CN1063058A - Fluorite technology and adjustment agent composition thereof - Google Patents
Fluorite technology and adjustment agent composition thereof Download PDFInfo
- Publication number
- CN1063058A CN1063058A CN 91112718 CN91112718A CN1063058A CN 1063058 A CN1063058 A CN 1063058A CN 91112718 CN91112718 CN 91112718 CN 91112718 A CN91112718 A CN 91112718A CN 1063058 A CN1063058 A CN 1063058A
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- acid
- salt
- composition
- waterglass
- fluorite
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Abstract
The present invention is the process in a kind of flotation fluorite ore deposit, and it is the improvement to No. 87105202 granted patents.Flotation fluorite ore deposit adopts acid to add alkali to add synergist and adjust agent in the prior art.The present invention then adds the composition that acid reaches and one or more soluble-salts of this acid composition mix with waterglass and adjusts agent, and formation composition series, be any acid and corresponding salt in available sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, the acetic acid, the portfolio ratio scope is a waterglass: acid: salt=1~2: 1~5: 0.5~1.Adaptability of the present invention is strong, good stability, concentrate high-quality, and rate of recovery height, cost is low.
Description
The present invention relates to the process in a kind of flotation fluorite ore deposit, it is to the improvement about flotation fluorite ore deposit method of No. 87105202 granted patents.
Method according to No. 87105202 patent applications, the adjustment agent of flotation fluorite is that acid adds alkali and adds synergist, effect is than the obvious improvement of prior art, but because of synergist (carboxymethyl cellulose or calgon or prodan) price expensive, solubility is low, the amount of allocating into is few, and effect is still very good inadequately, is of limited application.Take a broad view of domestic and international fluorite present situation, the improvement of adjusting agent in the traditional handicraft is had acid system and alkaline system, the former adds waterglass for acid, and is stronger to the inhibition of siliceous minerals such as quartz, but poor stability, the flotation froth breaking seldom adopts in the production; The latter for waterglass add slaine (as US3893915, US3207304, SU1128984, SU671855 SU1002014), strengthens the inhibition to calcite, but turbidity sediment and losing efficacy easily.From prior art, can find out, the someone did not expect adjusting adding acid in the agent at alkaline system, or in acid system, add salt and improve, main cause is " acidic water glass " easily agglutination and make and adjust agent and lost efficacy, those skilled in the art attentively work hard in alkaline system.Exhausted expect in alkaline system, adding acid less or in the acid system with salt.
The purpose of this invention is to provide a kind of medicament source easily, the adjustment agent composition of make up a prescription convenience, solubility height, stable transparent, said composition is used in the fluorite process of the present invention can suppress associated minerals such as barite, calcite, quartz, mica effectively, fluorite is fully swum, thereby improve the selectivity and the rate of recovery of fluorite.
Purpose of the present invention realizes by the following method: with waterglass add acid and one or more soluble-salts of forming with this acid (as multiple salt, then the ratio of its multiple salt is 0.5: 0.1~1.0), its combination is than being: waterglass: acid: salt=1~2: 1~5: 0.5~1(weight ratio, down together), combination liquid pH≤3, be the aqueous solution of stable transparent, its concentration is 1~20%(percentage by weight).
Purpose of the present invention can also realize by the following method:
1. add oxalic acid (H with waterglass
2C
2O
4), salt uses the solubility oxalates (as Na
2C
2O
4), it makes up than being: waterglass: oxalic acid: solubility oxalates=2: 3: 1.Use oxalic acid and oxalates to separate better effects if when flotation contains more fluorite ore deposit, pyroxene ore deposit, the fluorite rate of recovery is higher.
2. add acetic acid (CH with waterglass
3COOH) add solubility acetate (as CH
3COONa, CH
3COOK etc.) adjust the agent composition, it makes up than being: waterglass: acetic acid: solubility acetate=2: 5: 1.The composition that uses this type of acid and salt thereof to form more is adapted to fluorite to be separated with quartz.
3. add nitric acid (HNO with waterglass
3) and solubility nitrate (as NaNO
3, KNO
3Deng), it makes up than being: waterglass: nitric acid: solubility nitrate=1: 1: 0.5.This based composition is more effective to the fluorite flotation of fine-grained disseminated grain.
4. add hydrochloric acid (HCl) with waterglass and soluble-salt hydrochlorate (as NaCl, KCl etc.) adjusts the agent composition, it makes up than being: waterglass: hydrochloric acid: soluble-salt hydrochlorate=1: 1: 0.5, it more is applicable to separates fluorite and barite.
5. add sulfuric acid (H with waterglass
2SO
4) and soluble sulphate (as Na
2SO
4, FeSO
4, ZnSO
4, (NH
4)
2SO
4, Al
2(SO
4)
3) being mixed into composition, it makes up than being: waterglass: hydrochloric acid: soluble sulphate=1: 1: 0.5, this based composition is more effective to separating fluorite and calcite.
6. add sulfuric acid with waterglass and add multiple soluble sulphate (as Na
2SO
4Add (NH
4)
2SO
4) make composition, it makes up than being: waterglass: sulfuric acid: multiple soluble sulphate=1: 1: 0.5, the ratio of wherein multiple salt is: 0.5: 0.1~1.0.
Above-mentioned hydrochloric acid, nitric acid, sulfuric acid etc. can substitute mutually, also can substitute mutually with the corresponding salt of this acid.
Concrete grammar of the present invention is: take sample ore, with grinde ore to fluorite monomer dissociation rate greater than 95%, the rare one-tenth concentration of water is 25~30%(solid) ore pulp, available any composition of the present invention adjusts agent, with oleic acid (or fatty acid soaps) as the collecting foaming agent of holding concurrently, under near neutral (pH=6.5~7.0) medium and normal temperature (20~30 ℃) condition, carry out flotation, roughly select foam and promptly get fluorite concentrate selected 5~7 times, the consumption of composition is according to ore character and grade and decide, generally roughly select 500~1500 gram/tons, selected 500~800 gram/tons, flotation flowsheet adopts " set composite ".So obtain concentrate grade and can reach 98~99%CaF
2, the rate of recovery reaches 85~90%.
The invention will be further described with embodiment below:
Embodiment 1: take fluorite-pyroxene ore deposit, contain 45%CaF
2, be milled to less than 200 orders to the ore deposit and account for 88%, rare to pulp density 25%(solid), add composition (waterglass: oxalic acid: sodium oxalate=2: 3: 1) adjust agent, roughly select consumption 1200 gram/tons, stirred 3 minutes; Add oleic acid 360 gram/tons, stirred 3 minutes, flotation is 6 minutes under normal temperature (20~22 ℃) condition, foam after primary cleaning in chats 1 and the initial separatory cell ore pulp merging enter and scan, select foam to return again and roughly select or handle separately the inferior concentrate (loop I) of output; Selected composition 400 gram/tons that add for the second time, chats 2 returns in advance into roughly selecting, for the third time selected not dosing, the 4th the selected composition 200 gram/tons that add again, third and fourth, five, six selected chats return last operation (loop II) successively, the process that all sorts all adopts common flotation device, pH values of pulp=6.5~7.0, the final fluorite concentrate rate of recovery 85.3%, grade 98.6%CaF
2(primes).
Example 2. usefulness somewhere fluorite-quartz mines contain " sludge " up to 20%, the present invention are opposed than test experiment I intermixture (H with No. 87105202 patents
2SO
4: Na
2SiO
3: CMC=1: 1: 0.1) adjust agent, consumption is for roughly selecting 1000 gram/tons, and selected 500 gram/tons, grade is given the ore deposit by 67%() bring up to 98.5%CaF
2(concentrate), the fluorite rate of recovery 83%; (waterglass: acetic acid: sodium acetate=2: 5: 1), method is with example one, and consumption 800 gram/tons (roughly selecting) and 400 gram/tons (selected) obtain concentrate grade 99%CaF with composition for the experiment II
2(select quality), the rate of recovery 88%.
Example 3. methods are with example one.Fluorite ore deposit, somewhere grade is low (to contain 38.4CaF
2), embedding cloth grain carefully (is milled to the 90%-200 order, fluorite monomer rate is 93%), with composition (waterglass: nitric acid: sodium nitrate=1: 1: 0.5) adjust agent, consumption 1500 gram/tons (roughly selecting) and 800 gram/tons (selected), obtain fluorite concentrate grade 98.2%(primes), the rate of recovery 80%.Use KNO
3Replace NaNO
3Also get analog result.
Example 4. methods are with example one.Somewhere fluorite-calcite ore contains 65%CaF
2, 18.5%CaCO
3, conventional dose can not make fluorite separate with calcite, and (waterglass: sulfuric acid: sodium sulphate=1: 1: 0.5) adjust agent, consumption 1400 gram/tons (roughly selecting) and 600 gram/tons (selected) obtain fluorite concentrate grade 98.8%CaF with composition
2(select quality), the rate of recovery 90.5%.
Example 5. somewhere fluorite-barite deposits contain 60%CaF
2, 21%BaSO
4Adopt prior art can only obtain fluorite-barite bulk concentrate (defective), with composition (waterglass: hydrochloric acid: sodium chloride=1: 1: 0.5), consumption 900 gram/tons (roughly selecting) and 500 gram/tons (selected), method is with example one, fluorite is accurately separated, fluorite concentrate grade 98.5%CaF with barite
2(primes), the rate of recovery 89.4%.
The white tungsten mine tailing in example 6. somewheres (contains 20.5%CaF
2), handle because of the floatation process that does not have success, be forced to store up for a long time.(waterglass: sulfuric acid: ammonium sulfate=1: 1: 0.5) adjust agent, method is with example one, and consumption 1000 gram/tons (roughly selecting) and 300 gram/tons (selected) obtain unprecedented good index, concentrate grade 98.2%CaF with composition
2(primes), the rate of recovery>88%.
Example 7. somewhere Pb-Zn tailings (contain 25.6%CaF
2), with conventional beneficiation method flotation, concentrate sulfur-bearing severe overweight, (waterglass: sulfuric acid: ferrous sulfate=1: 1: 0.5), method is with example one, consumption 1600 gram/tons (roughly selecting) and 800 gram/tons (selected), fluorite concentrate grade 98.6%CaF with composition
2(primes), the rate of recovery 81.3%.
Example 8. somewhere fluorite-quartz-MICAs contain 70%CaF
2, (waterglass: sulfuric acid: zinc sulfate=1: 1: 0.5), method is with example one, consumption 800 gram/tons (roughly selecting) and 400 gram/tons (selected), fluorite concentrate grade 99.25%CaF with composition
2(select quality), the rate of recovery reaches 91.95%.
Example 9. somewheres contain the fluorite ore deposit of tourmaline, grade 61.5%CaF
2, use the prior art flotation, form " off standard " because of being mingled with tourmaline in the fluorite concentrate; (waterglass: sulfuric acid: aluminum sulfate=1: 1: 0.5), method is with example one, and consumption 1000 gram/tons (roughly selecting) and 400 gram/tons (selected) obtain fluorite concentrate grade 98.3%CaF with composition
2(primes), the rate of recovery reaches 90.4%.
Example 10. somewheres contain the fluorite ore deposit of garnet, pyroxene, grade 50.5%CaF
2, use the prior art test of many times, all the end obtains qualified fluorite concentrate, and (waterglass: sulfuric acid: sodium sulphate: ammonium sulfate=1: 1: 0.5: 0.5), method obtains fluorite concentrate grade 98.8%CaF with example one to adopt composition
2, (primes), the rate of recovery 86.8%.
Above embodiment as can be seen, the present invention compared with prior art has very big characteristics: promptly waterglass adds acid and adjusts agent composition series with the soluble-salt formation fluorite that this acid is formed, its adaptability is strong, good stability, the concentrate high-quality, rate of recovery height, cost is low, remarkable in economical benefits.
1. said composition can not only make fluorite ore deposit and quartz mine FLOTATION SEPARATION, and fluorite and barite, fluorite and calcite, fluorite and mica etc. are separated, and this is that prior art institute is inaccessible.
2. the easy gel of acidic water glass is rotten in the prior art, and salt waterglass was easily because of flocculation sediment lost efficacy, present composition stable performance, and the solubility height, preparation is convenient.
3. the fluorite concentrate grade that obtains usually of prior art is 97%CaF
2, the present invention can obtain grade and reach 98~99%CaF
2Fluorite concentrate.
4. the medicament of prior art use is more expensive, flotation recovery rate≤80%, and present composition cost is low, and flotation recovery rate is up to 85~90%.
Those of ordinary skills can do some improvement to the present invention fully, for example available some other acid and salt thereof, as sulfurous acid, phosphoric acid, etching acid and corresponding salt thereof, or monoxone, benzoic acid, phthalic acid and corresponding salt thereof or the like, obviously, these improve and all do not deviate from and surmount category of the present invention.
Claims (8)
1, a kind of composition as flotation fluorite adjustment agent comprises waterglass (Na
2SiO
3) add acid and one or more soluble-salts of forming with this acid (as multiple salt, then the ratio of its multiple salt is 0.5: 0.1~1.0), its combination is than being: waterglass: acid: salt=1~2:1~5:0.5~1 (weight ratio, combination liquid PH<3 down together), be the aqueous solution of stable transparent, its concentration is 1~20% (percentage by weight).
2,, it is characterized in that acid is oxalic acid (H according to the composition of claim 1
2C
2O
4), salt is that the solubility oxalates is (as Na
2C
2O
4), it makes up than being: waterglass: oxalic acid: solubility oxalates=2: 3: 1.
3,, it is characterized in that acid is acetic acid (CH according to the composition of claim 1
3COOH), salt is that solubility acetate is (as CH
3COONa), its combination is than being: waterglass: acetic acid: solubility acetate=2: 5: 1.
4,, it is characterized in that acid is nitric acid (HNO according to the composition of claim 1
3), salt is that solubility nitrate is (as NaNO
3), it makes up than being: waterglass: nitric acid: solubility nitrate=1: 1: 0.5.
5, according to the composition of claim 1, it is characterized in that acid is hydrochloric acid (HCl), salt is soluble-salt hydrochlorate (as NaCl), it makes up than being: waterglass: hydrochloric acid: soluble-salt hydrochlorate=1: 1: 0.5.
6,, it is characterized in that acid is sulfuric acid (H according to the composition of claim 1
2SO
4), salt is that soluble sulphate is (as Na
2SO
4, FeSO
4, ZnSO
4, (NH
4)
2SO
4, Al
2(SO
4)
3), it makes up than being: waterglass: sulfuric acid: soluble sulphate=1: 1: 0.5.
7,, it is characterized in that acid is sulfuric acid (H according to the composition of claim 1
2SO
4), salt is that multiple soluble sulphate is (as Na
2SO
4Add (NH
4)
2SO
4), it makes up than being: waterglass: sulfuric acid: multiple soluble sulphate=1: 1: 0.5, the ratio of wherein multiple salt is: 0.5: 0.1~1.0.
8, a kind of method of flotation fluorite, be to take sample ore, with grinde ore to fluorite monomer dissociation rate greater than 95%, the rare one-tenth concentration of water is 25~30%(solid) ore pulp after, available aforesaid right requires any composition in 1~7 to adjust agent, with oleic acid (or fatty acid soaps) as the collecting foaming agent of holding concurrently, under near neutral (PH=6.5~7.0) medium and normal temperature (20~30 ℃) condition, carry out flotation, roughly select foam and promptly get fluorite concentrate selected 5~7 times, the consumption of composition is according to the character of ore and grade and decide, generally roughly select consumption 500~1500 gram/tons, selected consumption 500~800 gram/tons, flotation flowsheet adopts " set composite ".
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 91112718 CN1023081C (en) | 1991-12-31 | 1991-12-31 | Floating selection process for fluorite and its modifier compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 91112718 CN1023081C (en) | 1991-12-31 | 1991-12-31 | Floating selection process for fluorite and its modifier compositions |
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Publication Number | Publication Date |
---|---|
CN1063058A true CN1063058A (en) | 1992-07-29 |
CN1023081C CN1023081C (en) | 1993-12-15 |
Family
ID=4911043
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---|---|---|---|
CN 91112718 Expired - Fee Related CN1023081C (en) | 1991-12-31 | 1991-12-31 | Floating selection process for fluorite and its modifier compositions |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102151615A (en) * | 2010-12-21 | 2011-08-17 | 北京矿冶研究总院 | Fluorite flotation method in high-salinity alkaline water environment |
CN101712014B (en) * | 2009-12-08 | 2012-03-21 | 湖南省铸万有实业有限公司 | Multicategory-impurity single fluorite ore dressing method |
CN101507948B (en) * | 2009-04-03 | 2012-04-25 | 陕西新星浮选剂有限责任公司 | Cold condition fluorite flotation collector |
CN102489408A (en) * | 2011-12-19 | 2012-06-13 | 湖南有色金属研究院 | Flotation method for separating copper form mica |
CN102658242A (en) * | 2012-04-25 | 2012-09-12 | 白银有色集团股份有限公司 | Mineral separation process of complex fluorite difficult to separate |
CN102896047A (en) * | 2012-10-08 | 2013-01-30 | 湖南有色金属研究院 | Method for beneficiating high-peat copper sulphide ore |
CN101583431B (en) * | 2007-01-12 | 2013-09-18 | Omya发展股份公司 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate |
CN104694736A (en) * | 2015-03-23 | 2015-06-10 | 东北大学 | Calcium roasting floatation separation method for bastnaesite |
CN105149100A (en) * | 2015-08-07 | 2015-12-16 | 广州有色金属研究院 | Method for recovering barite from lead and zinc tailings |
CN105689148A (en) * | 2016-04-22 | 2016-06-22 | 云南罗平锌电股份有限公司 | Method for inhibiting calcium and magnesium in mineral separation process |
CN106179763A (en) * | 2016-06-27 | 2016-12-07 | 洛阳丰瑞氟业有限公司 | Fluorite flotation calcium carbonate inhibitor and preparation method thereof |
CN106492994A (en) * | 2016-11-02 | 2017-03-15 | 广西大学 | A kind of preparation method of olivine mineral inhibitor |
CN115090409A (en) * | 2022-06-16 | 2022-09-23 | 中化地质矿山总局地质研究院 | Ore dressing method for fluorite ore |
-
1991
- 1991-12-31 CN CN 91112718 patent/CN1023081C/en not_active Expired - Fee Related
Cited By (18)
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---|---|---|---|---|
CN101583431B (en) * | 2007-01-12 | 2013-09-18 | Omya发展股份公司 | Process of purification of minerals based on calcium carbonate by flotation in the presence of quartenary imidazolium methosulfate |
CN101507948B (en) * | 2009-04-03 | 2012-04-25 | 陕西新星浮选剂有限责任公司 | Cold condition fluorite flotation collector |
CN101712014B (en) * | 2009-12-08 | 2012-03-21 | 湖南省铸万有实业有限公司 | Multicategory-impurity single fluorite ore dressing method |
CN102151615A (en) * | 2010-12-21 | 2011-08-17 | 北京矿冶研究总院 | Fluorite flotation method in high-salinity alkaline water environment |
CN102489408A (en) * | 2011-12-19 | 2012-06-13 | 湖南有色金属研究院 | Flotation method for separating copper form mica |
CN102489408B (en) * | 2011-12-19 | 2013-04-10 | 湖南有色金属研究院 | Flotation method for separating copper form mica |
CN102658242A (en) * | 2012-04-25 | 2012-09-12 | 白银有色集团股份有限公司 | Mineral separation process of complex fluorite difficult to separate |
CN102896047B (en) * | 2012-10-08 | 2014-12-24 | 湖南有色金属研究院 | Method for beneficiating high-peat copper sulphide ore |
CN102896047A (en) * | 2012-10-08 | 2013-01-30 | 湖南有色金属研究院 | Method for beneficiating high-peat copper sulphide ore |
CN104694736A (en) * | 2015-03-23 | 2015-06-10 | 东北大学 | Calcium roasting floatation separation method for bastnaesite |
CN105149100A (en) * | 2015-08-07 | 2015-12-16 | 广州有色金属研究院 | Method for recovering barite from lead and zinc tailings |
CN105149100B (en) * | 2015-08-07 | 2018-01-19 | 广州有色金属研究院 | A kind of method that barite is reclaimed from Pb-Zn tailings |
CN105689148A (en) * | 2016-04-22 | 2016-06-22 | 云南罗平锌电股份有限公司 | Method for inhibiting calcium and magnesium in mineral separation process |
CN105689148B (en) * | 2016-04-22 | 2018-05-08 | 云南罗平锌电股份有限公司 | It is a kind of to suppress calcium, the method for magnesium in ore dressing process |
CN106179763A (en) * | 2016-06-27 | 2016-12-07 | 洛阳丰瑞氟业有限公司 | Fluorite flotation calcium carbonate inhibitor and preparation method thereof |
CN106492994A (en) * | 2016-11-02 | 2017-03-15 | 广西大学 | A kind of preparation method of olivine mineral inhibitor |
CN106492994B (en) * | 2016-11-02 | 2018-11-20 | 广西大学 | A kind of preparation method of olivine mineral inhibitor |
CN115090409A (en) * | 2022-06-16 | 2022-09-23 | 中化地质矿山总局地质研究院 | Ore dressing method for fluorite ore |
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