CN113428877A - Method for recycling solid waste containing heavy metal, sodium salt and ammonium salt - Google Patents
Method for recycling solid waste containing heavy metal, sodium salt and ammonium salt Download PDFInfo
- Publication number
- CN113428877A CN113428877A CN202110696867.5A CN202110696867A CN113428877A CN 113428877 A CN113428877 A CN 113428877A CN 202110696867 A CN202110696867 A CN 202110696867A CN 113428877 A CN113428877 A CN 113428877A
- Authority
- CN
- China
- Prior art keywords
- solid waste
- heavy metals
- sodium
- containing heavy
- ammonium
- 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
- 239000002910 solid waste Substances 0.000 title claims abstract description 63
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 45
- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 38
- 159000000000 sodium salts Chemical class 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 41
- 230000008025 crystallization Effects 0.000 claims abstract description 39
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 38
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 38
- 238000001816 cooling Methods 0.000 claims abstract description 31
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 42
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 41
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 39
- 239000013078 crystal Substances 0.000 claims description 31
- 235000011152 sodium sulphate Nutrition 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 229910052720 vanadium Inorganic materials 0.000 description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- 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
- C01D5/04—Preparation of sulfates with the aid of sulfurous acid or sulfites, e.g. Hargreaves process
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recycling solid waste containing heavy metals, sodium salts and ammonium salts, and belongs to the technical field of metallurgical and chemical engineering. The method for recycling the solid waste containing heavy metals, sodium salts and ammonium salts comprises the following steps: a. crushing, ball milling, dissolving, and removing impurities by using a reducing agent; b. reducing, adding alkali for neutralization, and recovering heavy metal and nonmetal substances; c. cooling for crystallization, filtering, dissolving for crystallization, cooling for secondary crystallization to obtain high-purity Na2SO4·10H2And O. The method has simple process, recycles and recovers energy and substances in the operation process, efficiently recycles the solid wastes containing heavy metals, sodium salts and ammonium salts by adopting lower cost, and recovers the Na2SO4·10H2The purity of O is more than or equal to 98 percent, and the problem of the prior art on recycling is effectively solvedThe problem of low quality of recovered articles of solid wastes containing heavy metals, sodium salts and ammonium salts is solved.
Description
Technical Field
The invention belongs to the technical field of metallurgical chemical industry, and particularly relates to a method for recycling solid waste containing heavy metals, sodium salts and ammonium salts.
Background
The waste water produced in the production process of most metallurgy industries not only contains ions such as chromium and vanadium, but also contains more salts such as sodium sulfate and ammonium sulfate, heavy metals chromium and vanadium belong to toxic substances and have great influence on the environment and human health, and the waste water contains the salts such as sodium sulfate and ammonium sulfate and can also cause the pollution of water, for example, the vanadium precipitation solid waste in the production of the vanadium metallurgy industries.
At present, the treatment process of 'reduction neutralization-evaporation concentration' is mostly adopted for vanadium precipitation wastewater generated in the vanadium chemical industry vanadium precipitation process, various components of a concentrated crystallization mixture are complex, the components with the largest content are sodium salts and ammonium salts, and a small amount of heavy metal and other nonmetal mixed crystals are accompanied, so that great difficulty is brought to subsequent treatment and utilization.
At present, the method for treating the mixed crystallization solid waste containing heavy metals, sodium salts and ammonium salts mainly comprises the following steps:
1. preparing solid waste materials → calcining in a converter → dissolving alkali and precipitating → washing slag → precipitating → evaporating and concentrating → tabletting and packaging to prepare the industrial sodium sulfide. The method has the advantages of high cost, more pollution discharge nodes, serious secondary environmental pollution, poor finished product quality, complex equipment and poor benefit.
2. Mechanical impurity removal → crystallization treatment is carried out on the solid waste, although the method separates sodium salt and ammonium salt, the components are separated thoroughly, and the solid waste also contains a small amount of impurities of heavy metal and nonmetal components, which brings influence to the improvement of the quality of finished products.
3. And (4) drying the solid waste → spraying dust removal → carrying out crystallization → separation on the solution obtained after spraying → generating ammonium sulfate. Although the method can filter harmful gases generated by solid wastes and generate industrial ammonium sulfate, the method has the advantages of more input equipment, long operation flow and higher operation cost, cannot bring certain economic benefit and is not beneficial to popularization and development.
Therefore, the method for recycling the solid waste containing the heavy metals, the sodium salts and the ammonium salts, which is simple in process, low in operation cost and high in product quality, is developed, and the method for recycling the solid waste has important significance in recycling the solid waste.
Disclosure of Invention
The invention aims to solve the technical problem that the quality of recovered articles for recovering and treating solid wastes containing heavy metals, sodium salts and ammonium salts is low in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for recycling the solid waste containing heavy metals, sodium salts and ammonium salts comprises the following steps:
a. mechanically crushing solid waste containing heavy metals, sodium salts and ammonium salts, then ball-milling, adding a solvent, heating to 60-80 ℃ and dissolving to obtain waste liquid;
b. adjusting the pH of the waste liquid to 2.5-3, adding a reducing agent for full reaction, adjusting the pH to 6.5-7.2, and performing solid-liquid separation after precipitation to obtain a solution and precipitates of heavy metals and nonmetal;
c. b, sending the solution obtained in the step b into a cooling crystallization system, cooling to 5-8 ℃ for crystallization, and filtering to obtain sodium sulfate crystals and an ammonium sulfate solution;
d. c, adding water into the sodium sulfate crystals obtained in the step c, heating to 60-70 ℃ for dissolving, then sending into a cooling crystallization system, cooling to 5-8 ℃ for secondary crystallization, and filtering to obtain ammonium sulfate filtrate and high-purity Na2SO4·10H2O。
The solid waste containing heavy metal, sodium salt and ammonium salt mainly refers to vanadium precipitation solid waste, and also comprises other industrial production wastes containing heavy metal, sodium salt and ammonium salt.
In the step a, the solvent is at least one of water, the ammonium sulfate solution obtained in the step c and the ammonium sulfate filtrate obtained in the step d; the mass ratio of the solvent to the solid waste is controlled to be 1.2-2: 1.
Further, when the method is adopted for the first time, water is used as a solvent, and the mass ratio of the added water to the solid waste is 1.2-1.5: 1; in the subsequent production process, if the ammonium sulfate solution is used as a solvent, the mass ratio of the added ammonium sulfate solution to the solid waste is 1.5-2: 1; if the ammonium sulfate filtrate is used as the solvent, the mass ratio of the added ammonium sulfate filtrate to the solid waste is 1.2-1.4: 1.
In the step a, wet ball milling is adopted for ball milling.
When the concentration of the ammonium sulfate solution reaches 38-42 DEG Be, the (NH) is obtained by concentration and evaporation4)2SO4And (4) crystallizing.
In step b above, the pH is adjusted using sulfuric acid and NaOH.
In the step b, the mol ratio of the reducing agent to the heavy metal in the waste liquid is 0.7-0.9: 1.
The reducing agent is any one of sodium sulfite, sodium bisulfite and sodium thiosulfate.
Further, the reducing agent is sodium sulfite.
In the step d, the mass ratio of the added water to the sodium sulfate crystals is 1.0-1.4: 1.
In the step c, the solution obtained in the step b is cooled to 20-25 ℃ through a heat conduction system, and then enters a cooling crystallization system.
In the step d, the dissolved solution is cooled to 20-25 ℃ through a heat conduction system and then enters a cooling crystallization system.
Further, the heat obtained in the heat conduction system is returned to the temperature rise in the step a for use.
In the above steps c and d, the crystallization process is performed under stirring.
The heavy metal and nonmetal precipitates obtained in the step b can be used as raw materials of metal products.
(NH) obtained as described above4)2SO4The crystal can be used as an agricultural fertilizer material or for precipitating vanadium in the vanadium production industry.
The obtained high-purity Na2SO4·10H2The purity of O is more than or equal to 98 percent.
The invention has the beneficial effects that: the invention provides a method for recycling solid waste containing heavy metals, sodium salts and ammonium salts, which comprises the steps of completely dissolving the solid waste with a solvent at 60-80 ℃, adjusting the pH value of the solid waste, reducing the waste liquid with a reducing agent when the pH value is 2.5-3, ensuring that the reduction reaction is more complete, namely, the waste liquid can be reduced more completely, and then adjusting the pH value to 6.5-7.2, so that the heavy metals and partial non-metals in the solid waste can be completely precipitated.
Meanwhile, the method of the invention is adopted to reasonably classify the solid wastes (the mixture crystal containing heavy metal, sodium salt and ammonium salt), and the purity of the sodium sulfate crystal obtained by primary crystallization is not high, so that the purity of the sodium sulfate crystal is highOnly about 90 percent of ammonium salt is contained, and about 10 percent of ammonium salt is also contained, so in order to improve the purity and the quality of the sodium sulfate, the low-purity sodium sulfate crystal is dissolved, and the ammonium sulfate needs to be concentrated and evaporated at high temperature for crystallization, so that the ammonium salt in the solution can not be crystallized during secondary low-temperature crystallization, and the ammonium salt and Na can be well mixed2SO4·10H2Separating O to obtain Na with purity up to 98%2SO4·10H2And (4) O products. In order to control the production cost and reduce the energy loss, the temperature of the solution is reduced to 20-25 ℃ in advance through a heat conduction system before low-temperature crystallization, and the redundant heat obtained by cooling can be returned to a production line for use while the subsequent low-temperature crystallization energy consumption is reduced, so that the cost is further controlled.
The invention fully utilizes the circular conduction of energy, recycles heat, water and solvent, reduces energy consumption and lowers operation cost. In the process of recycling the ammonium sulfate solution, the concentration of the ammonium sulfate is gradually increased, and the ammonium sulfate is concentrated, evaporated and recovered (NH) after enrichment4)2SO4The crystal reaches the national industrial quality II-class standard, can be used as an agricultural fertilizer material or for precipitating vanadium in the vanadium production industry, and simultaneously, the invention also recycles heavy metals in solid wastes and can be used as raw materials of metal products. The method of the invention does not produce waste residue, waste water and smoke dust, does not produce secondary pollution, has simple process and low operation cost, and can obtain high-quality Na2SO4·10H2O，(NH4)2SO4Crystallization and heavy metals, and effectively resource utilization of solid wastes containing heavy metals, sodium salts and ammonium salts.
Drawings
FIG. 1 is a process flow diagram of the method for recycling solid waste containing heavy metals, sodium salts and ammonium salts.
Detailed Description
The technical solution of the present invention can be specifically implemented as follows.
The method for recycling the solid waste containing heavy metals, sodium salts and ammonium salts comprises the following steps:
a. mechanically crushing solid waste containing heavy metals, sodium salts and ammonium salts, then ball-milling, adding a solvent, heating to 60-80 ℃ and dissolving to obtain waste liquid;
b. adjusting the pH of the waste liquid to 2.5-3, adding a reducing agent for full reaction, adjusting the pH to 6.5-7.2, and performing solid-liquid separation after precipitation to obtain a solution and precipitates of heavy metals and nonmetal;
c. b, sending the solution obtained in the step b into a cooling crystallization system, cooling to 5-8 ℃ for crystallization, and filtering to obtain sodium sulfate crystals and an ammonium sulfate solution;
d. c, adding water into the sodium sulfate crystals obtained in the step c, heating to 60-70 ℃ for dissolving, then sending into a cooling crystallization system, cooling to 5-8 ℃ for secondary crystallization, and filtering to obtain ammonium sulfate filtrate and high-purity Na2SO4·10H2O。
In order to control the production cost and maximally utilize the solid waste as resources, it is preferable that the solvent in step a is at least one of water, the ammonium sulfate solution obtained in step c and the ammonium sulfate filtrate obtained in step d; the mass ratio of the solvent to the solid waste is controlled to be 1.2-2: 1. More preferably, when the method of the present invention is adopted for the first time, water is used as a solvent, and the mass ratio of the added water to the solid waste is 1.2-1.5: 1; in the subsequent production process, if the ammonium sulfate solution is used as a solvent, the mass ratio of the added ammonium sulfate solution to the solid waste is 1.5-2: 1; if the ammonium sulfate filtrate is used as a solvent, the mass ratio of the added ammonium sulfate filtrate to the solid waste is 1.2-1.4: 1; when the concentration of the ammonium sulfate solution reaches 38-42 DEG Be, the (NH) is obtained by concentration and evaporation4)2SO4And (4) crystallizing.
In order to fully react the solid wastes, it is preferable that the ball milling in the step a is wet ball milling.
In order to reduce the entry of foreign materials, it is therefore preferred that, in step b above, the pH is adjusted using sulfuric acid and NaOH.
In order to achieve better treatment effect, it is preferable that in the step b, the molar ratio of the reducing agent to the heavy metal in the waste liquid is 0.7-0.9: 1; the reducing agent is any one of sodium sulfite, sodium bisulfite and sodium thiosulfate; more preferably, the reducing agent is sodium sulfite.
In order to control the production cost, it is preferable that the mass ratio of the added water to the sodium sulfate crystals in the step d is 1.0-1.4: 1.
In order to reduce the production cost and reduce the energy consumption, it is preferable that in the step c, the solution obtained in the step b is cooled to 20-25 ℃ through a heat conduction system, and then enters a cooling crystallization system; in the step d, the dissolved solution is cooled to 20-25 ℃ through a heat conduction system and then enters a cooling crystallization system; more preferably, the heat obtained in the heat conduction system is returned to the step a for heating.
In order to achieve better crystallization effect, it is therefore preferable that the crystallization process is performed under stirring in the above-mentioned steps c and d.
In order to make better use of the solid waste as resources, it is preferable that the obtained heavy metal and non-metal precipitates can be used as raw materials of metal products; (NH) obtained as described above4)2SO4The crystal can be used as an agricultural fertilizer material or used for precipitating vanadium in the vanadium production industry; the obtained high-purity Na2SO4·10H2The purity of O is more than or equal to 98 percent and can be recycled.
The technical solution and effects of the present invention will be further described below by way of practical examples.
Examples
The invention selects vanadium precipitation solid waste (solid waste containing heavy metal, sodium salt and ammonium salt) as a treatment object, provides two groups of embodiments for treating vanadium precipitation solid waste by adopting the method, and comprises the following specific steps:
a. the main components of the vanadium precipitation solid waste mixed crystal are shown in table 1, the vanadium precipitation solid waste is mechanically crushed and then subjected to wet ball milling, water is added according to the ratio of solid waste to water of 1: 1.4, the temperature of example 1 is raised to 75 ℃, the temperature of example 2 is raised to 72 ℃, and the waste liquid 1 (example 1) and the waste liquid 2 (example 2) are obtained by dissolution;
table 1 main components (%) -of vanadium precipitation solid waste mixed crystals
| Na2SO4 | (NH40)2SO4 | H2O | SiO2 | NH4Cl | CaO | K2O | Fe2O3 | Cr2O3 | V2O5 | |
| Example 1 | 63 | 22 | 10 | 1.1 | 1.2 | 0.2 | 0.3 | 0.15 | 0.2 | 0.4 |
| Example 2 | 62.5 | 23 | 8 | 9 | 1.2 | 1.4 | 0.4 | 0.16 | 0.4 | 0.5 |
b. Adjusting the pH of the waste liquid 1 to 2.7 and the pH of the waste liquid 2 to 2.6 by using sulfuric acid, adding a reducing agent sodium sulfite, stirring to fully react, then adjusting the pH of the waste liquid 1 to 7 by using NaOH and the pH of the waste liquid 2 to 7.2, and carrying out solid-liquid separation after precipitation to obtain a solution 1 (example 1) and a solution 2 (example 2), a filter cake 1 (example 1) and a filter cake 2 (example 2), wherein the filter cake is a precipitate of heavy metals and non-metals which can be used as a raw material of a metal product, and the main components of the precipitate are shown in Table 2;
TABLE 2 major components (%)
| Cr2O3 | V2O5 | Na2SO4 | (NH4)2SO4 | H2O | SiO2 | NH4Cl | CaO | K2O | Fe2O3 | |
| Example 1 | 34.5 | 5.6 | 5.2 | 1.2 | 12 | 13 | 2 | 11 | 3 | 6 |
| Example 2 | 36.5 | 6.7 | 5.8 | 1.4 | 13 | 12 | 1.8 | 12 | 3.1 | 6.5 |
c. Cooling the solution 1 obtained in the step b to 23 ℃ through a heat conduction system, cooling the solution 2 to 21 ℃ through the heat conduction system, returning the heat obtained by cooling in the system to the step a for heating, then cooling to 6 ℃ through a cooling crystallization system, stirring once every 30 minutes, crystallizing, filtering to obtain low-purity sodium sulfate crystals and an ammonium sulfate solution, and returning the ammonium sulfate solution to the step a for use as a solvent;
d. adding water into the sodium sulfate crystals obtained in the step c according to the ratio of crystals to water of 1: 1.4, heating the temperature of the sodium sulfate crystals to 63 ℃ in the example 1, heating the temperature of the sodium sulfate crystals to 68 ℃ in the example 2, dissolving the sodium sulfate crystals, cooling the sodium sulfate crystals to 20 ℃ in the example 1 through a heat conduction system, cooling the sodium sulfate crystals to 21 ℃ in the example 2 through a heat conduction system, returning the redundant heat in the system to the step a for heating use, sending the dissolved solution into a cooling crystallization system, cooling the sodium sulfate crystals to 5.5 ℃ for secondary crystallization in the example 1, cooling the sodium sulfate crystals to 5.3 ℃ for secondary crystallization in the example 2, and filtering to obtain ammonium sulfate filtrate and high-purity Na2SO4·10H2O, ammonium sulfate filtrate is returned to the step a to be used as a solvent, and the obtained high-purity Na2SO4·10H2The main components of O are shown in Table 3.
TABLE 3 Na2SO4·10H2O main component (%)
| Name (R) | Na2SO4 | (NH4)2SO4 | H2O | SiO2 | NH4Cl | CaO | K2O | Fe2O3 | Cr2O3 | V2O5 |
| Example 1 | 98 | 0.31 | 1.5 | 0.2 | 0.15 | 0.09 | 0.1 | 0.15 | 0.015 | 0.012 |
| Example 2 | 98.2 | 0.28 | 1.2 | 0.12 | 0.1 | 0.07 | 0.12 | 0.13 | 0.018 | 0.015 |
e. Measuring to obtain ammonium sulfate solution and filtrate with concentration of 40 ° Be, concentrating in a concentration tank, concentrating, and evaporating to obtain (NH)4)2SO4Crystallization, technical quality standards for Fertilizer grade ammonium sulfate "national people's republic of China GB/T535-2020" (NH)4)2SO4The crystal quality is shown in Table 4.
TABLE 4 (NH4)2SO4 Crystal quality
From examples 1 and 2, it can be seen that Na recovered in the present invention2SO4·10H2O purity is more than or equal to 98 percent, and recovered (NH)4)2SO4The crystallization meets the national II-class standard, the process is simple, the energy and substances in the operation process are recycled, and the vanadium precipitation solid waste is efficiently recycled at lower cost.
Claims (10)
1. The method for recycling the solid waste containing heavy metals, sodium salts and ammonium salts is characterized by comprising the following steps:
a. mechanically crushing solid waste containing heavy metals, sodium salts and ammonium salts, then ball-milling, adding a solvent, heating to 60-80 ℃ and dissolving to obtain waste liquid;
b. adjusting the pH of the waste liquid to 2.5-3, adding a reducing agent for full reaction, adjusting the pH to 6.5-7.2, and performing solid-liquid separation after precipitation to obtain a solution and precipitates of heavy metals and nonmetal;
c. b, sending the solution obtained in the step b into a cooling crystallization system, cooling to 5-8 ℃ for crystallization, and filtering to obtain sodium sulfate crystals and an ammonium sulfate solution;
d. c, adding water into the sodium sulfate crystals obtained in the step c, heating to 60-70 ℃ for dissolving, then sending into a cooling crystallization system, cooling to 5-8 ℃ for secondary crystallization, and filtering to obtain ammonium sulfate filtrate and high-purity Na2SO4·10H2O。
2. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 1, which is characterized in that: in the step a, the solvent is at least one of water, the ammonium sulfate solution obtained in the step c and the ammonium sulfate filtrate obtained in the step d; the mass ratio of the solvent to the solid waste is controlled to be 1.2-2: 1.
3. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 2, which is characterized in that: when the concentration of the ammonium sulfate solution reaches 38-42 DEG Be, the ammonium sulfate solution is concentrated and evaporated to obtain (NH)4)2SO4And (4) crystallizing.
4. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 1, which is characterized in that: in the step b, the mol ratio of the reducing agent to the heavy metal in the waste liquid is 0.7-0.9: 1.
5. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 1, which is characterized in that: the reducing agent is any one of sodium sulfite, sodium bisulfite and sodium thiosulfate.
6. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 1, which is characterized in that: in the step d, the mass ratio of the added water to the sodium sulfate crystals is 1.0-1.4: 1.
7. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 1, which is characterized in that: in the step c, the solution obtained in the step b is cooled to 20-25 ℃ through a heat conduction system, and then enters a cooling crystallization system.
8. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 1, which is characterized in that: in the step d, the dissolved solution is cooled to 20-25 ℃ through a heat conduction system and then enters a cooling crystallization system.
9. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 7 or 8, which is characterized in that: and (c) returning the heat obtained in the heat conduction system to the step (a) for increasing the temperature for use.
10. The method for recycling solid waste containing heavy metals, sodium salts and ammonium salts according to claim 1, which is characterized in that: in steps c and d, the crystallization process is carried out under stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110696867.5A CN113428877A (en) | 2021-06-23 | 2021-06-23 | Method for recycling solid waste containing heavy metal, sodium salt and ammonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110696867.5A CN113428877A (en) | 2021-06-23 | 2021-06-23 | Method for recycling solid waste containing heavy metal, sodium salt and ammonium salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113428877A true CN113428877A (en) | 2021-09-24 |
Family
ID=77753536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110696867.5A Pending CN113428877A (en) | 2021-06-23 | 2021-06-23 | Method for recycling solid waste containing heavy metal, sodium salt and ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113428877A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB114236A (en) * | 1917-05-12 | 1918-03-28 | Harry Medforth Dawson | Process for the Production and Separation of Ammonium Sulphate and Glauber's Salt. |
| CN101948211A (en) * | 2010-09-20 | 2011-01-19 | 攀钢集团钢铁钒钛股份有限公司 | Method for treating vanadium oxide production wastewater |
| CN102531222A (en) * | 2010-12-09 | 2012-07-04 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method for vanadium precipitating waste water |
| CN104671577A (en) * | 2015-03-06 | 2015-06-03 | 张春雨 | Treatment and resource recycling method for wastewater with precipitated vanadium |
| CN107640778A (en) * | 2017-09-04 | 2018-01-30 | 超威电源有限公司 | A kind of method of the low cost recovery sodium sulphate from leaded desulfurization waste liquor |
| CN112794344A (en) * | 2020-12-14 | 2021-05-14 | 伊犁川宁生物技术股份有限公司 | Method for purifying sodium sulfate from antibiotic wastewater |
-
2021
- 2021-06-23 CN CN202110696867.5A patent/CN113428877A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB114236A (en) * | 1917-05-12 | 1918-03-28 | Harry Medforth Dawson | Process for the Production and Separation of Ammonium Sulphate and Glauber's Salt. |
| CN101948211A (en) * | 2010-09-20 | 2011-01-19 | 攀钢集团钢铁钒钛股份有限公司 | Method for treating vanadium oxide production wastewater |
| CN102531222A (en) * | 2010-12-09 | 2012-07-04 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method for vanadium precipitating waste water |
| CN104671577A (en) * | 2015-03-06 | 2015-06-03 | 张春雨 | Treatment and resource recycling method for wastewater with precipitated vanadium |
| CN107640778A (en) * | 2017-09-04 | 2018-01-30 | 超威电源有限公司 | A kind of method of the low cost recovery sodium sulphate from leaded desulfurization waste liquor |
| CN112794344A (en) * | 2020-12-14 | 2021-05-14 | 伊犁川宁生物技术股份有限公司 | Method for purifying sodium sulfate from antibiotic wastewater |
Non-Patent Citations (1)
| Title |
|---|
| 全英聪等: "含铬混合废水的净化技术及资源化利用现状", 《电镀与涂饰》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101161596B (en) | A method for resource processing non-ferro metals processing wastewater containing ammonia and sulfate radical | |
| JP5466749B2 (en) | Vanadium oxide production wastewater treatment method | |
| CN113336246B (en) | Resource treatment method of waste salt | |
| CN110143604B (en) | Method for recovering alkali, selenium and arsenic from antimony smelting arsenic alkali slag | |
| CN114105171A (en) | Method for recycling and comprehensively utilizing lepidolite and lithium hydroxide prepared by method | |
| CN113073202B (en) | Method for comprehensively treating liquid after vanadium precipitation of acidic ammonium salt in vanadium slag extraction | |
| WO2024212479A1 (en) | Method for leaching scheelite | |
| CN102701263B (en) | Method for preparing copper sulfate in mode that stanniferous copper slag is leached in selective mode and free of evaporation | |
| CN113636576A (en) | System and method for disposing and recycling miscellaneous salt in coal chemical industry | |
| CN114890443A (en) | System and process method for high-value utilization of lithium-containing waste | |
| CN109022806A (en) | A method of utilizing the vanadium liquid removal of impurities clay standby vanadic anhydride of vanadium | |
| CN102476884A (en) | Treatment method of ammonia nitrogen wastewater | |
| CN108128958B (en) | Production process for treating ammonia nitrogen wastewater | |
| CN117417084A (en) | Device system and method for extracting vanadium waste water and separating salt for purification | |
| CN113428877A (en) | Method for recycling solid waste containing heavy metal, sodium salt and ammonium salt | |
| CN116102211A (en) | Method for treating synthesis wastewater of battery anode material precursor | |
| CN110642317A (en) | Sodium sulfate wastewater resource utilization method | |
| CN114107698A (en) | Production method of high-stability high-purity arsenic | |
| CN114956126A (en) | Method for recycling mother solution in sodium method iron phosphate production process | |
| US2840455A (en) | Production of lithium carbonate | |
| CN113003606A (en) | Method for preparing vanadium pentoxide by utilizing multi-component circulation process and sodium vanadate solution | |
| CN110937634B (en) | Production method for preparing ammonium molybdate by calcium molybdate raw material ammonium phosphate mixed liquid transformation method | |
| CN113336252B (en) | Method for removing calcium from pickle liquor of coal-based solid waste | |
| EP4389707A1 (en) | Method for recycling ferrous sulfate heptahydrate and sulfuric acid from waste acid in titanium dioxide production | |
| CN103436717B (en) | Method for enriching gallium and comprehensively utilizing potassium and aluminum from alunite |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210924 |