CN116040656A - Method and device for removing organic matters in brine - Google Patents
Method and device for removing organic matters in brine Download PDFInfo
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- CN116040656A CN116040656A CN202211605389.3A CN202211605389A CN116040656A CN 116040656 A CN116040656 A CN 116040656A CN 202211605389 A CN202211605389 A CN 202211605389A CN 116040656 A CN116040656 A CN 116040656A
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 169
- 239000012267 brine Substances 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 88
- 150000003839 salts Chemical class 0.000 claims abstract description 66
- 238000007667 floating Methods 0.000 claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- 239000002101 nanobubble Substances 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 38
- 150000002367 halogens Chemical class 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003860 storage Methods 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 238000005192 partition Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 14
- 230000003068 static effect Effects 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000005416 organic matter Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 238000005065 mining Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005345 coagulation Methods 0.000 abstract description 9
- 230000015271 coagulation Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 9
- 238000005189 flocculation Methods 0.000 abstract description 7
- 230000016615 flocculation Effects 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 19
- 238000012546 transfer Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000701 coagulant Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005188 flotation Methods 0.000 description 5
- 238000007872 degassing Methods 0.000 description 4
- 241001131796 Botaurus stellaris Species 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 210000001503 joint Anatomy 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention provides a method and a device for removing organic matters in brine, wherein the device comprises a salt cavern gas-making brine-collecting unit, an air-compressing gas-storing unit, an air-floating unit, an air-exhausting unit and a concentrated liquid collecting and separating unit, the characteristics of nano bubble air-floating are organically combined with the density of the organic matters in the brine, stable brine quality is provided for salt cavern gas-storing and brine-making salt production, and solid insoluble matters and a small amount of organic matters in the brine are removed through the air-floating and air-exhausting device after the brine with the brine is produced, so that the purity of the brine is improved; flocculation or coagulation procedures are not needed before air floatation, so that the influence of flocculant residues on the safety of salt and the service life of a filter membrane is avoided; the air-floated brine passes through the exhaust device, so that the corrosion of residual gas in the brine to equipment and pipelines is solved, the prepared brine can be used as liquid salt or solid salt raw materials, high-quality salt products are produced, and the influence of salt cavity building brine discharge on the environment and the waste of resources are avoided.
Description
Technical Field
The invention relates to the technical field of salt production, in particular to a method and a device for removing organic matters in brine.
Background
Underground salt mine resource is rich and mined in ChinaThe history is long, the annual consumption of natural gas in China breaks through 3000 hundred million cubic meters, and the construction of gas storages is still lagged. The salt cavern stores natural gas, which is built in 2006, and is relatively late to develop and use; whereas developed countries in europe and america began to store natural gas on a large scale using salt caverns in the last 50 and 60 th century. The traditional underground salt mine mainly comprises 'brine production' and is idle after the exploitation of the generated salt caves is finished; the underground salt mine is used for gas storage, and is directly discharged into the sea for rapid cavity making and low halogen concentration. The brine production and the cavity making and gas storage are independent although the same underground salt mine resource is used due to different purposes and industries. The underground mineral salt resources of China are mainly distributed in inland provinces such as Sichuan, hubei, jiangsu and the like, and the brine sea-discharging technology for quickly building a cavity outside the country cannot be used for reference due to the requirements of geographic positions, environmental protection and the like. For example, the salt basin of the gold jar has the average NaCl content of about 85 percent and Na content in the extracted brine 2 SO 4 About 4% with a small amount of anhydrite, magnesium chloride, and other impurities; the nearby ocean resources are not available near the salt basin, so that foreign direct sea drainage cannot be used for reference; and the sodium chloride content in the brine is close to saturation, so that the brine cannot be discharged into the Yangtze river or river, otherwise, the environment, the water body and the like are polluted, and the optimal method for recycling the brine is to prepare a salt product.
The main way for solving the international problem of salt cavern idling or brine waste generated by cavity making is to adopt the coupling of cavity making and salt making technology, so that the core technology for cavity making is not applied in advance at home and abroad. The traditional salt making method has high energy consumption, large salt mud production amount and serious environmental problems. As a two-alkali raw material, from mining of mineral salt to soda ash production, on one hand, five times of conversion from solid to liquid are needed, and a large amount of energy is needed to be consumed; on the other hand, the brine refining process generates a large amount of brine sludge, and about 200 ten thousand tons of solid waste per year in China becomes a bottleneck for restricting the development of salt industry and two alkali industries, so that the development of low-energy-consumption clean salt production technology is urgently needed.
The method has no related research on the structure and shape of a bubble stable salt cavity, and the method is mainly used for decoloring, turbidity removing or suspended matter removing of brine, and adopts a coagulation or flocculation process and then air floatation, so that the method has low removal rate and low relative precision, and the suspended matter of a final product is more than 2 mg/L.
CN106219652a discloses a high-concentration brine-making water floatation treatment method, which comprises four steps: 1) A water inlet and drug adding stage; 2) A coagulation stage; 3) An air floatation stage; 4) And (3) a slag scraping and defoaming stage.
(1) And 4) effectively eliminating bubbles in the scum by using a spray pipe to spray and defoaming, and when the Baume degree of the brine is increased to 18-24 Bes of the Baume degree of the brine in actual salt manufacturing, rapidly reducing the micro bubbles generated by a releaser. Experiments prove that after the bubbles are introduced, the bubbles can be defoamed quickly, and defoaming treatment is not needed. Meanwhile, the spray water is downwards and the air floatation is upwards, so that mutual stress counteracts, suspended matters are suspended in brine, and the removal effect is influenced.
(2) And step 2) the coagulant polyaluminium chloride added in the coagulation stage is unfavorable for membrane filtration.
By adopting the method, table 1 shows that the water production color degree of the air floatation system is obviously reduced, the chromaticity removal rate can reach more than 30%, wherein the chromaticity removal rate is increased after the coagulant is added, but the increase is not obvious. The brine chromaticity removal rate is lower (30-36%), and the indication effect is not obvious.
CN108529788A discloses a purifying method and device for bromine extracting waste liquid.
(1) Coagulant needs to be added
And then the turbidity of bromine extraction waste liquid is reduced by a secondary coagulation process and an air floatation process. Inorganic high molecular coagulant is added for secondary coagulation, and 0-1.5 ppm of organic flocculant is added after coagulation is started for not less than 1 minute, and the addition of the flocculant can affect filtration of a brine film.
(2) The sodium chloride content in the waste liquid is not high
The sodium chloride content in the applicable waste liquid is shown in the first table in the example 3, the sodium chloride content is 31734+62847= 94581 mg/L= 94.851g/L, and the content difference is larger compared with the saturated brine with the sodium chloride content of 280-310g/L, so that the direct reference cannot be made.
(3) The turbidity of the treated wastewater is also very high
Finally, the turbidity of the bromine extraction waste liquid is reduced to 2.5 to 3.0NTU, and the precision of the chlor-alkali electrolytic salt water can not be reached, so the patent can not be directly referred to.
CN111039451a discloses a method for reducing turbidity of brine by air-float method, which adopts pressurized dissolved air-float method to remove sediment and Mg (OH) in primary brine 2 、Ca(OH) 2 And the purposes of reducing the turbidity of the brine are to wait for solid insoluble matters.
(1) Flocculation or coagulation
Adding flocculant and/or coagulant into primary brine, mixing with dissolved air water, and then entering an air floatation unit for treatment.
(2) The brine precision is not high
After the primary brine is treated by the air floatation unit, the suspended matters can be reduced to below 50mg/l, and the turbidity is reduced to below 5 NTU.
CN111547924a discloses a method and apparatus for refining bittern by air-float method, in which the clarified liquid is mixed with flocculant, and undergone the process of flocculation reaction-air-float purification, the insoluble material whose size is as small as 0.05 micrometer can be separated.
(1) Flocculation adding
Flocculation reaction-air floatation purification, wherein the flocculant comprises one or more of polyacrylamide, sodium polyacrylate, polymeric ferric sulfate, polymeric aluminum chloride and polymeric aluminum sulfate.
(2) The brine precision is not high
The turbidity of the brine can be reduced to below 5-10 NTU, and SS is less than 10mg/L; the whiteness of the obtained refined salt is more than 80, and the sodium chloride content is more than or equal to 99.1 percent.
CN113501606a discloses a saturated brine purifying method, which adopts a pressurized dissolved air method to remove organic matters and colloid substances in brine.
(1) The residence time of the whole purification process is long
Sequentially placing raw brine into three-stage serial brine storage tanks for sedimentation, wherein each brine storage tank is subjected to sedimentation for 48-72 hours. Minimum residence time of 6 days is required.
(2) The brine precision is not high
The saturated brine refined salt has good effect, can reduce suspended matters (ss) to below 20mg/l, and reduces turbidity to below 20 NTU.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to overcome the defects of the prior art, the invention provides the method and the device for removing the organic matters in the brine, which can effectively remove the impurities in the brine by a nano air floatation technology, and demonstrate the transformation of the traditional salt industry, realize the low-carbon clean production of the salt industry and have important promotion significance for the sustainable development of the salt industry.
The technical scheme adopted for solving the technical problems is as follows: the device for removing the organic matters in the brine comprises a salt cavern cavity-making brine-collecting unit, an air-compressing air-storing unit, an air-floating unit, an exhaust unit and a concentrated liquid collecting and separating unit; the salt cavern cavity-making brine-collecting unit comprises a brine-collecting pipe, wherein the brine-collecting pipe comprises a central pipe and a sleeve pipe arranged outside the central pipe; the inlet of the air floatation unit is communicated with a halogen production pipe pipeline, the outlet of the air floatation unit is communicated with an exhaust unit pipeline, and the exhaust unit is connected with a first-stage reaction barrel; the middle part of the air floatation unit is provided with a nano air disc, the air floatation unit is respectively provided with a brine static area, an air floatation area and a gas belt liquid separation area from bottom to top along the height direction, the nano air disc separates the brine static area from the air floatation area, the gas belt liquid separation area of the air floatation unit is connected with an overflow pipe, and the end part of the overflow pipe is connected with a concentrated liquid collecting and separating unit; the output pipeline of the air pressure air storage unit is divided into two parts, wherein one part of the output pipeline inputs compressed air to the bottom of an air floatation area of the air floatation unit, and the other part of the output pipeline inputs the compressed air to the lower part of the concentrated liquid collecting and separating unit; the liquid in the concentrated liquid collecting and separating unit comprises suspended matters at the upper part and clear liquid at the lower part, the lower part of the concentrated liquid collecting and separating unit is communicated with a halogen inlet area pipeline of the air floatation unit, the compressed air which is introduced into the concentrated liquid collecting and separating unit floats the liquid in the concentrated liquid collecting and separating unit, and the clear liquid enters the halogen inlet area through the pipeline.
Further, the air floatation unit comprises a brine inlet area, a coarse floatation area, a fine floatation area and a brine storage area which are sequentially arranged along the horizontal direction, wherein the two adjacent areas are separated by an interval partition board, and the coarse floatation area and the fine floatation area are respectively a brine static area, an air floatation area and a gas belt liquid separation area from bottom to top along the height direction; the brine inlet area is provided with an inlet and is communicated with a brine collecting pipe through the inlet; each partition plate is provided with a through hole for communicating two adjacent areas; the halogen storage area is communicated with the exhaust unit pipeline.
Preferably, a plurality of coarse floating guide baffles are arranged in the coarse floating region, the coarse floating guide baffles form an S-shaped flow channel for liquid in the coarse floating region, and 70-80% of suspended impurities are removed in the coarse floating region by the S-shaped flow channel.
Preferably, a plurality of fine floating guide baffles are also arranged in the fine floating region, the fine floating guide baffles form an S-shaped flow channel for liquid in the static floating region, and the S-shaped flow channel removes 20-29% of suspended impurities in the fine floating region.
Further, the exhaust unit include exhaust chamber and blast pipe, the blast pipe be serpentine structure and arrange in the exhaust chamber, and the entrance point of blast pipe is located the bottom of exhaust chamber, the exit end is located the top of exhaust chamber, wherein the blast pipe entrance point lets in and has comdenstion water, exit end then with mining area pipeline intercommunication, high temperature comdenstion water and the indoor bittern heat transfer back ore deposit and draw the bittern.
A method for removing organic matters in brine, comprising the following steps:
A. raw brine extracted from a salt cavity is fed into an air floatation unit, air floatation unit is filled with compressed nano-nano bubbles and micro-nano bubbles for coarse floatation and fine floatation to obtain brine, the brine is subjected to heat exchange and air exhaust by condensed water of an air exhaust unit to obtain fine brine, and the fine brine is fed into a first-stage reaction barrel to be subjected to a calcium and magnesium removal process to be used as a salt production raw material;
B. the brine static area, the air flotation area and the gas-liquid separation area are respectively arranged from bottom to top along the height direction, insoluble matters, floccules or organic matters in the brine float in the gas-liquid separation area in the coarse flotation and fine flotation processes, and the insoluble matters, the floccules or the organic matters are collected and transferred to the concentrated liquid collecting and separating unit for separation;
C. and compressed nano-sized and micro-nano-sized bubbles are introduced into the concentrated liquid collecting device to carry out air floatation reaction, insoluble matters, floccules or organic matters are driven to float upwards and are collected, brine at the bottom of the concentrated liquid collecting device is clear liquid, and the clear liquid and raw brine enter an air floatation unit together.
Preferably, in the method for removing organic matters in brine, the brine is produced by adopting a brine production pipe in a salt cavern cavity, the brine production pipe comprises a central pipe and a sleeve pipe arranged outside the central pipe, positive circulation is adopted in the initial stage of brine production, reverse circulation is adopted in the middle and later stages of brine production, and the concentration of sodium chloride in the raw brine produced by brine production is not lower than 296g/L.
Preferably, in the above method for removing organic matters in brine, the raw brine comprises the following components: the solid suspended matters are 20-50mg/L, and the organic matters are 30-100mg/L; the refined halogen comprises the following components: the solid suspension is 2-5mg/L, and the organic matter is 0.6-2.0mg/L.
Preferably, in the method for removing organic matters in brine, the compressed nano-sized and micro-nano bubbles are air; the pressure of the compressed nano-sized and micro-nano bubbles is 0.11-0.20 Mpa, the aperture of the nano bubbles is 20-500 nm, and the aperture of the micro-nano bubbles is 100-2000 nm; the air inlet positions of the compressed nano-nano and micro-nano bubbles are corresponding to the air floatation area of the air floatation unit and the clear liquid position of the concentrated liquid collecting and separating unit.
Preferably, in the method for removing organic matters in brine, the condensed water of the exhaust unit is high-temperature condensed water generated by evaporating salt production, the temperature of the high-temperature condensed water is 70-80 ℃, and the condensate water exchanges heat with refined brine and returns ore to collect brine; after the exhaust unit is used for exhausting, the gas content in the brine is reduced by 60-70%.
The method and the device for removing the brine organic matters have the beneficial effects that:
(1) The salt cavern underground space is an important underground space resource, and the seamless butt joint of the cavity establishment and the brine production provides stable salt cavern storage for the underground gas storage; the extracted raw brine is subjected to air floatation and degassing treatment and then is used for preparing salt, so that brine resources are fully utilized without river discharge; the influence of cavity-building brine discharge on the environment and the waste of resources are avoided;
(2) The physical method of air floatation and degassing is adopted, so that solid insoluble substances and a small amount of organic substances are effectively removed, and the purity of brine is improved; the flocculating or coagulating procedure is not needed before the air bubble, so that the influence of flocculant residue on the safety of salt and the service life of a filter membrane is avoided;
(3) In the air floatation and degassing process, the introduced gas is removed in an exhaust unit, so that corrosion of residual gas to equipment is avoided;
(4) The method has the advantages of clean production and green low carbon, and realizes high efficiency of resource utilization, modernization of mining modes, cleanliness of mining operation and minimization of environmental impact.
Drawings
The invention will be further described with reference to the drawings and examples.
Fig. 1 is a schematic structural view of the present invention.
Fig. 2 is a schematic structural view of the air-floating unit of the present invention.
Fig. 3 is a top view of an air bearing unit of the present invention at the air bearing zone.
Fig. 4 is a schematic view of the structure of the exhaust unit of the present invention.
In the figure, 1, an air compressor 2, an air outlet pipe 3, a concentrated solution collecting device 4, a first transfer pump 5, a mining area 6, an air floatation unit 6-1, a halogen inlet area 6-2, a coarse floatation area 6-3, a fine floatation area 6-4, a halogen storage area 6-5, an overflow pipe 6-6, a partition plate 6-7, a coarse floatation flow guide partition plate 6-8, a nano air disc 6-9, a fine floatation flow guide partition plate 6-10, a brine static area 6-11, an air floatation area 6-12, a gas-liquid separation area 7, a second transfer pump 8, a blower 9, an exhaust unit 9-1, an exhaust chamber 9-2, an exhaust pipe 10, a third transfer pump 11 and a first-stage reaction barrel.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings. The drawings are simplified schematic representations which merely illustrate the basic structure of the invention and therefore show only those features which are relevant to the invention, and orientation and reference (e.g., up, down, left, right, etc.) may be used solely to aid in the description of the features in the drawings. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the claimed subject matter is defined only by the appended claims and equivalents thereof.
The invention provides a method for removing organic matters in brine, which comprises the following steps:
A. raw brine extracted from the salt cavern cavity is fed into an air floatation unit 6, compressed nano-nano and micro-nano bubbles are fed into the air floatation unit 6 for coarse floatation and fine floatation to obtain brine, the brine is subjected to heat exchange and air exhaust by condensed water of an air exhaust unit 9 to obtain fine brine, and the fine brine is fed into a first-stage reaction barrel 11 for calcium and magnesium removal process to be used as a salt manufacturing raw material.
In the process, the salt cavern cavity-making brine-producing use brine-producing pipe comprises a central pipe and a sleeve pipe arranged outside the central pipe, the positive circulation is adopted in the initial brine-producing stage, the reverse circulation is adopted in the middle and later stages, and the concentration of sodium chloride in the brine-producing output raw brine is not lower than 296g/L. The raw halogen comprises the following components: the solid suspended matters are 20-50mg/L, and the organic matters are 30-100mg/L; the refined halogen comprises the following components: the solid suspension is 2-5mg/L, and the organic matter is 0.6-2.0mg/L.
Compressed nano-nano and micro-nano bubbles are introduced into the device to perform coarse flotation and fine flotation, and the compressed nano-nano and micro-nano bubbles are air; the pressure of the compressed nano-nano and micro-nano bubbles is 0.11-0.20 Mpa, the aperture of the nano bubbles is 20-500 nm, and the aperture of the micro-nano bubbles is 100-2000 nm; the air inlet positions of the compressed nano-nano bubbles and the micro-nano bubbles are corresponding to the positions of the air floatation areas 6-11 of the air floatation unit 6 and the clear liquid of the concentrated liquid collecting and separating unit 3.
The condensed water of the exhaust unit 9 is high-temperature condensed water generated by evaporating salt production, the temperature of the high-temperature condensed water is 70-80 ℃, and ore recovery and brine recovery are carried out after heat exchange with refined brine; after the exhaust unit 9 exhausts, the gas content in the brine is reduced by 60-70%.
B. The brine static area 6-10, the air floatation area 6-11 and the gas-liquid separation area 6-12 are respectively arranged from bottom to top along the height direction, insoluble matters, floccules or organic matters in the brine float in the gas-liquid separation area 6-12 in the coarse floatation and fine floatation processes, and the insoluble matters, floccules or organic matters are collected and transported to the concentrated solution collecting and separating unit 3 for separation.
C. The concentrated liquid collecting device is filled with compressed nano-sized and micro-nano-sized bubbles to carry out air floatation reaction, insoluble matters, floccules or organic matters are driven to float upwards and are collected, brine at the bottom of the concentrated liquid collecting device is clear liquid, and the clear liquid and raw brine enter an air floatation unit 6 together.
In the method, salt cavern cavity making is adopted for brine production, and the seamless butt joint of the cavity making and brine production provides stable salt cavern storage for the underground gas storage; the extracted raw brine is subjected to air floatation and degassing treatment and then is used for preparing salt, so that brine resources are fully utilized without river discharge; avoiding the influence of the drainage of the brine in the cavity on the environment and the waste of resources. In the air floatation process of the air floatation unit 6, the introduced bubbles are lightly connected with organic matters in the brine by utilizing the air floatation characteristic of nano bubbles, the bubble density is reasonably set, insoluble matters, floccules or organic matters are lifted up by the driving of the bubbles and are collected, the solid insoluble matters and a small amount of organic matters in the brine are removed, the purity of the brine is improved, no flocculation or coagulation process is needed before air floatation, and the influence of flocculant residues on the safety of salt and the service life of a filter membrane is avoided. The air floatation unit 6 is connected with the exhaust unit 9, so that the gas in the brine can be further removed, and the corrosion of residual gas to equipment is avoided. Meanwhile, the condensed water introduced into the exhaust unit 9 adopts high-temperature condensed water generated by evaporating salt production, so that the heat energy recycling in the salt production process is realized, the low-temperature condensed water subjected to heat exchange is recycled for ore recovery and brine recovery, the resource utilization is more efficient, and the advantages of clean production and green low carbon are realized.
Based on the principle of the method, the invention has a device for removing organic matters in brine as shown in fig. 1. The device comprises a salt cavern cavity-making brine-collecting unit, an air-compressing air-storing unit, an air-floating unit 6, an exhaust unit 9 and a concentrated liquid collecting and separating unit 3.
Brine is extracted from the mine 5. The brine is collected by a brine collecting unit for making cavities by salt caverns. The salt cavern cavity-making brine-producing unit comprises a brine-producing pipe, wherein the brine-producing pipe comprises a central pipe and a sleeve pipe arranged outside the central pipe. The inlet of the air floatation unit 6 is communicated with a halogen production pipe pipeline, and the outlet is communicated with an exhaust unit 9 pipeline.
The obtained raw halogen is conveyed to an air floatation unit 6 through a pipeline for air floatation treatment. The air floatation unit 6 comprises a halogen inlet area 6-1, a coarse floatation area 6-2, a fine floatation area 6-3 and a halogen storage area 6-4 which are sequentially arranged along the horizontal direction in the transverse direction, and the adjacent two areas are separated by an interval partition board 6-6. The middle parts of a coarse floating zone 6-2 and a fine floating zone 6-3 of the air floating unit 6 are provided with nano air discs 6-8, and the coarse floating zone 6-2 and the fine floating zone 6-3 are longitudinally provided with a brine static zone 6-10, an air floating zone 6-11 and a gas-liquid separation zone 6-12 from bottom to top in sequence.
In the longitudinal direction, the nano gas disc 6-8 separates the brine static region 6-10 from the gas floating region 6-11, the gas belt liquid separation region 6-12 of the gas floating unit 6 is connected with the overflow pipe 6-5, and the end part of the overflow pipe 6-5 is connected with the concentrated liquid collecting and separating unit 3. An air blower 8 is designed at the position corresponding to the gas-liquid separation zone 6-12, compressed nano-sized and micro-nano-sized bubbles are introduced into the bottom of the air floatation zone 6-11 after raw halogen enters the air floatation unit 6, the air floatation method is adopted to remove impurities in the raw halogen, the impurities float up to the gas-liquid separation zone 6-12 along with the compressed nano-sized and micro-nano-sized bubbles and enter the overflow pipe 6-5, and under the blowing action of the air blower 8, the impurities flow out from the end part of the overflow pipe 6-5 and enter the concentrated liquid collecting and separating unit 3.
The liquid in the concentrate collecting and separating unit 3 comprises suspended solids in the upper part and clear liquid in the lower part. The overflow liquid collected from the overflow pipe 6-5 is sent from the upper part of the concentrated liquid collecting and separating unit 3, suspended matters (namely impurities such as organic matters) suspended above the overflow liquid in the concentrated liquid collecting and separating unit 3 are discharged outside after being air-floated, and clear liquid is sunk at the lower part of the concentrated liquid collecting and separating unit 3, is sent to a pipeline for conveying raw halogen through a first transfer pump 4, and is continuously sent to a halogen inlet area 6-1 along with the pipeline for air-floated separation again.
In the transverse direction, the side wall of the air floatation unit 6 corresponding to the halogen inlet area 6-1 is provided with an inlet through which raw halogen is introduced into the halogen inlet area 6-1 of the air floatation unit 6, and clear liquid recovered from the concentrated liquid collecting and separating unit 3 also enters the halogen inlet area 6-1 from the inlet. Each partition plate 6-6 is provided with a through hole for communicating the two adjacent regions. Through the arrangement of the through holes and the arrangement of the partition plates 6-6, brine can be prevented from being short-circuited and reflowed in the device, and the brine is only communicated with holes in the through hole area, so that the impact of the flow velocity on bubbles is slowed down. The relative height of the through holes on the partition plate 6-6 between the brine inlet area 6-1 and the coarse floating area 6-2 is positioned below the inlet, and the through holes on the partition plate 6-6 between the fine floating area 6-3 and the brine storage area 6-4 are positioned below the relative height of the through holes on the partition plate 6-6 between the brine inlet area 6-1 and the coarse floating area 6-2. The halogen storage area 6-4 is communicated with the pipeline of the exhaust unit 9.
Specifically, three coarse floating guide baffles 6-7 are arranged in the coarse floating zone 6-2, the coarse floating guide baffles 6-7 form an S-shaped flow channel for liquid in the coarse floating zone 6-2, and 70-80% of suspended impurities are removed in the coarse floating zone 6-2 by the S-shaped flow channel. Two fine floating guide baffles 6-9 are also arranged in the fine floating region 6-3, the fine floating guide baffles 6-9 form an S-shaped flow channel for removing 20-29% of suspended impurities in the fine floating region 6-3. Through the design of the S-shaped flow channels of the coarse floating zone 6-2 and the fine floating zone 6-3, the flowing direction of brine in the air floating unit 6 is controllable, the flowing time of raw brine in the coarse floating zone 6-2 and the fine floating zone 6-3 is prolonged, and the air floating operation is convenient to complete.
Raw halogen sequentially passes through the coarse floating zone 6-2 and the fine floating zone 6-3 through the through holes on each partition plate 6-6, and then enters the halogen storage zone 6-4 through the through holes on the partition plates 6-6 between the fine floating zone 6-3 and the halogen storage zone 6-4. Finally, the brine with the organic matters and other impurities removed is sent to an exhaust unit 9 for exhaust treatment through pumping of a second transfer pump 7 through a brine storage area 6-4.
The exhaust unit 9 comprises an exhaust chamber 9-1 and an exhaust pipe 9-2, the exhaust pipe 9-2 is arranged in the exhaust chamber 9-1 in a serpentine structure, the inlet end of the exhaust pipe 9-2 is positioned at the bottom of the exhaust chamber 9-1, the outlet end of the exhaust pipe is positioned at the top of the exhaust chamber 9-1, condensed water is introduced into the inlet end of the exhaust pipe 9-2, the outlet end of the exhaust pipe is communicated with a pipeline of the mining area 5, and the high-temperature condensed water exchanges heat with brine in the exhaust chamber 9-1 and returns to mine for brine extraction. The halogen fed by the second transfer pump 7 is input from the upper position of the exhaust chamber 9-1 through a pipeline, is output from the lower position of the exhaust chamber 9-1 after heat exchange of the exhaust pipe 9-2, and is fed into the first-stage reaction barrel through the third transfer pump 10 to perform a calcium and magnesium removal process to be used as a salt-making raw material.
In the process, the condensed water introduced from the inlet of the exhaust pipe 9-2 adopts high-temperature condensed water generated by evaporating salt production, so that heat energy generated by salt production can be recycled, and the cooled low-temperature condensed water is sent back to the mining area 5 for ore recovery and brine recovery after heat exchange, thereby realizing the recycling of water sources and clean production. The refined halogen after the gas removal by the exhaust unit 9 is sent into the first-stage reaction barrel 11 for the next process by the third transfer pump 10.
In the whole process, an air pressure air storage unit is adopted for air supply. The air compressor air storage unit comprises an air compressor 1 and an air storage tank 2 connected to the air compressor 1 through a pipeline. The air pressure air storage unit is used for providing compressed nano and micro nano bubbles. The output pipeline of the air storage tank 2 is divided into two parts, wherein one part inputs compressed air into the lower part of the concentrated liquid collecting and separating unit 3, and the compressed air is used for carrying out air floatation operation on overflow liquid conveyed into the concentrated liquid collecting and separating unit 3, and floating and separating and discharging impurities such as organic matters. The other path is to input compressed air to the bottom of an air floatation zone 6-11 of the air floatation unit 6 for supplying air to the nano air tray 6-8, and air floatation operation is carried out in the air floatation unit 6.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (10)
1. The utility model provides a get rid of device of organic matter in brine which characterized in that: comprises a salt cavity-making brine-collecting unit, an air-compressing air-storing unit, an air-floating unit (6), an exhaust unit (9) and a concentrated liquid collecting and separating unit (3);
the salt cavern cavity-making brine-collecting unit comprises a brine-collecting pipe, wherein the brine-collecting pipe comprises a central pipe and a sleeve pipe arranged outside the central pipe;
the inlet of the air floatation unit (6) is communicated with a halogen production pipe pipeline, the outlet of the air floatation unit is communicated with an exhaust unit (9) pipeline, and the exhaust unit (9) is connected with a first-stage reaction barrel (11);
the middle part of the air floatation unit (6) is provided with a nano air tray (6-8), the air floatation unit (6) is respectively provided with a brine static area (6-10), an air floatation area (6-11) and a gas-liquid separation area (6-12) from bottom to top along the height direction, the nano air tray (6-8) separates the brine static area (6-10) from the air floatation area (6-11), the gas-liquid separation area (6-12) of the air floatation unit (6) is connected with an overflow pipe (6-5), and the end part of the overflow pipe (6-5) is connected with the concentrated liquid collecting and separating unit (3);
the output pipeline of the air pressure air storage unit is divided into two parts, wherein one part of the output pipeline inputs compressed air to the bottom of an air floatation area (6-11) of an air floatation unit (6), and the other part of the output pipeline inputs compressed air to the lower part of a concentrated liquid collecting and separating unit (3);
the liquid in the concentrated liquid collecting and separating unit (3) comprises suspended matters at the upper part and clear liquid at the lower part, the lower part of the concentrated liquid collecting and separating unit (3) is communicated with a halogen inlet area (6-1) of the air floatation unit (6) through a pipeline, and compressed air introduced into the concentrated liquid collecting and separating unit (3) floats the liquid in the concentrated liquid collecting and separating unit (3) through the compressed air, and the clear liquid enters the halogen inlet area (6-1) through the pipeline.
2. An apparatus for removing organic matter from brine as claimed in claim 1, wherein: the air floatation unit (6) comprises a halogen inlet zone (6-1), a coarse floatation zone (6-2), a fine floatation zone (6-3) and a halogen storage zone (6-4) which are sequentially arranged along the horizontal direction, wherein two adjacent zones are separated by a partition plate (6-6); the coarse floating zone (6-2) and the fine floating zone (6-3) are respectively a brine static zone (6-10), an air floating zone (6-11) and a gas-liquid separation zone (6-12) from bottom to top along the height direction; an inlet is formed in the halogen inlet area (6-1) and is communicated with a halogen collecting pipe through the inlet; each partition plate (6-6) is provided with a through hole for communicating two adjacent areas; the halogen storage area (6-4) is communicated with the pipeline of the exhaust unit (9).
3. An apparatus for removing organic matter from brine as claimed in claim 2, wherein: a plurality of coarse floating guide baffles (6-7) are arranged in the coarse floating region (6-2), the coarse floating guide baffles (6-7) form an S-shaped flow channel for liquid in the coarse floating region (6-2), and 70-80% of suspended impurities are removed in the coarse floating region (6-2) through the S-shaped flow channel.
4. An apparatus for removing organic matter from brine as claimed in claim 2, wherein: a plurality of fine floating guide baffles (6-9) are also arranged in the fine floating region (6-3), the fine floating guide baffles (6-9) form an S-shaped flow channel for removing 20-29% of suspended impurities in the fine floating region (6-3) by liquid in the static floating region.
5. An apparatus for removing organic matter from brine as claimed in claim 1, wherein: the exhaust unit (9) comprises an exhaust chamber (9-1) and an exhaust pipe (9-2), wherein the exhaust pipe (9-2) is arranged in the exhaust chamber (9-1) in a serpentine structure, the inlet end of the exhaust pipe (9-2) is positioned at the bottom of the exhaust chamber (9-1), the outlet end of the exhaust pipe is positioned at the top of the exhaust chamber (9-1), condensed water is introduced into the inlet end of the exhaust pipe (9-2), the outlet end of the exhaust pipe is communicated with a pipeline of a mining area (5), and the high-temperature condensed water exchanges heat with brine in the exhaust chamber (9-1) and returns to mine for collecting brine.
6. A method for removing organic matters in brine, which is characterized by comprising the following steps: the method comprises the following steps:
A. raw brine extracted from a salt cavity is fed into an air floatation unit (6), compressed nano-nano bubbles and micro-nano bubbles are introduced into the air floatation unit (6) for coarse floatation and fine floatation to obtain brine, the brine is subjected to heat exchange and exhaust by condensed water of an exhaust unit (9) to obtain fine brine, and the fine brine is fed into a first-stage reaction barrel (11) for calcium and magnesium removal process to be used as a salt preparation raw material;
B. the brine static area (6-10), the air floatation area (6-11) and the gas-liquid separation area (6-12) are respectively arranged from bottom to top along the height direction, insoluble matters, floccules or organic matters in the brine float in the gas-liquid separation area (6-12) in the coarse floatation and fine floatation processes, and the insoluble matters, floccules or organic matters are collected and transported to the concentrated solution collecting and separating unit (3) for separation;
C. the concentrated liquid collecting device is filled with compressed nano-sized and micro-nano-sized bubbles to carry out air floatation reaction, insoluble matters, floccules or organic matters are driven to float upwards and are collected, brine at the bottom of the concentrated liquid collecting device is clear liquid, and the clear liquid and raw brine enter an air floatation unit (6) together.
7. A method for removing organic matter from brine as claimed in claim 6, wherein: the salt cavern cavity-making brine-producing pipe comprises a central pipe and a sleeve pipe arranged outside the central pipe, the brine-producing pipe adopts positive circulation in the initial stage of brine production, and adopts reverse circulation in the middle and later stages, and the concentration of sodium chloride in the brine-producing raw brine is not lower than 296g/L.
8. A method for removing organic matter from brine as claimed in claim 7, wherein: the raw halogen comprises the following components: the solid suspended matters are 20-50mg/L, and the organic matters are 30-100mg/L; the refined halogen comprises the following components: the solid suspension is 2-5mg/L, and the organic matter is 0.6-2.0mg/L.
9. A method for removing organic matter from brine as claimed in claim 6, wherein: the compressed nano and micro nano bubbles are air; the pressure of the compressed nano-sized and micro-nano bubbles is 0.11-0.20 Mpa, the aperture of the nano bubbles is 20-500 nm, and the aperture of the micro-nano bubbles is 100-2000 nm; the air inlet positions of the compressed nano-nano and micro-nano bubbles are corresponding to the positions of the air floating areas (6-11) of the air floating unit (6) and the clear liquid of the concentrated liquid collecting and separating unit (3).
10. A method for removing organic matter from brine as claimed in claim 6, wherein: the condensed water of the exhaust unit (9) is high-temperature condensed water generated by evaporating salt production, the temperature of the high-temperature condensed water is 70-80 ℃, and the condensate water returns to mine for brine recovery after heat exchange with refined brine; after the exhaust unit (9) exhausts, the gas content in the brine is reduced by 60-70%.
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