CN1138031A - Alkyl xanthogenate type xanthate - Google Patents
Alkyl xanthogenate type xanthate Download PDFInfo
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- CN1138031A CN1138031A CN 95110804 CN95110804A CN1138031A CN 1138031 A CN1138031 A CN 1138031A CN 95110804 CN95110804 CN 95110804 CN 95110804 A CN95110804 A CN 95110804A CN 1138031 A CN1138031 A CN 1138031A
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Abstract
The alkylxanthate-type yellow chemical chemically named 1,3-sodium (or potassium) dimethylbutylxanthate is directly synthesized with methylisobutylmethanol, sodium (or potassium) hydroxide and CS2 and can be used as gold trapping agent to increase recovery rate of gold or for raising grade of copper ore concentrate without use of foamer.
Description
The present invention relates to a kind of xanthate and synthetic method thereof, be meant alkyl xanthogenate type xanthate particularly.
Alkyl xanthogenate type xanthate flotation agent mostly is four carbon atom and following rudimentary xanthate.Home products has ethyl xanthate, sec.-propyl xanthate, Isobutylxanthic acid, defends basic xanthate etc.Rudimentary xanthate character is not quite stable, and when being used for sorting between the sulphide ores, its selectivity is not ideal enough.To based on malachite, dihydrite, oxidation ratio is high, silt content is big refractory copper oxide ore, the rudimentary xanthate Floatation of Copper grade and the rate of recovery are lower.Particularly along with the minimizing gradually in easy ore dressing goods and materials source, the poor thin flotation that waits refractory mineral, the rate of recovery such as the comprehensive recovery of polymetallic ore and precious metal have much room for improvement.The trend of the research nineties and the use oriented long carbochain xanthate of xanthate and isomers development.The xanthate Floatation of Copper molybdenum sulphide ores that human butyl, 2-ethylhexyl, heptyl and C8-C10 are arranged, (Azizyan, L.v.a.t.al.c.a.Vol.115 (1991), 163498) study their consumption and the relation of the concentrate grade and the rate of recovery, and done commerical test with basic xanthate, it is said that the floatation indicators of copper and molybdenum increases.
The object of the present invention is to provide a kind of syntheticly simple, low toxicity can obviously improve the alkyl xanthogenate type xanthate of gold recovery.
Alkyl xanthogenate type xanthate provided by the invention has following structure:
Wherein M is Na or K.
This xanthate can be by methyl isobutyl carbinol, and sodium hydroxide or potassium and dithiocarbonic anhydride three are synthetic, and chemical equation is as follows:
This reaction is thermopositive reaction.Owing to proportion scale, the difference of reaction conditions, may generate the organic sulfide of small amounts of inorganic sulfide and non-xanthogenate.These pairs reaction product all can influence quality product.Alcohol, CS
2, the alkali three proportioning be 1.0: 0.5～2.0: 0.5～2.0 more suitable, productive rate is higher.
When synthetic, can earlier alcohol and alkali be added in the reactor, drip CS again
2React; In the aforesaid operations, charge temperature is controlled at below 50 ℃, is preferably 20～35 ℃, and temperature of reaction is below 80 ℃, is preferably 20～50 ℃.Also can be earlier with pure and mild CS
2Add reactor, again alkali is added in batches.In the aforesaid operations, charge temperature should be controlled at below 50 ℃, is preferably 20～40 ℃, and temperature of reaction is below 80 ℃, is preferably 20～50 ℃.Above two kinds of synthesis steps can be described as single stage method.As can be seen, aforesaid method is fairly simple, can produce the qualified product that satisfy the mine production requirement.In order further to improve the quality of products, on the basis of above-mentioned single stage method, improved, promptly before adding reaction mass, in reactor, add earlier reaction medium, again alcohol is added, add alkali then, drip CS at last
2Described reaction medium is the alcohol that participates in reaction, i.e. methyl isobutyl carbinol, perhaps other lightweight oils such as kerosene.If adopt alcohol to make reaction medium, after having reacted, material in the reduced pressure drying, can be obtained product, reclaimed alcohol simultaneously.If make reaction medium with kerosene or other lightweight oils, then after having reacted, first water extraction will promptly get product behind the water drying under reduced pressure, and oil phase can be recycled after refining.The amount of used solution medium is as 20～300% of the alcohol amount of reactant.When making reaction medium with kerosene or lightweight oil, the total amount of used extraction agent water is no more than effecting reaction thing total amount.Above-mentioned two kinds of synthetic methods can be described as the solvent synthesis method, when reinforced temperature below 50 ℃, best 20～30 ℃, during reaction temperature below 60 ℃, best 25～35 ℃.Solvent synthesis method flow process is complicated, but quality product is good than single stage method.
In synthetic, all sodium hydroxide or potassium are powdered.
Sintetics 1,3-dimethylbutyl sodium xanthonate has been done acute toxicity test at Guangzhou Medical College.The most frequently used index LD50 assay method is adopted in experiment, and contrasts with butyl xanthate.Experimental result shows, and is of the present invention 1, and 3-dimethylbutyl sodium xanthonate or potassium are lower than existing butyl xanthate toxicity.
Product of the present invention is powdery, the look Huang, and peculiar smell slightly, performance is more stable, and is soluble in water, stores the shady and cool ventilation place, and its flotation performance did not change more than 1 year.
In the concrete utilization experiment, selected for use Jiangxi Copper company Dexing copper mine alteration phyllite ore to carry out commerical test, and contrasted with former xanthate system.The final index of commerical test sees Table 1.It is remarkable that the result shows that new xanthate improves gold rate of recovery effect.Under the situation of copper index, improve the gold rate of recovery 5.17% a little more than former xanthate; The gold ore grade improves 0.76g/t.
Use product of the present invention to replace the butyl xanthate of extensive utilization at present simple and convenient, do not need to increase equipment, do not change flow process and dosing method, be easy to industrialization, and in industrial production, can save collecting agent 13.1g/t, save pore forming material 10.4g/t.The consideration new drug interior, is handled 1,650 ten thousand tons of head grade 0.226g/t meters of raw ore than more expensive this unfavorable factor of old medicine price per year, can increase production 186.45 kilograms of gold with product of the present invention, has a net increase of about 645.5 ten thousand yuan/year of incomes, remarkable benefit.
Embodiment 1
Raw material: methyl isobutyl carbinol (being called for short Y-OH) technical grade is more than 98%
CS
2Three grades
Three grades of NaOH (powdery)
Take by weighing Y-OH70g and add in the reaction flask, claim 8g powdery NaOH again, under agitation add in the reaction flask, stir, take by weighing CS at last
217g pours in the constant voltage glass cylinder, is added dropwise in the reaction flask under fully stirring, and keeps dropping temperature at 20～25 ℃, after adding, stirred one hour down for 25～30 ℃ in temperature, make temperature rise to 35 ℃ at last, kept 10 minutes, be cooled to 20 ℃, stop to stir, reactant is carried out underpressure distillation under the 650mm mercury column, steam alcohol excess, get solid product, be product.Product content 80～85%.
Embodiment 2
Raw material is with embodiment 1.
Earlier 50g kerosene is added in the reaction flask, then 20g alcohol is added, under agitation add the 7g mealy alkali, stir, take by weighing CS at last
218g pours in the permanent glass cylinder, is added dropwise in the reaction flask under fully stirring, and keep dropping temperature at 20～30 ℃, and stirred 2 hours, make temperature rise to 35 ℃ at last, kept 10 minutes, and be cooled to 20 ℃, stop to stir, gradation adds an amount of water in reactor, its total amount is no more than effecting reaction thing total amount, with the aqueous solution adding drying machine of gradation extraction, is to steam moisture content under the 600mmHg mercury column in its vacuum tightness, promptly get product, product content is 80～85%.
Embodiment 3
Raw material is with embodiment 1.
Taking by weighing 122g alcohol adds behind the reactor again with 105gCS
2Add, stir, lentamente the 58g mealy alkali is added reactor then in batches, this moment, temperature was 20～40 ℃, add alkali after, restir 2-4 hour, temperature of reaction was 20～50 ℃, treat that material is powdery after, cooling promptly gets product, its content is 75～81%.
Embodiment 4
Take by weighing 122g alcohol and add in the reactor, claim 65g alkali again, under agitation add in the reactor, stirred 1 hour, take by weighing CS then
2115g pours in the constant voltage glass cylinder, trembles down with CS stirring
2Slowly add reactor, this moment, temperature of reaction was controlled at 20～35 ℃, added CS
2After, stirring reaction 2-4 hour, behind the material powdering, temperature was reduced to below 20 ℃, and its content is 75～81%
Embodiment 5
Alcohol, CS2 are with embodiment 1, and powder alkali is potassium hydroxide (three grades)
Take by weighing pure 20g and add reactor, again with 20gCS
2Add, stir, lentamente 12g powder alkali KOH is added reactor then in batches, this moment temperature below 60 ℃, add alkali after, restir 2 hours, 20～80 ℃ of temperature of reaction, treat that material is powdery after, cooling promptly gets product.
The final index of table 1 commerical test
| System | Head grade | Concentrate grade | The rate of recovery (%) |
| Copper (%) gold (g/t) | Copper (%) gold (g/t) | The copper gold | |
| New xanthate system | 0.529????0.244 | ??24.83????8.95 | ??85.06??74.88 |
| Former medication system | 0.525????0.236 | ??23.39????8.19 | ??84.49??69.71 |
Claims (15)
1, a kind of alkyl xanthogenate type xanthate, its structure is:
Wherein M is Na or K.
2, the synthetic method of the described alkyl xanthogenate type xanthate of claim 1 is characterized in that it is by methyl isobutyl carbinol, sodium hydroxide or potassium hydroxide and dithiocarbonic anhydride three direct reaction synthetic.
3, xanthate synthetic method according to claim 2 is characterized in that methyl isobutyl carbinol, sodium hydroxide or potassium hydroxide, three kinds of reactant molar ratios of dithiocarbonic anhydride are 1.0: 0.5～2.0: 0.5～2.0.
4, xanthate synthetic method according to claim 2 is characterized in that earlier methyl isobutyl carbinol, dithiocarbonic anhydride being joined in the reactor, again powdered sodium hydroxide or potassium hydroxide is added reactor.
5, xanthate synthetic method according to claim 4 is characterized in that it being under agitation mealy alkali to be added reactor in batches, and temperature is controlled at below 50 ℃, after adding alkali, continue to stir, this moment, temperature was controlled at below 80 ℃, after treating that material is powdery, cool the temperature to 20 ℃ and promptly get product.
6, xanthate synthetic method according to claim 5, when it is characterized in that adding mealy alkali, temperature is controlled at 20～40 ℃, add alkali after, temperature is controlled at 20～50 ℃.
7, xanthate synthetic method according to claim 2 is characterized in that earlier methyl isobutyl carbinol being added in the reactor, under agitation mealy alkali is joined in the reactor, and then dithiocarbonic anhydride is added reactor.
8, xanthate synthetic method according to claim 7, temperature is controlled at below 50 ℃ when it is characterized in that feeding in raw material, and after dithiocarbonic anhydride added, temperature was controlled at below 80 ℃, continued to stir, and behind the material powdering, cooled the temperature to 20 ℃, promptly got product.
9, xanthate synthetic method according to claim 8, temperature is controlled at 20～35 ℃ when it is characterized in that adding dithiocarbonic anhydride, and after adding, temperature is controlled at 20～50 ℃.
10, xanthate synthetic method according to claim 7 is characterized in that also being added with kerosene in reactant or other lightweight oils are made reaction medium, and after having reacted, the water extracting and separating is drying to obtain product with the aqueous solution.
11, xanthate synthetic method according to claim 10 is characterized in that the total amount of the water that is used to extract is no more than effecting reaction thing total amount.
12, xanthate synthetic method according to claim 7 is characterized in that adding excessive methyl isobutyl carbinol as reaction medium, after having reacted, alcohol excess is steamed promptly get product.
13, according to claim 10 or 12 described xanthate synthetic methods, the amount that it is characterized in that reaction medium is for participating in the amount 20～300% of the alcohol that reacts.
14, according to claim 10 or 12 described xanthate synthetic methods, it is characterized in that charge temperature is below 50 ℃, temperature of reaction is below 60 ℃.
15, xanthate synthetic method according to claim 14 is characterized in that charge temperature is 20～30 ℃, and temperature of reaction is 25～35 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95110804A CN1041200C (en) | 1995-06-13 | 1995-06-13 | Alkyl xanthogenate type xanthate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95110804A CN1041200C (en) | 1995-06-13 | 1995-06-13 | Alkyl xanthogenate type xanthate |
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| Publication Number | Publication Date |
|---|---|
| CN1138031A true CN1138031A (en) | 1996-12-18 |
| CN1041200C CN1041200C (en) | 1998-12-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95110804A Expired - Fee Related CN1041200C (en) | 1995-06-13 | 1995-06-13 | Alkyl xanthogenate type xanthate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259451B (en) * | 2008-04-24 | 2012-01-11 | 中南大学 | Preparation of floating collector |
| CN102690218A (en) * | 2012-04-27 | 2012-09-26 | 中南大学 | Method for synthesizing xanthate |
| CN102744157A (en) * | 2012-07-18 | 2012-10-24 | 铁岭选矿药剂有限公司 | Composite copper ore collector |
| CN103304461A (en) * | 2013-06-14 | 2013-09-18 | 紫金矿业集团股份有限公司 | Synthesis and preparation method of gold-containing sulphide ore collecting agent compound |
| CN105344485A (en) * | 2015-10-16 | 2016-02-24 | 中南大学 | Method for recycling gold and interlocked mass of gold from refractory gold ore based on sulfur-oil aggregative flotation |
| CN105381784A (en) * | 2015-11-17 | 2016-03-09 | 苏州科技学院 | Preparation method and application of magnetic graphene oxide composite material |
| CN106191918A (en) * | 2016-08-19 | 2016-12-07 | 来宾华锡冶炼有限公司 | A kind of method preparing manganese sulfate solution removing impurities agent |
| CN108212538A (en) * | 2018-01-31 | 2018-06-29 | 中南大学 | A kind of alkyl thioether group alcohol compound and preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3864374A (en) * | 1973-11-19 | 1975-02-04 | Canadian Ind | Manufacture of alkali metal xanthates |
| FR2337199A1 (en) * | 1975-12-30 | 1977-07-29 | Ugine Kuhlmann | Flotation of ores using methyl-isobutyl-carbinol xanthate - which acts as foaming and collecting agent, is partic. useful for sulphur contg. ores |
-
1995
- 1995-06-13 CN CN95110804A patent/CN1041200C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259451B (en) * | 2008-04-24 | 2012-01-11 | 中南大学 | Preparation of floating collector |
| CN102690218A (en) * | 2012-04-27 | 2012-09-26 | 中南大学 | Method for synthesizing xanthate |
| CN102690218B (en) * | 2012-04-27 | 2013-11-27 | 中南大学 | Method for synthesizing xanthate |
| CN102744157A (en) * | 2012-07-18 | 2012-10-24 | 铁岭选矿药剂有限公司 | Composite copper ore collector |
| CN103304461A (en) * | 2013-06-14 | 2013-09-18 | 紫金矿业集团股份有限公司 | Synthesis and preparation method of gold-containing sulphide ore collecting agent compound |
| CN105344485B (en) * | 2015-10-16 | 2018-03-02 | 中南大学 | The method for reclaiming gold and its intergrowth from difficult-treating gold mine based on sulphur oil aggregative flotation |
| CN105344485A (en) * | 2015-10-16 | 2016-02-24 | 中南大学 | Method for recycling gold and interlocked mass of gold from refractory gold ore based on sulfur-oil aggregative flotation |
| CN105381784A (en) * | 2015-11-17 | 2016-03-09 | 苏州科技学院 | Preparation method and application of magnetic graphene oxide composite material |
| CN105381784B (en) * | 2015-11-17 | 2018-01-02 | 苏州科技学院 | A kind of preparation method and application of magnetic oxygenated graphene composite material |
| CN106191918A (en) * | 2016-08-19 | 2016-12-07 | 来宾华锡冶炼有限公司 | A kind of method preparing manganese sulfate solution removing impurities agent |
| CN106191918B (en) * | 2016-08-19 | 2018-08-10 | 来宾华锡冶炼有限公司 | A method of preparing manganese sulfate solution removing impurities agent |
| CN108212538A (en) * | 2018-01-31 | 2018-06-29 | 中南大学 | A kind of alkyl thioether group alcohol compound and preparation method and application |
| CN108212538B (en) * | 2018-01-31 | 2019-04-26 | 中南大学 | A kind of alkyl thioether group alcohol compound and the preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1041200C (en) | 1998-12-16 |
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