CN112007763B - Combined collecting agent for andalusite ore separation and preparation method and application thereof - Google Patents
Combined collecting agent for andalusite ore separation and preparation method and application thereof Download PDFInfo
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- CN112007763B CN112007763B CN201911295295.9A CN201911295295A CN112007763B CN 112007763 B CN112007763 B CN 112007763B CN 201911295295 A CN201911295295 A CN 201911295295A CN 112007763 B CN112007763 B CN 112007763B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
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Abstract
The invention relates to a combined collecting agent for andalusite ore separation, which belongs to the technical field of mineral processing, and the main components of the combined collecting agent comprise the following raw materials in percentage by mass: 45-70% of C14-C18 sodium alkyl petroleum sulfonate; 15-20% of naphthenic acid sulfonate; 5% -8% of fuel oil; 5-8% of sorbitan fatty acid ester; 5-10% of organic acid sodium salt. When the weight percentage of the combined collector is less than 100%, water is added for complementing. The invention also discloses a preparation method and application of the combined collector. The combined collector has better dispersity and selectivity, stable medicament property, no sticky foam, easy dissipation and low temperature resistance, and can realize normal-temperature flotation. The method has the advantages of simple preparation process, easy operation and low cost.
Description
Technical Field
The invention belongs to the technical field of mineral processing, and particularly relates to a combined collecting agent for andalusite ore separation; the invention also discloses a preparation method and application of the combined collector.
Background
The kyanite, andalusite and sillimanite are generally called kyanite minerals, and the three have the same chemical formula, namely Al2SiO5Or written as Al2O3·SiO2Chemical composition Al2O362.93%,SiO237.07% of the main components, all belong to silicate minerals and also belong to high-alumina mineral raw materials, wherein the structural formula of andalusite is AlAl [ SiO ]4]And O. According to incomplete statistics, 5.6 hundred million t andalusite ore in China has mineral content calculated according to 12%, mineral reserve is 0.67 hundred million t, and among kyanite group minerals, andalusite ore reserve in China is the most abundant and mainly concentrated in Xianhua rock Liaoning, Henan Xixia, Xinjiang Bauheng, Kuerle, Chunxi, Shanxi and the like. However, andalusite ore in China has high hardness and is not easy to separate from matrix minerals.
Andalusite is mainly applied to refractory materials, raw materials for producing aluminum-silicon alloy, paint and ceramics. According to the ore properties of andalusite ore, a single process of flotation, magnetic separation and gravity separation or a combined process of the flotation, the magnetic separation and the gravity separation is usually carried out by adopting a shaking table, a jigging process, a heavy medium and the like, the magnetic separation is a strong magnetic separation process, and the two common andalusite flotation processes are mainly used, wherein one process is to use a fatty acid collecting agent in a neutral medium, the flotation pH value is 6.5-7.5, and the other process is to use a sulfonate collecting agent in an acid environment with the pH value of 3-4 for flotation. Therefore, it is of great interest to develop new, more selective collectors.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel combined collector for andalusite ore separation, which has the advantages of good selectivity, good dispersibility, hard water resistance, stable property, environmental protection, safety and good adaptability and is used for overcoming the defects of the prior art.
The invention also provides a preparation method of the combined collector for andalusite ore separation.
The invention also aims to provide the application of the combined collector for andalusite ore separation.
The technical problem to be solved by the present invention is achieved by the following technical means. The invention relates to a combined collecting agent for andalusite ore separation, which is characterized in that: the combined collecting agent mainly comprises the following raw materials in parts by mass:
45-70% of C14-C18 sodium alkyl petroleum sulfonate;
15% -20% of naphthenic acid sulfonate;
5-8% of fuel oil;
5-8% of sorbitan fatty acid ester;
5-10% of organic acid sodium salt.
The invention relates to a combined collector for andalusite ore separation, which further adopts the preferable technical scheme that: the combined collecting agent mainly comprises the following raw materials in parts by mass:
45-70% of C14-C18 sodium alkyl petroleum sulfonate;
15% -18% of naphthenic acid sulfonate;
5-8% of fuel oil;
5-8% of sorbitan fatty acid ester;
5-8% of organic acid sodium salt;
when the weight percentage of the combined collector is less than 100%, water is added for complementing.
The invention relates to a combined collector for andalusite ore separation, which further adopts the preferable technical scheme that: the combined collecting agent mainly comprises the following raw materials in parts by mass:
50-65% of C14-C18 sodium alkyl petroleum sulfonate;
16% -18% of naphthenic acid sulfonate;
5-7% of fuel oil;
5-8% of sorbitan fatty acid ester;
5-7% of organic acid sodium salt;
when the weight percentage of the combined collector is less than 100%, water is added for complementing.
In the technical scheme of the combined collector for andalusite ore separation, the further preferable technical characteristics are as follows:
1. the naphthenic acid sulfonate is selected from one or more of amyl naphthenic acid sulfonate or hexyl naphthenic acid sulfonate. When the number of the compounds is selected from several, the compounds can be arbitrarily selected and used as follows.
2. The fuel oil is selected from one or more of No. 200 heavy oil, industrial fuel oil and asphalt.
3. The sorbitan fatty acid ester is selected from one or more of S-40, S-60 and S-80.
4. The organic acid sodium salt is selected from one or more of sodium oxalate, sodium citrate, sodium alginate or sodium tartrate.
The invention also discloses a combined collector for andalusite ore separation according to any one of the technical schemes, which is characterized in that: mixing and heating petroleum sodium sulfonate, naphthenate and fuel oil to 80-90 ℃, adding sorbitan fatty acid ester, adding organic acid sodium salt, adding a proper amount of water according to the weight percentage to complement the weight percentage to 100%, and uniformly mixing to obtain the composite fuel.
The invention also discloses a method for carrying out andalusite ore flotation by applying the combined collecting agent in any one of the technical schemes, which is characterized by comprising the following steps: the combined collector is used in the acid direct flotation process of andalusite in a manner of dropwise adding stock solution; the flotation temperature of the direct flotation process is preferably 20-30 ℃, the pH value is preferably 2-5, and the pH value is further preferably 3-4.
The combined collector for andalusite ore separation can be used as a combined collector in andalusite ore separation. The combined collecting agent is used for flotation when crude ore Al2O3When the grade is 22.00-28.00%, performing flotation to obtain concentrate Al2O3The grade is 39.00-43.00%, and concentrate Al is subjected to flotation operation2O3The recovery rate can reach 39.00-48.00%.
The combined collecting agent for andalusite ore separation is preferably suitable for a medicament developed for andalusite separation in an acidic environment with the pH of 3-4.
Compared with the prior art, the invention has the following beneficial effects:
the main medicine in the andalusite direct flotation collector is petroleum sodium sulfonate, the carbon chain length of the petroleum sodium sulfonate is C14-C18, the hydrophobicity is good, the medicament selectivity is good, the water solubility and the collecting capability of naphthenic acid sulfonate are strong, the naphthenic acid sulfonate has good synergistic effect after being compounded with the petroleum sodium sulfonate, the collecting capability of a combined medicament can be increased, the emulsifying, dispersing and solubilizing performances of sorbitan fatty acid ester are excellent, the dispersibility, the hard water resistance and the stability of the combined medicament can be increased after being compounded with the petroleum sodium sulfonate, and the fuel oil mainly has the effect of enhancing the collecting capability of the medicament.
The agent has the characteristics of good selectivity, strong collecting performance, low temperature resistance, low ore dressing cost and the like, and can be suitable for the flotation of low-grade andalusite ore.
The preparation method of the invention mixes a plurality of medicaments uniformly according to the limited sequence, can enhance the water solubility and better exert the drug effect. The product obtained by the method of the invention is oily liquid at normal temperature, and the preparation process is simple, easy to operate and low in production cost.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention.
Example 1, a combined collector for andalusite ore separation, which mainly consists of the following raw materials in percentage by mass:
67% of C14-C18 alkyl petroleum sodium sulfonate;
18% of naphthenic acid sulfonate;
5% of fuel oil;
5% of sorbitan fatty acid ester;
5% of organic acid sodium salt.
The naphthenic acid sulfonate is selected from one of amyl naphthenic acid sulfonate or hexyl naphthenic acid sulfonate.
The fuel oil is selected from one of No. 200 heavy oil, No. 120 fuel oil, No. 7 fuel oil, industrial fuel oil, mixed heavy oil and asphalt.
The sorbitan fatty acid ester is selected from one of S-20, S-40, S-60 and S-80.
The organic acid sodium salt is selected from one of sodium oxalate, sodium citrate, sodium alginate or sodium tartrate.
The preparation method comprises the following steps: mixing and heating the petroleum sodium sulfonate, the naphthenic acid sulfonate and the fuel oil to 85 ℃, adding the sorbitan fatty acid ester, finally adding the organic acid sodium salt, and uniformly mixing to obtain the product.
Example 2, a combined collector for andalusite ore separation, which mainly comprises the following raw materials in percentage by mass:
65% of C14-C18 alkyl petroleum sodium sulfonate;
18% of naphthenic acid sulfonate;
5% of fuel oil;
6% of sorbitan fatty acid ester;
6% of organic acid sodium salt.
The naphthenic acid sulfonate is selected from one of amyl naphthenic acid sulfonate or hexyl naphthenic acid sulfonate.
The fuel oil is selected from one of No. 200 heavy oil, No. 120 fuel oil, No. 7 fuel oil, industrial fuel oil, mixed heavy oil and asphalt.
The sorbitan fatty acid ester is selected from one of S-20, S-40, S-60 and S-80.
The organic acid sodium salt is selected from one of sodium oxalate, sodium citrate, sodium alginate or sodium tartrate.
The preparation method comprises the following steps: mixing and heating the petroleum sodium sulfonate, the naphthenic acid sulfonate and the fuel oil to 85 ℃, adding the sorbitan fatty acid ester, finally adding the organic acid sodium salt, and uniformly mixing to obtain the product.
The method for andalusite ore flotation by using the combined collector described in the example comprises the following steps: the combined collector is used in the acid direct flotation process of andalusite in a manner of dropwise adding stock solution; the flotation temperature of the direct flotation process is preferably 25 ℃ and the pH value is preferably 3.5.
Example 3, a combined collector for andalusite ore separation, which mainly comprises the following raw materials in parts by mass:
65% of C14-C18 alkyl petroleum sodium sulfonate;
18% of naphthenic acid sulfonate;
5% of fuel oil;
6% of sorbitan fatty acid ester;
6% of organic acid sodium salt.
The naphthenic acid sulfonate is selected from one of amyl naphthenic acid sulfonate or hexyl naphthenic acid sulfonate.
The fuel oil is selected from one of No. 200 heavy oil, No. 120 fuel oil, No. 7 fuel oil, industrial fuel oil, mixed heavy oil and asphalt.
The sorbitan fatty acid ester is selected from one of S-20, S-40, S-60 and S-80.
The organic acid sodium salt is selected from one of sodium oxalate, sodium citrate, sodium alginate or sodium tartrate.
The preparation method comprises the following steps: mixing and heating the petroleum sodium sulfonate, the naphthenic acid sulfonate and the fuel oil to 85 ℃, adding the sorbitan fatty acid ester, finally adding the organic acid sodium salt, and uniformly mixing to obtain the product.
The method for andalusite ore flotation by using the combined collector described in the example comprises the following steps: the combined collector is used in the acid direct flotation process of andalusite in a manner of dropwise adding stock solution; the flotation temperature of the direct flotation process is preferably 22 ℃ and the pH value is preferably 3.0.
Example 4, a combined collector for andalusite ore separation, which mainly comprises the following raw materials in parts by mass:
55% of C14-C18 sodium alkyl petroleum sulfonate;
18% of naphthenic acid sulfonate;
5% of fuel oil;
6% of sorbitan fatty acid ester;
6% of organic acid sodium salt;
adding water to make up to 100 percent.
The naphthenic acid sulfonate is selected from one or more of amyl naphthenic acid sulfonate or hexyl naphthenic acid sulfonate.
The fuel oil is selected from one or more of No. 200 heavy oil, No. 120 fuel oil, No. 7 fuel oil, industrial fuel oil, mixed heavy oil and asphalt.
The sorbitan fatty acid ester is selected from one or more of S-20, S-40, S-60 and S-80.
The organic acid sodium salt is selected from one or more of sodium oxalate, sodium citrate, sodium alginate or sodium tartrate.
The preparation method comprises the following steps: mixing and heating the petroleum sodium sulfonate, the naphthenic acid sulfonate and the fuel oil to 85 ℃, adding the sorbitan fatty acid ester, finally adding the organic acid sodium salt, adding a proper amount of water according to the weight percentage to complement the weight percentage to 100 percent, and uniformly mixing to obtain the product.
The method for andalusite ore flotation by using the combined collector described in the example comprises the following steps: the combined collector is used in the acid direct flotation process of andalusite in a manner of dropwise adding stock solution; the flotation temperature of the direct flotation process is preferably 22 ℃ and the pH value is preferably 3.0.
Example 5, a combined collector for andalusite ore separation, which mainly comprises the following raw materials in parts by mass:
65% of C14-C18 alkyl petroleum sodium sulfonate;
15% of naphthenic acid sulfonate;
6 percent of fuel oil;
6% of sorbitan fatty acid ester;
6% of organic acid sodium salt;
adding water to make up to 100 percent.
The naphthenic acid sulfonate is selected from one or more of amyl naphthenic acid sulfonate or hexyl naphthenic acid sulfonate.
The fuel oil is selected from one or more of No. 200 heavy oil, No. 120 fuel oil, No. 7 fuel oil, industrial fuel oil, mixed heavy oil and asphalt.
The sorbitan fatty acid ester is selected from one or more of S-20, S-40, S-60 and S-80.
The organic acid sodium salt is selected from one or more of sodium oxalate, sodium citrate, sodium alginate or sodium tartrate.
The preparation method comprises the following steps: mixing and heating the petroleum sodium sulfonate, the naphthenic acid sulfonate and the fuel oil to 80 ℃, adding the sorbitan fatty acid ester, finally adding the organic acid sodium salt, adding a proper amount of water according to the requirement to complement the weight percentage to 100 percent, and uniformly mixing to obtain the product.
The method for andalusite ore flotation by using the combined collector described in the example comprises the following steps: the combined collector is used in the acid direct flotation process of andalusite in a manner of dropwise adding stock solution; the flotation temperature of the direct flotation process is preferably 26 ℃ and the pH value is preferably 4.0.
Example 6, a combined collector preparation and application experiment one for andalusite ore sorting:
(1) preparing the following raw materials in percentage by mass: 65% of C14-C18 alkyl petroleum sodium sulfonate, 15% of amyl naphthenic acid sulfonate, 6% of No. 120 fuel oil, 6% of S-806% sodium oxalate and the balance of water, wherein the total amount of the components is 100%.
(2) Heating the mixture of sodium petroleum sulfonate, amyl naphthenic acid sulfonate and No. 120 fuel oil to 85 deg.C, adding S-80, stirring, adding sodium oxalate, and stirring.
(3) The prepared andalusite combined collector is used in an acid direct flotation process of andalusite in a manner of dropwise adding stock solution; the flotation temperature of the direct flotation process is 22 ℃, and the pH value is 3.5.
(4) As a result, the raw Al ore2O3The grade is 27.85 percent, and the concentrate Al is obtained after flotation2O3The grade is 42.50 percent, and concentrate Al is obtained in flotation operation2O3The recovery was 45.79%.
Example 7, a combined collector preparation and application experiment two for andalusite ore sorting:
(1) preparing the following raw materials in percentage by mass: 60% of C14-C18 alkyl petroleum sodium sulfonate, 18% of amyl naphthenic acid sulfonate, 7% of industrial fuel oil, S-806%, 5% of sodium citrate and the balance of water, wherein the total amount of the components is 100%.
(2) Mixing sodium petroleum sulfonate, amyl naphthenic acid sulfonate and industrial fuel oil, heating the mixture to 90 ℃, adding S-80, uniformly stirring, finally adding sodium citrate, and uniformly stirring.
(3) The prepared andalusite combined collector is used in an acid direct flotation process of andalusite in a manner of dropwise adding stock solution; the flotation temperature of the direct flotation process is 25 ℃, and the pH value is 3.0.
(4) As a result, the raw Al ore2O3The grade is 26.80 percent, and the concentrate Al is obtained after flotation2O3The grade is 41.53 percent, and concentrate Al is subjected to flotation operation2O3The recovery was 46.75%.
Example 8, a third combined collector preparation and application experiment for andalusite ore separation:
and (3) comparison test: the flotation effect of the combined reagent is compared with that of two collecting agents which are commonly used at present:
comparative experiment 1:
(1) the collecting agent is sodium petroleum sulfonate, and is used in the acid direct flotation process of andalusite after being prepared into a 5% solution; the flotation temperature of the direct flotation process is 22 ℃, the pH value is 3.5, and the using amount of the collecting agent is 2.8 kg/t.
(2) As a result, the raw Al ore2O3The grade is 27.68%, and the concentrate Al is obtained after flotation2O3The grade is 41.60 percent, and concentrate Al is subjected to flotation operation2O3The recovery rate is 42.83%
Comparative experiment 2:
(1) the collecting agent is prepared into 5% solution by adopting sodium dodecyl sulfate, and then is used in the acid direct flotation process of andalusite; the flotation temperature of the direct flotation process is 22 ℃, the pH value is 3.5, and the using amount of the collecting agent is 3.2 kg/t.
(2) As a result, the raw Al ore2O3The grade is 27.78 percent, and the concentrate Al is obtained after flotation2O3The grade is 40.95 percent, and concentrate Al is obtained in flotation operation2O3The recovery rate is 40.54 percent
The comparative test shows that: the combined collecting agent of the invention is adopted to replace two collecting agents commonly used at present, namely concentrate Al2O3The product potential can be improved by more than 1 percent, and Al2O3The recovery rate can be improved by more than 3 percent, and the economic efficiencyThe benefit is obvious.
The combination mode of the components of the collecting agent is not limited to the combination mode of the medicament provided in the example, and the single combination or multiple combinations of the components of the collecting agent are all protected by the patent.
Claims (10)
1. A combined collector for andalusite ore separation is characterized in that: the main components of the combined collector comprise the following raw materials in percentage by mass:
45-70% of C14-C18 sodium alkyl petroleum sulfonate;
15% -20% of naphthenic acid sulfonate;
5-8% of fuel oil;
5-8% of sorbitan fatty acid ester;
5-10% of organic acid sodium salt;
when the weight percentage of the combined collector is less than 100%, water is added for complementing.
2. A combined collector for andalusite ore separation according to claim 1, wherein: the main components of the combined collector comprise the following raw materials in percentage by mass:
45-70% of C14-C18 sodium alkyl petroleum sulfonate;
15% -18% of naphthenic acid sulfonate;
5-8% of fuel oil;
5-8% of sorbitan fatty acid ester;
5-8% of organic acid sodium salt;
when the weight percentage of the combined collector is less than 100%, water is added for complementing.
3. A combined collector for andalusite ore separation according to claim 2, wherein: the main components of the combined collector comprise the following raw materials in percentage by mass:
50-65% of C14-C18 sodium alkyl petroleum sulfonate;
16% -18% of naphthenic acid sulfonate;
5-7% of fuel oil;
5-8% of sorbitan fatty acid ester;
5-7% of organic acid sodium salt;
when the weight percentage of the combined collector is less than 100%, water is added for complementing.
4. A combined collector for andalusite ore classification according to claim 1, or 2, or 3, characterized in that: the naphthenic acid sulfonate is selected from one or more of amyl naphthenic acid sulfonate or hexyl naphthenic acid sulfonate.
5. A combined collector for andalusite ore classification according to claim 1, or 2, or 3, characterized in that: the fuel oil is selected from one or more of No. 200 heavy oil, No. 120 fuel oil, No. 7 fuel oil, industrial fuel oil, mixed heavy oil and asphalt.
6. A combined collector for andalusite ore separation according to claim 1, wherein: the sorbitan fatty acid ester is selected from one or more of S-20, S-40, S-60 and S-80.
7. A combined collector for andalusite ore separation according to claim 1, wherein: the organic acid sodium salt is selected from one or more of sodium oxalate, sodium citrate, sodium alginate or sodium tartrate.
8. A method of making a combined collector for andalusite ore separation according to any one of claims 1 to 7, wherein: mixing and heating petroleum sodium sulfonate, naphthenate and fuel oil to 80-90 ℃, adding sorbitan fatty acid ester, adding organic acid sodium salt, adding a proper amount of water according to the weight percentage to complement the weight percentage to 100%, and uniformly mixing to obtain the composite fuel.
9. A method of andalusite ore flotation using the combined collector of any one of claims 1-7, characterized in that: the combined collector is used in the acid direct flotation process of andalusite in a manner of dropwise adding stock solution; the flotation temperature of the direct flotation process is 20-30 ℃, and the pH value is 2-5.
10. Use of a combined collector for andalusite ore separation according to any one of claims 1 to 7 as a combined collector in andalusite ore separation.
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CN104624360A (en) * | 2014-12-24 | 2015-05-20 | 中国地质科学院郑州矿产综合利用研究所 | Combined reagent and method for sorting kyanite minerals under neutral condition |
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2019
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US4900431A (en) * | 1987-12-24 | 1990-02-13 | Denain-Anzin Mineraux Refractaire Ceramique S.A. | Process for upgrading andalusite |
RU2498861C1 (en) * | 2012-04-19 | 2013-11-20 | Федеральное государственное бюджетное учреждение науки Горный институт Кольского научного центра Российской академии наук | Method of disthene ore flotation |
CN104624360A (en) * | 2014-12-24 | 2015-05-20 | 中国地质科学院郑州矿产综合利用研究所 | Combined reagent and method for sorting kyanite minerals under neutral condition |
CN108927291A (en) * | 2017-05-24 | 2018-12-04 | 中蓝连海设计研究院 | A kind of combined capturing and collecting agent and preparation method and purposes for andalusite mine sorting |
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