CN107055616A - A kind of drop general labourer's skill of molybdenum disulfide - Google Patents
A kind of drop general labourer's skill of molybdenum disulfide Download PDFInfo
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- CN107055616A CN107055616A CN201710460301.6A CN201710460301A CN107055616A CN 107055616 A CN107055616 A CN 107055616A CN 201710460301 A CN201710460301 A CN 201710460301A CN 107055616 A CN107055616 A CN 107055616A
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Abstract
The invention discloses a kind of drop general labourer's skill of molybdenum disulfide, this method is：First, molybdenum concntrate is pre-processed；2nd, pretreated molybdenum concntrate, iron chloride, copper chloride and hydrochloric acid are added in water and are configured to reaction solution, the reaction solution reacts under conditions of 70 DEG C~85 DEG C, one section of filter cake is obtained after being washed out filtering；3rd, one section of filter cake, hydrofluoric acid and hydrochloric acid are added in water and are configured to reaction solution, the reaction solution reacts under conditions of 60 DEG C~95 DEG C, two sections of filter cakes are obtained after being washed out filtering；4th, two sections of filter cakes are subjected to drying and processing under vacuum, obtain the molybdenum disulfide that quality purity is not less than 98.5%.The present invention substitutes hydrochloric acid with iron chloride, can possess drop iron function while lead can be dropped；And the hydrogen sulfide produced in the process uses chlorination Copper uptakie, iron chloride also can absorb partial vulcanization hydrogen, so as to thoroughly prevent the generation of hydrogen sulfide gas, reduces impurity content, improves the purity of molybdenum disulfide.
Description
Technical field
The invention belongs to molybdenum disulfide technical field of purification, and in particular to a kind of drop general labourer's skill of molybdenum disulfide.
Background technology
The existing production technology of molybdenum disulfide fundamentally solves yellow iron in 57% molybdenum concntrate by preprocessing method of raw materials
Ore deposit (FeS2) the high influence produced to molybdenum disulfide of content, by pyrite (FeS2) magnetic iron ore (FeS) is converted into, it is follow-up work
Skill reduction iron tramp is ready；Adding hydrochloric acid by one section of acidleach again makes the Armco magnetic iron and other acid-soluble salts in molybdenum concntrate
Liquid phase is changed into from solid phase Deng impurity, eventually through washing so as to removing iron tramp；Enter two-stage acid leaching afterwards by adding hydrogen fluorine
Acid and hydrochloric acid remove silica and the nonmetallic inclusion of other silicon salts, impurity is changed into liquid phase from solid phase, by repeatedly washing
Suction filtration is washed so as to remove silicon class impurity, and reduces acid number and moisture content, the final purity for improving molybdenum disulfide.This method is in one section of acid
There is efficient drop iron ability during leaching, but substantial amounts of hypertoxic inflammable hydrogen sulfide gas can be produced in process of production, to the person
Safety and environment cause greatly to endanger；Simultaneously this method in raw material molybdenum concntrate with a huge sum of money that lead (predominantly PbS) is representative
Belong to impurity removal effect little, therefore typical products in mass production caused because of the too high and underproof phenomenon of lead content in actual production,
Therefore this method has larger drop miscellaneous and safety limitation, it is impossible to which large-scale application is in industrial production.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of molybdenum disulfide for above-mentioned the deficiencies in the prior art
Drop general labourer's skill.Hydrochloric acid is substituted using iron chloride in one section of acidleach of drop general labourer's skill, because iron chloride is a kind of strong oxidizer, its
The aqueous solution in highly acid and it is ionizable go out chlorion, therefore both can possess drop iron function while lead can be dropped；And in the process
The hydrogen sulfide of generation uses chlorination Copper uptakie, and iron chloride also can absorb partial vulcanization hydrogen, so as to thoroughly prevent hydrogen sulfide gas
Generation；The solid precipitation copper sulfide of generation is dissolved in the ferric chloride solution of heat again, so far by adding iron chloride and chlorination
Copper makes impurity iron, lead, copper be changed into liquid phase by solid phase, and does not produce hydrogen sulfide gas during this completely.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of drop general labourer's skill of molybdenum disulfide, it is special
Levy and be, this method comprises the following steps：
Step 1: pretreatment of raw material：Molybdenum concntrate is pre-processed；Molybdenum content is not less than in the molybdenum concntrate
56.5wt%, iron content is not more than 0.7wt%, and lead content is not more than 0.08wt%, and silica is not more than 2.0wt%, and carbon is not
More than 0.8wt%, oil content is not more than 0.5wt%；
Step 2: one section of acidleach：Molybdenum concntrate after pretreatment, iron chloride, copper chloride and hydrochloric acid in step one are added to
Reaction solution is configured in water, the reaction solution reacts 2h~4h under conditions of 70 DEG C~85 DEG C, is obtained after being washed out filtering
One section of filter cake；The concentration of iron chloride is 90g/L~100g/L in the reaction solution, and the concentration of copper chloride is 10g/L~15g/L,
The concentration of hydrochloric acid is 10g/L~20g/L, and the concentration of pretreated molybdenum concntrate is 1000g/L~1200g/L；
Step 3: two-stage acid leaching：Obtained in step 2 one section of filter cake, hydrofluoric acid and hydrochloric acid are added in water and are configured to instead
Liquid is answered, the reaction solution reacts 4h~6h under conditions of 60 DEG C~95 DEG C, two sections of filter cakes are obtained after being washed out filtering；It is described
The concentration of hydrofluoric acid is 130g/L~140g/L in reaction solution, and the concentration of hydrochloric acid is 45g/L~55g/L, the concentration of one section of filter cake
For 1400g/L~1500g/L；
Step 4: drying：Obtained in step 3 two sections of filter cakes are subjected to drying and processing under vacuum, quality is obtained
Purity is not less than iron content in 98.5% molybdenum disulfide, the molybdenum disulfide and is not more than 0.15wt%, and lead content is not more than
0.02wt%, silica is not more than 0.10wt%.
Drop general labourer's skill of above-mentioned a kind of molybdenum disulfide, it is characterised in that the process pre-processed described in step one is：Will
Molybdenum concntrate loads electromagnetic drying stove, and under nitrogen atmosphere protection, 3h~7h is incubated under conditions of 750 DEG C~900 DEG C of temperature.
A kind of drop general labourer's skill of above-mentioned molybdenum disulfide, it is characterised in that bar of the reaction solution described in step 2 at 75 DEG C
3h is reacted under part, one section of filter cake is obtained after being washed out filtering.
A kind of drop general labourer's skill of above-mentioned molybdenum disulfide, it is characterised in that iron chloride in reaction solution described in step 2
Concentration is 95g/L, and the concentration of copper chloride is 12.5g/L, and the concentration of hydrochloric acid is 15g/L, and the concentration of pretreated molybdenum concntrate is
1100g/L；
Drop general labourer's skill of above-mentioned a kind of molybdenum disulfide, it is characterised in that adopted in step 2 and be washed with deionized at least 5
It is secondary.
A kind of drop general labourer's skill of above-mentioned molybdenum disulfide, it is characterised in that bar of the reaction solution described in step 3 at 85 DEG C
5h is reacted under part, two sections of filter cakes are obtained after being washed out filtering.
A kind of drop general labourer's skill of above-mentioned molybdenum disulfide, it is characterised in that hydrofluoric acid in reaction solution described in step 3
Concentration is 135g/L, and the concentration of hydrochloric acid is 50g/L, and the concentration of one section of filter cake is 1450g/L.
Drop general labourer's skill of above-mentioned a kind of molybdenum disulfide, it is characterised in that adopted in step 3 and be washed with deionized at least 5
It is secondary.
Drop general labourer's skill of above-mentioned a kind of molybdenum disulfide, it is characterised in that the temperature of drying and processing is 140 DEG C in step 4
~200 DEG C, the time is 4h~6h.
The miscellaneous principle of drop of molybdenum disulfide of the present invention：Pretreated molybdenum concntrate makes miscellaneous in material by chemical reaction twice
Matter (such as iron, lead, silicon) is changed into liquid phase from solid phase, and molybdenum disulfide is not involved in reaction in the process, afterwards by washing and filtering
Separate impurity, molybdenum disulfide grade is improved.
The miscellaneous process of drop and the miscellaneous reaction mechanism of drop of the present invention：
1st, pretreatment of raw material is carried out to 57% molybdenum concntrate first：
By being pre-processed to 57% molybdenum concntrate, make the FeS in molybdenum concntrate2FeS is converted into, is that follow-up drop iron carries out standard
It is standby, meanwhile, oil content is fallen by vaporization at high temperature in molybdenum concntrate.The reaction mechanism of the step is：FeS2=FeS+S
2nd, one section of acidleach process
The process is that correlated response mechanism is as follows using iron chloride and copper chloride as removal of impurities medicament：
2.1 iron chloride effect one：Lead drops, using iron chloride as oxidant, with ore in vulcanized lead reaction generation lead
Complex compound, then by washing and filtering so that lead be separated：
PbS+2FeCl3=PbCl2↓+2FeCl2+S
PbCl2+2Cl-=[PbCl4]2-
2.2 iron chloride effect two：Iron is dropped, iron chloride produces hydrogen ion by hydrolysis, can be sent out with the Armco magnetic iron FeS in ore
The water-soluble ferrous ion of raw reaction generation and hydrogen sulfide gas, then by washing and filtering so that impurity iron be separated：
Fe3++3H2O=Fe (OH)3+3H+(reversible reaction)
FeS+2H+=Fe2++H2S↑
The effect of 2.3 copper chlorides is mainly absorption hydrogen sulfide gas, while iron chloride also can absorb partial vulcanization hydrogen,
The copper sulfide precipitation generated during the course of the reaction is dissolvable in water generation chlorine in the ferric chloride solution of heat and closes copper ion, so as to avoid
The generation of copper sulfide precipitation；Part chlorion is also provided simultaneously, the function with auxiliary drop lead.
Cu2++H2S=CuS ↓+2H+
CuS+2H++nCl2=[CuCln]2-n+H2S↑
H2S+2Fe3+=S+2H++2Fe2+
3rd, the 3rd step is two-stage acid leaching, main by adding hydrofluoric acid and hydrochloric acid removes silica and other silicon salts
Nonmetallic inclusion, makes impurity be changed into liquid phase from solid phase, by repeatedly washing suction filtration so as to remove silicon class impurity.Reaction mechanism is：
SiO2+ 6HF=H2SiF6+2H2O, the process performs former technological operation standard.
The present invention has advantages below compared with prior art：
1st, the present invention adds cleaner iron chloride and copper chloride, hydrochloric acid and hydrofluoric acid by being segmented, and makes molybdenum essence after pretreatment
Impurity lead, iron, silicon generation in ore deposit are dissolved in the material of water, and molybdenum disulfide is not involved in reaction in the process, afterwards by washing
Suction filtration makes impurity finally be separated, and the copper chloride of addition can absorb the hydrogen sulfide gas produced in course of reaction, finally gives
Molybdenum disulfide product (the MoS of high-purity2>=98.50%, Fe≤0.15%, Pb≤0.02%, Si≤0.10%), so as to be formed
Miscellaneous production method drops in new industrialization molybdenum disulfide.
2nd, the present invention forms a kind of new, safe and efficient molybdenum disulfide drop general labourer's skill first：Because this method can have
Impurity lead, iron in effect reduction material, especially can be efficiently separated the obstinate impurity vulcanized lead in molybdenum concntrate, not use
Dangerous high concentrated nitric acid is as drop lead medicament, and the strong oxidizing property of iron chloride and the strongly acidic solution that hydrolyzes to form are to pre-
Molybdenum concntrate after processing has comprehensive removal of impurities effect.Therefore this method fundamentally solves molybdenum concntrate lead height after pretreatment
The high influence produced to molybdenum disulfide of iron.
3rd, the present invention has eradicated the generation of hydrogen sulfide gas, and effective improvement has been carried out to hydrogen sulfide in the link of technique,
By adding iron chloride and copper chloride solution, the hydrogen sulfide gas produced during absorbable drop iron, while not introducing new impurity member
Element, original material mode is washed and opening is washed in material equipment, air also without hydrogen sulfide gas even if continuing to use.Fundamentally solve vulcanization
Hydrogen problem.
4th, the present invention improves processing safety, and the miscellaneous medicament iron chloride of drop and copper chloride corrosion hazards coefficient of selection are relatively low,
The concentrated nitric acid of conventional use severe corrosive has been abandoned as removal of impurities medicament, the security of operation is drastically increased.
5th, the present invention can efficiently drop miscellaneous comprehensively, improve product quality, can be effective by selecting the miscellaneous medicament of drop with strong points
The materials such as impurity iron, lead in reduction ore, while not introducing new impurity, drop miscellaneous ability comprehensively efficient.
6th, the present invention reduces the corrosivity to equipment, and the miscellaneous medicament corrosive nature of selected drop is relatively low, therefore to equipment
Erosion is significantly less than concentrated nitric acid, can extend one section of pickling equipment service life on long terms.
Technical scheme is described in further detail below by drawings and examples.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Fig. 2 is iron content and FeCl in the one section of filter cake obtained through step 2 in embodiment 1~3 and comparative example 1~83It is dense
The graph of relation of degree.
Fig. 3 is lead content and FeCl in the one section of filter cake obtained through step 2 in embodiment 1~3 and comparative example 1~83It is dense
The graph of relation of degree.
Embodiment
Embodiment 1
As shown in figure 1, drop general labourer's skill of the present embodiment molybdenum disulfide comprises the following steps：
Step 1: pretreatment of raw material：Molybdenum concntrate is pre-processed；Molybdenum content is 57.32% in the molybdenum concntrate, and iron contains
Measure as 0.62wt%, lead content is 0.065wt%, and silica is 1.42wt%, and carbon is 0.61wt%, and oil content is
0.35wt%；The process of the pretreatment is：Molybdenum concntrate is loaded into electromagnetic drying stove, under nitrogen atmosphere protection, temperature is 850
6h is incubated under conditions of DEG C；
Step 2: one section of acidleach：Molybdenum concntrate after pretreatment, iron chloride, copper chloride and hydrochloric acid in step one are added to
Reaction solution is configured in water, the reaction solution reacts 3h under conditions of 75 DEG C, then adopts and be washed with deionized 5 times, filtered
After obtain one section of filter cake；The concentration of iron chloride is 95g/L in the reaction solution, and the concentration of copper chloride is 12.5g/L, hydrochloric acid it is dense
Spend for 15g/L, the concentration of pretreated molybdenum concntrate is 1100g/L；
Step 3: two-stage acid leaching：Obtained in step 2 one section of filter cake, hydrofluoric acid and hydrochloric acid are added in water and are configured to instead
Liquid is answered, the reaction solution reacts 5h under conditions of 85 DEG C, then adopt and be washed with deionized 5 times, two sections of filters are obtained after filtering
Cake；The concentration of hydrofluoric acid is 135g/L in the reaction solution, and the concentration of hydrochloric acid is 50g/L, and the concentration of one section of filter cake is 1450g/
L；
Step 4: drying：By obtained in step 3 two sections of filter cakes under 170 DEG C of vacuum condition drying and processing 5h, obtain
To the molybdenum disulfide that quality purity is 98.69%, iron content is 0.05% in the molybdenum disulfide, and lead content is 0.0085%,
Silica is 0.04%.
Embodiment 2
The present embodiment is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 90g/L.
It is 0.06% that the present embodiment, which obtains iron content in the molybdenum disulfide that quality purity is 98.67%, the molybdenum disulfide,
Lead content is 0.0111%, and silica is 0.05%.
Embodiment 3
The present embodiment is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 100g/L.
It is 0.05% that the present embodiment, which obtains iron content in the molybdenum disulfide that quality purity is 99.21%, the molybdenum disulfide,
Lead content is 0.0079%, and silica is 0.04%.
Comparative example 1
This comparative example is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 40g/L.
It is 0.25% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 97.01%, the molybdenum disulfide,
Lead content is 0.0289%, and silica is 0.03%.
Comparative example 2
This comparative example is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 50g/L.
It is 0.21% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 97.21%, the molybdenum disulfide,
Lead content is 0.0295%, and silica is 0.04%.
Comparative example 3
This comparative example is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 60g/L.
It is 0.18% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.17%, the molybdenum disulfide,
Lead content is 0.0275%, and silica is 0.03%.
Comparative example 4
This comparative example is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 70g/L.
It is 0.15% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.25%, the molybdenum disulfide,
Lead content is 0.0241%, and silica is 0.03%.
Comparative example 5
This comparative example is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 80g/L.
It is 0.14% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.44%, the molybdenum disulfide,
Lead content is 0.0201%, and silica is 0.03%.
Comparative example 6
This comparative example is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 110g/L.
It is 0.13% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.56%, the molybdenum disulfide,
Lead content is 0.0063%, and silica is 0.04%.
Comparative example 7
This comparative example is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 120g/L.
It is 0.14% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.51%, the molybdenum disulfide,
Lead content is 0.0054%, and silica is 0.04%.
Comparative example 8
This comparative example is identical with the experimentation and experiment condition of embodiment 1, and difference is：It is anti-described in step 2
The concentration for answering iron chloride in liquid is 130g/L.
It is 0.17% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.46%, the molybdenum disulfide,
Lead content is 0.0039%, and silica is 0.03%.
After testing, the one section of filter cake prepared after the one section of acidleach of embodiment 1~3 and comparative example 1~8 through step 2 is obtained
Middle iron content and lead content, as shown in table 1.
Iron content and lead content in the one section of filter cake obtained in the embodiment 1~3 of table 1 and comparative example 1~8 through step 2
Table 1 is that iron contains in the one section of filter cake prepared after the one section of acidleach of embodiment 1~3 and comparative example 1~8 through step 2
Amount and lead content, by FeCl in table 13The data drafting pattern 2 of iron content in concentration and one section of filter cake, can be seen that from Fig. 2：
With the continuous improvement of ferric chloride concn, the lead content in one section of filter cake declines therewith；And the iron content in one section of filter cake starts
When with one section of filter cake of continuous improvement of ferric chloride concn iron content it is also on a declining curve, when iron content is reduced to certain point
Continue to increase iron content in one section of filter cake of ferric chloride concn and ascendant trend also but occur, the phenomenon is because of the dense of now iron chloride
Excessive state has been presented in degree, causes in one section of filter cake iron hydroxide content not as the continuous carry out iron chloride of reaction is constantly hydrolyzed
Disconnected to improve, monitoring result is improved with iron content and showed, and iron can be reduced when two-stage acid leaching adds hydrochloric acid and hydrofluoric acid, still
It can increase production cost by way of improving two-stage acid leaching hydrochloric acid content and reducing iron content.
Therefore, by FeCl in table 13The data drafting pattern 3 of lead content in concentration and one section of filter cake, from Fig. 3 can from
Arrive, require that lead, iron content are bent in (Pb≤0.02%) and one section of filter cake according to lead content technical conditions in high-purity molybdenum disulfide
Line and saving cost are drawn, when ferric chloride concn is 90g/L~100g/L, lead effect is dropped most for above-mentioned molybdenum concntrate index
It is good.
Embodiment 4
As shown in figure 1, drop general labourer's skill of the present embodiment molybdenum disulfide comprises the following steps：
Step 1: pretreatment of raw material：Molybdenum concntrate is pre-processed；Molybdenum content is 57.32% in the molybdenum concntrate, and iron contains
Measure as 0.62wt%, lead content is 0.065wt%, and silica is 1.42wt%, and carbon is 0.61wt%, and oil content is
0.35wt%；The process of the pretreatment is：Molybdenum concntrate is loaded into electromagnetic drying stove, under nitrogen atmosphere protection, temperature is 850
6h is incubated under conditions of DEG C；
Step 2: one section of acidleach：Molybdenum concntrate after pretreatment, iron chloride, copper chloride and hydrochloric acid in step one are added to
Reaction solution is configured in water, the reaction solution reacts 3h under conditions of 75 DEG C, then adopts and be washed with deionized 5 times, filtered
After obtain one section of filter cake；The concentration of iron chloride is 95g/L in the reaction solution, and the concentration of copper chloride is 12.5g/L, hydrochloric acid it is dense
Spend for 15g/L, the concentration of pretreated molybdenum concntrate is 1100g/L；
Step 3: two-stage acid leaching：Obtained in step 2 one section of filter cake, hydrofluoric acid and hydrochloric acid are added in water and are configured to instead
Liquid is answered, the reaction solution reacts 5h under conditions of 85 DEG C, then adopt and be washed with deionized 5 times, two sections of filters are obtained after filtering
Cake；The concentration of hydrofluoric acid is 135g/L in the reaction solution, and the concentration of hydrochloric acid is 50g/L, and the concentration of one section of filter cake is 1450g/
L；
Step 4: drying：By obtained in step 3 two sections of filter cakes under 140 DEG C of vacuum condition drying and processing 6h, obtain
To the molybdenum disulfide that quality purity is 98.68%, iron content is 0.04% in the molybdenum disulfide, and lead content is 0.01%, two
Silica is 0.03%, and copper is 0.018%.
Embodiment 5
The present embodiment is identical with the experimentation and experiment condition of embodiment 4, and difference is：It is anti-described in step 2
The concentration for answering copper chloride in liquid is 10g/L.
It is 0.05% that the present embodiment, which obtains iron content in the molybdenum disulfide that quality purity is 98.75%, the molybdenum disulfide,
Lead content is 0.009%, and silica is 0.04%, and copper is 0.015%.
Embodiment 6
The present embodiment is identical with the experimentation and experiment condition of embodiment 4, and difference is：It is anti-described in step 2
The concentration for answering copper chloride in liquid is 15g/L.
It is 0.04% that the present embodiment, which obtains iron content in the molybdenum disulfide that quality purity is 98.99%, the molybdenum disulfide,
Lead content is 0.0097%, and silica is 0.04%, and copper is 0.024%.
Comparative example 9
This comparative example is identical with the experimentation and experiment condition of embodiment 4, and difference is：It is anti-described in step 2
The concentration for answering copper chloride in liquid is 5g/L.
It is 0.06% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.59%, the molybdenum disulfide,
Lead content is 0.099%, and silica is 0.04%, and copper is 0.01%.
Comparative example 10
This comparative example is identical with the experimentation and experiment condition of embodiment 4, and difference is：It is anti-described in step 2
The concentration for answering copper chloride in liquid is 7.5g/L.
It is 0.05% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 99.01%, the molybdenum disulfide,
Lead content is 0.087%, and silica is 0.03%, and copper is 0.011%.
Comparative example 11
This comparative example is identical with the experimentation and experiment condition of embodiment 4, and difference is：It is anti-described in step 2
The concentration for answering copper chloride in liquid is 17.5g/L.
It is 0.06% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.71%, the molybdenum disulfide,
Lead content is 0.0076%, and silica is 0.03%, and copper is 0.036%.
Comparative example 12
This comparative example is identical with the experimentation and experiment condition of embodiment 4, and difference is：It is anti-described in step 2
The concentration for answering copper chloride in liquid is 20g/L.
It is 0.05% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.69%, the molybdenum disulfide,
Lead content is 0.0081%, and silica is 0.03%, and copper is 0.045%.
Influence of the different copper chloride concentrations of table 2 to solid copper in the stink damp scale of construction in course of reaction and one section of filter cake
By meticulously being analyzed the data in table 2, analysis result is as follows：The addition of copper chloride is primarily used to inhale
Receive the hydrogen sulfide gas produced in course of reaction.In one section of acidleach when copper chloride addition is enough, it can promote entirely to react
The abundant progress of journey, especially FeS+2H+=Fe2++H2S ↑, the hydrogen sulfide gas now produced can be chlorinated copper and iron chloride is complete
Hypersorption；When one section of acidleach copper chloride addition is not enough, can draw up FeS+2H+=Fe2++H2The progress of S ↑ course of reaction, though
The hydrogen sulfide gas that the right process is produced can be chlorinated copper and iron chloride is fully absorbed, but the iron tramp of portion of residual still with
FeS is present, and hydrochloric acid is added when two-stage acid leaching to be reacted with remaining FeS, so as to discharge hydrogen sulfide gas.Therefore when one section
When acidleach copper chloride addition is not enough, there can be hydrogen sulfide generation during two-stage acid leaching.Reaction mechanism is as follows：
PbS+2FeCl3=PbCl2↓+2FeCl2+S
PbCl2+2Cl-=[PbCl4]2-
Fe3++3H2O=Fe (OH)3+3H+(reversible reaction)
FeS+2H+=Fe2++H2S↑
Cu2++H2S=CuS ↓+2H+
CuS+2H++nCl-=[CuCln]2-n+H2S↑
H2S+2Fe3+=S+2H++2Fe2+
When being therefore 10g/L~15g/L by the mass concentration control of copper chloride, hydrogen sulfide gas can obtain thorough improvement,
One section of reaction mechanism is：Cu2++H2S=CuS ↓+2H+.Pass through CuS+2H simultaneously++nCl-=[CuCln]2-n+H2S ↑ and H2S+2Fe3+
=S+2H++2Fe2+Copper content in reaction, filter cake also meets quality requirement (Cu≤0.03%) and produced without hydrogen sulfide gas.
Embodiment 7
As shown in figure 1, drop general labourer's skill of the present embodiment molybdenum disulfide comprises the following steps：
Step 1: pretreatment of raw material：Molybdenum concntrate is pre-processed；Molybdenum content is 57.32% in the molybdenum concntrate, and iron contains
Measure as 0.62wt%, lead content is 0.065wt%, and silica is 1.42wt%, and carbon is 0.61wt%, and oil content is
0.35wt%；The process of the pretreatment is：Molybdenum concntrate is loaded into electromagnetic drying stove, under nitrogen atmosphere protection, temperature is 850
7h is incubated under conditions of DEG C；
Step 2: one section of acidleach：Molybdenum concntrate after pretreatment, iron chloride, copper chloride and hydrochloric acid in step one are added to
Reaction solution is configured in water, the reaction solution reacts 3h under conditions of 75 DEG C, then adopts and be washed with deionized 5 times, filtered
After obtain one section of filter cake；The concentration of iron chloride is 95g/L in the reaction solution, and the concentration of copper chloride is 12.5g/L, hydrochloric acid it is dense
Spend for 15g/L, the concentration of pretreated molybdenum concntrate is 1100g/L；
Step 3: two-stage acid leaching：Obtained in step 2 one section of filter cake, hydrofluoric acid and hydrochloric acid are added in water and are configured to instead
Liquid is answered, the reaction solution reacts 5h under conditions of 85 DEG C, then adopt and be washed with deionized 5 times, two sections of filters are obtained after filtering
Cake；The concentration of hydrofluoric acid is 135g/L in the reaction solution, and the concentration of hydrochloric acid is 50g/L, and the concentration of one section of filter cake is 1450g/
L；
Step 4: drying：By obtained in step 3 two sections of filter cakes under 140 DEG C of vacuum condition drying and processing 6h, obtain
To the molybdenum disulfide that quality purity is 98.79%, iron content is 0.04% in the molybdenum disulfide, and lead content is 0.0089%,
Silica is 0.04%, and copper is 0.016%.
Embodiment 8
The present embodiment is identical with the experimentation and experiment condition of embodiment 7, and difference is：It is anti-described in step 2
It is 70 DEG C to answer liquid temperature degree.
It is 0.09% that the present embodiment, which obtains iron content in the molybdenum disulfide that quality purity is 98.64%, the molybdenum disulfide,
Lead content is 0.0179%, and silica is 0.05%, and copper is 0.0216%.
Embodiment 9
The present embodiment is identical with the experimentation and experiment condition of embodiment 7, and difference is：It is anti-described in step 2
It is 80 DEG C to answer liquid temperature degree.
It is 0.05% that the present embodiment, which obtains iron content in the molybdenum disulfide that quality purity is 98.82%, the molybdenum disulfide,
Lead content is 0.0071%, and silica is 0.04%, and copper is 0.01%.
Comparative example 13
This comparative example is identical with the experimentation and experiment condition of embodiment 7, and difference is：It is anti-described in step 2
It is 40 DEG C to answer liquid temperature degree.
It is 0.21% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 97.22%, the molybdenum disulfide,
Lead content is 0.0409%, and silica is 0.05%, and copper is 0.0412%.
Comparative example 14
This comparative example is identical with the experimentation and experiment condition of embodiment 7, and difference is：It is anti-described in step 2
It is 50 DEG C to answer liquid temperature degree.
It is 0.15% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 97.74%, the molybdenum disulfide,
Lead content is 0.0321%, and silica is 0.04%, and copper is 0.0328%.
Comparative example 15
This comparative example is identical with the experimentation and experiment condition of embodiment 7, and difference is：It is anti-described in step 2
It is 60 DEG C to answer liquid temperature degree.
It is 0.13% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.22%, the molybdenum disulfide,
Lead content is 0.0234%, and silica is 0.04%, and copper is 0.0295%.
Comparative example 16
This comparative example is identical with the experimentation and experiment condition of embodiment 7, and difference is：It is anti-described in step 2
It is 90 DEG C to answer liquid temperature degree.
It is 0.04% that this comparative example, which obtains iron content in the molybdenum disulfide that quality purity is 98.90%, the molybdenum disulfide,
Lead content is 0.0069%, and silica is 0.04%, and copper is 0.012%.
In addition, inventor also studied (removes in step 2 reaction temperature not with the experimental procedure of embodiment 1 and experiment condition
Together) in the case of identical, the different influences for lead content of reaction temperature.
Influence of the reaction temperature to lead content in one section of filter cake during 3 one sections of acidleach of table
From table 3 it can be seen that reaction temperature is higher during one section of acid-leaching reaction, reaction drop lead effect is better, especially exists
Under the conditions of 70 DEG C, lead content in one section of filter cake has been set to be reduced to below 0.02wt%, therefore to ensure final product two
In the case of the quality of molybdenum sulfide, and reduction production cost, the reaction temperature of one section of acidleach is set in 70 DEG C~85 DEG C.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (9)
1. drop general labourer's skill of a kind of molybdenum disulfide, it is characterised in that this method comprises the following steps：
Step 1: pretreatment of raw material：Molybdenum concntrate is pre-processed；Molybdenum content is not less than 56.5wt%, iron in the molybdenum concntrate
Content is not more than 0.7wt%, and lead content is not more than 0.08wt%, and silica is not more than 2.0wt%, and carbon is not more than 0.8wt%,
Oil content is not more than 0.5wt%；
Step 2: one section of acidleach：Molybdenum concntrate after pretreatment, iron chloride, copper chloride and hydrochloric acid in step one are added in water
Reaction solution is configured to, the reaction solution reacts 2h~4h under conditions of 70 DEG C~85 DEG C, one section is obtained after being washed out filtering
Filter cake；The concentration of iron chloride is 90g/L~100g/L in the reaction solution, and the concentration of copper chloride is 10g/L~15g/L, hydrochloric acid
Concentration be 10g/L~20g/L, after pretreatment the concentration of molybdenum concntrate be 1000g/L~1200g/L；
Step 3: two-stage acid leaching：Obtained in step 2 one section of filter cake, hydrofluoric acid and hydrochloric acid are added in water and are configured to reaction
Liquid, the reaction solution reacts 4h~6h under conditions of 60 DEG C~95 DEG C, and two sections of filter cakes are obtained after being washed out filtering；It is described anti-
The concentration for answering hydrofluoric acid in liquid is 130g/L~140g/L, and the concentration of hydrochloric acid is 45g/L~55g/L, and the concentration of one section of filter cake is
1400g/L~1500g/L；
Step 4: drying：Obtained in step 3 two sections of filter cakes are subjected to drying and processing under vacuum, quality is finally obtained
Purity is not less than iron content in 98.5% molybdenum disulfide, the molybdenum disulfide and is not more than 0.15wt%, and lead content is not more than
0.02wt%, silica is not more than 0.10wt%.
2. drop general labourer's skill of a kind of molybdenum disulfide according to claim 1, it is characterised in that pre-processed described in step one
Process be：Molybdenum concntrate is loaded into electromagnetic drying stove, under nitrogen atmosphere protection, temperature is guarantor under conditions of 750 DEG C~900 DEG C
Warm 3h~7h.
3. a kind of drop general labourer's skill of molybdenum disulfide according to claim 1, it is characterised in that reaction solution described in step 2
3h is reacted under conditions of 75 DEG C, one section of filter cake is obtained after being washed out filtering.
4. a kind of drop general labourer's skill of molybdenum disulfide according to claim 1, it is characterised in that reaction solution described in step 2
The concentration of middle iron chloride is 95g/L, and the concentration of copper chloride is 12.5g/L, and the concentration of hydrochloric acid is 15g/L, pretreated molybdenum essence
The concentration of ore deposit is 1100g/L.
5. drop general labourer's skill of a kind of molybdenum disulfide according to claim 1, it is characterised in that deionization is used in step 2
Water washing at least 5 times.
6. a kind of drop general labourer's skill of molybdenum disulfide according to claim 1, it is characterised in that reaction solution described in step 3
5h is reacted under conditions of 85 DEG C, two sections of filter cakes are obtained after being washed out filtering.
7. a kind of drop general labourer's skill of molybdenum disulfide according to claim 1, it is characterised in that reaction solution described in step 3
The concentration of middle hydrofluoric acid is 135g/L, and the concentration of hydrochloric acid is 50g/L, and the concentration of one section of filter cake is 1450g/L.
8. drop general labourer's skill of a kind of molybdenum disulfide according to claim 1, it is characterised in that deionization is used in step 3
The number of times of water washing is at least 5 times.
9. drop general labourer's skill of a kind of molybdenum disulfide according to claim 1, it is characterised in that described in step 4 at drying
The temperature of reason is 140 DEG C~200 DEG C, and the time is 4h~6h.
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| CN107459061A (en) * | 2017-10-11 | 2017-12-12 | 河南省化工研究所有限责任公司 | A kind of method for being used to solve to remove iron content in molybdenum disulfide |
| CN109354070A (en) * | 2018-11-07 | 2019-02-19 | 洛阳申雨钼业有限责任公司 | A kind of molybdenum disulfide roasting method of purification |
| CN110668498A (en) * | 2019-10-15 | 2020-01-10 | 昆明理工大学 | Preparation method of high-purity molybdenum disulfide |
| CN113430364A (en) * | 2021-06-02 | 2021-09-24 | 昆明理工大学 | Method for removing iron from molybdenum concentrate |
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