CN112110591A - High-carbonate mine water zero-discharge treatment method and system - Google Patents
High-carbonate mine water zero-discharge treatment method and system Download PDFInfo
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
- C01D7/24—Crystallisation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
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- C02F2209/02—Temperature
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- C02F2209/03—Pressure
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention relates to a high-carbonate mine water zero-emission treatment method and a high-carbonate mine water zero-emission treatment system2(ii) a The evaporation concentration unit is used for evaporating and concentrating the decarburized mine water to obtain an evaporation concentration solution containing 9-11.8% by mass of sodium chloride and 18-20.5% by mass of sodium carbonate; a cooling crystallization unit for cooling the evaporated concentrateCrystallizing and centrifugally separating to obtain sodium carbonate decahydrate and a frozen mother solution; the evaporative crystallization unit is used for evaporating, concentrating and centrifugally separating the frozen mother liquor to obtain sodium chloride and evaporated mother liquor; and the drying unit is used for drying the evaporation mother liquor discharged by the evaporation crystallization unit to obtain the mixed salt. The method can realize the recycling of the sodium carbonate and the sodium chloride in the high-carbonate mine water with low cost and high efficiency, reduce the environmental protection pressure of enterprises, reduce the treatment cost of the high-salt mine water and realize the comprehensive utilization of wastewater resources.
Description
Technical Field
The invention relates to a mine water treatment method and system, in particular to a high-carbonate mine water zero-discharge treatment method and system, and belongs to the technical field of water treatment.
Background
With the rapid development of the coal industry, a large amount of wastewater is discharged in the coal mining process, and if the wastewater is directly discharged without being treated, the wastewater will cause serious pollution to the environment and simultaneously cause a large amount of waste of resources. Because the wastewater contains a large amount of salt, in order to improve the recovery rate of industrial wastewater, a combined treatment process of pretreatment, an ultrafiltration membrane, a reverse osmosis membrane and the like is generally adopted at present to generate two effluent qualities of product water (accounting for about 90% of the water inflow) and high-salt wastewater (accounting for about 10% of the water inflow), wherein the product water is used as make-up water of a boiler room or recycled water, and the generated high-salt wastewater is generally discharged as clean sewage, but a new environmental protection method strictly limits the discharge of the salt-containing wastewater. Therefore, the further treatment of the high-salinity wastewater becomes the key for improving the advanced treatment and reuse rate of the coal wastewater, and the further concentration and treatment (dual crystallization) of the high-salinity wastewater are the most core units for realizing the zero emission requirement. Therefore, the method solves the problem of high salt water, improves the sewage treatment reuse rate, and has important significance on the sewage zero discharge process in the coal industry.
At present, a plurality of methods for treating high-salt mine water are available, such as DTRO butterfly tube type reverse osmosis, nanofiltration, electro-adsorption, incineration, crystallization and the like. The DTRO disc tube type reverse osmosis membrane and the nanofiltration membrane are concentrated along with feed liquid, the salinity is higher and higher, the membranes are easy to block, the interception efficiency is greatly reduced, frequent cleaning and replacement are needed, and the operation cost is increased; electro-adsorption is generally aimed at removing chloride ions, the system desalting rate is low, the regeneration time is long, the concentrated water discharge amount is large, the cost of the electrode plate is high, and the method only stays in the research stage at present; incineration can cause salinity adhesion in the waste water to the inner wall of the incinerator, coking is caused, flue gas is separated out in cooling due to high salinity, waste heat recovery devices and flue gas treatment equipment are blocked, process operation is affected, and meanwhile, the salinity in the waste water after flue gas treatment is still high, and further treatment is needed.
Chinese patent CN106517417A discloses a new process based on recycling of titanium white three-washing water, which comprises the steps of firstly carrying out membrane washing on materials after surface treatment, and then carrying out primary DTRO membrane desalination and secondary DTRO membrane desalination on washing water in sequence; desalting by the primary DTRO membrane to discharge part of strong brine and enter a treatment solution for desalting by the secondary DTRO membrane; and (4) desalting by using a secondary DTRO membrane to discharge part of low-concentration brine and reuse water. Although the invention can utilize the recovered water, the high-salinity water of TDS4000mg/L is discharged at the same time, the environment is polluted, and if titanium dioxide micro-particles are difficult to treat, the titanium dioxide micro-particles are attached to the surface of the membrane to cause blockage, and the separation rate and the service life of the membrane are seriously influenced.
Chinese patent CN206308076U discloses an industry strong brine treatment is with receiving filter membrane filter equipment, including multistage receive filter membrane device, first section receive filter membrane device's water inlet pipeline to be connected on a anterior segment water supply line, preceding section receive filter membrane device's water discharge line and adjacent back section receive filter membrane device's water inlet pipeline between be linked together through an intermediate water supply line, last section receive filter membrane device's water discharge line is connected with a water pipeline. Although the method can recycle the concentrated solution, the concentrated solution is more and more concentrated, higher requirements are provided for a subsequent nanofiltration membrane component, the cost is greatly increased, and the concentrated solution of the last section of nanofiltration membrane device is directly discharged to cause environmental pollution.
Chinese patent CN102603040B discloses an electro-adsorption desalting water treatment method, wherein after water to be treated is subjected to electro-adsorption desalting in the electrifying working process, produced water reaching technical indexes enters a water production tank; the produced water which does not reach the technical index enters an intermediate water tank, at the moment, under the condition of continuing to supply water and power on, industrial hydrochloric acid is injected into the electro-adsorption module, the water after the hydrochloric acid is injected is controlled to just fill the electro-adsorption module system until the water is not discharged out of the system, the PH value of the electro-adsorption module system is controlled to be 2.0-6.0, and the produced water enters the production water tank normally and is switched to be discharged into the intermediate water tank when the hydrochloric acid is injected; and after the electro-adsorption module system is filled with hydrochloric acid, stopping water supply, cutting off a power supply, and entering a discharging, standing and regenerating process. The desalting efficiency of the electro-adsorption module is greatly influenced by the regeneration of the module, the use conditions of a module channel and an electrode, and the electro-adsorption module is difficult to apply in engineering.
Chinese patent CN202382255U discloses a contain salt waste liquid incineration device, including the high improvement that contains salt waste water incineration device, the incinerator body burns district upper portion tangential and is provided with high-pressure wind and combustible gas mixing nozzle, and the bottom is uncovered toper, and the furnace body lower part is uncovered and is submerged in the water cooling tank that has exhaust outlet and row's salt water export. The device greatly reduces the damage of high-temperature molten salt to the furnace wall, but the salt content in the treated wastewater is still high and needs to be further treated.
In conclusion, how to adopt a proper process method and a proper system to realize the further brine separation effect after the high carbonate mine water is treated is a technical problem which needs to be solved urgently by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a high-carbonate mine water zero-discharge treatment method and system, which can realize the recycling of sodium carbonate and sodium chloride in high-carbonate mine water with low cost and high efficiency, reduce the environmental protection pressure of enterprises, reduce the treatment cost of high-salt mine water, realize the comprehensive utilization of wastewater resources and solve the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high carbonate mine water zero emission treatment method specifically comprises the following steps:
step a, decarbonization; preheating mine water to 85 +/-5 deg.C, and stripping and decarbonizing in decarbonizing tower to obtain high-salt water containing sodium carbonate and sodium chloride as main components and CO2The mixed steam of (4);
step b, evaporation and concentration; b, mixing the effluent water obtained in the step a with the effluent liquid of a primary evaporator through a buffer tank, then feeding the mixture into a primary heat exchanger, feeding the superheated material subjected to heat exchange into the primary evaporator for flash evaporation to obtain an evaporation concentrated solution and secondary steam, and controlling the temperature of the evaporation concentrated solution at 90-95 ℃;
step c, cooling and crystallizing; b, the evaporation concentrated solution in the step b enters a cooling crystallizer after heat exchange and temperature reduction, cooling crystallization is carried out at the temperature of-5-0 ℃ to obtain crystal slurry, the crystal slurry is centrifugally separated to obtain sodium carbonate decahydrate and frozen mother liquor, and part of the frozen mother liquor flows back to a feeding pipeline of the cooling crystallizer and is used for adjusting the solid content of the crystal slurry in the cooling crystallizer;
step d, evaporating and crystallizing; preheating the frozen mother liquor in the step c by a secondary preheater, mixing the preheated mother liquor with the effluent of a secondary evaporator, feeding the mixture into a secondary heat exchanger, feeding the superheated material subjected to heat exchange into the secondary evaporator, evaporating and crystallizing at the temperature of 45-50 ℃ to obtain crystal mush and secondary steam, centrifugally separating the crystal mush to obtain sodium chloride and evaporated mother liquor, refluxing the evaporated mother liquor to the secondary evaporator for cyclic concentration, and periodically discharging the evaporated mother liquor according to the purity of the sodium chloride;
step e, drying; and d, drying the evaporation mother liquor discharged periodically in the step d to obtain the miscellaneous salt.
The high-carbonate mine water is mine water with total dissolubility of more than or equal to 3000mg/L and the largest or second proportion of carbonate and bicarbonate content.
Preferably, in the step b, the mass concentration of sodium chloride in the evaporation concentrated solution is controlled to be 9-11.8%, and the mass concentration of sodium carbonate in the evaporation concentrated solution is controlled to be 18-20.5%.
Preferably, the primary evaporator and the secondary evaporator are Mechanical Vapor Recompression (MVR) evaporators.
Preferably, in the step b, the amount of water evaporated in the flash evaporation is 70-80% of the feeding amount of the evaporator.
Preferably, the mass concentration of sodium carbonate in the frozen mother liquor in the step c is 0.3-0.8%.
Preferably, the ratio of the mass flow rate of the sodium carbonate decahydrate product in the cooling crystallization in the step c to the mass flow rate of the feed liquid of the crystallizer is 0.2-0.5.
Preferably, in the step d, the ratio of the mass flow rate of the sodium chloride product in evaporative crystallization to the mass flow rate of the feeding liquid of the crystallizer is 0.1-0.2, the mass ratio of the amount of evaporated water produced during evaporative concentration in the second evaporator to the feeding amount of the superheated material entering the second evaporator is 0.45-0.6: 1.
preferably, the amount of water evaporated in the process of extracting sodium chloride by evaporative crystallization accounts for 45-60% of the feeding amount of the second evaporator.
Preferably, the CO-containing product obtained in step a2The mixed steam is used as a heat source to preheat mine water and CO is preheated2Discharging, wherein water vapor in the mixed vapor forms condensed water to preheat the freezing mother liquor; in the step b, the secondary steam is used as a heat source of the primary heat exchanger to heat the material, the heated condensate water is used for preheating the frozen mother liquor, and the uncondensed steam returns to the primary heat exchanger for heat exchange;
in the step d, the secondary steam is used as a heat source of the secondary heat exchanger for heat exchange, the water vapor which is not condensed in the heat exchange process continuously returns to the secondary heat exchanger for heat exchange until condensed water is formed, and the condensed water is discharged.
Preferably, the temperature of the heat source steam of the primary heat exchanger in the step b is 95-100 ℃, and the absolute pressure is 95-100 kPa; and d, in the step d, the temperature of the heat source steam of the secondary heat exchanger is 50-60 ℃, and the absolute pressure is 12-16 kPa.
A high carbonate mine water zero discharge treatment system for the high carbonate mine water zero discharge treatment method comprises,
a decarbonization unit for converting bicarbonate radical in the high carbonate mine water into carbonate radical and removing CO dissolved in the mine water2；
The evaporation concentration unit is used for evaporating and concentrating the decarburized mine water to obtain an evaporation concentration solution containing 9-11.8% by mass of sodium chloride and 18-20.5% by mass of sodium carbonate;
the cooling crystallization unit is used for cooling, crystallizing and centrifugally separating the evaporation concentrated solution to obtain sodium carbonate decahydrate and a freezing mother solution;
the evaporative crystallization unit is used for evaporating, concentrating and centrifugally separating the frozen mother liquor to obtain sodium chloride and evaporative mother liquor, and periodically discharging the evaporative mother liquor according to the purity of the sodium chloride;
and the drying unit is used for drying the evaporation mother liquor discharged by the evaporation crystallization unit to obtain the mixed salt.
Preferably, the decarbonization unit is formed by sequentially connecting a raw material tank, a primary preheater and a decarbonization tower; high carbonate mine water enters a raw material tank, is pumped into a primary preheater through a pump to be preheated to 85 +/-5 ℃, then enters a decarbonization tower, and is subjected to steam stripping and decarbonization to respectively obtain high brine with sodium carbonate and sodium chloride as main components and CO2The mixed steam of (4); containing CO2The mixed steam is recycled as a heat source and enters a primary preheater through a pipeline to preheat mine water.
Preferably, the evaporation concentration unit comprises a buffer tank, a primary evaporator, a primary heat exchanger and a steam compressor, a water outlet pipeline of the decarbonization tower is connected to the buffer tank, the water outlet pipeline of the buffer tank is communicated with the water outlet pipeline of the primary evaporator and then connected to a water inlet pipe of the primary heat exchanger, a water outlet pipe of the primary heat exchanger is connected to the primary evaporator, a secondary steam outlet pipe of the primary evaporator is connected to a steam inlet pipe of the primary heat exchanger through a steam compressor pipeline, and the primary heat exchanger is also provided with a condensed water outlet pipe; the water outlet pipeline of the first-stage evaporator is connected to the main evaporation concentrated solution pipeline through a branch pipeline, and the main evaporation concentrated solution pipeline is additionally provided with a return pipeline communicated with the water outlet pipeline of the first-stage evaporator.
Preferably, the cooling crystallization unit comprises a secondary preheater, a cooling heat exchanger, a cooling crystallizer, a crystal slurry tank, a primary centrifuge and a freezing mother liquor tank which are sequentially connected, wherein a liquid outlet of the freezing mother liquor tank is connected to the secondary preheater for heat exchange and then enters the evaporation crystallization unit, a return pipeline is further arranged at a liquid outlet of the freezing mother liquor tank and communicated with a return pipeline of the cooling crystallizer, and the return pipeline of the cooling crystallizer is connected to the cooling heat exchanger; the effluent of the secondary preheater is connected with a cooling heat exchanger pipeline through a pump and enters a cooling crystallizer to continuously cool and crystallize the material; and an outlet pipeline of the cooling heat exchanger is communicated with a feed inlet of the cooling crystallizer.
Preferably, the evaporative crystallization unit comprises a secondary heat exchanger, a secondary evaporator, a secondary centrifuge and a mother liquor tank, a discharge pipeline of the secondary preheater is connected with a discharge pipeline of the secondary evaporator through a pump and enters the secondary heat exchanger, the secondary heat exchanger is connected with the secondary evaporator, a secondary steam outlet of the secondary evaporator is connected to a steam inlet pipe of the secondary heat exchanger through a steam compressor, and condensed water after heat exchange is discharged from a condensed water outlet pipe of the secondary heat exchanger. Furthermore, the mother liquor tank is connected with the drying unit pipeline, and a return pipeline is arranged to be connected to a discharge pipeline of the secondary evaporator. Furthermore, a water outlet pipeline of the secondary evaporator is connected to a main crystallization concentrated solution pipeline through a branch pipeline, and a return pipeline is additionally arranged on the main crystallization concentrated solution pipeline and communicated with a discharge pipeline of the secondary evaporator.
Preferably, the drying unit is a dryer.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the high-carbonate mine water zero-discharge treatment method and system, the characteristics of the mother liquor after high-salt water decarburization and evaporation concentration are fully considered, cooling crystallization and evaporation crystallization modes are adopted, forced circulation crystallization is carried out, the mother liquor is ensured to enter a system for circulation, the salt purity is improved, most of sodium carbonate and sodium chloride in the high-carbonate mine water and a small amount of miscellaneous salt are finally recovered, the sodium carbonate and the sodium chloride reach industrial grade, and the purpose of recycling and effective utilization is achieved;
2. the treatment method and the system have the advantages of simple process flow and high stability, no wastewater is discharged except for water evaporation in the whole treatment process, zero discharge treatment of high-salinity wastewater is realized, the wastewater treatment cost is reduced, the enterprise pressure is relieved, and the environment-friendly requirement is met;
3. compared with the existing treatment process of removing carbonate by adding lime or sulfuric acid in the high-carbonate mine water treatment process and finally crystallizing sodium sulfate, the treatment method and the treatment system provided by the invention have the advantages that lime or sulfuric acid is not required to be added in the high-carbonate mine water treatment process to remove carbonate, the operation medicament cost is extremely low, the value of sodium carbonate salt produced by crystallization is high, the market price is about 2000 yuan/ton, and is about ten times of that of sodium sulfate salt, and the treatment method and the treatment system have good economic benefits and social benefits.
4. The method aims at the high-salinity wastewater of the sodium carbonate, the sodium bicarbonate and the sodium carbonate system, and the method can realize the effective separation of salinity;
5. the decarbonization of the invention is to convert bicarbonate radical of the high-salinity wastewater into carbonate radical, change waste into valuable, and better realize resource utilization, while the conventional process is to add acid to blow off to remove carbonate radical and bicarbonate radical, which is opposite to the purpose of the invention.
6. The invention adopts a method of combining secondary evaporation and primary cooling, fully considers the characteristics of components after high-salinity water is decarburized, and adopts different crystallization modes according to the solubility curves of different components. And each stage of crystallizer adopts forced circulation of feed liquid and systemic circulation of mother liquid, and discharges the mother liquid regularly, so that the product purity of each stage of crystallizer is ensured, and the yield is maximized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a process flow diagram of a high carbonate mine water zero discharge treatment method of the invention;
FIG. 2 is a schematic structural diagram of a high carbonate mine water zero-discharge treatment system according to the invention;
description of reference numerals: 1-a raw material tank; 2-a primary preheater; 3-a decarbonizing tower; 4-a buffer tank; 5-first-stage evaporator; 6-first-stage heat exchanger; 7-a vapor compressor; 8-cooling the crystallizer; 9-cooling the heat exchanger; 10-crystal slurry tank; 11-a primary centrifuge; 12-a frozen mother liquor tank; 13-a secondary preheater; 14-a secondary evaporator; 15-a secondary heat exchanger; 16-a secondary centrifuge; 17-a mother liquor tank; 18-a dryer; 19-evaporation concentrated solution main pipeline; 20-main pipeline of crystallized concentrated solution.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The reagents used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.
The core of the invention is to provide a high carbonate mine water zero emission treatment method, the process flow chart of one specific embodiment of which is shown in figure 1 and is called as a first specific embodiment, and the method comprises the following steps:
step a, decarbonization; preheating mine water to 85 +/-5 deg.C, and stripping and decarbonizing in decarbonizing tower to obtain high-salt water containing sodium carbonate and sodium chloride as main components and CO2The mixed steam of (4);
step b, evaporation and concentration; b, mixing the effluent water obtained in the step a with the effluent liquid of a primary evaporator through a buffer tank, then feeding the mixture into a primary heat exchanger, feeding the superheated material subjected to heat exchange into the primary evaporator for flash evaporation to obtain an evaporation concentrated solution and secondary steam, and controlling the temperature of the evaporation concentrated solution at 90-95 ℃;
step c, cooling and crystallizing; b, the evaporation concentrated solution in the step b enters a cooling crystallizer after heat exchange and temperature reduction, cooling crystallization is carried out at the temperature of-5-0 ℃ to obtain crystal slurry, the crystal slurry is centrifugally separated to obtain sodium carbonate decahydrate and frozen mother liquor, and part of the frozen mother liquor flows back to a feeding pipeline of the cooling crystallizer and is used for adjusting the solid content of the crystal slurry in the cooling crystallizer;
step d, evaporating and crystallizing; preheating the frozen mother liquor in the step c by a secondary preheater, mixing the preheated mother liquor with the effluent of a secondary evaporator, feeding the mixture into a secondary heat exchanger, feeding the superheated material subjected to heat exchange into the secondary evaporator, evaporating and crystallizing at the temperature of 45-50 ℃ to obtain crystal mush and secondary steam, centrifugally separating the crystal mush to obtain sodium chloride and evaporated mother liquor, refluxing the evaporated mother liquor to the secondary evaporator for cyclic concentration, and periodically discharging the evaporated mother liquor according to the purity of the sodium chloride; the purity of the sodium chloride meets the relevant standards of industrial salt.
Step e, drying; and d, drying the evaporation mother liquor discharged periodically in the step d to obtain the miscellaneous salt.
On the basis of the first embodiment, the high carbonate mine water zero emission treatment method is further improved to obtain a second embodiment, and the difference between the second embodiment and the first embodiment is that,
in the step b, the mass concentration of sodium chloride in the evaporation concentrated solution is controlled to be 9-11.8%, and the mass concentration of sodium carbonate in the evaporation concentrated solution is controlled to be 18-20.5%. In the step b, the evaporation water amount in the flash evaporation is 70-80% of the feeding amount of the evaporator.
And c, the mass concentration of sodium carbonate in the frozen mother liquor in the step c is 0.3-0.8%. The ratio of the mass flow of the sodium carbonate decahydrate product in the cooling crystallization to the mass flow of the feed liquid of the crystallizer is 0.2-0.5.
Step d, the ratio of the mass flow of the sodium chloride product in evaporative crystallization to the mass flow of the feeding liquid of the crystallizer is 0.1-0.2, the mass ratio of the amount of evaporated water produced when the second evaporator carries out evaporative concentration to the feeding amount of the superheated material entering the second evaporator is 0.45-0.6: 1. the amount of the evaporated water accounts for 45-60% of the feeding amount of the second evaporator when the sodium chloride is extracted by evaporative crystallization.
And c, in the step b, the temperature of the heat source steam of the primary heat exchanger is 95-100 ℃, and the absolute pressure is 95-100 kPa. And d, in the step d, the temperature of the heat source steam of the secondary heat exchanger is 50-60 ℃, and the absolute pressure is 12-16 kPa.
Furthermore, the above process is further improved for better heat recovery, the CO-containing product obtained in step a2OfPreheating mine water by using synthetic steam as heat source and preheating CO2Discharging, wherein water vapor in the mixed vapor forms condensed water to preheat the freezing mother liquor; in the step b, the secondary steam is used as a heat source of the primary heat exchanger to heat the material, the heated condensate water is used for preheating the frozen mother liquor, and the uncondensed steam returns to the primary heat exchanger for heat exchange;
in the step d, the secondary steam is used as a heat source of the secondary heat exchanger for heat exchange, the water vapor which is not condensed in the heat exchange process continuously returns to the secondary heat exchanger for heat exchange until condensed water is formed, and the condensed water is discharged.
The other core of the invention is to provide a high carbonate mine water zero emission treatment system, which is called as a third embodiment, the system is used for implementing the high carbonate mine water zero emission treatment method, and as shown in fig. 2, the system comprises the following components in sequential pipeline connection:
a decarbonization unit for converting bicarbonate radical in the high carbonate mine water into carbonate radical and removing CO dissolved in the mine water2；
The evaporation concentration unit is used for evaporating and concentrating the decarburized mine water to obtain an evaporation concentration solution containing 9-11.8% by mass of sodium chloride and 18-20.5% by mass of sodium carbonate;
the cooling crystallization unit is used for cooling, crystallizing and centrifugally separating the evaporation concentrated solution to obtain sodium carbonate decahydrate and a freezing mother solution;
the evaporative crystallization unit is used for evaporating, concentrating and centrifugally separating the frozen mother liquor to obtain sodium chloride and evaporative mother liquor, and periodically discharging the evaporative mother liquor according to the purity of the sodium chloride;
and the drying unit is used for drying the evaporation mother liquor discharged by the evaporation crystallization unit to obtain the mixed salt.
On the basis of the second embodiment, the high carbonate mine water zero emission treatment system is further improved to obtain a fourth embodiment, and the difference between the fourth embodiment and the above embodiments is that,
the decarbonization unit is formed by sequentially connecting a raw material tank 1, a primary preheater 2 and a decarbonization tower 3; high carbonateThe mine water enters a raw material tank 1, is pumped into a primary preheater 2 by a pump to be preheated to about 85 ℃, then enters a decarbonization tower 3, and is subjected to steam stripping and decarbonization to respectively obtain high-salt water with sodium carbonate and sodium chloride as main components and CO-containing high-salt water2The mixed steam of (1). Containing CO2The mixed steam is recycled as a heat source and enters the primary preheater 2 through a pipeline to preheat the mine water.
The evaporative concentration unit comprises a buffer tank 4, a first-stage evaporator 5, a first-stage heat exchanger 6 and a vapor compressor 7, a water outlet pipeline of the decarburization tower 3 is connected to the buffer tank 4, a water outlet pipeline of the buffer tank 4 is communicated with a water outlet pipeline of the first-stage evaporator 5 and then is connected to a water inlet pipe of the first-stage heat exchanger 6, a water outlet pipe of the first-stage heat exchanger 6 is connected to the first-stage evaporator 5, a secondary vapor outlet pipe of the first-stage evaporator 5 is connected to a vapor inlet pipe of the first-stage heat exchanger 6 through the vapor compressor 7, and the first-stage heat. The water outlet pipeline of the first-stage evaporator 5 is connected to the main evaporation concentrate pipeline 19 through a branch pipeline, and the main evaporation concentrate pipeline is additionally provided with a return pipeline communicated with the water outlet pipeline of the first-stage evaporator 5.
The cooling crystallization unit comprises a secondary preheater 13, a cooling heat exchanger 9, a cooling crystallizer 8, a crystal slurry tank 10, a primary centrifuge 11 and a freezing mother liquor tank 12 which are sequentially connected, a liquid outlet of the freezing mother liquor tank 12 is connected to the secondary preheater 13 for heat exchange and then enters the evaporation crystallization unit, a liquid outlet of the freezing mother liquor tank 12 is also provided with a backflow pipeline communicated with the backflow pipeline of the cooling crystallizer 8, and the backflow pipeline of the cooling crystallizer 8 is connected to the cooling heat exchanger 9. The water outlet of the secondary preheater 13 is connected with a cooling heat exchanger 9 through a pipeline by a pump and enters a cooling crystallizer 8 to continuously cool and crystallize the materials. The outlet pipeline of the cooling heat exchanger 9 is communicated with the feed inlet of the cooling crystallizer 8.
The evaporative crystallization unit comprises a secondary heat exchanger 15, a secondary evaporator 14, a secondary centrifuge 16 and a mother liquor tank 17, a discharge pipeline of the secondary preheater 13 is connected with a discharge pipeline of the secondary evaporator 14 through a pump and enters the secondary heat exchanger 15, the secondary heat exchanger 15 is connected with the secondary evaporator 14, a secondary steam outlet of the secondary evaporator 14 is connected to a steam inlet pipe of the secondary heat exchanger 15 through a steam compressor, and condensed water after heat exchange is discharged from a condensed water outlet pipe of the secondary heat exchanger 15. The mother liquor tank 17 is connected with the drying unit pipeline, and a return pipeline is arranged to be connected to a discharge pipeline of the secondary evaporator 14. The water outlet pipeline of the secondary evaporator 14 is connected to the main crystallization concentrated solution pipeline 20 through a branch pipeline, and the main crystallization concentrated solution pipeline is additionally provided with a return pipeline communicated with the discharge pipeline of the secondary evaporator 14.
The drying unit is a dryer 18.
In the system, the first-stage evaporator and the second-stage evaporator are Mechanical Vapor Recompression (MVR) evaporators.
Application example 1
The process flow of the high carbonate mine water by adopting the treatment method and the treatment system in a certain coal mine enterprise is shown in figure 1, the water quality index of the high carbonate mine water after pretreatment and concentration treatment is shown in table 1, the high carbonate mine water enters the treatment system (the structural schematic diagram is shown in figure 2), the feeding temperature is 25 ℃, the mass flow is 27500kg/h, the following steps are sequentially carried out,
TABLE 1
| Index of water quality | Unit of | Quality of inlet water |
| K | mg/L | 313 |
| Na | mg/L | 42668 |
| Mg | mg/L | 13.5 |
| Ca | mg/L | 11.2 |
| CO3 | mg/L | 2996.5 |
| HCO3 | mg/L | 9718 |
| NO3 | mg/L | 91 |
| Cl | mg/L | 21457.5 |
| SO4 | mg/L | 4067 |
| TDS | mg/L | 109185.5 |
| pH | 9.7 |
a. Decarbonization: preheating the high carbonate mine water, the temperature after preheating being 85 DEG CHigh carbonate mine water enters a decarbonizing tower for steam stripping and decarbonization, the hydrogen carbonate in the raw material is converted into carbonate, and dissolved CO is removed2After decarbonization, wastewater (decarbonization liquid) mainly containing sodium carbonate and sodium chloride is obtained, and the wastewater contains 0.08t/h CO20.63t/h mixed steam.
b. Evaporating and concentrating, namely concentrating the decarbonized solution by adopting a Mechanical Vapor Recompression (MVR) evaporator to obtain 20000kg/h of secondary vapor and 7500kg/h of evaporated and concentrated solution. The evaporated concentrate temperature was 92 ℃ and contained: the mass concentration of sodium chloride is 11.8%, and the mass concentration of sodium carbonate is 20.5%.
c. Cooling and crystallizing, sending the evaporated concentrated solution into a cooling crystallizer, cooling to 0 ℃, and performing centrifugal separation to obtain 3280kg/h of sodium carbonate decahydrate and 6720kg/h of frozen mother liquor with the mass concentration of the sodium carbonate of 0.5%. Returning 2500kg/h of the frozen mother liquor to a cooling crystallizer to adjust crystal mush, and enabling 4220kg/h of the frozen mother liquor to enter a subsequent unit;
d. evaporating and crystallizing, wherein the frozen mother liquor with the temperature of 0 ℃ and the flow rate of 4220kg/h enters a secondary evaporator, heating to 47.5 ℃, generating secondary steam and forming 2100kg/h of evaporated condensed water and 2120kg/h of crystal mush. The magma was centrifuged to obtain sodium chloride at a mass flow of 638kg/h and 1482kg/h of mother liquor. The mother liquor returns to the secondary evaporator for cyclic concentration, and the mother liquor is periodically discharged according to the purity of the sodium chloride. The secondary evaporator is also an MVR evaporator.
e. Drying, and drying the discharged mother liquor in a dryer to obtain the miscellaneous salt.
By adopting the treatment method and the treatment system, steam generated in the steps of decarburization, evaporative concentration and evaporative crystallization is used as a heat source to exchange heat with the feed wastewater in each step, finally formed condensed water is qualified product water, TDS is less than or equal to 1000mg/L, and the method can be used for high-quality production and domestic water.
The invention has the following beneficial effects:
1. compared with the conventional process in which high-value medicaments are added to produce low-value sodium sulfate, the process has the advantages that the value of the sodium carbonate recovered by the process is ten times that of the sodium sulfate;
2. the recovery rate of the sodium chloride in the system is more than 90 percent, and usually reaches more than 95 percent; the recovery rate of the sodium sulfate is more than 90 percent, and usually reaches more than 94 percent; compared with the prior art, aiming at certain determined mine water, the impurity salt content of the method is lower than 20%.
The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The high carbonate mine water zero-discharge treatment method and system provided by the invention are introduced in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A high carbonate mine water zero emission treatment method is characterized by comprising the following steps: the high-carbonate mine water zero-emission treatment method specifically comprises the following steps:
step a, decarbonization; preheating mine water to 85 +/-5 deg.C, and stripping and decarbonizing in decarbonizing tower to obtain high-salt water containing sodium carbonate and sodium chloride as main components and CO2The mixed steam of (4);
step b, evaporation and concentration; b, mixing the effluent water obtained in the step a with the effluent liquid of a primary evaporator through a buffer tank, then feeding the mixture into a primary heat exchanger, feeding the superheated material subjected to heat exchange into the primary evaporator for flash evaporation to obtain an evaporation concentrated solution and secondary steam, and controlling the temperature of the evaporation concentrated solution at 90-95 ℃;
step c, cooling and crystallizing; b, the evaporation concentrated solution in the step b enters a cooling crystallizer after heat exchange and temperature reduction, cooling crystallization is carried out at the temperature of-5-0 ℃ to obtain crystal slurry, the crystal slurry is centrifugally separated to obtain sodium carbonate decahydrate and frozen mother liquor, and part of the frozen mother liquor flows back to a feeding pipeline of the cooling crystallizer and is used for adjusting the solid content of the crystal slurry in the cooling crystallizer;
step d, evaporating and crystallizing; preheating the frozen mother liquor in the step c by a secondary preheater, mixing the preheated mother liquor with the effluent of a secondary evaporator, feeding the mixture into a secondary heat exchanger, feeding the superheated material subjected to heat exchange into the secondary evaporator, evaporating and crystallizing at the temperature of 45-50 ℃ to obtain crystal mush and secondary steam, centrifugally separating the crystal mush to obtain sodium chloride and evaporated mother liquor, refluxing the evaporated mother liquor to the secondary evaporator for cyclic concentration, and periodically discharging the evaporated mother liquor according to the purity of the sodium chloride;
step e, drying; and d, drying the evaporation mother liquor discharged periodically in the step d to obtain the miscellaneous salt.
2. The high carbonate mine water zero emission treatment method according to claim 1, characterized in that: in the step b, the mass concentration of sodium chloride in the evaporation concentrated solution is controlled to be 9-11.8%, and the mass concentration of sodium carbonate in the evaporation concentrated solution is controlled to be 18-20.5%.
3. The high carbonate mine water zero emission treatment method according to claim 1, characterized in that: in the step b, the evaporation water amount in the flash evaporation is 70-80% of the feeding amount of the evaporator.
4. The high carbonate mine water zero emission treatment method according to claim 1, characterized in that: and c, the mass concentration of sodium carbonate in the frozen mother liquor in the step c is 0.3-0.8%.
5. The high carbonate mine water zero emission treatment method according to claim 1, characterized in that: the ratio of the mass flow of the sodium carbonate decahydrate product in the cooling crystallization to the mass flow of the feed liquid of the crystallizer is 0.2-0.5.
6. The high carbonate mine water zero emission treatment method according to claim 1, characterized in that: step d, the ratio of the mass flow of the sodium chloride product in evaporative crystallization to the mass flow of the feeding liquid of the crystallizer is 0.1-0.2, the mass ratio of the amount of evaporated water produced when the second evaporator carries out evaporative concentration to the feeding amount of the superheated material entering the second evaporator is 0.45-0.6: 1.
7. the high carbonate mine water zero emission treatment method according to claim 1, characterized in that: the amount of the evaporated water accounts for 45-60% of the feeding amount of the second evaporator when the sodium chloride is extracted by evaporative crystallization.
8. The high carbonate mine water zero emission treatment method according to claim 1, characterized in that: the CO content obtained in the step a2The mixed steam is used as a heat source to preheat mine water and CO is preheated2Discharging, wherein water vapor in the mixed vapor forms condensed water to preheat the freezing mother liquor; in the step b, the secondary steam is used as a heat source of the primary heat exchanger to heat the material, the heated condensate water is used for preheating the frozen mother liquor, and the uncondensed steam returns to the primary heat exchanger for heat exchange;
in the step d, the secondary steam is used as a heat source of the secondary heat exchanger for heat exchange, the water vapor which is not condensed in the heat exchange process continuously returns to the secondary heat exchanger for heat exchange until condensed water is formed, and the condensed water is discharged.
9. The high carbonate mine water zero emission treatment method according to claim 1, characterized in that: in the step b, the temperature of the heat source steam of the primary heat exchanger is 95-100 ℃, and the absolute pressure is 95-100 kPa; and d, in the step d, the temperature of the heat source steam of the secondary heat exchanger is 50-60 ℃, and the absolute pressure is 12-16 kPa.
10. A high carbonate mine water zero discharge treatment system for the high carbonate mine water zero discharge treatment method according to any one of claims 1 to 9, characterized in that: the high carbonate mine water zero-discharge treatment system comprises,
a decarbonization unit for converting bicarbonate radicals in the high carbonate mine water to carbonAcid radical and removing CO dissolved in mine water2；
The evaporation concentration unit is used for evaporating and concentrating the decarburized mine water to obtain an evaporation concentration solution containing 9-11.8% by mass of sodium chloride and 18-20.5% by mass of sodium carbonate;
the cooling crystallization unit is used for cooling, crystallizing and centrifugally separating the evaporation concentrated solution to obtain sodium carbonate decahydrate and a freezing mother solution;
the evaporative crystallization unit is used for evaporating, concentrating and centrifugally separating the frozen mother liquor to obtain sodium chloride and evaporative mother liquor, and periodically discharging the evaporative mother liquor according to the purity of the sodium chloride;
and the drying unit is used for drying the evaporation mother liquor discharged by the evaporation crystallization unit to obtain the mixed salt.
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