CN219735652U - Supercritical CO2 refrigeration cycle coupling high-salt water evaporation zero-emission system - Google Patents
Supercritical CO2 refrigeration cycle coupling high-salt water evaporation zero-emission system Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
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- 238000005057 refrigeration Methods 0.000 title claims abstract description 37
- 230000008878 coupling Effects 0.000 title claims description 16
- 238000010168 coupling process Methods 0.000 title claims description 16
- 238000005859 coupling reaction Methods 0.000 title claims description 16
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003507 refrigerant Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The utility model discloses a supercritical CO 2 The refrigerating cycle coupled high-salt water evaporating zero-emission system includes high-temperature supercritical CO 2 The heat extraction section, the low-temperature flash evaporation section, the crystallization section, the condensation section, a raw material liquid pump and a raw material liquid tank, wherein raw material liquid in the raw material liquid tank is pumped into the condensation section by the raw material liquid pump to be preheated, and then enters into the high-temperature supercritical CO 2 The heat extraction section heats, then enters the low-temperature flash evaporation section for flash evaporation and cooling, returns to the condensation section for condensation, and simultaneously heats the raw material liquid. The system willThe cold, the heat and the water are highly integrated, cold and heat energy is generated from the self-sales, only the flow water pump consumes electricity in the zero-emission process, a large amount of electric energy is not required to be consumed, high-grade energy is not required to be consumed, and the problems of heat energy waste and high zero-emission technical cost can be well solved; the system has compact structure, energy conservation and high efficiency, and can recycle supercritical CO with higher energy 2 Waste heat resources are used for high-salt water evaporation zero emission, the cost is greatly reduced, and the method is suitable for occasions requiring refrigeration and high-salt wastewater treatment at the same time.
Description
Technical Field
The utility model relates to the technical field of zero emission of high-salt wastewater, in particular to a supercritical CO 2 The refrigeration cycle is coupled with a high-salt water evaporation zero-emission system.
Background
CO 2 Is a natural refrigerant, which is nontoxic and nonflammable, has zero ozone depletion potential and has a global warming potential of 1. In this context, CO with supercritical cycle is used 2 The system is favored in the refrigeration field for its excellent environmental protection characteristics, low flow resistance, and a substantial amount of refrigeration per unit volume. Under the background of carbon peak and carbon neutralization, the carbon emission in the refrigeration industry of China comes from the carbon dioxide emission in the electricity utilization and production processes on one hand and the emission of non-carbon dioxide greenhouse gases such as refrigerants and the like on the other hand. Worldwide, commercial refrigeration is the main body of refrigeration, with the greatest refrigerant discharge (in terms of CO 2 Equivalent calculated), more than 30% of the total refrigerant discharge, if CO is used 2 As a refrigerant, the carbon footprint of a commercial refrigeration system can be reduced to almost zero, so that CO 2 The refrigerator has been used for the first time in the industries of chemical engineering, coal chemical engineering and the like. Supercritical CO 2 With higher energy content at higher temperatures, the efficiency of the overall system can be very high when the heat can be recovered for heating domestic water or similar applications. CO 2 The traditional condenser in the refrigeration system dissipates heat into the atmosphere, resulting in waste of heat energy and thermal pollution of air.
In addition, in the aspect of environmental management, a large amount of high-salt wastewater mainly containing sodium chloride and sodium sulfate can be generated in the production process of many industries such as chemical industry, coal chemical industry, steel, electronics, pharmacy and the like. Along with the strict environmental protection policy, particularly in areas with deficient water resources, how to reasonably treat and utilize the part of sewage or high-salt wastewater with complex components to realize zero emission of wastewater, and has important significance for protecting the surrounding environment and natural water body on which we depend to live, further improving the comprehensive utilization efficiency of water resources and relieving the shortage condition of water resources. Most of the existing zero-emission final processes adopt evaporative crystallization, and a heat source adopts on-site high-grade steam or mechanical compressor steam circulation, wherein the former is high in treatment cost of a zero-emission system due to high steam price; the latter is provided with a compressor, and the processing cost (the power consumption of the compressor is larger and accounts for about 90% of the total system power consumption) and the initial investment are high. The water treatment cost of the method is mostly more than 80 yuan/ton, even more than 150 yuan/ton.
Therefore, the end treatment technology of the high-salt wastewater still has a shortage, and a system and a method for treating the high-salt wastewater with low cost, green and high efficiency are lacked for the use. If the heat source of the high-salt wastewater zero-emission system is taken from on-site CO 2 The supercritical high-temperature high-pressure fluid of the refrigerator not only replaces a condenser of the refrigeration system, but also greatly reduces the running cost of the zero-emission system and enhances the market competitiveness because the coupling system has no external heat source or a large amount of power consumption caused by circulating steam. Meanwhile, the optimization of cold, hot and water systems in the industries is realized, and the efficient and extreme utilization of energy is realized.
Disclosure of Invention
The utility model aims at CO 2 The trend of refrigeration and the difficult problem of high cost of zero discharge treatment of high-salt wastewater in industrial application occasions provide a supercritical CO 2 The refrigeration cycle is coupled with a high-salt water evaporation zero-emission system. Replacing CO with heater of high-salt water zero-emission system 2 And the condenser of the refrigeration system realizes the coupling of refrigeration and a high-salt water evaporation zero-emission system, and reduces energy consumption and carbon emission.
The technical scheme of the utility model is as follows:
supercritical CO 2 The refrigerating cycle coupled high-salt water evaporating zero-emission system includes high-temperature supercritical CO 2 The heat extraction section (I), the low-temperature flash evaporation section (II), the crystallization section (III), the condensation section (IV), a raw material liquid pump and a raw material liquid tank, wherein raw material liquid in the raw material liquid tank is pumped into the condensation section (IV) by the raw material liquid pump to be preheated, and then enters into the high-temperature supercritical CO 2 Heating in the heat extraction section (I), and thenThe mixture enters a low-temperature flash evaporation section (II) for flash evaporation and cooling, and returns to a condensation section (IV) for condensation, and raw material liquid is heated at the same time; wherein: the high temperature supercritical CO 2 The heat extraction section (I) comprises one or more heaters which are connected with supercritical CO through pipelines 2 The refrigeration cycle system is connected; the low-temperature flash evaporation section (II) comprises one or more separators, the upper ends of the heaters are connected with the upper ends of the separators, and the lower ends of the separators are connected with the lower ends of the heaters through circulating pipelines provided with circulating pumps; the crystallization section (III) comprises a discharge pump, a centrifugal machine, a mother liquor pump and a mother liquor tank, wherein one end of the discharge pump is connected with the lower end of the separator, the other end of the discharge pump is connected with the centrifugal machine, the centrifugal machine is connected with a crystal outlet pipeline on one hand, the centrifugal machine is connected with the mother liquor tank through a pipeline on the other hand, and the mother liquor tank is connected with an inlet pipeline of the circulating pump after being connected with the mother liquor pump through a pipeline; the condensing section (IV) comprises a condenser, a raw material liquid preheater and a fresh water pump; the raw material liquid tank is sequentially connected with the raw material liquid preheater and the condenser through a pipeline by a raw material liquid pump and then connected with an inlet pipeline of a circulating pump; the outlet pipeline of the circulating pump is connected with the lower end of the heater; the upper end of the separator is connected with the condenser through a pipeline; the condenser is connected with the raw material liquid preheater and the fresh water pump through fresh water output pipelines.
Supercritical CO as described above 2 In the refrigeration cycle coupling high-salt water evaporation zero-emission system, the high-temperature supercritical CO 2 The heater of the heat extraction section I is a high-temperature corrosion-resistant heater, and the material of the heater can be selected from polyvinyl chloride, polytetrafluoroethylene, polyoxymethylene, polypropylene, titanium alloy and glass fiber reinforced plastic. The number and the number of stages of the heaters can be increased along with the process design, and the number of the heaters is generally not more than 5, and the heaters are connected in parallel or in series.
Supercritical CO as described above 2 In the refrigeration cycle coupling high-salt water evaporation zero-emission system, the separator of the low-temperature flash evaporation section II is a low-temperature separator, and the material of the separator can be selected from polyvinyl chloride, polytetrafluoroethylene, polyoxymethylene, polypropylene, carbon steel, stainless steel, titanium alloy, aluminum alloy and copper. The number and the number of stages of the separators can be increased along with the process design, and the number of the separators is generally not more than 5, and the separators are connected in parallel or in series.
Further, the supercritical CO 2 The refrigeration cycle coupling high-salt water evaporation zero-emission system is also provided with a vacuum system, a vacuum pump is arranged and connected with the heater, the separator and the condenser through pipelines respectively, noncondensable gas in the system is extracted, the influence of the noncondensable gas on the vacuum degree and heat exchange of the system is prevented, and the waste water is subjected to low-temperature effective flash evaporation.
Preferably, the vacuum pump is a water ring type vacuum pump, the fresh water pump is connected with the vacuum pump through a pipeline, and the water circulation of the vacuum pump adopts fresh water cooled by the system.
Supercritical CO as described above 2 In the refrigeration cycle coupling high-salt water evaporation zero-emission system, raw material liquid in a raw material liquid tank is preheated by a raw material liquid pump firstly, then enters a raw material liquid preheater, is heated by a condenser, is mixed with concentrated liquid from a separator, and is pumped into a heater and supercritical CO of a refrigeration system by a circulating pump 2 And circularly exchanging heat, and finally entering a separator. The secondary steam generated by the separator firstly heats the raw material liquid through the condenser, and is condensed into fresh water, then the fresh water is cooled again through the raw material liquid preheater, finally the fresh water is output by the fresh water pump, a small part of the secondary steam is provided with the water circulation of the vacuum pump, and the rest of the secondary steam is completely pumped out of the system. And discharging concentrated solution generated by the separator, after the concentration reaches a designed value, feeding the concentrated solution into a centrifugal machine through a discharge pump, and feeding mother solution generated by centrifugation into a heater and the separator through a mother solution pump and evaporating and crystallizing under negative pressure to obtain salt.
Referring to FIG. 1, the above supercritical CO 2 The implementation method of the refrigeration cycle coupling high-salt water evaporation zero-emission system is as follows:
1) The high-salt water raw material liquid in the raw material liquid tank 7 sequentially enters a raw material liquid preheater 13 and a condenser 3 for preheating through the raw material liquid pump 6;
2) The preheated high-temperature brine is taken as a feed to enter high-temperature supercritical CO through a circulating pump 10 2 The heater 1 of the heat extraction section I heats;
3) The heated high-salt water enters a separator 2 of a low-temperature flash evaporation section II, the pressure is reduced, flash evaporation is carried out, and steam is steamed out under negative pressure;
4) The steam generated by the separator 2 is introduced into the condenser 3 to be condensed, the raw material liquid is heated at the same time, the condensed product water is cooled by the raw material liquid preheater 13, and finally, the product water is output by the fresh water pump 5, a small part of the product water is provided for water circulation of the vacuum pump 4, and the rest of the product water is totally discharged out of the system;
5) After the concentrated solution produced by flash evaporation and concentration of the separator 2 reaches the designed concentration, the concentrated solution enters a centrifuge 9 to separate salt crystals, mother solution produced by centrifugation is added into a heater 1 and the separator 2 through a mother solution pump 11 to repeat the evaporation and crystallization process;
6) High temperature and high pressure CO produced by supercritical refrigeration cycle 2 The fluid enters the heater 1 to continuously provide heat energy for the high-salt water;
7) Under the action of the vacuum pump 4, high-temperature supercritical CO 2 The inside of each high-temperature corrosion-resistant heater 1 in the heat extraction section I, each separator 2 and condenser 3 of the low-temperature flash evaporation section II are kept in a negative pressure state, so that the operating temperature of the high-temperature corrosion-resistant heater 1 is 70-150 ℃; the operating temperature of each separator 2 of the low temperature flash stage is set at 70-40 ℃.
The utility model has the advantages and effects mainly as follows:
(1) The system of the utility model can directly utilize supercritical high-temperature high-pressure CO of refrigeration system circulation 2 The waste heat of the fluid exchanges heat with the high-temperature brine, thereby realizing high-temperature CO 2 The waste heat recovery and the low-temperature evaporation concentration are organically combined, so that high-grade energy is not consumed, and the operation parameters and the efficiency of a refrigeration system are not required to be changed; the heating fluid is supercritical CO 2 The heater has the advantages of high efficiency, good compactness and low cost due to the characteristics of good fluidity and high heat transfer efficiency;
(2) Compared with a conventional evaporative crystallization system, the system has the advantages of good energy saving effect, no steam consumption, no power consumption of a mechanical compressor, only power consumption of a process water pump and low operation cost; the high-salt water enters the system at normal temperature, is finally heated, evaporated, compressed, condensed and cooled, and the fresh water discharge temperature is close to the temperature of the material entering the system, so that the energy is taken away;
(3) The system is specially designed aiming at high-salt wastewater treatment, the corrosion resistance requirement of materials can be more in accordance with the wastewater treatment requirement, the heater is designed to resist high temperature and high pressure, the heat exchanger, the evaporator, the pipeline and other parts are required to be selected according to the salt-containing type of the wastewater, ti2 and 316L stainless steel or corrosion resistant materials with the same or more are required to be used for the chloride ion wastewater, and other types of wastewater can be 304 stainless steel or corrosion resistant materials with the same or more;
(4) The utility model has wide operating temperature range, generally 120-40 ℃, and reasonably combines the characteristics of high-temperature heat exchange efficiency and strong low-temperature corrosion resistance;
(5) The system can realize waste heat recovery and brine separation crystallization, can effectively solve the problems of difficult treatment and high treatment cost of high-salt wastewater, and is very suitable for occasions with refrigeration and wastewater treatment in coal mines, chemical industry and the like.
Drawings
FIG. 1 is a supercritical CO of the present utility model 2 A system structural schematic diagram of refrigeration cycle coupled high brine evaporation zero emission, wherein: 1-heater, 2-separator, 3-condenser, 4-vacuum pump, 5-fresh water pump, 6-raw material liquid pump, 7-raw material liquid tank, 8-discharge pump, 9-centrifuge, 10-circulating pump, 11-mother liquid pump, 12-mother liquid tank and 13-raw material liquid preheater.
Detailed Description
The utility model is further illustrated by the following examples and figures.
Taking zero discharge treatment of high-salt wastewater containing sodium chloride as an example:
taking high-salt water with TDS of 100000mg/L as raw material, as shown in figure 1, entering a raw material liquid preheater 13 and a condenser 3 through a raw material liquid pump (6) input system, preheating to 30-40 ℃, entering a heater 1 after preheating, and introducing high-temperature high-pressure supercritical CO at 100-120 ℃ into the heater 1 2 Heating sodium chloride wastewater, performing heat exchange by a tube nest to reach 60-70 ℃, entering the separator 2 from the top, and flashing in the separator 2. The pressure in the separator 2 is controlled to be 0.0078-0.0123 MPa.a, the residual concentrated wastewater after flash evaporation is heated by the circulating pump 10 and enters the heater 1, the heated wastewater enters the separator 2 for flash evaporation, sodium chloride wastewater is fed in the circulating evaporation process, after multiple times of circulation, when the sodium chloride solution in the system reaches more than 28%, supersaturated solution is formed, and sodium chloride crystals begin to be separated out. The sodium chloride wastewater with the precipitated crystals is introduced into a centrifugal machine 9 for solid-liquid separation, the separated mother liquor is returned to the heater 1 and the separator 2 for circulating concentration under the action of a mother liquor pump 11 through a mother liquor tank 12, and the sodium chloride crystals are separated out of the system. And (3) drying and packaging sodium chloride crystals generated by separation, wherein the concentration of the obtained sodium chloride reaches 98.5%. The centrifugal machine 9 is a two-stage piston pushing centrifugal machine. The top of the heater 1 is communicated with the separator 2, the bottom of the separator 2 is provided with a pipeline communicated with the bottom of the heater 1, and sodium chloride wastewater from the condenser 3 is conveyed to the heater 1 by the circulating pump 10 through the pipeline. After the high-salt water is flashed in the separator 2, gas and liquid are separated, the gas is discharged from the top of the separator 2, the liquid automatically flows to the bottom of the separator 2, and the liquid enters the bottom of the heater 1 again from the bottom through the circulating pump 10, and the concentrated liquid forms an internal circulation in the system until supersaturated solution is formed and crystallization begins.
The sodium chloride wastewater enters a system to be preheated, heated and flashed, evaporated secondary steam is subjected to 40-50 ℃, the part of secondary steam is subjected to heat exchange condensation with raw materials by a condenser 3, the sodium chloride wastewater is heated to 30-35 ℃, the steam is condensed into hot water of 40-50 ℃, the hot water is cooled again by a raw material liquid preheater 13, and finally fresh water is discharged by a fresh water pump 5, and the temperature is 20-30 ℃.
The system is also provided with a vacuum system, and the vacuum in the heater 1, the separator 2 and the condenser 3 is mainly formed by virtue of the vacuum pump 4, so that the wastewater can be effectively flashed at low temperature. The vacuum pump 4 is mainly used for extracting noncondensable gas in the system and preventing the noncondensable gas from affecting the vacuum degree and heat exchange of the system. The vacuum pump 4 is a water ring type vacuum pump, and the water circulation of the vacuum pump 4 adopts fresh water cooled by the system.
The fresh water produced by the system is fully recycled, no wastewater is discharged, and the effect of zero wastewater discharge is achieved.
It should be noted that the foregoing embodiments are illustrative, and the purposes, technical solutions and advantages of the present utility model have been further described in detail, and it should be understood that the foregoing embodiments are merely exemplary embodiments of the present utility model, and are not intended to limit the present utility model, but any modifications, equivalents, improvements and modifications within the spirit and principles of the utility model should be included in the scope of the present utility model.
Claims (8)
1. Supercritical CO 2 The refrigeration cycle coupling high-salt water evaporation zero-emission system is characterized by comprising high-temperature supercritical CO 2 The heat extraction section, the low-temperature flash evaporation section, the crystallization section, the condensation section, the raw material liquid pump (6) and the raw material liquid tank (7), wherein raw material liquid in the raw material liquid tank (7) is pumped into the condensation section by the raw material liquid pump (6) to be preheated, and then enters into the high-temperature supercritical CO 2 The heat extraction section is heated, then enters the low-temperature flash evaporation section for flash evaporation and cooling, returns to the condensation section for condensation, and simultaneously heats the raw material liquid; wherein:
the high temperature supercritical CO 2 The heat extraction section comprises one or more heaters (1), wherein the heaters (1) are connected with supercritical CO through pipelines 2 The refrigeration cycle system is connected; the low-temperature flash evaporation section comprises one or more separators (2), the upper ends of the heaters (1) are connected with the upper ends of the separators (2), and the lower ends of the separators (2) are connected with the lower ends of the heaters (1) through circulating pipelines provided with circulating pumps (10); the crystallization section comprises a discharge pump (8), a centrifugal machine (9), a mother liquor pump (11) and a mother liquor tank (12), wherein one end of the discharge pump (8) is connected with the lower end of the separator (2), the other end of the discharge pump is connected with the centrifugal machine (9), the centrifugal machine (9) is connected with a crystal outlet pipeline on one hand, the centrifugal machine is connected with the mother liquor tank (12) through a pipeline on the other hand, and the mother liquor tank (12) is connected with an inlet pipeline of the circulating pump (10) through the pipeline after being connected with the mother liquor pump (11); the condensing section comprises a condenser (3), a raw material liquid preheater (13) and a fresh water pump (5); the raw material liquid tank (7) is sequentially connected with the raw material liquid preheater (13) and the condenser (3) through a pipeline by a raw material liquid pump (6) and then connected with an inlet pipeline of the circulating pump (10); the outlet pipeline of the circulating pump (10) is connected with the lower end of the heater (1); the upper end of the separator (2) is connected with the condenser (3) through a pipeline; the condenser (3) is connected with the raw material liquid preheater (13) and the fresh water pump (5) through fresh water output pipelines.
2. The supercritical CO of claim 1 2 The refrigeration cycle coupling high-salt water evaporation zero-emission system is characterized in that the high-salt water evaporation zero-emission system comprises a high-salt water evaporation unit, a high-salt water evaporation unit and a high-salt water evaporation unit, wherein the highSupercritical CO 2 The plurality of heaters (1) of the heat extraction section are connected in parallel or in series.
3. The supercritical CO of claim 1 2 The refrigeration cycle coupling high-salt water evaporation zero-emission system is characterized in that a plurality of separators (2) of the low-temperature flash evaporation section are connected in parallel or in series.
4. The supercritical CO of claim 1 2 The refrigeration cycle coupling high-salt water evaporation zero-emission system is characterized in that the heater (1) is a high-temperature corrosion-resistant heater.
5. The supercritical CO of claim 1 2 The refrigeration cycle coupled high brine evaporation zero emission system is characterized in that the separator (2) is a low temperature separator.
6. The supercritical CO of claim 1 2 The refrigeration cycle coupling high-salt water evaporation zero-emission system is characterized by further comprising a vacuum pump (4), wherein the vacuum pump (4) is respectively connected with the heater (1), the separator (2) and the condenser (3) through pipelines.
7. The supercritical CO according to claim 6 2 The refrigeration cycle coupling high-salt water evaporation zero-emission system is characterized in that the vacuum pump (4) is a water ring type vacuum pump, and the fresh water pump (5) is connected with the vacuum pump (4) through a pipeline.
8. The supercritical CO of claim 1 2 The refrigeration cycle coupling high-salt water evaporation zero-emission system is characterized in that the centrifugal machine (9) is a double-stage piston pushing centrifugal machine.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117553456A (en) * | 2024-01-12 | 2024-02-13 | 瑞纳智能设备股份有限公司 | Waste water treatment and waste heat recovery system using heat pump |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117553456A (en) * | 2024-01-12 | 2024-02-13 | 瑞纳智能设备股份有限公司 | Waste water treatment and waste heat recovery system using heat pump |
| CN117553456B (en) * | 2024-01-12 | 2024-04-09 | 瑞纳智能设备股份有限公司 | Waste water treatment and waste heat recovery system using heat pump |
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