WO2020253182A1 - Système d'inhibition et d'élimination de formation de tartre à germes de cristal de gypse magnétisés, et système d'évaporation et de cristallisation - Google Patents

Système d'inhibition et d'élimination de formation de tartre à germes de cristal de gypse magnétisés, et système d'évaporation et de cristallisation Download PDF

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Publication number
WO2020253182A1
WO2020253182A1 PCT/CN2019/127409 CN2019127409W WO2020253182A1 WO 2020253182 A1 WO2020253182 A1 WO 2020253182A1 CN 2019127409 W CN2019127409 W CN 2019127409W WO 2020253182 A1 WO2020253182 A1 WO 2020253182A1
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Prior art keywords
seed
seed crystal
crystallizer
gypsum
magnetic field
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PCT/CN2019/127409
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English (en)
Chinese (zh)
Inventor
张化福
杨俊玲
张振涛
张钰
董艳华
越云凯
张鹏
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中国科学院理化技术研究所
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Publication of WO2020253182A1 publication Critical patent/WO2020253182A1/fr

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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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents

Definitions

  • This application relates to the technical field of scale inhibition and descaling, in particular to a gypsum magnetic seed scale inhibition and descaling system and an evaporation crystallization system.
  • the chemical production process includes fluid flow, heat transfer, mass transfer and other processes.
  • the progress of the chemical process requires the cooperation of chemical equipment.
  • the long-term operation of chemical equipment is prone to problems such as scaling and blockage. Problems such as scaling and blockage not only affect the operating efficiency of the equipment , There are still potential safety hazards.
  • Equipment fouling refers to a layer of solid matter accumulated by the components or impurities in the fluid gradually crystallized or adsorbed on the surface in contact with it. Among them, the fouling of heat exchange equipment is widely present in various heat transfer processes.
  • the fouling of the heat exchange surface is a very serious production problem, which affects the reasonable design and normal operation of the heat exchange equipment.
  • the dirt on the heat exchange surface usually exists in the form of a solid mixture, which is a poor conductor of heat, and its thermal conductivity is low, which seriously affects the heat exchange efficiency of the equipment.
  • Crystallization or fouling on the heat exchange surface not only deteriorates the heat transfer performance of the heat exchange equipment, increases the consumption of metal materials, but also reduces the cross-sectional area of fluid circulation after the thickening of the fouling layer, and increases the fluid resistance. Or the power of the fan also increases, increasing the energy consumption of equipment operation.
  • the rate of the evaporation and crystallization process is mainly controlled by the heat transfer rate.
  • the heat exchange part of the crystallizer often greatly reduces the production efficiency due to the formation of dirt, and sometimes it is necessary to stop production and clean the equipment to make production
  • the return to normal has brought great inconvenience to production, and at the same time caused energy consumption, reduced equipment production capacity, and increased production costs.
  • This application aims to solve at least one of the technical problems existing in the prior art or related technologies: (1) The traditional scale inhibition and descaling work cannot be performed online in real time and needs to be shut down for cleaning, causing production stagnation and equipment corrosion to varying degrees. The service life of the equipment is shortened, and the equipment is cleaned frequently and the cleaning work is complicated; (2) For the zero discharge process of high-salt wastewater, the pre-treatment of high-salt wastewater requires chemical softening treatment, which is costly, and chemical agents remove specific components. The scope of use is limited.
  • the present application provides a gypsum magnetic seed crystal scale inhibition and descaling system, including a seed crystal circulation subsystem, which is connected to the equipment to be treated through a pipeline to form a seed crystal circulation loop.
  • the seed crystal circulation subsystem includes a magnetic field generating device configured to magnetize the gypsum seed crystal flowing through the magnetic field generating device to form a gypsum magnetic seed crystal.
  • the seed crystal circulation subsystem further includes a seed crystal container and a seed crystal circulation pump, and both the seed crystal container and the seed crystal circulation pump are connected to the seed crystal circulation loop.
  • the magnetic field generating device generates a strong alternating magnetic field, and the magnetic field strength generated by the magnetic field generating device ranges from 5000 to 50000 Gauss.
  • the magnetic field generating device includes an induction power supply, an electromagnetic induction coil, a magnetic field receiving component, a fluid conveying pipeline, and a cooling circulation system.
  • the induction power supply is an electromagnetic induction coil with alternating current. Wound around the fluid conveying pipe, the magnetic field receiving component is built in the fluid conveying pipe, the fluid conveying pipe is connected to the pipeline of the seed crystal circulation loop, the electromagnetic induction coil is set as a hollow spiral pipe, so The electromagnetic induction coil is connected to the cooling circulation system.
  • it further includes a seed slurry separation and production subsystem, the seed slurry separation and production subsystem is connected to the equipment to be processed, and the seed slurry separation and production subsystem includes a layerer , The seed crystal thickener, the settler, the first solid-liquid separator and the first mother liquor buffer tank, the layerer is connected to the equipment to be processed, the seed slurry outlet of the layerer, the seed crystal The thickener, the settler, and the first solid-liquid separator are connected in sequence, the mother liquid outlet of the layerer, the mother liquid outlet of the seed thickener, the mother liquid outlet of the settler, the The mother liquor outlets of the first solid-liquid separator are all connected to the equipment to be treated and/or the first mother liquor buffer tank, and the first mother liquor buffer tank is connected to the equipment to be treated.
  • the present application also provides an evaporative crystallization system, including a crystallizer, including the seed crystal circulation subsystem, which is connected to the crystallizer through a pipeline to form a seed crystal circulation loop.
  • the added concentration of gypsum seeds in the crystallizer is set to 20-25 g/L, and the concentration of gypsum seeds discharged from the crystallizer is set to 30-40 g/L.
  • a salt slurry separation and production subsystem is also connected to the crystallizer, and the salt slurry separation and production subsystem includes a salt slurry thickener, a second solid-liquid separator, and a second mother liquor.
  • a buffer tank, the salt slurry thickener is connected to the crystallizer, the salt slurry outlet of the salt slurry thickener is connected to the second solid-liquid separator, the slurry outlet of the salt slurry thickener, the The slurry outlet of the second solid-liquid separator is connected to the second mother liquor buffer tank and/or crystallizer, and the second mother liquor buffer tank is connected to the crystallizer.
  • it further includes a heater and a vapor compression subsystem, the vapor outlet of the crystallizer is connected to the vapor compression subsystem, and the heat source outlet of the vapor compression subsystem is connected to the heat source side inlet of the heater, The cold source side of the heater is connected with the crystallizer to form a crystallization circulation loop.
  • the crystallizer is set to an axial reverse circulation type
  • the crystallizer includes an evaporation section, a crystallization section, and a salt leg section
  • the crystallizer is provided with a circulating liquid outlet pipe and a demister, so The circulating liquid outlet pipe extends into the evaporation section, the demister is arranged in the evaporation section and above the circulating liquid outlet pipe, the crystallization section is provided with a seed crystal sampling port, and the salt leg section Equipped with salt concentration sampling port and recoil port.
  • the operation process does not require chemical costs, no need to stop processing, greatly reduce the cost of scale inhibition and descaling, and solve the problems of traditional high-salt wastewater zero discharge process that requires the water quality to be softened in the early stage, the treatment process is complex, the cost is high, and the equipment is corroded .
  • the secondary steam waste heat of the crystallizer is recycled, and the evaporation equipment is highly efficient and energy-saving. It can be widely used in the zero-discharge evaporation and crystallization process of high-salt wastewater, especially suitable for the zero-discharge evaporation process of power plant desulfurization wastewater.
  • Fig. 1 is a schematic structural diagram of a preferred embodiment of a gypsum magnetic seed scale inhibition and descaling system of the present application
  • FIG. 2 is a schematic structural diagram of a preferred embodiment of the evaporation crystallization system of the present application
  • FIG. 3 is a schematic structural diagram of a preferred embodiment of a magnetic field generating device of the evaporation crystallization system of the present application
  • FIG. 4 is a schematic diagram of the internal structure of a preferred embodiment of the seed slurry separation and production subsystem of the evaporation crystallization system of the present application;
  • FIG. 5 is a schematic structural diagram of a preferred embodiment of the salt slurry separation and production subsystem of the evaporation crystallization system of the present application;
  • FIG. 6 is a schematic structural diagram of a preferred embodiment of the vapor compression subsystem of the evaporation crystallization system of the present application.
  • Fig. 7 is a schematic structural diagram of a preferred embodiment of the crystallizer of the evaporation crystallization system of the present application.
  • Seed container 2. Magnetic field generating device; 3. Seed circulating pump; 4. Seed slurry separation and production subsystem; 5. Evaporation circulating pump; 6. Salt slurry separation and production subsystem 7. Vapor compression subsystem; 8. Crystallizer; 9. Heater; 10. Condensate water tank.
  • 201 Magnetic core
  • 202 Fluid transport pipeline
  • 203 Pipe insulation layer
  • 204 Electromagnetic induction coil
  • 205 Sealed insulation cover
  • 206 First regulating valve
  • 207 Cooling water pump
  • 208 Cooling circulating water tank
  • 209 Sewage pipeline
  • 210 heat exchange coil
  • 211 control cabinet
  • 212 first pressure sensor
  • 214 first flow sensor
  • 216 induction power supply 217.
  • the second temperature sensor The second temperature sensor.
  • Salt slurry thickener 602.
  • the second solid-liquid separator 603.
  • the second mother liquor buffer tank 601.
  • the present application provides a gypsum magnetic seed scale inhibition and descaling system, as shown in FIGS. 1 to 7, including a seed crystal circulation subsystem, which is connected to the equipment to be treated through a pipeline to form a seed crystal circulation loop, The solution containing gypsum seed crystals flows in the seed crystal circulation circuit.
  • the seed crystal circulation subsystem includes a magnetic field generator 2.
  • the magnetic field generator 2 is configured to generate a magnetic field.
  • the magnetic field generated by the magnetic field generator 2 is used to magnetize and flow through the magnetic field generator. 2 gypsum seeds, gypsum seeds are affected by the magnetic field during the flow process to form gypsum magnetic seeds.
  • the gypsum seed crystal is formed by the action of a magnetic field to form a gypsum magnetic seed crystal.
  • the gypsum magnetic seed crystal optimizes the crystallization habit relative to the gypsum seed crystal.
  • the gypsum magnetic seed crystal can efficiently induce the calcium sulfate in the solution to adhere to it to form crystals and prevent the calcium sulfate from becoming
  • the wall surface of the equipment is attached to prevent calcium sulfate from adhering to the wall surface of the equipment and scaling, and the treatment efficiency of using gypsum magnetic seed crystal to remove the wall surface of the equipment to be treated is high.
  • the gypsum magnetic seed crystal can quickly and accurately remove calcium sulfate scale in the solution, and solves the problem of stubborn and difficult removal of calcium sulfate scale in the prior art, especially for solutions with high calcium sulfate scale content such as desulfurization wastewater and salt brine.
  • the magnetic field generator magnetizes the water in the solution at the same time.
  • the magnetic field changes the osmotic pressure and surface tension of the water, which can make the scale layer loose and easily fall off the wall surface to remove carbonic acid.
  • Scales with low content of calcium, silica, etc., and scales of multiple components are removed at the same time. Due to the existence of seed particles in the evaporation system, the seed particles accelerate calcium carbonate during the collision with the heat exchange wall. The removal of scale layers further improves the removal efficiency of other types of scale layers.
  • the seed recycling subsystem in the technical solution can run simultaneously with the equipment, without shutting down for processing, without affecting normal production, without adding other chemical components, and without adding impurities.
  • This technical solution is applicable to a variety of equipment, and the equipment to be processed can be crystallizers, evaporators, heaters, heat exchangers, etc.
  • the seed crystal is preferably a gypsum seed crystal, and the formation of the gypsum magnetic seed crystal mainly removes stubborn calcium sulfate scale.
  • different kinds of seed crystals can be used.
  • the seed crystals need to choose materials with the same composition as the scaled components.
  • the magnetic field magnetized the seed crystals induce the scaled components of the same composition to adhere to it. And prevent the fouling components from adhering to the wall surface of the equipment to be treated to form a scale layer to achieve the purpose of scale inhibition and descaling.
  • the gypsum magnetic seed fouling and descaling system in this technical scheme is also applicable to other types of systems that perform fouling and descaling after magnetization of the seed crystals, and is not limited to the application of gypsum seed crystals, nor is it limited to the removal of calcium sulfate scale.
  • the gypsum seed crystals in the equipment to be treated can be added to the equipment to be treated through the feeding port on the equipment to be treated, can also be added to the seed crystal circulation subsystem, and then added to the equipment to be treated through the seed crystal circulation subsystem.
  • the crystallizer 8 is used as the equipment to be processed for description.
  • the seed crystal circulation subsystem also includes a seed crystal container 1 and a seed crystal circulation pump 3.
  • the seed crystal container 1 and the seed crystal circulation pump 3 are both connected to the seed crystal circulation loop, the equipment to be processed, the seed crystal circulation pump 3, and the magnetic field
  • the generating device 2, the seed crystal container 1, and the equipment to be treated are connected to form a circulation loop, and each equipment is connected in turn through pipelines.
  • the solution carrying gypsum seed crystals in the equipment to be processed flows to the magnetic field generator 2 under the action of the seed crystal circulation pump 3, and flows into the seed crystal container 1, where it is buffered in the seed crystal container 1 or returned to the seed crystal container 1 In the equipment to be processed.
  • the seed crystal container 1 can also be provided with an addition port.
  • the gypsum seed crystals are added to the seed crystal container 1 through the addition port.
  • the gypsum magnetic seed crystals in the seed crystal container 1 magnetize the newly added gypsum seed crystals and flow them together to be processed. equipment.
  • a stirrer is installed in the seed container 1 to promote the mixing of the gypsum magnetic seed slurry in the seed crystal circulation loop with the newly added gypsum seed crystal.
  • the stirrer is driven by a frequency conversion motor to achieve variable speed adjustment, and the stirring speed is 0-20r/min.
  • the seed crystal recycling outlet and the seed slurry return port are set on the equipment to be processed.
  • the position of the seed recycling extractor is about 0.5m below the liquid level of the equipment to be processed, and the seed slurry circulating return port is set above the liquid level.
  • the distance from the liquid level is about 0.5m.
  • the seed crystal circulation subsystem is connected with the equipment to be processed through the seed crystal circulation extraction outlet and the seed slurry return port to form a seed crystal circulation loop.
  • the gypsum magnetic seed scale inhibition and descaling system also includes a seed slurry separation and production subsystem 4, and the gypsum magnetic seed in the equipment to be processed passes through the seed slurry
  • the separation and production subsystem 4 performs solid-liquid separation and production, so as to separate from the components in the equipment to be treated, and to facilitate the utilization of gypsum seeds.
  • Fig. 4 takes gypsum seed crystals as an example for description.
  • the seed slurry separation and production subsystem 4 includes a layerer 401, a seed crystal thickener 402, a settler 403, a first solid-liquid separator 404, and a first mother liquor buffer tank 405.
  • the layerer 401 is connected to the equipment to be processed .
  • the gypsum seed slurry in the equipment to be processed enters the layerer 401, the gypsum seed slurry is stratified in the layerer 401, and is divided into gypsum seed slurry and mother liquor.
  • the gypsum seed slurry continues to be separated and extracted. Reflow to the equipment to be treated.
  • the seed slurry outlet of the layerer 401, the seed seed thickener 402, the settler 403, and the first solid-liquid separator 404 are connected in sequence.
  • the gypsum seed slurry in the layerer 401 flows into the seed seed slurry through the seed slurry outlet.
  • the thickener 402, the settler 403, and the first solid-liquid separator 404 perform multiple separations, and the gypsum seeds separated by the first solid-liquid separator 404 are collected and used.
  • the mother liquor separated in each equipment is then returned to the equipment to be processed, specifically, the mother liquor outlet of the stratifier 401, the mother liquor outlet of the seed thickener 402, the mother liquor outlet of the settler 403, and the first solid-liquid separator 404
  • the mother liquor outlets are all connected to the equipment to be processed and/or the first mother liquor buffer tank 405, and the first mother liquor buffer tank 405 is connected to the equipment to be processed.
  • the separated mother liquor is buffered by the first mother liquor buffer tank 405 and then returned to the equipment to be processed or directly returned to the equipment to be processed, so that the mother liquor can be continuously used.
  • the equipment to be treated is connected to the layerer 401 by a connecting pipe, and the end of the connecting pipe connected to the layerer 401 is lower than the end connected to the equipment to be treated, so that the connecting pipe extends obliquely so that the slurry can flow out smoothly.
  • the inclination angle of the connecting pipeline is set to 5-10°.
  • the settler 403 is set as an inclined tube settler.
  • the seed slurry separation and production subsystem 4 recovers the gypsum seed crystals from the mother liquor, so that the gypsum seed crystals can be recycled and used, and the mother liquor is returned to the equipment to be treated for reprocessing or utilization.
  • the magnetic field generating device 2 generates a strong alternating magnetic field, and the high magnetic field strength enhances the magnetization of the fluid, which helps the fluid flow, thereby reducing the problem of accumulation of impurities in the fluid on the wall of the pipeline and fouling.
  • the magnetic field intensity generated by the magnetic field generator 2 is in the range of 5000-50000 Gauss, and the high-strength magnetic field fully magnetizes the gypsum seed crystals to improve the scale and scale removal effect of the gypsum magnetic seed crystals.
  • a high-strength magnetic field with a magnetic field strength ranging from 5000 to 50000 Gauss is generated by an alternating power supply.
  • the frequency of the alternating power supply is a medium/high frequency power supply with a frequency of 2000Hz-20000Hz.
  • the medium/high frequency power supply is converted into an ordinary power frequency 50Hz alternating current. Thousands or even tens of thousands of hertz.
  • the magnetic field generating device 2 includes an induction power supply 216, an electromagnetic induction coil 204, a magnetic field receiving component, a fluid delivery pipe 202 and a cooling circulation system.
  • the induction power supply 216 is the electromagnetic induction coil 204 with alternating current
  • the induction power supply 216 is the electromagnetic induction coil 204 with a medium/high frequency power supply with a frequency of 2000Hz-20000Hz to generate a magnetic field strength that meets the requirements of the device.
  • the fluid delivery pipeline 202 can be connected to the pipeline of the seed circulation subsystem, and the connection method can be threaded connection, flange connection and other structural forms.
  • the electromagnetic induction coil 204 is wound around the fluid conveying pipe 202.
  • a preset gap is left between the fluid conveying pipe 202 and the electromagnetic induction coil 204 to prevent the fluid conveying pipe 202 from contacting the electromagnetic induction coil 204 and cause a short circuit, while realizing the matching of the electromagnetic induction system.
  • the magnetic field receiving component is built in the fluid conveying pipeline 202.
  • the magnetic field receiving component includes a magnetizing core 201 and a tube core support frame.
  • the magnetizing core 201 is built into the fluid conveying pipe 202.
  • the core support frame is used to fix the magnetizing core 201 and the fluid conveying pipe 202 realize the magnetization of the fluid medium in the fluid conveying pipe 202.
  • the magnetic concentrating tube core 201 is set as a solid cylinder, and the magnetic concentrating tube core 201 is coaxial with the fluid conveying pipeline 202, that is, the magnetic concentrating tube core 201 is installed in the center of the fluid conveying pipeline 202 for the purpose of attracting and evenly distributing the magnetic field.
  • the magnetic core 201 is set as a cylindrical material to facilitate the homogenization of the magnetic field, and the solid material has a good absorption effect on the magnetic field.
  • a pipeline insulation layer 203 is provided on the fluid delivery pipeline 202, and the pipeline insulation layer 203 is sandwiched between the electromagnetic induction coil 204 and the fluid delivery pipeline 202 to insulate the pipeline and also to isolate the electromagnetic induction coil 204.
  • the role of. Specifically, the preset gap between the fluid conveying pipe 202 and the electromagnetic induction coil 204 may be 2 mm-5 mm, so as to avoid the heat loss of the fluid conveying pipe 202.
  • a sealed thermal insulation cover 205 is connected to the fluid transport pipeline 202, and the electromagnetic induction coil 204 is arranged between the pipeline thermal insulation layer 203 and the sealed thermal insulation cover 205 to protect the electromagnetic induction coil 204 and reduce the divergence loss of the magnetic field.
  • the electromagnetic induction coil 204 is set as a hollow spiral tube, and the electromagnetic induction coil 204 is connected to the cooling circulation system.
  • the cooling circulation system includes a cooling circulating water tank 208 and a cooling water pump 207.
  • the cooling fluid in the cooling circulating water tank 208 circulates in the electromagnetic induction coil 204 and the cooling circulating water tank 208 to perform heat exchange and cooling, and protect the electromagnetic induction coil 204.
  • the cooling water pump 207 is arranged at the cooling fluid outlet of the cooling circulating water tank 208, and the cooling water pump 207 provides flow power for the cooling fluid to ensure the circulating flow of the cooling fluid.
  • the induction power supply 216 is also provided with a cooling pipe inside, and the cooling fluid in the cooling circulating water tank 208 flows into the cooling pipe, and the induction power supply 216 is cooled and protected.
  • the cooling fluid circulates in the electromagnetic induction coil 204, the cooling pipe, and the cooling circulating water tank 208.
  • a heat exchange coil 210 is provided in the cooling circulating water tank 208, and the heat exchange coil 210 exchanges heat with the cooling fluid in the cooling circulating water tank 208.
  • the heat exchange coil 210 is a metal coil, preferably stainless steel.
  • a sewage pipe 209 is also connected to the cooling circulating water tank 208.
  • the material of the electromagnetic induction coil 204 can be copper, and the turn moment and the turn moment distribution of the electromagnetic induction coil 204 are made according to actual conditions.
  • the turn moment of the electromagnetic induction coil 204 is set to equal turns or gradually along the entrance end to the exit end. Increasing, it can be a sparse equal-turn moment distribution, a dense equal-turn moment distribution, or a variable-turn moment distribution with a dense front and a sparse turn.
  • the hollow spiral tube with equal turns is convenient to process and has low processing cost.
  • the cross section of the electromagnetic induction coil 204 is a circular or rectangular hollow circle.
  • the magnetic field generating device 2 further includes a control cabinet 211.
  • the control cabinet 211 is connected with a first pressure sensor 212, a first temperature sensor 213, and a first flow sensor 214.
  • the first pressure sensor 212 measures the outlet pressure of the cooling circulation system.
  • the first temperature sensor 213 measures the outlet temperature of the cooling circulation system
  • the first flow sensor 214 measures the outlet flow of the cooling circulation system, and monitors the temperature, pressure, and flow rate of the cooling circulation system to adjust the flow status of the cooling circulation system .
  • the control cabinet 211 is also connected with a first liquid level sensor 215, which is configured to detect changes in the liquid level of the cooling circulating water tank 208, and ensure that the liquid level fluctuates within a certain range for timely replenishment and discharge.
  • a second temperature sensor 217 is also connected to the control cabinet 211. The second temperature sensor 217 measures the wall surface temperature of the fluid conveying pipe 202 in order to understand the state of the fluid conveying pipe 202 and the temperature in the electromagnetic induction coil 204, so as to find problems in time. Adjust the cooling fluid flow rate.
  • the cooling circulation system is also provided with a first regulating valve 206, the first regulating valve 206 is connected to the circulation pipeline, the opening of the first regulating valve 206 can be adjusted to regulate the flow of the cooling fluid, the first regulating valve 206 is connected to the control cabinet 211.
  • the control cabinet 211 can remotely adjust the first regulating valve 206 as required.
  • control cabinet 211 is equipped with a PLC control system.
  • the first regulating valve 206 and the cooling water pump 207 on the cooling circulation system are both connected to the PLC control system.
  • the PLC control system has a built-in PID control program. Part of the process parameters are monitored and intelligently controlled in real time.
  • the control cabinet 211 is connected to the induction power supply 216 to control the current frequency of the induction power supply 216.
  • the control cabinet 211 realizes the information collection of each sensor, and realizes the functions of interlocking, feedback and protection according to the programmed control logic.
  • the gypsum seed crystals in the seed crystal circulation loop are magnetized by the magnetic field generating device 2, and the operation of the magnetic field generating device 2 is automatically controlled to ensure the smooth progress of the gypsum seed magnetization process, thereby ensuring scale inhibition and removal Scale effect.
  • This application also provides an evaporative crystallization system, as shown in FIGS. 1-7, comprising a crystallizer 8 and the above-mentioned seed crystal circulation subsystem.
  • the seed crystal circulation subsystem is connected to the crystallizer 8 through a pipeline to form a seed crystal circulation loop ,
  • the gypsum seeds in the seed circulation subsystem are used to remove calcium sulfate scale in the crystallizer 8.
  • the seed circulation subsystem is installed on the crystallizer 8 to perform scale inhibition and descaling on the crystallizer 8. The crystallization process and the scale inhibition and descaling process are carried out simultaneously without stopping the machine.
  • the gypsum magnetic seed crystal is used for scale inhibition and descaling. Compared with the existing chemical descaling, there is no need to stop the machine, the process is simplified, the cost is reduced, the cost is reduced by up to 90%, and the effect is remarkable.
  • the technical solution of the gypsum magnetic seed fouling and descaling system can be directly applied to the evaporation crystallization system, that is, the equipment to be treated in the gypsum magnetic seed fouling and descaling system is replaced with the crystallizer 8 in the technical solution.
  • the above-mentioned evaporative crystallization system is suitable for evaporative crystallization processes under various working conditions, and is especially suitable for chemical treatment processes with high calcium sulfate content such as sulfur-containing wastewater and industrial brine, and helps to induce the crystallization of inorganic salts in the solution. Reduce impurities in crystallization.
  • the added concentration of gypsum seed crystals in the crystallizer 8 is set to 20-25 g/L, and the gypsum seed crystal discharge concentration in the crystallizer 8 is set to 30-40 g/L to maintain the normal operation of the crystallization process.
  • the gypsum seed crystals in the crystallizer 8 are added through the seed crystal container 1 of the crystallization circulation subsystem.
  • the seed slurry separation and production subsystem 4 is connected to the crystallizer 8, and the layerer 401 is connected to the crystallizer 8 so that the slurry containing gypsum seeds enters the layerer 401, the slurry containing gypsum seed crystals is separated in the layerer 401 to form a gypsum seed crystal slurry and a mother liquor (generally, the gypsum seed slurry rises to the upper layer of the layerer 401, and the mother liquid sinks to the lower layer of the layerer 401) ,
  • the mother liquor outlet of the layerer 401 is connected to the crystallizer 8 and/or the first mother liquor buffer tank 405, so that the mother liquor is returned to the crystallizer 8; the gypsum seed slurry is connected to the seed thickener 402 through the slurry outlet of the layerer 401 , Separate again, the separated gypsum seed slurry enters the settler 403
  • the crystallizer 8 and the layerer 401 are connected by a connecting pipe, and the end of the connecting pipe connected to the layerer 401 is lower than the end connected to the crystallizer 8, so that the connecting pipe extends obliquely so that the slurry can flow out smoothly.
  • the inclination angle of the connecting pipeline is set to 5-10°.
  • the slurry containing gypsum seed crystals in the crystallizer 8 is separated several times to obtain gypsum seed crystals and mother liquor.
  • the gypsum seed crystals are reused, and the mother liquor is returned to the crystallizer 8 for processing.
  • the first mother liquor buffer tank 405 can be directly connected to the crystallizer 8 or can be connected to the heater 9.
  • a heater 9 is connected to the crystallizer 8.
  • the heater 9 circulates and heats the mother liquor in the crystallizer 8.
  • the first mother liquor buffer tank 405 is connected to the heater 9 and can be heated by the heater 9 and then returned to the crystallizer 8. It helps to maintain the temperature balance in the crystallizer 8 and ensure the crystallization efficiency.
  • the seed slurry separation and production subsystem 4 recovers the gypsum seed crystals, and the mother liquor containing the salt slurry is returned to the crystallizer 8 to continue crystallization, ensuring the continuous and efficient process of salt slurry crystallization .
  • the lower cone outlet of the seed thickener 402 is provided with a recoil port, and the feed is used as the recoil liquid to clean the gypsum seed slurry, and the axial flow rate of the recoil liquid is controlled at 5-10m/s , The salt content in desalted gypsum seed crystals is controlled within 1%.
  • the salt content in the desalted seed crystal is controlled within 1%.
  • the settler 403 adopts the inclined tube settler 403, and the inclined tube settler 403 preferably adopts the honeycomb inclined tube type, the inclined tube length is 1m, the inclination angle is 60 degrees, the inscribed circle diameter is between 35-50mm, and the material is glass fiber reinforced plastic or polyvinyl chloride.
  • the first solid-liquid separator 404 preferably adopts a horizontal screw discharge sedimentation centrifuge, the preferred range of the filterable solid particle diameter is 0.01-3 mm, and the preferred range of the centrifuge separation factor is 2000-4000.
  • the first solid-liquid separator 404 can also use a filter press to dehydrate the gypsum seed crystals, and the filter press adopts a box filter press.
  • the first mother liquor buffer tank 405 is provided with a stirrer, and the stirrer is preferably a frame-type stirring blade, and the stirring speed is controlled at 10-40 r/min.
  • the mother liquor inlet position of the first mother liquor buffer tank 405 should be lower than the mother liquor outlet positions of the seed thickener 402, the settler 403, and the first solid-liquid centrifuge.
  • the salt slurry separation and production subsystem 6 is also connected to the crystallizer 8 to separate the salt slurry to obtain a solid salt product.
  • the salt slurry separation and production subsystem 6 includes a salt slurry thickener 601, a second solid-liquid separator 602, and a second mother liquor buffer tank 603.
  • the salt slurry thickener 601 is connected to the crystallizer 8, and the salt slurry in the crystallizer 8 Enter the salt slurry thickener 601 for solid-liquid separation, and separate high-concentration salt slurry and mother liquor.
  • the high-concentration salt slurry enters the second solid-liquid separator 602 through the salt slurry outlet of the salt slurry thickener 601, and performs solid-liquid separation again , Separate solid salt and mother liquor.
  • the slurry outlet of the salt slurry thickener 601 and the slurry outlet of the second solid-liquid separator 602 are connected to the second mother liquor buffer tank 603 and/or crystallizer 8.
  • the second mother liquor buffer tank 603 is connected to the crystallizer 8, and the mother liquor is directly returned to the crystallization After being buffered by the second mother liquor buffer tank 603, the reactor 8 is returned to the crystallizer 8.
  • the second mother liquor buffer tank 603 can be directly connected to the crystallizer 8 or connected to the heater 9, and the mother liquor is heated by the heater 9 and then returned to the crystallizer 8.
  • the outlet of the lower cone of the salt slurry thickener 601 is provided with a recoil port, and the feed is used as the recoil liquid to clean the salt slurry.
  • the axial flow rate of the recoil liquid is controlled at 5-10m/s.
  • the solid-liquid ratio of the salt slurry at the outlet of the slurry thickener 601 is controlled at 50-70%.
  • the second solid-liquid separator 602 preferably adopts a horizontal two-stage pusher centrifuge.
  • the preferred range of the filterable solid particle diameter is greater than 0.15mm.
  • the preferred range of the separation factor of the horizontal two-stage pusher centrifuge is 200-1200.
  • the water content of the later salt slurry material is controlled within 5%.
  • the second mother liquor buffer tank 603 is also provided with a stirrer, the stirrer is preferably a frame-type stirring blade, and the stirring speed is controlled at 10-40r/min.
  • the second mother liquor buffer tank 603 is also provided with an insulating layer to prevent the temperature of the mother liquor from dropping sharply, causing the mother liquor to salt out and blocking the pipeline.
  • the thickness of the insulating layer is preferably 50-100 mm.
  • the mother liquor inlet position of the second mother liquor buffer tank 603 should be lower than the mother liquor outlet positions of the salt slurry thickener 601 and the second solid-liquid centrifuge.
  • the salt slurry output of the crystallizer 8 is less than 200 kg/h, it is preferable to use a four-foot large flip-type centrifuge.
  • the evaporative crystallization system further includes a heater 9 and a vapor compression subsystem 7.
  • the vapor outlet of the crystallizer 8 is connected to the vapor compression subsystem 7, and the heat source of the vapor compression subsystem 7
  • the outlet is connected to the heat source side inlet of the heater 9, and the cold source side of the heater 9 is connected to the crystallizer 8 to form a crystallization circulation loop.
  • the mother liquor in the crystallizer 8 flows into the cold source side of the heater 9 to exchange heat with the heat source side of the heater 9, and then flows back to the crystallizer 8.
  • the heat source side of the heater 9 comes from the vapor compression subsystem 7.
  • the subsystem 7 heats the steam flowing out of the crystallizer 8 as a heat source for heating the mother liquor, and makes full use of the heat of the steam flowing out of the crystallizer 8.
  • the heat source side inlet of the heater 9 is connected to the vapor compression subsystem 7, and the heat source side outlet of the heater 9 is connected to the condensate water tank 10, the hot steam forms condensate water after heat exchange in the heater 9 and is discharged into the condensate water tank 10.
  • the crystallizer 8 is connected to the cold source side of the heater 9 by a pipeline, and the pipeline is connected with an evaporation circulating pump 5.
  • the mother liquid material in the crystallizer 8 is driven by the evaporation circulating pump 5 and is input to the heater 9.
  • the material completes the heat exchange in the heater 9, and then returns to the crystallizer 8 to complete the flash evaporation and realize the concentrated crystallization to obtain the solid crystal salt.
  • a sampling port is provided at the inlet and outlet on the cold source side of the heater 9.
  • the sampling port is configured to detect the concentration of gypsum seed crystals in the circulating fluid. After reaching the specified concentration, the crystallizer 8 can pass through the seed slurry separation and extraction subsystem 4 Drain the gypsum seed slurry.
  • the medium flow rate of the evaporating circulating liquid in the heat exchange tube of the heater 9 is controlled at 1.0-2.5m/s, and the solid-to-liquid ratio of the evaporating circulating liquid is controlled at 20-30%; when the medium is a chloride ion inorganic salt solution, the heater 9’s
  • the heat exchange tube is preferably made of TA2.
  • the vapor compression subsystem 7 includes a compressor 701, a gas-liquid separator 702, a water tank 705, an oil supply pump 712, an oil tank 703, a liquid circuit and an oil circuit.
  • the vapor flowing out of the secondary vapor outlet of the crystallizer 8 enters the compressor 701 and is compressed Compressed inside the machine 701, it enters the gas-liquid separator 702.
  • the secondary steam separated by the gas-liquid separator 702 enters the heater 9 as a heat exchange source.
  • the liquid separated by the gas-liquid separator 702 flows into the water tank 705 and is connected to the water tank 705.
  • the liquid circuit flows into the compressor 701 and is compressed again.
  • An oil circuit, an oil supply pump 712 and an oil tank 703 are connected to the compressor 701.
  • the pressure oil in the compressor 701 flows into the oil tank 703 and the oil supply pump 712 through the oil circuit.
  • the oil supply pump 712 pressurizes the pressure oil and then flows into the compressor 701.
  • the compressor 701 is also connected with a steam filter 704, and the steam flowing out of the secondary steam outlet of the crystallizer 8 is filtered by the steam filter 704 and then enters the compressor 701, which extends the life of the compressor 701.
  • a water supply pump 706 and a water supply filter 707 are also connected to the liquid circuit between the water tank 705 and the compressor 701.
  • An oil supply filter 713 is also connected between the oil supply pump 712 and the compressor 701. Among them, both the water supply filter 707 and the oil supply filter 713 can use a Y-type filter with a filtering accuracy of 80 mesh.
  • a second liquid level sensor 708 is installed on the water tank 705, and a second regulating valve 709 is installed on the water supply pipe connected to the water tank 705.
  • the second regulating valve 709 adjusts its opening according to the liquid level state of the second liquid level sensor 708 , To ensure the stable level of the water tank 705.
  • the temperature of the water returning from the water tank 705 to the compressor 701 is not lower than the inlet steam temperature of the compressor 701.
  • the outlet pressure of the fuel supply pump 712 is preferably 4 bar to 10 bar.
  • the oil temperature in the oil tank 703 should not be higher than 60°C.
  • the oil tank 703 is provided with a cooling coil, and the cooling medium is input into the cooling coil to lower the temperature of the cooling oil in the oil tank 703.
  • the cooling coil can adopt an internal and external double coil type.
  • the fuel tank 703 uses cooling water as the cooling medium.
  • a third regulating valve 710 and a third temperature sensor 711 are installed on the water inlet pipe of the fuel tank 703. The third regulating valve 710 controls its opening according to the temperature collected by the third temperature sensor 711 to ensure The temperature of the cooling oil is within a reasonable range.
  • the steam flow rate of the compressor 701 is less than 100m 3 /min, a single screw compressor is used; when the steam flow rate is between 50m 3 /min ⁇ 500m 3 /min, a Roots type compressor is used. When the steam flow rate is higher than 200m 3 /min, a centrifugal compressor is used.
  • the crystallizer 8 is set to an axial reverse circulation type.
  • the crystallizer 8 includes an evaporation section 804, a crystallization section 806, and a salt leg section 807.
  • the crystallizer 8 is provided with a circulating liquid outlet pipe 803 and a The frother 802, the circulating liquid outlet pipe 803 extends into the evaporation section 804, and the demister 802 is arranged in the evaporation section 804 and is located in the gas phase space above the circulating liquid outlet pipe 803.
  • the end of the circulating liquid outlet pipe 803 that extends into the evaporation section 804 is set as a bell mouth type, the evaporation section 804 is set as a cylindrical cylinder, the top of the evaporation section 804 is provided with an upper cone 801; the crystallization section 806 is set as a cone.
  • the circulating liquid outlet pipe 803 extends out of the crystallizer 8 along the crystallization section 806, and the crystallization section 806 is provided with a circulating liquid inlet 805 so that the mother liquor separated in the seed circulation subsystem can be returned to the crystallizer 8;
  • the salt leg section 807 is provided It has a cylindrical structure and its cross-sectional area is 10-15% of the cross-sectional area of the evaporation section.
  • the salt leg section 807 is provided with a recoil port 808, and the material flows into the crystallizer 8 through the recoil port 808 to prevent salt from crystallizing in the salt leg section 807 blocked.
  • the height of the vapor phase space of the crystallizer 8 is set above 2m, the distance between the end of the circulating liquid outlet pipe 803 extending into the evaporation section and the liquid surface in the evaporation section is set to 0.5-1.0m, and the evaporation intensity of the crystallizer 8 is controlled at 1.0-1.5m 3 /m 3 .
  • the demister 802 is preferably a wire mesh demister.
  • the crystallization section 806 is provided with a seed sampling port to detect the concentration of gypsum seed crystals in the circulating fluid. After reaching a specified concentration, the high-concentration gypsum seed slurry is discharged.
  • the salt leg section 807 is provided with a salt concentration sampling port to detect the concentration of the salt slurry. After reaching the specified concentration, the high-concentration salt slurry can be discharged.
  • the cylinder of the evaporation section 804 should be provided with reinforcing rings, which are arranged at intervals of 1 m along the axial direction of the cylinder to improve the strength of the cylinder.
  • the heater 9 and the crystallizer 8 should also be set for heat preservation, preferably using heat preservation rock wool or heat preservation materials with a temperature resistance of 200°C or more.
  • the above technical scheme can be applied to the evaporation process with zero discharge of high-salt wastewater and the evaporation crystallization operation unit of the salt industry. Specifically, it is especially suitable for the zero-discharge evaporation process of desulfurization wastewater, the zero-discharge evaporation process of pesticide wastewater, the evaporation treatment process of other high-salt wastewater, and the salt-making evaporation system.
  • the above technical scheme has the advantages of good scale and scale removal effect, wide application range, convenient operation, low operating cost, etc.
  • connection should be interpreted broadly unless otherwise clearly specified and limited.
  • it can be a fixed connection or a detachable connection. Connected or integrally connected; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • connection should be interpreted broadly unless otherwise clearly specified and limited.
  • it can be a fixed connection or a detachable connection. Connected or integrally connected; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • multiple means two or more than two.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un système d'inhibition et d'élimination de formation de tartre à germes de cristal de gypse magnétisés, et un système d'évaporation et de cristallisation, le système d'inhibition et d'élimination de formation de tartre à germes de cristal de gypse magnétisés comprenant un sous-système de circulation de germes de cristal, le sous-système de circulation de germes de cristal étant connecté à un équipement à traiter au moyen d'une canalisation de façon à former une boucle de circulation de germes de cristal ; le sous-système de circulation de germes de cristal comprend un dispositif de génération de champ magnétique (2) ; et le dispositif de génération de champ magnétique (2) est configuré pour magnétiser des germes de cristal de gypse traversant le dispositif de génération de champ magnétique de façon à former des germes de cristal de gypse magnétisés. Le système d'évaporation et de cristallisation comprend un cristalliseur (8) et le sous-système de circulation de germe de cristal ; et le sous-système de circulation de germe de cristal est relié au cristalliseur (8) au moyen d'une conduite de manière à former une boucle de circulation de germe de cristal. Au moyen de la magnétisation des germes de cristal pour inhiber et éliminer les dépôts de l'équipement à traiter, les germes de cristal magnétisés circulent et s'écoulent entre l'équipement à traiter et le sous-système de circulation de germes de cristal pour maintenir de manière stable leur état de magnétisation. Par conséquent, les effets d'inhibition et d'élimination de tartre sont améliorés.
PCT/CN2019/127409 2019-06-20 2019-12-23 Système d'inhibition et d'élimination de formation de tartre à germes de cristal de gypse magnétisés, et système d'évaporation et de cristallisation WO2020253182A1 (fr)

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CN110171859B (zh) * 2019-06-20 2021-07-20 中国科学院理化技术研究所 石膏磁晶种阻垢除垢系统以及蒸发结晶系统

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WO2009006575A1 (fr) * 2007-07-03 2009-01-08 Aquatech International Corporation Procédé de traitement de saumures de silice de ph élevé
CN102060312A (zh) * 2010-11-15 2011-05-18 江苏井神盐化股份有限公司 防止盐卤输送管道结垢的方法及装置
CN108585227A (zh) * 2018-04-17 2018-09-28 天津科技大学 一种高温硫酸钙型卤水预热器表面防垢方法
CN109368818A (zh) * 2018-12-03 2019-02-22 中国科学院理化技术研究所 电磁阻垢除垢装置以及蒸发系统
CN110171859A (zh) * 2019-06-20 2019-08-27 中国科学院理化技术研究所 石膏磁晶种阻垢除垢系统以及蒸发结晶系统

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