CN115849539A - Fluorine removal agent and preparation method and application thereof - Google Patents
Fluorine removal agent and preparation method and application thereof Download PDFInfo
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- CN115849539A CN115849539A CN202310025719.XA CN202310025719A CN115849539A CN 115849539 A CN115849539 A CN 115849539A CN 202310025719 A CN202310025719 A CN 202310025719A CN 115849539 A CN115849539 A CN 115849539A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 100
- 239000011737 fluorine Substances 0.000 title claims abstract description 85
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 85
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 70
- 239000011707 mineral Substances 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002351 wastewater Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- -1 fluorine ions Chemical class 0.000 claims abstract description 20
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 235000010755 mineral Nutrition 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 238000002386 leaching Methods 0.000 claims description 20
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- 229910052791 calcium Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 12
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- 238000003756 stirring Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000006115 defluorination reaction Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
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- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 9
- 235000012255 calcium oxide Nutrition 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052598 goethite Inorganic materials 0.000 claims description 7
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229910001570 bauxite Inorganic materials 0.000 claims description 5
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 4
- 239000001639 calcium acetate Substances 0.000 claims description 4
- 229960005147 calcium acetate Drugs 0.000 claims description 4
- 235000011092 calcium acetate Nutrition 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 3
- 239000001354 calcium citrate Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 230000003311 flocculating effect Effects 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 235000013337 tricalcium citrate Nutrition 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 12
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a fluorine removal agent and a preparation method and application thereof, wherein the fluorine removal agent comprises the following components in percentage by mass: 10-20% of natural mineral material, 0-5% of aluminum salt, 0-2% of iron salt, 0-2% of calcium salt, 10-18% of acid and the balance of pure water; the natural mineral material is a single mineral or a mixture of multiple minerals containing Al, fe, si, ca and Mg. The main effective components of the fluorine removal agent are derived from leached salt of natural mineral materials and supplement a small amount of soluble inorganic salt, so that the direct resource utilization of the mineral materials is promoted, the fluorine removal agent has more raw material selectivity, the preparation cost of the fluorine removal agent is greatly reduced, the fluorine removal agent has higher cost performance, and the fluorine removal agent can be applied to treatment of mineral processing wastewater to simultaneously and efficiently remove fluorine ions and organic suspended matters in water.
Description
Technical Field
The invention discloses a fluorine removal agent and a preparation method and application thereof, and particularly relates to a reagent and a process for treating beneficiation wastewater.
Background
Mineral resources are an important foundation for national economic development, directly influence aspects of human production and life, and along with the rapid development of national social economy, the demand and development and utilization strength of mineral resources are increased year by year. However, during the ore mining process, a large amount of beneficiation wastewater is generated, and fluorine and organic suspended matters are common pollutants in the wastewater. Wherein the fluorine is mainly derived from fluorine-containing compounds in the ore; the organic suspended matter mainly comes from the residue of the flotation agent in the flotation process and is also the main source of COD in the water.
The wastewater has the characteristics of large water quantity, excessive fluorine concentration, complex chemical components, high turbidity, slow settling rate and the like. The existing beneficiation wastewater treatment method combines an acid-base neutralization method, a chemical coagulation/precipitation method, a chemical oxidation method and the like. Wherein, the chemical precipitation method of calcium salt has low removal efficiency, large reagent dosage and high cost, the generated sludge is much and excessive and can only be reduced to about 15 to 20, and the pH value of water is over-alkaline. The most extensive chemical coagulation method that uses can utilize flocculation to subside organic suspended solid in the sewage when removing fluorine, reaches the purpose that the suspended solid subsided and reduced COD, but the chemical coagulation used medicament mostly is through high-purity raw and other materials preparation, and the raw materials derive from finished product salt and composition singleness mostly, receives the water quality to influence greatly, and the medicament is with high costs and the quantity leads to sewage to remove fluorine with high costs greatly, and preparation technology is complicated.
Disclosure of Invention
The technical problem solved by the invention is as follows: aiming at the problems of high cost and great influence of water quality of the existing defluorinating agent, an improved defluorinating agent, a preparation method and application thereof are provided, and fluoride ions and organic suspended matters in beneficiation wastewater are synchronously removed at low cost and high efficiency.
The invention is realized by adopting the following technical scheme:
the invention discloses a fluorine removal agent which comprises the following components in parts by mass:
10 to 20 percent of natural mineral material,
0 to 5 percent of aluminum salt,
0 to 2 percent of ferric salt,
0 to 2 percent of calcium salt,
10 to 18 percent of acid,
the others are pure water;
the natural mineral material is a single mineral or a mixture of multiple minerals containing Al, fe, si, ca and Mg;
one or more of aluminum salt, ferric salt and calcium salt are added into the defluorination agent, so that the percentage content ratio of Al, fe and Ca in the defluorination agent is (2 to 5): (0.56 to 2): (0.5 to 3).
In the fluorine removing water agent of the invention, further, the natural mineral material comprises one or more of bauxite, ferro-aluminium ore, goethite and calcium aluminate, which comprises the primary mineral material and also comprises the primary mineral processing product.
In the fluorine removal water agent of the present invention, the acid is one or more of sulfuric acid with a mass concentration of 30%, hydrochloric acid with a mass concentration of 10%, and glacial acetic acid.
The invention further discloses a preparation method of the fluorine removal agent, which comprises the following steps:
firstly, immersing natural mineral materials in acid, stirring, heating and leaching, then cleaning the surface of minerals with pure water, carrying out solid-liquid separation, and uniformly mixing filtrate with leachate;
and secondly, measuring the contents of Al, fe and Ca in the mixed solution prepared in the first step, additionally supplementing soluble salt according to the measured content result, and adjusting the percentage content ratio of the Al, fe and Ca in the mixed solution to (2 to 5): (0.56 to 2): (0.5 to 3), neutralizing and adjusting the pH of the mixed solution back to 3 +/-0.5, and supplementing pure water until the Al content in the mixed solution is 2 to 3 percent to obtain the defluorinating water agent.
In the preparation method of the fluorine removal agent, further, in the first step, a natural mineral material is firstly crushed into mineral powder of 100-200 meshes, the mineral powder is immersed by acid with twice volume, then stirred, heated and leached, leaching reaction is carried out for 1.5-3h at the temperature of 80-100 ℃, upper-layer leachate is separated, leaching is repeated, two times of leachate are combined, the surface of the mineral is respectively washed by pure water with the same volume for three times, solid-liquid separation is carried out, and filtrate and the leachate are uniformly mixed.
In the preparation method of the fluorine removal agent, further, the soluble salt supplemented in the second step comprises at least one of aluminum salt, iron salt and calcium salt, wherein,
the aluminum salt is one or more of polyaluminium chloride, polyaluminium sulfate, polyaluminium ferric sulfate, aluminum sulfate and aluminum oxide;
the ferric salt is one or more of ferric sulfate, ferric chloride, polymeric ferric sulfate and ferrous sulfate;
the calcium salt is one or more of calcium oxide, calcium hydroxide, calcium acetate, calcium chloride and calcium citrate.
The invention finally discloses an application of the fluorine removal agent, the fluorine removal agent is used for removing fluorine ions and organic suspended matters in mineral processing wastewater simultaneously, and the specific operation is as follows: firstly, adding a fluorine removal agent into treated beneficiation wastewater, wherein the adding amount of the fluorine removal agent is selected according to the concentration of fluoride ions and COD in the beneficiation wastewater and a treatment target, and the fluorine removal agent is selectively added within the range of 6 to 10 ten thousandths of the treated beneficiation wastewater. Stirring and mixing for 10 to 30min, adjusting the pH of the mixed solution to 6 to 7 by using an acid-base solution, then adding a 0.1% PAM solution, fully stirring and flocculating for 5 to 15min, and taking the supernatant after settling for 5 to 10min as the effluent reaching the standard after treatment.
In the application of the fluorine removal agent, the acid-base solution of the mixed solution is adjusted to be one or more of a polymeric ferric sulfate solution, a calcium oxide solution, a sodium hydroxide solution, a dilute hydrochloric acid solution and a dilute sulfuric acid solution.
The invention also discloses another process for treating the beneficiation wastewater by using the fluorine removal agent, which comprises the steps of firstly adjusting the pH of raw water of the beneficiation wastewater to 9-10.5 by using an acid-base solution, then adding the fluorine removal agent into the beneficiation wastewater, adding a 0.1% PAM solution, fully stirring and flocculating for 5-15min, and taking supernatant after settling for 5-10min as treated effluent reaching the standard.
The invention has the following beneficial effects:
(1) The main effective components of the fluorine removal agent are derived from leached salt of natural mineral materials and supplement a small amount of soluble inorganic salt. The natural mineral material extract is selected to provide a large amount of Al, fe, si, ca, mg and the like, wherein the Si, ca and Mg and fluoride ions in the beneficiation wastewater easily form insoluble precipitates, cation colloids generated in the hydrolysis process of the Al and the Fe can easily adsorb the fluoride ions with extremely high electronegativity in the beneficiation wastewater, the reaction of the multiple cations and the fluoride ions is more in line with the mineralization reaction process of the fluoride ions, the concentration of the residual fluoride ions is lower, and the fluoride removal efficiency is improved.
(2) The natural mineral material adopted by the invention has diversity, and the final relative percentages of Al, fe and Ca are kept only by supplementing a small amount of inorganic salt for component adjustment regardless of a certain mineral source. Compared with the existing defluorinating agent, the preparation method of the defluorinating agent promotes the direct resource utilization of mineral materials, so that the defluorinating agent has more raw material selectivity, greatly reduces the preparation cost of the defluorinating agent, and has higher cost performance.
(3) The defluorination agent has larger adaptability to the treated wastewater, is not limited by the pH of raw water, and has simple treatment process: the pH of raw water can be adjusted to 9-10.5, a fluorine removal agent is added for reaction, PAM is added for flocculation and precipitation, or the pH of the raw water can be adjusted to 6-7 before PAM flocculation without adjusting the pH of the raw water, so that a good fluorine removal flocculation effect can be achieved.
(4) COD in the mineral processing wastewater is mainly from the use of a flotation reagent, is easy to generate saponification reaction in the mineral processing technology and the water treatment process and is partially dissolved in water, and a part of the saponification reaction forms colloidal suspended matters to become main sources of SS and COD. The main component of the fluorine removal agent is from natural mineral materials, the fluorine removal agent contains abundant cationic colloids, can effectively adsorb organic suspended matters and part of soluble organic matters, is particularly suitable for treating polluted water such as mineral processing wastewater and the like which needs fluoride ions and organic suspended matters simultaneously, is low in dosage, and further flocculates and precipitates under the synergistic effect of the fluorine removal agent and a PAM solution, so that the effects of removing fluorine while removing organic suspended matters and reducing SS and COD are achieved.
In conclusion, the fluorine removal agent disclosed by the invention is a high-efficiency low-cost fluorine removal agent utilizing natural mineral materials, and can be used for efficiently removing fluorine ions and organic suspended matters in water simultaneously when being applied to treatment of mineral processing wastewater.
The present invention will be further described with reference to the following embodiments.
Drawings
FIG. 1 is a process flow diagram of treatment of beneficiation wastewater by a fluorine removal agent in an embodiment.
Detailed Description
The fluorine removal agent comprises the following components in percentage by mass: 10-20% of natural mineral material, 0-5% of aluminum salt, 0-2% of iron salt, 0-2% of calcium salt, 10-18% of acid and the balance pure water; the natural mineral material is a single mineral or a mixture of multiple minerals containing Al, fe, si, ca and Mg, and can be bauxite, ferro-aluminium ore, goethite and calcium aluminate.
One or more of aluminum salt, ferric salt and calcium salt are added into the defluorination agent, so that the percentage content ratio of Al, fe and Ca in the defluorination agent is (2 to 5): (0.56 to 2): (0.5 to 3), and the dosage of the added aluminum salt, iron salt and calcium salt is correspondingly supplemented according to the content of Al, fe and Ca in the selected natural mineral material.
The acid in the fluorine removal agent is one or more of sulfuric acid with the mass concentration of 30%, hydrochloric acid with the mass concentration of 10%, glacial acetic acid and the like, wherein the acetic acid is a cosolvent.
The preparation method of the fluorine removal water agent comprises the following steps:
firstly, crushing a natural mineral material into mineral powder of 100-200 meshes, immersing the mineral powder with acid of twice volume, stirring, heating and leaching, reacting at 80-100 ℃ for 1.5-3 h, separating an upper-layer leaching solution, repeating the leaching, combining the two leaching solutions, respectively cleaning the surface of the mineral with pure water of the same volume for three times, carrying out solid-liquid separation, and mixing the filtrate and the leaching solution.
And secondly, measuring the contents of Al, fe and Ca in the mixed solution prepared in the first step, additionally supplementing soluble salt according to the measured content result, and adjusting the percentage content ratio of the Al, fe and Ca in the mixed solution to (2 to 5): (0.56 to 2): (0.5 to 3), adjusting the pH of the mixed solution to 3 +/-0.5 by using a calcium salt, and supplementing pure water until the Al content in the mixed solution is 2 to 3 percent to obtain the fluorine removal water agent.
The soluble salt supplemented in the preparation process of the fluorine removal agent comprises at least one of aluminum salt, ferric salt and calcium salt, wherein the aluminum salt is one or more of polyaluminium chloride, polyaluminium sulfate, polyaluminium ferric sulfate, aluminium oxide and the like; the ferric salt is one or more of ferric sulfate, ferric chloride, polymeric ferric sulfate, ferrous sulfate and the like; the calcium salt is one or more of calcium oxide, calcium hydroxide, calcium acetate, calcium chloride, calcium citrate, etc.
The defluorination agent is used for simultaneously removing fluoride ions and organic suspended matters in mineral processing wastewater, as shown in a treatment process in figure 1, firstly, the defluorination agent is added into the treated mineral processing wastewater in a coagulation tank, stirred and mixed for 10 to 30min, the pH value of the mixed solution is adjusted to be between 6 and 7 by using acid-base solution, then the mixed solution enters a flocculation tank, a PAM solution with the concentration of 0.1% is added, fully stirred and flocculated for 5 to 15min, and the mixed solution is sent to an inclined plate tank for sedimentation for 5 to 10min, and then the supernatant is the effluent reaching the standard after treatment.
Specifically, the acid-base solution of the mixed solution is adjusted to be one or more of a polymeric ferric sulfate solution, a calcium oxide solution, a sodium hydroxide solution, a dilute hydrochloric acid solution and a dilute sulfuric acid solution.
The fluorine removal agent is acidic, and in practical application, the pH of raw water of beneficiation wastewater can be adjusted to 9-10.5 by using acid-base solution, then the fluorine removal agent is added into the beneficiation wastewater, the pH of the mixed solution is neutralized, and then 0.1% concentration PAM is added to achieve the effect of treating fluorine ions and organic suspended matters in the beneficiation wastewater.
Specific examples are provided below for the practice of the fluorine removal agent and the method for producing the same of the present invention.
Example 1
In the example, the fluorine removal agent is prepared from the following preparation raw materials: 10-15% of natural mineral material, 6.75% of aluminum salt, 0.6% of calcium salt, 12% of acid and the balance of pure water, wherein the natural mineral material is natural mineral powder mixed by bauxite and goethite according to a mass ratio of 7.5: 0.8:0.5.
the preparation process of the fluorine removal agent is as follows:
selecting bauxite and goethite, preparing 50g of a mixture according to a mass ratio of 7.5:1, heating to 80-100 ℃, stirring and leaching for 3 hours, separating supernatant of the leachate by using a 200-mesh nylon filter screen, repeating the leaching once, and combining the leachate obtained in two times. Washing the mineral surface with pure water of the same volume for three times, separating with nylon filter screen, and mixing the separated filtrate with all the lixivium. And (3) after detecting the contents of Al, fe and Ca in the mixed solution, supplementing 27 g of polyaluminum sulfate and a small amount of 4.3 g of calcium oxide, neutralizing and adjusting the pH of the mixed solution to about 3 by using sodium hydroxide, and supplementing pure water to obtain 400 mL of the defluorinating water agent.
Example 2
In the example, the fluorine removal agent is prepared from the following preparation raw materials: the fluorine removal water comprises, by mass, 15-20% of a natural mineral material, 5% of aluminum salt, 1.8% of calcium salt, 15% of acid and the balance pure water, wherein the natural mineral material is natural mineral powder mixed by calcium aluminate powder and goethite according to a mass ratio of 7.5: 1.0: 2.9.
the preparation process of the fluorine removal agent is as follows:
selecting calcium aluminate powder and goethite to prepare 50g of a mixture according to a mass ratio of 7.5:1, heating to 80-100 ℃, stirring and leaching for 3 hours, separating supernatant of the leachate by using a 200-mesh nylon filter screen, repeating the leaching once, and combining the leachate obtained in two times. Washing the mineral surface with pure water of the same volume for three times, separating with nylon filter screen, and mixing the separated filtrate with all the lixivium. After the contents of Al, fe and Ca in the mixed solution are detected, 15g of polyaluminium chloride is supplemented, the pH =3 of the mixed solution is adjusted by neutralization with CaO, and pure water is supplemented to obtain 300 mL of the fluorine removal agent.
Comparative example 1
The fluorine removal agent is replaced by soluble inorganic salt, and the preparation raw materials of the fluorine removal agent comprise the following components in percentage by mass: 23% of aluminum salt, 7% of iron salt, 8.6% of calcium salt, 12% of acid and the balance of pure water. The preparation method comprises the following steps:
15g of polyaluminium chloride, 4.5 g of polyferric sulfate and 5.5 g of calcium acetate are dissolved into 40 mL of water in batches, and the mixture is heated and stirred to assist dissolution. pH =3 was adjusted with hydrochloric acid or CaO, and pure water was supplemented to 50 mL. Obtaining a contrast water agent. Calculated element percentage content is Al: fe: ca = 2.4: 1: 1.5, similar to the components of the above examples, was used as a comparative aqueous solution 1.
Comparative example 2
The fluorine removal III type fluorine removal agent produced by Shenzhen Shanghong science and technology Limited is selected as the contrast water agent 2.
In order to verify the flocculation removal effect of the fluorine removal agent on fluoride ions and organic suspended matters in mineral processing wastewater, the following comparative tests are performed on the fluorine removal agent in the examples and the comparative water agent in the comparative examples.
Test 1
Taking tungsten ore beneficiation wastewater in Hunan as an example, the fluorine removal water agents in the examples 1 and 2 and the comparison water agents in the comparative examples 1 and 2 are respectively subjected to a small experiment, and the beneficiation wastewater has the fluorine ion content of 13.3 mg/L, the COD concentration of 87 mg/L and the pH of 9.7. The wastewater from this pilot plant was filtered and no SS was detected. The defluorination test comprises the following specific steps:
the test is divided into 4 groups, 100mL of beneficiation wastewater is weighed in each group, and 0.08 mL of the defluorination water agent prepared in the embodiment 1 and 2 and the comparison water agent 1 and the comparison water agent 2 are respectively weighed in the four groups of beneficiation wastewater. The following operations refer to the process route of fig. 1, after stirring for 20 min at normal temperature, adjusting the pH of the wastewater to 6-7, then adding 1 drop of 0.1% PAM solution into the wastewater, stirring for 5min, standing for 5min, settling, and filtering. And (4) taking the filtrate to detect the concentration of fluorine ions and COD. The four groups of beneficiation wastewater repeat the process according to the process.
The measurement results before and after the treatment of four groups of beneficiation wastewater are shown in table 1.
TABLE 1
Test 2
The fluorine removal water agents of the embodiment 1 and the embodiment 2 and the comparison water agent 2 of the comparison example 2 are selected to be sequentially subjected to field experiments in a tungsten ore dressing wastewater treatment plant in Hunan province.
The wastewater treatment capacity of the sewage treatment plant is 1 ten thousand square per day, the content of fluoride ions in the wastewater is 10-18 mg/L, suspended matters in water are mainly mineral dressing agents, namely SS organic suspended matters with the content of 60-150mg/L, COD in the water is 80-150 mg/L, and the pH value is 9-10.5.
Wherein, the addition amount of the fluorine removal agent of the example 1 and the comparison water agent 2 is 10m 3 The addition amount of the fluorine removal agent in example 2 is 8 m/day 3 The addition amount of 0.1% PAM solution is 10m 3 The wastewater pH was adjusted daily using dilute sulfuric acid or polyferric sulfate solution, the specific treatment process being referred to test 1.
The fluoride ion concentration, the COD concentration and the SS concentration before and after the on-site treatment of the beneficiation wastewater by the three agents were measured, and the results are shown in Table 2.
TABLE 2
The comparison of the two test results shows that: under the same treatment effect, the fluorine removal agent of the embodiments 1 and 2 has higher adsorption and flocculation efficiency of fluorine ions and organic suspended matters in mineral processing wastewater, and under the condition of the same medicament dosage, the fluorine removal agent has better treatment effect, can achieve the treatment effect of the existing fluorine removal agent on the market under the condition of using less medicament dosage (reducing by 20 percent), and is beneficial to the reduction of sludge quantity. In addition, natural mineral materials including mineral intermediate products are directly used in the preparation process of the fluorine removal agent, and the preparation method is favorable for reducing the cost of the agent. Therefore, the fluorine removal agent provided by the embodiment of the invention is a novel high-efficiency fluorine removal agent which is low in cost and can synchronously remove fluorine ions and organic suspended matters in mineral processing wastewater.
The above examples are merely illustrative for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Nor is it intended to be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (9)
1. The fluorine removal agent is characterized by comprising the following components in percentage by mass:
10 to 20 percent of natural mineral material,
0 to 5 percent of aluminum salt,
0 to 2 percent of ferric salt,
0 to 2 percent of calcium salt,
10 to 18 percent of acid,
the others are pure water;
the natural mineral material is a single mineral or a mixture of multiple minerals containing Al, fe, si, ca and Mg;
one or more of aluminum salt, ferric salt and calcium salt are added into the defluorination agent, so that the percentage content ratio of Al, fe and Ca in the defluorination agent is (2 to 5): (0.56 to 2): (0.5 to 3).
2. The fluorine removal agent of claim 1, wherein the natural mineral material comprises one or more of bauxite, goethite, calcium aluminate.
3. The fluorine removal agent of claim 1, wherein the acid is one or more of sulfuric acid with a mass concentration of 30%, hydrochloric acid with a mass concentration of 10% and glacial acetic acid.
4. The method for preparing a fluorine-removing water agent according to any one of claims 1 to 3, characterized by comprising the steps of:
firstly, immersing natural mineral materials in acid, stirring, heating and leaching, then cleaning the surface of minerals with pure water, carrying out solid-liquid separation, and uniformly mixing filtrate with leachate;
and secondly, measuring the contents of Al, fe and Ca in the mixed solution prepared in the first step, additionally supplementing soluble salt according to the measured content result, and adjusting the percentage content ratio of the Al, fe and Ca in the mixed solution to (2 to 5): (0.56 to 2): (0.5 to 3), adjusting the pH value of the mixed solution to 3 +/-0.5 by neutralization, and supplementing pure water until the Al content in the mixed solution is 2 to 3 percent to obtain the fluorine removal water agent.
5. The preparation method of the fluorine removal agent according to claim 4, wherein in the first step, a natural mineral material is firstly crushed into mineral powder of 100 to 200 meshes, the mineral powder is immersed in acid of twice volume and then stirred and heated for leaching, the leaching reaction is carried out for 1.5 to 3 hours at the temperature of 80 to 100 ℃, the upper layer leaching solution is separated, the leaching is repeated, the two leaching solutions are combined, the surface of the mineral is respectively cleaned by pure water with the same volume as the volume of the two leaching solutions for three times, solid-liquid separation is carried out, and the filtrate and the leaching solution are mixed uniformly.
6. The method of claim 5, wherein the soluble salt supplemented in the second step comprises at least one of aluminum salt, iron salt and calcium salt, wherein,
the aluminum salt is one or more of polyaluminium chloride, polyaluminium sulfate, polyaluminium ferric sulfate, aluminum sulfate and aluminum oxide;
the ferric salt is one or more of ferric sulfate, ferric chloride, polymeric ferric sulfate and ferrous sulfate;
the calcium salt is one or more of calcium oxide, calcium hydroxide, calcium acetate, calcium chloride and calcium citrate.
7. Use of a fluorine-removing water agent according to any one of claims 1 to 3, characterized in that: the method is used for removing fluoride ions and organic suspended matters in beneficiation wastewater, and comprises the steps of firstly adding a fluorine removal water agent into treated beneficiation wastewater, stirring and mixing for 10-30min, then adjusting the pH of the mixed solution to 6-7 by using an acid-base solution, then adding a 0.1% PAM solution, fully stirring and flocculating for 5-15min, and taking supernatant after settling for 5-10min as treated effluent reaching the standard.
8. The use of the fluorine removal agent according to claim 7, wherein the acid-base solution of the mixed solution is one or more of a polymeric ferric sulfate solution, a calcium oxide solution, a sodium hydroxide solution, a dilute hydrochloric acid solution and a dilute sulfuric acid solution.
9. Use of a fluorine-removing water agent according to any one of claims 1 to 3, characterized in that: the method is used for removing fluoride ions and organic suspended matters in beneficiation wastewater, firstly, the pH of raw water of the beneficiation wastewater is adjusted to be 9-10.5 by using acid-base solution, then, a fluorine removal water agent is added into the beneficiation wastewater, a PAM solution with the concentration of 0.1% is added, the mixture is fully stirred and flocculated for 5-15min, and supernatant after sedimentation for 5-10min is taken as treated effluent reaching the standard.
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