CN107055886B - A kind of depth graded divides salt technique - Google Patents
A kind of depth graded divides salt technique Download PDFInfo
- Publication number
- CN107055886B CN107055886B CN201710424416.XA CN201710424416A CN107055886B CN 107055886 B CN107055886 B CN 107055886B CN 201710424416 A CN201710424416 A CN 201710424416A CN 107055886 B CN107055886 B CN 107055886B
- Authority
- CN
- China
- Prior art keywords
- water
- calcium
- ion
- enters
- sodium chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 52
- 150000003839 salts Chemical class 0.000 title claims abstract description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 101
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 88
- 239000013078 crystal Substances 0.000 claims abstract description 61
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 57
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 57
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 57
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 49
- 239000011780 sodium chloride Substances 0.000 claims abstract description 48
- 239000002351 wastewater Substances 0.000 claims abstract description 48
- 229910052796 boron Inorganic materials 0.000 claims abstract description 46
- 230000023556 desulfurization Effects 0.000 claims abstract description 46
- -1 boron ion Chemical class 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 120
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 50
- 235000011132 calcium sulphate Nutrition 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 34
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 32
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 28
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 25
- 239000012065 filter cake Substances 0.000 claims description 22
- 239000006228 supernatant Substances 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 238000001223 reverse osmosis Methods 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- 230000003009 desulfurizing effect Effects 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000013505 freshwater Substances 0.000 claims description 17
- 238000001728 nano-filtration Methods 0.000 claims description 17
- 238000004062 sedimentation Methods 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003546 flue gas Substances 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 16
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 16
- 238000000108 ultra-filtration Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000000909 electrodialysis Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000010828 elution Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 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 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 238000011118 depth filtration Methods 0.000 claims description 7
- 239000008394 flocculating agent Substances 0.000 claims description 7
- 239000010440 gypsum Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000001175 calcium sulphate Substances 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 238000013327 media filtration Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 7
- 239000003245 coal Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 10
- 208000028659 discharge Diseases 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 5
- 102000005393 Sodium-Potassium-Exchanging ATPase Human genes 0.000 description 5
- 108010006431 Sodium-Potassium-Exchanging ATPase Proteins 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
-
- 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
- C01D3/14—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses technology (the Complete Recycle-Enhanced Separation Technology that a kind of complete resource-reinforcing graded divides salt technology, abbreviation CREST), belong to the processing of thermal power plant desulfurization wastewater and other industry field of industrial waste water treatment, comprising the following steps: specifically includes the following steps: the 1) extraction of crystal magnesium hydroxide；2) extraction of calcium sulfate；3) enrichment of boron ion；4) purification of sodium chloride solution.The depth graded that the invention provides divides salt technique, for the first time by Coal,steam plant with FGD waste water complete resource, after this system is handled, new waste water and solid waste will not be generated, it realizes zero-emission and recycling truly, there is the extremely huge market demand and benefit.
Description
Technical field
The present invention relates to a kind of methods of Coal,steam plant with FGD waste water complete resource, and in particular to a kind of depth
Graded divides salt technique.
Background technique
Lime stone ~ gypsum wet desulfurization is widely used in the flue gas desulfurization technique that thermal power plant generates, and what is generated is useless
Water, it is serious, complex in composition with suspension content height, fouling tendency, and become the maximum difficult point in power plant's Industrial Wastewater Treatment, such as
What realizes the harmless discharge of desulfurization wastewater and recycles that " zero-emission " of i.e. realization desulfurization wastewater becomes very urgent class
Topic.
Due to containing heavy metal element in fire coal, most of heavy metal by flue gas through desulphurization system, by smoke stack emission into
Enter atmosphere, a small amount of heavy metal can be discharged with desulfurization wastewater, in addition, the chloride ion being enriched in absorption tower is also required to be discharged in time.
Therefore, desulfurizer will discharge a certain amount of waste water, to guarantee the security reliability of FGD system operation, according to DL/T5196
Regulation, have desulfurization wastewater generate power plant, desulfurization wastewater treatment system should be separately provided.Desulfurization wastewater effluent quality reaches
The requirement of the secondary discharge standard of integrated wastewater discharge standard GB 8978-1996.Although desulfurization wastewater amount is generally little, by
It is more special in water quality, it cannot be directly discharged into power plant's industrial wastewater treatment system, and any situation does not allow to discharge.
According to the requirement in " DL/T997-2006 thermal power plant Limestone-gypsum Wet Flue Gas Desulfurization Process waste water quality Con trolling index ",
Increase the monitoring project of sulfate in plant area's discharge outlet, highest allows concentration of emission value to be 2000 mg/L.And DL/T997-
2006 and " 8978-1996 integrated wastewater discharge standard of GB ", the concentration of emission of Cl- is not limited, it is useless in desulfurization
In water conventional treatment process, desulfurization wastewater outlet Cl takes concentration identical with 20000 ppm of entrance to be discharged.
Currently, desulfurization wastewater processing mostly uses conventional processes, mainly based on chemical treatment, it is divided into wastewater treatment system
System and sludge treating system.Wherein, waste water treatment system can be divided into the processes such as neutralization, flocculation, precipitating and clarification.Traditional desulfurization
Waste water treatment process is more single, and there are the problems such as ineffective, operation is complicated, and operational percentage is low.It exists simultaneously to chemical oxygen demand
Amount and fluoride poor removal effect；Medicine system is unreliable, and three header pH abilities of regulation and control are poor；Technique specific aim is poor, dispensing at
This height；The problems such as sludge yield is big.Wherein, Cl?Not can be removed is the problem and desulfurization wastewater follow-up study for perplexing zero-emission
The significant challenge faced.
In fact, even the desulfurization wastewater by conventional process, still has many characteristics, such as high salinity, highly corrosive,
No matter direct emission or can all environment be adversely affected by being incorporated to municipal sewage plant, in addition by the shadow of national environmental protection policy
It rings, it is domestic in recent years that the management of desulfurization wastewater is increasingly stringenter.Therefore, desulfurization wastewater zero-emission will be at the following desulfurization wastewater
The Main way of reason.
Realize recycling for desulfurization wastewater, the processing including two stages, the i.e. pretreatment and depth of desulfurization wastewater
Processing.Preprocess method is mainly the treatment process for utilizing lime clarifloccuation, filtering.By lime clarification process, can remove
Most carbonate alkalinity, organic matter can remove 1/4 or so, reduce the content of TDS, but still containing a large amount of in desulfurization wastewater
Organic matter and colloidal substance.At this moment, a large amount of flocculants can be added, most suspended substances is removed, mitigates the burden of follow up device.
Advanced treating mainly uses membrane separation technique, and including just permeating, the method for reverse osmosis and electrodialysis etc., this method will realize water
Salt separation, then Nacl and demineralized water are obtained by subsequent purification, the reclamation rate of waste water and the recycling degree of waste are improved, it is real
" zero-emission " of existing desulfurization wastewater.
Flue gas desulfurization uses wet desulfurization of flue gas by limestone-gypsum method technique, contains the band from raw coal on a small quantity in coal-fired flue-gas
The F- and Cl- and various impurity come, into desulfuration absorbing tower after be washed down and enter slurries, F- combines with the aluminium in slurries
It acts on the dissolution to desulfurization absorbent lime stone and generates screening effect, cause lime stone dissolubility to weaken, desulfuration efficiency reduces；Together
When, Cl-Excessive concentration has corrosiveness to absorption tower system and structure.Therefore, Limestone/Gypsum-based Wet Process Flue Gas Desulfuration is logical
Often need to be discharged a part of filtrate water (absorption tower slurries generate after being dehydrated) as desulfurization wastewater, to reach control CI-、F-From
Sub- concentration and the purpose for maintaining absorption tower material balance.Impurity in desulfurization wastewater is mainly derived from flue gas and lime stone.In coal
Multiple element, such as F, Cl, Cd generate multiple compounds in combustion, enter desulfurizer absorbing tower with flue gas, molten
Xie Yu absorbs in slurries.
Domestic and international desulfurization wastewater advanced treatment process generally comprises following several: 1) evaporation+crystallization processes, the treatment process
It individually to establish a set of waste water and be evaporated system, treatment process will expend a certain amount of steam and station service, since it belongs to end
Technique will not impact the other equipment of power plant and system, but build higher with operating cost.Most of all, through being evaporated
Solids be mixed salt, without utility value, in fact, producing secondary solid waste again；2) salt concentration technology, equipment are thrown
Enter greatly, energy consumption is high, and requirement for anticorrosion is high, because chloride ion is further concentrated；3) high-temperature flue evaporation technology is drained into, evaporation is passed through
Method by desulfurization wastewater water and impurity separate, accomplished the zero-emission of desulfurization wastewater.It needs newly added equipment less, runs
Cost is relatively low.This method has more application case in developed country.This is partly dissolved salt and is transferred in ash or is individually precipitated again,
New solid waste is generated again, it is difficult to be handled.In addition, due to chloride ion content height, the influence to equipment is difficult to control if spraying into flue
System, there is larger security risk.4) multistage filtering+reverse osmosis process, power industry has been obtained commonly used at home, but
Desulfurization wastewater field, since desulfurization waste water quality is poor, reverse osmosis and pretreating process is costly, and popularization is not yet received；5)
Automatic control efflux technology, this method are limited by deslagging mode, are not particularly suited for all power plant.
Summary of the invention
The present invention overcomes above-mentioned disadvantages, and the first purpose of the invention is to provide a kind of depth gradeds to divide salt technique,
Specifically includes the following steps:
1) extraction of crystal magnesium hydroxide: it is brilliant that crystal magnesium hydroxide is added in the flue gas desulfurization waste-water after modifier treatment
Kind and crystal seed promotor adjust water temperature by heater, sodium hydroxide are added, into isothermal reactor, in 120 ~ 150 rpm
Revolving speed under stir, control pH value and reaction time, into sedimentation basin, supernatant overflow enters calcium sulfate reaction tank.Contain crystalline substance
The precipitated liquid of body magnesium hydroxide enters washer-extractor, and filtrate (crystal seed containing magnesium hydroxide) returns to magnesium hydroxide isothermal reactor,
Filter cake automatically falls into kitchen sink, is further washed to magnesium hydroxide crystal, after washing, carries out again into dewaterer
Dehydration, filter cake enters dryer, after drying, crystal magnesium hydroxide is packaged and is packed.Product is crystal magnesium hydroxide；
2) extraction of calcium sulfate, aluminum sulfate: in the calcium sulfate reaction tank of step 1), compound sulfur elimination is added, adjusts pH value
It is 11,50 DEG C of reaction temperature, generates sulfuric acid calcium-aluminate precipitating, after the reaction was completed, into sedimentation basin, supernatant enters deliming
Pond enters conversion pool containing sulfuric acid calcium-aluminate precipitated liquid, by adjust pH value, by sulfuric acid calcium-aluminate be decomposed into calcium sulfate and
Aluminum sulfate, sulfuric acid molten aluminum are used as flocculating agent, and solid calcium sulphate is sent into washer-extractor, and into washing dehydration, filtrate is sent into
Calcium sulfate reaction tank, filter cake are packaged pack after drying and use.Product is calcium sulfate and aluminum sulfate；
3) extraction of calcium carbonate: sodium bicarbonate is used, calcium carbonate is isolated.Desulfurizing agent of the calcium carbonate as desulfurizing tower, weight
It is multiple to utilize, sodium bicarbonate solution to be prepared, deliming pond is added, calcium ion and reaction of sodium bicarbonate in water generate precipitation of calcium carbonate,
The supernatant in deliming pond enters neutralization pond, and drain squeezes into desulfurizing tower through calcium carbonate charging pump；
4) enrichment of boron ion: in the waste liquid for removing calcium ion, magnesium ion, sulfate ion, being pressurized through booster pump,
Sodium hydroxide solution is added on outlet pipe and adjusts pH value, into boron absorption tower, the boron ion in water is absorbed with resin chelating, when
When having boron in water outlet, absorption tower failure being sentenced, being transferred to boron elution procedure, regenerated liquid is the B solution being enriched with；
5) purification of sodium chloride solution: by the water after extracting magnesium, sulfate radical, boron, calcium, at most a matter is pumped through pressurization
Filter, into water tank with strainer, filtered water enters ultrafiltration apparatus through ultrafiltration feed pump again, carries out in-depth filtration, is sent into super
Water filtering tank is sent into nanofiltration device through nanofiltration high-pressure hydraulic pump, by water divalent and the above ion mutually separate with monovalent ion, (sulphur
Acid group removes substantially, and calcium, magnesium remove 90%, and nanofiltration concentrated water is returned demagging pond again, is handled, the first liquid of obtained sodium chloride,
Electrodialysis plant is sent into be concentrated, when concentration of sodium chloride solution reaches 15% or more, concentrate enters sodium chloride solution case,
When fresh water conductivity lower than 3000 gemmbos/centimetre when, into fresh-water tank, by reverse osmosis high-pressure water pump, into reverse osmosis unit,
Reverse osmosis fresh water, into reuse water tank, concentrated water returns electrodialysis plant, is handled.Into the molten of sodium chloride solution case
Liquid is pumped into ion-exchanger through salt water, removes the calcium and magnesium in water, obtain the sodium chloride solution that purity is more than 99.5% or more,
Ion-exchanger sets three altogether, and sodium chloride solution is sent into sodium hypochlorite hair by two series operations a, zeolite regeneration or spare
Sodium chloride is converted into liquor natrii hypochloritis and used by raw device.
Preferably, in the step 1) lower water temperature to 50 ~ 60 DEG C.
Preferably, pH value is not less than 11 in the step 1).
Preferably, the time is 2 hours.
Preferably, the mass percent concentration of sodium bicarbonate solution is 10 ~ 20% in the step 2.
Preferably, it is 8 ~ 10 that sodium hydroxide solution is added in the step 3) on outlet pipe and adjusts pH value.
A second object of the present invention is to provide another depth gradeds to divide salt technique, specifically includes the following steps:
1) extraction of crystal magnesium hydroxide: it is brilliant that crystal magnesium hydroxide is added in the flue gas desulfurization waste-water after modifier treatment
By heater, by lower water temperature to 50 ~ 60 DEG C, sodium hydroxide is added in kind, crystal seed promotor, into isothermal reactor, solid
Determine to stir under revolving speed, control pH value is not less than 11, and time 2 h or so, into sedimentation basin, it is anti-that supernatant overflow enters calcium sulfate
Ying Chi.Precipitated liquid containing crystal magnesium hydroxide enters washer-extractor, and filtrate (crystal seed containing magnesium hydroxide) returns to magnesium hydroxide
Isothermal reactor, filter cake automatically fall into kitchen sink, are further washed to magnesium hydroxide crystal, after washing, into de-
Water dispenser is dehydrated again, and filter cake enters dryer, after drying, crystal magnesium hydroxide is packaged and is packed, and product is crystal hydrogen-oxygen
Change magnesium；
2) extraction of calcium sulfate: in the calcium sulfate reaction tank of step 1), aluminium salt is added and is added according to the concentration of calcium, sulfate radical
Enter the PAM of 2 ~ 10 ppm, sodium hydroxide is added, adjusts pH value, stirring intensity control is 80 rpm, and it is small that the reaction time is no less than 1
When, mixed liquor enters sedimentation basin, and the supernatant in sedimentation basin enters deliming pond, and lower drain enters washing dehydration by feeding engine
Machine, filter cake enter sink, add water, are made into underflow liquid, and returning pH value with sulfuric acid solution is 6 ~ 8, and stirring intensity controls 50rpm, when
Between 30min, be again introduced into dewaterer, filtrate returns reactor, and filter cake washs repeatedly, until calcium sulfate purity reaches requirement.Product
To refine gypsum；
3) enrichment of boron ion: in the waste liquid for removing calcium ion, magnesium ion, sulfate ion, being pressurized through booster pump,
Sodium hydroxide solution is added on outlet pipe and adjusts pH value 8 ~ 10, into boron absorption tower, boron ion and resin in water chelate quilt
It absorbs, when there is boron in water outlet, sentences absorption tower failure, be transferred to boron elution procedure, regenerated liquid is the B solution being enriched with；
4) purification of sodium chloride solution: by the water after extracting magnesium, sulfate radical, boron, calcium, at most a matter is pumped through pressurization
Filter, into water tank with strainer, filtered water enters ultrafiltration apparatus through ultrafiltration feed pump again, carries out in-depth filtration, is sent into super
Water filtering tank is sent into nanofiltration device through nanofiltration high-pressure hydraulic pump, by water divalent and the above ion mutually separate with monovalent ion, will receive
Filter concentrated water returns demagging pond again, is handled, and just liquid, feeding electrodialysis plant are concentrated obtained sodium chloride, works as chlorination
When sodium solution concentration reaches 15% or more, concentrate enters sodium chloride solution case, when fresh water conductivity lower than 3000 gemmbos/centimetre
When, into fresh-water tank, by reverse osmosis high-pressure water pump, into reverse osmosis unit, reverse osmosis fresh water is dense into reuse water tank
Water returns electrodialysis plant, is handled.Into the solution of sodium chloride solution case, it is pumped into ion-exchanger through salt water, is removed
The calcium and magnesium in water is gone, the sodium chloride solution that purity is more than 99.5% or more is obtained, ion-exchanger sets three altogether, two series connection fortune
Row, a zeolite regeneration or spare, obtained sodium chloride solution can enter evaporated crystallization device such as MVR, multi-effect evaporating device
Deng crystallizing out Nacl, after drying, quality reaches national purified salt primes standard.
Preferably, the revolving speed in the step 1) is 120 ~ 150 rpm.
Preferably, pH value is greater than 11 in the step 2.
Depth graded of the present invention divides in salt technique, for the first time by Coal,steam plant with FGD waste water complete resource, through this
After system processing, new waste water and solid waste will not be generated, realizes zero-emission and recycling truly, had extremely huge
The market demand and benefit.
Specific embodiment
Embodiment 1
Depth graded divides salt technique, specifically includes following steps (for handling 30t/h desulfurization wastewater):
1) extraction of crystal magnesium hydroxide:
The modifier treatment of desulfurization wastewater: in quenched pond, being added lime slurry 5000ppm, PAM5ppm, organic sulfur 1ppm,
Adjusting pH value is 7, and sediment slurry returns to desulfurizing tower bottom row.Supernatant, which enters, removes magnesium apparatus；
Flue gas desulfurization waste-water after modifier treatment is added crystal magnesium hydroxide crystal seed (reflux of dewaterer filtrate) and brilliant
Kind promotor adjusts water temperature by heater, and sodium hydroxide is added and stirs under the revolving speed of 130 rpm into isothermal reactor
It mixes, controls pH value 11 and reaction time 120min, into sedimentation basin, supernatant overflow enters calcium sulfate reaction tank.Contain crystal
The precipitated liquid of magnesium hydroxide enters washer-extractor, and filtrate (crystal seed containing magnesium hydroxide) returns to magnesium hydroxide isothermal reactor, filter
Cake automatically falls into kitchen sink, is further washed to magnesium hydroxide crystal, after washing, is taken off again into dewaterer
Water, filter cake enters dryer, after drying, crystal magnesium hydroxide is packaged and is packed.Product is crystal magnesium hydroxide；
2) extraction of calcium sulfate, aluminum sulfate: in the calcium sulfate reaction tank of step 1), compound sulfur elimination is added, adjusts pH value
It is 11, reaction temperature controls 50 DEG C, reaction time 60min, sulfuric acid calcium-aluminate precipitating is generated, after the reaction was completed, into
Enter sedimentation basin, supernatant enters denitrification tank (if having ammonia in water), with being pumped into deliming pond.Contain sulfuric acid calcium-aluminate precipitated liquid
Sulfuric acid calcium-aluminate is decomposed into calcium sulfate and aluminum sulfate, sulfuric acid molten aluminum is as flocculating agent by adjusting pH value into conversion pool
It uses, solid calcium sulphate is sent into washer-extractor, carries out washing dehydration, and filtrate is sent into calcium sulfate reaction tank, is made as flocculating agent
With filter cake is packaged pack after drying and uses.Product is calcium sulfate；
3) extraction of calcium carbonate: sodium bicarbonate is used, calcium carbonate is isolated.Desulfurizing agent of the calcium carbonate as desulfurizing tower, weight
It is multiple to utilize, sodium bicarbonate solution to be prepared, deliming pond is added, calcium ion and reaction of sodium bicarbonate in water generate precipitation of calcium carbonate,
The supernatant in deliming pond enters neutralization pond, and drain squeezes into desulfurizing tower through calcium carbonate charging pump；
4) enrichment of boron ion: in the waste liquid for removing calcium ion, magnesium ion, sulfate ion, being pressurized through booster pump,
Sodium hydroxide solution is added on outlet pipe and adjusts pH value 9, into boron absorption tower, the boron ion in water is inhaled with resin chelating
It receives, when there is boron in water outlet, sentences absorption tower failure, be transferred to boron elution procedure, regenerated liquid is the B solution being enriched with；
The hydrochloric acid solution for preparing 1mmol/l elutes the resin of absorption boron ion, condition are as follows: elution time:
30min, into 40 ~ 80 times of sour volume of resins volume, the resin after elution is regenerated with the sodium hydroxide solution of 1mmol/l, until
When draining is neutral, terminate regeneration；
5) purification of sodium chloride solution: by the water after extracting magnesium, sulfate radical, boron, calcium, at most a matter is pumped through pressurization
Filter, into water tank with strainer, filtered water enters ultrafiltration apparatus through ultrafiltration feed pump again, carries out in-depth filtration, is sent into super
Water filtering tank is sent into nanofiltration device through nanofiltration high-pressure hydraulic pump, by water divalent and the above ion mutually separate with monovalent ion, will receive
Filter concentrated water returns demagging pond again, is handled, and just liquid, feeding electrodialysis plant are concentrated obtained sodium chloride, works as chlorination
When sodium solution concentration reaches 15% or more, concentrate enters sodium chloride solution case, when fresh water conductivity lower than 3000 gemmbos/centimetre
When, into fresh-water tank, by reverse osmosis high-pressure water pump, into reverse osmosis unit, reverse osmosis fresh water is dense into reuse water tank
Water returns electrodialysis plant, is handled.Into the solution of sodium chloride solution case, it is pumped into ion-exchanger through salt water, is removed
The calcium and magnesium in water is gone, the sodium chloride solution that purity is more than 99.5% or more is obtained, ion-exchanger sets three altogether, two series connection fortune
Sodium chloride solution is sent into hypochlorite generator by row, a zeolite regeneration or spare, and it is molten that sodium chloride is converted into sodium hypochlorite
Liquid, concentration 8000-10000ppm.
In this example, about 8 tons of the crystal magnesium hydroxide (95% or more purity) obtained daily, calcium sulfate (purity 98% with
On) about 12 tons, 600 tons of the liquor natrii hypochloritis (98% or more purity) of 0.8-1%.
Embodiment 2
Depth graded divides salt technique, specifically includes the following steps:
1) extraction of crystal magnesium hydroxide:
The modifier treatment of desulfurization wastewater: in quenched pond, being added lime slurry 5000ppm, PAM5ppm, organic sulfur 1ppm,
Adjusting pH value is 7, and sediment slurry returns to desulfurizing tower bottom row.Supernatant, which enters, removes magnesium apparatus；
Flue gas desulfurization waste-water after modifier treatment is added crystal magnesium hydroxide crystal seed (reflux of dewaterer filtrate) and brilliant
Kind promotor adjusts water temperature by heater, and sodium hydroxide is added and stirs under the revolving speed of 130 rpm into isothermal reactor
It mixes, controls pH value 11 and reaction time 120min, into sedimentation basin, supernatant overflow enters calcium sulfate reaction tank.Contain crystal
The precipitated liquid of magnesium hydroxide enters washer-extractor, and filtrate (crystal seed containing magnesium hydroxide) returns to magnesium hydroxide isothermal reactor, filter
Cake automatically falls into kitchen sink, is further washed to magnesium hydroxide crystal, after washing, is taken off again into dewaterer
Water, filter cake enters dryer, after drying, crystal magnesium hydroxide is packaged and is packed, and product is crystal magnesium hydroxide；
2) extraction of calcium sulfate: in the calcium sulfate reaction tank of step 1), aluminium salt is added, concentration is according to calcium, the ratio of sulfate radical
Value determines, the PAM of 2 ~ 10ppm is added, and sodium hydroxide is added, and adjusts pH value and is greater than 11, stirring intensity controls 80rpm, when reaction
Between 1 hour, mixed liquor enters sedimentation basin, and the supernatant in sedimentation basin enters deliming pond, and lower drain enters dehydration by feeding engine
Machine, filter cake enter sink, add water, are made into underflow liquid, and returning pH value with sulfuric acid solution is 7, and stirring intensity controls 50rpm, time
30min is again introduced into dewaterer, and filtrate returns reactor, and filter cake washs repeatedly, until calcium sulfate purity reaches requirement.Product is
Refine gypsum；
3) extraction of calcium carbonate: sodium bicarbonate is used, calcium carbonate is isolated.Desulfurizing agent of the calcium carbonate as desulfurizing tower, weight
It is multiple to utilize, sodium bicarbonate solution to be prepared, deliming pond is added, calcium ion and reaction of sodium bicarbonate in water generate precipitation of calcium carbonate,
The supernatant in deliming pond enters neutralization pond, and drain squeezes into desulfurizing tower through calcium carbonate charging pump；
4) enrichment of boron ion: in the waste liquid for removing calcium ion, magnesium ion, sulfate ion, being pressurized through booster pump,
Sodium hydroxide solution is added on outlet pipe and adjusts pH value 9, into boron absorption tower, the boron ion in water is inhaled with resin chelating
It receives, when there is boron in water outlet, sentences absorption tower failure, be transferred to boron elution procedure, regenerated liquid is the B solution being enriched with；
The hydrochloric acid solution for preparing 1mmol/l elutes the resin of absorption boron ion, condition are as follows: elution time:
30min, into 60 times of sour volume of resins volume, the resin after elution is regenerated with the sodium hydroxide solution of 1mmol/l, until draining
When for neutrality, terminate regeneration；
5) purification of sodium chloride solution: by the water after extracting magnesium, sulfate radical, boron, calcium, at most a matter is pumped through pressurization
Filter, into water tank with strainer, filtered water enters ultrafiltration apparatus through ultrafiltration feed pump again, carries out in-depth filtration, is sent into super
Water filtering tank is sent into nanofiltration device through nanofiltration high-pressure hydraulic pump, by water divalent and the above ion mutually separate with monovalent ion, will receive
Filter concentrated water returns demagging pond again, is handled, and just liquid, feeding electrodialysis plant are concentrated obtained sodium chloride, works as chlorination
When sodium solution concentration reaches 15% or more, concentrate enters sodium chloride solution case, when fresh water conductivity lower than 3000 gemmbos/centimetre
When, into fresh-water tank, by reverse osmosis high-pressure water pump, into reverse osmosis unit, reverse osmosis fresh water is dense into reuse water tank
Water returns electrodialysis plant, is reprocessed.Into the solution of sodium chloride solution case, it is pumped into ion-exchanger through salt water,
The calcium and magnesium in water is removed, the sodium chloride solution that purity is more than 99.5% or more is obtained, ion-exchanger sets three altogether, two series connection
Operation, a zeolite regeneration or spare, obtained sodium chloride solution can enter evaporated crystallization device such as MVR, multiple-effect evaporation and fill
It sets, crystallizes out Nacl, after drying, quality reaches national purified salt primes standard.
In this example, about 8 tons of the crystal magnesium hydroxide (95% or more purity) obtained daily, calcium sulfate (purity 98% with
On) about 12 tons, 25 tons of Nacl (national purified salt primes, 99.2% or more purity), (conductivity is less than 600 tons of deionized water
10 μm/cm).
Embodiment 3
Depth graded divides salt technique, specifically includes following steps (for handling 30t/h desulfurization wastewater)；
This example is for riverine, the coastal thermal power plant using open circulation water system；
1) extraction of crystal magnesium hydroxide:
The modifier treatment of desulfurization wastewater: in quenched pond, being added lime slurry 5000ppm, PAM5ppm, organic sulfur 1ppm,
Adjusting pH value is 7, and sediment slurry returns to desulfurizing tower bottom row.Supernatant, which enters, removes magnesium apparatus,
Flue gas desulfurization waste-water after modifier treatment is added crystal magnesium hydroxide crystal seed (reflux of dewaterer filtrate) and brilliant
Kind promotor adjusts water temperature by heater, and sodium hydroxide is added and stirs under the revolving speed of 130 rpm into isothermal reactor
It mixes, controls pH value 11 and reaction time 120min, into sedimentation basin, supernatant overflow enters calcium sulfate reaction tank.Contain crystal
The precipitated liquid of magnesium hydroxide enters washer-extractor, and filtrate (crystal seed containing magnesium hydroxide) returns to magnesium hydroxide isothermal reactor, filter
Cake automatically falls into kitchen sink, is further washed to magnesium hydroxide crystal, after washing, is taken off again into dewaterer
Water, filter cake enters dryer, after drying, crystal magnesium hydroxide is packaged and is packed.Product is crystal magnesium hydroxide；
2) extraction of calcium sulfate, aluminum sulfate: in the calcium sulfate reaction tank of step 1), compound sulfur elimination is added, adjusts pH value
It is 11, reaction temperature controls 50 DEG C, reaction time 60min, sulfuric acid calcium-aluminate precipitating is generated, after the reaction was completed, into
Enter sedimentation basin, supernatant enters denitrification tank (if having ammonia in water), with being pumped into deliming pond.Contain sulfuric acid calcium-aluminate precipitated liquid
Sulfuric acid calcium-aluminate is decomposed into calcium sulfate and aluminum sulfate, sulfuric acid molten aluminum is as flocculating agent by adjusting pH value into conversion pool
It uses, solid calcium sulphate is sent into washer-extractor, carries out washing dehydration, and filtrate is sent into calcium sulfate reaction tank, is made as flocculating agent
With filter cake is packaged pack after drying and uses.Product is calcium sulfate；
3) extraction of calcium carbonate: sodium bicarbonate is used, calcium carbonate is isolated.Desulfurizing agent of the calcium carbonate as desulfurizing tower, weight
It is multiple to utilize, sodium bicarbonate solution to be prepared, deliming pond is added, calcium ion and reaction of sodium bicarbonate in water generate precipitation of calcium carbonate,
The supernatant in deliming pond enters neutralization pond, and drain squeezes into desulfurizing tower through calcium carbonate charging pump；
4) enrichment of boron ion: in the waste liquid for removing calcium ion, magnesium ion, sulfate ion, being pressurized through booster pump,
Sodium hydroxide solution is added on outlet pipe and adjusts pH value 9, into boron absorption tower, the boron ion in water is inhaled with resin chelating
It receives, when there is boron in water outlet, sentences absorption tower failure, be transferred to boron elution procedure, regenerated liquid is the B solution being enriched with；
The hydrochloric acid solution for preparing 1mmol/l elutes the resin of absorption boron ion, condition are as follows: elution time:
30min, into 60 times of sour volume of resins volume, the resin after elution is regenerated with the sodium hydroxide solution of 1mmol/l, until draining
When for neutrality, terminate regeneration；
5) purification of sodium chloride solution: by the water after extracting magnesium, sulfate radical, boron, calcium, at most a matter is pumped through pressurization
Filter, into water tank with strainer, filtered water enters ultrafiltration apparatus through ultrafiltration feed pump again, carries out in-depth filtration, is sent into super
Water filtering tank is sent into nanofiltration device through nanofiltration high-pressure hydraulic pump, by water divalent and the above ion mutually separate with monovalent ion, will receive
Filter concentrated water returns demagging pond again, is handled, obtained sodium chloride solution, is sent into electrodialysis plant and is concentrated, works as chlorination
When sodium solution concentration reaches 5% or more, concentrate enters sodium chloride solution case, and sodium chloride solution is sent into hypochlorite generator,
Sodium chloride is converted into liquor natrii hypochloritis, concentration about 8000-10000ppm is added in recirculated water, uses as biocide.
Condenser end differential temperature degree is effectively improved, into raising unit operation efficiency.
In this example, about 8 tons of the crystal magnesium hydroxide (95% or more purity) obtained daily, calcium sulfate (purity 98% with
On) about 12 tons, 600 tons of the liquor natrii hypochloritis (92% or more purity) of 0.8-1%.
Claims (7)
1. a kind of depth graded divides salt technique, which is characterized in that specifically includes the following steps:
1) extraction of crystal magnesium hydroxide: the flue gas desulfurization waste-water after modifier treatment, be added crystal magnesium hydroxide crystal seed and
Crystal seed promotor adjusts water temperature by heater, sodium hydroxide is added, into isothermal reactor, in the revolving speed of 120-150rpm
Lower stirring controls pH value and reaction time, and into sedimentation basin, supernatant overflow enters calcium sulfate reaction tank, contains crystal hydrogen-oxygen
The precipitated liquid for changing magnesium enters washer-extractor, and filtrate crystal seed containing magnesium hydroxide returns to magnesium hydroxide isothermal reactor, and filter cake is automatic
Kitchen sink is fallen into, magnesium hydroxide crystal is further washed, after washing, is dehydrated again into dewaterer, is filtered
Cake enters dryer, after drying, crystal magnesium hydroxide is packaged and is packed, and product is crystal magnesium hydroxide；
2) extraction of calcium sulfate, aluminum sulfate: in the calcium sulfate reaction tank of step 1), being added compound sulfur elimination, and adjusting pH value is 11,
50 DEG C of reaction temperature, sulfuric acid calcium-aluminate precipitating is generated, after the reaction was completed, into sedimentation basin, supernatant enters deliming pond, contains
Sulfuric acid calcium-aluminate precipitated liquid enters conversion pool, and by adjusting pH value, sulfuric acid calcium-aluminate is decomposed into calcium sulfate and aluminum sulfate,
Sulfuric acid molten aluminum is used as flocculating agent, and solid calcium sulphate is sent into washer-extractor, and into washing dehydration, it is anti-that filtrate is sent into calcium sulfate
Ying Chi, filter cake are packaged pack after drying and use, and product is calcium sulfate；
3) extraction of calcium carbonate: using sodium bicarbonate, isolates calcium carbonate, and desulfurizing agent of the calcium carbonate as desulfurizing tower repeats benefit
With deliming pond is added in preparation sodium bicarbonate solution, and calcium ion and reaction of sodium bicarbonate in water generate precipitation of calcium carbonate, deliming
The supernatant in pond enters neutralization pond, and drain squeezes into desulfurizing tower through calcium carbonate charging pump；
4) it the enrichment of boron ion: in the waste liquid for removing calcium ion, magnesium ion, sulfate ion, is pressurized, is being discharged through booster pump
Sodium hydroxide solution is added on pipe and adjusts pH value, into boron absorption tower, the boron ion in water is absorbed with resin chelating, works as water outlet
In when having boron, sentence absorption tower failure, be transferred to boron elution procedure, regenerated liquid is the B solution being enriched with；
5) purification of sodium chloride solution: by the water after extracting magnesium, sulfate radical, boron, calcium, through pressurization pumping at most media filtration
Device, into water tank with strainer, filtered water enters ultrafiltration apparatus through ultrafiltration feed pump again, carries out in-depth filtration, is sent into ultrafiltration water
Case is sent into nanofiltration device through nanofiltration high-pressure hydraulic pump, by water divalent and the above ion mutually separate with monovalent ion, sulphate groups
This removing, calcium, magnesium remove 90%, nanofiltration concentrated water are returned demagging pond again, is handled, and the first liquid of obtained sodium chloride is sent into
Electrodialysis plant is concentrated, and when concentration of sodium chloride solution reaches 15% or more, concentrate enters sodium chloride solution case, when light
Water conductivity lower than 3000 gemmbos/centimetre when, into fresh-water tank, by reverse osmosis high-pressure water pump, into reverse osmosis unit, reverse osmosis
Saturating fresh water, into reuse water tank, concentrated water returns electrodialysis plant, is handled, into the solution of sodium chloride solution case, warp
Salt water is pumped into ion-exchanger, removes the calcium and magnesium in water, obtains the sodium chloride solution that purity is more than 99.5% or more, and ion is handed over
Parallel operation sets three altogether, and sodium chloride solution is sent into hypochlorite generator by two series operations a, zeolite regeneration or spare,
Sodium chloride is converted into liquor natrii hypochloritis to use.
2. a kind of depth graded divides salt technique, which is characterized in that specifically includes the following steps:
1) extraction of crystal magnesium hydroxide: the flue gas desulfurization waste-water after modifier treatment, be added crystal magnesium hydroxide crystal seed and
Crystal seed promotor adjusts water temperature by heater, sodium hydroxide is added, into isothermal reactor, in the revolving speed of 120-150rpm
Lower stirring controls pH value and reaction time, and into sedimentation basin, supernatant overflow enters calcium sulfate reaction tank, contains crystal hydrogen-oxygen
The precipitated liquid for changing magnesium enters washer-extractor, and filtrate crystal seed containing magnesium hydroxide returns to magnesium hydroxide isothermal reactor, and filter cake is automatic
Kitchen sink is fallen into, magnesium hydroxide crystal is further washed, after washing, is dehydrated again into dewaterer, is filtered
Cake enters dryer, after drying, crystal magnesium hydroxide is packaged and is packed, and product is crystal magnesium hydroxide；
2) extraction of calcium sulfate: in the calcium sulfate reaction tank of step 1), being added aluminium salt, and according to the concentration of calcium, sulfate radical, 2- is added
Sodium hydroxide is added in the PAM of 10ppm, adjusts pH value, and stirring intensity control is 80rpm, and the reaction time is no less than 1 hour, is mixed
Liquid enters sedimentation basin, and the supernatant in sedimentation basin enters deliming pond, and lower drain enters washer-extractor by feeding engine, filter cake into
Enter sink, add water, is made into underflow liquid, returning pH value with sulfuric acid solution is 6-8, and stirring intensity controls 50rpm, time 30min, then
Secondary to enter dewaterer, filtrate returns reactor, and filter cake washs repeatedly, until calcium sulfate purity reaches requirement, product is purification gypsum；
3) it the enrichment of boron ion: in the waste liquid for removing calcium ion, magnesium ion, sulfate ion, is pressurized, is being discharged through booster pump
Sodium hydroxide solution is added on pipe and adjusts pH value in 8-10, into boron absorption tower, the boron ion in water is absorbed with resin chelating,
When there is boron in water outlet, absorption tower failure being sentenced, being transferred to boron elution procedure, regenerated liquid is the B solution being enriched with；
4) purification of sodium chloride solution: by the water after extracting magnesium, sulfate radical, boron, calcium, at most a medium mistake is pumped through pressurization
Filter, into water tank with strainer, filtered water enters ultrafiltration apparatus through ultrafiltration feed pump again, carries out in-depth filtration, is sent into ultrafiltration
Water tank is sent into nanofiltration device through nanofiltration high-pressure hydraulic pump, by water divalent and the above ion mutually separate with monovalent ion, by nanofiltration
Concentrated water returns demagging pond again, is handled, and just liquid, feeding electrodialysis plant are concentrated obtained sodium chloride, works as sodium chloride
When solution concentration reaches 15% or more, concentrate enters sodium chloride solution case, when fresh water conductivity lower than 3000 gemmbos/centimetre
When, into fresh-water tank, by reverse osmosis high-pressure water pump, into reverse osmosis unit, reverse osmosis fresh water is dense into reuse water tank
Water returns electrodialysis plant, is handled, and into the solution of sodium chloride solution case, is pumped into ion-exchanger through salt water, removes
The calcium and magnesium in water is gone, the sodium chloride solution that purity is more than 99.5% or more is obtained, ion-exchanger sets three altogether, two series connection fortune
Row, a zeolite regeneration or spare, obtained sodium chloride solution, into evaporated crystallization device MVR, multi-effect evaporating device, crystallization
Nacl out, after drying, quality reach national purified salt primes standard.
3. depth graded according to claim 2 divides salt technique, which is characterized in that lower water temperature is extremely in the step 1)
50-60℃。
4. depth graded according to claim 2 divides salt technique, which is characterized in that pH value is not less than in the step 1)
11。
5. depth graded according to claim 2 divides salt technique, which is characterized in that the step 1) time is 2 hours.
6. depth graded according to claim 1 divides salt technique, which is characterized in that sodium bicarbonate solution in the step 3)
Mass percent concentration be 10-20%.
7. depth graded according to claim 2 divides salt technique, which is characterized in that pH value is greater than 11 in the step 2).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710424416.XA CN107055886B (en) | 2017-06-07 | 2017-06-07 | A kind of depth graded divides salt technique |
| PCT/CN2017/088511 WO2018223414A1 (en) | 2017-06-07 | 2017-06-15 | Graded deep salt separation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710424416.XA CN107055886B (en) | 2017-06-07 | 2017-06-07 | A kind of depth graded divides salt technique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107055886A CN107055886A (en) | 2017-08-18 |
| CN107055886B true CN107055886B (en) | 2019-10-15 |
Family
ID=59616523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710424416.XA Active CN107055886B (en) | 2017-06-07 | 2017-06-07 | A kind of depth graded divides salt technique |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN107055886B (en) |
| WO (1) | WO2018223414A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110510645A (en) * | 2019-09-27 | 2019-11-29 | 青海盐湖工业股份有限公司 | A kind of method and system cleaning loop production magnesium hydroxide |
| WO2021126859A1 (en) * | 2019-12-19 | 2021-06-24 | Fairlife, Llc | Preparation of high solids and high protein lactose-free aseptic milk concentrates and milk powders with forward osmosis |
| CN113896370A (en) * | 2021-11-18 | 2022-01-07 | 西安西热水务环保有限公司 | Novel mine water zero discharge system and method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8197696B1 (en) * | 2009-12-03 | 2012-06-12 | Bader Mansour S | Methods to control the precipitation of inorganic materials and/or to scrub flue gas |
| CN103979702A (en) * | 2013-02-07 | 2014-08-13 | 上海凯鑫分离技术有限公司 | Magnesium hydroxide washing water recovery technology |
| CN105457479A (en) * | 2015-12-31 | 2016-04-06 | 上海世渊环保科技有限公司 | Flue gas desulphurization zero-emission resource disposal system and method |
| CN106007046A (en) * | 2016-05-10 | 2016-10-12 | 上海电力学院 | Resource pretreatment technology for desulfurization waste water hardness ions |
| CN106186499A (en) * | 2016-08-31 | 2016-12-07 | 江苏久吾高科技股份有限公司 | The Zero discharge treatment method of a kind of wastewater desulfurized by fume wet and device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456635B (en) * | 2008-12-17 | 2011-04-27 | 深圳市能源环保有限公司 | A method and system for treating wastewater from a power plant |
| CN105923822B (en) * | 2016-05-31 | 2019-06-14 | 江苏京源环保股份有限公司 | Desulfurization wastewater divides mud, divides salt technique of zero discharge |
-
2017
- 2017-06-07 CN CN201710424416.XA patent/CN107055886B/en active Active
- 2017-06-15 WO PCT/CN2017/088511 patent/WO2018223414A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8197696B1 (en) * | 2009-12-03 | 2012-06-12 | Bader Mansour S | Methods to control the precipitation of inorganic materials and/or to scrub flue gas |
| CN103979702A (en) * | 2013-02-07 | 2014-08-13 | 上海凯鑫分离技术有限公司 | Magnesium hydroxide washing water recovery technology |
| CN105457479A (en) * | 2015-12-31 | 2016-04-06 | 上海世渊环保科技有限公司 | Flue gas desulphurization zero-emission resource disposal system and method |
| CN106007046A (en) * | 2016-05-10 | 2016-10-12 | 上海电力学院 | Resource pretreatment technology for desulfurization waste water hardness ions |
| CN106186499A (en) * | 2016-08-31 | 2016-12-07 | 江苏久吾高科技股份有限公司 | The Zero discharge treatment method of a kind of wastewater desulfurized by fume wet and device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107055886A (en) | 2017-08-18 |
| WO2018223414A1 (en) | 2018-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101891330B (en) | Power plant wastewater treatment system and method | |
| CN106430786B (en) | Desulfurization wastewater treatment method and device | |
| CN104860461B (en) | A kind of desulfurization wastewater zero-emission prepares the method and device of NaCl Nacls | |
| CN108623063A (en) | A kind of processing method and processing system of desulfurization wastewater | |
| CN106946395A (en) | A kind of method and device of desulfurization wastewater sub-prime crystallization treatment | |
| CN209835879U (en) | System for preparing acid and alkali by utilizing desulfurization wastewater | |
| CN209276303U (en) | Coal water slurry gasification waste water divides salt to crystallize zero-discharge treatment system | |
| CN111718048A (en) | Wet desulphurization waste water and salt separation zero-emission system and salt separation zero-emission method | |
| CN113800690A (en) | Power plant desulfurization wastewater zero-discharge treatment process and system based on electrodialysis technology | |
| CN106966535A (en) | Strong brine zero-emission film is concentrated and sub-prime crystallization processes and equipment | |
| CN208684674U (en) | Processing system for garbage filter concentrate zero-emission | |
| CN111777220A (en) | Novel softening treatment method for high-salinity and high-permanent-hardness wastewater | |
| CN108017213A (en) | A kind of high slat-containing wastewater recycling treatment system and technique | |
| CN110316897A (en) | A kind of system and method for the full factory waste water zero discharge of power plant and resource utilization | |
| CN207130086U (en) | A kind of salt-containing waste water treating device | |
| CN107055886B (en) | A kind of depth graded divides salt technique | |
| CN205653287U (en) | Device that zero release of desulfurization waste water was handled | |
| CN205603385U (en) | Concentrated and branch matter crystallization equipment of strong brine zero release membrane | |
| CN113401923A (en) | Method and system for performing cooperative treatment on hazardous waste incineration wet deacidification and fly ash washing | |
| CN206858347U (en) | A kind of device of desulfurization wastewater sub-prime crystallization treatment | |
| CN105481160B (en) | Method and device for preparing industrial salt by strong brine with zero discharge | |
| CN214570785U (en) | System for extracting magnesium sulfate and sodium chloride from desulfurization wastewater | |
| CN108793569A (en) | A kind of high ammonia nitrogen, high organic matter desulfurization wastewater dish tubular type film processing system and method | |
| CN112441601A (en) | System and method for extracting magnesium sulfate and sodium chloride from desulfurization wastewater | |
| CN207726913U (en) | A kind of device of desulfurization wastewater processing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 226000 Jiangsu mayor of Nantong Road No. 695 Patentee after: Jiangsu Hairong Water Co.,Ltd. Address before: 226000 Jiangsu mayor of Nantong Road No. 695 Patentee before: JIANGSU HAI RONG THERMAL ENERGY ENVIRONMENTAL ENGINEERING Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A Deep Gradual Salt Separation Process Granted publication date: 20191015 Pledgee: China Merchants Bank Limited by Share Ltd. Nantong branch Pledgor: Jiangsu Hairong Water Co.,Ltd. Registration number: Y2024980004711 |