CN1063627A - Make sulfide mineral collector with α-nitroso phosphonate ester - Google Patents
Make sulfide mineral collector with α-nitroso phosphonate ester Download PDFInfo
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- CN1063627A CN1063627A CN 91106627 CN91106627A CN1063627A CN 1063627 A CN1063627 A CN 1063627A CN 91106627 CN91106627 CN 91106627 CN 91106627 A CN91106627 A CN 91106627A CN 1063627 A CN1063627 A CN 1063627A
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- nitroso
- phosphonate
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- ester
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Abstract
Make the method for sulfide mineral collector with α-nitroso phosphate, be used for the separation of sulphide ore, this compounds can be partly or entirely exists with the form of its isomers α-oximido phosphonate, and the working concentration of medicament is 1.0 * 10
-5-1.0 * 10
-3Mol/l, pH are 1-13.The present invention has the following advantages: 1. the medicament selectivity is good, collecting ability is strong; 2. medicament itself has frothing capacity, can not add or add less foaming agent; 3. the applicable pH value scope of medicament is wide.
Description
The present invention relates to the method for α-nitroso phosphonate ester as the sulfide flotation agent.
Sulphide ore comprises chalcopyrite, pyrite, galena, zincblende, mispickel etc.SNa(K xanthic acid salt ROC(S)), dialkyl group/aryl dithio acid esters (RO) in order to separate above-mentioned sulphide ore, at present industrially be to use following flotation agent: morely
2P(S) SH(Na or NH
4), diphenylamines phosphordithiic acid, two sulfo-lignocaine formates (C
2H
5)
2NC(S) SNa or the like, but the common selectivity of these medicaments is relatively poor, and the pH narrow range of application is not suitable for the multicomponent sulphide flotation and separates; Develop multi-series polarity nonionic flotation agent such as Z-200,23 yellow hydrocyanic esters, OS-43, ester 105, double xanthate, black powder ester in recent years again, though some improves these medicaments to multicomponent sulphide ore separation selectivity, also has suitable distance apart from the requirement that separates these mineral effectively.
The relatively poor problem of floating agent selectivity when the objective of the invention is at the sulfide mineral sorting proposes the novel chelating flotation agent of a class.
Described flotation agent is α-nitroso phosphonate ester (full name α-nitroso alkyl phosphonic acids dialkyl ester), has general formula to be:
（Ⅰ）
This compounds can be partly or entirely exists with the form of its isomers α-oximido phosphonate, promptly has general formula:
Wherein:
R, R ' and R " can be H, 1-10 carbon alkyl, cycloalkyl, unsaturated alkyl, hetero atom alkyl;
As alkyl R, R ' and R " carbon chain lengths sum when being 7-9 carbon (phenyl ring is converted into 2 carbon), have best flotation effect.
The working concentration of medicament is 1.0 * 10
-5-1.0 * 10
-3Mol/l, pH are 1-13.
This class medicament is a kind of chelating agent, and selectivity is good, and collecting ability is strong.By the oxygen atom of phosphono and the oxygen atom in nitroso (I) or the oximido (II), the utmost point forms chelate and is attracted to mineral surfaces with the metal ion on sulphide ore surface selectively, makes its hydrophobic and flotation.The pH scope of medicament is wide, can reach 1-13, and this is because the chemical property of medicament is stablized and is flotation performance is preferably especially arranged the cause of polarity nonionic under condition of neutral pH.The best pH scope that various mineral are suitable for is:
The scope of chalcopyrite: pH≤5, pH 〉=7 is all floated admirably;
The scope of zincblende: pH≤3.5, pH 〉=5 is all by collecting effectively;
The scope of galena: 7-11 is all floated effectively;
Pyrite and mispickel: in whole pH scope, have certain floatability, but poorer than other mineral.
The α of common various alkyl carbon chain lengths-nitroso phosphonate ester or α-oximido phosphonate are all effective to chalcopyrite, galena, zincblende, and difficult floating pyrite and mispickel, therefore suitable Cu, Pb, Zn sulphide ore separate with these two kinds of mineral.And when its hydrocarbon chain short (R, R ', R " sum≤7, phenyl length is in 2C), be applicable to separating of pyrite and mispickel, for example, use α-nitroso benzylphosphonic acid diethyl ester can separate pyrite and mispickel effectively.
The medicament preparation method is as follows:
Obtain the alpha-carbonyl phosphonic acid diester with phosphite ester and acyl chloride reaction, just have alkali such as pyridine, NaOH etc. in the presence of make α-oximido phosphonate with the hydroxylamine hydrochloride oximate, the latter obtains α-nitroso phosphonate ester through rearrangement, reaction equation is as follows:
Usually, equimolar acyl chlorides and phosphite ester are used in reaction (1), at room temperature react 0.5-5 hour (when using active lower phosphite ester such as triphenyl phosphite to make raw material, must add hot reflux), stir simultaneously, can place then 2-24 hour so that react more complete.Reaction (2) be the alpha-carbonyl phosphonic acid diester that will obtain join contain excessive 5-50%(mol ratio) hydroxylamine hydrochloride and excessive 5-50%(mol ratio) solvent (as the ethanol) mixed liquor of alkali (as pyridine) in carry out, hydroxylamine hydrochloride and alkali consumption are all with excessive 10-15%(mol ratio) be good.
Because of being exothermic reaction, should control charging rate and make temperature≤30 ℃, finish, stirring at room 2-72 hour, reactant liquor through washing, dry, separate and promptly get α-nitroso phosphonate ester or/and its isomers α-oximido phosphonate.Should notice in the separation process that temperature can not be too high, in the time of＞150 ℃, alpha-carbonyl phosphonate ester and α-nitroso phosphonate ester all very easily decomposes.
When using asymmetric phosphite ester (R'O) as (RO)
2P or (RO) (RO') (RO ") can obtain asymmetric α-nitroso phosphonate ester or asymmetric α-oximido phosphonate when P makes raw material.
The present invention has the following advantages:
1. the medicament selectivity is good, collecting ability is strong.
2. medicament itself has frothing capacity, can not add or add less foaming agent.
3. the applicable pH value scope of medicament is wide.
Embodiment:
(1) medicament preparation
1. the preparation of α-nitroso diethyl ethylphosphate: the 25g triethyl phosphite is added drop-wise to (exothermic heat of reaction) in the 12g chloroacetic chloride under stirring, drip and finish, stirring at room 2h, decompression distillation is collected 69-72 ℃/0.267KPa distillate and is got 20.5g Alpha-hydroxy diethyl ethylphosphate.Alpha-hydroxy diethyl ethylphosphate 19g splashed under stirring condition contain in 10g hydroxylamine hydrochloride, 11.1g pyridine and the 50ml alcohol mixeding liquid, course of reaction control temperature＜30 ℃, decompression distillation behind the 3h, collect 140 ℃/93.3Pa fraction, get 18g α-nitroso diethyl ethylphosphate product, content 98.0%.
2. the preparation of α-oximido benzylphosphonic acid diethylester: the 25g triethyl phosphite is added drop-wise to (exothermic heat of reaction) in the 21g chlorobenzoyl chloride under stirring, after adding, in 35 ℃ of reaction 3h, decompression distillation, getting the 28g boiling point is α-oximido benzylphosphonic acid diethylester of 127-131 ℃/0.267-0.4KPa.This compound 14.5g is joined under stirring condition in 7g hydroxylamine hydrochloride, 8g pyridine and the 50ml alcohol mixeding liquid, after adding, successive reaction 5h, reactant liquor is treated, gets 13.8g α-oximido benzylphosphonic acid diethyl ester product, content 82.0% behind the purifying.
3. the preparation of α-nitroso ethylphosphonic acid diphenyl: 31g tricresyl phosphite phenylester is mixed with the 8g chloroacetic chloride, stirring also adds hot reflux, reaction 5h, reactant liquor is through separation, purifying and dry, the Alpha-hydroxy ethylphosphonic acid diphenyl that obtains is added drop-wise in 9.2g hydroxylamine hydrochloride, 11.85g pyridine and the 170ml absolute ethyl alcohol mixed liquor, stirring reaction 24h, reactant liquor is through decompression distillation (following decomposition), obtain 9.7g(160 ℃/0.4KPa) α-nitroso ethylphosphonic acid diphenyl product, content 97.3%.
(2) as collecting agent
1. be collecting agent with α-nitroso diethyl ethylphosphate, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) chalcopyrite-mispickel mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH7.4, a flotation, flotation time 2 minutes, raw ore copper grade 15.10% obtains concentrate copper grade 26.57%, concentrate copper recovery 89.3%, mine tailing copper grade 2.92%.
2. be collecting agent with α-nitroso ethylphosphonic acid dibutyl ester, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) chalcopyrite-mispickel mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH9.6, a flotation, flotation time 2 minutes, raw ore copper grade 15.10% obtains concentrate copper grade 22.97%, the rate of recovery 95.9%, mine tailing copper grade 2.46%.
3. be collecting agent with α-nitroso ethylphosphonic acid dibutyl ester, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) chalcopyrite-mispickel mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH2.6, a flotation, flotation time 2 minutes, raw ore copper grade 15.10% obtains concentrate copper grade 24.6%, the rate of recovery 98.0%, mine tailing copper grade 0.75%.
4. be collecting agent with α-nitroso ethylphosphonic acid dibutyl ester, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) galena-chalcopyrite mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH1.5, a flotation, flotation time 2 minutes, raw ore copper grade 15.10% obtains concentrate copper grade 20.80%, the rate of recovery 96.7%, mine tailing copper grade 1.86%.
5. be collecting agent with α-nitroso ethylphosphonic acid dibutyl ester, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) chalcopyrite-zincblende mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH2.5, a flotation, flotation time 2 minutes, raw ore copper grade 15.10% obtains concentrate copper grade 19.11%, the rate of recovery 74.1%, mine tailing copper grade 9.08%.
6. be collecting agent with α-nitroso ethylphosphonic acid dibutyl ester, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) chalcopyrite-pyrite mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH10.4, a flotation, flotation time 2 minutes, raw ore copper grade 15.10% obtains concentrate copper grade 20.99%, the rate of recovery 79.2%, mine tailing copper grade 1.14%.
7. be collecting agent with α-nitroso ethylphosphonic acid dihexyl, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) zincblende-mispickel mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH10.4, a flotation, flotation time 2 minutes, raw ore zinc grade 32.52% obtains concentrate zinc grade 46.07%, the rate of recovery 51.3%, mine tailing zinc grade 22.44%.
8. be collecting agent with α-nitroso ethylphosphonic acid dihexyl, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) chalcopyrite-mispickel mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH9.4, a flotation, flotation time 2 minutes, raw ore copper grade 15.10% obtains concentrate copper grade 23.88%, the rate of recovery 91.4%, mine tailing copper grade 2.28%.
9. be collecting agent with α-oximido benzylphosphonic acid diethylester, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) chalcopyrite-mispickel mixture, sample 2g, drug concentration 2.0 * 10
-4Mol/l, pH3.1, a flotation, flotation time 2 minutes, raw ore copper grade 15.10% obtains concentrate copper grade 23.34%, concentrate copper recovery 96.2%, mine tailing copper grade 1.14%.
10. be collecting agent with α-oximido benzylphosphonic acid diethylester, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) pyrite-mispickel mixture, sample 2g, drug concentration 6.0 * 10
-4Mol/l, pH3.3, a flotation, flotation time 2 minutes, raw ore arsenic grade 23.00% obtains concentrate arsenic grade 11.33%, the rate of recovery 24.6%, mine tailing arsenic grade 38.49%.
11. with α-oximido benzylphosphonic acid diethylester is collecting agent, 1 of FLOTATION SEPARATION-76 μ: the 1(weight ratio) zincblende-mispickel mixture, sample 2g, drug concentration 6.0 * 10
-4Mol/l, pH3.1, a flotation, flotation time 2 minutes, raw ore zinc grade 32.52% obtains concentrate zinc grade 54.76%, the rate of recovery 97.0%, mine tailing zinc grade 2.00%.
Claims (10)
1, a kind ofly make the method for sulfide mineral collector, it is characterized in that with α-nitroso phosphonate ester: described collecting agent has general formula and is:
This compounds can be partly or entirely exists with the form of its isomers, promptly has general formula:
Wherein: R, R ' and R " can be H, 1-10 carbon alkyl, cycloalkyl, unsaturated alkyl, hetero atom alkyl;
The working concentration of medicament is 1.0 * 10
-5-1.0 * 10
-3Mol/l, pH are 1-13.
2, method according to claim 1 is characterized in that, as hydroxyl R, R ' and R " carbon chain lengths sum when being 7-9 (phenyl ring is converted into 2 carbon), have best flotation effect.
3, method according to claim 1 is characterized in that, the pH scope of chalcopyrite is pH≤5, pH 〉=7.
4, method according to claim 1 is characterized in that, the pH scope of zincblende is pH≤3.5, pH 〉=5.
5, method according to claim 1 is characterized in that, the pH scope of galena is 7-11.
6, method according to claim 1 is characterized in that, when pyrite and mispickel are separated from each other, with the medicament of alkyl carbon chain lengths sum≤7 be advisable (phenyl ring is converted into 2 carbon).
7, a kind of preparation method who is used as the α-nitroso phosphonate ester of sulfide mineral collector is characterized in that following steps and condition:
1) with equimolar phosphite ester and acyl chloride reaction 0.5-5 hour, obtains the alpha-carbonyl phosphonic acid diester;
2) in solvent, in the presence of alkali, use the hydroxylamine hydrochloride oximate, make α-oximido phosphonate;
3) obtain α-nitroso phosphonate ester through rearrangement then;
4) stirring at room 2-72 hour, reactant liquor through washing, dry, separation promptly gets α-nitroso phosphonate ester or/and it leads structure body α-oximido phosphonate.
8, preparation method according to claim 7 is characterized in that, uses triphenyl phosphite to make raw material, must be heated to reflux temperature and react, and stirs simultaneously.
9, preparation method according to claim 7 is characterized in that, described solvent is an ethanol.
10, preparation method according to claim 7 is characterized in that, during with the hydroxylamine hydrochloride oximate, and each excessive 5-50%(mol ratio of hydroxylamine hydrochloride and alkali).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106627 CN1038397C (en) | 1991-02-02 | 1991-02-02 | Sulfrized mine trap using alpha-nitrosyl phosphate ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106627 CN1038397C (en) | 1991-02-02 | 1991-02-02 | Sulfrized mine trap using alpha-nitrosyl phosphate ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063627A true CN1063627A (en) | 1992-08-19 |
| CN1038397C CN1038397C (en) | 1998-05-20 |
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ID=4908019
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91106627 Expired - Fee Related CN1038397C (en) | 1991-02-02 | 1991-02-02 | Sulfrized mine trap using alpha-nitrosyl phosphate ester |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305577C (en) * | 2002-08-03 | 2007-03-21 | 科莱恩产品（德国）有限公司 | Collecting agent for sulphidic ores |
| CN101337205B (en) * | 2008-08-13 | 2011-04-20 | 中南大学 | Use of diester isosulfocyanate in sulphide ore floation and preparation method thereof |
| CN101549326B (en) * | 2009-05-15 | 2012-07-04 | 江西理工大学 | Technique for floatation separation of hard washing copper zinc sulfuration mine |
| CN103386366A (en) * | 2012-05-08 | 2013-11-13 | 上海喜若飞精细化工有限公司 | Preparation method of phosphidation ore dressing collector |
| CN112973968A (en) * | 2021-02-04 | 2021-06-18 | 中南大学 | Flotation reagent and flotation separation method for pyrite-chalcopyrite |
-
1991
- 1991-02-02 CN CN 91106627 patent/CN1038397C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305577C (en) * | 2002-08-03 | 2007-03-21 | 科莱恩产品（德国）有限公司 | Collecting agent for sulphidic ores |
| CN101337205B (en) * | 2008-08-13 | 2011-04-20 | 中南大学 | Use of diester isosulfocyanate in sulphide ore floation and preparation method thereof |
| CN101549326B (en) * | 2009-05-15 | 2012-07-04 | 江西理工大学 | Technique for floatation separation of hard washing copper zinc sulfuration mine |
| CN103386366A (en) * | 2012-05-08 | 2013-11-13 | 上海喜若飞精细化工有限公司 | Preparation method of phosphidation ore dressing collector |
| CN103386366B (en) * | 2012-05-08 | 2017-08-04 | 上海喜若飞精细化工有限公司 | A kind of preparation method of phosphotidic beneficiation collecting agent |
| CN112973968A (en) * | 2021-02-04 | 2021-06-18 | 中南大学 | Flotation reagent and flotation separation method for pyrite-chalcopyrite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1038397C (en) | 1998-05-20 |
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