CN110127772A - Method for preparing high-purity ammonium ferric chloride from sulfuric acid cinder - Google Patents
Method for preparing high-purity ammonium ferric chloride from sulfuric acid cinder Download PDFInfo
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- CN110127772A CN110127772A CN201910490612.6A CN201910490612A CN110127772A CN 110127772 A CN110127772 A CN 110127772A CN 201910490612 A CN201910490612 A CN 201910490612A CN 110127772 A CN110127772 A CN 110127772A
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- hydrochloric acid
- purity
- pyrite cinder
- flores martiales
- acid solution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a method for preparing high-purity ferric ammonium chloride from sulfuric acid cinder, which comprises the steps of mixing sulfuric acid cinder with TFe content of 30-50% and hydrochloric acid solution with mass concentration of 40-50% in a mass ratio of 1: 15-1: 8, heating, stirring, and filtering to obtain hydrochloric acid solution containing ferric chloride; heating and concentrating the hydrochloric acid solution containing the ferric chloride to obtain a hydrochloric acid concentrated solution containing the ferric chloride, wherein the volume of the concentrated solution is 1/8-1/3 of that of the hydrochloric acid solution containing the ferric chloride before concentration; cooling and crystallizing the hydrochloric acid concentrated solution containing ferric chloride, filtering out crystallized impurities, then adding a certain amount of ammonium chloride into the obtained filtrate, stirring and heating until the ammonium chloride is dissolved, cooling and crystallizing again to obtain ammonium ferric chloride crystals, filtering to obtain high-purity ammonium ferric chloride, and returning the obtained waste liquid for recycling. The crystallization temperature of the two times of cooling is the same and is 2-8 ℃. Solves the problem of environmental hazard after the sulfuric acid cinder is discharged and the problems of reduction and resource utilization.
Description
Technical field
The invention belongs to inorganic chemical industry sulfuric acid industries to discard slag improvement and utility technical field, be related to a kind of being burnt with sulfuric acid
The method that slag prepares high-purity flores martiales.
Background technique
Pyrite cinder is sulfuric acid industry or the waste residue that gold smelting industry generates, and is mainly characterized in that: most pyrite cinder
Middle iron content is higher, and mainly exists in the form of bloodstone；Gangue is based on quartz in pyrite cinder, with valuable metal mine
The coexisting structure of object is complicated.
Recently as the increase of gold mine treating capacity, the discharge amount of pyrite cinder is also increase accordingly, the harm to environment
It is gradually increased, therefore how by pyrite cinder progress secondary recovery utilization, can not only be brought to enterprise and society good
Economic benefit and environmental benefit, and also help environmental protection and improvement of the ecological environment.
More to the research of pyrite cinder progress recycling both at home and abroad, be broadly divided into following six class: pyrite cinder production is built
Build material；Pyrite cinder produces iron series dyestuff；Pyrite cinder prepares molysite；Pyrite cinder is used as wastewater purificant；Pyrite cinder
As iron-smelting raw material；Non-ferrous metal and noble metal are recycled from pyrite cinder.
The patent of invention of Publication No. CN102153152A discloses that a kind of to prepare pyrite cinder with chemical method be chloride
Method, obtained iron chloride, aluminium chloride, magnesium chloride, calcium chloride crystals.The patent of invention of Publication No. CN101817563A is public
A kind of technique that high-purity ferrous sulfate is prepared using pyrite cinder of cloth, has obtained high-purity ferrous sulfate product.Publication No.
The patent of invention of CN107739816A discloses a kind of method that pyrite cinder prepares iron powder, has obtained being suitable for increasing titanium white white
The iron powder of degree.Application No. is 200510030016.8 patents of invention to disclose a kind of method acidizing fired slags of gold ores containing sulfur
The method for preparing iron oxide red has obtained the iron oxide red for meeting pigment demand.Have no the relevant report that flores martiales is prepared with pyrite cinder.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that pyrite cinder prepares high-purity flores martiales, to solve pyrite cinder
Environmentally hazardous problem and the problem of pyrite cinder minimizing, recycling after discharge.
The technical scheme adopted by the invention is that the method that pyrite cinder prepares high-purity flores martiales, the specific steps are as follows:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio；
Step S2, heating stirring；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron, obtains the hydrochloric acid concentrate of chloride containing iron；
Step S5, crystallisation by cooling is carried out to the hydrochloric acid concentrate of chloride containing iron, and filters out the impurity of crystallization；
Step S6, a certain amount of ammonium chloride is added into filtrate obtained by step S5, is heated with stirring to dissolution；
Step S7, crystallisation by cooling is carried out again, obtains flores martiales crystal；
Step S8, high-purity flores martiales is obtained by filtration；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
Further, the TFe content of pyrite cinder is 30~50% in the step S1, and hydrochloric acid solution mass concentration is 40
~50%, the mass ratio of pyrite cinder and hydrochloric acid solution is 1:15~1:8.
Further, whipping temp is 80~95 DEG C in the step S2, and mixing time is 30~50min.
Further, the hydrochloric acid volume of the concentrated liquid of chloride containing iron is that the hydrochloric acid of chloride containing iron before being concentrated is molten in the step S4
The 1/8~1/3 of liquid product.
Further, crystallisation by cooling temperature is identical in the step S5 and step S7, and the crystallisation by cooling temperature is 2~8
℃。
Further, ammonium chloride dosage is the 60~85% of pyrite cinder weight in the step S6.
Further, the filtering is all made of corrosion-resistant vacuum ceramic filter and carries out.
Further, the step S4 heating thickening temperature is 60~80 DEG C.
Further, the step S6 mixing speed is 500~2000r/min.
Further, the flores martiales purity that the step S7 is obtained reaches the pure rank of chemistry.
The invention has the advantages that proposing a kind of new application of pyrite cinder, a kind of preparation of flores martiales is provided
Raw material carries out secondary recovery utilization to pyrite cinder, pyrite cinder waste is prepared into the flores martiales of high added value, and chlorine
Change the purity that iron ammonium meets analysis net product, solves the problems, such as pyrite cinder minimizing, recycling and pyrite cinder row
Put rear environmentally hazardous problem.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is a kind of process flow chart for the method that high-purity flores martiales is prepared with pyrite cinder of the present invention；
Fig. 2 is the XRD diagram of present invention gained flores martiales.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The method that pyrite cinder prepares high-purity flores martiales, includes the following steps:
Step S1, by TFe content is 30~50% pyrite cinders and mass concentration is 40~50% hydrochloric acid solution with 1:
The mass ratio of 15~1:8 mixes；
Pyrite cinder and hydrochloric acid solution mass ratio are smaller, and concentration is just for ore pulp (mixed solution of pyrite cinder and hydrochloric acid solution)
Smaller, the reaction time will be shorter, appropriate to reduce pyrite cinder and hydrochloric acid solution quality if in addition iron content is larger in raw material
Than increasing hydrochloric acid mass concentration, being conducive to the rate of recovery for increasing reaction rate, improving iron.
Step S2, heating stirring, whipping temp are 80~95 DEG C, and mixing time is 30~50min.Temperature is higher, reaction
Rate is faster, can shorten mixing time accordingly, conversely, then needing suitably to increase the reaction time.
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, obtains the hydrochloric acid of chloride containing iron
Concentrate；There is vapor volatilization after heating, solution concentration improves, and concentration is higher, and the crystallization for being more conducive to impurity is precipitated.Chloride containing
The hydrochloric acid volume of the concentrated liquid of iron is 1/8~1/3 of original solution before being concentrated, i.e. the hydrochloric acid volume of the concentrated liquid of chloride containing iron is chloride containing
The 1/8~1/3 of the hydrochloric acid solution volume of iron.Concentrate is denseer, i.e. the hydrochloric acid volume of the concentrated liquid of chloride containing iron is smaller, is more conducive to
Crystallization removal of impurities, but concentrate overrich are not only unfavorable for crystallization removal of impurities, but also will increase energy consumption cost.
Step S5, crystallisation by cooling is carried out to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, filters out impurity；
Step S6, a certain amount of ammonium chloride is added, dissolution is heated with stirring to；
Ammonium chloride dosage is the 60~85% of pyrite cinder weight, and not only iron chloride consumes ammonium chloride, other objects in solution
Matter if there is no impurity, then can be calculated, but in solution there is also ammonium chloride is consumed with chemical equation
Often there is impurity, type, the quantity of impurity all have certain variation, therefore the amount of different consumption of raw materials ammonium chloride also will
It is fluctuated, need to be judged by detailed test.Iron content is higher in raw material, in order to guarantee that ferro element sufficiently carries out chemistry
Reaction, ammonium chloride dosage also can be higher, to improve the rate of recovery of iron.
Step S7, crystallisation by cooling is carried out again with the crystallisation by cooling temperature of step S4, obtains flores martiales crystal；
Step S8, high-purity flores martiales is obtained by filtration；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
Crystallisation by cooling temperature is 2~8 DEG C in step S5, S7.Cooling temperature is lower, and crystalline rate is faster, reduces cold
But temperature is conducive to improve production efficiency, but production cost can also be increase accordingly.Temperature is lower, the solubility of flores martiales
Lower, easier crystallization is precipitated, but temperature is too low, and production cost will increase, therefore also need under the premise of guaranteeing crystalline rate
Production cost is reduced as far as possible.
Filtering is to obtain the hydrochloric acid solution of chloride containing iron to filter out insoluble substance to the present invention for the first time；Second
Filtering is to improve final products purity to filter the impurity for being easy crystallization；Third time filtering is that flores martiales is solid in order to obtain
Body.Therefore it needs to filter three times, be filtered together if merged, it will seriously affect product quality.Cooling is because of high before crystallizing
The solubility of the lower flores martiales of temperature is higher, and percent crystallization in massecuite can be reduced by not cooling in advance, reduce the rate of recovery of Fe, reduce iron chloride
The purity of ammonium.The present invention is filtered work using corrosion-resistant vacuum ceramic filter.
The present invention integrates the professional techniques such as chemical industry, environmental protection, mining industry, material, has stronger comprehensive.Of the invention
Difficult point is: 1. the hydrochloric acid solution of chloride containing iron being concentrated, the crystallization that concentrated solution is conducive to impurity is precipitated, if dense after concentration
Degree control is improper, then impurity crystallization not exclusively, influences final products purity；2. the crystallization temperature control of flores martiales solution of the present invention
System first carries out crystallisation by cooling at 2~8 DEG C to the hydrochloric acid concentrate of chloride containing iron and impurity is precipitated at 2~8 DEG C, with step S7
In the same range, freezing and crystallizing can guarantee that impurity is sufficiently precipitated for control, can ensure product purity and accelerate knot
Brilliant rate；3. the dosage of ammonium chloride determines complex, it is necessary first to the chemical component of pyrite cinder is analyzed, it is rough true
The amount ranges for determining ammonium chloride, since the ingredient of pyrite cinder is different, impurity component is also different, if the dosage of flores martiales is not
When being then difficult to prepare the flores martiales product of purity assay.The hydrochloric acid volume of the concentrated liquid that the present invention controls chloride containing iron is dense
1/8~1/3 before contracting, and crystallisation by cooling gettering, and cooling temperature and later period are carried out before ammonium chloride is added and prepares flores martiales
Crystallisation by cooling obtain flores martiales temperature it is identical, guarantee the crystallization gained purity of the flores martiales and rate of recovery of Fe.This hair
Bright high purity product reaches the pure rank of chemistry, wherein level-one is excellent pure grade, and second level is that analysis is pure, and three-level is that chemistry is pure.
Embodiment 1
Pyrite cinder sample comes from Henan solution of gold smelting plant, carries out constituent analysis to sample, analysis the results are shown in Table 1, sample
Essential element is Fe and Si in product, and TFe content is 37.88%, SiO2Content is 32.61%.
1 sample composition of table analyzes result
| Element category | TFe | SiO2 | Al2O3 | CaO | S | Na2O | It is other |
| Content/% | 37.88 | 32.61 | 3.97 | 2.04 | 1.68 | 1.85 | 19.97 |
Using the pyrite cinder sample preparation flores martiales, process flow chart such as Fig. 1 includes the following steps:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with the mass ratio of 1:15, hydrochloric acid mass concentration is 40%；
Step S2, heating stirring, whipping temp are 80 DEG C, mixing time 50min；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, heating temperature is 60 DEG C, is obtained
The hydrochloric acid concentrate of chloride containing iron, the hydrochloric acid volume of the concentrated liquid of chloride containing iron are the hydrochloric acid solution volume of chloride containing iron before being concentrated
1/8；
Step S5, crystallisation by cooling is carried out at 8 DEG C to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, with corrosion-resistant true
Empty ceramic filter filters out impurity；
Step S6, it is added in an amount of 85% ammonium chloride of pyrite cinder weight, is heated with stirring to dissolution, mixing speed is
500r/min；
Step S7, crystallisation by cooling goes out flores martiales crystal at 8 DEG C；
Step S8, high-purity flores martiales is obtained by filtration with corrosion-resistant vacuum ceramic filter；Through corrosion-resistant vacuum ceramic mistake
Filter filtering, filter cake (flores martiales) is on filter disc surface, and hanging collection by scraper plate can be obtained flores martiales, and liquid then enters
In disc interiors hole, waste liquid can be obtained after collection；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
TFe content is 19.45% in the obtained flores martiales of the present embodiment, the theoretical content of iron in flores martiales
19.48% to get purity was 99.85% (meet analysis net product purity), and the Fe rate of recovery is 90.38%.
Embodiment 2
Pyrite cinder sample in embodiment 1 is carried out to prepare flores martiales, process flow chart such as Fig. 1, including is walked as follows
It is rapid:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio, the two mass ratio is 1:8, hydrochloric acid matter
Measuring concentration is 50%；
Step S2, heating stirring, whipping temp are 95 DEG C, mixing time 30min；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, heating temperature is 60 DEG C, is obtained
The hydrochloric acid concentrate of chloride containing iron, the volume of the concentrated liquid are the 1/3 of original solution volume；
Step S5, crystallisation by cooling is carried out at 8 DEG C to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, with corrosion-resistant true
Empty ceramic filter filters out impurity；
Step S6, it is added in an amount of 60% ammonium chloride of pyrite cinder weight, is heated with stirring to dissolution, mixing speed is
500r/min；
Step S7, crystallisation by cooling goes out flores martiales crystal at 8 DEG C；
Step S8, high-purity flores martiales product is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
TFe content is 19.39% in the obtained flores martiales product of the present embodiment, i.e., purity is 99.54% (meeting
Learn net product purity), the Fe rate of recovery is 86.47%.
Embodiment 3
Pyrite cinder sample in embodiment 1 is carried out to prepare flores martiales, process flow chart such as Fig. 1, including is walked as follows
It is rapid:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio, the two mass ratio is 1:10, hydrochloric acid matter
Measuring concentration is 45%；
Step S2, heating stirring, whipping temp are 90 DEG C, mixing time 40min；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, heating temperature is 70 DEG C, is obtained
The hydrochloric acid concentrate of chloride containing iron, the volume of the concentrated liquid are the 1/5 of original solution volume；
Step S5, crystallisation by cooling is carried out at 5 DEG C to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, with corrosion-resistant true
Empty ceramic filter filters out impurity；
Step S6, it is added in an amount of 60% ammonium chloride of pyrite cinder weight, is heated with stirring to dissolution, mixing speed is
1000r/min；
Step S7, crystallisation by cooling goes out flores martiales crystal at 5 DEG C；
Step S8, high-purity flores martiales product is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
TFe content is 19.45% in the obtained flores martiales product of the present embodiment, i.e., purity is 99.85% (to meet point
Analyse net product purity), the Fe rate of recovery is 92.41%.
Embodiment 4
Pyrite cinder sample in embodiment 1 is carried out to prepare flores martiales, process flow chart such as Fig. 1, including is walked as follows
It is rapid:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio, the two mass ratio is 1:10, hydrochloric acid matter
Measuring concentration is 50%；
Step S2, heating stirring, whipping temp are 95 DEG C, mixing time 30min；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, heating temperature is 70 DEG C, is obtained
The hydrochloric acid concentrate of chloride containing iron, the volume of the concentrated liquid are the 1/5 of original solution volume；
Step S5, crystallisation by cooling is carried out at 5 DEG C to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, with corrosion-resistant true
Empty ceramic filter filters out impurity；
Step S6, it is added in an amount of 60% ammonium chloride of pyrite cinder weight, is heated with stirring to dissolution, mixing speed is
1500r/min；
Step S7, crystallisation by cooling goes out flores martiales crystal at 5 DEG C；
Step S8, high-purity flores martiales product is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
TFe content is 19.44% in the obtained flores martiales product of the present embodiment, i.e., purity is 99.79% (to meet point
Analyse net product purity), the Fe rate of recovery is 92.28%.
Embodiment 5
Pyrite cinder sample in embodiment 1 is carried out to prepare flores martiales, process flow chart such as Fig. 1, including is walked as follows
It is rapid:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio, the two mass ratio is 1:10, hydrochloric acid matter
Measuring concentration is 50%；
Step S2, heating stirring, whipping temp are 95 DEG C, mixing time 30min；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, heating temperature is 80 DEG C, is obtained
The hydrochloric acid concentrate of chloride containing iron, the volume of the concentrated liquid are the 1/5 of original solution volume；
Step S5, crystallisation by cooling is carried out at 5 DEG C to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, with corrosion-resistant true
Empty ceramic filter filters out impurity；
Step S6, it is added in an amount of 70% ammonium chloride of pyrite cinder weight, is heated with stirring to dissolution, mixing speed is
2000r/min；
Step S7, crystallisation by cooling goes out flores martiales crystal at 5 DEG C；
Step S8, high-purity flores martiales product is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
TFe content is 19.44% in the obtained flores martiales product of the present embodiment, i.e., purity is 99.79% (to meet point
Analyse net product purity), the Fe rate of recovery is 93.21%.
Embodiment 6
Pyrite cinder sample in embodiment 1 is carried out to prepare flores martiales, process flow chart such as Fig. 1, including is walked as follows
It is rapid:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio, the two mass ratio is 1:10, hydrochloric acid matter
Measuring concentration is 45%；
Step S2, heating stirring, whipping temp are 85 DEG C, mixing time 30min；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, heating temperature is 80 DEG C, is obtained
The hydrochloric acid concentrate of chloride containing iron, the volume of the concentrated liquid are the 1/5 of original solution volume；
Step S5, crystallisation by cooling is carried out at 2 DEG C to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, with corrosion-resistant true
Empty ceramic filter filters out impurity；
Step S6, it is added in an amount of 60% ammonium chloride of pyrite cinder weight, is heated with stirring to dissolution, mixing speed is
2000r/min；
Step S7, crystallisation by cooling goes out flores martiales crystal at 2 DEG C；
Step S8, high-purity flores martiales product is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
TFe content is 19.39% in the obtained flores martiales product of the present embodiment, i.e., purity is 99.54% (meeting
Learn net product purity), the Fe rate of recovery is 90.12%.
Embodiment 7
Pyrite cinder sample comes from Henan solution of gold smelting plant, carries out constituent analysis to sample, analysis the results are shown in Table 2, sample
Essential element is Fe and Si in product, and TFe content is 30.00%, SiO2Content is 37.54%.
2 sample composition of table analyzes result
| Element category | TFe | SiO2 | Al2O3 | CaO | S | Na2O | It is other |
| Content/% | 30.00 | 37.54 | 5.86 | 1.54 | 3.87 | 0.56 | 20.63 |
Using the pyrite cinder sample preparation flores martiales, process flow chart such as Fig. 1 includes the following steps:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio, the two mass ratio is 1:10, hydrochloric acid matter
Measuring concentration is 50%；
Step S2, heating stirring, whipping temp are 95 DEG C, mixing time 30min；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, heating temperature is 80 DEG C, is obtained
The hydrochloric acid concentrate of chloride containing iron, the volume of the concentrated liquid are the 1/5 of original solution volume；
Step S5, crystallisation by cooling is carried out at 5 DEG C to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, with corrosion-resistant true
Empty ceramic filter filters out impurity；
Step S6, it is added in an amount of 70% ammonium chloride of pyrite cinder weight, is heated with stirring to dissolution, mixing speed is
2000r/min；
Step S7, crystallisation by cooling goes out flores martiales crystal at 5 DEG C；
Step S8, high-purity flores martiales product is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
TFe content is 19.43% in the obtained flores martiales product of the present embodiment, i.e., purity is 99.74% (to meet point
Analyse net product purity), the Fe rate of recovery is 95.54%.
Embodiment 8
Pyrite cinder sample comes from Henan solution of gold smelting plant, carries out constituent analysis to sample, analysis the results are shown in Table 3, sample
Essential element is Fe and Si in product, and TFe content is 50.00%, SiO2Content is 18.23%.
3 sample composition of table analyzes result
| Element category | TFe | SiO2 | Al2O3 | CaO | S | Na2O | It is other |
| Content/% | 50.00 | 18.23 | 2.56 | 0.89 | 1.35 | 1.02 | 25.95 |
Using the pyrite cinder sample preparation flores martiales, process flow chart such as Fig. 1 includes the following steps:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio, the two mass ratio is 1:10, hydrochloric acid matter
Measuring concentration is 50%；
Step S2, heating stirring, whipping temp are 95 DEG C, mixing time 30min；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron obtained by step S3, heating temperature is 80 DEG C, is obtained
The hydrochloric acid concentrate of chloride containing iron, the volume of the concentrated liquid are the 1/5 of original solution volume；
Step S5, crystallisation by cooling is carried out at 5 DEG C to the hydrochloric acid concentrate of chloride containing iron obtained by step S4, with corrosion-resistant true
Empty ceramic filter filters out impurity；
Step S6, it is added in an amount of 70% ammonium chloride of pyrite cinder weight, is heated with stirring to dissolution, mixing speed is
2000r/min；
Step S7, crystallisation by cooling goes out flores martiales crystal at 5 DEG C；
Step S8, high-purity flores martiales product is obtained by filtration with corrosion-resistant vacuum ceramic filter；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
TFe content is 19.46% in the obtained flores martiales product of the present embodiment, i.e., purity is 99.90% (to meet point
Analyse net product purity), the Fe rate of recovery is 86.46%.
TFe content is higher than embodiment 5 in embodiment 8, therefore under identical extract technology parameter, especially hydrochloric acid content phase
Than embodiment 5 is more abundant, therefore the iron reaction in embodiment 5 is more abundant, and the rate of recovery of iron is higher in embodiment 5；In addition, by
TFe content is higher than embodiment 5 in embodiment 8, therefore embodiment 8 leaches the mole of iron chloride in concentrated liquor higher than implementation
Example 5, when the ammonium chloride for adding same dosage, then embodiment 8 leaches iron chloride in concentrated liquor and cannot react completely, therefore unfavorable
In the iron recovery for improving embodiment 8, but since ammonium chloride is not excessive, ammonium chloride will not crystallize precipitation, so
8 ammonia chloride crystal of embodiment is smaller to the impurities affect of flores martiales, and the purity of flores martiales can be relatively higher in embodiment 8.
Compared with Example 4, ammonium chloride additional amount is promoted embodiment 5, but the two purity is identical, the rate of recovery of embodiment 5
But it is higher than embodiment 4, this is because in certain trial stretch, although increasing the dosage of ammonium chloride to improving flores martiales purity not
Benefit, but while increase ammonium chloride, the production quantity of flores martiales is also increased, therefore increases ammonium chloride dosage by a small margin,
Purity can't be reduced, increases the rate of recovery of iron instead, i.e., increased ammonium chloride has both participated in reaction, had no remaining chlorination
Ammonium influences the purity of flores martiales in later crystallization.
Compared with Example 3, concentration of hydrochloric acid is promoted embodiment 4, and heating stirring temperature is also promoted, if in phase
In the same reaction time, the leaching rate of embodiment 4 should be higher than that in embodiment 3 and embodiment 4 iron is reacted with hydrochloric acid and more fill
Point, but in fact, the heating stirring time of embodiment 4 be less than in embodiment 3, therefore in embodiment 4 iron and hydrochloric acid
It is fixed more abundant compared with embodiment 3 that reactions vary.
Embodiment 1 and embodiment 3 are in the processing to same pyrite cinder, concentration of hydrochloric acid and ammonium chloride additional amount, cooling
Crystallization temperature is different, but its purity is identical, and the rate of recovery is different, and embodiment 1 and embodiment 3 compare, and liquid-solid ratio is different, hydrochloric acid is dense
Degree is different, the time is different, temperature is different, the concentration after concentration is different, and the additive amount of ammonium chloride is also different, the influence of multiple factors
Leading to the rate of recovery, there are deviations, identical as purity, some factors to improve purity it is advantageous, some conditions to improve purity not
Benefit, but be not absolute, whole experiment process, purity fluctuation range is smaller, and the variation of multiple factors causes purity to occur one
It causes.It should be noted that the liquid-solid ratio the big more is conducive to improve the rate of recovery, but the concentration after concentration is not necessarily suitable；Hydrochloric acid is dense
It spends leaching that is more high more being conducive to iron and improves the rate of recovery, but excessive concentration is then unfavorable；Extend mixing time and is conducive to filling for iron
Sub-dip goes out, and improves the rate of recovery, but will increase leaching cost；The temperature the high more is conducive to the leaching of iron, and same condition, temperature is got over
The rate of recovery of height, iron is higher, but when the rate of recovery reaches capacity, then the result that can be not necessarily predicted；It is molten after concentration
The concentration of iron chloride is higher in liquid, more advantageous to crystallizing, but excessive concentration is then unfavorable to the rate of recovery of purity and iron；Chlorination
The additive amount of ammonium is excessive very few unfavorable, and excessively then purity will receive influence, and the rate of recovery of too low then iron is undesirable.
Embodiment 5 is presently preferred embodiments of the present invention, and the XRD spectrum of gained flores martiales is as shown in Fig. 2, its spectral line list
One, it is the characteristic peak of flores martiales, can illustrates that flores martiales purity obtained by the present invention is higher.Product quality can reached
Under the premise of it is required that, the rate of recovery is more desirable, it also requires the problem of considering cost, then in Examples 1 to 6, purity is equal
It is able to satisfy the pure rank of chemistry (99.5 or more purity are pure for chemistry), therefore the higher embodiment 5 of the rate of recovery is preferably, for embodiment
7, it is caused by excessive acid degree is larger that the rate of recovery is higher, and 8 rate of recovery of embodiment is lower, is caused by acid amount is insufficient, if
Embodiment 8 puts on liquid-solid ratio, can also equally obtain the higher rate of recovery.Solid-to-liquid ratio is smaller in trial stretch, hydrochloric acid is dense
Degree is bigger, whipping temp is higher, the mixing time the long more is conducive to the leaching of iron, is also more conducive to the recycling for improving ferro element
Rate；Concentrate is denseer, is more conducive to the crystallization of flores martiales, is also more conducive to the rate of recovery of iron, but it is dense to increase concentrate
Degree also has the risk for increasing impurity；Temperature when crystalline impurities is lower, and impurity crystallization is more abundant, is more conducive to improve chlorination
Iron ammonium purity；Ammonium chloride dosage is inadequate, then it reacts insufficient with iron chloride, and the rate of recovery of iron can be relatively low, conversely, flores martiales
Dosage is excessive, then when final flores martiales crystallizes, has ammonia chloride crystal precipitation, influence product purity；When flores martiales crystallizes,
Temperature is lower, and the solubility of flores martiales is lower, and easier crystallization is precipitated, and is more conducive to the recycling of iron.
The present invention, which prepares gained flores martiales, can be used as the catalyst of organic synthesis, and for taking a picture, making a plate and print and dye
Industry etc..
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention
It is interior.
Claims (10)
1. the method that pyrite cinder prepares high-purity flores martiales, which is characterized in that specific step is as follows:
Step S1, pyrite cinder is mixed with hydrochloric acid solution with certain mass ratio；
Step S2, heating stirring；
Step S3, the hydrochloric acid solution of chloride containing iron is obtained by filtration；
Step S4, heating concentration is carried out to the hydrochloric acid solution of chloride containing iron, obtains the hydrochloric acid concentrate of chloride containing iron；
Step S5, crystallisation by cooling is carried out to the hydrochloric acid concentrate of chloride containing iron, and filters out the impurity of crystallization；
Step S6, a certain amount of ammonium chloride is added into filtrate obtained by step S5, is heated with stirring to dissolution；
Step S7, crystallisation by cooling is carried out again, obtains flores martiales crystal；
Step S8, high-purity flores martiales is obtained by filtration；
Step S9, waste liquid obtained by step S8 is back to step S1, is recycled.
2. the method that pyrite cinder according to claim 1 prepares high-purity flores martiales, which is characterized in that the step S1
The TFe content of middle pyrite cinder is 30~50%, and hydrochloric acid solution mass concentration is 40~50%, pyrite cinder and hydrochloric acid solution
Mass ratio is 1:15~1:8.
3. the method that pyrite cinder according to claim 1 or 2 prepares high-purity flores martiales, which is characterized in that the step
Whipping temp is 80~95 DEG C in rapid S2, and mixing time is 30~50min.
4. the method that pyrite cinder according to claim 3 prepares high-purity flores martiales, which is characterized in that the step S4
The hydrochloric acid volume of the concentrated liquid of middle chloride containing iron is 1/8~1/3 of the hydrochloric acid solution volume of chloride containing iron before being concentrated.
5. the method that pyrite cinder according to claim 1,2 or 4 prepares high-purity flores martiales, which is characterized in that described
Crystallisation by cooling temperature is identical in step S5 and step S7, and the crystallisation by cooling temperature is 2~8 DEG C.
6. the method that pyrite cinder according to claim 5 prepares high-purity flores martiales, which is characterized in that the step S6
Middle ammonium chloride dosage is the 60~85% of pyrite cinder weight.
7. the method that pyrite cinder according to claim 5 prepares high-purity flores martiales, which is characterized in that the filtering is equal
It is carried out using corrosion-resistant vacuum ceramic filter.
8. the according to claim 1, method that pyrite cinder described in 2,4,6 or 7 prepares high-purity flores martiales, which is characterized in that
The step S4 heating thickening temperature is 60~80 DEG C.
9. the according to claim 1, method that pyrite cinder described in 2,4,6 or 7 prepares high-purity flores martiales, which is characterized in that
The step S6 mixing speed is 500~2000r/min.
10. the according to claim 1, method that pyrite cinder described in 2,4,6 or 7 prepares high-purity flores martiales, which is characterized in that
The flores martiales purity that the step S7 is obtained reaches the pure rank of chemistry.
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Application publication date: 20190816 |