CN106564914B - Reduce method and brine sulfate radical removing system that brine sulfate radical prepares crude brine - Google Patents
Reduce method and brine sulfate radical removing system that brine sulfate radical prepares crude brine Download PDFInfo
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- CN106564914B CN106564914B CN201610996947.1A CN201610996947A CN106564914B CN 106564914 B CN106564914 B CN 106564914B CN 201610996947 A CN201610996947 A CN 201610996947A CN 106564914 B CN106564914 B CN 106564914B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/12—Controlling or regulating
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/14—Pressure control
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- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of methods that reduction brine sulfate radical prepares crude brine, include the following steps：(1) brine is pre-processed, to reduce the Ca in brine2+Ion concentration, and removal halogen water float sundries；(2) pretreated brine is filtered through fine filter, to remove suspended particulate in brine；(3) the filtered brine of essence passes through nanofiltration membrane system, by bating liquor be crude brine.Simultaneously, the invention also discloses a kind of brine sulfate radicals to remove system, method and system using the present invention, sulfate radical in brine, calcium and magnesium ion can be retained, concentrated water can be used for producing saltcake, filtrate is directly entered follow-up salt refining process, effectively controls sulfate radical to the subsequent influence of soda manufacture, while reducing production cost.
Description
Technical field
The present invention relates to crude salt preparing technical field, especially it is a kind of reduce brine sulfate radical prepare crude brine method and
Brine sulfate radical removes system.
Background technology
During soda manufacture, the higher (Na of nitre content in used raw brine2SO4Content is in 25g/L or so),
Due to meeting and Ca2+Deng generation insoluble salt, occluding device and pipeline aggravate the fouling of ammonia still and conveyance conduit, influence to conduct heat
And final product quality, it cannot be directly used in alkaline production, so sulfuric acid of the brine in it must first remove brine before entering production
Root, while reducing calcium ion in brine.
The method of common removing sulfate radical mainly has at present：Chemical precipitation method (including barium chloride method, Calcium Chloride Method, carbonic acid
Barium method), freezing, ion-exchange, membrane separation process and absorption method.
Chemical precipitation method is to react to generate sulfate precipitation with sulfate ion using chemical substance, to reach sulphur removal
The purpose of acid group.
Barium chloride method technological operation is simple, and removal effect is preferable, has the characteristics that ripe, reliable, investment is low.Using chlorination
Barium method removes, and the mass concentration in brine can generally controlled in 0.4mg/L or less.Its disadvantage is：1. barium chloride has stronger
Toxicity, storage request is higher, and human body is poisoned greatly in operating process；2. production cost is higher；3. not except the concentration in rear brine
It is easy to control.Calcium Chloride Method goes sulfate radical investment to save, and calcium chloride price is relatively cheap, but due to the solubility product of calcium sulfate compared with
Greatly, the effect of removal is poor compared with barium chloride method, and the mass concentration in treated brine is also up to 7g/L requirements below, typically up to
Less than 5g/L or less.
Barium carbonate method is the solubility product moment using barium carbonate with barium sulfate and realizes the purpose for detaching sulfate radical.Barium carbonate valence
Lattice are low compared with barium chloride, and by-product soda ash in reaction process, can reduce crude brine refining agent usage amount, but barium carbonate dissolves
Degree is smaller, often occurs line clogging phenomenon in actual use, technique is still immature.
Freezing is that separation is realized the characteristics of variation with the variation of temperature using the solubility of sodium sulphate and sodium chloride.
The method advantage is can be with by-product saltcake, and removal effect is preferable, disclosure satisfy that brine sulphate-containing ion 5g/L or less needed for electrolysis
Requirement.The disadvantage is that investing big, high energy consumption, the mass concentration in raw material does not have economy when being less than 25g/L.
The key of ion-exchange is the selection of ion exchange resin, and in recent years, Japanese Zhong Yuan chemical industrial companies open
The de- new type resin of hair has many advantages, such as that adsorption and desorption rate is fast, resistance to oxidation, salt damage are small, easy to operate, but there are capital costs
The shortcomings of with height, environmental pollution.
Membrane separation process is a kind of newer removal methods, and most representative is by Canadian Kvaerner Chenetics
The SRS membrane separation techniques of company's exploitation, SRS technologies have many advantages, such as that easy to operate, operating cost is low, investment repayment is fast, are mesh
The preceding relatively advanced method for removing sulfate radical in the world.
Absorption method removal has the characteristics that easy to operate, adsorption effect is excellent, at low cost, basic non-environmental-pollution.At present
More famous is the NDS methods developed by Japanese Zhong Yuan chemical industrial companies and Japanese Chlorine Engineering Co., Ltd on the basis of NDS methods
Improved RNDS methods.NDS methods are using zirconium hydroxide as ion exchanger, by operations such as a series of absorption, separation, desorption, separation
Program continuously removes sulfate radical from brine, have it is non-toxic, do not generate solid waste, running expense it is low, will not be to metal
Anode and amberplex have an impact, the mass fraction in brine can arbitrarily control, remove the efficiency and salt of sulfate radical
The advantages such as water concentration is unrelated.For NDS methods, RNDS methods decrease again in equipment investment and running expense.
The brine provided using southern buck minery before our company, nitre content (Na2SO4Content) it is 50g/L or so,
Why can be used in alkaline, is due to there is frozen saltpeter mention device, using freezing removal while by-product saltcake.But in recent years
Come, with being continuously increased for soda ash yield, the brine supply amount day in southern buck minery is becoming tight, daily need to also be from central scroll salt mine
A large amount of brine is bought to supplement.Nitre content is 25g/L or so in central scroll brine, it is clear that the frozen saltpeter mention method before continuing to use
It is very uneconomical.Due to 1 ton of soda ash of every production, 10m is generated3The slops of left and right contains CaCl in slops2100g/L is left
The right side, 50g/L containing NaCl or so, utility value is not high, currently as discharging of waste liquid.If handling central scroll with evaporated waste ammonia liquid
Brine uses calcium method denitrating technique to handle central scroll brine, the salt in recyclable waste liquid, while reducing the discharge of waste liquid, calcium
Method denitrating technique is simple, and equipment investment is few, and energy consumption is low.But in actual calcium method denitration flow, the CaSO of generation4Particle is outstanding
Float in system and be difficult to settle down, sulfate radical removal effect is poor, leverages subsequent production.
Our company adopts the technology that dragon returns Brine of Salt Mine (NaCl 275g/L, Na at present2SO4It is 55g/L) chilled to carry
Nitre, the ten water nitre crystal crystallized out through filtering, evaporation, dry saltcake product processed, carry low nitre halogen after nitre (NaCl 293g/L,
Na2SO411g/L) enter salt manufacturing to evaporate, evaporates the brine mixed dissolution of rear salt slurry (solid-to-liquid ratio 25~28%) and mining area extraction
Crude brine (NaCl 309g/L, Na is made2SO416g/L), because of SO in crude brine4 2-Content height causes follow-up alkaline destilling tower easy
Fouling.
Invention content
Based on this, a kind of reduction brine sulphur is provided it is an object of the invention to overcome above-mentioned the deficiencies in the prior art place
The method that acid group prepares crude brine, method of the invention can effectively remove sulfate radical in brine, effectively control sulfate radical to pure
Alkali produces subsequent influence, while reducing production cost.
To achieve the above object, the technical solution that the present invention takes is：A kind of reduction brine sulfate radical prepares crude brine
Method includes the following steps：
(1) brine is pre-processed, to reduce the Ca in brine2+Ion concentration, and removal halogen water float sundries；
(2) pretreated brine is filtered through fine filter, to remove suspended particulate in brine；
(3) the filtered brine of essence passes through nanofiltration membrane system, by bating liquor be crude brine.
In the above-mentioned technical solutions, nanofiltration membrane system can retain divalent Ca2+、Mg2+Ion, sulfate ion, and monovalence Na+、Cl-Major part can be transferred through NF membrane.
As advanced optimizing for said program, in the step (1), pretreatment, which is included in brine, is added sodium carbonate.
As advanced optimizing for said program, the filtering accuracy of fine filter is 10~100 μm in the step (2)；
Further, the filtering accuracy of fine filter is 55 μm in the step (2).Applicant of the present invention sends out through test of many times
Existing, when the filtering bore dia of fine filter is more than 100 μm, fine filter cannot effectively remove suspended particulate in brine；Filter
Filtering bore dia be less than 10 μm when, be easy by brine suspended particulate block filter hole, influence production efficiency；When filter hole is straight
When diameter is 55 μm, suspended particulate in most of brine can be retained and block filter hole, smart filter efficiency is optimal.
As advanced optimizing for said program, the step (3) further includes：Through nanofiltration membrane system retention concentrate into
Enter to freeze denitrating system, for producing saltcake.
As advanced optimizing for said program, when brine passes through nanofiltration membrane system in the step (3), transmembrane pressure is controlled
Power is 0.75~1.35MPa.Applicant of the present invention has found that force (forcing) pump is pressurized to transmembrane pressure to brine and is more than through test of many times
When 1.35MPa, NF membrane can be deformed due to being under pressure excessive, caused it to retain bivalent ions ability and continuously decreased；When
When transmembrane pressure is less than 0.75MPa, the efficiency of nanofiltration UF membrane divalent ion and monovalent ion reduces obviously.
As advanced optimizing for said program, the pH value of brine is controlled 6.3~6.8 in the step (2)；More into one
Step, the pH value of brine is 6.57 in the step (2).Applicant of the present invention has found through test of many times, the pH value mistake of brine
Gao Shi, hydroxyl therein can be combined to form precipitation with the calcium ions and magnesium ions of wherein divalent, fouling and be attached to fine filter, nanofiltration
On film so that the ability of filtering gradually weakens, and influences production efficiency；And the pH value of brine be less than 6.3 when, brine can be passed through
Equipment causes to corrode, and damages equipment；When the pH value of brine is 6.57, brine is sufficiently low to the equipment degree of corrosion of process, and not
Filter efficiency can be influenced because of fouling.
As advanced optimizing for said program, after adding research of non-phosphorus scale inhibitor in brine in the step (3), using receiving
Filter membrane system；Further, the research of non-phosphorus scale inhibitor includes one kind in polyacrylic acid, poly, poly-epoxy succinic acid
Or multiple combinations.Research of non-phosphorus scale inhibitor under the conditions of low concentration use can to cause incrustation ion carry out effectively disperse, chelate and
The effects that lattice is twisted, to be effectively prevented the fouling of equipment water side, long-time service can also make old dirt soft and then gradually molten
Solution, to improving, device efficiency, extending service life of equipment, guarantee, normal production has remarkable result for a long time；Research of non-phosphorus scale inhibitor is not
Containing any type of phosphorus, pollution will not be generated to water body, it is environmentally protective；When research of non-phosphorus scale inhibitor is polyacrylic acid, poly, gathers
The mixture of Epoxysuccinic acid, and the mass ratio of polyacrylic acid, poly, poly-epoxy succinic acid is 3:2:When 7, carbon is prevented
Sour calcium, calcium sulfate scaling effect reach best, still will not fouling when the LSI of calcium carbonate is up to 3.2.
On the other hand, the present invention also provides a kind of brine sulfate radical remove system, including set gradually brine storage tank,
The water outlet of preprocessor, fine filter and nanofiltration membrane system, the brine storage tank is connected to the water inlet of the preprocessor,
The water outlet of the preprocessor is connected to the water inlet of the fine filter, the water outlet of the fine filter and the nanofiltration
The water inlet of membranous system is connected to.
As advanced optimizing for said program, the brine sulfate radical removing system further includes the out of stock system of freezing, institute
It states and freezes the water inlet of out of stock system and be connected to the water outlet of the nanofiltration membrane system.
As advanced optimizing for said program, brine sulfate radical removing system further include brine pump, charge pump and
Force (forcing) pump；
The water inlet of the brine pump is connected to the water outlet of the brine storage tank, the water outlet of the brine pump with it is described
The water inlet of preprocessor is connected to；
The water inlet of the charge pump is connected to the water outlet of the preprocessor, the water outlet of the charge pump with it is described
The water inlet of fine filter is connected to；
The water inlet of the force (forcing) pump is connected to the water outlet of the fine filter, the water outlet of the force (forcing) pump with it is described
The water inlet of nanofiltration membrane system is connected to.
In conclusion beneficial effects of the present invention are：
Sulfate radical in method and system using the present invention removing brine, can retain sulfate radical in brine, calcium, magnesium from
Son, is not easy the fouling in equipment, and the concentrated water of NF membrane retention can be used for producing saltcake, is directly entered by the filtrate of NF membrane
Follow-up salt refining process effectively controls sulfate radical to the subsequent influence of soda manufacture, while reducing production cost.
Description of the drawings
Fig. 1 is the flow chart for reducing brine sulfate radical in the present invention and preparing the method for crude brine；
Fig. 2 is the idiographic flow schematic diagram of one embodiment of the invention；
Fig. 3 is the structure diagram that brine sulfate radical removes system in the present invention.
Specific implementation mode
Fig. 1, which is shown, reduces the main flow that brine sulfate radical prepares the method for crude brine in the present invention comprising following
Step：
S1, brine is pre-processed；
Wherein, pretreatment is primarily to reduce the Ca in brine2+Ion concentration, and removal halogen water float sundries；
It generally can be by introducing carbonate and Ca2+Precipitation is formed, to remove floating material；Sodium carbonate or potassium carbonate can be added in the application
To remove Ca2+, follow-up salt producing craft, is preferred so that sodium carbonate pretreatment brine is added for convenience.
S2, pretreated brine are filtered through fine filter；
Wherein, the purpose of essence filtering is to remove suspended particulate in brine, in order to avoid block subsequent NF membrane；Preferably,
The filtering accuracy of fine filter is 10~100 μm, more preferably 55 μm, when filter hole is 55 μm a diameter of, can retain big portion
Divide suspended particulate in brine, and filter hole will not be blocked, smart filter efficiency is optimal.
S3, the filtered brine of essence pass through nanofiltration membrane system.
Bating liquor by nanofiltration membrane system is crude brine, and the concentrate retained through nanofiltration membrane system enters freezing denitration
System, for producing saltcake.Wherein, the filtered brine of essence needs pressurized pump pressurization, to improve nanofiltration membrane efficiency, but
It is that transmembrane pressure again cannot be excessive, in order to avoid damage NF membrane；Meanwhile research of non-phosphorus scale inhibitor can be added in brine, it can be effectively
The fouling of equipment water side is prevented, device efficiency is improved, extends service life of equipment；Research of non-phosphorus scale inhibitor is free of any type of phosphorus,
Pollution will not be generated to water body, it is environmentally protective.
NF membrane is non-porous film, it is generally recognized that its mechanism of mass transfer is dissolving-diffusion way.Most of NF membranes be with
The composite membrane of three-dimensional crosslinking structure, compared with reverse osmosis membrane, due to larger-sized " pore structure ", thus NF membrane is three-dimensional
Cross-linked structure is more loose, i.e., network has the solid space of bigger.Meanwhile most nanofiltration film surface bear electricity, to not
Ion with charge and different valence state has different Donnan effects, the pore structure and surface charge property of NF membrane to determine it
Unique separating property：Being hundreds of organic molecule ingredients to relative molecular mass in aqueous solution has separating property；For
There are Donnan effects for the anion of different valence state, and their Donnan current potentials have bigger difference.
Nanofiltration Membrane Separation Technology is detached using non-porous film, and mechanism is a kind of by means of selecting to penetrate (semi-permeable) property
The function of film, using pressure difference as the membrane separation technique of motive force, due to the selectivity of film itself, the different solutes in solution penetrate
The rate of film is different, to realize the separation between different solutes.
Referring to Fig. 3, the structural schematic diagram of the embodiment of system is removed for brine sulfate radical of the present invention.
Specifically, a kind of brine sulfate radical removes system, including the brine storage tank 1 for storing brine set gradually,
For reducing the Ca in brine2+Ion concentration simultaneously removes the preprocessor 3 of halogen water float sundries and for removing in brine
The fine filter 5 and nanofiltration membrane system 7 of suspended particulate；The water inlet of the water outlet and the preprocessor 3 of the brine storage tank 1
Connection, the water outlet of the preprocessor 3 is connected to the water inlet of the fine filter 5, the water outlet of the fine filter 5 and
The water inlet of the nanofiltration membrane system 7 is connected to.
Preferably, the brine sulfate radical removing system further includes the freezing denitrating system for producing saltcake, described cold
The water inlet for freezing out of stock system is connected to the water outlet of the nanofiltration membrane system 7.
Preferably, the brine sulfate radical removing system further includes brine pump 2, charge pump 4 and force (forcing) pump 6；The brine
The water inlet of pump 2 is connected to the water outlet of the brine storage tank 1, the water outlet of the brine pump 2 and the preprocessor 3 into
The mouth of a river is connected to；The water inlet of the charge pump 4 is connected to the water outlet of the preprocessor 3, the water outlet of the charge pump 4 with
The water inlet of the fine filter 5 is connected to；The water inlet of the force (forcing) pump 6 is connected to the water outlet of the fine filter 5, described
The water outlet of force (forcing) pump 6 is connected to the water inlet of the nanofiltration membrane system 7.
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with the drawings and specific embodiments pair
The present invention is described further.
Embodiment 1
As shown in Figures 2 and 3, the brine of mining area extraction is stored in brine storage tank 1 (Ca in brine2+Ion concentration is
283ppm), it is sent to brine preprocessor 3 through brine pump 2, while sodium carbonate is added, (carbonate and calcium are pre-processed to brine
Ionic reaction generates precipitation of calcium carbonate, that is, reduces the Ca in brine2+Ion, removal halogen water float sundries), pretreated halogen
Water is sent through charge pump 4 to fine filter 5, removes suspended particulate in brine, and filtering accuracy is 55 μm, and the filtered brine of essence is through adding
Press pump 6 squeezes into nanofiltration membrane system 7, and nanofiltration membrane system retains divalent Ca2+、Mg2+Ion, and monovalence Na+、Cl-Major part can lead to
Cross NF membrane；Concentrate (NaCl 296g/L, Na through retention2SO454g/L) enter freezing denitrating system, and by softening
Liquid (NaCl 310g/L, Na2SO41.6g/L, Ca2+It is 56ppm) crude brine, brine can be directly entered without carrying out dissolved salt
Refining step.
Embodiment 2
As shown in Figures 2 and 3, the brine that mining area produces is stored in brine storage tank 1 (Ca in brine2+Ion concentration is
300ppm), it is sent to brine preprocessor 3 through brine pump 2, while sodium carbonate is added, (carbonate and calcium are pre-processed to brine
Ionic reaction generates precipitation of calcium carbonate, that is, reduces the Ca in brine2+Ion concentration, removal halogen water float sundries), after pretreatment
Brine pH value control 6.3, sent to fine filter 5 through charge pump 4, remove suspended particulate in brine, filtering accuracy is 10 μ
M, the pressurized pump of the filtered brine of essence 6 squeeze into nanofiltration membrane system 7, and control transmembrane pressure is 0.75MPa, and nanofiltration membrane system retains
Divalent Ca2+、Mg2+Ion, and monovalence Na+、Cl-Major part can be transferred through NF membrane, concentrate through retention (NaCl 342g/L,
Na2SO422g/L) enter freezing denitrating system, and by bating liquor (NaCl 226g/L, Na2SO45.7g/L, Ca2+
It is 80ppm) crude brine, salt refining process can be directly entered without carrying out dissolved salt.
Embodiment 3
As shown in Figures 2 and 3, the brine that mining area produces is stored in brine storage tank 1 (Ca in brine2+Ion concentration is
287ppm), it is sent to brine preprocessor 3 through brine pump 2, while sodium carbonate is added, (carbonate and calcium are pre-processed to brine
Ionic reaction generates precipitation of calcium carbonate, that is, reduces the Ca in brine2+Ion concentration, removal halogen water float sundries), after pretreatment
Brine pH value control 6.41, sent to fine filter 5 through charge pump 4, remove suspended particulate in brine, filtering accuracy 33
μm, the pressurized pump of the filtered brine of essence 6 squeezes into nanofiltration membrane system 7, and control transmembrane pressure is 0.87MPa, nanofiltration membrane system section
Stay divalent Ca2+、Mg2+Ion, and monovalence Na+、Cl-Major part can be transferred through NF membrane, the concentrate (NaCl325g/ through retention
L, Na2SO437g/L) enter freezing denitrating system, and by bating liquor (NaCl 262g/L, Na2SO43.6g/L, Ca2+
It is 68ppm) crude brine, salt refining process can be directly entered without carrying out dissolved salt.
Embodiment 4
As shown in Figures 2 and 3, the brine that mining area produces is stored in brine storage tank 1 (Ca in brine2+Ion concentration is
291ppm), it is sent to brine preprocessor 3 through brine pump 2, while sodium carbonate is added, (carbonate and calcium are pre-processed to brine
Ionic reaction generates precipitation of calcium carbonate, that is, reduces the Ca in brine2+Ion concentration, removal halogen water float sundries), after pretreatment
Brine pH value control 6.52, sent to fine filter 5 through charge pump 4, remove suspended particulate in brine, filtering accuracy 55
μm, the pressurized pump of the filtered brine of essence 6 squeezes into nanofiltration membrane system 7, and control transmembrane pressure is 0.99MPa, nanofiltration membrane system section
Stay divalent Ca2+、Mg2+Ion, and monovalence Na+、Cl-Major part can be transferred through NF membrane, the concentrate (NaCl288g/ through retention
L, Na2SO459g/L) enter freezing denitrating system, and by bating liquor (NaCl 318g/L, Na2SO41.5g/L, Ca2+
It is 54ppm) crude brine, salt refining process can be directly entered without carrying out dissolved salt.
Embodiment 5
As shown in Figures 2 and 3, the brine that mining area produces is stored in brine storage tank 1 (Ca in brine2+Ion concentration is
296ppm), it is sent to brine preprocessor 3 through brine pump 2, while sodium carbonate is added, (carbonate and calcium are pre-processed to brine
Ionic reaction generates precipitation of calcium carbonate, that is, reduces the Ca in brine2+Ion concentration, removal halogen water float sundries), after pretreatment
Brine pH value control 6.57, sent to fine filter 5 through charge pump 4, remove suspended particulate in brine, filtering accuracy 71
μm, the filtered brine addition research of non-phosphorus scale inhibitor polyacrylic acid of essence, poly and poly-epoxy succinic acid (polyacrylic acid, poly- horse
It is 3 to carry out sour, poly-epoxy succinic acid mass ratio:2:7) after, pressurized pump 6 squeezes into nanofiltration membrane system 7, and control transmembrane pressure is
1.11MPa, nanofiltration membrane system retain divalent Ca2+、Mg2+Ion, and monovalence Na+、Cl-Major part can be transferred through NF membrane, through cutting
Concentrate (the NaCl 275g/L, Na stayed2SO471g/L) enter freezing denitrating system, and by bating liquor (NaCl 331g/
L, Na2SO41.3g/L, Ca2+It is 50ppm) crude brine, salt refining process can be directly entered without carrying out dissolved salt.
Embodiment 6
As shown in Figures 2 and 3, the brine that mining area produces is stored in brine storage tank 1 (Ca in brine2+Ion concentration is
280ppm), it is sent to brine preprocessor 3 through brine pump 2, while sodium carbonate is added, (carbonate and calcium are pre-processed to brine
Ionic reaction generates precipitation of calcium carbonate, that is, reduces the Ca in brine2+Ion concentration, removal halogen water float sundries), after pretreatment
Brine pH value control 6.73, sent to fine filter 5 through charge pump 4, remove suspended particulate in brine, filtering accuracy 86
μm, after the filtered brine addition research of non-phosphorus scale inhibitor poly of essence, pressurized pump 6 squeezes into nanofiltration membrane system 7, controls transmembrane pressure
Power is 1.23MPa, and nanofiltration membrane system retains divalent Ca2+、Mg2+Ion, and monovalence Na+、Cl-Major part can be transferred through NF membrane,
Concentrate (NaCl 317g/L, Na through retention2SO443g/L) enter freezing denitrating system, and by bating liquor (NaCl
277g/L, Na2SO42.9g/L, Ca2+It is 61ppm) crude brine, salt refining process can be directly entered without carrying out dissolved salt.
Embodiment 7
As shown in Figures 2 and 3, the brine that mining area produces is stored in brine storage tank 1 (Ca in brine2+Ion concentration is
294ppm), it is sent to brine preprocessor 3 through brine pump 2, while sodium carbonate is added, (carbonate and calcium are pre-processed to brine
Ionic reaction generates precipitation of calcium carbonate, that is, reduces the Ca in brine2+Ion concentration, removal halogen water float sundries), after pretreatment
Brine pH value control 6.8, sent to fine filter 5 through charge pump 4, remove suspended particulate in brine, filtering accuracy 100
μm, after essence filtered brine addition research of non-phosphorus scale inhibitor poly-epoxy succinic acid, pressurized pump 6 squeezes into nanofiltration membrane system 7, control across
Film pressure is 1.35MPa, and nanofiltration membrane system retains divalent Ca2+、Mg2+Ion, and monovalence Na+、Cl-Major part can be transferred through nanofiltration
Film, concentrate (NaCl 334g/L, Na through retention2SO429g/L) enter freezing denitrating system, and by bating liquor
(NaCl 245g/L, Na2SO44.5g/L, Ca2+It is 73ppm) crude brine, salt crystal can be directly entered without carrying out dissolved salt
Process processed.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than is protected to the present invention
The limitation of range is protected, although being explained in detail to the present invention with reference to preferred embodiment, those skilled in the art should
Understand, technical scheme of the present invention can be modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And range.
Claims (5)
1. a kind of method for reducing brine sulfate radical and preparing crude brine, which is characterized in that include the following steps：
(1) brine is pre-processed, to reduce the Ca in brine2+Ion concentration, and removal halogen water float sundries；
(2) pretreated brine is filtered through fine filter, to remove suspended particulate in brine；
(3) after essence filtered brine addition research of non-phosphorus scale inhibitor, using nanofiltration membrane system, by bating liquor be crude salt
Water；The filtering accuracy of fine filter is 10~100 μm in the step (2)；The research of non-phosphorus scale inhibitor is polyacrylic acid, poly- Malaysia
The mixture of acid, poly-epoxy succinic acid, and the mass ratio of polyacrylic acid, poly, poly-epoxy succinic acid is 3：2：7.
2. reducing the method that brine sulfate radical prepares crude brine according to claim 1, which is characterized in that the step (1)
Middle pretreatment, which is included in brine, is added sodium carbonate.
3. reducing the method that brine sulfate radical prepares crude brine according to claim 1, which is characterized in that the step (3)
Further include：The concentrate retained through nanofiltration membrane system enters freezing denitrating system, for producing saltcake.
4. reducing the method that brine sulfate radical prepares crude brine according to claim 1, which is characterized in that the step (3)
When middle brine passes through nanofiltration membrane system, control transmembrane pressure is 0.75~1.35MPa.
5. reducing the method that brine sulfate radical prepares crude brine according to claim 1, which is characterized in that the step (2)
The pH value of middle brine is controlled 6.3~6.8.
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