CN108754140A - A method of it is produced containing zinc complexes using containing zinc ore crude - Google Patents
A method of it is produced containing zinc complexes using containing zinc ore crude Download PDFInfo
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- CN108754140A CN108754140A CN201810817537.5A CN201810817537A CN108754140A CN 108754140 A CN108754140 A CN 108754140A CN 201810817537 A CN201810817537 A CN 201810817537A CN 108754140 A CN108754140 A CN 108754140A
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- 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
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
-
- 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
- C22B19/34—Obtaining zinc oxide
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
This disclosure relates to which a kind of producing the method containing zinc complexes, including leach step, optional purifying step, settling step, optional rinse step, calcium zincates synthesis step, drying and calcining step using containing zinc ore crude.Disclosed method is combined wet-leaching with synthesis technology, realize the economic and environment-friendly utilization of super low-grade zinc, it is applied widely, without ammonia still process, it is simple and easy to do, greatly reduce the energy consumption of technique, also avoid various problems such as water process pressure caused by ammonia still process, high temperature and pressure security risk and equipment corrosion, it solves in ammonia circulation technology because steam brings the environmental issue faced due to water more than needed influences process water balance into, solve the problems, such as the technique rate of recovery and fine work grade, pollute small, supplies are recyclable；The disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, be related to the low-grade recycling containing zinc ore crude, more particularly to one
The method that kind produces zinc oxide and calcium oxide composite using low-grade zinc oxide raw ore.
Background technology
The production of China's zinc is ranked the first in the world with consumption, and domestic zinc resource cannot meet production, need import a large amount of every year
Zinc raw material.China is one and aoxidizes the abundanter country of zinc resource, and zinc metal reserves are about 2800 in China's zinc oxide ore
Ten thousand tons, account for about 27.7% of zinc metal reserves in world's zinc oxide ore.Zinc oxide ore generally zinc grade in China's is low, average grade
Less than 5%, be still unable to the slow-witted mine of economic utilization at present, lean ore reserves account for the overwhelming majority, wherein existing stockpiling containing zinc oxide 3%~
The 5% more than one hundred million tons of mining tailing and milltailings.
Therefore, Efficient Development utilizes low-grade zinc oxide ore resource, the problem insufficient for alleviating domestic zinc raw material supply
With important strategic importance.
The main technique that low-grade zinc oxide ore utilizes includes：Pyrogenic process produces secondary zinc oxide, due to the high energy consumption of the technique
With high pollution, limited by national industrial policies.
Flotation is the main technique of current processing zinc oxide ore, but for zinc oxide floatation process, external zinc oxide ore
Sorting index is：Zinc grade 36%~40%, the rate of recovery 60%~70%, up to 78%；China's zinc oxide ore sorting index
For：Zinc grade 35%~38%, rate of recovery average out to 68%, up to 73%.Therefore recovery rate in ore-dressing is low, and concentrate grade is low etc.
Problem is common problem existing for domestic and international zinc oxide ore ore dressing, while Flotation of Zinc Oxide needs that a large amount of vulcanized sodium progress sulphur are added
Change is handled, and the zinc after vulcanization package is needed could be directly as production metallic zinc or life after pyrogenic process or pressure oxidation after-treatment
Produce the raw material of zinc oxide.
For the wet underwater welding of zinc ore, mainly there are sulfuric acid leaching, Calcium Chloride Method, ammonium chloride method etc. in the prior art.
Sulfuric acid leaching is selectively low, can largely leach the solvable silicon in ore, and the colloidal state silicon of generation is difficult to filter, and the acid-hatching of young eggs is given birth to
At a large amount of sulfate slags, great environmental protection treatment pressure is caused；Sulfuric acid leaching also can not be effectively to zinc silicate, the iron in ore
The ingredients such as sour zinc are handled.The leaching of the ingredients such as zinc silicate in raw ore, zinc ferrite can not be effectively treated in Calcium Chloride Method, and leaches
Rate is undesirable, and high temperature is needed to leach, and overall economic efficiency is bad.And in ammonium chloride method, after being leached to raw ore, from leaching
The process that zinc ingredient is recycled in liquid is extremely difficult, is unsuitable for commercial Application.
Therefore, existing technique is unsatisfactory to the low-grade utilization containing zinc ore crude.
Invention content
Problems to be solved by the invention
Low-grade zinc oxide ore utilizes at present technique exist energy consumption is high, recovery rate in ore-dressing is low, cause Heavy environmental pollution,
The problems such as economic value is low.The present invention is solved by the improvement to zinc oxide ore treatment process present in zinc oxide ore utilization
The above problem.
The solution to the problem
In order to solve the problems existing in the prior art, the disclosure provides a kind of using containing side of the zinc ore crude production containing zinc complexes
Method includes the following steps：
Leach step：Being mixed containing zinc ore crude and digestion agent after will be levigate, then filters, obtains leachate, wherein
The digestion agent be ammonia and ammonium hydrogen carbonate mixed aqueous solution or ammonia and the mixed aqueous solution or ammonia of ammonium carbonate, ammonium hydrogen carbonate and
The mixed aqueous solution of ammonium carbonate；
Optionally, the leachate obtained in the leach step is purified；
Settling step：Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains first
Solid and the first filtrate；
Calcium zincates synthesis step：Calcium hydroxide and/or calcium oxide are added into first filtrate, stirring is reacted,
Filtering, obtains the second solid and the second filtrate；
Optionally, first solid and/or second solid are rinsed with water；
Drying and calcining step：Some or all of some or all of described first solid and second solid is mixed
It closes, then dries, calcined at 850~1050 DEG C, obtain containing zinc complexes containing zinc oxide and calcium oxide.
In the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude, in institute
The amount for stating the substance of the calcium oxide and/or calcium hydroxide that are added in settling step is the object of effective carbonate in the leachate
The 100% to 130% of the amount of matter, preferably 100% to 110%.
It is described in the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude
Settling step is divided into pre-treatment step, heavy zinc step two step carries out：
Pre-treatment step：Calcium hydroxide and/or calcium oxide are added in the leachate obtained to the leach step, are stirred,
Filtering obtains pre-treated solid and intermediate filtrate,
Heavy zinc step：The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to pre-treatment step, stirring,
Filtering obtains heavy zinc solid and the first filtrate；
In the drying and calcining step, the pre-treated solid, the heavy zinc solid are mixed with second solid,
Then it dries, is calcined at 850~1050 DEG C：Or mix the heavy zinc solid with second solid, then do
It is dry, it is calcined at 850~1050 DEG C.
In the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude, in institute
The amount for stating the calcium hydroxide and/or calcium oxide that are added in pre-treatment step is：
nPretreatment=(nLeachate carbonate-nZinc ammonium complex ion)×b
Wherein,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in the leachate,
The value of b is 0<B≤110%, the preferably value of b are 90%≤b≤110%.
In the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude, in institute
The amount for stating the calcium hydroxide and/or calcium oxide that are added in heavy zinc step is：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein,
nHeavy zincTo sink the amount of the substance of calcium hydroxide and/or calcium oxide added in zinc step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in the pre-treatment step,
The value of c is 100%≤c≤130%, preferably 100%≤c≤110%.
It is described in the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude
The mass concentration of total ammonia in digestion agent is 5%~15%, and the molar concentration of effective carbonate in the digestion agent is：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein,
CDigestion agent carbonateFor the molar concentration of effective carbonate in the digestion agent,
nThe total zinc of raw oreFor the amount of the substance containing the Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude,
VDigestion agentFor the volume of the digestion agent,
The value range of a is 100%~600%, and preferably the value range of a is 150%~250%.
In the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude, in institute
The amount for stating the substance of the calcium hydroxide and/or calcium oxide that are added in calcium zincates synthesis step and the zinc ammino in first filtrate
The ratio between amount of substance of ion is 1~1.2:2, preferably 1~1.1:2.
In the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude, to institute
State second filtrate that calcium zincates synthesis step obtains and be passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as
Digestion agent is recycled for the extraction containing zinc ore crude.
It is described in the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude
The concentration (in terms of Zn-ef ficiency quality) of zinc ammonium complex ion is 10~50g/L, preferably 10~25g/L in first filtrate.
In the utilization that disclosure further embodiment provides produces the method containing zinc complexes containing zinc ore crude, in institute
It states in settling step, stirs and reacted at a temperature of 15~25 DEG C.
The effect of invention
The disclosure realizes the Advantageous techniques effect of following one or more aspects：
1) wet-leaching is combined with synthesis technology, realizes the economic and environment-friendly utilization of super low-grade zinc.
2) disclosed method is applied widely, and ammonia-ammonium bicarbonate Leaching Systems can be effectively former containing zinc to diversified forms
Mine is extracted and is utilized.
3) break traditional ammonia-ammonium carbonate method zinc complexing extracting technology by heating evaporation ammonia destroy complexing environment realize zinc from
Calcium oxide or hydroxide are added creatively into ammonium bicarbonate-zinc ammonia complex system by the orthodox practice of sub- Crystallization Separation, the application
Calcium makes the balance of zinc ammonium complex ion-zinc ion-zinc hydroxide move, passes through under the premise of not destroying solution ammonia environment
Balance moving principle realizes the selective crystallization separation of Zn-ef ficiency, and avoiding existing heating ammonia still process method from destroying ammonia environment causes impurity big
The phenomenon that amount co-precipitation.The technique of the disclosure is not necessarily to ammonia still process, simple and easy to do, greatly reduces the energy consumption of technique, it is thus also avoided that steams
Water process pressure caused by ammonia, high temperature and pressure security risk, a large amount of ammonia of equipment burn into steam volatilization and cause additional environmental protection treatment
Various problems such as burden.
4) leaching and separation that zinc is realized by the cycle of carbonate solve in ammonia circulation technology because steam brings water more than needed into
Measure the environmental issue for influencing process water balance and facing.
5) relative to zinc oxide floatation process, disclosed method solves the problems, such as the technique rate of recovery and fine work grade, institute
The raw material that the combination product obtained directly as product, can also can be used as other industrial process uses.
6) disclosed method pollution is small, and supplies are recyclable, and it is former to solve existing zinc oxide treatment process auxiliary
The problem of environmental pollution that material strip comes.
7) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time, and the reaction of calcium zincates is synthesized from zinc ammonium complex ion
High selectivity, it is simple and quick.
Specific implementation mode
It will be detailed below various exemplary embodiments, feature and the aspect of the disclosure.Dedicated word " example herein
Property " mean " being used as example, embodiment or illustrative ".Any embodiment here as illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiments.
In addition, in order to which the disclosure is better described, numerous details is given in specific implementation mode below.
In some instances, method well known to those skilled in the art, means, reagent and equipment are not described in detail, but ability
Field technique personnel can realize the technical solution of the disclosure according to the general knowledge of this field.
The scope of application of disclosed method is not particularly limited, and is widely portable to the various utilizations containing zinc ore crude.?
When using low-grade zinc oxide raw ore as raw materials for production, the advantages of method disclosed herein, is particularly pertinent.For example, low-grade former containing zinc
Mine can be zinc content contains zinc ore crude 3%~15%；Particularly, before the disclosure, zinc content contains 3%~6%
Zinc ore crude (lean ore, milltailings) is largely stored up, and existing various techniques are to can not make the utilization of existing economic value in fact
At prodigious processing pressure, and disclosed method is not only technically realized to such low-grade containing the effective of zinc ore crude
It utilizes, and simple process is easy, it is of low cost, there is very high economic value.
In the disclosure, the existence form containing zinc ingredient in zinc ore crude is not particularly limited, such as zinc ingredient can be with packet
The one or more forms for including but being not limited to zinc oxide, zinc carbonate, zinc silicate etc. exist.Explanation of nouns
Herein, unless otherwise indicated, " ammine carbonate zinc " is the compound that zinc ammonium complex ion is formed with carbonate
General name, including [Zn (NH3)4]CO3(four ammino zinc of carbonic acid), [Zn (NH3)3]CO3(three ammino zinc of carbonic acid), [Zn (NH3)2]CO3
(two ammino zinc of carbonic acid), [Zn (NH3)]CO3(one ammino zinc of carbonic acid) etc..
Herein, unless otherwise indicated, " zinc ammonium complex ion " is the general name of ammino zinc complex ions at different levels, including [Zn
(NH3)4]2+(four ammino zinc ions), [Zn (NH3)3]2+(three ammino zinc ions), [Zn (NH3)2]2+(two ammino zinc ions), [Zn
(NH3)]2+(an ammino zinc ion) etc..
Herein, unless otherwise indicated, solution (includes but not limited to the various liquid such as digestion agent, leachate, intermediate filtrate
Body) in " effective carbonate " refer to carbonate and bicarbonate radical in the solution summation.
" optional " or " optionally " indicates that the then described step can carry out, or can be without, and the table
State the situation carried out including the then described step and the then described step without situation.
Chemical equation
1. extraction
A. zinc oxide extracts
Ammonia is with ammonium hydrogen carbonate as digestion agent
ZnO+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O (integer that i is 1 to 4)
Ammonia is with ammonium carbonate as digestion agent
ZnO+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+H2O (integer that i is 2 to 4)
B. zinc hydroxide extracts
Ammonia is with ammonium hydrogen carbonate as digestion agent
Zn(OH)2+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+2H2O
(integer that i is 1 to 4)
Ammonia is with ammonium carbonate as digestion agent
Zn(OH)2+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+2H2O
(integer that i is 2 to 4)
C. zinc carbonate (smithsonite) extracts
ZnCO3+iNH3=[Zn (NH3)i]CO3(integer that i is 1 to 4)
D. zinc silicate extracts
Ammonia is with ammonium hydrogen carbonate as digestion agent
ZnSiO3+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 1 to 4)
Ammonia is with ammonium carbonate as digestion agent
ZnSiO3+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 2 to 4)
2. precipitation
Lime is reacted with water
CaO+H2O=Ca (OH)2
It precipitates (pretreatment)
Ca(OH)2+(NH4)2CO3=CaCO3↓+2NH3·H2O
Ca(OH)2+NH4HCO3=CaCO3↓+NH3+2H2O
It precipitates (heavy zinc)
Ca(OH)2+[Zn(NH3)i]CO3=CaCO3↓+Zn(OH)2↓+iNH3
(integer that i is 1 to 4)
Ca(OH)2+[Zn(NH3)i]CO3=[Zn (NH3)i](OH)2+CaCO3↓
(integer that i is 1 to 4)
3. calcium zincates synthesize
2[Zn(NH3)i](OH)2+Ca(OH)2+2H2O=Ca (OH)2·2Zn(OH)2·2H2O+2iNH3
(integer that i is 1 to 4)
4. calcining
Zn(OH)2=ZnO+H2O
CaCO3=CaO+CO2
Ca(OH)2·2Zn(OH)2·2H2O=CaO+2ZnO+5H2O
Specific process step
Step 1 extracts
Low-grade be mixed in a certain ratio with prepared digestion agent containing zinc ore crude after will be levigate is stirred leaching.Leaching
Proposing agent can be selected from：The mixed aqueous solution of ammonia and ammonium hydrogen carbonate；The mixed aqueous solution of ammonia and ammonium carbonate；Ammonia, ammonium hydrogen carbonate and carbon
The mixed aqueous solution of sour ammonium.
Total ammonia density and effective carbonate concentration in digestion agent are not particularly limited, and those skilled in the art can be according to original
The factors such as mine ingredient, grade, are selected in conjunction with actual needs.
In the preferred scheme, the mass concentration of total ammonia is 5%~15%, more preferable 6%~8% in digestion agent, preferably
Concentration range can reach sufficient extracting effect, and avoid excessive ammonia cause waste and environmental issue.
In the preferred scheme, the amount of effective carbonate is to subtract original in complexing zinc theory carbonate consumption in digestion agent
Increase by 0~500% on the basis of the difference obtained by carbonate amount that zinc carbonate is brought into material, the amount of carbonate in more preferable digestion agent
Increase on the basis of zinc theory carbonate consumption is complexed and subtracts the difference obtained by effective carbonate amount that zinc carbonate in raw material is brought into
Add 50%-150%.It refers to that the Zn-ef ficiency in raw ore is fully converted to ammine carbonate zinc institute that zinc theory carbonate consumption, which is complexed,
The amount of the carbonate of consumption.Therefore, the molar concentration of effective carbonate may be calculated as in digestion agent：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein, CDigestion agent carbonateFor the molar concentration of effective carbonate in digestion agent, nThe total zinc of raw oreFor containing the Zn-ef ficiency in zinc ore crude
Substance amount, nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude, VDigestion agentFor digestion agent volume, a is coefficient, a's
Value is 100%~600%, preferably 150%~250%.The mass concentration of carbonate can be changed according to molar concentration in digestion agent
It calculates.
It is complete that the preferred effective carbonate concentration of digestion agent can be such that the zinc in raw ore leaches, and carbonate can be realized in work
Cycle in skill, and it is avoided that excessive carbonate causes stress subsequent technique processing.
The weight ratio of digestion agent and the powder containing zinc ore crude is not particularly limited, as long as zinc ingredient can be leached.It is preferred that
The weight ratio of digestion agent and the powder containing zinc ore crude is 3:1 to 5:1, satisfied extracting effect can be not only obtained, but also avoid the wave of digestion agent
Take.
The temperature of extraction is not particularly limited, as long as the zinc ingredient in raw ore is made to be leached.It is preferred that at normal temperatures into
Row extraction, such as extracted at 15~30 DEG C；Also it (such as 30~55 DEG C) can be extracted at slightly higher temperature.It also can root
Suitable temperature is selected according to physical condition.
It will contain after zinc ore crude is mixed with digestion agent and be stirred, mixing time is not particularly limited, as long as making in raw ore
Zinc ingredient is leached, and preferably mixing time is 1~4 hour, more preferable 1~2 hour.
In leaching process, the Zn-ef ficiency in raw ore is converted into zinc ammonium complex ion (predominantly zinc ammonium complex ions at different levels), into
Enter in liquid phase.It is filtered after extraction, the leachate containing zinc ammonium complex ion is obtained after filtering, leachate can be used for subsequent heavy
Shallow lake process.Zinc ammonium complex ion concentration in leachate is not particularly limited, but preferably in leachate zinc ammonium complex ion concentration (with
The quality meter of Zn-ef ficiency) disclosed method overall economic efficiency can be made best in 10g/L or more, more preferable 10~50g/L.
Step 2 purifies
Step 2 be optional step, it is necessary to when selection carry out step 2.Leachate is purified by known method,
Remove the impurity elements such as iron, manganese, lead, copper.A kind of illustrative purification method is then addition zinc powder is filtered into line replacement, to
Heavy metal contaminants are removed, but other various well known purification methods can also be used.Purifying step helps to improve finished product
Purity.
Step 3 precipitates
In settling step, calcium hydroxide and/or calcium oxide are added into the leachate containing zinc ammonium complex ion, will leach
Carbonate/bicarbonate in liquid is converted into calcium carbonate, at the same in leachate zinc ammonium complex ion-zinc ion-zinc hydroxide it is flat
Weighing apparatus moves, and part zinc ammonium complex ion is decomposed, and part zinc ingredient is mainly co-precipitated in the form of zinc hydroxide with calcium carbonate.
In settling step, the additive amount of calcium hydroxide and/or calcium oxide is not particularly limited, as long as making in leachate
Carbonate/bicarbonate is converted into calcium carbonate, and part zinc conversion is the form of zinc hydroxide precipitation.Preferably, hydrogen
The content of effective carbonate in the substantially matching leachate of the additive amount of calcium oxide and/or calcium oxide, for example, precipitation process addition
The amount of the substance of calcium hydroxide and/or calcium oxide is 100% to 130% of the amount of the substance of effective carbonate in leachate, more
It is preferred that 100% to 110%.Calcium hydroxide and/or calcium oxide are appropriately added, helps to control process costs, it helps change
Kind finished product zinc product grade.
In settling step, calcium hydroxide and/or calcium oxide are added into leachate, stirring is reacted, and solid is generated
Precipitation.The temperature of reaction is not particularly limited, but can be carried out well since reaction is not necessarily to heating, therefore particularly preferably normal
It is reacted under temperature (such as 15~25 DEG C), on the one hand energy saving, environmental pollution caused by the other hand also reducing ammonia volatilization.
Mixing time is not particularly limited, as long as being precipitated, preferably stirs 1~2 hour.
It is filtered after stirring, obtains the first solid and the first filtrate.The main component of first solid be zinc hydroxide and
Calcium carbonate.First filtrate continues on for subsequent calcium zincates synthesis.
Preferably, the concentration (in terms of quality of Zn-ef ficiency) of zinc ammonium complex ion is 10~50g/L in the first filtrate, more preferably
10~25g/L is conducive to being smoothed out for subsequent calcium zincates synthesis step.
Step 4 calcium zincates synthesize
Calcium hydroxide and/or calcium oxide are added into the first filtrate, stirring is reacted.The hydroxide being added in this step
The ratio between the amount of the substance of calcium and/or calcium oxide and the amount of substance of zinc ammonium complex ion in the first filtrate preferably 1~1.2:2, it is more excellent
Select 1~1.1:2.Reaction temperature is not particularly limited, and can be such as 15~90 DEG C, preferably 20~90 DEG C, and further preferred 30
~60 DEG C；Or it is also preferred that 15~25 DEG C of reaction temperature, which has without heating, energy saving and reduce ammonia volatilization
Advantage.Being stirred to react 0.5~2 hour can be filtered after (preferably 0.5~1 hour), without prolonged reaction and ageing
Process.The second solid and the second filtrate is obtained by filtration.The main component of second solid is calcium zincates, in addition can be logical to the second filtrate
Enter carbon dioxide, then recycles for the extraction containing zinc ore crude.
Step 5 rinses
Step 5 be optional step, it is necessary to when selection carry out step 5.Take the first solid that step 3 obtains and/or
The second solid that step 4 obtains, adds water to be rinsed, liquid-solid ratio 5~10:1, rinsing times 1~2 time.
Step 6 drying and calcining
In this step, the portion of the second solid some or all of the first solid that step 3 obtains obtained with step 4
Divide or all ratio mixing according to actual needs, drying are calcined at 850~1050 DEG C.If having carried out rinse step,
It then takes the solid after rinsing to be dried, is then calcined at 850~1050 DEG C.Calcining is obtained containing zinc oxide and oxidation
The compound of calcium.The compound of gained can also can be used as other industrial uses directly as rubber additive or feed addictive.
In addition, in further embodiment, the higher compound of zinc oxide percentage in order to obtain, step 3 (precipitation) can
It is divided into step 3a (pretreatment), step 3b (heavy zinc) two steps carry out：
Step 3a pretreatments
In pre-treatment step, a certain amount of calcium hydroxide and/or oxygen is added in the leachate obtained to step 1 (extraction)
Change partly or entirely effective carbonate more than needed formation precipitation of calcium carbonate in calcium, with leachate, to will partly or entirely have more than needed
Effective carbonate removed from leachate.Effective carbonate more than needed refers to participating in being formed except the carbonate of ammine carbonate zinc
Effective carbonate.The amount of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step can according in leachate have more than needed
The amount of effective carbonate and suitably determine.
Such as：Effective carbonate total concentration in leachate is detected, in conjunction with leachate total volume, calculates and is participated in leachate
Ammine carbonate zinc formed carbonate except effective carbonate more than needed amount (for ammonium carbonate close zinc for, zinc ammino from
The amount substantially 1 of son and carbanion:1 relationship), then obtain the effective carbonate for removing and partly or entirely having more than needed in leachate
Calcium hydroxide and/or Calcium Oxide Dosage (allowing slightly excessive) to be added needed for ion.For example, the hydrogen-oxygen added in this step
Changing the amount of the substance of calcium and/or calcium oxide can be calculated as follows：
nPretreatment=(nLeachate carbonate-nZinc ammonium complex ion)×b
Wherein, nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step, nLeachate carbonateFor
The amount of the substance of effective carbonate in leachate, nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in leachate, b is to be
Number.The value range of b can be such as 0<B≤110%：If it is desired to effective carbonate more than needed is substantially removed, then b
Value can be such as 90%≤b≤110%；If it is desired to only remove a part effective carbonate more than needed, then the value of b can
Think such as 60%≤b<90% or 30%≤b<60% or 0<b<30%.Under conditions of 90%≤b≤110%,
This technique can be made to obtain the high final product of zinc grade.
Required calcium hydroxide and/or calcium oxide are added into leachate, are filtered after being stirred to react 1~2 hour, mistake
Filter to obtain pre-treated solid and intermediate filtrate.Reaction preferably carries out under such as 15~25 DEG C of room temperature.Pre-treated solid it is main
Ingredient is calcium carbonate.Intermediate filtrate is taken to enter step 3b (heavy zinc) operations.
Step 3b sinks zinc
Calcium hydroxide and/or calcium oxide is added to the intermediate filtrate obtained by step 3a, makes the effective carbonic acid of residue in filtrate
Root is converted into calcium carbonate, while the balance of zinc ammonium complex ion-zinc ion-zinc hydroxide moves in filtrate, part zinc ammino
Ion dissociation, part zinc ingredient are mainly co-precipitated in the form of zinc hydroxide with calcium carbonate.
In step 3b, the dosage of calcium hydroxide and/or calcium oxide is not particularly limited, as long as the residue in filtrate is made to have
Effect carbonate is converted into calcium carbonate, and part zinc is at fractional precipitation.Preferably, calcium hydroxide and/or calcium oxide in this step
Dosage matches substantially with the amount of remaining effective carbonate in intermediate filtrate, such as calcium hydroxide and/or oxygen are added in this step
The amount of the amount and the substance of remaining effective carbonate in intermediate filtrate of changing the substance of calcium is 1:1, allow certain error；But it reflects
Complicated equilibrium system, also can make calcium hydroxide and/or calcium oxide suitably excessive present in extraction-precipitation solution system,
To promote, the reaction was complete.Based on theory matches dosage, the excess of calcium hydroxide and/or calcium oxide preferably no more than
30%, if excess is excessively high, subsequent calcium zincates settling step may be adversely affected.For example, in heavy zinc step
The amount of the calcium hydroxide of addition and/or the substance of calcium oxide can be calculated as follows：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein, nHeavy zincFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in heavy zinc step, nLeachate carbonateTo leach
The amount of the substance of effective carbonate in liquid, nPretreatmentFor the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step
Amount, c is coefficient, value preferably 100%≤c≤130% of c, more preferable 100%≤c≤110%.
In step 3b, required calcium hydroxide and/or calcium oxide are added into the intermediate filtrate obtained by step 3a, stirs
Reaction 1~2 hour, reaction preferably carry out under such as 15~25 DEG C of room temperature.It is filtered after reaction, it is filtered to obtain
Liquid is the first filtrate, and the first filtrate is used for subsequent calcium zincates synthesis step；The solid being obtained by filtration is heavy zinc solid,
Main component includes zinc hydroxide and calcium carbonate.
The heavy zinc solid that pre-treated solid that step 3a (pretreatment) obtains, step 3b (heavy zinc) can be obtained with it is follow-up
The ratio mixing of the second solid that step 4 (calcium zincates synthesis) obtains according to actual needs, is optionally rinsed, then drying is forged
It burns, obtains the compound containing zinc oxide and calcium oxide.The heavy zinc solid that step 3b (heavy zinc) obtains can also be walked with follow-up
The ratio mixing of the second solid that rapid 4 (calcium zincates synthesis) obtain according to actual needs, is optionally rinsed, then drying is forged
It burns, obtains the compound containing zinc oxide and calcium oxide.
The embodiment of the disclosure is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the disclosure, and is not construed as the restriction to the scope of the present disclosure.It is not specified in embodiment
Actual conditions person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer,
Being can be with conventional products that are commercially available.
Embodiment 1
Yunnan somewhere zinc ore, Zn content 11.67%, raw ore oxygenation efficiency 95.2%, the zinc ingredient in the mine are with zinc carbonate
It is primarily present form.
300 grams of oxidation zinc ore crudes are taken, 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate are put into
Mass concentration 5%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then filtered, liquid after filtering
Zinc mass concentration 3.374% in body (it is then 4.2% to be calculated by zinc oxide), carbonate mass concentration 6.21% in liquid, increases
Part is that zinc carbonate is brought into raw ore.According to inspection data, solvable zinc recovery is 91.11% in leaching process raw ore, total zinc
The rate of recovery is 86.74%.
The zinc ammonia complexing liquid zinc ammonia complexing liquid being obtained by filtration is subjected to purified treatment.
600 milliliters of purified zinc ammonia complexing liquid are taken, 19.69 grams of calcium oxide are added, ammine carbonate is formed for that will participate in
Carbonate more than needed except the carbonate of zinc, which sinks, to be removed, and is stirred after calcium hydroxide is added, reaction is filtered after 1 hour.It takes
500 milliliters of filtered liquid is added 9.29 grams of calcium hydroxides and is used for depositing zinc ingredient, and stirring at normal temperatures is reacted, instead
It is filtered after answering 1 hour, the solid being obtained by filtration is calcium carbonate and zinc hydroxide mixture.
Remaining Zn content (working as gauge with zinc oxide) is 15.12 gram per liters in filtered fluid, adds 2.21 grams of oxygen
It is stirred after changing calcium, reaction is filtered after 1 hour, remaining Zn content (working as gauge with zinc oxide) in filtered filtrate
For 2.3 gram per liters, the solid being obtained by filtration is the mainly mixture containing calcium zincates.
The mixture of calcium carbonate, zinc hydroxide is merged with the mixture mainly containing calcium zincates, adds water to be rinsed, liquid is solid
Than 10:1, rinsing times 2 times.It is dried at 105 DEG C after rinsing, after the mixture after drying is calcined 2 hours under 950 degree
It is sampled analysis, zinc oxide content 55.2% in mixture, calcium oxide content 44.5%
Embodiment 2
Chongqing somewhere zinc ore, Zn content 12.93%, raw ore oxygenation efficiency 94.82%, the zinc ingredient in the mine are with zinc silicate
It is primarily present form.
It takes 300 grams to contain zinc ore crude, is put into 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate matter
Measure concentration 6%) in carry out heating stirring extraction, 50 DEG C of extraction temperature, then mixing time 2 hours is filtered, liquid after filtering
Zinc mass concentration 3.681% in body, carbonate mass concentration 6.34% in liquid, increased portion are divided into zinc carbonate in raw ore and bring into.
According to inspection data, solvable zinc recovery 90.07% in leaching process raw ore, total zinc recovery 85.41%.
The zinc ammonia complexing liquid zinc ammonia complexing liquid being obtained by filtration is subjected to purified treatment.
600 milliliters of purified zinc ammonia complexing liquid are taken, 18.98 grams of calcium hydroxides are added, carbonic acid ammonia is formed for that will participate in
Carbonate more than needed except the carbonate of conjunction zinc, which sinks, to be removed, and is stirred after calcium hydroxide is added, reaction is filtered after 1 hour.
500 milliliters of filtered liquid is taken, 10.6 grams of calcium hydroxides are added and are used for depositing zinc composition, stirring at normal temperatures is reacted,
Reaction is filtered after 1 hour, and the solid being obtained by filtration is calcium carbonate and zinc hydroxide mixture.
Remaining Zn content (working as gauge with zinc oxide) is 15.03 gram per liters in filtered fluid, adds 2.26 grams of oxygen
It is stirred after changing calcium, reaction is filtered after 1 hour, remaining Zn content (working as gauge with zinc oxide) in filtered filtrate
For 1.9 gram per liters, the solid being obtained by filtration is the mainly mixture containing calcium zincates.
The mixture of calcium carbonate, zinc hydroxide is merged with the mixture mainly containing calcium zincates, adds water to be rinsed, liquid is solid
Than 10:1, rinsing times 2 times.It is dried at 105 DEG C after rinsing, after the mixture after drying is calcined 2 hours under 950 degree
It is sampled analysis, zinc oxide content 54.7% in mixture, calcium oxide content 44.9%.
The presently disclosed embodiments is described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.The selection of term used herein, purport
In principle, the practical application or to the technological improvement in market for best explaining each embodiment, or make the art its
Its those of ordinary skill can understand each embodiment disclosed herein.
Claims (10)
1. a kind of producing the method containing zinc complexes using containing zinc ore crude, which is characterized in that described to be contained using the production containing zinc ore crude
The method of zinc complexes includes the following steps：
Leach step：Being mixed containing zinc ore crude and digestion agent after will be levigate, then filters, obtains leachate, wherein is described
Digestion agent is ammonia and the mixed aqueous solution or ammonia of ammonium hydrogen carbonate and mixed aqueous solution or ammonia, the ammonium hydrogen carbonate and carbonic acid of ammonium carbonate
The mixed aqueous solution of ammonium；
Optionally, the leachate obtained in the leach step is purified；
Settling step：Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains the first solid
With the first filtrate；
Calcium zincates synthesis step：Calcium hydroxide and/or calcium oxide are added into first filtrate, stirring is reacted, and is filtered,
Obtain the second solid and the second filtrate；
Optionally, first solid and/or second solid are rinsed with water；
Drying and calcining step：Some or all of some or all of described first solid and described second solid are mixed, so
After dry, calcined at 850~1050 DEG C, obtain containing zinc complexes containing zinc oxide and calcium oxide.
2. according to claim 1 produce the method containing zinc complexes using containing zinc ore crude, which is characterized in that described heavy
The amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the step of shallow lake is the substance of effective carbonate in the leachate
The 100% to 130% of amount, preferably 100% to 110%.
3. according to claim 1 or 2 produce the method containing zinc complexes using containing zinc ore crude, which is characterized in that described
Settling step is divided into pre-treatment step, heavy zinc step two step carries out：
Pre-treatment step：Calcium hydroxide and/or calcium oxide are added in the leachate obtained to the leach step, are stirred, filtering,
Pre-treated solid and intermediate filtrate are obtained,
Heavy zinc step：The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to pre-treatment step, is stirred, filtering,
Obtain heavy zinc solid and the first filtrate；
In the drying and calcining step, the pre-treated solid, the heavy zinc solid are mixed with second solid, then
It is dry, it is calcined at 850~1050 DEG C：Or mix the heavy zinc solid with second solid, then dry,
It is calcined at 850~1050 DEG C.
4. according to claim 3 produce the method containing zinc complexes using containing zinc ore crude, which is characterized in that described pre-
The amount of the calcium hydroxide and/or calcium oxide that are added in processing step is：
nPretreatment=(nLeachate carbonate-nZinc ammonium complex ion)×b
Wherein,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in the leachate,
The value of b is 0<B≤110%, the preferably value of b are 90%≤b≤110%.
5. according to claim 3 or 4 produce the method containing zinc complexes using containing zinc ore crude, which is characterized in that in institute
The amount for stating the calcium hydroxide and/or calcium oxide that are added in heavy zinc step is：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein,
nHeavy zincTo sink the amount of the substance of calcium hydroxide and/or calcium oxide added in zinc step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in the pre-treatment step,
The value of c is 100%≤c≤130%, preferably 100%≤c≤110%.
6. according to any one of claims 1 to 5 produce the method containing zinc complexes using containing zinc ore crude, feature exists
In the mass concentration of total ammonia in the digestion agent is 5%~15%, the molar concentration of effective carbonate in the digestion agent
For：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein,
CDigestion agent carbonateFor the molar concentration of effective carbonate in the digestion agent,
nThe total zinc of raw oreFor the amount of the substance containing the Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude,
VDigestion agentFor the volume of the digestion agent,
The value range of a is 100%~600%, and preferably the value range of a is 150%~250%.
7. according to any one of claims 1 to 6 produce the method containing zinc complexes using containing zinc ore crude, feature exists
In in the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in the calcium zincates synthesis step and first filtrate
The ratio between the amount of substance of zinc ammonium complex ion be 1~1.2:2, preferably 1~1.1:2.
8. according to any one of claims 1 to 7 produce the method containing zinc complexes using containing zinc ore crude, feature exists
In second filtrate obtained to the calcium zincates synthesis step is passed through carbon dioxide, will be passed through the second of carbon dioxide
Filtrate recycles as digestion agent for the extraction containing zinc ore crude.
9. being utilized according to claim 1 to 8 any one of them and producing the method containing zinc complexes containing zinc ore crude, feature exists
In the concentration (in terms of Zn-ef ficiency quality) of zinc ammonium complex ion is 10~50g/L, preferably 10~25g/L in first filtrate.
10. being utilized according to claim 1 to 9 any one of them and producing the method containing zinc complexes containing zinc ore crude, feature exists
In in the settling step, stirring and reacted at a temperature of 15~25 DEG C.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810817537.5A CN108754140A (en) | 2018-07-24 | 2018-07-24 | A method of it is produced containing zinc complexes using containing zinc ore crude |
| PCT/CN2019/084003 WO2020019777A1 (en) | 2018-07-24 | 2019-04-24 | Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate |
| CN201980001299.3A CN110896643B (en) | 2018-07-24 | 2019-04-24 | Method for producing zinc-containing compound or zinc oxide from zinc-containing raw ore through intermediate step of calcium zincate synthesis |
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| CN201810817537.5A CN108754140A (en) | 2018-07-24 | 2018-07-24 | A method of it is produced containing zinc complexes using containing zinc ore crude |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020019777A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate |
| WO2020019834A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Mineral processing method for low-grade zinc-containing raw ore |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020019777A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate |
| WO2020019834A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Mineral processing method for low-grade zinc-containing raw ore |
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