CN106756093B - A kind of difficult zinc oxide material heat chemistry surface modification-floatation and recovery of lead zinc method - Google Patents
A kind of difficult zinc oxide material heat chemistry surface modification-floatation and recovery of lead zinc method Download PDFInfo
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- CN106756093B CN106756093B CN201611141161.8A CN201611141161A CN106756093B CN 106756093 B CN106756093 B CN 106756093B CN 201611141161 A CN201611141161 A CN 201611141161A CN 106756093 B CN106756093 B CN 106756093B
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- zinc oxide
- oxide material
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- lead
- floatation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/02—Preliminary treatment of ores; Preliminary refining of zinc oxide
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
Abstract
The present invention discloses a kind of difficult zinc oxide material surface active modification-floatation and recovery of lead zinc method, includes the following steps: 1) comminution；2) dry；3) zinc oxide material after drying is uniformly mixed according to a certain percentage with vulcanizing agent, reducing agent；4) it is modified to carry out heat chemistry surface for roasting；5) slow cooling, water quenching；6) flotation.Heat chemistry Process of Surface Modification of the present invention is generated without sulfur dioxide substantially, and modified material can recycle lead zinc by vulcanization mine floating agent, green and pollution-free.
Description
Technical field
The present invention relates to smelting field is selected, specially a kind of difficult zinc oxide material heat chemistry surface is modified, modified material
Slow cooling, water quenching and the selecting smelting combination of flotation processing method.
Background technique
With being continuously increased for zinc demand, vulcanize the continuous exploitation of ore resources, zinc oxide ore and with steel mill's metallurgical dust sludge
Secondary zinc development of resources the most typical and extraction become inevitable.However, usual valuable metal grade is not high in this kind of material, grain
Thinner, complicated components and association relationship is close are spent, are caused larger using conventional ore dressing or metallurgical technology processing difficulty.Common oxygen
Changing zinc material treatment process includes pyrometallurgy, hydrometallurgy and three kinds of beneficiating method, and thermal process has that process flow is short, processing
The big advantage of ability, but exist simultaneously the drawbacks such as high, big, the waste residue resource difficulty of pollution of energy consumption.Wet processing is divided into acidleach again
With alkali soaking technology, although acid leaching process technology maturation, while Leaching Zinc, iron also can be leached largely, keep zincate solution electric
Iron burden is removed before solution.Although alkali leaching selectivity is preferably, usually bad to zinc leaching effect in difficult material.Opposite smelting
Gold process, beneficiating method are a kind of environmental-friendly, inexpensive valuable metal recovery technologies.
In zinc oxide material method for floating, " vulcanization-amine floatation " and " vulcanization-xanthate floatation " research is more, but
Do not obtain wide range of industrial applications.The former usually can obtain preferable zinc recovering effect, but industrial production zinc recovering in laboratory
Rate is lower, this is mainly caused by sludge inevitable in industrial production.Although after being handled by predictive desliming, partial oxidation
Zinc ore floating process and technical indicator can be obviously improved, but the recycling of sludge partial oxidation zinc ore is still difficult." vulcanization-
Xanthate floatation " is the main method of cupric oxide ore and lead oxide ore flotation, but remote to the flotation recovery index of zinc oxide ore
Not as good as sulfidization-amine method floatation process, this is because " vulcanization-xanthate floatation " usually requires that oxide mineral surface sulfide is completeer
Entirely, and the vulcanization of zinc oxide is relatively difficult, so in vulcanization-xanthate method floatation process zinc the rate of recovery lower than vulcanization-
Amine method floatation process.However, " vulcanization-xanthate floatation " is influenced smaller by sludge, or even do not influenced by sludge.
For the vulcanization effect of enhanced oxidation zinc mineral, patent application CN200610010909.0 is in inert atmosphere and carbon containing
Under the conditions of coverture, it converts artificial sulphide ore as far as possible by the lead zinc in oxidase complex Pb-Zn deposits and then uses flotation, takes
Preferable lead zinc vulcanization effect is obtained, but vulcanizes conversion process complex process, atmosphere requirements harshness, operating difficulties.In order to simplify sulphur
Change conversion process, pass through control temperature in patent application CN200710065654.2, reaction mass separately or concurrently add
Heat, so that lead zinc oxide is partly or entirely converted into artificial sulphide ore in ore, however there are still cryogenic conditions to convert not
Sufficiently, the problems such as hot conditions vulcanizing agent dosage is big, low-concentration sulfur dioxide pollutes.In addition, more being related in patent application
And the vulcanization conversion of lead zinc oxide, the correlation of calcining matter material with flotation is not had a detailed description.
Summary of the invention
Difficult big for the direct metallurgy method processing of difficult zinc oxide material, conventional beneficiation method recycles valuable metal index
A series of problems, such as undesirable, the present invention is intended to provide a kind of difficult zinc oxide material is through the modified flotation again in heat chemistry surface
The method for recycling lead zinc, zinc oxide material is carried out comminution, drying first by this method, then is uniformly mixed with vulcanizing agent and reducing agent
It closes, then raising temperature, which is roasted, is modified its surface, material Slow cooling, water quenching is roasted, finally to roasting material
Flotation is carried out, the bulk concentrate of the modified lead oxide in surface or zinc oxide concentrate or both is obtained.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of difficult zinc oxide material heat chemistry surface modification-floatation and recovery of lead zinc method, includes the following steps:
1) comminution: difficult zinc oxide material is subjected to muck, ore grinding processing, obtains -74 μm of materials for accounting for 65 ~ 85wt%；
2) dry: the material after comminution to be subjected to heat drying processing, drying temperature is 100 ~ 300 DEG C, and drying time is
0.5 ~ 3h, preliminary hydro-extraction；
3) it mixes: the zinc oxide material after drying is uniformly mixed according to a certain percentage with vulcanizing agent, reducing agent；It is described
Vulcanizing agent is the one or more of sulphur, pyrite and magnetic iron ore, and vulcanizing agent dosage is the zinc oxide material weight after drying
1-5%；The reducing agent is the one or more of coke, coal or graphite powder, and reducing agent dosage is the zinc oxide material after drying
The 1-4% of weight；
4) heat chemistry surface is modified: carrying out calcination process to mixed uniformly material, control maturing temperature is 400 ~ 900
DEG C, calcining time is 15 ~ 60min, involved reaction equation in roasting system are as follows:
PbCO3=PbO+CO2(g) (1)
ZnCO3=ZnO+CO2(g) (2)
CaCO3=CaO+CO2(g) (3)
MgCO3= MgO+CO2(g) (4)
FeS2= FeS+1/2S2(g) (5)
S→S2(g) (6)
2PbO+ C+S2 (g)=2PbS+CO2 (g) (7)
2ZnO+C+S2 (g)=2ZnS+CO2 (g) (8)
2PbO+ C+2FeS2 (g)=2PbS+2FeS+CO2 (g) (9)
2ZnO+ C+2FeS2 (g)=2ZnS+2FeS+CO2 (g) (10)
Reaction equation (1) ~ (4) are the decomposition reaction of carbonate in difficult zinc oxide ore；Reaction equation (5) ~ (6) are vulcanizing agent
High-temperature decomposition reaction；Reaction equation (7) ~ (10) are lead zinc oxide surface sulfide reaction in zinc oxide material；
5) after roasting, nitrogen or carbon dioxide slow cooling, water quenching: are passed through as protective gas, with 150 ~ 400 DEG C/h's
Speed carries out Slow cooling, and the water quenching after temperature is down to 200 DEG C or less obtains water quenching material；
6) flotation: water quenching material carries out FLOTATION SEPARATION, and using conventional sulfide flotation regime of agent, it is modified to obtain surface
Oxide ore concentrate afterwards.
Further improved technical solution:
To obtain preferable surface sulfide effect, the additives such as the vulcanizing agent and reducing agent are levigate to -74 μm before roasting.
To obtain ideal lead zinc recovering index, in step 6), the FLOTATION SEPARATION is obtained using diffeential floatation
The modified lead oxide in surface or zinc oxide concentrate, or it is mixed using the modified lead oxide in bulk flotation acquisition surface and zinc oxide
Close concentrate.
By the above method, a kind of difficult zinc oxide material heat chemistry surface modification-flotation recovery of the present invention
Lead zinc method carries out calcination process to difficult zinc oxide material under sulfenyl atmosphere, by controlling the dosage of vulcanizing agent, realizes
The selectivity on the lead zinc oxide surface in ore is modified, Water Quenching is carried out after roasting material Slow cooling, finally to roasting
Material carries out flotation, obtains the modified oxide ore concentrate in individual surface or bulk concentrate.
Compared with existing vulcanizing-flotation method, the beneficial effect of the method for the present invention is:
A) heat chemistry Process of Surface Modification of the present invention is generated without sulfur dioxide substantially, and roasting material can pass through vulcanization mine
Floating agent recycles lead zinc, green and pollution-free；
B) present invention is only modified the surface of lead zinc oxide, therefore the conventional vulcanized roasting vulcanization of vulcanizing agent amount ratio
Agent dosage reduces 40 ~ 70%, and calcining time 0.5 ~ 1.0h of shorter reduction reduces costs, eliminates sulfur dioxide pollution；
C) present invention no longer evaluates vulcanization effect with vulcanization conversion ratio, but directly characterizes flotation with lead zinc flotation recovery rate
Effect.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is further elaborated.
Embodiment 1
Process object: low-grade difficult zinc oxide ore.
Certain low-grade difficult zinc oxide ore, main chemical compositions (mass percent) are as follows: Pb 1.86%, Zn
8.22%, Fe 12%, the chemical and physical phase (mass percent) of lead are as follows: PbCO388.68%, PbS 4.95%, other 6.37%, zinc
Chemical and physical phase (mass percent) are as follows: ZnCO383.23%, ZnS 8.6%, other 8.17%.
As shown in Figure 1, -74 μm of samples for accounting for 85wt% are obtained, at 280 DEG C after the zinc oxide ore is carried out comminution processing
Dry 1.0h.Weigh sample 200g, 1.9%(sample weight be added) sulphur and 2.5%(sample weight) fine coal, mix laggard
Row roasting, maturing temperature are 650 DEG C, calcining time 30min, with nitrogen do protective gas after roasting and with 250 DEG C/h
Speed carry out Slow cooling, start water quenching when temperature is down to 100 DEG C or less.Obtained water quenching material carries out preferentially floating lead again
Floating zinc test, the final grade that obtains is 51.5%, and the modified oxidation lead concentrate in the surface that the rate of recovery is 86.7% and grade are
42.5%, the modified zinc oxide concentrate in surface that the rate of recovery is 79.37%.
Embodiment 2
Process object: the metallurgical dust sludge of steel mill containing zinc.
Certain steel mill's metallurgical dust sludge, main chemical compositions (mass percent) are as follows: Pb 1.67%, Zn 14.67%, Fe
15.49%, C 14.65%, the chemical and physical phase (mass percent) of lead are as follows: PbO 82.5%, other 17.85%, the chemical and physical phase of zinc
(mass percent) are as follows: ZnO 89.96%, other 10.04%.
As shown in Figure 1, obtain the sample that -74 μm account for 78.45wt% after steel mill's Zinc-Bearing Wastes are carried out ore grinding and exist,
Dry 2h at 200 DEG C.Weigh sample 200g, 2.8%(sample weight be added) sulphur and magnetic iron ore mixture and 1.5%
The lignite of (sample weight) and the mixture of graphite powder, are roasted after mixing, and maturing temperature is 850 DEG C, and calcining time is
20min does protective gas with nitrogen after roasting and carries out Slow cooling with the speed of 350 DEG C/h, is down to 150 DEG C to temperature
Start water quenching when following.Obtained water quenching material carries out bulk flotation test, finally obtains lead, zinc and carbon grade and is respectively
24.37%, 41.67% and 26.5%, lead, zinc and the carbon rate of recovery are respectively 89.65%, 83.12% and 78% bulk concentrate.In concentrate
Carbon can be used as the fuel of lead and zinc bulk concentrate desulphurizing roasting, lead zinc grade increases substantially after roasting, is conducive to subsequent
Metallurgical extraction.
Embodiment 3
Process object: oxidation lead and zinc industry.
Certain oxidation lead and zinc industry, main chemical compositions (mass percent) are as follows: Pb 5.56%, Zn 7.31%, Fe
9.25%, the chemical and physical phase (mass percent) of lead are as follows: PbCO387.4%, PbS 5.8%, other 6.8%, the chemical and physical phase of zinc
(mass percent) are as follows: ZnCO385.66%, ZnS 6.34%, other 8%.
As shown in Figure 1, -74 μm of samples for accounting for 75wt% are obtained after the oxidation lead and zinc industry is carried out comminution processing,
Dry 2.8h at 120 DEG C.Weigh sample 200g, 4.5%(sample weight be added) pyrite and 3.5%(sample weight) coke
It levigate to -74 μm of charcoal, pyrite and coke, being roasted after mixing, maturing temperature is 450 DEG C, calcining time 50min,
Do protective gas with carbon dioxide after roasting and Slow cooling carried out with the speed of 150 DEG C/h, to temperature be down to 200 DEG C with
Start water quenching when lower.Obtained water quenching material carries out lead zinc bulk flotation test, and the final lead zinc grade that obtains is respectively 48.9% He
42.6%, lead zinc recovery is respectively 92.55% and 88.46% bulk concentrate.
Claims (8)
1. a kind of difficult zinc oxide material heat chemistry surface modification-floatation and recovery of lead zinc method, includes the following steps:
1) comminution: difficult zinc oxide material is subjected to muck, ore grinding processing, until -74 μm of particle accounts for 65 ~ 85wt%；
2) dry: by the material after comminution in 100 ~ 300 DEG C of dry 0.5 ~ 3h, preliminary hydro-extraction；
3) it mixes: the zinc oxide material after drying is uniformly mixed with vulcanizing agent, reducing agent；
4) heat chemistry surface is modified: to mixed uniformly material in 400 ~ 900 DEG C of 15 ~ 60min of roasting；
5) slow cooling, water quenching: after roasting, nitrogen or carbon dioxide is passed through as protective gas and carries out Slow cooling, to temperature
Water quenching after being down to 200 DEG C or less, obtains water quenching material；
6) flotation: water quenching material carries out flotation using conventional sulfide flotation regime of agent.
2. the method according to claim 1, wherein vulcanizing agent described in step 3) is sulphur, pyrite, magnetic Huang iron
The one or more of mine.
3. the method according to claim 1, wherein step 3) vulcanizing agent dosage is the zinc oxide material after drying
The 1-5wt% of dosage.
4. the method according to claim 1, wherein reducing agent described in step 3) is coke, coal or graphite powder
It is one or more of.
5. the method according to claim 1, wherein step 3) reducing agent dosage is the zinc oxide material after drying
The 1-4wt% of dosage.
6. the method according to claim 1, wherein in step 3) by vulcanizing agent and reducing agent first it is levigate to-
It 74 μm, is then uniformly mixed with the zinc oxide material after drying again.
7. the method according to claim 1, wherein the cooling velocity of step 5) is 150 ~ 400 DEG C/h.
8. the method according to claim 1, wherein method for floating is that diffeential floatation or mixing are floating in step 6)
Choosing.
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| CN201611141161.8A CN106756093B (en) | 2016-12-12 | 2016-12-12 | A kind of difficult zinc oxide material heat chemistry surface modification-floatation and recovery of lead zinc method |
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| CN114908246B (en) * | 2021-02-10 | 2023-09-15 | 郑州大学 | Method for comprehensively dressing and smelting lead-zinc sulfide mixed ore |
| CN113528854A (en) * | 2021-07-23 | 2021-10-22 | 昆明冶金研究院有限公司 | Method for extracting zinc from oxygen-sulfur mixed lead-zinc ore |
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| CN101024863A (en) * | 2007-02-06 | 2007-08-29 | 云南冶金集团总公司 | Method for pyrogenic sulfurizing difficult selected zinc oxide ore |
| CN103088209B (en) * | 2013-03-01 | 2014-08-27 | 中南大学 | Floating and smelting combined method for air-granulating lead smelting slag and utilizing waste heat |
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