CN105923835B - A method of vanadium industrial wastewater is handled using magnesium processes desulfuration waste - Google Patents
A method of vanadium industrial wastewater is handled using magnesium processes desulfuration waste Download PDFInfo
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- CN105923835B CN105923835B CN201610438154.8A CN201610438154A CN105923835B CN 105923835 B CN105923835 B CN 105923835B CN 201610438154 A CN201610438154 A CN 201610438154A CN 105923835 B CN105923835 B CN 105923835B
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- industrial wastewater
- vanadium
- magnesium
- waste
- desulfuration
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- 238000000034 method Methods 0.000 title claims abstract description 75
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 58
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 39
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 38
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011777 magnesium Substances 0.000 title claims abstract description 36
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 36
- 239000002351 wastewater Substances 0.000 claims abstract description 36
- 239000011651 chromium Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000013049 sediment Substances 0.000 claims abstract description 6
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 230000023556 desulfurization Effects 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 7
- 239000003344 environmental pollutant Substances 0.000 claims description 7
- 231100000719 pollutant Toxicity 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- -1 magnesium salts magnesium chloride Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to waste water and fixed-end forces technical field, and in particular to a method of vanadium industrial wastewater is handled using magnesium processes desulfuration waste.The present invention is that magnesium processes desulfuration waste is added into vanadium industrial wastewater and is stirred, it is adjusted with acid pH=1.0-3.0, control oxidation-reduction potential >=270mv, react 10-30min, the vanadium of high-valence state and chromium are reduced to lower valency in reaction process, ease of solubility magnesium salts is added into the waste water after reduction and continues to stir, after ease of solubility magnesium salts all dissolution, it persistently stirs and appropriate phosphorus source is added, pH=9.0-10.0 is adjusted with alkali, reaction time 10-30min, make the vanadium in waste water, chromium and ammonia nitrogen co-precipitation, stand 0.5-3.0h, obtained sediment is through filter-press dehydration, obtained filtrate and supernatant are as water outlet.This process effect is good, and process is short, and processing speed is fast, low in cost, can be applied with existing equipment, without increasing capital cost.
Description
Technical field
The invention belongs to waste water and fixed-end forces technical field, and in particular to a kind of to handle vanadium using magnesium processes desulfuration waste
The method of industrial wastewater.
Background technique
Vanadium has the title of metal " vitamin ", is widely used in the industries such as metallurgy, chemical industry, is used as alloy addition and organic chemical industry
Catalyst etc..Currently, the production technology of its major product vanadic anhydride is mostly sodium roasting technique, the technique main flow
Are as follows: vanadium slag is crushed-sodium roasting-water logging vanadium extraction-purification of leaching liquor-acid ammonium salt vanadium-fusing and decomposes, and finally obtains five oxygen of sheet
Change two vanadium.The technique generates a large amount of high pollution acid waste waters, and feature is that salinity is high, discharge amount is big, content of beary metal is higher, right
Environmental hazard is very big, according to " GB 26452-2011 vanadium emission of industrial pollutants standard " require, the total Chromium in Waste, Cr VI,
Total vanadium and ammonia nitrogen severely exceed (CTCr=3500-4500mg/L, CCr 6+=3300-3800mg/L, CV 5+=50-200mg/L, CNH3-N=
2800-4000mg/L).Currently, the common processing method of such waste water have evaporation concentration method crystallisation, reduction neutralization precipitation method,
The electroreduction precipitation method, ion-exchange, adsorption treatment method and liquid membrane separating method etc..Though these methods have certain effect,
In the prevalence of processing cost is high, treatment effeciency is low, be also easy to produce secondary pollution and cannot complete qualified discharge the problems such as.It answers at present
It is reduction neutralization precipitation method with wider method, this method is usually using a large amount of ferrous salts or sulphite as reducing agent, the party
Law technology is mature, and treating capacity is big, and effect is preferable, but dosage is larger, higher cost.
Magnesium method flue gas desulphurization technique be after magnesia to be added to water the curing through a period of time so that certain density hydrogen be made
Magnesia absorbs slurries, which, with smoke contacts and absorbing and removing sulfur dioxide therein, is mainly characterized by absorption tower
Desulfuration efficiency is high, and capital cost is low, non-scaling, without secondary pollution.There are two types of its final common processing modes of desulfurization product: one
Kind is that the slurries pressure oxidation direct emission that will absorb saturation or crystallization prepare magnesium sulfate, and this method need to increase oxidation furnaces, increase
Add capital cost, and the magnesium sulfate prepared is poor quality；Another method is heat resolve after being dehydrated desulfurization product, can be again
Magnesia and sulfur dioxide are obtained, the former can be recycled as desulfurizing agent, and the latter can produce sulphur or sulfuric acid, this method operation
Complexity, and desulfurization stage need to add oxygen scavenger to reduce desulfurization product pyrolysis temperature, invest larger.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of using magnesium processes desulfuration waste processing vanadium industrial wastewater
Method, it is therefore an objective to by combining waste water treatment and smoke gas treatment, realization markets one's own products, the treatment of wastes with processes of wastes against one another, to generate bright
Aobvious economic benefit, social benefit and environmental benefit.
Realize that the technical solution of the object of the invention follows the steps below:
(1) vanadium industrial wastewater is introduced into reduction reaction pond, magnesium processes desulfuration waste is added into vanadium industrial wastewater and carried out
Stirring, is adjusted with acid pH=1.0-3.0, controls oxidation-reduction potential (ORP) >=270mv, reacts 10-30min, in reaction process
The vanadium of high-valence state and chromium are reduced to lower valency；
(2) waste water after reduction is introduced into sedimentation basin, ease of solubility magnesium salts is added into the waste water after reduction and continues to stir,
After ease of solubility magnesium salts all dissolution, phosphorus source is persistently stirred and be added, adjusts pH=9.0-10.0, reaction time 10- with alkali
30min makes vanadium, chromium and ammonia nitrogen co-precipitation in waste water, stands 0.5-3.0h, and obtained sediment is obtained through filter-press dehydration
Filtrate and supernatant as water outlet, the C of water outletTCr< 0.4mg/L, CCr 6+< 0.08mg/L, CV 5+< 0.07mg/L, CNH3-N
< 150mg/L, CTP< 15mg/L.
Wherein, the vanadium industrial wastewater is V2O5And its esters produces waste water, water 500-900t/d, pH=1-3 are
Highly acid, 50-100 DEG C of leaving water temperature, major pollutants index therein: CTCr=3500-4500mg/L；CCr 6+=3300-
3800mg/L；CV 5+=50-200mg/L, CNH3-N=2800-4000mg/L。
The magnesium processes desulfuration waste is the desulfuration waste of wet-type magnesia, and additional amount is in vanadium industrial wastewater
Cr6+And V5+5-10 times of gross mass.
The acid of the tune pH is one or more of sulfuric acid, hydrochloric acid, nitric acid.
The ease of solubility magnesium salts is one or more of magnesium chloride, magnesium sulfate, magnesia, and additional amount is after restoring
0.5-1.5 times of the ammonia nitrogen mole of waste water.
The phosphorus source is one or more of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, is added
Amount is 0.5-1.5 times of the ammonia nitrogen mole of waste water after restoring.
The alkali of the tune pH is sodium hydroxide.
The water outlet is mixed with sanitary sewage carries out subsequent processing.
Compared with prior art, the features of the present invention and beneficial effect are:
The technical scheme is that by vanadium industrial wastewater major pollutants vanadium, total chromium, Cr VI, ammonia nitrogen and phosphorus it is same
Step removal, enormously simplifies existing vanadium Industrial Wastewater Treatment process and processing time, treated waste water clear, wherein
Vanadium, total chromium, Cr VI are up to state standards GB 26452-2011, and ammonia nitrogen and phosphorus significantly reduce, the C of water outletNH3-N< 150mg/
L、CTP< 15mg/L, can be with sanitary sewage mixed processing.
The present invention realizes the resource utilization of sweetening solid waste, both reduces cost for wastewater treatment, also solves
The pollution and land occupation problem of magnesium processes desulfuration waste, being even more for smelting iron and steel enterprise can be by waste water treatment and smoke gas treatment phase
In conjunction with realization is marketed one's own products, the treatment of wastes with processes of wastes against one another, environmental benefit, economic benefit and social benefit with higher.
Compared with the prior art, this process effect is good, and process is short, and processing speed is fast, low in cost, with existing equipment
It can apply, without increasing capital cost.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the magnesium processes desulfuration waste XRD spectra used in the embodiment of the present invention.
Specific embodiment
Methods and techniques of the present invention are illustrated below by example, it is without being limited thereto in practical application.
The magnesium processes desulfuration waste XRD spectra used in the embodiment of the present invention is as shown in Fig. 2, be the desulfurization of wet-type magnesia
Waste, essential element component list are as shown in table 1.
Embodiment 1
The method using magnesium processes desulfuration waste processing vanadium industrial wastewater of the present embodiment, as shown in Figure 1, according to following step
It is rapid to carry out:
(1) the vanadium industrial wastewater of Hebei factory is introduced into reduction reaction pond, it is useless that magnesium processes desulfurization is added into vanadium industrial wastewater
Gurry is simultaneously stirred, and magnesium processes desulfuration waste additional amount is Cr in vanadium industrial wastewater6+And V5+10 times of gross mass, use sulfuric acid
PH=3.0 are adjusted, ORP300mv is controlled, react 30min, the vanadium of high-valence state and chromium are reduced to lower valency in reaction process；
(2) by after reduction waste water introduce sedimentation basin, into the waste water after reduction be added ease of solubility magnesium salts magnesium chloride and after
Continuous stirring, 0.5-1.5 times of the ammonia nitrogen mole of waste water after the reduction of magnesium chloride, magnesium to be chlorinated all after dissolution, persistently stir
And tertiary sodium phosphate is added, tertiary sodium phosphate additional amount is 0.5 times of the ammonia nitrogen mole of waste water after restoring, adjusts pH with sodium hydroxide
=9.0, reaction time 30min make vanadium, chromium and ammonia nitrogen co-precipitation in waste water, stand 0.5h, obtained sediment is through filters pressing
Dehydration, obtained filtrate and supernatant are used as water outlet, C in water outletTCr =0.31mg/L、CCr 6+=0.071mg/L、CV 5+=
0.065mg/L、CNH3-N=120.40mg/L、CTP=9.5mg/L, can be with sanitary sewage mixed processing.
Wherein, the vanadium industrial wastewater is V2O5Waste water is produced, factory's water is 800t/d, and pH=1-3 is highly acid,
50-100 DEG C of leaving water temperature, major pollutants index therein: CTCr=4500mg/L；CCr 6+=3350mg/L；CV 5+=174mg/
L, CNH3-N=3051mg/L。
Embodiment 2
The method using magnesium processes desulfuration waste processing vanadium industrial wastewater of the present embodiment, as shown in Figure 1, according to following step
It is rapid to carry out:
(1) the vanadium industrial wastewater of Heilungkiang factory is introduced into reduction reaction pond, magnesium processes desulfurization is added into vanadium industrial wastewater
Waste is simultaneously stirred, and magnesium processes desulfuration waste additional amount is Cr in vanadium industrial wastewater6+And V5+8 times of gross mass, use hydrochloric acid
PH=2.5 are adjusted, ORP270mv is controlled, react 10min, the vanadium of high-valence state and chromium are reduced to lower valency in reaction process；
(2) waste water after reduction is introduced into sedimentation basin, magnesium sulfate is added into the waste water after reduction and continues to stir, to sulphur
Sour magnesium all after dissolution, persistently stirs and is added phosphoric acid, and phosphoric acid additional amount is 1.5 times of the ammonia nitrogen mole of waste water after restoring,
PH=9.5 are adjusted with sodium hydroxide, reaction time 10min makes vanadium, chromium and the ammonia nitrogen co-precipitation in waste water, stands 2h, obtains
The filtrate that is obtained through filter-press dehydration of sediment and supernatant as water outlet, C in water outletTCr =0.27mg/L、CCr 6+=
0.039mg/L、CV 5+=0.042mg/L、CNH3-N=130.21mg/L、CTP=7.5mg/L, can be with sanitary sewage mixed processing.
The vanadium industrial wastewater is that vanadic salts class produces waste water, and water 900t/d, pH=1-3 are highly acid, out water temperature
50-100 DEG C of degree, major pollutants index therein: CTCr=4432mg/L；CCr 6+=3309mg/L；CV 5+=168mg/L, CNH3-N=
3950mg/L。
Embodiment 3
The method using magnesium processes desulfuration waste processing vanadium industrial wastewater of the present embodiment, as shown in Figure 1, according to following step
It is rapid to carry out:
(1) the vanadium industrial wastewater of Heilungkiang factory is introduced into reduction reaction pond, magnesium processes desulfurization is added into vanadium industrial wastewater
Waste is simultaneously stirred, and magnesium processes desulfuration waste additional amount is Cr in vanadium industrial wastewater6+And V5+5 times of gross mass, use nitric acid
PH=1.0 are adjusted, ORP350mv is controlled, react 20min, the vanadium of high-valence state and chromium are reduced to lower valency in reaction process；
(2) waste water after reduction is introduced into sedimentation basin, magnesia is added into the waste water after reduction and continues to stir, aoxidized
Magnesium additional amount is 1 times of the ammonia nitrogen mole of waste water after restoring, and magnesium to be oxidized all after dissolution, persistently stirs and phosphoric acid hydrogen is added
Disodium, disodium hydrogen phosphate additional amount are 1 times of the ammonia nitrogen mole of waste water after restoring, adjust pH=10.0, reaction time with alkali
20min, makes vanadium, chromium and ammonia nitrogen co-precipitation in waste water, stands 3.0h, and obtained sediment is through filter-press dehydration, obtained filter
Liquid and supernatant are used as water outlet, C in water outletTCr =0.22mg/L、CCr 6+=0.035mg/L、CV 5+=0.040mg/L、CNH3-N=
141.56mg/L、CTP=6.9mg/L, can be with sanitary sewage mixed processing.
The vanadium industrial wastewater is that vanadic salts class produces waste water, and water 900t/d, pH=1-3 are highly acid, out water temperature
50-100 DEG C of degree, major pollutants index therein: CTCr=4432mg/L；CCr 6+=3309mg/L；CV 5+=168mg/L, CNH3-N=
3950mg/L。
The above, the only present invention preferably specific implementation case, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of method using magnesium processes desulfuration waste processing vanadium industrial wastewater, it is characterised in that follow the steps below:
(1) vanadium industrial wastewater is introduced into reduction reaction pond, magnesium processes desulfuration waste is added into vanadium industrial wastewater and is stirred,
It is adjusted with acid pH=1.0-3.0, controls oxidation-reduction potential >=270mv, react 10-30min, by high-valence state in reaction process
Vanadium and chromium are reduced to lower valency, in which: the vanadium industrial wastewater is V2O5And its esters produces waste water, water 500-900t/
D, pH=1-3 be highly acid, 50-100 DEG C of leaving water temperature, major pollutants index therein: CTCr=3500-4500mg/L；
CCr 6+=3300-3800mg/L；CV 5+=50-200mg/L, CNH3-N=2800-4000mg/L, the magnesium processes desulfuration waste are magnesium
Method flue gas desulfurization waste；
(2) waste water after reduction is introduced into sedimentation basin, ease of solubility magnesium salts is added into the waste water after reduction and continues to stir, to easy
Soluble magnesium salt all after dissolution, persistently stirs and is added phosphorus source, adjusts pH=9.0-10.0 with alkali, reaction time 10-30min makes
Vanadium, chromium and ammonia nitrogen co-precipitation in waste water stand 0.5-3.0h, obtained sediment through filter-press dehydration, obtained filtrate and
Supernatant is as water outlet, the C of water outletTCr< 0.4mg/L, CCr 6+< 0.08mg/L, CV 5+< 0.07mg/L, CNH3-N< 150mg/
L、CTP< 15mg/L.
2. a kind of method using magnesium processes desulfuration waste processing vanadium industrial wastewater according to claim 1, it is characterised in that
The magnesium processes desulfuration waste is the desulfuration waste of wet-type magnesia, and additional amount is Cr in vanadium industrial wastewater6+And V5+Always
5-10 times of quality.
3. a kind of method using magnesium processes desulfuration waste processing vanadium industrial wastewater according to claim 1, it is characterised in that
The acid of the tune pH is one or more of sulfuric acid, hydrochloric acid, nitric acid.
4. a kind of method using magnesium processes desulfuration waste processing vanadium industrial wastewater according to claim 1, it is characterised in that
The ease of solubility magnesium salts is one or more of magnesium chloride, magnesium sulfate, magnesia, and additional amount is the ammonia of waste water after reduction
0.5-1.5 times of nitrogen mole.
5. a kind of method using magnesium processes desulfuration waste processing vanadium industrial wastewater according to claim 1, it is characterised in that
The phosphorus source is one or more of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, and additional amount is reduction
0.5-1.5 times of the ammonia nitrogen mole of waste water afterwards.
6. a kind of method using magnesium processes desulfuration waste processing vanadium industrial wastewater according to claim 1, it is characterised in that
The alkali of the tune pH is sodium hydroxide.
7. a kind of method using magnesium processes desulfuration waste processing vanadium industrial wastewater according to claim 1, it is characterised in that
The water outlet is mixed with sanitary sewage carries out subsequent processing.
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