CN106082275A - A kind of salt extraction process and salt making system - Google Patents

A kind of salt extraction process and salt making system Download PDF

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Publication number
CN106082275A
CN106082275A CN201610412626.2A CN201610412626A CN106082275A CN 106082275 A CN106082275 A CN 106082275A CN 201610412626 A CN201610412626 A CN 201610412626A CN 106082275 A CN106082275 A CN 106082275A
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crystallization
water
salt
reverse osmosis
dense
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CN106082275B (en
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熊日华
卫昶
陈权
霍卫东
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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Shenhua Group Corp Ltd
National Institute of Clean and Low Carbon Energy
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • 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
    • C02F2301/04—Flow arrangements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

Abstract

The present invention relates to water treatment field, disclose a kind of salt extraction process and salt making system.The method includes: brackish water is carried out reverse-osmosis treated, obtains reverse osmosis concentrated water and reverse osmosis produced water；Reverse osmosis concentrated water is carried out the first Crystallization Separation process, obtains the first crystal salt and first and crystallize dense water, be the first backflow crystallization water outlet and cation exchange water inlet by the first dense moisture of crystallization；Cation is exchanged water inlet and carries out cation exchange process, obtain cation exchange water outlet；Cation is exchanged water outlet and carries out the second Crystallization Separation process, obtain the second crystal salt and second and crystallize dense water；The second dense water of crystallization is carried out the 3rd Crystallization Separation process, obtain the 3rd crystal salt and the 3rd and crystallize dense water.The method and system using the present invention can prepare highly purified one-component salt, and Water Sproading rate is high, cation exchange load is low, and carnallite cost of disposal, cost of investment and operating cost can be greatly reduced.

Description

A kind of salt extraction process and salt making system
Technical field
The present invention relates to water treatment field, in particular it relates to a kind of salt extraction process and salt making system.
Background technology
Along with the continuous lifting of environmental requirement, the contradictions such as water resource is not enough and environmental carrying capacity is limited highlight day by day.At stone In the production processes such as oiling work, Coal Chemical Industry, electric power, iron and steel and desalinization, substantial amounts of brine waste can be produced.In order to reduce Outer displacement, improves the service efficiency of water, and current brine waste generally uses reuse after the embrane method based on reverse osmosis processes, Improve the service efficiency of water to a certain extent.Requiring the occasion of zero liquid discharge, reverse osmosis concentrated water is used steaming further Send out crystallization processes, obtain distilled water and solid carnallite.
Existing zero liquid discharge process generally exists that the membrance concentration response rate is limited, solid carnallite is difficult to that disposal etc. is prominent asks Topic.Therefore, it is necessary to improve on the basis of existing zero liquid discharge process, improve the response rate of membrance concentration process, To higher degree one-component salt using as side-product sell, reduce carnallite cost of disposal and realize zero liquid discharge comprehensive Cost.
Summary of the invention
The invention aims to overcome drawbacks described above present in prior art, it is provided that a kind of salt extraction process and salt manufacturing System, the salt extraction process of the present invention can prepare highly purified one-component salt, and Water Sproading rate is high, cation exchange load is low, And carnallite cost of disposal, cost of investment and operating cost can be greatly reduced.
To achieve these goals, first aspect, the invention provides a kind of salt extraction process, the method includes:
(1) brackish water containing dianion salt and univalent anion salt is carried out reverse-osmosis treated, with by brackish water Carry out initial concentration, obtain reverse osmosis concentrated water and the reverse osmosis produced water of lean salt of rich salt；
(2) reverse osmosis concentrated water that step (1) obtains is carried out the first Crystallization Separation process, obtain the first crystal salt and first Crystallizing dense water, crystallizing dense moisture by described first is two strands, is back to step (1) respectively as the first backflow crystallization water outlet and carries out Described reverse-osmosis treated and carry out follow-up cation exchange process as cation exchange；
(3) cation exchange water inlet step (2) obtained carries out cation exchange process, obtains rich monovalent cation salt Cation exchange water outlet；
(4) cation exchange water outlet step (3) obtained carries out the second Crystallization Separation process as crystallization water inlet, obtains Second crystal salt and second crystallizes dense water；
(5) the second dense water of crystallization step (4) obtained carries out the 3rd Crystallization Separation and processes, and obtains the 3rd crystal salt and the Three crystallize dense water.
Second aspect, the invention provides a kind of salt making system, and this salt making system includes reverse osmosis units, the first crystallization point From unit, cation crosspoint, the second Crystallization Separation unit and the 3rd Crystallization Separation unit,
Described reverse osmosis units is for carrying out reverse osmosis by the brackish water containing dianion salt and univalent anion salt Process, obtain reverse osmosis concentrated water and the reverse osmosis produced water of lean salt of rich salt；
Described first Crystallization Separation unit is for carrying out the first crystallization by the reverse osmosis concentrated water from described reverse osmosis units Separating treatment, obtains the first crystal salt and first and crystallizes dense water, and described first Crystallization Separation unit and described reverse osmosis units It is connected, at least part of first crystallization concentrate recirculation is carried out reverse-osmosis treated to described reverse osmosis units；
Described cation crosspoint is not for being back to described reverse osmosis from described first Crystallization Separation unit The first dense water of crystallization of unit carries out cation exchange process as cation exchange water inlet, obtains the sun of rich monovalent cation salt Ion exchange water outlet；
Described second Crystallization Separation unit for using from described cation crosspoint cation exchange water inlet as Crystallization water inlet carries out the second Crystallization Separation process, obtains the second crystal salt and second and crystallizes dense water；
Described 3rd Crystallization Separation unit is for carrying out the second dense water of crystallization from described second Crystallization Separation unit 3rd Crystallization Separation processes, and obtains the 3rd crystal salt and the 3rd and crystallizes dense water.
Use the present invention method and system, it is possible to produce highly purified one-component salt (include sulfate crystal salt and Sodium chloride crystal salt), the one-component salt response rate, the Water Sproading rate of system and the calcium sulfate response rate are all significantly increased, sulfur simultaneously The high efficiente callback of acid calcium also greatly reduces the load of follow-up cation exchange, and the method can be greatly reduced energy consumption and throwing Money cost.
Cation preferred embodiment, before carrying out the second Crystallization Separation process, is first handed over by the one according to the present invention The water that swaps out is evaporated processing, and then evaporation process obtained carries out second close to the saturated dense water of evaporation as crystallization water inlet Crystallization Separation processes, it is possible to energy consumption and cost of investment are greatly reduced.
One according to the present invention preferred embodiment, the 3rd Crystallization Separation process in, the 3rd crystallization that will obtain Dense moisture is two strands, processes to the second Crystallization Separation respectively as the 3rd crystallization backflow mother liquor reflux and carries out as the dense water of system Post processing, it is possible to achieve the concentration again of one-component salt and fractional crystallization, it is possible to realize comparing one-component salt thoroughly Separating and crystallization, be effectively improved the response rate of one-component salt so that whole operating process realizes continuous operation, stable state produces salt, There is preferable economic worth and use value.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the salt extraction process of one embodiment of the present invention.
Fig. 2 is the schematic flow sheet of the salt extraction process of comparative example 1 of the present invention.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The end points of scope disclosed in this article and any value are not limited to this accurate scope or value, these scopes or Value should be understood to the value comprised close to these scopes or value.For numerical range, between the endpoint value of each scope, respectively Between endpoint value and the single point value of individual scope, and can obtain one or more between single point value with combination with one another New numerical range, these numerical rangies should be considered the most specifically to disclose.
First aspect, the invention provides a kind of salt extraction process, and the method includes:
(1) brackish water containing dianion salt and univalent anion salt is carried out reverse-osmosis treated, with by brackish water Carry out initial concentration, obtain reverse osmosis concentrated water and the reverse osmosis produced water of lean salt of rich salt；
(2) reverse osmosis concentrated water that step (1) obtains is carried out the first Crystallization Separation process, obtain the first crystal salt and first Crystallizing dense water, crystallizing dense moisture by described first is two strands, is back to step (1) respectively as the first backflow crystallization water outlet and carries out Described reverse-osmosis treated and carry out follow-up cation exchange process as cation exchange；
(3) cation exchange water inlet step (2) obtained carries out cation exchange process, obtains rich monovalent cation salt Cation exchange water outlet；
(4) cation exchange water outlet step (3) obtained carries out the second Crystallization Separation process as crystallization water inlet, obtains Second crystal salt and second crystallizes dense water；
(5) the second dense water of crystallization step (4) obtained carries out the 3rd Crystallization Separation and processes, and obtains the 3rd crystal salt and the Three crystallize dense water.
In the salt extraction process of the present invention, in order to energy consumption is greatly reduced, under preferable case, the method also includes: carrying out Before two Crystallization Separation process, the exchange water outlet of the cation that step (3) obtained is evaporated processing, and obtains distilled water and close The dense water of saturated evaporation, then carries out described second Crystallization Separation using dense for described evaporation water as crystallization water inlet and processes.
Preferably, the condition of described evaporation process includes: temperature is 50-135 DEG C, more preferably 90-120 DEG C.
Preferably, the described saturation close to sodium sulfate in the saturated dense water of evaporation or sodium chloride is 50-99%, further It is preferably 70-95%, the most preferably 90-95%.Wherein, saturation can be come real by controlling suitable concentration rate Existing.
In the salt extraction process of the present invention, in order to realize more effectively concentrating under normal temperature condition, improve the response rate of water, and Reduce load and the energy consumption of subsequent evaporation crystallization process, under preferable case, in step (1), containing dianion salt and monovalence The brackish water of anion salt contains the first backflow crystallization water outlet described in raw water and step (2)；And total matter of salt in raw water < when 2.5%, < Y/ (2.5-Y), R1 are cation exchange water inlet and reverse osmosis produced water to amount percentage composition Y% to meet relational expression R1 Volume flow ratio.
In the salt extraction process of the present invention, under preferable case, in step (1), the condition of reverse-osmosis treated includes: temperature is 10-40 DEG C, more preferably 15-30 DEG C；Pressure is 1-6MPa, more preferably 1.6-4MPa；Described reverse osmosis concentrated water It is 0.2-2:1, more preferably 0.3-1:1 with the volume flow ratio of described reverse osmosis produced water.
In the salt extraction process of the present invention, under preferable case, the method also includes: in step (1), is being carried out instead by brackish water Before infiltration processes, in described brackish water, add at least one antisludging agent；And in the first Crystallization Separation described in step (2) In process, control condition makes described antisludging agent inactivate, to carry out Crystallization Separation.
Preferably, relative to brackish water described in 1L, the consumption of antisludging agent is 2-15mg, more preferably 3-7mg.
Preferably, described antisludging agent be organic phosphine type antisludging agent, organic phospho acid salt form antisludging agent, polycarboxylic acid-based inhibitor and At least one in composite scale agent.
In the salt extraction process of the present invention, under preferable case, in the following ways at least one mode make described scale inhibition Agent inactivates:
Mode one: add at least one solid matter that can act as room temperature crystalline seed in described reverse osmosis concentrated water；
Mode two: add at least one flocculant in described reverse osmosis concentrated water；
Mode three: regulate the pH value of described reverse osmosis concentrated water.
Preferably, in mode one, the addition of solid matter makes the mass concentration of crystal seed in reverse osmosis concentrated water be 2%- 12%, more preferably 4%-8%.
Preferably, in mode one, solid matter is identical with the kind of the difficultly water soluble salts in reverse osmosis concentrated water, the most excellent Choosing is selected from calcium sulfate and/or the hydrate of calcium sulfate.
Preferably, in mode two, relative to the reverse osmosis concentrated water described in 1L, the consumption of flocculant is 2-20mg, further Being preferably 5-15mg, described flocculant is preferably iron chloride and/or iron sulfate；
Preferably, in mode three, the pH value of described reverse osmosis concentrated water is adjusted to 3-6, is further preferably adjusted to 3.5- 4.5。
In the salt extraction process of the present invention, under preferable case, in step (2), the condition that the first Crystallization Separation processes includes: temperature Degree is 10-40 DEG C, more preferably 15-30 DEG C；First backflow crystallization water outlet and the volume flow ratio of cation exchange water inlet For 1-20:1, more preferably 3-9:1.
In the salt extraction process of the present invention, processed by reverse-osmosis treated and the first Crystallization Separation and be capable of brackish water Efficient concentration, and can substantially reduce the load of follow-up cation exchange.Wherein, the first Crystallization Separation processes and grasps at normal temperatures Make, the solution supersaturation that causes mainly by reverse osmosis concentration and spontaneous generation crystallization process, it is not necessary to expend big energy or chemistry Medicament.Processed by the first Crystallization Separation and can get rid of most low solubility divalent salts, the first crystal salt obtained It is the calcium sulfate that purity is higher under normal circumstances, and the calcium sulfate degree of supersaturation of the first dense water of crystallization obtained significantly reduces.
In the salt extraction process of the present invention, under preferable case, in step (3), the condition that cation exchange processes includes: temperature For 10-40 DEG C, more preferably 15-30 DEG C；The time of staying is 2-30 minute, more preferably 5-15 minute；Cation In exchange water outlet, the concentration of calcium ion is 0.01-5mg/L, more preferably 0.05-1mg/L.
In the salt extraction process of the present invention, under preferable case, in step (4), the mode that the second Crystallization Separation processes is first Evaporative crystallization processes or crystallisation by cooling processes.
Preferably, the condition that described first evaporative crystallization processes includes: temperature is 50-120 DEG C；
Preferably, the condition that described crystallisation by cooling processes includes: the freezing point that temperature is intake less than 5 DEG C and higher than described crystallization Temperature, more preferably-2～2 DEG C.
In the salt extraction process of the present invention, under preferable case, in step (5), the mode that described 3rd Crystallization Separation processes is Second evaporative crystallization processes.
Preferably, the condition that described second evaporative crystallization processes includes: temperature is 50-120 DEG C.
During it is further preferred that the mode that described second Crystallization Separation processes is the first evaporative crystallization process, described second The temperature that evaporative crystallization processes is lower at least 20 DEG C than the temperature that described first evaporative crystallization processes；Described second Crystallization Separation processes Mode be crystallisation by cooling process time, described second evaporative crystallization process temperature be 50-80 DEG C.
Wherein, the mode that the second Crystallization Separation processes is the mode that the first evaporative crystallization processes, the 3rd Crystallization Separation processes When being the second evaporative crystallization process, first the first evaporative crystallization can be processed the second dense water of crystallization that obtain and carry out cooling process, Preferably, described cooling processes and carries out in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger, and described second Crystallize dense water to flow in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger as tube side fluid.This area skill Art personnel can select the concrete kind of heat exchanger according to practical situation, and this is well known to those skilled in the art, at this no longer Repeat.Wherein, the second crystal salt is mainly sodium sulfate, and the 3rd crystal salt is mainly sodium chloride.
Wherein, the mode that the second Crystallization Separation processes be the mode that crystallisation by cooling processes, the 3rd Crystallization Separation processes be the Two evaporative crystallizations process time, can first evaporation process be obtained carry out cooling process close to the saturated dense water of evaporation after as tie Crystalline substance carries out crystallisation by cooling process, is then processed by crystallisation by cooling after the second dense water of crystallization obtained carries out hyperthermic treatment and carries out Second evaporative crystallization processes.
Preferably, the method that cooling processes includes: will lower the temperature by the way of heat exchange processes close to the saturated dense water that evaporates To crystallisation by cooling temperature, the freezing point temperature that described crystallisation by cooling temperature is intake less than 5 DEG C and higher than described crystallization, further preferably For-2～2 DEG C；And control described crystallization water inlet heat exchange process in flow velocity be 1-20m/s, more preferably 2-5m/s；
Preferably, described heat exchange processes and carries out in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger, and Described crystallization water inlet is flowed in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger as tube side fluid.Ability Field technique personnel can select the concrete kind of heat exchanger according to practical situation, and this is well known to those skilled in the art, at this Repeat no more.Wherein, the second crystal salt is mainly sodium sulfate, and the 3rd crystal salt is mainly sodium chloride.
Preferably, the embodiment of described hyperthermic treatment is that heat exchange processes, and this is well known to those skilled in the art, at this Repeat no more.
In the salt extraction process of the present invention, in order to improve the response rate of dianion salt, under preferable case, the party further Method also includes: the 3rd dense moisture of crystallization step (5) obtained is two strands, respectively as the 3rd crystallization backflow mother liquor reflux to step Suddenly (4) carry out the second described Crystallization Separation process and carry out post processing as the dense water of system.
Preferably, described 3rd crystallization backflow mother solution is 1-100:1 with the volume flow ratio of the dense water of described system, further It is preferably 3-50:1.
In the salt extraction process of the present invention, it is preferable that the method also includes dense for described system water is evaporated crystallization treatment To obtain containing univalent anion salt and the salt-mixture of dianion salt.
In the salt extraction process of the present invention, under preferable case, the exchange water outlet of described cation contains dianion salt and one In valency anion salt, and the exchange water outlet of described cation, the weight/mass percentage composition of dianion salt is 0.2%-5%；Further Preferably, described dianion salt contains sodium sulfate, and described univalent anion salt contains sodium chloride；It is further preferred that Described dianion salt is sodium sulfate, and described univalent anion salt is sodium chloride.
Second aspect, as it is shown in figure 1, the invention provides a kind of salt making system, this salt making system include reverse osmosis units, First Crystallization Separation unit, cation crosspoint, the second Crystallization Separation unit and the 3rd Crystallization Separation unit,
Described reverse osmosis units is for carrying out reverse osmosis by the brackish water containing dianion salt and univalent anion salt Process, obtain reverse osmosis concentrated water and the reverse osmosis produced water of lean salt of rich salt；
Described first Crystallization Separation unit is for carrying out the first crystallization by the reverse osmosis concentrated water from described reverse osmosis units Separating treatment, obtains the first crystal salt and first and crystallizes dense water, and described first Crystallization Separation unit and described reverse osmosis units It is connected, at least part of first crystallization concentrate recirculation is carried out reverse-osmosis treated to described reverse osmosis units；
Described cation crosspoint is not for being back to described reverse osmosis from described first Crystallization Separation unit The first dense water of crystallization of unit carries out cation exchange process as cation exchange water inlet, obtains the sun of rich monovalent cation salt Ion exchange water outlet；
Described second Crystallization Separation unit for using from described cation crosspoint cation exchange water inlet as Crystallization water inlet carries out the second Crystallization Separation process, obtains the second crystal salt and second and crystallizes dense water；
Described 3rd Crystallization Separation unit is for carrying out the second dense water of crystallization from described second Crystallization Separation unit 3rd Crystallization Separation processes, and obtains the 3rd crystal salt and the 3rd and crystallizes dense water.
In the salt making system of the present invention, under preferable case, this salt making system also includes evaporation element, and described evaporation element is used It is evaporated processing in the cation from described cation crosspoint is exchanged water outlet, obtains distilled water and close to saturated Evaporate dense water；And described second Crystallization Separation unit for using from described evaporation element the dense water of described evaporation as crystallize into Water carries out described second Crystallization Separation and processes.
Preferably, described evaporation element includes vaporizer.
In the salt making system of the present invention, under preferable case, reverse osmosis units includes at least one reverse-osmosis membrane element, enters one Preferably, reverse osmosis units includes at least two reverse-osmosis membrane elements being used in series to step.
In the salt making system of the present invention, under preferable case, the first Crystallization Separation unit includes the first crystalline element and first Solid-liquid separation unit,
Described first crystalline element is used for the reverse osmosis concentrated water from described reverse osmosis units is carried out the first crystallization treatment, Obtain crystallizing, as first, the first crystallization water outlet and the first crystallization solidliquid mixture that dense water uses,
Described first solid-liquid separation unit is for entering the first crystallization solidliquid mixture from described first crystalline element Row the first solid-liquid separation processes, and obtains the first crystal salt and crystallizes, as first, the first crystalline mother solution that dense water uses.
In the salt making system of the present invention, according to a kind of preferred implementation (mode processed corresponding to the second Crystallization Separation Process for crystallisation by cooling, the mode of the 3rd Crystallization Separation process is that the second evaporative crystallization processes), this salt making system also includes cooling Unit and intensification unit, described cooling unit is for by lowering the temperature close to the saturated dense water of evaporation from described evaporation element Process, then cooling product is carried out crystallisation by cooling process as crystallization water inlet supply to the second Crystallization Separation unit.Described liter Temperature unit is carried out at intensification for the second dense water of the crystallization cooled crystallization treatment from the second Crystallization Separation unit obtained Supply after reason to the 3rd Crystallization Separation unit and carry out the second evaporative crystallization process.
Preferably, intensification unit includes heat exchanger, it is further preferred that described heat exchanger is spiral tube exchanger, tubulation Formula heat exchanger or double pipe heat exchanger.
In the salt making system of the present invention, according to a kind of preferred implementation (mode processed corresponding to the second Crystallization Separation It is that the first evaporative crystallization processes, the mode of the 3rd Crystallization Separation process is that the second evaporative crystallization processes), this salt making system also includes Cooling unit, for will supply to the 3rd Crystallization Separation unit after the second dense water for cooling of crystallization of the second Crystallization Separation unit Carry out the second evaporative crystallization process.
Preferably, cooling unit includes heat exchanger, it is further preferred that described heat exchanger is spiral tube exchanger, tubulation Formula heat exchanger or double pipe heat exchanger.Those skilled in the art can select the concrete kind of heat exchanger according to practical situation, this It is well known to those skilled in the art, does not repeats them here.
In the salt making system of the present invention, under preferable case, the second Crystallization Separation unit includes the second crystalline element and second Solid-liquid separation unit,
Described second crystalline element is for intaking the crystallization from described cation crosspoint or described evaporation element Carry out the second crystallization treatment, obtain crystallizing, as second, the second crystallization water outlet and the second crystallization solidliquid mixture that dense water uses,
Described second solid-liquid separation unit is for entering the second crystallization solidliquid mixture from described second crystalline element Row the second solid-liquid separation processes, and obtains the second crystal salt and crystallizes, as second, the second crystalline mother solution that dense water uses.
Preferably, described second crystalline element includes crystallizing evaporator or cooler crystallizer.
In the salt making system of the present invention, under preferable case, described 3rd Crystallization Separation unit include the 3rd crystalline element and 3rd solid-liquid separation unit,
Described 3rd crystalline element is for carrying out the 3rd crystallization by the second dense water of crystallization from described second crystalline element Process, obtain crystallizing, as the 3rd, the 3rd crystallization water outlet and the 3rd crystallization solidliquid mixture that dense water uses,
Described 3rd solid-liquid separation unit is for entering the 3rd crystallization solidliquid mixture from described 3rd crystalline element Row the 3rd solid-liquid separation processes, and obtains the 3rd crystal salt and crystallizes, as the 3rd, the 3rd crystalline mother solution that dense water uses；
Preferably, described 3rd crystalline element includes crystallizing evaporator.
Preferably, this salt making system also includes that crystallizing evaporator is for by the dense water of system from the 3rd Crystallization Separation unit It is evaporated crystallization treatment to obtain containing univalent anion salt and the salt-mixture of dianion salt.
Embodiment
Hereinafter will be described the present invention by embodiment, but and be not so limited the scope of the present invention.Below In embodiment, if no special instructions, the method used is method commonly used in the art.
Inductively coupled plasma (ICP) method and chromatography of ions (IC) is used to determine each component in water and content thereof.
Using synthesis brackish water analog raw material water, its component is as shown in table 1.
Table 1
Project Na<sup>+</sup> Ca<sup>2+</sup> Cl<sup>-</sup> SO<sub>4</sub><sup>2-</sup>
Unit mg/L mg/L mg/L mg/L
Numerical value 612.2 413.2 301.8 1859.3
Embodiment 1
In conjunction with Fig. 1, the present embodiment is for illustrating the salt extraction process of the present invention.
The reverse osmosis units used in the present embodiment is to include that 3 putaminas in parallel, every putamina are built with 6 series connection One section of counter-infiltration system of the one-level of DOW BW30FR-400 reverse-osmosis membrane element；First Crystallization Separation unit includes a total measurement (volume) For 12.5m3Reaction depositing reservoir and centrifugal separating device；Cation crosspoint be a volume be 0.15m3, filling DOWEX The cation exchanger of MAC-3 Weak-acid cation exchange resin；Evaporation element be a heat exchange area be 20m2Mechanical compress Formula vaporizer；Second Crystallization Separation unit includes that a heat exchange area is 1.0m2Forced-circulation evaporation crystallizer and centrifugal point From device；3rd Crystallization Separation unit includes that a heat exchange area is 0.2m2Forced-circulation evaporation crystallizer and centrifugation Device.The flow of inlet water of raw water is 11.0m3/ h, concrete technology flow process is as follows:
(1) it is 11.0m by flow3/ h, temperature are that the synthesis brackish water shown in table 1 of 25 DEG C is with flow as raw water 4.0m3After/h, temperature are the first backflow crystallization water outlet mixing of 25 DEG C, add the antisludging agent (effective ingredient of 5.0mg/L wherein For organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) after, with 15.0m3The total flow of/h, the temperature of 25 DEG C are made For, in reverse osmosis mixing water inlet supply to reverse osmosis units, carrying out reverse-osmosis treated at 25 DEG C.Wherein, reverse osmosis units uses Part dense water circulation operator scheme, dense water circulating load is 15.0m3/ h, the intake pressure of reverse osmosis units is 1.6MPa.Through anti- After permeation unit processes, obtaining flow is 10.0m3/ h, temperature are the reverse osmosis produced water of 25 DEG C and flow is 5.0m3/ h, temperature are The reverse osmosis concentrated water of 25 DEG C.In reverse osmosis concentrated water, the degree of supersaturation of calcium sulfate is 352.0%.
(2) to flow be 5.0m3/ h, temperature are to add the iron chloride flocculant of 10.0mg/L in the reverse osmosis concentrated water of 25 DEG C After, supply to the first Crystallization Separation unit carries out room temperature (25 DEG C) Crystallization Separation and processes.Owing to the effect of flocculant makes part Antisludging agent loses the effect stoping crystallization, separates out part of sulfuric acid calcium crystalline solid in the oversaturated reverse osmosis concentrated water of calcium sulfate, To the first crystallization water outlet and the first crystallization solidliquid mixture of clarification, the first crystallization solidliquid mixture centrifugal separating device is entered Row centrifuging treatment, obtains crystal of calcium sulfate salt (for 13.8kg/h after deduction water of crystallization) and the first crystalline mother solution, becomes split-phase It is two strands that the first same crystallization water outlet crystallizes dense moisture with the first crystalline mother solution as first, and one flow is 4.0m3/ h, temperature Be 25 DEG C first backflow crystallization water outlet and another plume amount be 1.0m3/ h, temperature are the cation exchange water inlet of 25 DEG C.By One backflow crystallization water outlet supply enters reverse osmosis units after mixing with raw water to step (1) and is circulated process.
(3) it is 1.0m by flow3/ h, temperature are that the cation exchange water inlet feeding cation crosspoint of 25 DEG C carries out sun Ion-exchange treatment, wherein, cation exchange water inlet is 9 minutes in the time of staying of cation crosspoint, and obtaining flow is 1.0m3The cation exchange water outlet that/h, temperature are 25 DEG C, calcium ion concentration is 0.05mg/l.
(4) it is 1.0m by flow3/ h, temperature are that the cation exchange water outlet of 25 DEG C supplies to evaporation element, at 105 DEG C It is evaporated concentration.The concentration rate controlling evaporation element is 16.7 times, and obtaining flow is 0.94m3Water is produced in the condensation of/h It is 0.06m with flow3/ h, temperature be 105 DEG C close to the saturated dense water of evaporation element (saturation 81.3% of sodium sulfate).
(5) it is 0.06m by flow3/ h, temperature be the dense water of evaporation element and the flow of 105 DEG C be 0.14m3/ h, temperature are 60 DEG C the 3rd crystallization backflow mother solution mixing after as second crystallized mixed water inlet supply to the second Crystallization Separation unit, at 100 DEG C Under be evaporated Crystallization Separation process.Owing to sodium sulfate reaches saturated prior to sodium chloride, part of sulfuric acid sodium separates out, and uses centrifugal point After device is centrifuged separating treatment, obtain sulfate crystal salt (for 13.3kg/h after deduction water of crystallization).Simultaneously, it is thus achieved that stream Amount is 0.047m3The distilled water of/h and flow are 0.153m3/ h, temperature are the second dense water of crystallization of 100 DEG C.
(6) it is 0.153m by flow3/ h, temperature are that the second dense water of crystallization of 100 DEG C is cooled to 60 through tubular heat exchanger Supply after DEG C to the 3rd Crystallization Separation unit, at 60 DEG C, be evaporated Crystallization Separation process.At this temperature, due to sodium chloride Reaching saturated prior to sodium sulfate, partial oxidation sodium separates out, and after using centrifugal separating device to be centrifuged separating treatment, obtains chlorination Sodium crystal salt (being 3.7kg/h after deduction water of crystallization).Simultaneously, it is thus achieved that flow is 0.009m3The distilled water of/h and flow are 0.144m3/ h, temperature are the 3rd dense water of crystallization of 60 DEG C.It is two strands by the 3rd dense moisture of crystallization, will flow be wherein 0.140m3/ One of h sends the second Crystallization Separation unit circular treatment in step (5) back to as the 3rd crystallization backflow mother solution, by flow is 0.004m3Another stock of/h is evaporated crystallization treatment as the supply of system dense water to crystallizing evaporator, is mainly comprised chlorine Change sodium and the salt-mixture of sodium sulfate.
Table 2 gives flow and the component of each material stream in embodiment 1.
Table 2
From table 2 it can be seen that the raw water that temperature is 25 DEG C contains higher calcium, sodium, chloride ion and sulfate radical simultaneously, Obtain after the first backflow crystallization water outlet mixes with temperature is 25 DEG C temperature be 25 DEG C, calcium sulfate degree of supersaturation be 99.0% anti- Infiltration mixing water inlet, after reverse-osmosis treated, the calcium sulfate degree of supersaturation of the reverse osmosis concentrated water obtained is 352.0%, due to The effect of antisludging agent, now reverse osmosis concentrated water remains stable.Reverse osmosis concentrated water makes antisludging agent lose resistance by flocculant Only after the effect of crystallization, room temperature Crystallizing process separates out calcium sulphate solid, the calcium sulfate mistake of the first backflow crystallization water outlet Saturation declines to a great extent to 116.6%, close to saturation (calcium sulfate degree of supersaturation 100%), reaches a kind of new stablizing State, is back to reverse osmosis units afterwards and is circulated process.This circular treatment also makes Water Sproading rate and the sulphuric acid of system The calcium response rate all increases considerably, in the present embodiment, and the combined system being made up of reverse osmosis units and the first Crystallization Separation unit Water Sproading rate be 90.9%, the response rate (in terms of calcium) of crystal of calcium sulfate salt is then 89.5%.The efficient crystallization of calcium sulfate Reclaim the load also greatly reducing the exchange of follow-up cation.In the present embodiment, for raw water, cation exchanges Unit is only 10.5% for the ion exchange load of cation exchange water inlet, greatly reduces investment and the operation of ion exchange Cost.
On the other hand, utilize the difference that the solubility with temperature of sodium sulfate and sodium chloride changes (60 DEG C of-100 DEG C of scopes In, sodium sulfate solubility with temperature in water raises and reduces, the rising of the solubility with temperature of sodium chloride and raise), adopt Combine with the 3rd Crystallization Separation (60 DEG C) by the second Crystallization Separation (100 DEG C), furthermore achieved that sodium sulfate and sodium chloride Separate.In the present embodiment, the response rate of sodium sulfate (in terms of the sulfate radical in ion exchange water outlet) for 91.4%, returning of sodium chloride Yield (chloride ion with in ion exchange water outlet), for 74.6%, all achieves the higher response rate.
Embodiment 2
In conjunction with Fig. 1, the present embodiment is for illustrating the salt extraction process of the present invention.
The reverse osmosis units used in the present embodiment is to include that 3 putaminas in parallel, every putamina are built with 6 series connection One section of counter-infiltration system of the one-level of DOW BW30FR-400 reverse-osmosis membrane element；First Crystallization Separation unit includes a total measurement (volume) For 12.5m3Reaction depositing reservoir and centrifugal separating device；Cation crosspoint be a volume be 0.15m3, filling DOWEX The cation exchanger of MAC-3 Weak-acid cation exchange resin；Evaporation element be a heat exchange area be 20m2Mechanical compress Formula vaporizer；Second Crystallization Separation unit includes that the volume of a band heat-insulation layer is 0.15m3Rustless steel container and centrifugation Device；3rd Crystallization Separation unit includes that a heat exchange area is 1.0m2Forced-circulation evaporation crystallizer and centrifugation dress Put.The flow of inlet water of raw water is 11.0m3/ h, concrete technology flow process is as follows:
(1) it is 11.0m by flow3/ h, temperature are that the synthesis brackish water shown in table 1 of 25 DEG C is with flow as raw water 4.0m3After/h, temperature are the first backflow crystallization water outlet mixing of 25 DEG C, add the antisludging agent (effective ingredient of 5.0mg/L wherein For organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) after, with 15.0m3The total flow of/h, the temperature of 25 DEG C are made For, in reverse osmosis mixing water inlet supply to reverse osmosis units, carrying out reverse-osmosis treated at 25 DEG C.Wherein, reverse osmosis units uses Part dense water circulation operator scheme, dense water circulating load is 15.0m3/ h, the intake pressure of reverse osmosis units is 1.6MPa.Through anti- After permeation unit processes, obtaining flow is 10.0m3/ h, temperature are the reverse osmosis produced water of 25 DEG C and flow is 5.0m3/ h, temperature are The reverse osmosis concentrated water of 25 DEG C.In reverse osmosis concentrated water, the degree of supersaturation of calcium sulfate is 352.0%.
(2) to flow be 5.0m3/ h, temperature are to add the iron chloride flocculant of 10.0mg/L in the reverse osmosis concentrated water of 25 DEG C After, supply to the first Crystallization Separation unit carries out room temperature (25 DEG C) Crystallization Separation and processes.Owing to the effect of flocculant makes part Antisludging agent loses the effect stoping crystallization, separates out part of sulfuric acid calcium crystalline solid in the oversaturated reverse osmosis concentrated water of calcium sulfate, To the first crystallization water outlet and the first crystallization solidliquid mixture of clarification, the first crystallization solidliquid mixture centrifugal separating device is entered Row centrifuging treatment, obtains crystal of calcium sulfate salt (for 13.8kg/h after deduction water of crystallization) and the first crystalline mother solution, becomes split-phase It is two strands that the first same crystallization water outlet crystallizes dense moisture with the first crystalline mother solution as first, and one flow is 4.0m3/ h, temperature Be 25 DEG C first backflow crystallization water outlet and another plume amount be 1.0m3/ h, temperature are the cation exchange water inlet of 25 DEG C.By One backflow crystallization water outlet supply enters reverse osmosis units after mixing with raw water to step (1) and is circulated process.
(3) it is 1.0m by flow3/ h, temperature are that the cation exchange water inlet feeding cation crosspoint of 25 DEG C carries out sun Ion-exchange treatment, wherein, cation exchange water inlet is 9 minutes in the time of staying of cation crosspoint, and obtaining flow is 1.0m3The cation exchange water outlet that/h, temperature are 25 DEG C, calcium ion concentration is 0.05mg/l.
(4) it is 1.0m by flow3/ h, temperature are that the cation exchange water outlet of 25 DEG C supplies to evaporation element, at 105 DEG C It is evaporated concentration.The concentration rate of control evaporation element is to 16.7 times, and obtaining flow is 0.94m3Water is produced in the condensation of/h It is 0.06m with flow3/ h, temperature be 105 DEG C close to the saturated dense water of evaporation element (saturation 81.3% of sodium sulfate).
(5) it is 0.06m by flow3/ h, temperature be the dense water of evaporation element and the flow of 105 DEG C be 0.01m3/ h, temperature are 60 DEG C the 3rd crystallization backflow mother solution mixing, after being cooled to 0 DEG C by spiral tube exchanger as second crystallized mixed water inlet supply To the second Crystallization Separation unit, at 0 DEG C, carry out crystallisation by cooling separating treatment.Due to sodium sulfate dissolubility the most drastically Declining (at 0 DEG C, sodium sulfate dissolubility in water is about 4.9 grams), part of sulfuric acid sodium separates out, and uses centrifugal separating device to carry out After centrifuging treatment, obtain sulfate crystal salt (for 14.0kg/h after deduction water of crystallization).Simultaneously, it is thus achieved that flow is 0.07m3/ h, temperature are the second dense water of crystallization of 0 DEG C.
(6) it is 0.07m by flow3/ h, temperature are that the second dense water of crystallization of 0 DEG C is after tubular heat exchanger is warming up to 60 DEG C Supply, to the 3rd Crystallization Separation unit, is evaporated Crystallization Separation at 60 DEG C and processes.At this temperature, due to sodium chloride prior to Sodium sulfate reaches saturated, and partial oxidation sodium separates out, and after using centrifugal separating device to be centrifuged separating treatment, obtains sodium chloride knot Brilliant salt (being 4.4kg/h after deduction water of crystallization).Simultaneously, it is thus achieved that flow is 0.058m3The distilled water of/h and flow are 0.012m3/h、 Temperature is the 3rd dense water of crystallization of 60 DEG C.It is two strands by the 3rd dense moisture of crystallization, will flow be wherein 0.010m3One of/h is made It is the 3rd the second Crystallization Separation unit circular treatment crystallizing that backflow mother solution is sent back in step (5), is 0.002m by flow3/ h's Another stock is evaporated crystallization treatment as the supply of system dense water to crystallizing evaporator, is mainly comprised sodium chloride and sodium sulfate Salt-mixture.
Table 3 gives flow and the component of each material stream in embodiment 2.
Table 3
From table 3 it can be seen that the raw water that temperature is 25 DEG C contains higher calcium, sodium, chloride ion and sulfate radical simultaneously, Obtain after the first backflow crystallization water outlet mixes with temperature is 25 DEG C temperature be 25 DEG C, calcium sulfate degree of supersaturation be 99.0% anti- Infiltration mixing water inlet, after reverse-osmosis treated, the calcium sulfate degree of supersaturation of the reverse osmosis concentrated water obtained is 352.0%, due to The effect of antisludging agent, now reverse osmosis concentrated water remains stable.Reverse osmosis concentrated water makes antisludging agent lose resistance by flocculant Only after the effect of crystallization, room temperature Crystallizing process separates out calcium sulphate solid, the calcium sulfate mistake of the first backflow crystallization water outlet Saturation declines to a great extent to 116.6%, close to saturation (calcium sulfate degree of supersaturation 100%), reaches a kind of new stablizing State, is back to reverse osmosis units afterwards and is circulated process.This circular treatment also makes Water Sproading rate and the sulphuric acid of system The calcium response rate all increases considerably, in the present embodiment, and the combined system being made up of reverse osmosis units and the first Crystallization Separation unit Water Sproading rate be 90.9%, the response rate (in terms of calcium) of crystal of calcium sulfate salt is then 89.5%.The efficient crystallization of calcium sulfate Reclaim the load also greatly reducing the exchange of follow-up cation.In the present embodiment, for raw water, cation exchanges Unit is only 10.5% for the ion exchange load of cation exchange water inlet, greatly reduces investment and the operation of ion exchange Cost.
On the other hand, utilize significant difference that the dissolubility of sodium sulfate and sodium chloride varies with temperature at low-temperature region (from 40 DEG C to 0 DEG C, sodium sulfate dissolubility in water drastically reduces to about 4.9 grams from about 49 grams, and the dissolubility of sodium chloride only from 36.6 grams faint is reduced to 35.7 grams), use the second Crystallization Separation (0 DEG C) to combine with the 3rd Crystallization Separation (60 DEG C), enter one Step achieves sodium sulfate and separates with sodium chloride.In the present embodiment, the response rate of sodium sulfate is (with the sulphuric acid in ion exchange water outlet Root meter) it is 96.1%, the response rate (chloride ion with in ion exchange water outlet) of sodium chloride, for 89.1%, all achieves higher The response rate.
Embodiment 3
According to the method for embodiment 2, except for the difference that, in step (6), using the 3rd whole dense water of crystallization as the dense water of system Supplying to crystallizing evaporator and be evaporated crystallization treatment, specifically, step (5) and step (6) be:
(5) it is 0.06m by flow3/ h, temperature are that the dense water of evaporation element of 105 DEG C is cooled to 0 by spiral tube exchanger As the second crystallization water inlet supply to the second Crystallization Separation unit after DEG C, at 0 DEG C, carry out crystallisation by cooling separating treatment.Due to sulfur The dissolubility of acid sodium the most drastically declines, and part of sulfuric acid sodium separates out, and uses centrifugal separating device to be centrifuged separating treatment After, obtain sulfate crystal salt (for 11.6kg/h after deduction water of crystallization).Simultaneously, it is thus achieved that flow is 0.06m3/ h, temperature are 0 DEG C Second crystallization dense water.
(6) it is 0.06m by flow3/ h, temperature are that the second dense water of crystallization of 0 DEG C is after tubular heat exchanger is warming up to 60 DEG C Supply, to the 3rd Crystallization Separation unit, is evaporated Crystallization Separation at 60 DEG C and processes.At this temperature, due to sodium chloride prior to Sodium sulfate reaches saturated, and partial oxidation sodium separates out, and after using centrifugal separating device to be centrifuged separating treatment, obtains sodium chloride knot Brilliant salt (being 2.3kg/h after deduction water of crystallization).Simultaneously, it is thus achieved that flow is 0.05m3The distilled water of/h and flow are 0.01m3/ h, temperature Degree is the 3rd dense water of crystallization of 60 DEG C.Crystallize dense water all to supply to crystallizing evaporator as the dense water of system be evaporated the 3rd Crystallization treatment, is mainly comprised the salt-mixture of sodium chloride and sodium sulfate.
Table 4 gives flow and the component of each material stream in embodiment 3.
Table 4
In the present embodiment, the response rate of sodium sulfate (in terms of the sulfate radical in ion exchange water outlet) for 79.8%, sodium chloride The response rate (chloride ion with in ion exchange water outlet) for 45.3, respectively significantly lower than the recovery of sodium sulfate of embodiment 2 The response rate (89.1%) of rate (96.1%) and sodium chloride.Show to crystallize dense water using at least part of 3rd as the 3rd crystallization backflow Mother liquor reflux processes to the second Crystallization Separation, it is possible to achieve the concentration again of one-component salt and fractional crystallization, it is possible to realize ratio The separation of one-component salt more thoroughly and crystallization, be effectively improved the response rate of one-component salt.
Comparative example 1
This comparative example uses flow process shown in Fig. 2, for the advance of the salt extraction process of the comparative illustration present invention.
The reverse osmosis units used in this comparative example is to include that 3 putaminas in parallel, every putamina are built with 6 series connection One section of counter-infiltration system of the one-level of DOW BW30FR-400 reverse-osmosis membrane element；Cation crosspoint is that a volume is 0.80m3, filling DOWEX MAC-3 Weak-acid cation exchange resin cation exchanger；Evaporation element is a heat exchange area For 60m2Mechanical compression type vaporizer；Crystallization Separation unit includes that a heat exchange area is 3.0m2Forced-circulation evaporation crystallization Device and centrifugal separating device.The flow of inlet water of raw water is 11.0m3/ h, concrete technology flow process is as follows:
(1) it is 11.0m by flow3/ h, temperature be the synthesis brackish water shown in table 1 of 25 DEG C as raw water, wherein After adding the antisludging agent (effective ingredient is organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) of 5.0mg/L, supply To reverse osmosis units, at 25 DEG C, carry out reverse-osmosis treated.Wherein, reverse osmosis units uses part dense water circulation operation mould Formula, dense water circulating load is 19.0m3/ h, the intake pressure of reverse osmosis units is 0.9MPa.After reverse osmosis units processes, It is 7.72m to flow3/ h, temperature are the reverse osmosis produced water of 25 DEG C and flow is 3.28m3/ h, temperature are 25 DEG C reverse osmosis concentrated Water.Now, the degree of supersaturation of reverse osmosis concentrated water during the degree of supersaturation of calcium sulfate is 353.0%, with embodiment 1 in reverse osmosis concentrated water Quite.
(2) it is 3.28m by flow3/ h, temperature be 25 DEG C reverse osmosis concentrated water send into cation crosspoint carry out sun from Sub-exchange processes, and wherein, cation exchange water inlet is 15 minutes in the time of staying of cation crosspoint, and obtaining flow is 3.28m3The cation exchange water outlet that/h, temperature are 25 DEG C, calcium ion concentration is 0.1mg/l.
(3) it is 3.28m by flow3/ h, temperature are the cation exchange water outlet supply evaporation element of 25 DEG C, at 105 DEG C It is evaporated concentration.The concentration rate controlling evaporation element is 25 times, and obtaining flow is 3.15m3The condensation of/h produce water and Flow is 0.13m3/ h, temperature be 105 DEG C close to the dense water of saturated evaporation element (saturation 75.8% of sodium sulfate).
(4) it is 0.13m by flow3/ h, temperature are that the evaporation element dense water supply of 105 DEG C is steamed to Crystallization Separation unit Send out crystallization treatment, obtain comprising the salt-mixture of sodium chloride and sodium sulfate.
Table 5 gives flow and the component of each material stream in comparative example 1.
Table 5
As can be seen from Table 5, temperature is to contain higher calcium, sodium, chloride ion and sulfate radical in the raw water of 25 DEG C simultaneously, Calcium sulfate degree of supersaturation is 80.7%, is in undersaturated condition, after reverse-osmosis treated, and the sulphuric acid of the reverse osmosis concentrated water obtained Calcium degree of supersaturation is 353.0%, suitable with the fouling risk of embodiment 1.Owing to not introducing the first crystallization in embodiment 1-2 Unit (room temperature crystallization), calcium sulfate is all gathered in reverse osmosis concentrated water, limits the Water Sproading rate of reverse osmosis units (only 70.2%, far below 90.9% in embodiment 1).Suffer from this, in this comparative example, the load (3.15m of evaporation element3/h) It is about the load (0.94m of evaporation element in embodiment 13/ h) 3.4 times, evaporation energy consumption increases accordingly.
Owing to not having room temperature crystallization to remove part of sulfuric acid calcium, the load (in terms of Ca) of this comparative example cationic exchange is 4.48kg/h, is 10 times of the load (being calculated as 0.42kg/h with Ca) that the cation in embodiment 1 exchanges, the investment of ion exchange Dramatically increase with regenerative agent expense.
Owing to not introducing combination crystalline element that operation temperature and condensing crystallizing control respectively (the second crystalline element and the Three crystalline elements), the dense water of evaporation element comprises sodium sulfate and sodium chloride by can only obtain after single evaporative crystallization cell processing Salt-mixture, under the condition of water quality that this comparative example uses, in this salt-mixture, the weight/mass percentage composition of sodium sulfate and sodium chloride is about It is respectively 85.0% and 15.0%.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this The thought of invention, it should be considered as content disclosed in this invention equally.

Claims (18)

1. a salt extraction process, it is characterised in that the method includes:
(1) brackish water containing dianion salt and univalent anion salt is carried out reverse-osmosis treated, to be carried out by brackish water Initial concentration, obtains reverse osmosis concentrated water and the reverse osmosis produced water of lean salt of rich salt；
(2) reverse osmosis concentrated water that step (1) obtains is carried out the first Crystallization Separation process, obtain the first crystal salt and the first crystallization Dense water, crystallizing dense moisture by described first is two strands, is back to step (1) respectively as the first backflow crystallization water outlet and carries out described Reverse-osmosis treated and carry out follow-up cation exchange process as cation exchange；
(3) cation exchange water inlet step (2) obtained carries out cation exchange process, obtains the sun of rich monovalent cation salt Ion exchange water outlet；
(4) cation exchange water outlet step (3) obtained carries out the second Crystallization Separation process as crystallization water inlet, obtains second Crystal salt and second crystallizes dense water；
(5) the second dense water of crystallization step (4) obtained carries out the 3rd Crystallization Separation and processes, and obtains the 3rd crystal salt and the 3rd knot Brilliant dense water.
Method the most according to claim 1, wherein, the method also includes: before carrying out the second Crystallization Separation process, will The cation exchange water outlet that step (3) obtains is evaporated processing, and obtains distilled water and close to the saturated dense water of evaporation, then will The dense water of described evaporation carries out described second Crystallization Separation as crystallization water inlet and processes；
Preferably, the condition of described evaporation process includes: temperature is 50-135 DEG C, more preferably 90-120 DEG C；
Preferably, the described saturation close to sodium sulfate in the saturated dense water of evaporation or sodium chloride is 50-99%, further preferably For 70-95%, the most preferably 90-95%.
Method the most according to claim 1 and 2, wherein, in step (1), described cloudy containing dianion salt and monovalence The brackish water of ion salt contains the first backflow crystallization water outlet described in raw water and step (2)；And the gross mass of salt in raw water < when 2.5%, < Y/ (2.5-Y), R1 are cation exchange water inlet and the body of reverse osmosis produced water to percentage composition Y% to meet relational expression R1 Long-pending flow-rate ratio.
4. according to the method described in any one in claim 1-3, wherein, in step (1), the condition bag of reverse-osmosis treated Include: temperature is 10-40 DEG C, preferably 15-30 DEG C；Pressure is 1-6MPa, preferably 1.6-4MPa；Described reverse osmosis concentrated water and institute The volume flow ratio stating reverse osmosis produced water is 0.2-2:1, preferably 0.3-1:1.
5. according to the method described in any one in claim 1-4, wherein, the method also includes: in step (1), will contain Before saline carries out reverse-osmosis treated, in described brackish water, add at least one antisludging agent；And in described in step (2) During one Crystallization Separation processes, control condition makes described antisludging agent inactivate, to carry out Crystallization Separation；
Preferably, relative to brackish water described in 1L, the consumption of described antisludging agent is 2-15mg, more preferably 3-7mg；
Preferably, described antisludging agent is organic phosphine type antisludging agent, organic phospho acid salt form antisludging agent, polycarboxylic acid-based inhibitor and is combined At least one in type antisludging agent.
Method the most according to claim 5, wherein, in the following ways at least one mode make described antisludging agent lose Live:
Mode one: add at least one solid matter that can act as room temperature crystalline seed in described reverse osmosis concentrated water；
Mode two: add at least one flocculant in described reverse osmosis concentrated water；
Mode three: regulate the pH value of described reverse osmosis concentrated water；
Preferably, in mode one, the addition of described solid matter makes the mass concentration of crystal seed in reverse osmosis concentrated water be 2%- 12%, more preferably 4%-8%；
Preferably, in mode one, described solid matter is identical with the kind of the difficultly water soluble salts in reverse osmosis concentrated water, the most excellent Choosing is selected from calcium sulfate and/or the hydrate of calcium sulfate；
Preferably, in mode two, relative to the reverse osmosis concentrated water described in 1L, the consumption of described flocculant is 2-20mg, further Being preferably 5-15mg, described flocculant is preferably iron chloride and/or iron sulfate；
Preferably, in mode three, the pH value of described reverse osmosis concentrated water is adjusted to 3-6, is further preferably adjusted to 3.5-4.5.
7., according to the method described in any one in claim 1-6, wherein, in step (2), described first Crystallization Separation processes Condition include: temperature is 10-40 DEG C, preferably 15-30 DEG C；First backflow crystallization water outlet and the volume of cation exchange water inlet Flow-rate ratio is 1-20:1, preferably 3-9:1.
8., according to the method described in any one in claim 1-7, wherein, in step (3), described cation exchange processes Condition includes: temperature is 10-40 DEG C, preferably 15-30 DEG C；The time of staying is 2-30 minute, preferably 5-15 minute；Cation In exchange water outlet, the concentration of calcium ion is 0.01-5mg/L, preferably 0.05-1mg/L.
9., according to the method described in any one in claim 1-8, wherein, in step (4), described second Crystallization Separation processes Mode be first evaporative crystallization process or crystallisation by cooling process,
Preferably, the condition that described first evaporative crystallization processes includes: temperature is 50-120 DEG C；
Preferably, the condition that described crystallisation by cooling processes includes: the freezing point temperature that temperature is intake less than 5 DEG C and higher than described crystallization Degree, more preferably-2～2 DEG C.
Method the most according to claim 9, wherein, in step (5), the mode that described 3rd Crystallization Separation processes is the Two evaporative crystallizations process,
Preferably, the condition that described second evaporative crystallization processes includes: temperature is 50-120 DEG C；
During it is further preferred that the mode that described second Crystallization Separation processes is the first evaporative crystallization process, described second evaporation The temperature of crystallization treatment is lower at least 20 DEG C than the temperature that described first evaporative crystallization processes；The side that described second Crystallization Separation processes When formula is crystallisation by cooling process, the temperature that described second evaporative crystallization processes is 50-80 DEG C.
11. according to the method described in any one in claim 1-10, and wherein, the method also includes: step (5) obtained The 3rd dense moisture of crystallization is two strands, carries out the second described crystallization respectively as the 3rd crystallization backflow mother liquor reflux to step (4) Separating treatment and carry out post processing as the dense water of system；
Preferably, described 3rd crystallization backflow mother solution is 1-100:1 with the volume flow ratio of the dense water of described system, further preferably For 3-50:1.
12. according to the method described in any one in claim 1-11, and wherein, it is cloudy that the exchange water outlet of described cation contains bivalence In ion salt and univalent anion salt, and the exchange water outlet of described cation, the weight/mass percentage composition of dianion salt is 0.2%- 5%；
Preferably, described dianion salt is sodium sulfate, and described univalent anion salt is sodium chloride.
13. 1 kinds of salt making systems, it is characterised in that this salt making system include reverse osmosis units, the first Crystallization Separation unit, sun from Sub-crosspoint, the second Crystallization Separation unit and the 3rd Crystallization Separation unit,
Described reverse osmosis units is used for the brackish water containing dianion salt and univalent anion salt is carried out reverse-osmosis treated, Obtain reverse osmosis concentrated water and the reverse osmosis produced water of lean salt of rich salt；
Described first Crystallization Separation unit is for carrying out the first Crystallization Separation by the reverse osmosis concentrated water from described reverse osmosis units Process, obtain the first crystal salt and first and crystallize dense water, and described first Crystallization Separation unit is connected with described reverse osmosis units, For at least part of first crystallization concentrate recirculation is carried out reverse-osmosis treated to described reverse osmosis units；
Described cation crosspoint is not for being back to described reverse osmosis units from described first Crystallization Separation unit The first dense water of crystallization carry out cation exchange process as cation exchange water inlet, obtain the cation of rich monovalent cation salt Exchange water outlet；
Described second Crystallization Separation unit is for exchanging water inlet as crystallization using the cation from described cation crosspoint Carry out the second Crystallization Separation process, obtain the second crystal salt and second and crystallize dense water；
Described 3rd Crystallization Separation unit is for carrying out the 3rd by the second dense water of crystallization from described second Crystallization Separation unit Crystallization Separation processes, and obtains the 3rd crystal salt and the 3rd and crystallizes dense water.
14. salt making systems according to claim 13, wherein, this salt making system also includes evaporation element, described evaporation list Unit is evaporated processing for the cation from described cation crosspoint is exchanged water outlet, obtains distilled water and close to full The dense water of evaporation of sum；And described second Crystallization Separation unit for using the dense water of described evaporation from described evaporation element as knot Crystalline substance carries out described second Crystallization Separation and processes.
15. according to the salt making system described in claim 13 or 14, and wherein, described reverse osmosis units includes at least one reverse osmosis Membrane component,
Preferably, described reverse osmosis units includes at least two reverse-osmosis membrane elements being used in series.
16. according to the salt making system described in any one in claim 13-15, wherein, and described first Crystallization Separation unit bag Include the first crystalline element and the first solid-liquid separation unit,
Described first crystalline element, for the reverse osmosis concentrated water from described reverse osmosis units is carried out the first crystallization treatment, obtains The first crystallization water outlet and the first crystallization solidliquid mixture that dense water uses is crystallized as first,
Described first solid-liquid separation unit is for carrying out the by the first crystallization solidliquid mixture from described first crystalline element One solid-liquid separation processes, and obtains the first crystal salt and crystallizes, as first, the first crystalline mother solution that dense water uses.
17. according to the salt making system described in any one in claim 13-16, wherein, and described second Crystallization Separation unit bag Include the second crystalline element and the second solid-liquid separation unit,
Described second crystalline element is for carrying out the crystallization from described cation crosspoint or described evaporation element Second crystallization treatment, obtains crystallizing, as second, the second crystallization water outlet and the second crystallization solidliquid mixture that dense water uses,
Described second solid-liquid separation unit is for carrying out the by the second crystallization solidliquid mixture from described second crystalline element Two solid-liquid separation process, and obtain the second crystal salt and crystallize, as second, the second crystalline mother solution that dense water uses；
Preferably, described second crystalline element includes crystallizing evaporator or cooler crystallizer.
18. according to the salt making system described in any one in claim 13-17, wherein, and described 3rd Crystallization Separation unit bag Include the 3rd crystalline element and the 3rd solid-liquid separation unit,
Described 3rd crystalline element is used for the second dense water of crystallization from described second crystalline element is carried out the 3rd crystallization treatment, Obtain crystallizing, as the 3rd, the 3rd crystallization water outlet and the 3rd crystallization solidliquid mixture that dense water uses,
Described 3rd solid-liquid separation unit is for carrying out the by the 3rd crystallization solidliquid mixture from described 3rd crystalline element Three solid-liquid separation process, and obtain the 3rd crystal salt and crystallize, as the 3rd, the 3rd crystalline mother solution that dense water uses；
Preferably, described 3rd crystalline element includes crystallizing evaporator.
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