CN102476880A - Treatment method of vanadium precipitation wastewater - Google Patents
Treatment method of vanadium precipitation wastewater Download PDFInfo
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- CN102476880A CN102476880A CN201010574183XA CN201010574183A CN102476880A CN 102476880 A CN102476880 A CN 102476880A CN 201010574183X A CN201010574183X A CN 201010574183XA CN 201010574183 A CN201010574183 A CN 201010574183A CN 102476880 A CN102476880 A CN 102476880A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 159
- 238000000034 method Methods 0.000 title claims abstract description 79
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 51
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000001556 precipitation Methods 0.000 title abstract description 4
- 239000012528 membrane Substances 0.000 claims abstract description 64
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 40
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 40
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 30
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 24
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 24
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000009615 deamination Effects 0.000 claims description 30
- 238000006481 deamination reaction Methods 0.000 claims description 30
- 230000002829 reductive effect Effects 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 235000019600 saltiness Nutrition 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229910001430 chromium ion Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000001223 reverse osmosis Methods 0.000 abstract description 16
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 5
- -1 ammonium ions Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000013043 chemical agent Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 125000002091 cationic group Chemical group 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 241000894006 Bacteria Species 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
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- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The treatment method of the vanadium precipitation wastewater, wherein the vanadium precipitation wastewater contains sodium sulfate and ammonium sulfate, and the method comprises the following steps: (1) converting ammonium ions in the wastewater into ammonia, and removing ammonia through an ammonia nitrogen separation membrane; (2) performing membrane electrolysis on the deaminated wastewater, and performing reverse osmosis; or directly carrying out reverse osmosis on the deaminated wastewater. The method for treating wastewater by combining different membrane treatment methods has the advantages of simple process route, no secondary pollution, no need of additional chemical agents and full resource utilization. In particular, the problem of separate separation of different substances in the wastewater is solved, purer ammonium sulfate products and sodium sulfate products are recovered, the wastewater with lower salt content can be obtained, and acid, alkali, hydrogen and oxygen can be recovered.
Description
Technical field
The present invention relates to a kind of treatment process of vanadium wastewater.
Background technology
Traditional vanadium oxide production technique generally includes the vanadium slag sodium roasting, and alkalescence leaches, steps such as acid ammonium salt precipitation.Specifically; General earlier with vanadium slag and sodium salt additive mixing briquetting roasting (additive commonly used can be one or more the mixture in salt, sodium sulfate and the yellow soda ash); The water logging product of roasting, the product of roasting infusion that obtains through concentrate, filtration, ammonium salt transform, separate out ammonium poly-vanadate after adding Acid precipitation, and filter; Filter cake promptly gets powdery Vanadium Pentoxide in FLAKES product through dry, deamination, or the filter cake direct fusion is obtained the piece of Vanadium product.
In the production process of five oxygen, two vanadium, will inevitably produce and contain vanadium (like (NH
4)
2V
6O
16, NaVO
3), chromium (Na
2Cr
2O
7), the vanadium wastewater of pollutent such as ammonia nitrogen.In the prior art, the treatment process of said vanadium wastewater comprises that elder generation places equalizing tank to regulate waste water, reduces then---neutralization, and with vanadium in the waste water and chromium (Cr (OH)
3, VO (OH)
2) carrying out sedimentation, the waste water after the neutralization is sent clear liquor into surge tank through after concentrating, clarifying; To pass through clarifying waste water then and send into the evaporation concentration processing unit; Be about to the waste water heating, from waste water, overflow after making water vapor wherein, and then with water vapor condensation.Through this process, the water in the waste water is steamed, and concentrates the solid mixture that obtains containing sodium sulfate and ammonium sulfate.Adopt the treatment process of the vanadium wastewater of prior art respectively sodium sulfate and ammonium sulfate to be separated separately, and it is bigger to carry out the environmental protection pressure of last handling process at the solid mixture to sodium sulfate and ammonium sulfate.
Summary of the invention
The invention provides a kind of treatment process of new vanadium wastewater; Adopt the method for the processing vanadium wastewater that the different membrane technologies of utilization of the present invention combine; Can the sodium sulfate in the waste water be separated separately with ammonium sulfate; Reclaim more purified ammonium sulfate product and sodium sulfate product, solved the handling problem of supersalinity waste water simultaneously.
The invention provides a kind of treatment process of vanadium wastewater, said vanadium wastewater contains sodium sulfate, ammonium sulfate and heavy metal compound, and wherein, this method comprises the steps:
(1) ammonium ion in the waste water is converted into ammonia,, carries out deamination through the ammonia nitrogen separatory membrane;
(2) waste water behind the deamination is carried out the film electrolysis, and carry out r-o-; Perhaps directly the waste water behind the deamination is carried out r-o-.
Method of the present invention proposes is a kind ofly to utilize different embrane methods to combine to handle the novel process of vanadium wastewater; At first utilize the ammonia nitrogen separatory membrane; Remove the ammonia in the waste water, and then carry out electrolysis with ion-exchange film and reverse osmosis membrane or directly handle through reverse osmosis membrane after obtain reuse water.The operational path of the processing method for waste water that the different membrane processing method of employing provided by the invention combines is simple, and has non-secondary pollution, need not add the advantage of chemical agent, full resource utilization.Particularly, solved the independent separation problem of different substances in the waste water, reclaimed more purified ammonium sulfate product and sodium sulfate product, simultaneously can obtain the lower waste water of saltiness, and can recovered acid, alkali, hydrogen and oxygen.Wherein, sodium hydroxide that obtains and sulfuric acid are recycled, the handling problem that has solved bronsted lowry acids and bases bronsted lowry in the ammonia nitrogen separation system, and in addition, hydrogen that produces in the electrolytic process and oxygen can produce certain economic benefits, create higher value.
Description of drawings
Fig. 1 is the schema of the treatment process of vanadium wastewater provided by the invention;
Fig. 2 is the schema of the treatment process of vanadium wastewater provided by the invention.
Embodiment
According to the treatment process of vanadium wastewater provided by the invention, said vanadium wastewater contains sodium sulfate, ammonium sulfate and heavy metal, and wherein, this method comprises the steps:
(1) ammonium ion in the waste water is converted into ammonia,, carries out deamination through the ammonia nitrogen separatory membrane;
(2) waste water behind the deamination is carried out the film electrolysis, and carry out r-o-; Perhaps directly the waste water behind the deamination is carried out r-o-.
According to the present invention, said membrane technique is the element of fluid operative technique of dividing dried up intermediate ion or molecule through a kind of special semi-permeable membranes.For example, membrane technique commonly used comprises ultrafiltration, micro-filtration, nanofiltration, r-o-, electrodialysis, electrolysis with ion-exchange film.And contriver of the present invention is according to the processing feature of vanadium wastewater; Through different membrane technologies is made up vanadium wastewater is handled; Thereby can carry out selective removal to different materials targetedly, can reach the purpose that reduces the salts contg in the waste water simultaneously.Wherein, electrolysis with ion-exchange film and electrodialysis belong to potential gradient as motivating force, and other several kinds of embrane methods belong to pressure gradient as motivating force.Membrane technique does not follow great amount of heat energy to change, have energy-conservation, but advantages such as robotization are convenient in operate continuously.
According to the present invention, in step (1), the ammonium ion in the waste water is converted into ammonia; Through the ammonia nitrogen separatory membrane, the method for carrying out deamination comprises that the pH value of regulating waste water is 10-13, is preferably 10-12; Make the ammonium ion in the waste water be converted into ammonia; Adopt the ammonia nitrogen separatory membrane to isolate ammonia wherein, make that ammonia-nitrogen content is below 100 mg/litre in the waste water behind the deamination, be preferably the 40-80 mg/litre.
The pH value of said adjusting waste water is 10-13, and preferred pH value can adopt the conventional method in this area for the method for 10-12, for example, regulates with alkaline matter, and said alkaline matter can be a solid, also can be the aqueous solution of alkaline matter.Said alkaline matter can be the alkaline matter that this area is commonly used, for example, can be selected from sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, sodium oxide, sodiumperoxide, potassium oxide, Potassium peroxide 85, quicklime, calcium superoxide and the salt of wormwood one or more.Generally, can use alkaline aqueous solution, regulate like aqueous sodium hydroxide solution, the weight ratio of waste water and alkaline aqueous solution can be 1: 0.03-0.06, the concentration of said alkaline aqueous solution generally can be 20-50 weight %.
According to the present invention, obtain purer ammonium sulfate in order to reclaim ammonia, thereby reach the purpose of reclaim(ed) sulfuric acid ammonium, said method also comprises the step of the ammonia that goes out with the diluted acid absorption extraction.And can be with the ammonium sulfate that obtains through obtaining the concentrated vitriol ammonium solution after concentrating or obtaining ammonia sulfate crystal with recycling through after the evaporation concentration.
Said employing ammonia nitrogen separatory membrane can adopt conventional method and condition to carry out to method and the condition that waste water carries out deamination; For example; Waste water is contacted with the ammonia nitrogen separating film module with alkaline matter, and ammonia escapes into outside the film through film, and uses diluted acid; Like mass percent concentration is that the ammonia gas react of dilute sulphuric acid and the effusion of 15-20 weight % obtains and the reclaim(ed) sulfuric acid ammonium, and the consumption of said diluted acid can according to how many suitably adjustment of the amount of the ammonia that overflows.The temperature that the condition of said deamination generally comprises deamination is 10-40 ℃, and in order to save the energy, preferred deamination under lower temperature is as 10-25 ℃; Pressure can be the 0.02-0.15 MPa.
According to the present invention, said ammonia nitrogen separatory membrane can be the ammonia nitrogen separatory membrane of various routines well known in the art, for example, and polypropylene hollow fiber membrane or modification ps hollow fiber uf membrane.Said ammonia nitrogen separatory membrane can be commercially available, and can be selected from suitable film wire material and water flux according to different purposes and to the processing requirements of waste water.
According to the present invention; Electrolytic method of said film and principle are conventionally known to one of skill in the art, for example, and for the present invention; Can the waste water that contain sodium sulfate be fed in the anolyte compartment of cationic membrane electrolyzer; Water is imported in the cathode compartment, and the cationic membrane that the sodium ion in the waste water in the anolyte compartment sees through between anolyte compartment and the cathode compartment under electric field action moves to cathode compartment, and the sodium ion that gets into catholyte combines to generate sodium hydroxide with the hydroxide ion that cathode compartment produces; And the sulfate ion in the waste water receives the restriction of film; Basically can not get into cathode compartment and generate sulfuric acid (mixing solutions of sulfuric acid and sodium sulfate) in the hydrogen ions with anolyte compartment's electrolysis generation, anode electrolysis generates oxygen simultaneously, and catholyte generates hydrogen.To reach the purpose that reduces the concentration of sodium sulfate in the waste water.
In addition, for fear of through the pH value of the mixing solutions after the electrolysis of cationic membrane film low and can't reach the requirement of carrying out r-o-(that is, making the pH value of waste water satisfy the Working environment (pH is 2-11) of reverse osmosis membrane); Under the preferable case, also comprise in the cathode compartment with the mixing solutions importing anionic membrane electrolyzer that carries out sulfuric acid and sodium sulfate after the film electrolysis through cationic membrane, water is imported in the anolyte compartment; Under the effect of electrical forces, sulfate radical gets into the anolyte compartment by cathode compartment, and the catholyte hydrogen ion produces hydrogen; PH raises; Because Na ion concentration is constant basically, so the solution saltiness is constant basically, thereby reaches the purpose of rising wastewater pH.
The electrolytic operational condition of said film can adopt the conventional operational condition in this area.For example; The temperature of utilizing positively charged ion to carry out the waste water (perhaps utilizing anionic membrane to carry out sulfuric acid and the mixing solutions of sodium sulfate in the electrolytic cathode compartment of film) in the electrolytic anolyte compartment of film can be 30-50 ℃, and the temperature of water in the cathode compartment (perhaps utilizing anionic membrane to carry out the water in the electrolytic anolyte compartment of film) can be 30-50 ℃.Current density can be 1000-1500A/m
2, said mould material also can be the cationic membrane material or the anionic membrane material of various routines known in those skilled in the art.
According to the present invention; Difference according to the salts contg in the pending vanadium wastewater; Can the waste water behind the deamination be carried out r-o-after the saltiness through film electrolysis further reduction waste water earlier again; Also can the waste water behind the deamination directly be carried out r-o-, through obtaining dense water and pure water that can reuse after the r-o-.
According to a kind of embodiment of the present invention; Contriver of the present invention finds; The total content of sodium sulfate and ammonium sulfate is greater than 8 to 12 weight % in vanadium wastewater, need the waste water behind the deamination be carried out the film electrolysis, behind the salts contg that reduces waste water, carries out reverse-osmosis treated again; The electrolytic condition of film makes that the saltiness through the waste water after the film electrolysis is 5 to being less than or equal to 8 weight %.
According to other a kind of embodiment of the present invention, contriver of the present invention finds that the total content of sodium sulfate and ammonium sulfate is less than or equal to 8 weight % in vanadium wastewater, can the waste water behind the deamination directly be carried out r-o-.
Be used after acid, the alkali that can in the film electrolytic process, produce concentrates, and, also can be used obtaining purified hydrogen of high density and oxygen after hydrogen that obtains and the recovery of oxygen process gas concentration unit.
According to the present invention; Said r-o-is a kind of reverse locomotory movement of infiltration; Be a kind of under pressure-driven; The separation method that solute in the solution and solvent is separated by means of the selection crown_interception of semi-permeable membranes is with Impurity removals such as the mineral ion in the former water, bacterium, virus, organism and colloids, to obtain high-quality pure water.
According to the present invention, the condition of said r-o-can comprise that pressure generally can preferably can be the 5-8 MPa for being less than or equal to 8 MPas; Temperature is 20-40 ℃; Be preferably 20-30 ℃; The kind of reverse osmosis membrane also can adopt and well known to a person skilled in the art reverse osmosis membrane; And can be selected from suitable bore dia and water flux according to different purposes and to the processing requirements of waste water, as, said reverse osmosis membrane can be purchased from Hydranautics etc.
Utilize reverse osmosis membrane to handle, obtain reuse water and the dense water that contains sodium sulfate.The saltiness of the reuse water after the r-o-of the feasible process of the condition of r-o-is less than 0.1 weight %.The dense water that contains sodium sulfate through obtaining after the r-o-can be through obtaining sodium sulfate crystal after the evaporation concentration; In addition; If the content amount of dense water is higher as; Greater than 8 weight %, also can said dense water be got into membrane-electrode unit and after reducing its saltiness, carry out r-o-once more, thereby can realize the circular treatment of waste water.
Industriallization reduction with in vanadium wastewater after, and before according to method of the present invention said vanadium wastewater being handled,, therefore, need through adding Na owing to also contain a small amount of suspended substance in the said vanadium wastewater and not have thoroughly to handle clean heavy metal
2S
2O
5Reductive agent and alkaline matter carry out pre-treatment once more to vanadium wastewater; After obtaining clarifying waste water; Get into the ammonia separatory membrane again and carry out deamination, be beneficial to the processing efficiency that improves waste water on the one hand, can effectively prolong the work-ing life of ammonia nitrogen separatory membrane and reverse osmosis membrane on the other hand.
Under the preferable case, according to the present invention, this method also is included in before the deamination, removes the heavy metal compound in the waste water, and chromium ion concentration residual in the said vanadium wastewater is generally 5-30mg/L, and vanadium ion concentration is generally 10-50mg/L.Said method of removing the heavy metal in the waste water can be the whole bag of tricks known in those skilled in the art, for example, under 20-50 ℃, waste water is mixed with reductive agent and alkaline matter, and removes the deposition in the waste water that obtains.In order to reach better effect, preferred earlier with waste water with mix with alkaline matter again after reductive agent mixes.In addition, for the ease of the carrying out of reduction reaction, said waste water carried out under acidic conditions with mixing preferably of reductive agent,, can use acid that is, below the pH regulator to 5 of sulfuric acid with waste water, more preferably below 4.The weight ratio of said reductive agent and waste water generally can be 0.5-1: 1000, be preferably 0.5-0.8: 1000; Said reductive agent generally can be Na
2S
2O
5The weight ratio of said alkaline matter and waste water generally can be 1: 2000-5000 is preferably 1: 2200-4000.Said alkaline matter can be the aqueous solution of solid or alkaline matter; Said alkaline matter can be selected from one or more in sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, sodium oxide, sodiumperoxide, potassium oxide, Potassium peroxide 85, quicklime, calcium superoxide and the salt of wormwood.Said sedimentary method of removing in the waste water that obtains can adopt and well known to a person skilled in the art conventional various separation methods, for example, method such as filters, centrifugal.
According to the present invention, in order to guarantee the quality of subsequent film sepn process, the work-ing life that prevents that film obstruction and film pollution take place in the film treating processes and prolong film; Under the preferable case, behind the heavy metal compound in removing waste water, waste water is passed through the ammonia nitrogen separatory membrane; Carry out before the deamination; This method also preferably includes carries out settled step with waste water, and settled condition makes that the turbidity of waste water is below 20, to be preferably below 15.Generally speaking, the said settled time can be 1-3 hour, and settled temperature can be 20-40 ℃.
The measuring method of the turbidity of said water can adopt and well known to a person skilled in the art turbidity determination method, for example, can adopt turbidimeter (WGZ-200 turbidimeter) to measure.
To further describe in detail the present invention through specific embodiment below.
Used ammonia nitrogen separatory membrane is X50 parent gas type ammonia nitrogen separatory membrane (the film wire material: polypropylene screen silk material available from the triumphant clean membrane separation technique in Hangzhou ltd among the following embodiment; Film external diameter: 420-480 μ m; Membranous wall is thick: 40-50 μ m; Micropore size: 0.1-0.2 μ m, porosity: 45-55%, air penetrability:＞8.0 * 10
-2(cm
3/ cm
2ScmHg)), the water inlet WP of said ammonia nitrogen separatory membrane: 0.02-0.15Mpa.
Said reverse osmosis membrane is the SWC series available from Hydranautics, and membrane material is an aramid materials, effective film area 370-400ft
2, bore dia is less than 1 nanometer, and MOP is 8 MPas, the highest flooding velocity 17m
3/ h, Working environment pH are 2-11.
The used mould material of said film electrolysis is the JAM-II type homogeneous-phase anion exchange film available from the N324 type cationic membrane material of du pont company and the court of a feudal ruler, Beijing profit membrane technique development corporation, Ltd.; Operational condition: 30 ℃ of waste water in the anolyte compartment (or in the cathode compartment sodium sulfate and sulfuric acid mixture liquid) temperature, the temperature of water in the cathode compartment (the perhaps Zhong Shui of anolyte compartment) is 30 ℃, current density is 1000A/m
2
Adopt turbidimeter (WGZ-200 turbidimeter) that turbidity is measured.
Adopt nessler reagent spectrophotometric colorimetric method for determining ammonia-nitrogen content.
Vanadium wastewater described in the following embodiment comes from Pangang Group Panzhihua Steel Vanadium Co., Ltd. vanadium products factory vanadium oxide production operation district.
Embodiment 1
Present embodiment is used to explain the treatment process of vanadium wastewater provided by the invention.
In the vanadium wastewater after said industriallization (reduction neutralization) is handled, sodium sulphate content is 3-5 weight %, and ammonium sulfate content is 2-3 weight %, and chromium ion concentration is 5-30mg/L, and vanadium ion concentration is 10-20mg/L.
As shown in Figure 1, the treatment process of said vanadium wastewater comprises the steps:
(1) pre-treatment of vanadium wastewater
Earlier waste water is adjusted to acidity (pH＜4) with dilute sulfuric acid aqueous solution (the dilute sulfuric acid aqueous solution mass concentration is 15 weight %), then under 40 ℃, with waste water successively with reductive agent Na
2S
2O
5And aqueous sodium hydroxide solution (the aqueous sodium hydroxide solution mass concentration is 42 weight %) mixes; The weight ratio of said reductive agent and waste water is 0.5: 1000; The weight ratio of said aqueous sodium hydroxide solution and waste water is 1: 1000; And left standstill 1 hour, filter then, to remove heavy metal compound wherein;
Waste water is placed subsider, and 40 ℃ of following sedimentations 1 hour, to remove suspended impurity wherein, the water turbidity that overflows was controlled at and is lower than 20.
(2) ammonia nitrogen separates
With aqueous sodium hydroxide solution (the aqueous sodium hydroxide solution mass concentration is 42 weight %) under 25 ℃; 0.05 under the MPa pressure, pump in the pretreated waste water of process of step (1) with the flow velocity of 40L/h, the pH that regulates waste water is 13 (weight ratio of waste water and aqueous sodium hydroxide solution is 1: 0.05); Through the ammonia nitrogen separation membrane system; Make the ammonia nitrogen in the waste water be reduced to 80mg/L, simultaneously the ammonia of separating being used mass percent concentration is the dilute sulphuric acid absorption of 15 weight %, and (ammonium sulfate is converted into sodium sulfate in the waste water to obtain ammonium sulfate product; Therefore, the sodium sulfate total concn is 5-8 weight %).
(3) r-o-
Under 20 ℃, under the 5 MPa pressure, the waste water behind the removal of ammonia and nitrogen through reverse osmosis membrane, is obtained the dope of contains sodium sulfate and the product water that saltiness is lower than 0.1 weight %, produce water and can recycle, with the dope evaporation concentration, obtain sodium sulfate crystal.
Embodiment 2
Present embodiment is used to explain the treatment process of vanadium wastewater provided by the invention.
In the vanadium wastewater after said industriallization (reduction neutralization) is handled, sodium sulphate content is 6-8 weight %, and ammonium sulfate content is 3-4 weight %, and chromium ion concentration is 15-30mg/L in the said waste water, and vanadium ion concentration is 10-50mg/L.
As shown in Figure 2, the treatment process of said vanadium wastewater comprises the steps:
(1) pre-treatment of vanadium wastewater
Earlier waste water is adjusted to acidity (pH＜4), then under 25 ℃, with waste water and reductive agent Na with dilute sulfuric acid aqueous solution (the dilute sulfuric acid aqueous solution mass concentration is 15 weight %)
2S
2O
5And aqueous sodium hydroxide solution (the aqueous sodium hydroxide solution mass concentration is 42 weight %) mixes; The weight ratio of said reductive agent and waste water is 0.8: 1000; The weight ratio of said aqueous sodium hydroxide solution and waste water is 1: 1300; And left standstill 1 hour, filter then, to remove heavy metal compound wherein;
Waste water is placed subsider, and 30 ℃ of following sedimentations 2 hours, to remove suspended impurity wherein, the water turbidity that overflows was controlled at and is lower than 20.
(2) ammonia nitrogen separates
With aqueous sodium hydroxide solution (the aqueous sodium hydroxide solution mass concentration is 42 weight %) under 30 ℃; 0.03 under the MPa pressure, pump in the pretreated waste water of process of step (1) with the flow velocity of 35L/h, the pH that regulates waste water is 12 (weight ratio of waste water and aqueous sodium hydroxide solution is 1: 0.04); Through the ammonia nitrogen separation membrane system; Make the ammonia nitrogen in the waste water be reduced to 60mg/L, simultaneously the ammonia of separating being used mass percent concentration is the dilute sulphuric acid absorption of 15 weight %, and (ammonium sulfate is converted into sodium sulfate in the waste water to obtain ammonium sulfate product; Therefore, the sodium sulfate total concn is 9-12 weight %).
(3) electrolysis with ion-exchange film
Place the electrolyzer of membrane electrolyser (cationic membrane) to carry out electrolysis the isolating waste water of process ammonia nitrogen of step (2); Electrolysis obtains contains sodium sulfate (sodium sulphate content is 5-8 weight %) and vitriolic waste water and sodium hydroxide, produces hydrogen and oxygen in the electrolytic process simultaneously.Contain sodium sulfate (sodium sulphate content is 5-8 weight %) and vitriolic waste water places the electrolyzer of membrane electrolyser (anionic membrane) to carry out electrolysis with said, after the anionic membrane electrolysis, obtain metabisulfite solution (sodium sulphate content is 5-8 weight %) and sulfuric acid respectively.
(4) r-o-
At 40 ℃; Under the 8 MPa pressure; The metabisulfite solution that will pass through after the electrolysis with ion-exchange film of step (3) carries out reverse-osmosis treated through reverse osmosis membrane, obtains containing the dope of sodium sulfate and the product water that saltiness is lower than 0.1 weight %, produces water and can recycle; Can the dope evaporation concentration be obtained carrying out reverse-osmosis treated again after sodium sulfate crystal perhaps returns dope to the ion membrane electrolysis unit desalination.
Embodiment 3
Present embodiment is used to explain the treatment process of vanadium wastewater provided by the invention.
Method according to embodiment 1 is handled vanadium wastewater; Different is before processing, waste water not to be carried out sedimentation and directly carries out the ammonia nitrogen membrane sepn; And at the ammonia nitrogen separation phase; The pH value of regulating waste water is 10 (weight ratio of waste water and aqueous sodium hydroxide solution is 1: 0.03), through the ammonia nitrogen separation membrane system, makes the ammonia nitrogen in the waste water be reduced to 90mg/L.
Method according to embodiment 1 to embodiment 3; The ammonium sulfate product that can step (2) be obtained is through obtaining liquid concentrator after concentrating or crystal utilizes again; Method according to embodiment 2 can reclaim at sub product sodium hydroxide, sulfuric acid, hydrogen and the oxygen that step (3) obtains again; And can sodium hydroxide wherein be back in the ammonia nitrogen separation system, hydrogen wherein and oxygen obtain purified hydrogen of high density and oxygen product after reclaiming through gas concentration unit.
Claims (12)
1. the treatment process of a vanadium wastewater, said vanadium wastewater contains sodium sulfate and ammonium sulfate, it is characterized in that, and this method comprises the steps:
(1) ammonium ion in the waste water is converted into ammonia,, carries out deamination through the ammonia nitrogen separatory membrane;
(2) waste water behind the deamination is carried out the film electrolysis, and carry out r-o-; Perhaps directly the waste water behind the deamination is carried out r-o-.
2. method according to claim 1; Wherein, step (1) comprises that the pH value of regulating waste water is 10-13, makes the ammonium ion in the waste water be converted into ammonia; Adopt the ammonia nitrogen separatory membrane to isolate ammonia wherein, make that ammonia-nitrogen content is below 100 mg/litre in the waste water behind the deamination.
3. method according to claim 2, wherein, ammonia-nitrogen content is the 40-80 mg/litre in the waste water behind the deamination.
4. method according to claim 2, wherein, the temperature of deamination is 20-40 ℃.
5. method according to claim 2, wherein, this method also comprises the ammonia that goes out with the diluted acid absorption extraction.
6. method according to claim 1, wherein, the total content of sodium sulfate and ammonium sulfate is greater than 8 to 12 weight % in the vanadium wastewater, step (2) comprises carries out the film electrolysis with the waste water behind the deamination, and carries out r-o-; The electrolytic condition of film makes that the saltiness through the waste water after the film electrolysis is 5 to being less than or equal to 8 weight %; The total content of sodium sulfate and ammonium sulfate is less than or equal to 8 weight % in the vanadium wastewater, and step (2) comprises directly carries out r-o-with the waste water behind the deamination.
7. according to claim 1 or 6 described methods, wherein, the saltiness of the pure water that obtains after the r-o-of the feasible process of the condition of r-o-is less than 0.1 weight %.
8. method according to claim 7, wherein, the condition of said r-o-comprises pressure for being less than or equal to 8 MPas, temperature is 20-40 ℃.
9. method according to claim 1, wherein, said vanadium wastewater also contains heavy metal compound, and wherein, chromium ion concentration is 5-30mg/L, and vanadium ion concentration is 10-50mg/L, and this method also is included in before the deamination, removes the heavy metal compound in the waste water.
10. method according to claim 9 wherein, after this method also is included in the heavy metal compound of removing in the waste water, and before deamination, is carried out sedimentation with waste water, and settled condition makes that the turbidity of waste water is below 20.
11. according to claim 1,9 or 10 described methods, wherein, the method for removing the heavy metal compound in the waste water is included under 20-50 ℃, waste water is mixed with reductive agent and alkaline matter, and remove the deposition in the waste water that obtains.
12. method according to claim 11, wherein, the weight ratio of said reductive agent and waste water is 0.5-1: 1000, and said reductive agent is Na
2S
2O
5The weight ratio of said alkaline matter and waste water is 1: 2000-5000; Said alkaline matter is the aqueous solution of solid or alkaline matter, and said alkaline matter is selected from one or more in sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, sodium oxide, sodiumperoxide, potassium oxide, Potassium peroxide 85, quicklime, calcium superoxide and the salt of wormwood.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104058523A (en) * | 2013-10-31 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium oxide production industrial wastewater processing method |
| CN104411641A (en) * | 2012-07-13 | 2015-03-11 | 栗田工业株式会社 | Ultrapure water production device |
| CN104710081A (en) * | 2015-03-18 | 2015-06-17 | 河海大学 | Sewage nitrogen and phosphorus removal method and device |
| CN105861829A (en) * | 2016-04-18 | 2016-08-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for separating vanadium and chromium solution and recycling vanadium and chromium |
| CN104411641B (en) * | 2012-07-13 | 2016-11-30 | 栗田工业株式会社 | Ultrapure Water Purifiers |
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| CN108178372A (en) * | 2017-12-29 | 2018-06-19 | 攀枝花钢企欣宇化工有限公司 | A kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt |
| CN113003606A (en) * | 2021-02-09 | 2021-06-22 | 东北大学 | Method for preparing vanadium pentoxide by utilizing multi-component circulation process and sodium vanadate solution |
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| CN101215636A (en) * | 2008-01-11 | 2008-07-09 | 中南大学 | Stone coal sodium roasting vanadium-extracting method |
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| CN101215636A (en) * | 2008-01-11 | 2008-07-09 | 中南大学 | Stone coal sodium roasting vanadium-extracting method |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104411641A (en) * | 2012-07-13 | 2015-03-11 | 栗田工业株式会社 | Ultrapure water production device |
| CN104411641B (en) * | 2012-07-13 | 2016-11-30 | 栗田工业株式会社 | Ultrapure Water Purifiers |
| CN104058523A (en) * | 2013-10-31 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium oxide production industrial wastewater processing method |
| CN104058523B (en) * | 2013-10-31 | 2015-12-30 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind for the treatment of process of vanadium oxide manufacture waste water |
| CN104710081A (en) * | 2015-03-18 | 2015-06-17 | 河海大学 | Sewage nitrogen and phosphorus removal method and device |
| CN106565050A (en) * | 2015-10-08 | 2017-04-19 | 黄冈华阳药业有限公司 | Folic acid wastewater treatment process |
| CN105861829A (en) * | 2016-04-18 | 2016-08-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for separating vanadium and chromium solution and recycling vanadium and chromium |
| CN106587424A (en) * | 2016-12-13 | 2017-04-26 | 广东致远新材料有限公司 | Resourceful treatment method for tantalum-niobium industrial fluorine-containing ammonia-nitrogen wastewater |
| CN108178372A (en) * | 2017-12-29 | 2018-06-19 | 攀枝花钢企欣宇化工有限公司 | A kind of method for removing chlorinated exhaust and absorbing vanadium in abraum salt |
| CN113003606A (en) * | 2021-02-09 | 2021-06-22 | 东北大学 | Method for preparing vanadium pentoxide by utilizing multi-component circulation process and sodium vanadate solution |
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