CN110803753B - Starting system and method based on supercritical water oxidation technology - Google Patents

Starting system and method based on supercritical water oxidation technology Download PDF

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Publication number
CN110803753B
CN110803753B CN201910969357.3A CN201910969357A CN110803753B CN 110803753 B CN110803753 B CN 110803753B CN 201910969357 A CN201910969357 A CN 201910969357A CN 110803753 B CN110803753 B CN 110803753B
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water
pressure
starting
fuel
electric heater
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CN110803753A (en
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王树众
李建娜
宋文瀚
李艳辉
张熠姝
杨健乔
徐海涛
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Xian Jiaotong University
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Xian Jiaotong University
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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
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C02F2101/32—Hydrocarbons, e.g. oil
    • 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
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/322—Volatile compounds, e.g. benzene
    • 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
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a starting system and a starting method based on a supercritical water oxidation technology. The power of the electric heater required by the temperature rise process of the system is reduced by adopting small-flow starting in the starting process of the supercritical water oxidation system. Meanwhile, in the starting process of the system, the alcohol fuel with the same material concentration as that in normal operation is switched firstly, the system is enabled to reach a stable operation state, the electric heater is bypassed, then the material to be treated is switched to pass through the bypass, and the reaction temperature is controlled by adjusting the concentration of the added alcohol fuel, so that the problem that the electric heating pipe is blocked due to coking, carbon deposition, salt crystallization and deposition, solid particle deposition and the like when the material directly passes through the electric heater is avoided, and meanwhile, the alcohol addition can generate a co-oxidation reaction with the material, and the supercritical water oxidation degradation effect of the material is enhanced.

Description

Starting system and method based on supercritical water oxidation technology
[ 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 a starting system and method based on a supercritical water oxidation technology.
[ background of the invention ]
Dangerous waste generated in the current high-pollution chemical industry has corrosivity, toxicity, inflammability, reactivity or infectivity, according to incomplete statistics, in 2016, the yield of dangerous waste reaches 5347 ten thousand tons, and 1153 thousand tons of dangerous waste is still in a storage state, actually, enterprises keep the reported yield for avoiding high treatment cost of dangerous waste, the actual yield of dangerous waste exceeds 8000 thousand tons, and the actual treatment proportion of the dangerous waste enterprises is only 25%. Waste water and sludge caused by hazardous waste in the environment contain halogen, sulfur, nitrogen, heavy metal, aliphatic and aromatic pollutants and the like which are difficult to degrade, and if the waste water and the sludge are not efficiently treated, the waste water and the sludge become important factors causing water source, soil, ocean pollution and other outstanding environmental problems, and the health and the safety of people are seriously threatened.
At present, hazardous wastes are treated by a common incineration method, the volume reduction and the decrement of the hazardous wastes can be realized by the incineration method, but the equipment investment amount is large, and the operation cost is high (2000-5000 yuan/ton); in addition, secondary pollution such as SOx, NOx, PM2.5, dioxin, etc. may be generated by the incineration method, and the generated fly ash needs to be buried, resulting in an adjacency effect. Therefore, the great generation of hazardous wastes and the difficulty in treatment are outstanding contradictions in the present stage, and the realization of the efficient, thorough and harmless treatment is an urgent need for building good ecological environment and realizing sustainable development.
Supercritical water oxidation (SCWO) technology is a promising technology for treating hazardous waste. The technology utilizes the special property of water in a supercritical state (the temperature is more than 374.1 ℃ and the pressure is more than 22.1MPa), supercritical water is used as a reaction medium of organic matters and oxygen to carry out homogeneous and rapid oxidation reaction, the organic matters are thoroughly oxidized and decomposed, and C, H and N elements in the organic matters are respectively converted into harmless CO2、H2O、N2The heterocyclic atoms Cl, S and P are respectively converted into corresponding inorganic acids or salts, and heavy metals are mineralized into stable solid phases to be stored in residues to realize stabilization.
However, when supercritical water oxidation technology is used for treating high-salt or inherent organic waste, some problems exist:
(1) when high-salinity organic waste is treated by the supercritical water oxidation system, since supercritical water has a special property of low dielectric constant, water becomes a nonpolar solvent in a supercritical state, and the solubility of inorganic substances in the supercritical water is rapidly reduced. In the supercritical water oxidation system, the whole system is generally preheated by the electric heater, materials are switched in the system starting process or the system normally runs, if high-salt organic wastes directly pass through the electric heater, inorganic salt is continuously crystallized and precipitated in the electric heater in the heating process, finally deposits and blocks a heating pipeline in the electric heater, normal starting of the whole system is influenced, and system faults are caused.
(2) If the supercritical water oxidation system is used for treating the organic waste containing the insoluble inert solid particles, when the materials are switched or the system normally operates in the starting process, due to the existence of the insoluble solid particles, when the organic waste is electrically heated, the insoluble solid particles are continuously deposited in the electric heating pipe due to low flow velocity, and the heating efficiency of the electric heater is deteriorated.
(3) If the supercritical water oxidation system is used for treating the municipal/industrial sludge, when the materials are switched in the starting process, due to the high viscosity of the municipal/industrial sludge, the sludge has poor flow property in the heating process and is easy to block in an electric heating pipeline when passing through an electric heater, and in addition, due to the fact that the sludge contains a large amount of protein, the sludge is easy to coke in the continuous heating process, coke is generated and accumulated on the inner pipe wall of the electric heating pipe, the heating efficiency is deteriorated, and the pipeline can be blocked in serious cases.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provide a starting system and a starting method based on a supercritical water oxidation technology, which can effectively solve the problems of electric heater coking, salt deposition, blockage and the like in the starting and normal operation processes of a system when high-salt or inherent organic waste is treated by the supercritical water oxidation system and can improve the safety and reliability of the system.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a start-up system based on supercritical water oxidation technology includes:
the water supply unit comprises a water storage tank, a starting water supply pump, a first electric heater and a water distribution tank which are connected in sequence;
the material pretreatment unit comprises a material blending tank, a high-pressure material pump, a preheater and a second electric heater which are sequentially connected; the high-pressure material pump is connected with the second electric heater through an inner pipe of the preheater; the outlet of the water distribution tank is connected to the inlet of the high-pressure material pump;
the inlet of the supercritical water oxidation reactor is connected with the outlet of the second electric heater; the supercritical water oxidation reactor is connected with an inlet of a heat exchange coil in the batching tank through an outer pipe of the preheater;
the outlet of the heat exchange coil is sequentially connected with the pressure reduction unit and the water outlet storage tank;
and the fuel supply unit comprises a fuel storage tank and a fuel metering pump which are sequentially connected, and an outlet of the fuel metering pump is connected with the material pretreatment unit.
The invention further improves the following steps:
a mixer is arranged between the high-pressure material pump and the preheater, the fuel storage tank is connected with the mixer through a fuel metering pump, and the mixer mixes the materials and the fuel and then sends the mixed materials and the fuel into an inner pipe of the preheater.
A mixer is arranged between the material blending tank and the high-pressure material pump, the fuel storage tank is connected with the mixer through a fuel metering pump, and the mixer mixes the materials and the fuel and then sends the mixed materials and the fuel into an inner pipe of the preheater through the high-pressure material pump; the water distribution tank is also connected with a constant pressure device.
Still include oxygen supply unit, oxygen supply unit includes high-pressure oxygen buffer tank, and the export of high-pressure oxygen buffer tank links to each other with supercritical water oxidation reactor's import.
A stirrer is arranged in the material blending tank, and the stirrer adopts a frame type stirrer, a frame type impeller-added stirrer or a helical ribbon type stirrer; the supercritical water oxidation reactor adopts a tubular or kettle type reactor and is provided with a plurality of temperature measuring points; the pressure reduction unit adopts a capillary tube pressure reducer, a back pressure valve pressure reducer or a multi-stage valve for pressure reduction.
The preheater includes a double pipe heat exchanger, a shell and tube heat exchanger or a spiral coil heat exchanger.
The first electric heater and the second electric heater comprise electric heaters, electromagnetic induction heaters or natural gas stove heaters.
Tap water, softened water or desalted water is arranged in the water storage tank; the fuel in the fuel storage tank is methanol, ethanol or isopropanol.
A starting method based on supercritical water oxidation technology comprises the following steps:
step 1: the method comprises the following steps of (1) filling materials into a material preparation tank in advance; filling fuel into a fuel storage tank, and injecting water into a water distribution tank;
step 2: starting a starting water feeding pump to fill water, wherein the flow of the water during starting is half of the material flow during normal operation, and when the liquid level in the water outlet storage tank is detected to be increased, the water filling is finished;
and step 3: the pressure reduction unit is used for gradually increasing the pressure, so that the pressure behind the supercritical water oxidation reactor can be maintained in a supercritical state, and the pressure increase is completed;
and 4, step 4: carrying out gradual temperature rise; starting the first electric heater to enable the temperature rise rate of the outlet temperature TIC 1 of the water distribution tank to be 20-30 ℃/h until the outlet temperature TIC 1 of the water distribution tank is maintained at the outlet temperature of the materials in the material distribution tank after the materials are preheated by the heat exchange coil pipe during normal operation;
and 5: starting a second electric heater to enable the temperature rise rate of the wall temperature TIC 2 of the supercritical water oxidation reactor to be 50-60 ℃/h until the wall temperature TIC 2 of the supercritical water oxidation reactor is maintained at the reaction temperature during normal operation;
step 6: in the temperature rising process of the system, if the material in the material preparation tank is preheated by the hot fluid at the outlet of the supercritical water oxidation reactor and reaches the outlet temperature after the heat exchange coil is preheated, bypassing the hot fluid;
and 7: when the outlet temperature TIC 1 of the water distribution tank and the wall temperature TIC 2 of the supercritical water oxidation reactor reach preset temperatures, finishing heating and switching materials; the specific method for switching the materials is as follows:
closing an outlet valve of the material blending tank, and closing the second electric heater; injecting fuel through a fuel metering pump, enabling the mixing concentration of the fuel and water in the mixer 13 to be consistent with the material concentration of the system in normal operation, and keeping the operation for 5-20 min, so that the inlet temperature of the supercritical water oxidation reactor is reduced;
and 8: injecting oxygen into the system through a high-pressure oxygen buffer tank, and keeping the operation for 20-30 min;
and step 9: gradually increasing the flow of the starting water feeding pump, the fuel metering pump and the high-pressure material pump to a normal flow, maintaining normal operation for 20-30 min, bypassing the second electric heater after the wall temperature of the second electric heater is reduced, and enabling the fuel to enter an inlet of the supercritical water oxidation reactor through a bypass;
step 10: and opening an outlet valve of the material blending tank, closing the first electric heater, stopping starting the water feed pump, closing the outlet valve of the water feed pump, gradually switching the materials to be processed according to the normal operation flow, and finishing the system starting.
The further improvement is that:
replacing the step 3 with:
and step 3: the pressure reduction unit is used for gradually increasing the pressure, so that the pressure behind the supercritical water oxidation reactor can be maintained in a supercritical state, and the pressure increase is completed; and then the water distribution tank is subjected to constant pressure through a constant pressure device.
Compared with the prior art, the invention has the following beneficial effects:
in the starting process of the system, half of the flow of the materials in normal operation is adopted to fill and heat the whole supercritical water oxidation system, and because a large specific heat area exists near the critical point of water, the enthalpy of the water is sharply increased along with the slight change of the temperature, and if the system is heated by adopting the normal operation flow, the power of a required electric heater is very high, so that the operation cost in the starting process of the system is high. Therefore, the starting method adopts small-flow temperature rise, so that the power loss in the temperature rise process of the system is saved, the running cost of the system is reduced, meanwhile, the starting time of the system is shortened due to small-flow starting, and the efficiency is improved.
Furthermore, when the materials are switched during the starting process of the supercritical water oxidation system, the alcohol fuel with the same concentration as the materials is firstly adopted for switching the materials, so that the system reaches a normal and stable operation state, high-salinity wastewater, inherent organic waste or sludge is prevented from directly passing through a heating pipe in an electric heater during the material switching process, and the problem that the electric heating pipe is blocked due to coking, carbon deposition, salt crystallization and deposition, solid particle deposition and the like in the electric heater is avoided.
Furthermore, in the normal operation process of the supercritical water oxidation system, the high-salinity wastewater, the wastes containing inherent organisms or the sludge do not pass through the inside of the electric heater but pass through the bypass of the electric heater, and the reaction temperature in the reactor is regulated not by the power of the electric heater but by the addition amount of the alcohol fuel in the normal operation process. On the one hand, supercritical water oxidation follows the free radical reaction mechanism, the production of free radical can be strengthened in the addition of alcohol fuel, through with organic waste co-oxidation reinforcing organic waste's degradation, on the other hand, through the addition control reaction temperature of alcohol, can break away from electric heater completely in system normal operating, guarantee that entire system can not have the material directly to pass through electric heater at start-up and operation in-process, avoided taking place salt crystallization and deposit, solid particle deposit etc. in the electric heater and caused the problem of electric heater jam.
[ description of the drawings ]
FIG. 1 is a schematic diagram of the system configuration of embodiment 1 of the present invention;
fig. 2 is a schematic system configuration diagram according to embodiment 2 of the present invention.
Wherein: 1-a water storage tank; 2-starting a water supply pump; 3-a first electric heater; 4-water distribution tank; 5-a material blending tank; 6-high pressure material pump; 7-a preheater; 8-a second electric heater; 9-supercritical water oxidation reactor; 10-heat exchange coil pipe; 11-a fuel storage tank; 12-fuel metering pump; 13-a mixer; 14-a pressure reduction unit; 15-a water outlet storage tank; 16-a high pressure oxygen buffer tank; 17-constant pressure device.
[ 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:
example 1:
referring to fig. 1, this embodiment takes supercritical water oxidation technology to treat industrial sludge as an example, and describes a starting scheme of a supercritical water oxidation system in detail:
the invention discloses a starting system based on a supercritical water oxidation technology, which comprises a material pretreatment unit, an oxygen supply unit, a water supply unit, a fuel supply unit, a supercritical water oxidation reaction and post-treatment unit. The connection mode of each device is as follows:
the export of material blending tank 5 links to each other with the entry of high-pressure material pump 6, and the export of high-pressure material pump 6 links to each other with the inner tube import of pre-heater 7, and the inner tube export of pre-heater 7 links to each other with the import of second electric heater 8, and the export of second electric heater 8 links to each other with the import of supercritical water oxidation reactor 9.
The oxygen supply unit includes high-pressure oxygen buffer tank 16, and the export of high-pressure oxygen buffer tank 16 links to each other with the import of supercritical water oxidation reactor 9, and the export of supercritical water oxidation reactor 9 links to each other with the outer tube import of pre-heater 7, and the outer tube export of pre-heater 7 links to each other with heat exchange coil 10's import, and heat exchange coil 10's export links to each other with the import of step-down unit 14, and step-down unit 14's export links to each other with the import of play water storage tank 15.
The outlet of the water storage tank 1 is connected with the inlet of the starting water feeding pump 2, the outlet of the starting water feeding pump 2 is connected with the inlet of the first electric heater 3, the outlet of the first electric heater 3 is connected with the inlet of the water distribution tank 4, and the outlet of the water distribution tank 4 is connected with the inlet of the high-pressure material pump 6.
The outlet of the fuel storage tank 11 is connected to the inlet of a fuel metering pump 12, the outlet of the fuel metering pump 12 is connected to the inlet of a mixer 13, and the outlet of the mixer 13 is connected to the inlet of the preheater 7.
In the above scheme, the material blending tank 5 is provided with a stirrer, the stirrer is in the form of a frame stirrer and an impeller, and the stirrer can also be in the form of a helical ribbon stirrer. The preheater 7 includes, but is not limited to, a double pipe heat exchanger, and may be a shell-and-tube heat exchanger, a spiral coil heat exchanger. The first electric heater 3 and the second electric heater 8 include, but are not limited to, electric heaters, and electromagnetic induction heaters and natural gas stove heaters can also be adopted. The supercritical water oxidation reactor 9 includes, but is not limited to, a tubular or tank reactor, wherein the tubular reactor is provided with a plurality of temperature measuring points. The depressurization unit 14 includes, but is not limited to, a capillary tube pressure reducer, a back pressure valve pressure reducer, a multi-stage valve pressure reduction.
The water storage tank 1 includes, but is not limited to, tap water, softened water, demineralized water, etc. The fuel in the fuel tank 11 includes, but is not limited to, alcohol fuel such as methanol, ethanol, isopropanol, etc.
The outlet temperature TIC 1 of the distribution tank 4 is interlocked with the power of the first electric heater 3. The wall temperature TIC 2 of the supercritical water oxidation reactor 9 is linked with the power of the second electric heater 8 and the methanol injection amount.
Materials treated by the supercritical water oxidation system include, but are not limited to, various organic industrial hazardous wastes, high-concentration organic wastewater, municipal sludge, industrial sludge, various organic model compounds and the like.
The starting method based on the supercritical water oxidation technology comprises the following steps:
1) before the system is started, firstly, industrial sludge which is already blended to a certain water content and a certain concentration is loaded into a material blending tank 5, so that the industrial sludge keeps a normal liquid level, and a stirrer is started to stir the sludge in order to avoid the sludge from settling in the sludge blending tank; the fuel storage tank 11 is filled with industrial methanol of 99 wt.% purity to maintain a normal level; the water distribution tank 4 is filled with tap water at a normal level. Then, the tap water in the water storage tank 1 is utilized, the water feeding pump 2 is started to fill the whole system with half of the material flow rate when the system normally operates, when the liquid level is detected to be continuously increased in the water outlet storage tank 15, the water filling of the system is completed, the system is operated for 5-10 min after the water filling is completed, whether leakage points exist in the system is checked, and meanwhile, the whole system is exhausted.
2) Before the system is started, the whole system is gradually boosted by using the voltage reduction unit 14, the system can be gradually boosted according to the pressure boosting gradients of 5MPa, 10MPa, 15MPa and 25MPa, and finally the pressure after the supercritical water oxidation reactor 9 is maintained to be stably maintained at 25MPa +/-0.5 MPa.
3) After the system is filled with water, exhausted and pressurized, the system is gradually heated through electric heating. And starting the first electric heater 3, interlocking the output temperature TIC 1 of the water distribution tank 4 and the power of the first electric heater 3, and controlling the temperature rise rate of the TIC 1 to be 20-30 ℃/h until the output temperature TIC 1 of the water distribution tank 4 is maintained at T1, wherein T1 is the output temperature T1' of the materials in the material distribution tank 5 after being preheated by the heat exchange coil 10 when the system is in normal operation.
4) And simultaneously starting a second electric heater 8, putting the supercritical water oxidation reactor 9 wall temperature TIC 2 and the second electric heater 8 into power linkage, and controlling the temperature rise rate of the TIC 2 to be 50-60 ℃/h until the supercritical water oxidation reactor 9 wall temperature TIC 2 is maintained at T2, wherein T2 is the reaction temperature T2 'when the system normally operates, and can be slightly lower than the reaction temperature T2'.
5) Meanwhile, in the temperature rise process of the system, if the material in the material preparation tank 5 reaches T1' after being preheated by the hot fluid at the outlet of the supercritical water oxidation reactor 9, the hot fluid bypasses the strand of hot fluid and enters a subsequent unit for cooling, so that the continuous rise of the temperature of the material is avoided.
6) And when the temperature measuring point TIC 1 in the system reaches the preset temperature T1 and the temperature measuring point TIC 2 in the system reaches the preset temperature T2, the system is heated, and at the moment, the materials are switched. The methanol solution with the same concentration as the material in normal operation is first switched, and the outlet valve V2 of the material preparation tank 5 is closed. At the moment, the system still runs at half normal flow, and a certain amount of methanol is injected through the fuel metering pump 12, so that COD (chemical oxygen demand) of the methanol and the water in the mixer 13 is consistent with the COD of sludge during normal running of the system, and the heat release amount in the reaction process is equal. But at the moment, the system does not feed oxygen, the normal operation of the methanol solution in the system is maintained for 5-20 min, so that the inlet temperature of the reactor is reduced, the rapid over-temperature of the reactor in the subsequent reaction is avoided, meanwhile, the second electric heater 8 is closed, the flow of the injected alcohols is interlocked with the temperature of the wall temperature TIC 2 of the supercritical water oxidation reactor 9, the reaction temperature of the system is adjusted by the injection amount of the methanol, and the wall temperature of the reactor is controlled.
7) After the temperature of the inlet of the reactor is reduced by 50-60 ℃, oxygen is injected into the system through the high-pressure oxygen buffer tank 16, and the pressure in the high-pressure oxygen buffer tank 16 is at least 0.5MPa higher than the pressure in the reactor. At the moment, the system performs supercritical water oxidation reaction of methanol solution with the same concentration as the sludge to be treated and oxygen, the normal operation of the system is maintained for 20-30 min, the wall temperature TIC 2 of the reactor is controlled by adjusting the injection amount of methanol, and the temperature of the system is maintained to be stable in a certain range.
8) After the system normally operates, the flow of the starting water feeding pump 2, the fuel metering pump 12 and the high-pressure material pump 6 is gradually increased to the normal flow, the normal operation of the system is maintained for 20-30 min, meanwhile, after the wall temperature of the second electric heater 8 is reduced to the appropriate temperature, the second electric heater 8 is bypassed, and the methanol solution enters the inlet of the supercritical water oxidation reactor 9 through the bypass.
9) After the system operates stably according to the normal flow, the outlet valve V2 of the material blending tank 5 is opened, the first electric heater 3 is closed, the water feed pump 2 stops starting, the outlet valve V1 of the water feed pump 2 is closed, the sludge to be treated is gradually switched according to the normal operation flow, and at the moment, the normal starting of the system is completed.
Example 2
As shown in fig. 2, the starting system based on the supercritical water oxidation technology of the present embodiment includes a material pretreatment unit, an oxygen supply unit, a water supply unit, a fuel supply unit, a supercritical water oxidation reaction and a post-treatment unit.
The difference from example 1 is that:
the fuel supply unit includes a fuel storage tank 11, a fuel metering pump 12, and a mixer 13. The outlet of the fuel storage tank 11 is connected with the inlet of the fuel metering pump 12, the outlet of the fuel metering pump 12 is connected with the inlet of the mixer 13, and the outlet of the mixer 13 is connected with the inlet of the high-pressure material pump 6.
The water supply unit comprises a water storage tank 1, a starting water supply pump 2, a first electric heater 3, a water distribution tank 4 and a constant pressure device 17. The outlet of the water storage tank 1 is connected with the inlet of the starting water feeding pump 2, the outlet of the starting water feeding pump 2 is connected with the inlet of the first electric heater 3, the outlet of the first electric heater 3 is connected with the inlet of the water distribution tank 4, the outlet of the water distribution tank 4 is connected with the inlet of the high-pressure material pump 6, and the outlet of the constant pressure device 17 is connected with the inlet of the water distribution tank 4.
The constant pressure device 17 includes, but is not limited to, a nitrogen constant pressure and an air constant pressure.
The remaining devices and their connections are the same as the system described in example 1.
The starting method of the embodiment based on the supercritical water oxidation technology is different from the starting method of the embodiment 1 in that:
in the step 2), after the system gradually increases the pressure and stabilizes at 25MPa +/-0.5 MPa, the pressure of the water distribution tank 4 is regulated by the pressure regulating device 17, so that the alcohol solution is not gasified after being mixed with water in the mixer 13 when the outlet water temperature of the water distribution tank 4 is T1. The rest of the procedure was the same as in example 1.
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 (2)

1. A starting method based on a supercritical water oxidation technology is based on a starting system based on the supercritical water oxidation technology, and the system comprises a water supply unit, a material pretreatment unit, a supercritical water oxidation reactor (9), a heat exchange coil (10) and a fuel supply unit;
the water supply unit comprises a water storage tank (1), a starting water supply pump (2), a first electric heater (3) and a water distribution tank (4) which are connected in sequence;
the material pretreatment unit comprises a material blending tank (5), a high-pressure material pump (6), a preheater (7) and a second electric heater (8) which are connected in sequence; the high-pressure material pump (6) is connected with the second electric heater (8) through an inner pipe of the preheater (7); the outlet of the water distribution tank (4) is connected to the inlet of the high-pressure material pump (6); a mixer (13) is arranged between the high-pressure material pump (6) and the preheater (7), the fuel storage tank (11) is connected with the mixer (13) through a fuel metering pump (12), and the mixer (13) mixes the materials and the fuel and then sends the mixed materials and the fuel into an inner pipe of the preheater (7); the water distribution tank (4) is also connected with a constant pressure device (17); a stirrer is arranged in the material blending tank (5), and the stirrer adopts a frame type stirrer, a frame type impeller-added stirrer or a helical ribbon type stirrer; the supercritical water oxidation reactor (9) adopts a tubular or kettle type reactor and is provided with a plurality of temperature measuring points; the pressure reduction unit (14) adopts a capillary tube pressure reducer, a back pressure valve pressure reducer or a multi-stage valve for pressure reduction;
an inlet of the supercritical water oxidation reactor (9) is connected with an outlet of the second electric heater (8); the supercritical water oxidation reactor (9) is connected with an inlet of a heat exchange coil (10) in the material blending tank (5) through an outer pipe of the preheater (7); the preheater (7) comprises a double-pipe heat exchanger, a shell-and-tube heat exchanger or a spiral coil heat exchanger;
the outlet of the heat exchange coil (10) is sequentially connected with a pressure reduction unit (14) and an effluent storage tank (15);
the fuel supply unit comprises a fuel storage tank (11) and a fuel metering pump (12) which are sequentially connected, and an outlet of the fuel metering pump (12) is connected with the material pretreatment unit; tap water, softened water or desalted water is arranged in the water storage tank (1); the fuel in the fuel storage tank (11) is methanol, ethanol or isopropanol;
characterized in that the method comprises the following steps:
step 1: the materials are filled in the material blending tank (5) in advance; filling fuel into the fuel storage tank (11), and filling water into the water distribution tank (4);
step 2: starting a starting water feeding pump (2) to fill water, wherein the flow of the water during starting is half of the material flow during normal operation, and when the liquid level is detected to increase in a water outlet storage tank (15), the water filling is finished;
and step 3: the pressure reduction unit (14) is utilized to gradually increase the pressure, so that the pressure of the supercritical water oxidation reactor (9) can be maintained in a supercritical state, and the pressure increase is completed;
and 4, step 4: carrying out gradual temperature rise; starting the first electric heater (3) to enable the temperature rising rate of the outlet temperature TIC 1 of the water distribution tank (4) to be 20-30 ℃/h until the outlet temperature TIC 1 of the water distribution tank (4) is maintained at the outlet temperature of the materials in the material preparation tank (5) preheated by the heat exchange coil (10) in normal operation;
and 5: starting a second electric heater (8) to enable the temperature rise rate of the wall temperature TIC 2 of the supercritical water oxidation reactor (9) to be 50-60 ℃/h until the wall temperature TIC 2 of the supercritical water oxidation reactor (9) is maintained at the reaction temperature during normal operation;
step 6: in the temperature rising process of the system, if the material in the material preparation tank (5) is preheated by the hot fluid at the outlet of the supercritical water oxidation reactor (9) and then reaches the outlet temperature after the heat exchange coil (10) is preheated, the hot fluid enters a bypass;
and 7: when the outlet temperature TIC 1 of the water distribution tank (4) and the wall temperature TIC 2 of the supercritical water oxidation reactor (9) reach the preset temperature, finishing heating and switching materials; the specific method for switching the materials is as follows:
closing an outlet valve of the material blending tank (5) and closing the second electric heater (8); injecting fuel through a fuel metering pump (12), enabling the mixing concentration of the fuel and water in a mixer 13 to be consistent with the material concentration of the system in normal operation, and keeping the operation for 5-20 min, so that the inlet temperature of the supercritical water oxidation reactor (9) is reduced;
and 8: injecting oxygen into the system through a high-pressure oxygen buffer tank (16), and keeping the operation for 20-30 min;
and step 9: gradually increasing the flow of the starting water feeding pump (2), the fuel metering pump (12) and the high-pressure material pump (6) to a normal flow, maintaining normal operation for 20-30 min, simultaneously connecting the second electric heater (8) into a bypass after the wall temperature of the second electric heater (8) is reduced, and enabling the fuel to enter an inlet of the supercritical water oxidation reactor (9) through the bypass;
step 10: opening an outlet valve of the material blending tank (5), closing the first electric heater (3), stopping starting the water feeding pump (2), closing the outlet valve for starting the water feeding pump (2), gradually switching the materials to be processed according to the normal operation flow, and finishing the system starting.
2. The starting method based on supercritical water oxidation technology of claim 1, characterized by replacing step 3 with:
and step 3: the pressure reduction unit (14) is utilized to gradually increase the pressure, so that the pressure of the supercritical water oxidation reactor (9) can be maintained in a supercritical state, and the pressure increase is completed; and then the water distribution tank (4) is subjected to constant pressure through a constant pressure device (17).
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