CN109607582A - A kind of method and system recycling magnesium salts from desulfurization wastewater - Google Patents
A kind of method and system recycling magnesium salts from desulfurization wastewater Download PDFInfo
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- CN109607582A CN109607582A CN201811552927.0A CN201811552927A CN109607582A CN 109607582 A CN109607582 A CN 109607582A CN 201811552927 A CN201811552927 A CN 201811552927A CN 109607582 A CN109607582 A CN 109607582A
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- ion
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- desulfurization wastewater
- water body
- magnesium
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 46
- 230000023556 desulfurization Effects 0.000 title claims abstract description 45
- 159000000003 magnesium salts Chemical class 0.000 title claims abstract description 12
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 238000005352 clarification Methods 0.000 claims abstract description 15
- 230000008014 freezing Effects 0.000 claims abstract description 14
- 238000007710 freezing Methods 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 42
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 27
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 23
- 235000011152 sodium sulphate Nutrition 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000010812 mixed waste Substances 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 238000005057 refrigeration Methods 0.000 claims description 3
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 abstract description 12
- 239000010802 sludge Substances 0.000 description 16
- 238000005189 flocculation Methods 0.000 description 14
- 230000016615 flocculation Effects 0.000 description 14
- 239000013078 crystal Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000001223 reverse osmosis Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 208000028659 discharge Diseases 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 238000001728 nano-filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011552 falling film Substances 0.000 description 6
- 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 5
- 230000008901 benefit Effects 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- -1 carbanion Chemical compound 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229940096405 magnesium cation Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C01F5/40—Magnesium sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A method of recycling magnesium salts from desulfurization wastewater, it includes the following steps: step A, heavy metal processing is removed to desulfurization wastewater, step B removes Calcium treatment, step C for the clarification water body further progress of step A institute output, the clarification water body of step B institute output is concentrated, step D carries out freezing and crystallizing for the water body of institute's output after step C concentration, obtains sulfuric acid magnesium products.The method provided by the present invention that magnesium salts is recycled from desulfurization wastewater, technology is advanced, pretreatment is simple, overall craft route is greatly shortened than the prior art, and can effectively recycle the magnesium resource in waste water.The present invention also provides the systems for the above method.
Description
Technical field
The present invention relates to environmentally friendly technical field of resource recovery more particularly to a kind of methods that magnesium salts is recycled from desulfurization wastewater
And system.
Background technique
Desulfurization wastewater is primarily referred to as the discharge water on absorption tower in boiler smoke process of wet desulphurization, and wet desulphurization includes with stone
Calcium method desulfurization based on lime stone, quick lime and the magnesium processes desulfurization based on magnesia, relative to calcium method desulfurization, magnesium processes desulfurization
Have many advantages: the desulphurization reaction activity of Mg-base desulfurizing agent is high, dosage is only the 40% of lime stone, circulation slurry pump energy consumption
Low, tower body size reduces, and not only desulfuration efficiency is high, also reduces equipment investment and operating cost, and can avoid in desulphurization system
The problems such as fouling, blocking occurs.
Desulfurization wastewater has following water quality characteristics: pH value 4-6.5, weakly acidic, sub- comprising a large amount of suspended matters, supersaturation
Sulfate, sulfate and heavy metal；Suspension content it is high (gypsum, silica, aluminium and iron hydroxide), generally exist
Between 6000-15000mg/L；Salt content is high；Contain the anion such as a large amount of calcium, magnesium cation and chloride ion, sulfate radical, dissolubility
Solid amount (TDS) is between 25000-60000mg/L, and wherein chloride ion content is generally between 5000-20000mg/L, both
Easy fouling, and have strong corrosive.
At present desulfurization wastewater zero discharge treatment technology mainly there are several types of:
1, electroosmose process handles desulfurization wastewater；It can be found in desulfurization wastewater zero provided by Chinese patent 201611024049.6
Arrange processing method comprising: electric flocculation: desulfurization wastewater electric flocculation caused by producing removes partial organic substances, ss, and a huge sum of money
Belong to；Double alkali chemical tenderings: electric flocculation organic matter produced is entered into double alkali chemical settlings；Tubular membrane ultrafiltration: by sedimentation
Water body afterwards carries out readjustment pH using the acid of Bipolar Membrane output, is allowed to keep alkalescence；Nanofiltration membrane: using nanofiltration, by water
Divalent salts removal in body, which is realized, divides salt；ED concentration: the salt water of purifying is then concentrated into homogeneous ED, the dense salt after concentration and
Separation of cutting off the water supply is discharged；Prepare soda acid；Salt water after concentration prepares soda acid, the acid of preparation by BPED bipolar membrane electrodialysis system
Alkali is for alkali softenings double in step 2 and other production applications.Such methods defect is: electrocoagulation electrode is easily passivated, energy consumption
Height, consumption of electrode is fast, and operating cost is caused to increase；Desalination rate, the rate of recovery of ED concentration are lower；ED clean and maintenance is frequently complicated；
Power plant desulfurization wastewater monovalent salt content after nanofiltration is still very high, and ED energy consumption is big.
2, lime sodium carbonate pretreatment+weakly acidic cation exchanger+reverse osmosis+mixed salt crystallizing evaporator；It can be found in China
Desulfurization wastewater zero-discharge treatment system and technique provided by patent 201510529034.4 comprising: Step 1: in and adjusting
The medical fluid centainly measured is added in pond in section, so that the hydroxide that most heavy metal ion generate indissoluble in alkaline environment is heavy
It forms sediment；Step 2: most of heavy metal ion have been respectively formed difficulty after medicament is added in desulfurization wastewater when pH value reaches 9.0 to 9.5
Molten hydroxide, while the Ca2+ in water can also be reacted with the part F- in waste water, generated the CaF2 precipitating of indissoluble and reached
Go the effect of fluorine removal；Step 3: flocculation sedimentation, makes colloidal solid and suspended particulate that cohesion and aggregation occur, flocculant, which is added, to be made
Sufficiently, after precipitating the regular hour, the top of flocculation sedimentation tank is supernatant, and its underpart is dope for medical fluid reaction；Under Step 4:
After dope is by sludge condensation case and sheet frame sludge filter press, solid waste and waste water is discharged, waste water is imported to neutralize by pipeline and be adjusted
Pond is recycled and is handled again.Supernatant effectively removes the calcium ion in waste water by full-automatic softening filter, the purpose is to
Protect the reverse osmosis unit in subsequent processing；Demineralizer has the effect of filtering concurrently simultaneously；Step 5: ultrafilter in the process of running
Automatic backwash ensure that and not be contaminated；Step 6: crystal salt is made by I and II RO reverse osmosis and crystallizing evaporator in concentrated water,
The salinity in waste water is improved by reverse osmosis concentration, energy consumption is saved on evaporative crystallization；The purification generated through reverse osmosis concentration
Water reuse.The defect of this kind of technology is: no nanofiltration membrane carries out a point salt, is directly concentrated with RO, causes RO system pressure higher,
Concentrate evaporation gained crystal salt is impure.Evaporation gained solid sodium chloride purity is not high, can not transport outward or sell, also answer in field
With little, therefore it is worth not high；Pretreatment needs additional addition soda acid, consumes medicament.
3, lime sodium carbonate pretreatment+weakly acidic cation exchanger+nanofiltration divides salt+reverse osmosis+sodium chloride and sodium sulphate knot
Brilliant device；It can be found in power plant desulfurization wastewater technique of zero discharge method provided by Chinese patent 201610901996.2 comprising: step
Rapid one, power plant desulfurization wastewater initially enters raw water box, and homogeneous adjusting is carried out in raw water box, and waste water quality is made to keep relatively steady
It is fixed；Step 2: raw water box water outlet enters the first flocculation reaction slot, flocculant and high molecular polymer are added in the first flocculation tank
Flocculation sedimentation, the waste water after the flocculation of the first flocculation reaction slot enter the first precipitation tank, are formed in the waste water of the first precipitation tank
Floc sedimentation be down to slot bottom and form sludge, be sent into sludge holding tank, then send to sludge concentration tank, the sludge after concentration enters filter press
Dehydration, mud cake are sent to designated place landfill, and filtrate returns to sludge concentration tank；Step 3: the supernatant to the first precipitation tank enters
UF ultrafiltration system further removes jelly and macromolecule organic in waste water；Step 4: water outlet, which enters NF sodium, filters system,
Concentrated water enters the second flocculation reaction slot；Step 5: sodium filter system water outlet enters RO counter-infiltration system, it is anti-that concentrated water enters the second flocculation
Answer slot；Step 6: it is mainly NaOH, Na2CO3 and Polymer that chemical agent is added in the second flocculation reaction slot, dosage is
In 1-5ppm；Concentrated water after flocculation enters the second precipitation tank, and precipitation tank bottom sludge enters sludge concentration tank, and water outlet enters first and subtracts
Evaporator is pressed, evaporation output Na2SO4 send to the first centrifuge and is separated by solid-liquid separation, obtains Na2SO4 crystal, and filtrate portion returns
It is flow to evaporator, remaining enters drying machine, forms sludge cake, and the sludge cake of formation send to designated place and fills, and drying process produces
The raw steam containing pollutant enters scrubbing tower, and washing water returns to raw water box；It is used as back Step 7: RO counter-infiltration system produces water
With water reuse, concentrated water enters the second decompression evaporator, and evaporation is precipitated NaCl, send to the second centrifuge and be separated by solid-liquid separation, obtained
NaCl crystal, filtrate portion are back to evaporator, remaining enters drying machine, form sludge cake, landfill.The defect of patent 4 is as follows:
Flocculant and high molecular polymer are added in preprocessing process, if dosage control is bad, can be polluted subsequent ultrafiltration and be received
Filter system；Due to having added part chemical agent before evaporation, it is easy to cause evaporator heat exchanger fouling, influences the heat transfer of evaporator
Efficiency；Mud cake after evaporation needs to reprocess, and cannot achieve the utilization of resources；Pretreatment needs additional addition soda acid, consumes medicament.
Above-mentioned technology has been all made of ultrafiltration, nanofiltration or the membrane technologies feature such as reverse osmosis, because desulfurization wastewater hardness is high, water at
Divide complexity, preprocessing process purification process, which slightly fluctuates, will result in the risks such as film blocking or damage.In addition, above-mentioned technology for
Valuable substance extracts insufficient in desulfurization wastewater, and the economic benefit is not high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of from desulfurization wastewater recycles the method and system of magnesium salts, to subtract
Less or avoid the problem that being formerly mentioned.
In order to solve the above technical problems, the method that the invention proposes a kind of to recycle magnesium salts from desulfurization wastewater, described de-
Cationic main component in the raw water of sulphur waste water are as follows: magnesium ion, calcium ion, sodium ion and micro potassium ion and a measurement huge sum of money
Belong to ion, anion is mainly sulfate ion, chloride ion and micro inferior sulfate radical and nitrate ion.It includes following step
It is rapid:
Step A is removed heavy metal processing to desulfurization wastewater,
Step B removes Calcium treatment for the clarification water body further progress of step A institute output, first to the clear of step A institute output
Clear water body is added micro lye and adjusts pH value to 8-12, and sodium sulphate saturated solution is then added, and forms calcium sulfate precipitation.And it will
Magnesium chloride in water body is converted to magnesium sulfate.
The clarification water body of step B institute output is concentrated in step C,
Step D carries out freezing and crystallizing for the water body of institute's output after step C concentration, obtains sulfuric acid magnesium products.
Preferably, the main component of the desulfurization wastewater is in following parameter area, cation mole ratio: Mg:Na >=2:
1；Mg:Ca >=4:1, anion: SO4:Cl >=3:1.
Preferably, in stepb, the dosage of sodium sulphate can be 1:1 setting according to the molar ratio of sodium sulphate and calcium ion.
Preferably, in stepb, the dosage of sodium sulphate makes the concentration of sodium sulphate reach the 1~1.2 of calcium ion concentration
Times.
Preferably, in step C, specific concentration process be can be, first by the pH value tune of the clarification water body of step B institute output
Section is faintly acid, and water temperature is preheated to 40-60 DEG C later, is then de-gassed, is later adjusted to water PH value
6-9, then it is evaporated concentration.
Preferably, in step C, by the investment concentrated sulfuric acid or dilute sulfuric acid, by the pH value of the clarification water body of step B institute output
It is adjusted to 3-4.
Preferably, in step C, sodium hydroxide is launched by investment and is carried out pH value adjustment to 6-9.
Preferably, in step D, the process of freezing and crystallizing is freezed using vacuum flashing or is freezed using outer circulation cold
Freeze, after the water body of institute's output cools to 0-10 degree after by step C concentration, is transported to whizzer and is separated, obtain sulphur
Sour magnesium products.
Preferably, in step D, the mixing mother liquor for the sodium chloride containing higher concentration isolated for whizzer
Salt therein can be recycled by sodium chloride crystallizer, it can also be using flue gas bypass evaporation drying system to mixed waste liquor
Carry out desiccation.
The present invention also provides the systems for the above method comprising by pipeline be linked in sequence three header devices,
Adjust buffer pool, reaction tank, clarifying basin, vaporising device, freezing and crystallizing device, whizzer.
The method provided by the present invention that magnesium salts is recycled from desulfurization wastewater, technology is advanced, pretreatment is simple, overall
Process route is greatly shortened than the prior art, and can effectively recycle the magnesium resource in waste water.The present invention also provides for above-mentioned
The system of method.
Detailed description of the invention
The following drawings are only intended to schematically illustrate and explain the present invention, not delimit the scope of the invention.Wherein,
A kind of system that magnesium salts is recycled from desulfurization wastewater of a specific embodiment according to the present invention is shown in Fig. 1
Schematic illustration.
Specific embodiment
For a clearer understanding of the technical characteristics, objects and effects of the present invention, this hair of Detailed description of the invention is now compareed
Bright specific embodiment.Wherein, identical component uses identical label.
The present invention be directed to the high desulfurization wastewater of content of magnesium, provide that a kind of technology is advanced, pretreatment is simple, overall
The technology and methods of the wastewater zero discharge for the recycling magnesium resource that process route shortens.
A kind of method recycling magnesium salts from desulfurization wastewater provided by the present invention comprising following steps:
Step A is removed heavy metal processing to desulfurization wastewater, and the processing step technology is more mature, for example, can be used
Common three headers pretreating process, for details, reference can be made in Chinese patent patent CN108249646A to three header preprocessing process
Detailed description, details are not described herein.
Step B removes Calcium treatment for the clarification water body further progress of step A institute output, specifically, first to step A
The clarification water body of institute's output is added micro lye and adjusts pH value to 8-12, compares calcium sulfate using the solubility due to calcium carbonate
It is small, so the principle of precipitation of calcium carbonate is firstly generated when sodium ion, calcium ion, carbanion, sulfate ion coexist,
Basicity and calcium ion in water body are removed, sodium sulphate method deliming is then utilized, that is, sodium sulphate saturated solution is added, forms sulfuric acid
Calcium precipitate.In addition, also the magnesium chloride in water body can be converted to magnesium sulfate.
Softening agent used in this step is sodium sulphate.Sodium sulphate is decided by the clear of step A institute output using molar ratio
Calcium ion concentration and basicity in clear water body, it is generally the case that dosage can be set according to the molar ratio of sodium sulphate and calcium ion for 1:1
It is fixed；Certainly, can also be according to the magnesium ion concentration of the clarification water body of step A institute output the case where, the appropriate dosing for increasing sodium sulphate
Amount, such as: when magnesium ion concentration is higher, the dosage of sodium sulphate can be increased, the concentration of sodium sulphate is made to reach the 1 of calcium ion concentration
~1.2 times.
The clarification water body of step B institute output is concentrated in step C, and specific concentration process can be, first by step B
The pH value adjustment of the clarification water body of institute's output is faintly acid (such as can use the concentrated sulfuric acid or dilute sulfuric acid, pH value is adjusted to 3-4), it
Water temperature is preheated to 40-60 DEG C afterwards, is then de-gassed (using degasser), will may be dissolved in water body two
The soluble gas such as carbonoxide, oxygen carry out stripping, and water PH value is adjusted to 6-9 later (can be carried out by launching sodium hydroxide
Adjust), then be evaporated concentration and (crystal seed method vertical falling-film evaporator can be used and be evaporated concentration, such as Nan Huan water utilities producer
JM-20T falling film evaporator, or such as Chinese patent 201580035331.1,201711155395.2 steamings recorded in the literature
Device is sent out, and seed concentration can be controlled in 2%--6%, such benefit is it is possible to prevente effectively from the fouling and holding of evaporator are steamed
Hair process is stablized).
Step D carries out freezing and crystallizing for the water body of institute's output after step C concentration, obtains sulfuric acid magnesium products, freezing and crystallizing
Process can be used vacuum flashing freezing, or use outer circulation refrigeration cold.The water body of institute's output drops after by step C concentration
Temperature is transported to whizzer and is separated to after 0-10 degree, obtain sulfuric acid magnesium products, and isolate containing higher concentration
The mixing mother liquor of sodium chloride can recycle salt therein by sodium chloride crystallizer, can also be dry using flue gas bypass evaporation
Drying system carries out desiccation to mixed waste liquor, finally realizes zero-emission.
Technique of the invention has the advantage that pretreatment is very simple, and minute quantity medicament is added, and pretreatment expense is low；
After pretreatment, the water quality system generated after some column physical-chemical reactions is improved, and water-quality constituents is mainly chlorine
Change sodium and magnesium sulfate, calcium sulfate system, it is subsequent that higher degree magnesium sulfate Product recycling is realized using process for freezing and crystallizing and equipment,
Realize that valuable byproduct recycles.Final concentrated mother liquor, which can continue recycling crystal salt sodium chloride, can also be used maturation
Flue gas spray drying technology desiccation is realized to solid therein, it is final to realize the discharge of zero liquid.
Technical solution of the present invention is mainly used for handling the desulfurization wastewater of High Contents of Magnesium low content sodium, High Contents of Magnesium
The desulfurization wastewater of low content sodium refers to: cationic main component in desulfurization wastewater raw water are as follows: magnesium ion, calcium ion, sodium ion with
And micro potassium ion and measure heavy metal ion, anion be mainly sulfate ion, chloride ion and micro inferior sulfate radical and
Nitrate ion.
When desulfurization wastewater is in following parameter area, cation mole ratio: Mg:Na >=2:1；Mg:Ca >=4:1, yin from
Son: SO4:Cl >=3:1；The efficiency-cost ratio of technical solution of the present invention is best.
A kind of system that magnesium salts is recycled from desulfurization wastewater of a specific embodiment according to the present invention is shown in Fig. 1
Schematic illustration, shown in Figure 1, the present invention also provides a kind of systems for the above method comprising passes through pipeline
Be linked in sequence three header devices 1, adjust buffer pool 2, reaction tank 3, clarifying basin 4, vaporising device 5, freezing and crystallizing device 6, from
Centrifugal separator 7.
Desulfurization wastewater initially enters three header device 1 and is pre-processed, from the water outlet of three header device 1
Clear liquid flows into 2 buffer-precipitation of adjusting buffer pool and is added in the reaction tank 3 micro subsequently into the reaction tank 3
Lye adjusts pH value to 8-12, then adds sodium sulphate saturated solution, the magnesium chloride in water body can be converted to sulfuric acid in this way
Magnesium enters the clarifying basin 4 later with coagulation liquid status, and sludge discharging port (not regarding out in figure) is arranged in 4 bottom of clarifying basin, this
Sample outlet sludge (can not regard out) periodically to sludge concentration tank in figure, (can not be regarded in figure by plate and frame filter press after sludge condensation
Filters pressing is processed into mud cake out), and mud cake is periodically transported outward or utilized.
The supernatant of the clarifying basin 4 enters the vaporising device 5 and is evaporated concentration, and the vaporising device 5 includes logical
Inlet tank 51, preheater 52, degasser 53 and the crystal seed method vertical falling-film crystallizing evaporator 54 of pipeline sequential connection are crossed, it is described clear
The supernatant in clear pond 4 enters the inlet tank 51 by pipeline, passes through the investment concentrated sulfuric acid or dilute sulfuric acid in the inlet tank 51
PH value is adjusted to faintly acid (3-4), the preheater 52 (such as plate type preheater) is then entered by elevator pump and is preheated,
Temperature is promoted to 40-60 DEG C, the waste water after preheating enters the degasser 53, the dioxy that will may be dissolved in raw water herein
Change carbon, the soluble gas such as oxygen carry out stripping, enter finally into be evaporated in crystal seed method vertical falling-film crystallizing evaporator 54 it is dense
Contracting.The preheater 52 can be connect by pipeline with the outlet of the crystal seed method vertical falling-film crystallizing evaporator 54, can be returned in this way
Receive the heat from the concentration water body of the outlet of the crystal seed method vertical falling-film crystallizing evaporator 54.
From the concentration water body of 5 output of vaporising device by pipeline enter the freezing and crystallizing device 6 cool down it is cold
But, the freezing and crystallizing device 6 can be using vacuum flashing principle device (such as HPD producer vacuum flashing crystallization set
The equipment of technical solution standby or using the record of such as Chinese patent 201710311611.1,201020218243.X document),
It is also possible to the device using outer circulation refrigeration principle (such as such as Chinese patent 201680069762.4,201720900359.3
The equipment for the technical solution that equal documents are recorded), after the temperature of concentration water body is reduced to 0-10 DEG C, magnesium sulfate crystals, that is, crystallizable
It is precipitated, solidliquid mixture is then delivered to by the whizzer 7 by pipeline and is separated by solid-liquid separation, can be obtained magnesium sulfate
Product.
The whizzer 7 can further be connected with a mother liquor tank 71, in this way can the centralized collection storage centrifugation
Separator 7 be separated by solid-liquid separation after the completion of remaining mother liquor, due in mother liquor containing the sodium chloride of higher concentration, the mother liquor
Tank 71 can further be connected with a sodium chloride crystallizer and (not regard out in figure, for example, by using such as Chinese patent
201410234006.5, the equipment for the technical solution that the documents such as 201520508913.4 are recorded) sodium chloride is extracted back
It receives, certainly, the mother liquor tank 71 directly can also bypass evaporation drying system (such as Xi'an thermal technology by piping connection to flue gas
The series of products of research institute's research and development) carry out desiccation, finally realize that zero liquid is discharged to desulfurization wastewater, the lime-ash of generation can and powder
It is handled together after coal ash mixing, to realize the zero-emission of desulfurization wastewater.
The present invention provides that a kind of technology is advanced, pretreatment is simple, overall work for the high desulfurization wastewater of content of magnesium
The technology of the wastewater zero discharge for the recycling magnesium resource that skill route shortens.Technical solution of the present invention avoid using ultrafiltration, nanofiltration or
Reverse osmosis equal membrane technologies, so that also just there is no risks such as film blocking or damage in the prior art documented by background technique.This
Outside, the magnesium sulfate salt of higher degree can be recycled in the present invention, and magnesium sulfate is as one of industrial foundation raw material, and market value is very
Height, therefore greatly improve resource reclaim benefit.
It will be appreciated by those skilled in the art that although the present invention is described in the way of multiple embodiments,
It is that not each embodiment only contains an independent technical solution.So narration is used for the purpose of for the sake of understanding in specification,
The skilled in the art should refer to the specification as a whole is understood, and by technical solution involved in each embodiment
Regard as and can be combined with each other into the modes of different embodiments to understand protection scope of the present invention.
The foregoing is merely the schematical specific embodiment of the present invention, the range being not intended to limit the invention.It is any
Those skilled in the art, made equivalent variations, modification and combination under the premise of not departing from design and the principle of the present invention,
It should belong to the scope of protection of the invention.
Claims (10)
1. a kind of method for recycling magnesium salts from desulfurization wastewater, cationic main component in the raw water of the desulfurization wastewater are as follows: magnesium
Ion, calcium ion, sodium ion and micro potassium ion and measurement heavy metal ion, anion is mainly sulfate ion, chlorine
Ion and micro inferior sulfate radical and nitrate ion.It is characterized in that, it includes the following steps:
Step A is removed heavy metal processing to desulfurization wastewater,
Step B removes Calcium treatment for the clarification water body further progress of step A institute output, first to the primary water of step A institute output
Body is added micro lye and adjusts pH value to 8-12, and sodium sulphate saturated solution is then added, and forms calcium sulfate precipitation.And by water body
In magnesium chloride be converted to magnesium sulfate.
The clarification water body of step B institute output is concentrated in step C,
Step D carries out freezing and crystallizing for the water body of institute's output after step C concentration, obtains sulfuric acid magnesium products.
2. the method as described in claim 1, which is characterized in that the main component of the desulfurization wastewater in following parameter area,
Cation mole ratio: Mg:Na >=2:1；Mg:Ca >=4:1, anion: SO4:Cl >=3:1.
3. the method as described in claim 1, which is characterized in that in stepb, the dosage of sodium sulphate can according to sodium sulphate with
The molar ratio of calcium ion is 1:1 setting.
4. the method as described in claim 1, which is characterized in that in stepb, the dosage of sodium sulphate makes the concentration of sodium sulphate
Reach 1~1.2 times of calcium ion concentration.
5. the method as described in claim 1, which is characterized in that in step C, specific concentration process be can be, first by step B
The pH value adjustment of the clarification water body of institute's output is faintly acid, and water temperature is preheated to 40-60 DEG C later, is then de-gassed place
Reason, is adjusted to 6-9 for water PH value later, then be evaporated concentration.
6. method as claimed in claim 5, which is characterized in that in step C, by the investment concentrated sulfuric acid or dilute sulfuric acid, will walk
The pH value of the clarification water body of rapid B institute output is adjusted to 3-4.
7. method as claimed in claim 5, which is characterized in that in step C, launch sodium hydroxide by investment and carry out PH
Value is adjusted to 6-9.
8. the method as described in claim 1, which is characterized in that in step D, the process of freezing and crystallizing is cold using vacuum flashing
Freeze or use outer circulation refrigeration cold, after the water body of institute's output cools to 0-10 degree after by step C concentration, is transported to centrifugation
Separator is separated, and sulfuric acid magnesium products are obtained.
9. method according to claim 8, which is characterized in that in step D, for whizzer isolate containing compared with
The mixing mother liquor of the sodium chloride of high concentration can recycle salt therein by sodium chloride crystallizer, can also be using by flue gas
Road evaporation drying system carries out desiccation to mixed waste liquor.
10. a kind of system for method described in one of claim 1-9, which is characterized in that it includes by pipeline sequence
Three header devices 1 of connection adjust buffer pool 2, reaction tank 3, clarifying basin 4, vaporising device 5, freezing and crystallizing device 6, centrifugation point
From device 7.
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