity organic wastewater and sludge, some problems still exist: because supercritical water has a low dielectric constant, which is equivalent to a nonpolar solvent, the solubility of inorganic salt in the supercritical water is extremely low, and after the system normally operates for a period of time, the inorganic salt is very easy to precipitate and crystallize and continuously deposits and adheres to the surfaces of a heat exchanger, a heater and a reactor, so that the inorganic salt in small-diameter tubular equipment such as the heat exchanger, the reactor and the like and a conveying pipeline can be continuously accumulated, the system pressure drop is increased, and the heat transfer is deteriorated. If the system is not cleaned for a long time, the heat exchanger, the heater and the reactor are blocked, the whole system for supercritical water oxidation is forced to be shut down, and then cleaning, assembling, pressure testing and restarting of each device can be carried out. In addition, because heat exchanger and reactor are high temperature high pressure welding equipment, be difficult to dismantle after the equipment blocks up and restore and reuse, this has undoubtedly influenced the reliability and the economic nature of supercritical water oxidation unit operation, has reduced the treatment effeciency of material simultaneously.
[ summary of the invention ]
The invention aims to overcome the defects that when a supercritical water oxidation system in the prior art is used for treating organic wastewater or sludge, the surfaces of a heat exchanger, a heater and a reactor are easily attached by precipitated inorganic salt, so that the system is unstable in operation and low in treatment efficiency, and provides an online cleaning system and method based on a supercritical water oxidation technology.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
an on-line cleaning system based on supercritical water oxidation technology comprises:
the outlet of the material pretreatment device is sequentially connected with a material pump, a mixer, a heat exchanger inner tube and a first electric heater; the outlet of the first electric heater is divided into two paths, one path is connected with the inlet of the supercritical water oxidation reactor, and the other path is connected with the inlet of the water distribution tank;
the outlet of the cleaning water tank is connected with a cleaning water pump, and the outlet of the cleaning water pump is divided into two paths which are respectively connected with the inlets of the first electric heater and the second electric heater; the outlet of the first electric heater is divided into two paths, one path is connected to the inlet of the supercritical water oxidation reactor, and the other path is connected with the inlet of the water distribution tank; the outlet of the second electric heater is also divided into two paths, one path is connected to the inlet of the first electric heater, and the other path is connected with the inlet of the water distribution tank; the outlet of the water distribution tank is connected to the inlet of the material pump;
the outlet of the alcohol storage tank is connected with the inlet of an alcohol metering pump, and the outlet of the alcohol metering pump is connected with the other inlet of the mixer;
and the outlet of the oxygen unit is connected to the inlet of the supercritical water oxidation reactor.
The invention further improves the following steps:
the outlet of the mixer is connected with the inlet of an inner pipe of the heat exchanger, the outlet of the inner pipe of the heat exchanger is divided into two paths, one path is connected with the inlet of the first electric heater, and the other path is connected with the inlet of the supercritical water oxidation reactor; the exit linkage of supercritical water oxidation reactor exports the outer tube import of heat exchanger, and the outer tube exit linkage of heat exchanger steps down the unit, and the exit linkage of step down the unit goes out the water storage tank.
The material pretreatment device comprises a material stirrer, a material preheating device, a material grinding pump and a material iron remover.
The heat exchanger is a double-pipe heat exchanger, a spiral coil heat exchanger or a shell-and-tube heat exchanger.
The heating power of the first electric heater is larger than that of the second electric heater, and the first electric heater and the second electric heater are electric heaters, electromagnetic induction heaters or natural gas furnace heaters.
The supercritical water oxidation reactor comprises a tubular reactor or a kettle type reactor.
The pressure reduction unit comprises a capillary tube pressure reducer, a back pressure valve pressure reducer or a multi-stage valve pressure reduction unit.
The cleaning water tank is filled with tap water, softened water or desalted water, and the fuel storage tank is filled with methanol, ethanol or isopropanol.
A cleaning method based on supercritical water oxidation technology comprises the following steps:
step 1: closing a material control valve V110 of an outlet pipeline of the material pretreatment device, opening an alcohol control valve V108 of an outlet pipeline of an alcohol metering pump, opening an alcohol metering pump, simultaneously opening a cleaning water control valve V101 of an outlet pipeline of a cleaning water pump, opening a cleaning water pump and a second electric heater, switching the materials into a mixed alcohol solution of alcohol and water, and adjusting the proportion of the alcohol and the cleaning water by adjusting the opening degrees of the alcohol control valve V108 and the cleaning water control valve V101 so that the Chemical Oxygen Demand (COD) of the alcohol solution is consistent with the COD concentration of the materials being treated;
step 2: adjusting the heating power of the second electric heater to make the heating temperature T1 of the cleaning water passing through the second electric heater consistent with the temperature T1 'of the preheated material in the material pretreatment device, and make the feeding flow F1 of the alcohol solution consistent with the feeding flow F1' of the material in normal operation; under the conditions that the concentration of the alcohol solution is consistent with that of the processed material, the preheating temperature is consistent, and the flow rate is consistent, the alcohol material is switched, the stable operation of the system is maintained after the material switching is finished, and the primary cleaning of the system by the alcohol solution is finished;
and step 3: increasing the operation flow rate of the system to F2, keeping the COD concentration of the fed alcohol solution unchanged, increasing the flow rate of cleaning water and the flow rate of alcohol, increasing the preheating temperature of the cleaning water, closing an inlet pipeline control valve V109 of a first electric heater, opening an inlet pipeline control valve V106 of a second electric heater, opening an outlet pipeline control valve V104 and a pipeline control valve V105 of the second electric heater, switching the second electric heater to heat the cleaning water with the flow rate of F2 to enable the cleaning water to reach the normal preheating temperature T1' of the material, and finishing the secondary cleaning of the system by the alcohol solution;
and 4, step 4: increasing the operation flow rate of the system to F3, keeping the COD concentration of the fed alcohol solution unchanged, increasing the flow rate of the cleaning water and the flow rate of the alcohol, keeping the temperature of the alcohol solution entering the system unchanged, and increasing the preheating temperature of the cleaning water, at the moment, closing the cleaning water control valve V106, opening the inlet pipeline control valve V109 and the outlet pipeline control valve V102 and V103 of the second electric heater, so that the first electric heater and the second electric heater are used in series, and the cleaning water with the flow rate of F3 is heated to the normal preheating temperature T1' of the material, thereby completing the three-stage cleaning of the system by the alcohol solution;
and 5: after the third-stage cleaning is finished, if the system is cleaned to meet the requirement, executing the step 6; otherwise, executing step 7;
step 6: closing all control valves of a cleaning water pipeline, closing a cleaning water pump, a first electric heater and a second electric heater, opening a material pipeline control valve V110 and a first electric heater bypass material control valve V107, and switching the feeding of the alcohol solution into the material to be processed so that the system recovers the normal operation process of processing the material;
and 7: and (3) closing the alcohol pipeline control valve V108, closing the alcohol metering pump, stopping the entry of the alcohol, only adopting cleaning water, heating the cleaning water to the subcritical temperature in a mode of serially connecting a first electric heater and a second electric heater, carrying out four-stage cleaning on the system by using the cleaning water, and returning to the step 6 after the cleaning is finished.
Compared with the prior art, the invention has the following beneficial effects:
the supercritical water oxidation system of high-concentration and high-salinity organic hazardous waste, organic wastewater, municipal sludge, industrial sludge and the like is separated from an electric heater during normal operation, the system is supplemented with heat by adopting a way of supplementing an alcohol auxiliary agent when the temperature of the system changes, the alcohol auxiliary agent is used as an organic fuel, and a large amount of heat released in the reaction process can improve the reaction temperature of the system, so that the problems of crystallization and deposition in the electric heater and system blockage caused finally when the electric heater is used for supplementing heat to the high-salinity wastewater or the supercritical water oxidation system containing solid materials are solved.
Further, when the system normally processes high salt content or solid content materials for a period of time, the equipment such as the preheater, the reactor and the like and the transportation pipeline in the system can cause the equipment to be blocked due to continuous precipitation, crystallization and deposition of inorganic salt or continuous deposition and accumulation of insoluble solid particles, and finally the system is forced to be shut down. The invention discloses an on-line cleaning method for a supercritical water oxidation system, which can periodically carry out on-line cleaning on the system during the normal operation period of the system, continuously increase the operation flow of the system by switching alcohol solutions with the same concentration as materials, carry out three-stage cleaning on the system, and take away insoluble deposited solids and precipitated inorganic salts in a heat exchanger, a reactor and a conveying pipeline in the cleaning process by adopting the alcohol solutions, thereby greatly reducing the feasibility of blocking the system under the condition of maintaining the normal operation of the system without shutdown, and improving the reliability of the supercritical water oxidation system for treating high-salt-content materials or solid-content materials.
Furthermore, the system also provides a fourth-stage cleaning method adopting high-flow subcritical water for cleaning, if the system is blocked and is difficult to completely clean by adopting alcohol solution in normal operation, the system can be cleaned by adopting high-flow subcritical water, and under the subcritical condition, subcritical water with high solubility and high flow rate can dissolve and take away inorganic salt which is difficult to clean, so that shutdown cleaning of the system is avoided, and the reliability of normal operation of the system is ensured by adopting the fourth-stage cleaning measure.
Furthermore, the supercritical water oxidation system disclosed by the invention adopts two electric heaters with different powers, and the two electric heaters are heated separately during starting, so that the starting time of the system is shortened; when the system is cleaned by adopting different flow rates, the two electric heaters with different powers can be used independently or in series, so that the normal operation of the system is ensured, the energy in the system is comprehensively utilized, the system energy is saved, the system operation cost is reduced, and the system economy is improved.
[ description of the drawings ]
FIG. 1 is a schematic view of a first reaction system of the present invention.
In the figure: 1-material pretreatment device; 2-a material pump; 3-a mixer; 4-a heat exchanger; 5-a first electric heater; 6-supercritical water oxidation reactor; 7-a depressurization unit; 8-a water outlet storage tank; 9-cleaning the water tank; 10-cleaning a water pump; 11-a second electric heater; 12-a water distribution tank; 13-alcohol storage tank; 14-alcohol metering pump; 15-oxygen unit.
[ detailed description ] embodiments
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments, and are not intended to limit the scope of the present disclosure. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Various structural schematics according to the disclosed embodiments of the invention are shown in the drawings. The figures are not drawn to scale, wherein certain details are exaggerated and possibly omitted for clarity of presentation. The shapes of various regions, layers and their relative sizes and positional relationships shown in the drawings are merely exemplary, and deviations may occur in practice due to manufacturing tolerances or technical limitations, and a person skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions, according to actual needs.
In the context of the present disclosure, when a layer/element is referred to as being "on" another layer/element, it can be directly on the other layer/element or intervening layers/elements may be present. In addition, if a layer/element is "on" another layer/element in one orientation, then that layer/element may be "under" the other layer/element when the orientation is reversed.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, the on-line cleaning system based on the supercritical water oxidation technology of the present invention includes a material pretreatment unit, an oxygen unit, a cleaning water unit, an alcohol unit, a supercritical water oxidation reaction and a subsequent unit.
In this system, the connection of the devices is as follows:
the material pretreatment unit comprises a material pretreatment device 1, a material pump 2, a mixer 3, a heat exchanger 4 and a first electric heater 5. The outlet of the material pretreatment device 1 is connected with the inlet of a material pump 2, the outlet of the material pump 2 is connected with the inlet of a mixer 3, the outlet of the mixer 3 is connected with the inlet of an inner tube of a heat exchanger 4, and the outlet of the inner tube of the heat exchanger 4 is connected with the inlet of a first electric heater 5. Wherein, the outlet pipeline of the material pretreatment device 1 is provided with a material control valve V110, the inlet and outlet pipelines of the first electric heater 5 are provided with material control valves V103 and V104, and the bypass pipeline of the first electric heater 5 is provided with a material control valve V107.
The alcohol unit comprises an alcohol storage tank 13 and an alcohol metering pump 14. The outlet of the alcohol storage tank 13 is connected with the inlet of an alcohol metering pump 14, the outlet of the alcohol metering pump 14 is connected with the inlet of the mixer 3, the outlet of the mixer 3 is connected with the inner pipe of the inlet of the heat exchanger 4, and the outlet of the alcohol metering pump 14 is provided with an alcohol control valve V108.
The washing water unit comprises a washing water tank 9, a washing water pump 10, a second electric heater 11 and a water distribution tank 12. The outlet of the cleaning water tank 9 is connected with the inlet of a cleaning water pump 10, the outlet of the cleaning water pump 10 is connected with the inlet of a second electric heater 11, the outlet of the second electric heater 11 is connected with the inlet of a water distribution tank 12, and the outlet of the water distribution tank 12 is connected with the inlet of a material pump 2. Wherein, the outlet pipeline of the washing water pump 10 is provided with washing water control valves V101 and V109. According to the operation condition, the outlet of the cleaning water pump 10 can also be connected with the inlet of the first electric heater 5, and the outlet of the first electric heater 5 is connected with the inlet of the water distribution tank 12; according to the operation condition, the outlet of the second electric heater 11 can be connected with the inlet of the first electric heater 5, and the outlet of the first electric heater 5 is connected with the outlet of the water distribution tank 12. Wherein the connection lines of the first electric heater 5 and the second electric heater 11 are provided with cleaning water control valves V102, V105, V106.
The oxygen unit 15 comprises an oxygen supply line. The supercritical water oxidation reaction and subsequent units comprise a supercritical water oxidation reactor 6, a pressure reduction unit 7 and a water outlet storage tank 8. The export of first electric heater 5 links to each other with 6 imports of supercritical water oxidation reactor, and the 15 exports of oxygen unit link to each other with 6 imports of supercritical water oxidation reactor, and 6 exports of supercritical water oxidation reactor link to each other with 4 outer tube intakes of heat exchanger, and 4 outer tube exports of heat exchanger link to each other with 7 imports of step-down unit, and 7 exports of step-down unit link to each other with 8 imports of play water storage tank.
In the above scheme, the material pretreatment device 1 includes, but is not limited to, a material stirrer, a material preheating device, a material grinding pump, a material iron remover, and the like according to the properties of the treated materials. The heat exchanger 4 is a double-pipe heat exchanger, and can also be a spiral coil type heat exchanger or a shell-and-tube type heat exchanger. The heating power of the first electric heater 5 is larger than that of the second electric heater 11, and the first electric heater 5 and the second electric heater 11 can also adopt an electromagnetic induction heater and a natural gas furnace heater. The supercritical water oxidation reactor 6 includes, but is not limited to, a tubular reactor, and may also be a tank reactor. The depressurization unit 7 includes, but is not limited to, a capillary pressure reducer, a back pressure valve pressure reducer, a multi-stage valve depressurization. The wash water includes, but is not limited to, tap water, demineralized water, and the like. The alcohol storage tank 13 includes, but is not limited to, pure alcohols such as methanol, ethanol, and isopropanol. The material control valve, the cleaning water control valve and the alcohol control valve comprise but are not limited to a pneumatic control valve and an electric control valve.
The materials treated by the supercritical water oxidation system include, but are not limited to, various high-concentration high-salinity organic hazardous wastes, organic wastewater, municipal sludge, industrial sludge, typical organic pollutants such as alcohols, phenols and the like.
The invention also discloses an online cleaning method based on the system, which mainly comprises the following steps:
1) the supercritical water oxidation system gradually finishes normal starting of the system through water filling, gas exhausting, pressure boosting and temperature rising, wherein the temperature rising process of the system is finished through the first electric heater 5 and the second electric heater 11 when the system is started.
2) After the temperature and pressure of the system are raised, the material control valve V110 is closed, a methanol solution with the same concentration and temperature as the material to be treated is switched, the concentration of the methanol solution is adjusted through matching of the outlet flow of the water distribution tank 12 and the outlet flow of the alcohol metering pump 14, the temperature of the methanol solution is determined through heating the cleaning water by the second electric heater 11, and the temperature of the clear water at the outlet of the water distribution tank is ensured to be the same as the temperature of the material to be treated after passing through the pretreatment device 1. And after the system is switched to the methanol solution, maintaining the stable operation of the system for 20-30 min.
3) When the system switches the materials to be processed to normally operate, closing the cleaning water control valve V101, closing the cleaning water pump 10 and stopping the operation of the cleaning water pipeline; closing an inlet material control valve V103 and an outlet material control valve V104 of the first electric heater 5, opening a bypass material control valve V107 of the first electric heater 5, switching a bypass, preheating the material to be treated by the heat exchanger 4, entering an inlet of the supercritical water oxidation reactor 6 through a bypass of the first electric heater 5, and normally operating the system.
4) After the system normally operates for a period of time, the system is periodically cleaned. Closing a material control valve V110 of an outlet pipeline of the material pretreatment device 1, opening an alcohol control valve V108 of an outlet pipeline of an alcohol metering pump 14, opening the alcohol metering pump 14, simultaneously opening a cleaning water control valve V101 of an outlet pipeline of a cleaning water pump 10, opening the cleaning water pump 10 and a second electric heater 11, switching the materials being treated in the system into a mixed alcohol solution of alcohol and water, and adjusting the opening degrees of the alcohol control valve V108 and the cleaning water control valve V101 to adjust the proportion of the alcohol and the cleaning water so that the Chemical Oxygen Demand (COD) of the alcohol solution is consistent with the concentration of the COD of the materials being treated; by adjusting the heating power of the second electric heater 11, the heating temperature T1 of the cleaning water passing through the second electric heater 11 is consistent with the material temperature T1 'of the material pre-treatment device 1 after preheating, and the feeding flow F1 of the alcohol solution is consistent with the feeding flow F1' of the material during normal operation. Under the condition that the concentration of the alcohol solution is consistent with that of the processed materials, the preheating temperature is consistent, and the flow rate is consistent, the alcohol materials are switched step by step and stably, the system is maintained to operate stably for a certain time after the materials are switched, and the alcohol solution with the normal flow rate is used for carrying out primary cleaning on the system.
5) Based on the step 4), gradually increasing the system operation flow to F2, keeping the COD concentration of the fed alcohol solution unchanged, increasing the flow rate of the cleaning water and the flow rate of the alcohol, in order to ensure that the temperature of the alcohol solution entering the system is kept unchanged, the preheating temperature of the cleaning water needs to be increased, closing the inlet pipeline control valve V109 of the first electric heater 5, opening the inlet pipeline control valve V106 of the second electric heater 11, opening the outlet pipeline control valves V104 and V105 of the second electric heater 11, and switching the high-power second electric heater 11 to heat the cleaning water with the flow rate of F2 to reach the normal preheating temperature T1' of the material, so that the system is cleaned in a secondary mode by using the alcohol solution with relatively large flow rate under the condition of stable operation.
6) Based on the step 5), gradually increasing the system operation flow to F3, at which time the COD concentration of the fed alcohol solution is still kept constant, at which time the flow rate of the cleaning water and the flow rate of the alcohol are further increased, and in order to ensure that the temperature of the alcohol solution entering the system is kept constant, the preheating temperature of the cleaning water needs to be further increased, at which time the cleaning water control valve V106 is closed, the inlet pipeline control valve V109 of the second electric heater 11 is opened, and the outlet pipeline control valves V102 and V103 of the second electric heater 11 are opened, so that the first electric heater 5 and the second electric heater 11 are used in series, the cleaning water with the flow rate of F3 is heated to the normal preheating temperature T1' of the material, and the system is ensured to be cleaned in three stages by using the alcohol solution with a large.
7) After the three-stage cleaning of the system is completed, if the system is cleaned, closing the cleaning water pipeline control valves V101, V102, V103, V104, V105, V106 and V109, closing the cleaning water pump 10, the first electric heater 5 and the second electric heater 11, opening the material pipeline control valve V110 and the first electric heater 5 bypass material control valve V107, and gradually switching the feeding of the alcohol solution to the material to be treated with the normal flow rate, so that the system recovers the normal operation process of treating the material.
8) After the three-stage cleaning of the system is finished, if the crystal salt remained in the pipeline needs to be further cleaned, the alcohol pipeline control valve V108 is closed, the alcohol metering pump 14 is closed, the entry of alcohol is stopped, only large-flow clean water is adopted, a mode that the first electric heater 5 and the second electric heater 11 are connected in series is adopted, large-flow cleaning water is heated to subcritical temperature, the system is cleaned in four stages by using large-flow pure cleaning water, and after the cleaning is finished, the normal operation material is switched according to the steps in 6).
Example (b):
in this embodiment, the supercritical water oxidation technology is used to treat municipal sludge, and methanol is used as an alcohol auxiliary agent for example, and the on-line cleaning method of the supercritical water oxidation system is described in detail as follows:
1) firstly, water in a cleaning water tank is extracted by a cleaning water pump 10 to replenish water for each storage tank in the system, so that the liquid level in the storage tank of the system reaches the liquid level in normal operation, then the whole system is flushed, when fluid is detected in a water outlet storage tank 8, the water filling of the system is completed, and when the system operates for 5-10 min, whether a leakage point exists in the system is checked. Then exhaust whole system, after the exhaust is accomplished, step up whole system through the pressure reduction means among the governing system, when the outlet pressure of supercritical water oxidation reactor 6 risees to 25 ~ 26MPa, the system is promoted voltage and is accomplished. And then heating the supercritical water oxidation reaction system by the first electric heater 5 at a heating rate of 50-60 ℃/h, heating the cleaning water unit by the second electric heater 11 at a heating rate of 20-30 ℃/h, when the outlet temperature of the reactor reaches 580-590 ℃, and when the outlet temperature of the water distribution tank 12 reaches the outlet temperature of the municipal sludge after passing through the pretreatment device 1 during normal operation of the system, completing the heating of the system.
2) After the system is heated and pressurized, the material control valve V110 is closed, the methanol solution with the same concentration and temperature as the urban sludge to be treated is switched firstly, the concentration of the methanol solution is ensured to be the same as the concentration of the urban sludge to be treated by adjusting the outlet flow of the water distribution tank 12 and the outlet flow of the alcohol metering pump 14, the temperature of the methanol solution is ensured to be the same as the temperature of the urban sludge to be treated by heating the cleaning water by the second electric heater 11, and the temperature of the clear water at the outlet of the water distribution tank 12 is ensured to be the same as the temperature. And after the system is switched to the methanol solution, maintaining the stable operation of the system for 20-30 min.
3) Then switching to-be-treated municipal sludge, opening a material control valve V110, closing a cleaning water control valve V101, closing a cleaning water pump 10, closing a second electric heater 11, and stopping the operation of a cleaning water pipeline; closing the alcohol control valve V108 and closing the alcohol metering pump 14; closing an inlet material control valve V103 and an outlet material control valve V104 of the first electric heater 5, opening a bypass material control valve V107 of the first electric heater 5, switching a bypass, preheating the municipal sludge to be treated by the heat exchanger 4, entering an inlet of the supercritical water oxidation reactor 6 through a bypass of the first electric heater 5, and normally operating the system.
4) And after the system normally operates for 3-5 days, periodically cleaning the system for treating the municipal sludge by adopting a methanol solution. Closing a material control valve V110 of an outlet pipeline of the material pretreatment device 1, opening an alcohol control valve V108 of an outlet pipeline of an alcohol metering pump 14, opening the alcohol metering pump 14, simultaneously opening a cleaning water control valve V101 of an outlet pipeline of a cleaning water pump 10, opening the cleaning water pump 10 and a second electric heater 11, switching the municipal sludge being treated in the system into a mixed methanol solution of methanol and water, and adjusting the proportion of the methanol and the cleaning water by adjusting the opening degrees of the alcohol control valve V108 and the cleaning water control valve V101 so that the Chemical Oxygen Demand (COD) of the methanol solution is consistent with the COD concentration of the material being treated; by adjusting the heating power of the second electric heater 11, the heating temperature T1 of the cleaning water passing through the second electric heater 11 is consistent with the temperature T1 'of the preheated municipal sludge in the material pretreatment device 1, and the feeding flow F1 of the methanol solution is ensured to be consistent with the feeding flow F1' of the municipal sludge in normal operation. Under the condition that the concentration of the methanol solution is consistent with that of the urban sludge to be treated, the preheating temperature is consistent and the flow rate is consistent, the methanol material is switched step by step and stably, the system is maintained to operate stably for a certain time after the methanol solution is switched, and the methanol solution with normal flow rate is used for carrying out primary cleaning on the system.
5) Based on the step 4), gradually increasing the operation flow of the methanol solution of the system to F2, keeping the COD concentration of the fed methanol solution unchanged, increasing the flow of cleaning water and the flow of methanol, in order to ensure that the temperature of the methanol solution fed into the system is kept unchanged, increasing the preheating temperature of the cleaning water, closing an inlet pipeline control valve V109 of a first electric heater 5, opening an inlet pipeline control valve V106 of a second electric heater 11, opening outlet pipeline control valves V104 and V105 of the second electric heater 11, switching a high-power second electric heater 11 to heat the cleaning water with the flow of F2 to reach the normal preheating temperature T1' of the municipal sludge, and enabling the system to carry out secondary cleaning on the system by using the methanol solution with relatively large flow under the condition of stable operation.
6) Based on the step 4), further increasing the operation flow rate of the methanol solution of the system to F3, and at the same time, still keeping the COD concentration of the fed methanol solution unchanged, at the same time, further increasing the flow rate of the cleaning water and the flow rate of the methanol, and in order to ensure that the temperature of the methanol solution fed into the system is kept unchanged, further increasing the preheating temperature of the cleaning water, at the same time, closing the cleaning water control valve V106, opening the inlet pipeline control valve V109 of the second electric heater 11, and opening the outlet pipeline control valves V102 and V103 of the second electric heater 11, so that the first electric heater 5 and the second electric heater 11 are used in series, the cleaning water with the flow rate of F3 is heated to the normal preheating temperature T1' of the municipal sludge, and the system is ensured to be cleaned in three stages by using the methanol solution.
7) After the three-stage cleaning of the system is finished, if the system is cleaned, closing the cleaning water pipeline control valves V101, V102, V103, V104, V105, V106 and V109, closing the cleaning water pump 10, the first electric heater 5 and the second electric heater 11, opening the material pipeline control valve V110 and the first electric heater 5 bypass material control valve V107, and gradually switching the feeding of the methanol solution into the material to be treated with the normal flow rate, so that the system recovers the normal operation process of treating the municipal sludge.
8) After the three-stage cleaning of the system is finished, if the crystal salt remained in the pipeline needs to be further cleaned, closing the alcohol pipeline control valve V108, closing the alcohol metering pump 14, stopping the methanol solution from entering, only adopting large-flow clean water, adopting a mode that the first electric heater 5 and the second electric heater 11 are connected in series for use, heating the large-flow cleaning water to the subcritical temperature of 200-300 ℃, carrying out four-stage cleaning on the system by utilizing the large-flow pure cleaning water, and after the cleaning is finished, switching to normal operation materials according to the steps in 6).
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. An online cleaning system based on supercritical water oxidation technology, which is characterized by comprising:
the device comprises a material pretreatment device (1), wherein an outlet of the material pretreatment device (1) is sequentially connected with a material pump (2), a mixer (3), a heat exchanger (4) inner pipe and a first electric heater (5); the outlet of the first electric heater (5) is divided into two paths, one path is connected with the inlet of the supercritical water oxidation reactor (6), and the other path is connected with the inlet of the water distribution tank (12);
the outlet of the cleaning water tank (9) is connected with a cleaning water pump (10), the outlet of the cleaning water pump (10) is divided into two paths, and the two paths are respectively connected to the inlets of the first electric heater (5) and the second electric heater (11) for connection; the outlet of the first electric heater (5) is divided into two paths, one path is connected to the inlet of the supercritical water oxidation reactor (6), and the other path is connected to the inlet of the water distribution tank (12); the outlet of the second electric heater (11) is also divided into two paths, one path is connected to the inlet of the first electric heater (5), and the other path is connected with the inlet of the water distribution tank (12); the outlet of the water distribution tank (12) is connected to the inlet of the material pump (2);
an outlet of the alcohol storage tank (13) is connected with an inlet of an alcohol metering pump (14), and an outlet of the alcohol metering pump (14) is connected with the other inlet of the mixer (3);
an outlet of the oxygen unit (15) is connected to an inlet of the supercritical water oxidation reactor (6).
2. The on-line cleaning system based on supercritical water oxidation technology of claim 1, characterized in that the outlet of the mixer (3) is connected with the inlet of the inner tube of the heat exchanger (4), the outlet of the inner tube of the heat exchanger (4) is divided into two paths, one path is connected with the inlet of the first electric heater (5), and the other path is connected with the inlet of the supercritical water oxidation reactor (6); the outlet of the supercritical water oxidation reactor (6) is connected with the inlet of the outer pipe of the heat exchanger (4), the outlet of the outer pipe of the heat exchanger (4) is connected with the pressure reduction unit (7), and the outlet of the pressure reduction unit (7) is connected with the water outlet storage tank (8).
3. The on-line cleaning system based on supercritical water oxidation technology of claim 1, characterized in that the material pretreatment device (1) comprises a material stirrer, a material preheating, a material grinding pump and a material de-ironing separator.
4. The on-line cleaning system based on supercritical water oxidation technology of claim 1, characterized in that the heat exchanger (4) is a double pipe heat exchanger, a spiral coil heat exchanger or a shell and tube heat exchanger.
5. The on-line cleaning system based on supercritical water oxidation technology of claim 1, characterized in that the heating power of the first electric heater (5) is larger than the heating power of the second electric heater (11), and the first electric heater (5) and the second electric heater (11) adopt electric heaters, electromagnetic induction heaters or natural gas furnace heaters.
6. The on-line cleaning system based on supercritical water oxidation technology of claim 1, characterized in that supercritical water oxidation reactor (6) comprises a tubular reactor or a tank reactor.
7. The on-line cleaning system based on supercritical water oxidation technology of claim 1, characterized in that the depressurization unit (7) comprises a capillary pressure reducer, a backpressure valve pressure reducer or a multi-stage valve depressurization.
8. The on-line cleaning system based on supercritical water oxidation technology of claim 1 is characterized in that tap water, softened water or demineralized water is in the cleaning water tank (9), and methanol, ethanol or isopropanol is in the fuel storage tank (13).
9. A cleaning method based on supercritical water oxidation technology using the system of claim 1, characterized by comprising the following steps:
step 1: closing a material control valve V110 of an outlet pipeline of the material pretreatment device (1), opening an alcohol control valve V108 of an outlet pipeline of an alcohol metering pump (14), opening the alcohol metering pump (14), simultaneously opening a cleaning water control valve V101 of an outlet pipeline of a cleaning water pump (10), opening the cleaning water pump (10) and a second electric heater (11), switching the materials into a mixed alcohol solution of alcohol and water, and adjusting the opening degrees of the alcohol control valve V108 and the cleaning water control valve V101 to adjust the proportion of the alcohol and the cleaning water so that the Chemical Oxygen Demand (COD) of the alcohol solution is consistent with the COD concentration of the materials being treated;
step 2: adjusting the heating power of the second electric heater (11) to make the heating temperature T1 of the cleaning water passing through the second electric heater (11) consistent with the material temperature T1 'after preheating in the material pretreatment device (1), and make the feeding flow rate F1 of the alcohol solution consistent with the feeding flow rate F1' when the material normally runs; under the conditions that the concentration of the alcohol solution is consistent with that of the processed material, the preheating temperature is consistent, and the flow rate is consistent, the alcohol material is switched, the stable operation of the system is maintained after the material switching is finished, and the primary cleaning of the system by the alcohol solution is finished;
and step 3: increasing the operation flow rate of the system to F2, keeping the COD concentration of the fed alcohol solution unchanged, increasing the flow rate of cleaning water and the flow rate of alcohol, increasing the preheating temperature of the cleaning water, closing an inlet pipeline control valve V109 of a first electric heater (5), opening an inlet pipeline control valve V106 of a second electric heater (11), opening an outlet pipeline control valve V104 and a pipeline control valve V105 of the second electric heater (11), switching the second electric heater (11) to heat the cleaning water with the flow rate of F2 to enable the cleaning water to reach the normal preheating temperature T1' of the material, and finishing the secondary cleaning of the system by the alcohol solution;
and 4, step 4: increasing the operation flow rate of the system to F3, keeping the COD concentration of the fed alcohol solution unchanged, increasing the flow rate of the cleaning water and the flow rate of the alcohol, keeping the temperature of the alcohol solution entering the system unchanged, and increasing the preheating temperature of the cleaning water, closing the cleaning water control valve V106 at the moment, opening an inlet pipeline control valve V109 of a second electric heater (11), and opening an outlet pipeline control valve V102 and a pipeline control valve V103 of the second electric heater (11), so that the first electric heater (5) and the second electric heater (11) are used in series, and the cleaning water with the flow rate of F3 is heated to the normal preheating temperature T1' of the materials, and the alcohol solution is used for carrying out three-stage cleaning on the system;
and 5: after the third-stage cleaning is finished, if the system is cleaned to meet the requirement, executing the step 6; otherwise, executing step 7;
step 6: closing all control valves of a cleaning water pipeline, closing a cleaning water pump (10), a first electric heater (5) and a second electric heater (11), opening a material pipeline control valve V110 and a bypass material control valve V107 of the first electric heater (5), and switching alcohol solution feeding into a material to be processed so that the system recovers the normal operation process of processing the material;
and 7: and (3) closing the alcohol pipeline control valve V108, closing the alcohol metering pump (14), stopping the entry of the alcohol, only adopting cleaning water, heating the cleaning water to the subcritical temperature in a mode of serially connecting the first electric heater (5) and the second electric heater (11), carrying out four-stage cleaning on the system by using the cleaning water, and returning to the step 6 after the cleaning is finished.
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