CN115159746A - Deep purification method for brine - Google Patents
Deep purification method for brine Download PDFInfo
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- CN115159746A CN115159746A CN202210942582.XA CN202210942582A CN115159746A CN 115159746 A CN115159746 A CN 115159746A CN 202210942582 A CN202210942582 A CN 202210942582A CN 115159746 A CN115159746 A CN 115159746A
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- 239000012267 brine Substances 0.000 title claims abstract description 151
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000000746 purification Methods 0.000 title claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 13
- 241001131796 Botaurus stellaris Species 0.000 claims abstract description 11
- 238000005086 pumping Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000002347 injection Methods 0.000 claims abstract description 6
- 239000007924 injection Substances 0.000 claims abstract description 6
- 238000002834 transmittance Methods 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 21
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 235000014413 iron hydroxide Nutrition 0.000 claims description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010802 sludge Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000011780 sodium chloride Substances 0.000 abstract description 7
- 238000004134 energy conservation Methods 0.000 abstract description 5
- 238000005189 flocculation Methods 0.000 abstract description 5
- 230000016615 flocculation Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000011734 sodium Substances 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 7
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 6
- 229910001626 barium chloride Inorganic materials 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 230000003311 flocculating effect Effects 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a brine deep purification method, which comprises the following steps: the brine enters a brine pool from a mine through a brine pipeline, and SO in the brine is detected 4 2‑ 、Ca 2+ 、Mg 2+ The content of (A) is calculated by adding BaCl 2 、NaOH、Na 2 CO 3 The amount of (a); the brine enters a reaction tank, and BaCl with the calculated value of 65-75% is added at the same time 2 Adding NaOH to adjust the pH value; after the bittern feeding of the reaction tank meets the requirement, determining Ba in the bittern 2+ The content and pH of the solution of (1) and, if appropriate, the remainder of BaCl 2 Adjusting the pH value to 10-11 by NaOH, and stirring for reaction; after the reaction is finished, na accounting for 104 to 106 percent is added 2 CO 3 (ii) a Simultaneously carrying out an electric flocculation reaction; and (3) continuously stirring for reaction, standing, discharging the brine to a salt-making refined brine barrel through a pump when the light transmittance reaches over 96%, and pumping the slag mud back to the mine injection well after the slag mud is subjected to filter pressing through a plate-and-frame filter press. The purification method can be combined with vacuum productionThe salt main process is matched, a full countercurrent process is realized, energy conservation, environmental protection and deep purification are realized, and the NaCl content in the salt product is ensured to reach more than 99.8 percent.
Description
Technical Field
The invention relates to the technical field of brine purification, in particular to a brine deep purification method.
Background
In recent years, with the increasing quality of life of people, the demand for high-quality and high-purity edible salt is increasing. The high-purity and high-quality multi-variety edible salt is the mainstream of the future edible salt market and the development direction of salt manufacturing enterprises, and the market price of the edible salt is also multiplied. But SO in brine 4 2- 、Ca 2+ 、Mg 2+ MiscellaneousDeep purification of the quality is always a difficult problem in the vacuum salt manufacturing industry.
The bittern and CaSO purified by the existing lime, mirabilite and flue gas process (i.e. gypsum crystal seed process) 4 、MgSO 4 When the impurity content is about 0.5%, the impurities can be separated out due to supersaturation in the production process, and a part of the impurities are attached to the inner walls of the evaporation tank and the heating chamber to form a scale layer; a portion is entrained in the product, reducing product purity. The cleaning of the scale layer, especially the once-a-year acid cleaning, has great corrosion and damage to the equipment, and reduces the service life of the equipment.
Although the purity of the product produced by the gypsum seed crystal method can meet the national standard, the NaCl content is generally lower than 99.5 percent. The gypsum crystal seed method can not adopt a fractional preheating technology, can not adopt a full countercurrent process with better energy-saving effect, and is not beneficial to energy conservation; the gypsum, the by-product of the gypsum seed crystal method, still contains about 2% -3% of salt after washing and filtering, is not easy to process and is not environment-friendly.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a brine deep purification method which can be matched with a vacuum salt making main process, realize a full countercurrent process, simultaneously realize energy conservation, environmental protection and deep purification, and can remove SO in raw brine 4 2- 、Ca 2 + 、Mg 2+ And impurities are added to ensure that the NaCl content in the salt product reaches more than 99.8 percent.
The technical scheme adopted by the invention is as follows:
s1, enabling brine to enter a brine pool from a mine through a brine pipeline, and detecting SO in the brine 4 2- 、Ca 2+ 、Mg 2+ Calculated by adding BaCl 2 、NaOH、Na 2 CO 3 The amount of (a);
s2, feeding brine into a reaction tank, and simultaneously adding BaCl with the calculated value of 65-75% 2 Adding NaOH to adjust the pH value; after the bittern feeding of the reaction tank meets the requirement, determining Ba in the bittern 2+ The content and pH of the solution of (1) and, if appropriate, the remainder of BaCl 2 Adjusting the pH value to 10-11 by NaOH, and stirring for reaction;
s3, after the reaction is finished, adding Na accounting for 104-106 percent 2 CO 3 (ii) a Meanwhile, the cleaned anode iron plate and cathode stainless steel plate are placed in a reaction tank and are connected with the anode and cathode output ends of a power supply through electrode wires, electrolysis is carried out under the stirring condition, and the precipitate in the brine is flocculated by iron hydroxide colloid released by the electrodes;
s4, after the electrolysis is finished, continuously stirring for reaction, and standing until the light transmittance reaches over 96 percent, namely qualified brine;
and S5, discharging the qualified brine to a salt-making refined brine barrel through a pump, and pumping the slag mud back to the mine injection well after the slag mud is subjected to filter pressing by a plate-and-frame filter press.
In the method for deeply purifying the brine disclosed by the application, in the step S1, the temperature of the brine entering the brine pool from the mine through the brine pipeline is 40-60 ℃.
In the brine deep purification method disclosed in the present application, in step S1, baCl is weighed respectively according to the calculated amount 2 、NaOH、Na 2 CO 3 Dissolving the brine from the mine.
In the brine deep purification method disclosed in the application, the BaCl 2 、Na 2 CO 3 Respectively configuring in a preparation barrel, and pumping to a reaction tank through a pump after configuration is finished; and the NaOH is stored in a caustic soda storage barrel and is pumped into the reaction tank through a pump.
In the method for deep purification of brine disclosed in the present application, in the step S2, the brine feeding manner of the reaction tank is to feed brine in the brine coming pipeline and brine in the brine tank at the same time.
In the deep purification method of brine disclosed in the application, in the step S2, when Ba in brine is contained 2+ After the consumption, the rest BaCl is added 2 。
In the brine deep purification method disclosed by the application, in the step S2, the stirring speed is 300-600 rpm, and the stirring time is 40-80 min.
In the brine deep purification method disclosed by the application, in the step S3, the stirring speed of electrolysis is 50-150 rpm, and the electrolysis time is 20-30 min.
In the brine deep purification method disclosed by the application, in the step S4, the brine is continuously stirred for 40-80 min at a stirring speed of 50-150 rpm, and then is kept stand for 6-8 h.
In the brine deep purification method disclosed by the application, in the step S5, after the slag mud is subjected to pressure filtration by a plate-and-frame filter press, the plate-and-frame filter press liquid converges into a boiling water tank, and the clear liquid overflows to a clear liquid tank and is pumped to a fine brine barrel.
Compared with the prior art, the invention has the beneficial effects that:
the application provides a brine deep purification method, which solves the problem of brine deep purification, and high-purity edible salt with the purity of more than 99.8 percent can be produced after brine deep purification treatment; the purification method can be matched with a main vacuum salt making process, a full countercurrent process is realized, the heat efficiency is improved by about 10 percent, and the energy is fully utilized; the production period can reach half a year at the longest, and the inner wall of equipment does not need to be pickled frequently; the waste residue can be injected back into the brine production well without being filtered, and zero emission is realized. The purification method can achieve energy conservation, environmental protection and deep purification, solves the environmental protection problem of slag mud reinjection into mines and realizes zero emission, and is a development trend of brine purification treatment in the vacuum salt manufacturing industry in the future.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the embodiments or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a brine deep purification method.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, embodiments accompanying the present application are described in detail below with reference to the accompanying drawings. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not limiting of the application. It should be further noted that, for the convenience of description, only some of the structures related to the present application are shown in the drawings, not all of the structures. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The terms "comprising" and "having," as well as any variations thereof, in this application are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the specification. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
Referring to fig. 1, an embodiment of the present application provides a brine deep purification method, which mainly aims to solve the problem of SO in brine 4 2- 、Ca 2+ 、Mg 2+ And the deep purification of impurities is always a difficult problem in the vacuum salt manufacturing industry.
The application discloses a brine deep purification method, which comprises the following steps:
step S1, enabling brine to enter brine from a mine through a brine pipelinePool for detecting SO in brine 4 2- 、Ca 2+ 、Mg 2+ The content of (A) is calculated by adding BaCl 2 、NaOH、Na 2 CO 3 The amount of (c). The parameters of each impurity in the original halogen are relatively stable, the addition amount of the auxiliary materials is strictly determined according to the content measured in real time, and new impurities brought into refined halogen caused by excessive addition of the auxiliary materials are avoided. Brine purification, namely measuring the components of the brine before adding reactants to avoid large fluctuation. The specific reaction is as follows:
CaSO 4 +BaCl 2 →CaCl 2 +BaSO 4 ↓
MgCl 2 +2NaOH→Mg(OH) 2 ↓+2NaCl
CaCl 2 +Na 2 CO 3 →CaCO 3 ↓+2NaCl
s2, feeding brine into a reaction tank, and simultaneously adding BaCl with the calculated value of 65-75% 2 Adding NaOH to adjust the pH value; after the bittern feeding of the reaction tank meets the requirement, determining Ba in the bittern 2+ The content and pH of the solution of (1) and, if appropriate, the remainder of BaCl 2 And adjusting the pH value to 10-11 by NaOH, and stirring for reaction. Barium chloride is used to remove sulfate ions from brine and sodium hydroxide is used to remove magnesium ions from brine. Most of barium chloride and sodium hydroxide are added when brine enters the reaction tank, so that the brine is quickly mixed with the barium chloride and the sodium hydroxide when the brine enters the reaction tank, the initial concentration is high, sulfate ions and magnesium ions can be quickly precipitated, and the reaction time is shortened. After the bittern feeding of the reaction tank meets the requirement, determining Ba in the bittern 2+ The content and pH of the solution of (1) and, if appropriate, the remainder of BaCl 2 And adjusting the pH to precipitate the remaining sulfate ions and magnesium ions. Because barium chloride is a toxic substance, the ratio of barium chloride to barium chloride is strictly 1:1 in a ratio of 1. Specifically, when the brine enters the reaction tank, baCl is added 2 May be added in an amount of 65%, 68%, 70%, 72%, 75%, preferably 70% of the calculated value.
S3, after the reaction is finished, adding Na accounting for 104-106 percent 2 CO 3 (ii) a Simultaneously, the cleaned anode iron plate and the cathode stainless steel plate are placed in a reaction tank and pass through electrodesThe wire is connected with the output ends of the positive and negative electrodes of the power supply, electrolysis is carried out under the stirring condition, and the precipitate in the brine is flocculated by the iron hydroxide colloid released by the electrodes. Sodium carbonate is used for removing calcium ions in the brine, and residual barium ions and magnesium ions can be removed by adding excessive sodium carbonate. The precipitation reaction in the electric flocculation process is as follows:
Ca 2+ +CO 3 2- →CaCO 3 ↓
Mg 2+ +CO 3 2- →MgCO 3 ↓
Ba 2+ +CO 3 2- →BaCO 3 ↓
Ca 2+ +2OH 2- →Ca(OH) 2 ↓
Mg 2+ +2OH 2- →Mg(OH) 2 ↓
the electric flocculation can accelerate the proceeding of the precipitation reaction, further remove calcium ions, magnesium ions and barium ions in the brine, and simultaneously the iron hydroxide colloid released by the anode iron plate adsorbs the precipitate in the brine through the actions of compressing a double electric layer, adsorbing bridging, collecting and catching a roll, and the like to form polymer precipitate, thereby facilitating the subsequent removal of the precipitate in the brine and realizing deep purification.
And S4, after the electrolysis is finished, continuously stirring for reaction, and standing until the light transmittance reaches over 96 percent, thus obtaining qualified brine. And after the electrolysis is finished, continuously stirring to enable the generated flocculating agent to fully adsorb the precipitate in the brine, standing and settling, and obtaining the deeply purified brine when the light transmittance reaches over 96 percent.
And S5, discharging the qualified brine to a salt-making refined brine barrel through a pump, and pumping the slag mud back to the mine injection well after the slag mud is subjected to filter pressing by a plate-and-frame filter press. After the brine is deeply purified, high-purity edible salt with the purity of more than 99.8 percent can be produced. Qualified brine is discharged to a salt-making refined brine barrel through a pump and is connected with a vacuum salt-making main process, so that a full-countercurrent process can be realized. The slag and mud are reinjected into the mine, so that the environmental protection problem is solved, and zero emission is realized. And the filter residues are sent back to the mine injection well, and production practices prove that the condition that the residues are brought back to the ground is not found, and the normal production phenomenon of the brine well is not influenced by the slag injection.
The method solves the problem of brine deep purification, and can produce high-purity edible salt with the purity of more than 99.8 percent after brine deep purification treatment; the purification method can be matched with a main vacuum salt making process, a full countercurrent process is realized, the heat efficiency is improved by about 10 percent, and the energy is fully utilized; the production period can reach half a year at the longest, and the inner wall of equipment does not need to be pickled frequently; the waste residue can be injected back into the brine extraction well without being filtered, and zero emission is realized.
In one embodiment, in step S1, the temperature of brine entering the brine pool through the brine pipeline of the mine is 40-60 ℃. The brine is high in temperature, so that the precipitation reaction speed can be accelerated, and the reaction time can be shortened.
In a specific embodiment, in step S1, according to the calculated amount, baCl is weighed respectively 2 、NaOH、Na 2 CO 3 Dissolving the brine from the mine. The brine with higher temperature is used for dissolving, the dissolving speed is higher, and more reactants can be dissolved. The reactants are dissolved to form homogeneous phase solution, and then the homogeneous phase solution is added into a brine pool to perform precipitation reaction with brine, so that the mass transfer and heat transfer of the homogeneous phase solution are more uniform, the precipitation effect is effectively prevented from being influenced by local uneven heating, and the reaction efficiency is improved.
In a specific embodiment, baCl 2 、Na 2 CO 3 Respectively configuring in a preparation barrel, and pumping the mixture to a reaction tank through a pump after the configuration is finished; naOH is stored in a caustic soda storage barrel and is pumped into a reaction tank through a pump. The feeding is realized through the pump, so that the automatic control can be realized, and the production efficiency is improved.
In a specific embodiment, in step S2, the brine in the reaction tank is fed in a manner that the brine in the brine inlet pipeline and the brine in the brine tank are fed simultaneously. Simultaneously, the feeding time can be shortened by feeding, so that the brine deep purification time is shortened, and the production efficiency is improved.
In a specific embodiment, in step S2, when Ba in the brine 2+ After the consumption, the rest BaCl is added 2 So as to remove the sulfate ions in the brine sufficiently.
In a specific embodiment, in step S2, the stirring speed is 300 to 600rpm, and the stirring time is 40 to 80min. Specifically, the stirring speed may be 300rpm, 400rpm, 500rpm, 600rpm, and the reaction speed may be increased and the reaction time may be shortened by stirring. The stirring time may be 40min, 50min, 60min, 70min, 80min, preferably 60min.
In a specific embodiment, in step S3, the stirring speed of electrolysis is 50-150 rpm, and the electrolysis time is 20-30 min. Specifically, the electrolysis time may be 20min, 25min, 30min. The stirring speed in the electrolytic process can be 50rpm, 80rpm, 100rpm, 120rpm and 150rpm, and a certain time is needed because the formation of the flocculating constituent is in process, the stirring in the flocculation process can increase the ion movement in the brine, shorten the flocculating constituent formation time and promote the formation of the flocculating constituent, but at a higher stirring speed, the higher flow rate of the brine generates turbulence to break the flocculating constituent, so that the flocculating constituent is difficult to form, and the stirring speed in the flocculation process is not easy to be overlarge, preferably 100rpm.
In a specific embodiment, in step S4, after the electrolysis is finished, the mixture is continuously stirred for 40 to 80min at a stirring speed of 50 to 150rpm and then is kept still for 6 to 8 hours. Specifically, after the electrolysis is finished, the stirring time may be 40min, 50min, 60min, 70min, 80min, preferably 60min; the standing time can be 6h, 7h and 8h.
In a specific embodiment, in the step S5, after the sludge is subjected to pressure filtration by the plate-and-frame filter press, the plate-and-frame filter press liquid is converged into the boiling water pool, and the clear liquid overflows to the clear liquid pool and is then pumped to the refined brine barrel.
In a specific implementation scenario, the edible salt sold on the market meets the national standard GB/T5461-2016, wherein the purity requirement of NaCl is 99.1% at the highest. The market selling price (factory price) is generally not higher than 1000 yuan/ton. In recent years, with the increasing quality of people's lives, the demand for high-quality and high-purity edible salt is increasing. The high-purity and high-quality multi-variety edible salt is the mainstream of the future edible salt market and the development direction of salt manufacturing enterprises, and the market price of the edible salt is also multiplied. According to different varieties, the factory price of various kinds of salt taking high-quality and high-purity edible salt as base salt is more than 2000 yuan/ton, and the factory price of part of varieties breaks through 5000 yuan/ton. The average increase of sales income per ton is 1200 yuan. In conclusion, if the yield is 30 ten thousand tons, the high-quality and high-purity edible salt accounts for 50 percent, and the sales income can be increased by 18000 ten thousand yuan each year.
Example 1
Brine components from mine:
NaCl:295g/l；CaSO 4 :4.5g/l；CaCl 2 :0.083g/l；MgCl 2 0.28g/l; temperature: at 40 ℃.
Additive consumption:
1L brine consumption: baCl 2 :6.68g，Na 2 CO 3 :3.78g，NaOH:0.24g。Na 2 CO 3 The amount of excess base is 0.2g.
1L brine produced precipitate:
BaSO 4 :7.71g，Mg(OH) 2 :0.17g，CaCO 3 3.38g. Total precipitate: 11.26g/l.
Newly adding NaCl to 1L of brine: 4.29g.
Indexes of the purified brine are as follows:
NaCl≥299g/l，SO 4 2- ：0.3-0.5g/l，Ca 2+ ：10-50mg/l，Mg 2+ ：10-50mg/l。
after the brine is deeply purified, the high-purity edible salt with the purity of more than 99.8 percent can be produced.
Comparative example 1
Brine is purified by lime, mirabilite and flue gas methods, and the ingredients of the brine from the mine are the same as those in example 1.
The brine enters a reaction tank, emulsified lime water is pumped into a first reaction tank, stirred and reacted, a flocculating agent is added, clear liquid is pumped into a second reaction tank after clarification, and slurry is pumped into a slurry barrel; introducing the brine into the purified flue gas, stirring for reaction, adding a flocculating agent, clarifying, pumping clear liquid into a brine-clearing barrel, and pumping slurry into a slurry barrel.
Indexes of the purified brine are as follows:
SO 4 2- :2.5-3.0g/l，Ca 2+ :1.3-2.0g/l，Mg 2+ :30-50mg/l。
after the brine is deeply purified, the purity of the produced edible salt is about 99.5 percent.
Example 1 was compared to comparative example 1:
the application provides a brine deep purification method, which solves the problem of brine deep purification, and high-purity edible salt with the purity of more than 99.8 percent can be produced after brine deep purification treatment; the purification method can be matched with a main vacuum salt making process, a full countercurrent process is realized, the heat efficiency is improved by about 10 percent, and the energy is fully utilized; the production period can reach half a year at the longest, and the inner wall of equipment does not need to be pickled frequently; the waste residue can be injected back into the brine production well without being filtered, and zero emission is realized. The purification method can achieve energy conservation, environmental protection and deep purification, solves the environmental protection problem of slag mud reinjection into mines and realizes zero emission, and is a development trend of brine purification treatment in the vacuum salt manufacturing industry in the future.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The brine deep purification method is characterized by comprising the following steps:
s1, enabling brine to enter a brine pool from a mine through a brine pipeline, and detecting SO in the brine 4 2- 、Ca 2+ 、Mg 2+ The content of (A) is calculated by adding BaCl 2 、NaOH、Na 2 CO 3 The amount of (c);
s2, feeding brine into a reaction tank, and simultaneously adding BaCl with the calculated value of 65-75% 2 Adding NaOH to adjust the pH value; after the bittern feeding of the reaction tank meets the requirement, determining Ba in the bittern 2+ The content and pH of the solution of (1) and, if appropriate, the remainder of BaCl 2 Adjusting the pH value to 10-11 by NaOH, and stirring for reaction;
s3, after the reaction is finished, adding Na accounting for 104-106 percent 2 CO 3 (ii) a Meanwhile, the cleaned anode iron plate and cathode stainless steel plate are placed in a reaction tank and are connected with the anode and cathode output ends of a power supply through electrode wires, electrolysis is carried out under the stirring condition, and the precipitate in the brine is flocculated by iron hydroxide colloid released by the electrodes;
s4, after the electrolysis is finished, continuously stirring for reaction, and standing until the light transmittance reaches over 96 percent, namely qualified brine;
and S5, discharging the qualified brine to a salt-making refined brine barrel through a pump, and pumping the slag mud back to the mine injection well after the slag mud is subjected to filter pressing through a plate-and-frame filter press.
2. The brine deep purification method according to claim 1, wherein in the step S1, the temperature of brine entering the brine pool from the mine through the brine pipeline is 40-60 ℃.
3. The brine deep purification method according to claim 2, wherein in the step S1, baCl is weighed according to calculated amount 2 、NaOH、Na 2 CO 3 Dissolving the brine from the mine.
4. The brine deep purification method of claim 3, wherein the BaCl is 2 、Na 2 CO 3 Respectively configuring in a preparation barrel, and pumping to a reaction tank through a pump after configuration is finished; and the NaOH is stored in a caustic soda storage barrel and is pumped into the reaction tank through a pump.
5. The brine deep purification method of claim 1, wherein in the step S2, the brine in the reaction tank is fed in a manner that the brine in the brine pipeline and the brine in the brine tank are fed simultaneously.
6. The brine deep purification method according to claim 1, wherein in step S2, ba in the brine 2+ After consumption, addThe balance of BaCl 2 。
7. The brine deep purification method according to claim 1, wherein in the step S2, the stirring speed is 300-600 rpm, and the stirring time is 40-80 min.
8. The brine deep purification method as claimed in claim 1, wherein in the step S3, the stirring speed of electrolysis is 50-150 rpm, and the electrolysis time is 20-30 min.
9. The brine deep purification method according to claim 1, wherein in the step S4, after the electrolysis is finished, the brine is continuously stirred at a stirring speed of 50-150 rpm for 40-80 min and then kept still for 6-8 h.
10. The brine deep purification method according to claim 1, wherein in the step S5, after the sludge is subjected to pressure filtration by a plate-and-frame filter press, the plate-and-frame filter press liquid is converged into a boiling water tank, and the clear liquid overflows to a clear liquid tank and is pumped to a refined brine barrel.
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| Title |
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| 吕延利: "优化卤水精制工艺", 中国井矿盐, vol. 36, no. 04, pages 10 - 13 * |
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