CN115321737A - Method for treating sodium-containing wastewater in vanadium slag sodium modification vanadium extraction process - Google Patents
Method for treating sodium-containing wastewater in vanadium slag sodium modification vanadium extraction process Download PDFInfo
- Publication number
- CN115321737A CN115321737A CN202211041688.9A CN202211041688A CN115321737A CN 115321737 A CN115321737 A CN 115321737A CN 202211041688 A CN202211041688 A CN 202211041688A CN 115321737 A CN115321737 A CN 115321737A
- Authority
- CN
- China
- Prior art keywords
- sodium
- vanadium
- containing wastewater
- vanadium slag
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011734 sodium Substances 0.000 title claims abstract description 125
- 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 title claims abstract description 113
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 113
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 89
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002351 wastewater Substances 0.000 title claims abstract description 78
- 239000002893 slag Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000000605 extraction Methods 0.000 title claims abstract description 27
- 230000004048 modification Effects 0.000 title claims abstract description 8
- 238000012986 modification Methods 0.000 title claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000000926 separation method Methods 0.000 claims abstract description 43
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 23
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 23
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 18
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 18
- 239000004571 lime Substances 0.000 claims abstract description 18
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 18
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008020 evaporation Effects 0.000 claims abstract description 17
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012452 mother liquor Substances 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 31
- 239000011575 calcium Substances 0.000 claims description 23
- 238000001556 precipitation Methods 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 238000002386 leaching Methods 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012629 purifying agent Substances 0.000 claims description 6
- 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 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 5
- 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
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 57
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- 238000004065 wastewater treatment Methods 0.000 description 7
- 239000008267 milk Substances 0.000 description 6
- 210000004080 milk Anatomy 0.000 description 6
- 235000013336 milk Nutrition 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011029 spinel Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002308 calcification Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a method for treating sodium-containing wastewater in a vanadium slag sodium modification vanadium extraction process, which belongs to the technical field of vanadium chemical industry and comprises the following steps: s1, performing sodium salt roasting on vanadium slag, immersing a sodium vanadate solution in water, precipitating calcium vanadate with lime to realize sodium-vanadium separation, and performing solid-liquid separation to obtain sodium-containing wastewater; s2, purifying the sodium-containing wastewater to remove calcium ions in the sodium-containing wastewater, and performing solid-liquid separation to obtain purified sodium-containing wastewater; s3, evaporating and concentrating the purified sodium-containing wastewater to obtain an evaporation concentrated solution; s4, carbonating the evaporated and concentrated solution by using carbon dioxide, and carrying out solid-liquid separation to obtain sodium bicarbonate solid and sodium bicarbonate mother liquor; s5, returning the sodium bicarbonate mother liquor to an evaporation concentration system for circular treatment; and returning the sodium bicarbonate solid to the vanadium slag sodium roasting system for recycling. The method solves the problem of treatment of the by-product in the wastewater process, reduces the production cost, and has important significance for the production of extracting vanadium from vanadium slag by sodium modification.
Description
Technical Field
The invention belongs to the technical field of vanadium chemical industry, and particularly relates to a method for treating sodium-containing wastewater in a vanadium slag sodium modification vanadium extraction process.
Background
Vanadium slag is a main raw material for extracting vanadium oxide, at present, two main industrial processes for extracting vanadium are vanadium slag sodium salt roasting conversion-water leaching-ammonium vanadate precipitation (sodium salt process) and vanadium slag calcification roasting conversion-sulfuric acid leaching-vanadate precipitation (calcification process), the common point of the two processes is to add a salt forming additive for oxidation roasting, then a vanadium solution is prepared by adopting a water leaching or acid leaching method, red vanadium or ammonium vanadate is prepared by adopting a hydrolysis vanadium precipitation method or an ammonium salt vanadium precipitation method, and a vanadium oxide product is prepared by calcining and decomposing.
In the current industrialized production process, the vanadium slag sodium salt vanadium extraction process occupies a dominant position, and the general process flow is as follows: vanadium slag and sodium carbonate → oxidizing roasting → water leaching → ammonium salt vanadium precipitation → wastewater treatment, wherein the sodium carbonate needs to be purchased externally, the roasting temperature is usually 800-850 ℃, and the roasting temperature is not more than 800 ℃ when the roasting temperature is lower; the waste water treatment is usually evaporation crystallization to obtain sodium sulfate mixed salt. According to industrial production experience, when sodium sulfate is used as a sodium salt additive, the effect is achieved only by roasting at a temperature of over 1000 ℃, and obviously, under the existing industrial production conditions, sodium sulfate miscellaneous salts produced by wastewater treatment are not technically feasible to be roasted as the sodium salt additive. Therefore, sodium sulfate miscellaneous salts obtained by wastewater treatment cannot be directly returned to the roasting process for recycling, sodium carbonate is still purchased to maintain sodium salt consumption in production, and not only is the sodium sulfate difficult to dispose, but also the production cost is increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for treating sodium-containing wastewater in a vanadium slag sodium modification vanadium extraction process. The invention provides a solution for solving the problems that the treatment of sodium sulfate is difficult and the production cost is high because sodium sulfate miscellaneous salt obtained by evaporation concentration and crystallization treatment of sulfate wastewater generated in the existing vanadium slag sodium salt extraction process cannot be returned to the roasting process for recycling.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the method for treating the sodium-containing wastewater in the vanadium slag sodium salt extraction process comprises the following steps:
s1, performing sodium salt roasting on vanadium slag, and then leaching a sodium vanadate solution to precipitate calcium vanadate by using lime to realize sodium-vanadium separation, and performing solid-liquid separation to obtain calcium vanadate solid and sodium-containing wastewater taking sodium hydroxide as a main component;
s2, purifying the sodium-containing wastewater to remove calcium ions in the sodium-containing wastewater, and performing solid-liquid separation to obtain purified residues and purified sodium-containing wastewater;
s3, evaporating and concentrating the purified sodium-containing wastewater to obtain evaporated condensate water and an evaporated concentrated solution;
s4, carbonating the evaporated and concentrated solution by using carbon dioxide, and carrying out solid-liquid separation to obtain sodium bicarbonate solid and sodium bicarbonate mother liquor;
s5, returning the sodium bicarbonate mother liquor to an evaporation concentration system for circular treatment; returning the sodium bicarbonate solid to the vanadium slag sodium salt roasting system for cyclic utilization; returning the evaporated condensate water to a vanadium slag sodium salt roasting clinker water leaching system for cyclic utilization; the calcium vanadate solid is used for preparing a vanadium oxide product.
Further, in the step S1, the water-immersed sodium vanadate solution is a water-immersed solution of vanadium slag sodium roasting clinker, the vanadium content is 15-60 g/l, the sodium content is 20-80 g/l, and the pH value is more than 9.
Further, in step S1, the calcium salt for precipitating calcium vanadate with lime is one or more of calcium oxide and calcium hydroxide.
Further, in the step S1, in the process of realizing sodium-vanadium separation by precipitating calcium vanadate with lime, the molar ratio of calcium/vanadium is controlled to be 1.5-2.0; the end point of precipitation is reached when the vanadium content is below 0.10 g/l.
Further, in step S2, the purifying agent for purifying the sodium-containing wastewater is one or more of sodium carbonate and carbon dioxide.
Further, in step S2, when the purifying agent is sodium carbonate, the sodium carbonate is added in an amount of Ca/Na 2 CO 3 The molar ratio is 1.0-1.5.
Further, in step S3, the sodium hydroxide content of the evaporation concentrate in the evaporation concentration process is 20% to 40%.
Further, in step S4, the carbon dioxide is outsourced industrial grade carbon dioxide.
Further, in step S4, during the carbonation of carbon dioxide, the pH value at the carbonation end point is controlled to be 8.0 to 8.5.
The invention has the beneficial effects that:
the sodium-containing wastewater of a sodium hydroxide system is obtained by precipitating calcium vanadate from a sodium vanadate solution by using calcium oxide, sodium bicarbonate solid is obtained by adopting a method of evaporating concentration and acidifying the evaporated concentrated solution by using carbon dioxide acid, and the sodium bicarbonate solid is returned to a sodium salt roasting system for cyclic utilization, so that the problem of treatment of a byproduct in a wastewater procedure is solved, the production cost is reduced, and the method has important significance for the production of extracting vanadium from vanadium slag by sodium salt.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate the understanding of the present invention by those skilled in the art, but it should be understood that the present invention is not limited to the scope of the embodiments, and it will be apparent to those skilled in the art that various changes may be made without departing from the spirit and scope of the invention as defined and defined in the appended claims, and all matters produced by the invention using the inventive concept are protected.
The invention provides a method for treating sodium-containing wastewater in a vanadium slag sodium salt extraction process, which comprises the following steps:
a. sodium vanadium separation is realized by immersing a water sodium vanadate solution obtained after sodium roasting of vanadium slag with lime to precipitate calcium vanadate, and the molar ratio of calcium/vanadium is controlled to be 1.5-2.0; the end point of precipitation is reached when the vanadium content is below 0.10 g/l. Solid-liquid separation to obtain calcium vanadate solid and sodium-containing wastewater (sodium-containing wastewater for short, the same is applied later) taking sodium hydroxide as a main component. Specifically, the water leaching sodium vanadate solution is a water leaching solution of vanadium slag sodium roasting clinker, the vanadium content is 15-60 g/l, the sodium content is 20-80 g/l, and the pH value is more than 9. The calcium salt for precipitating calcium vanadate by lime is one or more of calcium oxide and calcium hydroxide.
b. And (3) purifying the sodium-containing wastewater to remove calcium ions in the sodium-containing wastewater, and performing solid-liquid separation to obtain purified residues and purified sodium-containing wastewater. Specifically, the purifying agent for purifying the sodium-containing wastewater is one or more of sodium carbonate and carbon dioxide. When the purifying agent is sodium carbonate, the addition amount of sodium carbonate is Ca/Na 2 CO 3 The molar ratio is 1.0-1.5.
c. And evaporating and concentrating the purified sodium-containing wastewater to obtain evaporated condensate water and an evaporated concentrated solution. Preferably, the sodium hydroxide content of the evaporation concentrated solution in the evaporation concentration process is 20-40%.
d. And (3) carbonating the evaporated concentrated solution by using purchased industrial-grade carbon dioxide, and performing solid-liquid separation to obtain sodium bicarbonate solid and sodium bicarbonate mother liquor. Preferably, the pH value at the carbonation end point is controlled to be 8.0-8.5 during the carbonation treatment of the carbon dioxide.
e. Returning the sodium bicarbonate mother liquor to an evaporation concentration system for circular treatment; returning the sodium bicarbonate solid to the vanadium slag sodium salt roasting system for cyclic utilization; returning the evaporated condensate water to the vanadium slag sodium salt roasting clinker water leaching system for cyclic utilization; the calcium vanadate solid is further treated to produce a vanadium oxide product.
In the step a, calcium oxide is used for precipitating calcium vanadate from a sodium vanadate solution, acid radical anions are not introduced, sodium-containing wastewater of a sodium hydroxide system is obtained, and conditions are created for preparing useful sodium salt through subsequent wastewater treatment.
In the step b, the purpose of the sodium-containing wastewater purification treatment is to remove a small amount of calcium ions in the sodium-containing wastewater so as to obtain sodium bicarbonate solid with low calcium content through subsequent wastewater treatment.
In the step c, the purpose of evaporation concentration is to realize sodium water separation, obtain nearly saturated sodium hydroxide concentrated solution and evaporation condensate water, and facilitate carbonation treatment and water recycling.
In the step d, the purpose of the carbonation treatment of the evaporated concentrated solution of carbon dioxide is to convert sodium hydroxide into sodium bicarbonate, so that the sodium bicarbonate can be recycled in the roasting process.
The main reactions in the process are as follows:
(1) Sodium oxide reaction of vanadium spinel in vanadium slag with sodium carbonate and sodium bicarbonate
4FeV 2 O 4 +4Na 2 CO 3 +7O 2 ＝8NaVO 3 +2Fe 2 O 3 +4CO 2
4MnV 2 O 4 +4Na 2 CO 3 +7O 2 ＝8NaVO 3 +ZMn 2 O 3 +4CO 2
The reaction of the vanadium spinel and the sodium salt has better effect generally at about 800 ℃.
(2) Sodium oxide reaction of vanadium spinel and sodium sulfate in vanadium slag
4FeV 2 O 4 +4Na 2 SO 4 +3O 2 ＝8NaVO 3 +2Fe 2 O 3 +4SO 2
4FeV 2 O 4 +4Na 2 SO 4 +5O 2 ＝8NaVO 3 +2Fe 2 O 3 +4SO 3
4MnV 2 O 4 +4Na 2 SO 4 +3O 2 ＝8NaVO 3 +2Mn 2 O 3 +4SO 2
4MnV 2 O 4 +4Na 2 SO 4 +5O 2 ＝8NaVO 3 +2Mn 2 O 3 +4SO 3
The reaction of the vanadium spinel with sodium sulfate usually starts to have certain effect under the high temperature condition of 1000 ℃.
Obviously, sodium sulfate can not be used as a sodium treatment agent in the existing vanadium slag sodium treatment vanadium extraction process. The sodium bicarbonate obtained by the wastewater treatment of the invention is returned to sodium salt roasting to be used as a sodium salt additive, can replace sodium carbonate, and has the following reaction:
4FeV 2 O 4 +8NaHCO 3 +5O 2 ＝8NaVO 3 +2Fe 2 O 3 +8CO 2 +4H 2 O
4MnV 2 O 4 +8NaHCO 3 +5O 2 ＝8NaVO 3 +2Mn 2 O 3 +8CO 2 +4H 2 O
obviously, the invention better solves the defects existing in the prior art and has important significance in reaction.
The present invention will be further illustrated by the following specific examples.
The following examples used the sodium vanadate solution composition: vanadium content [ V ] 54g/l, sodium content [ Na ] 48g/l. Lime (CaO 85%) was ground to 0.080mm powder for use.
Example 1
Taking 500ml of sodium vanadate solution, adding 52.3g of lime powder for precipitation reaction, and performing solid-liquid separation after the reaction end point is reached to obtain 480ml of sodium-containing wastewater, wherein the detection shows that the vanadium content (V) is 0.08g/l and the calcium content (Ca) is 2.40g/l; adding 3.1g of industrial sodium carbonate with the purity of 98% into the sodium-containing wastewater, and after the reaction is finished, carrying out solid-liquid separation to obtain 465ml of purified sodium-containing wastewater, wherein the sodium content (Na) is 47.0g/l; after the purified sodium-containing wastewater is evaporated to 95ml, introducing carbon dioxide gas for carbonation treatment, ending the carbonation reaction when the pH value of the reaction solution reaches 8.0, and performing solid-liquid separation to obtain 71.4g of sodium carbonate solid (dry basis), wherein the dry basis purity is 98.5%, and the requirements of vanadium slag sodium treatment and vanadium extraction are met. The conversion rate of sodium element in the whole process is 81.22%.
Example 2
Adding 69.8g equivalent of lime milk into 500ml of sodium vanadate solution for precipitation reaction, and performing solid-liquid separation after the reaction end point is reached to obtain 475ml of sodium-containing wastewater, wherein the detected vanadium content (V) is 0.09g/l, and the detected calcium content (Ca) is 2.21g/l; adding 2.8g of 98% purity industrial sodium carbonate into the sodium-containing wastewater, and after the reaction is finished, carrying out solid-liquid separation to obtain 470ml of purified sodium-containing wastewater, wherein the sodium content [ Na ] is 47.1g/l; after the purified sodium-containing wastewater is evaporated to 110ml, introducing carbon dioxide gas for carbonation treatment, finishing the carbonation reaction when the pH value of the reaction solution reaches 8.5, and carrying out solid-liquid separation to obtain 71.3g of sodium carbonate solid (dry basis), wherein the purity of the dry basis is 98.0 percent, and the requirement of vanadium slag sodium salt vanadium extraction is met. The conversion rate of sodium element in the whole process is 79.69 percent.
Example 3
Adding 55.8g of lime milk into 500ml of sodium vanadate solution for precipitation reaction, and performing solid-liquid separation after the reaction end point is reached to obtain 487ml of sodium-containing wastewater, wherein the detection shows that the vanadium content (V) is 0.11g/l and the calcium content (Ca) is 1.85g/l; adding 2.4g 98% industrial sodium carbonate into the sodium-containing wastewater, and after the reaction is finished, carrying out solid-liquid separation to obtain 473ml of purified sodium-containing wastewater, wherein the sodium content [ Na ] is 46.8g/l; after the purified sodium-containing wastewater is evaporated to 113ml, introducing carbon dioxide gas for carbonation treatment, ending the carbonation reaction when the pH value of the reaction solution reaches 8.3, and performing solid-liquid separation to obtain 70.9g of sodium carbonate solid (dry basis), wherein the dry basis purity is 98.1%, and the requirements of vanadium slag sodium salt extraction are met. The conversion rate of sodium element in the whole process is 79.34 percent.
Example 4
Adding 59.3g equivalent of lime milk into 500ml of sodium vanadate solution for precipitation reaction, and performing solid-liquid separation after the reaction is finished to obtain 470ml of sodium-containing wastewater, wherein the detected vanadium content (V) is 0.07g/l, and the detected calcium content (Ca) is 2.34g/l; 3.0g of 98% industrial sodium carbonate is added into the sodium-containing wastewater, and after the reaction is finished, the solid-liquid separation is carried out to obtain 468ml of purified sodium-containing wastewater, wherein the sodium content [ Na ] is 46.5g/l; after the purified sodium-containing wastewater is evaporated to 95ml, introducing carbon dioxide gas for carbonation treatment, ending the carbonation reaction when the pH value of the reaction solution reaches 8.2, and carrying out solid-liquid separation to obtain 71.6g of sodium carbonate solid (dry basis), wherein the dry basis purity is 97.8%, and the requirements of vanadium slag sodium salt extraction are met. The conversion rate of sodium element in the whole process is 79.84%.
Example 5
Adding 62.8g of lime powder into 500ml of sodium vanadate solution for precipitation reaction, and performing solid-liquid separation after the reaction end point is reached to obtain 470ml of sodium-containing wastewater, wherein the vanadium content (V) is detected to be 0.09g/l, and the calcium content (Ca) is detected to be 1.96g/l; adding 2.6g of 98% purity industrial sodium carbonate into the sodium-containing wastewater, and after the reaction is finished, carrying out solid-liquid separation to obtain 465ml of purified sodium-containing wastewater, wherein the sodium content (Na) is 47.5g/l; after the purified sodium-containing wastewater is evaporated to 112ml, introducing carbon dioxide gas for carbonation treatment, finishing the carbonation reaction when the pH value of the reaction solution reaches 8.1, and carrying out solid-liquid separation to obtain 71.0g of sodium carbonate solid (dry basis), wherein the dry basis purity is 97.9 percent, and the requirement of vanadium slag sodium salt vanadium extraction is met. The conversion rate of sodium element in the whole process is 79.25 percent.
Example 6
Adding 66.3g equivalent of lime milk into 500ml of sodium vanadate solution for precipitation reaction, and performing solid-liquid separation after the reaction is finished to obtain 470ml of sodium-containing wastewater, wherein the detected vanadium content (V) is 0.12g/l, and the detected calcium content (Ca) is 1.76g/l; adding 2.3g of 98% purity industrial sodium carbonate into the sodium-containing wastewater, and after the reaction is finished, carrying out solid-liquid separation to obtain 478ml of purified sodium-containing wastewater, wherein the sodium content (Na) is 47.5g/l; after the purified sodium-containing wastewater is evaporated to 115ml, introducing carbon dioxide gas for carbonation treatment, finishing the carbonation reaction when the pH value of the reaction solution reaches 8.0, and carrying out solid-liquid separation to obtain 72.4g of sodium carbonate solid (dry basis), wherein the purity of the dry basis is 98.2%, and the requirement of vanadium slag sodium salt vanadium extraction is met. The conversion rate of sodium element in the whole process is 81.09%.
Example 7
Adding 52.3g of lime milk into 500ml of sodium vanadate solution for precipitation reaction, and performing solid-liquid separation after the reaction end point is reached to obtain 482ml of sodium-containing wastewater, wherein the detected vanadium content (V) is 0.07g/l, and the detected calcium content (Ca) is 2.13g/l; adding 2.8g of 98% purity industrial sodium carbonate into the sodium-containing wastewater, and after the reaction is finished, carrying out solid-liquid separation to obtain 465ml of purified sodium-containing wastewater, wherein the sodium content (Na) is 46.8g/l; after the purified sodium-containing wastewater is evaporated to 93ml, introducing carbon dioxide gas for carbonation treatment, ending the carbonation reaction when the pH value of the reaction solution reaches 8.5, and performing solid-liquid separation to obtain 71.5g of sodium carbonate solid (dry basis), wherein the dry basis purity is 98.1%, and the requirements of vanadium slag sodium treatment and vanadium extraction are met. The conversion rate of sodium element in the whole process is 80.06%.
Example 8
Adding 69.8g equivalent of lime milk into 500ml of sodium vanadate solution for precipitation reaction, and performing solid-liquid separation after the reaction end point is reached to obtain 479ml of sodium-containing wastewater, wherein the detected vanadium content (V) is 0.06g/l, and the detected calcium content (Ca) is 2.36g/l; adding 3.1g of 98% industrial sodium carbonate into the sodium-containing wastewater, and after the reaction is finished, carrying out solid-liquid separation to obtain 462ml of purified sodium-containing wastewater, wherein the sodium content (Na) is 46.6g/l; after the purified sodium-containing wastewater is evaporated to 90ml, introducing carbon dioxide gas for carbonation treatment, ending the carbonation reaction when the pH value of the reaction solution reaches 8.4, and carrying out solid-liquid separation to obtain 70.8g of sodium carbonate solid (dry basis), wherein the dry basis purity is 98.3%, and the requirements of vanadium slag sodium salt extraction are met. The conversion rate of sodium element in the whole process is 79.44%.
Starting from the requirement of roasting sodium salt additive, the invention starts from the conversion of primary sodium salt system (converting sulfate into sodium hydroxide) and the conversion of secondary sodium salt (converting sodium hydroxide into sodium bicarbonate), solves the contradiction between the requirement and the reality, realizes the recycling of sodium salt, solves the problem of disposing mixed sodium sulfate salt, reduces the consumption of purchased sodium carbonate and reduces the production cost.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A method for treating sodium-containing wastewater in a vanadium slag sodium modification vanadium extraction process is characterized by comprising the following steps:
s1, performing sodium salt roasting on vanadium slag, and then leaching a sodium vanadate solution to precipitate calcium vanadate by using lime to realize sodium-vanadium separation, and performing solid-liquid separation to obtain calcium vanadate solid and sodium-containing wastewater taking sodium hydroxide as a main component;
s2, purifying the sodium-containing wastewater to remove calcium ions in the sodium-containing wastewater, and performing solid-liquid separation to obtain purified residues and purified sodium-containing wastewater;
s3, evaporating and concentrating the purified sodium-containing wastewater to obtain evaporated condensate water and an evaporated concentrate;
s4, carbonating the evaporation concentrated solution by using carbon dioxide, and carrying out solid-liquid separation to obtain sodium bicarbonate solid and sodium bicarbonate mother liquor;
s5, returning the sodium bicarbonate mother liquor to an evaporation concentration system for circular treatment; returning the sodium bicarbonate solid to a vanadium slag sodium roasting system for cyclic utilization; returning the evaporation condensate water to a vanadium slag sodium salt roasting clinker water leaching system for cyclic utilization; the calcium vanadate solid is used for preparing a vanadium oxide product.
2. The sodium salt recycling method in the vanadium slag sodium salt extraction process of claim 1, wherein in the step S1, the water immersion sodium vanadate solution is a water immersion solution of vanadium slag sodium salt roasting clinker, the vanadium content is 15-60 g/l, the sodium content is 20-80 g/l, and the pH value is more than 9.
3. The method for treating the sodium-containing wastewater in the sodium salt extraction process of vanadium slag according to claim 1, wherein in step S1, the calcium salt for precipitating calcium vanadate with lime is one or more of calcium oxide and calcium hydroxide.
4. The method for treating the sodium-containing wastewater in the sodium salt extraction process of vanadium slag according to claim 1, wherein in the step S1, the calcium/vanadium molar ratio is controlled to be 1.5-2.0 in the sodium-vanadium separation process of the calcium vanadate precipitated by lime; the end point of precipitation is reached when the vanadium content is below 0.10 g/l.
5. The method for treating the sodium-containing wastewater in the sodium salt extraction process of vanadium slag according to claim 1, wherein in step S2, the purifying agent for purifying the sodium-containing wastewater is one or more of sodium carbonate and carbon dioxide.
6. The method for treating sodium-containing wastewater in the sodium salt extraction process of vanadium slag as claimed in claim 5, wherein in step S2, when the purifying agent is sodium carbonate, the addition amount of sodium carbonate is Ca/Na 2 CO 3 The molar ratio is 1.0-1.5.
7. The method for treating sodium-containing wastewater in the process of sodium modification and vanadium extraction of vanadium slag according to claim 1, wherein in the step S3, the sodium hydroxide content of the evaporation concentrate is 20-40% in the evaporation concentration process.
8. The method for treating sodium-containing wastewater in the sodium salt extraction process of vanadium slag according to claim 1, wherein in step S4, the carbon dioxide is outsourced industrial carbon dioxide.
9. The method for treating the sodium-containing wastewater in the sodium salt vanadium extraction process of the vanadium slag as claimed in claim 1, wherein in the step S4, the pH value at the carbonation end point is controlled to be 8.0-8.5 in the carbonation process of the carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211041688.9A CN115321737A (en) | 2022-08-29 | 2022-08-29 | Method for treating sodium-containing wastewater in vanadium slag sodium modification vanadium extraction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211041688.9A CN115321737A (en) | 2022-08-29 | 2022-08-29 | Method for treating sodium-containing wastewater in vanadium slag sodium modification vanadium extraction process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115321737A true CN115321737A (en) | 2022-11-11 |
Family
ID=83928871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211041688.9A Pending CN115321737A (en) | 2022-08-29 | 2022-08-29 | Method for treating sodium-containing wastewater in vanadium slag sodium modification vanadium extraction process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115321737A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506285A (en) * | 2015-12-21 | 2016-04-20 | 中南大学 | Method for separating vanadium and chromium from vanadium or/and chromium-contained solution |
| CN105821221A (en) * | 2016-03-28 | 2016-08-03 | 河北钢铁股份有限公司承德分公司 | Method for producing vanadium products cleanly with vanadium-containing raw materials |
| CN109837384A (en) * | 2019-03-14 | 2019-06-04 | 广东省稀有金属研究所 | A kind of sodium roasting vanadium-extracting technique |
| CN110358935A (en) * | 2019-08-15 | 2019-10-22 | 攀钢集团钒钛资源股份有限公司 | The method of vanadium and sodium is recycled from sodium vanadate solution |
| CN110408789A (en) * | 2019-09-11 | 2019-11-05 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of sodium is recycled from solution containing vanadium |
-
2022
- 2022-08-29 CN CN202211041688.9A patent/CN115321737A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506285A (en) * | 2015-12-21 | 2016-04-20 | 中南大学 | Method for separating vanadium and chromium from vanadium or/and chromium-contained solution |
| CN105821221A (en) * | 2016-03-28 | 2016-08-03 | 河北钢铁股份有限公司承德分公司 | Method for producing vanadium products cleanly with vanadium-containing raw materials |
| CN109837384A (en) * | 2019-03-14 | 2019-06-04 | 广东省稀有金属研究所 | A kind of sodium roasting vanadium-extracting technique |
| CN110358935A (en) * | 2019-08-15 | 2019-10-22 | 攀钢集团钒钛资源股份有限公司 | The method of vanadium and sodium is recycled from sodium vanadate solution |
| CN110408789A (en) * | 2019-09-11 | 2019-11-05 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of sodium is recycled from solution containing vanadium |
Non-Patent Citations (1)
| Title |
|---|
| 杨守志编著: "《国外钒冶金》", 冶金工业出版社, pages: 158 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102093004B1 (en) | Method for comprehensive recovery of magnesium-containing smelting wastewater | |
| CN103146930B (en) | Method for preparing vanadium oxide | |
| CN107445209B (en) | Method for preparing saturated manganese sulfate slurry and manganese sulfate by removing manganese dithionate in pyrolusite slurry leaching solution | |
| CN106517621B (en) | Recycling process of ammonium chloride-containing wastewater | |
| CN104404274B (en) | A kind of method from reclaiming vanadium containing precipitate and separate vanadium solution | |
| CN108707748B (en) | Method for purifying stone coal pickle liquor and recovering aluminum, potassium and iron | |
| CN110002415B (en) | Method for recovering phosphate radicals and sulfate radicals from iron phosphate production wastewater | |
| CN102070198A (en) | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron | |
| CN106319214B (en) | It is a kind of from acid more methods of the impurity containing precipitation direct in vanadium solution | |
| CN109207717B (en) | Method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water extract | |
| CN104775041A (en) | Clean vanadium extraction method for self-circulation utilization of vanadium-solution-calcium-process precipitated vanadium, mother liquor and solid waste | |
| CN101182037A (en) | Method for reclaiming vanadium oxide from dephosphorization underflow slag | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN102336437A (en) | Process for producing vanadium pentoxide by vanadium-contained solution | |
| CN108728649B (en) | Method for resource utilization of stone coal acidic wastewater | |
| CN111748702A (en) | Method for preparing vanadium oxide and circulating sodium and ammonium by using vanadium solution | |
| CN106629847B (en) | Method for preparing vanadium trioxide from sodium vanadate | |
| CN102531055A (en) | Method for preparing sodium metavanadate/potassium metavanadate | |
| CN113896209A (en) | Method for preparing sodium carbonate and byproducts potassium sulfate, ammonium sulfate and ammonium chloride from waste salt | |
| CN1390786A (en) | Process for preparing standard sodium carbonate from sodium sulfate | |
| CA2653718A1 (en) | Process to produce sodium sulfate and magnesium hydroxide | |
| CN115321737A (en) | Method for treating sodium-containing wastewater in vanadium slag sodium modification vanadium extraction process | |
| CN115536124B (en) | Quality and efficiency improving method for ammonium sulfate product produced by using flue gas desulfurization wastewater by adopting ammonia-acid method | |
| CN115108584B (en) | Method for efficiently preparing vanadium pentoxide and calcium carbonate by utilizing calcium vanadate | |
| CN114182112B (en) | Method for extracting vanadium and recycling medium by carbonation leaching of vanadium slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |