CN1041200C - Alkyl xanthogenate type xanthate - Google Patents

Abstract

I) The present invention relates to alkyl xanthogenate type xanthate and a synthetic method thereof. The alkyl xanthogenate type xanthate has a structure in the formula (I) and has the chemical name of 1, 3-sodium (or potassium) dimethylbutylxanthate which is directly synthesized by methyl isobutyl carbinol, sodium (or potassium) hydroxide and CS2 and can be used as gold trapping agent to increase the recovery rate of gold obviously or increase the grade of copper ore concentrate without the use of foamer. Compared with the original xanthate, the recovery rate of the gold can be increased by 5.17%.

Description

1, the synthetic method of 3-dimethylbutyl sodium xanthonate or potassium

The present invention relates to a kind of alkyl xanthogenate type xanthate and synthetic method, be meant 1 particularly, the synthetic method of 3-dimethylbutyl sodium xanthonate or potassium.

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.Human butyl, 2-ethyl base in the sixth of the twelve Earthly Branches, heptyl and C are arranged ₈-C ₁₀Xanthate Floatation of Copper molybdenum sulphide ores, (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 the sixth of the twelve Earthly Branches base xanthate, it is said that the floatation indicators of copper and molybdenum increases.Therefore, seek the production technique of high efficiently carbon number xanthogenate type xanthate, be very important.

Traditional view is thought: alkyl xanthogenate type xanthate synthetic yield under the condition that has water to exist is very low.United States Patent (USP) the 3rd, 864, provide a kind of method of synthesis of alkyl xanthogenate type xanthate No. 374, it is the method for producing xanthate with the CS2 reaction under NaOH or KOH condition, wherein alkali metal hydroxide is a pressed powder, place on the reaction bed, the pure and mild CS2 of gasiform brings reaction bed into by rare gas element, temperature of reaction is 50--120 ℃, this method is based on above-mentioned traditional view, therefore when synthetic, adopt higher temperature of reaction, so that byproduct of reaction water can evaporate, and taken away by inert gas, but the equipment that this method adopts is comparatively complicated, and the easily right explosion hazard owing to reaction and the pure and mild dithiocarbonic anhydride of reactant under comparatively high temps makes to equipment and operational condition requirement very high.

The object of the present invention is to provide a kind of equipment, synthesis step simple, 1, the 3 dimethylbutyl sodium xanthonate that productive rate is high or the synthetic method of potassium.

Technical scheme of the present invention is by methyl isobutyl carbinol, and sodium hydroxide or potassium and dithiocarbonic anhydride three are synthetic.Alcohol, CS ₂, the alkali three proportioning be 1.0: 0.5～2.0: 0.5～2.0 more suitable.When synthetic, 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 ℃.Also 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 ℃.Above two kinds of synthesis steps can be described as single stage method.

As can be seen, aforesaid method is very 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 CS2 at last.Described 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 than the single stage method complexity, but quality product is good than single stage method.

The building-up reactions of xanthate 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.Therefore control reaction temperature is very important condition.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.

The productive rate of synthetic method of the present invention reaches 88%, and content reaches 85%.

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.

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 ₂As go into, stir, lentamente the 58g mealy alkali is added reactor in batches then, this moment temperature be 20～40 ℃, add alkali after, restir 2-4 hour, temperature of reaction was 20～50 ℃, treat that material is powdery after, the cooling promptly get 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, CS ₂With embodiment 1, 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 (10)

1,1, the synthetic method of 3-dimethylbutyl sodium xanthonate or potassium, it is characterized in that this xanthate is by methyl isobutyl carbinol, sodium hydroxide or potassium hydroxide and dithiocarbonic anhydride three 1.0: 0.5 in molar ratio～2.0: 0.5～2.0 direct reaction synthetic, earlier methyl isobutyl carbinol, dithiocarbonic anhydride are joined in the reactor, under agitation mealy alkali is added reactor then in batches, temperature is controlled at below 50 ℃, after adding alkali, continue to stir, this moment, temperature was controlled at below 80 ℃, treated promptly to get product after material is powdery.

2, xanthate synthetic method according to claim 1, when it is characterized in that adding mealy alkali, temperature is controlled at 20～40 ℃, add alkali after, temperature is controlled at 20～50 ℃.

3,1,3-dimethylbutyl sodium xanthonate or process for synthesis of potassium, it is characterized in that this xanthate is by methyl isobutyl carbinol, sodium hydroxide or potassium hydroxide and dithiocarbonic anhydride three 1.0: 0.5 in molar ratio～2.0: 0.5～2.0 direct reaction synthetic, earlier methyl isobutyl carbinol is added in the reactor, under agitation mealy alkali is joined in the reactor, and then dithiocarbonic anhydride is added reactor; Temperature is controlled at below 50 ℃ when reinforced, and after dithiocarbonic anhydride added, temperature was controlled at below 80 ℃, continues to stir, and promptly gets product behind the material powdering.

4, xanthate synthetic method according to claim 3, temperature is controlled at 20～35 ℃ when it is characterized in that adding dithiocarbonic anhydride, and after adding, temperature is controlled at 20～50 ℃.

5, xanthate synthetic method according to claim 3 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.

6, xanthate synthetic method according to claim 5 is characterized in that the total amount of the water that is used to extract is no more than effecting reaction thing total amount.

7, xanthate synthetic method according to claim 3 is characterized in that adding excessive methyl isobutyl carbinol as reaction medium, after having reacted, alcohol excess is steamed promptly get product.

8, according to claim 5 or 7 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.

9,, it is characterized in that temperature of reaction is below 60 ℃ according to claim 5 or 7 described xanthate synthetic methods.

10, xanthate synthetic method according to claim 9 is characterized in that charge temperature is 20～30 ℃, and temperature of reaction is 25～35 ℃.