CN114644358A - Method for comprehensively utilizing ammonium salt-containing wastewater after vanadium extraction - Google Patents
Method for comprehensively utilizing ammonium salt-containing wastewater after vanadium extraction Download PDFInfo
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- CN114644358A CN114644358A CN202210276396.7A CN202210276396A CN114644358A CN 114644358 A CN114644358 A CN 114644358A CN 202210276396 A CN202210276396 A CN 202210276396A CN 114644358 A CN114644358 A CN 114644358A
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- ammonium salt
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- 239000002351 wastewater Substances 0.000 title claims abstract description 100
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 52
- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000605 extraction Methods 0.000 title claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 67
- 239000000706 filtrate Substances 0.000 claims abstract description 58
- 238000001914 filtration Methods 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 33
- 239000000047 product Substances 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 32
- 238000001704 evaporation Methods 0.000 claims abstract description 31
- 239000010446 mirabilite Substances 0.000 claims abstract description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000011780 sodium chloride Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000011812 mixed powder Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 16
- 239000001110 calcium chloride Substances 0.000 claims description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 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 description 8
- 239000003599 detergent Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000008247 solid mixture Substances 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 ammonium salt ions Chemical class 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 20
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for comprehensively utilizing waste water containing ammonium salt after vanadium extraction, which comprises the following steps: adding a separating agent into the wastewater containing ammonium salt after vanadium extraction; evaporating, concentrating and crystallizing the pretreated wastewater, filtering the concentrated solution after the Baume degree of the concentrated solution meets the requirement, and drying the filtered crystal after multi-stage washing to obtain a mirabilite finished product; evaporating, concentrating and crystallizing the filtrate, filtering the concentrated solution after the Baume degree of the concentrated solution meets the requirement, and drying the filtered crystal after multi-stage washing to obtain a mirabilite finished product; evaporating, concentrating and crystallizing the filtrate, filtering the concentrated solution after the Baume degree of the concentrated solution meets the requirement, and drying the filtered crystal after multi-stage washing to obtain a mirabilite finished product; and cooling and crystallizing the filtrate, and drying the filtered crystals after multistage washing to obtain the ammonium chloride finished product. The method has simple process, does not generate waste water and solid waste, is suitable for the comprehensive treatment of the vanadium extraction waste water by the ammonium method, and has extremely high recovery rates of ammonium salt and sulfate.
Description
Technical Field
The invention belongs to the technical field of comprehensive treatment of wastewater, and particularly relates to a method for comprehensively utilizing ammonium salt-containing wastewater after vanadium extraction.
Background
Vanadium is an important alloying element and is mainly used in the steel industry. The vanadium-containing steel has the excellent characteristics of high strength, high toughness, good wear resistance and the like, so that the vanadium-containing steel is widely applied to industries such as machinery, automobiles, shipbuilding, railways, aviation, bridges, electronic technologies, national defense industry and the like, the consumption of the vanadium-containing steel accounts for about 85 percent of the consumption of the vanadium, and the consumption of the steel industry accounts for the maximum proportion in the application of the vanadium. The demand of the steel industry directly influences the market quotation of vanadium. About 10% of vanadium is used to produce titanium alloys required by the aerospace industry. Vanadium can be used as a stabilizer and a reinforcer in the titanium alloy, so that the titanium alloy has good ductility and plasticity. In addition, vanadium is used primarily as a catalyst and colorant in the chemical industry. Vanadium has also been used to produce rechargeable hydrogen or vanadium redox batteries.
The vanadium extraction technology in China generally adopts a sodium salt roasting vanadium extraction technology to mix vanadium slag with sodium carbonate (Na)2CO3) Mixing the materials in proportion, roasting at high temperature, and leaching the roasted material to obtain sodium metavanadate solution. The solution is stirred with H under heating2SO4Neutralization by reaction with (NH)4)2SO4Precipitating vanadium to obtain red amorphous precipitate APV containing a large amount of water, washing, press-filtering, and melting vanadium to obtain V2O5Drying and reducing to obtain V2O3. Wherein, the waste water generated by the system mainly comprises the pressure filtrate after vanadium precipitation and APV washing liquid. At present, the waste waterContains high content of Na+、SO4 2+、NH4+、Cr6+、V5+、Cl-And so on.
The existing vanadium extraction wastewater treatment process comprises the following steps: and reducing the wastewater treated by the primary settling tank by using sodium metabisulfite, precipitating by using NaOH with the concentration of 30%, and performing filter pressing to form vanadium-chromium filter residue. The filtrate after heavy metal treatment contains a large amount of sodium sulfate and ammonium sulfate, multi-effect evaporation concentration is adopted, the concentrated solution after evaporation enters a salt precipitation pool, the salt precipitation pool is cooled and crystallized, the salt generated by crystallization is a compound salt of sodium sulfate and ammonium sulfate, the comprehensive utilization value is low, and the separated concentrated solution returns to multi-effect evaporation.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for the comprehensive utilization of ammonium salt-containing wastewater after vanadium extraction, comprising the steps of:
step one, adding a separating agent into the waste water containing ammonium salt after vanadium extraction, and adjusting the pH value;
step two, evaporating, concentrating and crystallizing the wastewater pretreated in the step one, filtering after the Baume degree of a concentrated solution meets the requirement, drying crystals obtained by filtering after multi-stage washing to obtain a mirabilite finished product, returning washing liquid to a primary concentration system, and feeding filtrate to the next process;
step three, evaporating, concentrating and crystallizing the filtrate obtained in the step two, filtering the concentrated solution after the Baume degree of the concentrated solution meets the requirement, drying the filtered crystal after multi-stage washing to obtain a mirabilite finished product, returning the washing solution to a primary concentration system, and feeding the filtrate to the next process;
step four, evaporating, concentrating and crystallizing the filtrate obtained in the step three, filtering the concentrated solution after the Baume degree of the concentrated solution meets the requirement, drying the filtered crystal after multi-stage washing to obtain a mirabilite finished product, returning the washing solution to a primary concentration system, and feeding the filtrate to the next process;
and step five, cooling and crystallizing the filtrate obtained in the step four, drying the filtered crystals after multistage washing to obtain ammonium chloride finished products, and returning the filtrate to a tertiary concentration system.
Preferably, the separating agent in the first step is sodium chloride, and the molar mass of ammonium ions in the wastewater is 1: and adding sodium chloride into the waste water at a ratio of 0.8-1.05, wherein the pH value is adjusted by adding sulfuric acid and sodium hydroxide into the waste water containing ammonium salt, and the pH value is adjusted to be 6.5-7.
Preferably, the volume of the concentrated solution in the second step is reduced to 20-50% of the volume of the original wastewater, and the concentration baume degree is required to be 24-30 baume degrees; the detergent in the second step is steam condensate water for concentration, and the washing times are 2-5 times; the drying temperature in the second step is 150-400 ℃.
Preferably, the volume of the concentrated solution in the third step is reduced to 5-20% of the volume of the original wastewater, and the concentration baume degree is required to be 20-25 baume degrees; the detergent in the third step is steam condensate water for concentration, and the washing times are 2-5 times; the drying temperature in the third step is 150-.
Preferably, the volume of the concentrated solution in the step four is reduced to 5-10% of the volume of the original wastewater, and the concentration baume degree is required to be 20-25 baume degrees; the detergent in the fourth step is steam condensate water for concentration, and the washing times are 2-5 times; the drying temperature in the fourth step is 150-400 ℃.
Preferably, the temperature for cooling and crystallizing in the fifth step is 30-60 ℃; the detergent in the step five is steam condensate water for concentration, and the washing times are 2-5 times; the drying temperature in the fifth step is 50-100 ℃.
Preferably, the separating agent used in the first step is a composite separating agent, and the components of the composite separating agent comprise: 15-20 parts of sodium chloride powder and 5-8 parts of calcium chloride powder; the preparation method of the composite separating agent comprises the following steps:
step S11, uniformly mixing sodium chloride and calcium chloride powder to obtain mixed powder, adding the mixed powder into 200-300 parts of an alcohol solution, uniformly stirring at a rotating speed of 1050-2300 r/min, and heating and preserving heat to 40-50 ℃ to obtain mixed slurry;
s12, performing ultrasonic dispersion on the mixed slurry by using an ultrasonic dispersion instrument, wherein the ultrasonic dispersion frequency is 50-60 kHz, the dispersion time is 30-40 min, so as to obtain dispersed slurry, and evaporating, concentrating and washing so as to obtain a solid mixture; drying the solid mixture at 80-200 ℃, and crushing to obtain 10-200 mesh solid mixed powder;
step S13, putting the solid mixed powder obtained in the step S12 into a calcining furnace, calcining at 500-600 ℃ for 1.5-2 h, and continuously introducing nitrogen into the calcining furnace at a nitrogen introduction rate of 20-48 sccm during calcining; and (3) obtaining a mixed calcined substance, carrying out ball milling on the mixed calcined substance, wherein a ball milling medium is a zirconia sphere, and carrying out ball milling to obtain the composite separating agent with 200-300 meshes.
Preferably, the alcohol solution used in step S11 is one of a methanol solution, an ethanol solution or an ethylene glycol solution, wherein the mass fraction of the methanol solution is 65%, the mass fraction of the ethanol solution is 60%, and the mass fraction of the ethylene glycol solution is 68%.
Preferably, the molar mass ratio of ammonium ions in the wastewater is 1: 1.1-1.8 adding a composite separating agent, and adjusting the pH value of the wastewater containing ammonium salt to 5-6 by using sulfuric acid before adding the composite separating agent; after the composite separating agent is put into the reactor, a small amount of calcium vanadate precipitate is generated in the ammonium salt-containing wastewater, sodium hydroxide is added after the calcium vanadate precipitate is separated out, the pH value of the solution is adjusted to 7, a small amount of sodium carbonate is added to remove redundant calcium ions in the filtrate, and the adding amount of the sodium carbonate is one tenth of the mass of calcium chloride powder in the composite separating agent.
The invention at least comprises the following beneficial effects:
1. on the basis of vanadium extraction wastewater treatment, the treatment mode of salt-containing wastewater is changed, only sulfate in the wastewater can be recycled, and the produced mirabilite and ammonium chloride meet the national standard.
2. Realizes the comprehensive cyclic utilization of waste water, realizes the zero discharge of three wastes and meets the requirements of modern novel green, safe and environment-friendly chemical enterprises.
3. Meanwhile, the invention reduces the pollution risk of the ammonium-containing waste salt stockpiling to the environment.
4. According to the method for comprehensively utilizing the ammonium salt-containing wastewater after vanadium extraction, the ammonium salt-containing wastewater is subjected to separation pretreatment by using the composite separating agent consisting of sodium chloride and calcium chloride, and a small amount of vanadium element which is not completely extracted is separated by the calcium chloride, so that the extraction rate of the vanadium element is greatly improved; sodium carbonate is then added to remove the balance of the calcium ions so that the solution is free of calcium ions. In the preparation method of the composite separating agent, the sodium chloride powder and the calcium chloride powder are firstly put into the alcohol solution, and the ultrasonic dispersion instrument is used for carrying out ultrasonic dispersion on the mixed slurry, so that the mixing uniformity of the calcium chloride and the sodium chloride in the mixed slurry is improved, the mixed slurry has higher dispersibility, and the sodium chloride and the calcium chloride are prevented from agglomerating in the mixed slurry; and finally, the dispersed solid mixed powder is treated by calcining and ball milling, so that the solid mixed powder has better shearing force resistance mechanical property by calcining, and the solid mixed powder is conveniently subjected to full ball milling and crushing in the full subsequent process, thereby obtaining more uniform mixed powder with smaller particle size. The composite separating agent prepared by the method can fully react with the waste water after being added into the waste water containing ammonium salt, thereby improving the conversion rate of mirabilite and ammonium chloride.
5. According to the method, sodium chloride is used as a separating agent, and after the sodium chloride is added into the wastewater containing ammonium salt, the content of sodium sulfate in the wastewater is increased, so that a large amount of mirabilite is rapidly separated out in the subsequent concentration and crystallization process, the yield of the mirabilite is increased, and the production efficiency is improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is described in further detail below to enable those skilled in the art to practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
A method for comprehensively utilizing waste water containing ammonium salt after vanadium extraction comprises the following steps:
step one, wastewater pretreatment: 2L of ammonium salt-containing wastewater (NH) after vanadium extraction4 +The concentration of the ammonium salt is 6.7g/L), adding 17.5g of sodium chloride, and adding sulfuric acid and sodium hydroxide into the waste water containing the ammonium salt to adjust the pH value of the waste water to 7;
step two, primary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the wastewater pretreated in the step one, filtering after the Baume degree of a concentrated solution reaches 27.1 (the volume is reduced to 30% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 134.26g of mirabilite finished products, wherein the main content is 94.45%, and returning washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step three, secondary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the second step, filtering after the Baume degree of the concentrated solution reaches 26.0 (the volume is reduced to 20% of the volume of the original wastewater), washing crystals obtained by filtering with distilled water, drying at 150 ℃ to obtain 62.87g of mirabilite finished products with main content of 92.16%, and returning the washing liquid to the primary concentration system. The filtrate enters the next working procedure;
step four, concentration and crystallization for three times: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the third step, filtering after the Baume degree of the concentrated solution reaches 25.5 (the volume is reduced to 10% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 51.24g of mirabilite finished products, wherein the main content is 92.94%, and returning the washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step five, cooling and crystallizing: and cooling and crystallizing the filtrate obtained in the fourth step at 40 ℃, washing the crystal obtained by filtering with distilled water, drying at 80 ℃ to obtain 43.15g of finished ammonium chloride product with the main content of 93.11%, and returning the filtrate to a tertiary concentration system.
Example 2
A method for comprehensively utilizing waste water containing ammonium salt after vanadium extraction comprises the following steps:
step one, wastewater pretreatment: 2L of wastewater containing ammonium salt after vanadium extraction(NH4 +The concentration of the ammonium salt is 6.7g/L), adding 20g of sodium chloride, adding sulfuric acid and sodium hydroxide into the waste water containing ammonium salt to adjust the pH value of the waste water to 7;
step two, primary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the wastewater pretreated in the step one, filtering after the Baume degree of a concentrated solution reaches 27.5 (the volume is reduced to 28% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 144.22g of mirabilite finished products, wherein the main content is 95.27%, and returning washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step three, secondary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the second step, filtering after the Baume degree of the concentrated solution reaches 26.4 (the volume is reduced to 18% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 69.53g of mirabilite finished products, wherein the main content is 93.31%, and returning the washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step four, concentration and crystallization for three times: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the third step, filtering after the Baume degree of the concentrated solution reaches 25.1 (the volume is reduced to 7% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 60.21g of mirabilite finished products, wherein the main content is 91.56%, and returning the washing solution to a primary concentration system. The filtrate enters the next working procedure;
step five, cooling and crystallizing: and cooling and crystallizing the filtrate obtained in the fourth step at 40 ℃, washing the crystal obtained by filtering with distilled water, drying at 80 ℃ to obtain 44.98g of finished ammonium chloride product with the main content of 90.57%, and returning the filtrate to a third concentration system.
Example 3
A method for comprehensively utilizing waste water containing ammonium salt after vanadium extraction comprises the following steps:
step one, wastewater pretreatment: 2L of wastewater (NH) containing ammonium salt after vanadium extraction4 +The concentration of the ammonium salt is 6.7g/L), 22g of sodium chloride is added, and sulfuric acid and sodium hydroxide are added into the waste water containing ammonium salt to adjust the pH value of the waste water to 7;
step two, primary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the wastewater pretreated in the first step, filtering after the Baume degree of a concentrated solution reaches 27.6 (the volume is reduced to 28% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 145.53g of mirabilite finished products, wherein the main content is 95.95%, and returning washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step three, secondary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the second step, filtering after the Baume degree of the concentrated solution reaches 26.4 (the volume is reduced to 18% of the volume of the original wastewater), washing crystals obtained by filtering with distilled water, drying at 150 ℃ to obtain 70.27g of mirabilite finished products with the main content of 93.36%, and returning the washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step four, concentration and crystallization for three times: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the third step, filtering after the Baume degree of the concentrated solution reaches 25.1 (the volume is reduced to 7% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 60.99g of mirabilite finished products, wherein the main content is 90.57%, and returning the washing solution to a primary concentration system. The filtrate enters the next working procedure;
step five, cooling and crystallizing: and cooling and crystallizing the filtrate obtained in the fourth step at 40 ℃, washing the crystal obtained by filtering with distilled water, drying at 80 ℃ to obtain 45.67g of finished ammonium chloride product with the main content of 91.49%, and returning the filtrate to a tertiary concentration system.
Example 4
A method for comprehensively utilizing waste water containing ammonium salt after vanadium extraction comprises the following steps:
step one, wastewater pretreatment: 2L of ammonium salt-containing wastewater (NH) after vanadium extraction4 +With the concentration of 6.7g/L) was added 17.5g of a composite separating agent; wherein, the components of the composite separating agent comprise: 15g of sodium chloride powder and 5g of calcium chloride powder; the preparation method of the composite separating agent comprises the following steps:
step S11, uniformly mixing sodium chloride and calcium chloride powder to obtain mixed powder, adding the mixed powder into 200g of ethanol solution, uniformly stirring the ethanol solution with the mass fraction of 60% at the rotating speed of 1050r/min, and heating and preserving the temperature to 40 ℃ to obtain mixed slurry;
s12, performing ultrasonic dispersion on the mixed slurry by using an ultrasonic dispersion instrument, wherein the ultrasonic dispersion frequency is 50kHz, the dispersion time is 30min, obtaining dispersed slurry, and evaporating, concentrating and washing to obtain a solid mixture; drying the solid mixture at 110 ℃, and crushing to obtain 50-mesh solid mixed powder;
step S13, putting the solid mixed powder obtained in the step S12 into a calcining furnace, calcining at 500 ℃ for 1.5h, and continuously introducing nitrogen into the calcining furnace at a nitrogen introduction rate of 20sccm during calcining; and (3) obtaining a mixed calcined substance, carrying out ball milling on the mixed calcined substance, wherein a ball milling medium is a zirconia sphere, and carrying out ball milling to obtain the 200-mesh composite separating agent.
Before the compound separating agent is put into use, firstly, sulfuric acid is used for adjusting the pH value of the waste water containing ammonium salt to 6; after the compound separating agent is put into the waste water containing ammonium salt, a small amount of calcium vanadate precipitate is generated, sodium hydroxide is added after the calcium vanadate precipitate is separated out, the pH value of the solution is adjusted to 7, a small amount of sodium carbonate is added to remove redundant calcium ions in the filtrate, and the adding amount of the sodium carbonate is 0.5 g.
Step two, primary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the wastewater pretreated in the step one, filtering after the Baume degree of a concentrated solution reaches 27.1 (the volume is reduced to 30% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 146.48g of mirabilite finished products, wherein the main content is 96.56%, and returning washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step three, secondary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the second step, filtering after the Baume degree of the concentrated solution reaches 26.0 (the volume is reduced to 20% of the volume of the original wastewater), washing crystals obtained by filtering with distilled water, drying at 150 ℃ to obtain 60.15g of mirabilite finished products with the main content of 93.86%, and returning the washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step four, concentration and crystallization for three times: and (4) evaporating, concentrating and crystallizing the filtrate obtained in the step three, filtering after the Baume degree of the concentrated solution reaches 25.5 (the volume is reduced to 10% of the volume of the original wastewater), washing crystals obtained by filtering with distilled water, drying at 150 ℃ to obtain 52.36g of mirabilite finished products with main content of 94.43%, and returning the washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step five, cooling and crystallizing: and cooling and crystallizing the filtrate obtained in the fourth step at 40 ℃, washing the crystal obtained by filtering with distilled water, drying at 80 ℃ to obtain 48.20g of finished ammonium chloride product with the main content of 93.31%, and returning the filtrate to a tertiary concentration system.
Example 5
A method for comprehensively utilizing waste water containing ammonium salt after vanadium extraction comprises the following steps:
step one, wastewater pretreatment: 2L of ammonium salt-containing wastewater (NH) after vanadium extraction4 +The concentration of the sodium chloride is 6.7g/L) is added with 17.5g of composite separating agent; wherein, the components of the composite separating agent comprise: according to the weight portion, 20g of sodium chloride powder and 8g of calcium chloride powder; the preparation method of the composite separating agent comprises the following steps:
step S11, uniformly mixing sodium chloride and calcium chloride powder to obtain mixed powder, adding the mixed powder into 300g of ethanol solution, uniformly stirring the ethanol solution at the mass fraction of 60% at the rotating speed of 2300r/min, and heating and preserving the temperature to 50 ℃ to obtain mixed slurry;
s12, performing ultrasonic dispersion on the mixed slurry by using an ultrasonic dispersion instrument, wherein the ultrasonic dispersion frequency is 60kHz, and the dispersion time is 40min to obtain dispersed slurry, and evaporating, concentrating and washing to obtain a solid mixture; drying the solid mixture at 120 ℃, and crushing to obtain 150-mesh solid mixed powder;
step S13, putting the solid mixed powder obtained in the step S12 into a calcining furnace, calcining at 550 ℃ for 2 hours, and continuously introducing nitrogen into the calcining furnace at a nitrogen introduction rate of 48sccm during calcining; and (3) obtaining a mixed calcined substance, carrying out ball milling on the mixed calcined substance, wherein a ball milling medium is a zirconia sphere, and carrying out ball milling to obtain the 300-mesh composite separating agent.
Before the composite separating agent is added, the pH value of the ammonium salt-containing wastewater is adjusted to 6 by using sulfuric acid; after the compound separating agent is put into the waste water containing ammonium salt, a small amount of calcium vanadate precipitate is generated, sodium hydroxide is added after the calcium vanadate precipitate is separated out, the pH value of the solution is adjusted to 7, a small amount of sodium carbonate is added to remove redundant calcium ions in the filtrate, and the adding amount of the sodium carbonate is 0.8 g.
Step two, primary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the wastewater pretreated in the step one, filtering after the Baume degree of a concentrated solution reaches 27.1 (the volume is reduced to 30% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 148.54g of mirabilite finished products, wherein the main content is 96.47%, and returning washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step three, secondary concentration and crystallization: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the second step, filtering after the Baume degree of the concentrated solution reaches 26.0 (the volume is reduced to 20% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 63.26g of mirabilite finished products, wherein the main content is 93.74%, and returning the washing liquid to a primary concentration system. The filtrate enters the next working procedure;
step four, concentrating and crystallizing for three times: and (3) evaporating, concentrating and crystallizing the filtrate obtained in the third step, filtering after the Baume degree of the concentrated solution reaches 25.5 (the volume is reduced to 10% of the volume of the original wastewater), washing crystals obtained by filtering by using distilled water, drying at 150 ℃ to obtain 58.38g of mirabilite finished products, wherein the main content is 94.22%, and returning the washing solution to a primary concentration system. The filtrate enters the next working procedure;
step five, cooling and crystallizing: and cooling and crystallizing the filtrate obtained in the fourth step at 40 ℃, washing the crystal obtained by filtering with distilled water, drying at 80 ℃ to obtain 48.76g of ammonium chloride finished product with main content of 95.64%, and returning the filtrate to a tertiary concentration system.
It can be seen from the above examples that the method provided by the present invention is adopted to treat the ammonium salt-containing wastewater to obtain the finished products of mirabilite and ammonium chloride with high yield and high main content, thereby realizing the recycling of sulfate ions and ammonium ions in the ammonium salt-containing wastewater and reducing the pollution to the environment. After the ammonium salt-containing wastewater is pretreated by using the composite separating agent consisting of sodium chloride and calcium chloride, the residual vanadium element is recovered, and the recovery rates of mirabilite and ammonium chloride are further improved.
The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be apparent to those skilled in the art.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the examples shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (9)
1. A method for comprehensively utilizing waste water containing ammonium salt after vanadium extraction is characterized by comprising the following steps:
step one, adding a separating agent into the waste water containing ammonium salt after vanadium extraction, and adjusting the pH value;
step two, evaporating, concentrating and crystallizing the wastewater pretreated in the step one, filtering after the baume degree of a concentrated solution meets the requirement, drying crystals obtained by filtering after multi-stage washing to obtain a mirabilite finished product, returning washing liquid to a primary concentration system, and feeding filtrate to the next process;
step three, evaporating, concentrating and crystallizing the filtrate obtained in the step two, filtering the concentrated solution after the Baume degree of the concentrated solution meets the requirement, drying the filtered crystal after multi-stage washing to obtain a mirabilite finished product, returning the washing solution to a primary concentration system, and feeding the filtrate to the next process;
step four, evaporating, concentrating and crystallizing the filtrate obtained in the step three, filtering the concentrated solution after the Baume degree of the concentrated solution meets the requirement, drying the filtered crystal after multi-stage washing to obtain a mirabilite finished product, returning the washing solution to a primary concentration system, and feeding the filtrate to the next process;
and step five, cooling and crystallizing the filtrate obtained in the step four, drying the filtered crystals after multistage washing to obtain ammonium chloride finished products, and returning the filtrate to a tertiary concentration system.
2. The method for comprehensively utilizing the ammonium salt-containing wastewater after vanadium extraction according to claim 1, wherein the separating agent in the first step is sodium chloride, and the mass ratio of the separating agent to the ammonium salt ions in the wastewater is 1: and adding sodium chloride into the waste water at a ratio of 0.8-1.05, wherein the pH value is adjusted by adding sulfuric acid and sodium hydroxide into the waste water containing ammonium salt, and the pH value is adjusted to be 6.5-7.
3. The method for comprehensively utilizing the ammonium salt-containing wastewater after vanadium extraction according to claim 1, wherein the volume of the concentrated solution in the second step is reduced to 20-50% of the volume of the original wastewater, and the concentration Baume degree is required to be 24-30 Baume degrees; the detergent in the second step is steam condensate water for concentration, and the washing times are 2-5 times; the drying temperature in the second step is 150-400 ℃.
4. The method for comprehensively utilizing the ammonium salt-containing wastewater after vanadium extraction according to claim 1, wherein the volume of the concentrated solution in the third step is reduced to 5-20% of the volume of the original wastewater, and the concentration baume degree is required to be 20-25 baume degrees; the detergent in the third step is steam condensate water for concentration, and the washing times are 2-5 times; the drying temperature in the third step is 150-400 ℃.
5. The method for comprehensively utilizing the ammonium salt-containing wastewater after vanadium extraction according to claim 1, wherein the volume of the concentrated solution in the fourth step is reduced to 5-10% of the volume of the original wastewater, and the concentration baume degree is required to be 20-25 baume degrees; the detergent in the fourth step is steam condensate water for concentration, and the washing times are 2-5 times; the drying temperature in the fourth step is 150-400 ℃.
6. The method for comprehensively utilizing the ammonium salt-containing wastewater after vanadium extraction according to claim 1, wherein the cooling crystallization temperature in the fifth step is 30-60 ℃; the detergent in the step five is steam condensate water for concentration, and the washing times are 2-5 times; the drying temperature in the fifth step is 50-100 ℃.
7. The method for comprehensively utilizing the ammonium salt-containing wastewater after vanadium extraction according to claim 1, wherein the separating agent used in the first step is a composite separating agent, and the components of the composite separating agent comprise: 15-20 parts of sodium chloride powder and 5-8 parts of calcium chloride powder; the preparation method of the composite separating agent comprises the following steps:
step S11, uniformly mixing sodium chloride and calcium chloride powder to obtain mixed powder, adding the mixed powder into 200-300 parts of alcohol solution, uniformly stirring at the rotating speed of 1050-2300 r/min, and heating and preserving heat to 40-50 ℃ to obtain mixed slurry;
s12, performing ultrasonic dispersion on the mixed slurry by using an ultrasonic dispersion instrument, wherein the ultrasonic dispersion frequency is 50-60 kHz, the dispersion time is 30-40 min, so as to obtain dispersed slurry, and evaporating, concentrating and washing so as to obtain a solid mixture; drying the solid mixture at 80-200 ℃, and crushing to obtain 10-200 mesh solid mixed powder;
step S13, putting the solid mixed powder obtained in the step S12 into a calcining furnace, calcining at 500-600 ℃ for 1.5-2 h, and continuously introducing nitrogen into the calcining furnace at a nitrogen introduction rate of 20-48 sccm during calcining; and (3) obtaining a mixed calcined substance, carrying out ball milling on the mixed calcined substance, wherein a ball milling medium is a zirconia sphere, and carrying out ball milling to obtain the composite separating agent with 200-300 meshes.
8. The method for comprehensively utilizing ammonium salt-containing wastewater after vanadium extraction according to claim 7, wherein the alcohol solution used in the step S11 is one of a methanol solution, an ethanol solution or an ethylene glycol solution, wherein the mass fraction of the methanol solution is 65%, the mass fraction of the ethanol solution is 60%, and the mass fraction of the ethylene glycol solution is 68%.
9. The method for comprehensively utilizing ammonium salt-containing wastewater after vanadium extraction according to claim 7, wherein the molar mass of ammonium ions in the wastewater is 1: 1.1-1.8 adding a composite separating agent, and adjusting the pH value of the wastewater containing ammonium salt to 5-6 by using sulfuric acid before adding the composite separating agent; after the composite separating agent is put into the reactor, a small amount of calcium vanadate precipitate is generated in the ammonium salt-containing wastewater, sodium hydroxide is added after the calcium vanadate precipitate is separated out, the pH value of the solution is adjusted to 7, a small amount of sodium carbonate is added to remove redundant calcium ions in the filtrate, and the adding amount of the sodium carbonate is one tenth of the mass of calcium chloride powder in the composite separating agent.
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| US20180305221A1 (en) * | 2017-04-21 | 2018-10-25 | China Petroleum & Chemical Corporation | Apparatus and Method for Treating Waste Water Containing Ammonium Salts |
| US20190169056A1 (en) * | 2017-12-04 | 2019-06-06 | Aquatech International, Llc | Salt production from wastewater |
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