CN110396610A - A kind of method of the processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral - Google Patents
A kind of method of the processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral Download PDFInfo
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- CN110396610A CN110396610A CN201910689165.7A CN201910689165A CN110396610A CN 110396610 A CN110396610 A CN 110396610A CN 201910689165 A CN201910689165 A CN 201910689165A CN 110396610 A CN110396610 A CN 110396610A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
- C01F7/26—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with sulfuric acids or sulfates
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
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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
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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
The invention discloses a kind of methods of ammonium salt pressurized pyrolysis processing titanium mineral and metal silicate.The present invention is will uniformly to mix by a certain percentage after titanium mineral and metal silicate pretreatment with ammonium salt, the low temperature pyrogenation in autoclave, the closed roasting when sampling gas pH in acidity, it can efficient valuable metal in salinization mineral using confined condition ammonium salt, valuable element of the release in lattice, fired slags acidleach in diluted acid, the pickle liquor of obtained high-concentration titanic magnalium；Titanium magnalium fractional hydrolysis in pickle liquor carries out step recycling, obtains high purity product；Ammonium hydroxide reuse simultaneously, through evaporative crystallization, it can be achieved that ammonium salt recycles.The method achieve the step recycling of titanium magnalium in titanium mineral and metal silicate, ammonium salt is recycled, and has achieved the purpose that waste resource recovery recycles.
Description
Technical field
The invention belongs to Industrial Solid Waste resource utilization field, be related to it is a kind of using ammonium salt pressurized pyrolysis processing titanium mineral and
The method of metal silicate mineral extraction titanium magnalium.
Background technique
Titanium reserves very abundant on earth, crustal abundance 0.61%, content is all than common copper, nickel, tin, lead, zinc
Want high, it is known that mineral there are about more than 140 kinds, but be essentially all paragenous mineral, the form of being primarily present has ilmenite, titanomagnetite
With red arizonite.Chinese Panxi Diqu vanadium titano-magnetite is world's oversized mineral deposit of more metal symbiosis, reserves up to 96.6 hundred million t,
Wherein titanium (TiO2) 8.73 hundred million t (the 90.5% of Zhan Quanguo, the 35.17% of the world), compact structure, gangue content is high, crystallization
Granularity substantially at 10 μm or so, mutually separate therein containing titanium ore by the beneficiation method for being difficult to adopt pure physics.Vanadium titanium at present
There is 53% or so titanium to enter blast furnace process link in a manner of iron ore concentrate in magnetic iron ore, ultimately forms titanium-containing blast furnace slag.For many years,
Major part is directly stored up or as production cement ingredient, not only serious waste of resources, occupies a large amount of soil, and pollute ring
Border.And metal silicate mineral are a kind of oxysalt mineral being bound up by metal cation and silicate, are to constitute ground
The essential mineral of shell, outer mantle, magnesium, aluminium content are very high in many silicate minerals, such as kaolinite, montmorillonite, zeolite are weights
The nonmetallic ore raw material and material wanted, the more preservations of valuable metal in metal silicate mineral are in gangue mineral, granularity pole
Carefully, it is difficult to separate.
Currently, to sulfuric acid direct leaching main in the technical study of titanium mineral, Asia/molten-salt growth method and having pyrocarbon nitrogen
Change-low temperature chlorination method.Sulfuric acid direct leaching requires sulfuric acid concentration high, larger to equipment corrosion, while a large amount of pickle liquors and acid
Leaching residue will cause secondary pollution；Asia/molten-salt growth method is not aqueous less than 50% or in fused salt area system in sub-molten salt area water content
The method that titanium-containing blast furnace slag is decomposed in system, but usually frit reaction object viscosity is larger, while the raw material sulphuric acid oxygen titanium hydrolyzed
The preparation of solution is influenced very big by fused salt reaction and washing.High temperature selective reduction carbon nitridation-low temperature chlorination method 1500 DEG C with
Upper high-temperature process, energy consumption is huge, and the raw materials such as nitrogen, charcoal and chlorine used are both needed to contact with entire clinker, and utilization rate is low, cost compared with
It is high.Floatation or alkaline leaching are mostly used for metal silicate mineral, but inevitably there is gold in mineral floating system
Belong to ion, the metal ion in solution is other than having activation or inhibition effect to silicate mineral, sometimes also because changing mineral
Surface electrical behavior and the dispersion behavior for influencing mineral grain, cause flotation extremely unstable；And alkali solution technique higher cost and product impurity
Element is more.
Patent document " a method of directly titanium alloy is produced from titaniferous ore " (CN1888101A), it discloses a kind of straight
The method for preparing titanium alloy using titaniferous ore is connect, using titaniferous ore as raw material, reducing agent is added and carries out arc melting except iron
High titanium slag is made, above-mentioned high titanium slag is powered on to solution aluminium reducing titanium oxide in plasma high-temperature furnace, obtains titanium-aluminium alloy mother liquor,
Then it is incorporated 1~10% calcirm-fluoride and deoxidier, is melted in vacuum electric furnace, the titanium aluminium that oxygen content is 0.05~0.15% can be obtained
Alloy.Although the invention realizes metal smelting and alloying in metallothermic reduction, process cycle, entire technique are shortened
When being carried out in electric furnace, higher cost, while removing impurity element using the method for electroslag remelting, under powerful electric current, electricity
Pole consumption is serious.
Patent document " method for preparing titanium dioxide using high-titanium blast furnace slag " (CN108975393A), discloses one kind
Through high temperature cabonization break process, carbide slag is obtained；Carbide slag and chlorine are reacted through low temperature chlorination, must contain TiCl4The chlorine of gas
Change reaction mixture, condensed thick TiCl4；Using fatty acid to thick TiCl4Handle except vanadium, rectifying obtains rectifying TiCl4,
Rectifying TiCl4With O2Oxidation reaction is carried out, is obtained containing TiO2And Cl2Oxidation reaction mix products, cold filtration obtains titanium
White powder product.Although the invention sufficiently recycles the titanium in high-titanium blast furnace slag, high temperature cabonization temperature is up to 1580~
1700 DEG C, the high requirements on the equipment, process is complicated, while needing fatty-acid flo(a)tation except vanadium processing, and industrial application possibility is smaller.
Patent document " a kind of method of silicate navajoite asynchronous conversion recycling vanadium and silicon " (CN105331816A) discloses
A kind of silicate soaks the method to recycle silicon and vanadium through two sections of alkali of low concentration and high concentration, is suitable for the various silicon such as bone coal, clay
Hydrochlorate mineral.This method is mainly finely ground to -200 mesh to silicate mineral and accounts for 80% or more, then high through low-concentration alkali liquor high temperature
Pressure leaches, filtering, collects the waterglass that filtrate prepares modulus >=2；Filter residue obtains high-grade concentrate through high-temperature alkali leaching-low-temperature alkaline leaching
Powder, in the retrieval of sulfuric acid vanadium by adding 25-40%.Although the invention soaks silicate mineral using two sections of alkali of high-concentration and low-concentration, improve
Comprehensive resource utilization rate, but final vanadium product impurity element is more, grade is lower, only can be used as preliminary concentration, while acid
Alkali consumption is big, higher cost.
In conclusion present titaniferous ore and metal silicate mineral treatment processes are since structure is complicated, valuable metal
Attendant phenomenon is serious, and generally existing product purity is low, cannot achieve clean manufacturing, the disadvantages of processing cost is high, not yet looks for so far
It is reasonable to a kind of technology, the economically viable method using titanium-containing blast furnace slag.
Summary of the invention
Titanium magnalium leaching in titanium mineral and metal silicate mineral is extracted the technical problem to be solved by the present invention is how to overcome
The low problem of purity that takes rate low and products thereof, provides the side of a kind of processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral
Method.
The method that the present invention proposes a kind of processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral, high efficiente callback
Titanium, magnesium, aluminium valuable metal effectively will solve the problems, such as that product purity is low, obtain high-valued product, and realize ammonium salt circulation benefit
With for the efficient using having highly important theoretical and realistic meaning of titaniferous ore and metal silicate.
The method of a kind of processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral provided by the invention, including it is following
Step:
Step 1: drying and breaing up titanium mineral and metal silicate mineral, powder material is obtained；
Step 2: the powder material that step 1 is obtained and ammonium salt mix, 250~450 DEG C of roastings 0.5 in calciner
~2h, calciner sample tap are open in the initial stage, collect the ammonia of generation, and are passed through water and form ammonium hydroxide, when sampling implication
Closed pressurized pyrolysis when body pH is in acidity；
Step 3: being filtered after dilute acid soln acidleach is added in the fired slags that step 2 is pyrolyzed；
Step 4: the filtered fluid that step 3 is obtained keeps the temperature 0.5~1h under fluidized state, water is added and is diluted, then
0.5~2h is kept the temperature under fluidized state, is then recrystallized, canescence hydrolysate occurs, filtrate and filter residue is collected by filtration, it will
It is calcined after the removal of impurities of filter residue dilute acid wash, obtains titanium dioxide.
Method according to the present invention, wherein being used as a kind of selection, the method can also include:
Step 5: there is hydrolysate, mistake to pH=5~6 in the ammonium hydroxide that the filtrate added drop-wise step 2 that step 4 is obtained is formed
Filtrate and filter residue are collected in filter, after filter residue is washed with water removal of impurities and is calcined, obtain alumina product；
Step 6: there is hydrolysate, filters to pH >=12 in the ammonium hydroxide that the filtrate added drop-wise step 2 that step 5 is obtained is formed
Filtrate and filter residue are collected, is calcined after removal of impurities is washed with water in filter residue, obtains magnesium oxide product；
Step 7: the filtrate obtained to step 6 is added in the ammonium hydroxide that step 2 is formed, evaporative crystallization obtains ammonium salt crystalline substance
Body.
Method according to the present invention, wherein it is used as a kind of selection, after step 5 cleans residue washing 4~8 times, in
1000~1300 DEG C of 1~5h of calcining；
Step 6 cleans residue washing 3~6 times, in 400~800 DEG C of 2~4h of calcining.
Method according to the present invention, wherein being used as a kind of selection, step 1 is by titanium mineral and metal silicate mineral
It is milled to -0.074mm >=75%, dries and breaks up at 50~110 DEG C, obtains moisture≤2wt% grey powder material.
Any method according to the present invention, wherein being used as a kind of selection, control sample tap valve is opened in step 2
Closing judgment criteria is that sampling gas pH≤7 are detected by pH meter, realizes the abundant salinization of valuable elements in minerals, is generated soluble
Salt.Calciner described in step 2 can be the arbitrary high pressure calciner in this field, including but not limited to autoclave etc..
Any method according to the present invention, wherein being used as a kind of selection, powder material and ammonium salt are pressed 1 by step 2:
0.5~1:5 ratio mixes, wherein the ammonium salt is ammonium sulfate and/or ammonium chloride.
Any method according to the present invention, wherein being used as a kind of selection, fired slags are pressed liquid-solid ratio 10:1 by step 3
The H that mass fraction is 2%~30% is added in~2:12SO4Or HCl solution, under 40~90 DEG C, 100~400rpm mixing speed
0.5~4h of acidleach.
Any method according to the present invention, wherein being used as a kind of selection, it is 0.4~2 that filtered fluid, which is added, in step 4
The water of times volume fraction is diluted.
Any method according to the present invention, wherein be used as a kind of selection, step 4 by filter residue concentration be 1%~
5% dilute sulfuric acid or dilute hydrochloric acid washing impurity-removing 6~10 times calcine in 850~1000 DEG C, obtain titanium dioxide.
Titanium mineral and metal silicate mineral of the present invention are mainly perovskite, anosovite, diopside, grossularite and magnalium
Spinelle converts water-soluble sulfate/chlorination for the valuable element of indissoluble by ammonium salt in pressurized pyrolysis under confined conditions
Salt achievees the purpose that efficiently to leach valuable element.
In order to more easily recycle ammonium salt crystalline product, as a preference, when ammonium sulfate is added in ammonium salt roasting,
Preferentially using vitriol lixiviation and washing；When ammonium chloride is added in ammonium salt roasting, preferentially using hydrochloric acid acidleach and washing.
Ammonium sulfate and/or ammonium chloride thermal decomposition generate SO in the present invention2、SO3Or HCl gas, it can be by adjusting sample tap valve
Door realizes the abundant salinization of mineral valuable metal, while decomposing the NH of generation3It returns and participates in reactant salt, evaporative crystallization realizes ammonium salt
It is recycled, save the cost, to more environment-friendly.
The advantageous effects of the above technical solutions of the present invention are as follows:
(1) by the opening and closing of control sample tap valve, by SO2、SO3Or HCl gas gas is all closed in reaction kettle,
It is set sufficiently with titanium magnalium valuable metal salinization, to generate soluble sulphate/chlorate, titanium magnalium leaching rate is greatly mentioned
Height effectively increases resource utilization；
(2) present invention carries out the recycling of titanium magnalium step to titanium mineral and metal silicate mineral, soaks through ammonium salt roasting-diluted acid
After out, titanium leaching rate >=90%, aluminium leaching rate >=80%, magnesium leaching rate >=95% pass through NH3Reuse adjusts pH value, and step returns
Titanium, aluminium, the high-valued product of magnesium are received, economic benefit is obvious；
(3) present invention only needs the H of low concentration2SO4/ HCl can leach titanium magnalium in product of roasting, effectively reduce sour consumption；
(4) present invention collects ammonia by control sample tap valve, is added to final filtrate, evaporative crystallization, generates ammonium salt
Crystal realizes that it is recycled, and reduces cost, environmentally protective.
Detailed description of the invention
Fig. 1 is the method and process process that a kind of ammonium salt pressurized pyrolysis of the invention handles titanium mineral and metal silicate mineral
Schematic diagram.
Specific embodiment
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool
Body embodiment is explained.
As a kind of preferred implementation method of the invention, ammonium salt pressurized pyrolysis processing titanium mineral of the invention and metal metasilicate
The method of salt mineral, comprising the following steps:
Step 1: titanium mineral and metal silicate mineral are milled to -0.074mm >=75%, dried at 50~110 DEG C
And break up, obtain moisture≤2wt% grey powder material；
Step 2: the powder material that step 1 is obtained and ammonium salt (ammonium sulfate and/or ammonium chloride) are by 1:0.5~1:5 ratio
Example mixes, 250~450 DEG C of 0.5~2h of roasting in autoclave, and sample tap is open in the initial stage, collects the ammonia of generation, leads to
Enter distilled water and forms ammonium hydroxide, the closed pressurized pyrolysis when sampling gas pH in acidity；
Step 3: the fired slags that step 2 is obtained are by liquid-solid ratio 10:1~2:1, it is 2%~30% that mass fraction, which is added,
H2SO4Or HCl solution, under 40~90 DEG C, 100~400rpm mixing speed, 0.5~4h of acidleach is filtered, titanium in filtered fluid
Leaching rate >=96%, aluminium leaching rate >=92%, magnesium leaching rate >=97%；
Step 4: the filtered fluid that step 3 is obtained keeps the temperature 0.5~1h under fluidized state, 0.4~2 times of distillation is added
Water is diluted, and 0.5~2h is kept the temperature under fluidized state, is recrystallized, canescence hydrolysate is occurred, filtrate is collected by filtration
And filter residue, it is 1%~5% dilute sulfuric acid or dilute hydrochloric acid washing impurity-removing 6-10 times by filter residue concentration, is forged in 850~1000 DEG C
It burns, obtains the titanium dioxide that purity is > 98%；
Further, the present invention can also continue to follow the steps below five-seven:
Step 5: there is hydrolysate, mistake to pH=5~6 in the ammonium hydroxide that the filtrate added drop-wise step 2 that step 4 is obtained is formed
Filtrate and filter residue are collected in filter, and filter residue is washed with distilled water removal of impurities 4~8 times, in 1000~1300 DEG C of 1~5h of calcining, is obtained pure
The alumina product of degree > 95%；
Step 6: there is hydrolysate, filters to pH >=12 in the ammonium hydroxide that the filtrate added drop-wise step 2 that step 5 is obtained is formed
Collect filtrate and filter residue, filter residue be washed with distilled water removal of impurities 3~6 times, in 400~800 DEG C of 2~4h of calcining, obtain purity >
97% magnesium oxide product；
Step 7: the filtrate obtained to step 6 is added in the ammonium hydroxide that step 2 is formed, evaporative crystallization obtains ammonium salt crystalline substance
Body, realization recycle.
It is that sampling gas pH≤7 are detected by pH meter that sample tap valve opening and closing judgment criteria is controlled in the step 2, with
It realizes the abundant salinization of valuable elements in minerals, generates soluble-salt.
Embodiment 1
Ning Gang group steel slag, chemical composition analysis are as follows:
1 steel slag composition analysis result of table
Sample is derived from the steel slag that Ning Gang group oxygen blows top converter, and chemical composition analysis result such as table 1, essential mineral is calcium
Pyralspite, red nepheline.
Step recovery Pd magnalium valuable metal is carried out by the method for Fig. 1, the specific steps are as follows:
(1) ammonium sulfate roasts
It is 81.09% by steel slag ball-milling to -0.074mm, dries and break up at 90 DEG C, by above-mentioned powder material and sulfuric acid
Ammonium is mixed in the ratio of 1:3, is pyrolyzed 1.5h in autoclave under the conditions of temperature is 300 DEG C, and sample tap is open in the initial stage, is received
Collect the ammonia generated, is passed through distilled water and forms ammonium hydroxide, the closed pressurized pyrolysis when sampling gas pH≤7.
(2) acidleach
Fired slags that step (1) obtains are added to the H of mass fraction 10% by liquid-solid ratio 5:12SO4In solution, it is in temperature
70 DEG C, mixing speed be 350rpm water-bath in acidleach 3h, after acidleach, leachate is filtered, is measured and is calculated by ICP
The leaching rate of titanium magnalium is respectively 97.69%, 94.29%, 98.45% in pickle liquor out.
(3) high-valued Product recycling
1 times of dilution water is added after keeping the temperature 0.5h under fluidized state in the acidleach filtrate that step (2) is obtained, then keeps the temperature 1h,
It is recrystallized, canescence hydrolysate occurs, filtrate and filter residue is collected by filtration, by filter residue with 2% dilute sulfuric acid washing impurity-removing 5 times,
It is calcined in 920 DEG C, obtains 98.59% titanium dioxide of purity；The ammonium hydroxide that filtrate added drop-wise step (1) is collected is adjusted to pH=5.5, occurs
Filtrate and filter residue is collected by filtration in hydrolysate, filter residue is washed with distilled water removal of impurities 5 times, in 1100 DEG C of calcining 3h, obtaining purity is
96.34% alumina product；The ammonium hydroxide that above-mentioned filtered fluid a dropping step (1) is collected adjusts pH=13, hydrolysate occurs, filters
Filtrate and filter residue are collected, filter residue is washed with distilled water removal of impurities 5 times, in 650 DEG C of calcining 3h, obtains the oxygen that purity is 98.57%
Change magnesium products；Remained ammonia is added to above-mentioned filtered fluid, evaporative crystallization obtains ammonia sulfate crystal, realizes that it is recycled.
Embodiment 2
The titanium-containing blast furnace slag of Pan Gang group, chemical composition analysis are as follows:
2 titanium-containing blast furnace slag composition analysis result of table
Sample is derived from the titanium-containing blast furnace slag after the ironmaking of Pan Gang group, and chemical composition analysis result such as table 2, essential mineral is calcium
Titanium ore and diopside.
Step recovery Pd magnalium valuable metal is carried out by the method for Fig. 1, the specific steps are as follows:
(1) ammonium sulfate roasts
It is 77.28% that titanium-containing blast furnace slag, which is milled to -0.074mm, dries and breaks up at 95 DEG C, by above-mentioned powder material
It is mixed with ammonium sulfate in the ratio of 1:2, is pyrolyzed 2h in autoclave under the conditions of temperature is 350 DEG C, sample tap is opened in the initial stage
Mouthful, the ammonia of generation is collected, distilled water is passed through and forms ammonium hydroxide, the closed pressurized pyrolysis when sampling gas pH≤7.
(2) acidleach
Fired slags that step (1) obtains are added to the H of mass fraction 8% by liquid-solid ratio 8:12SO4In solution, Yu Wendu 80
DEG C, mixing speed be 390rpm water-bath in acidleach 2.5h, after acidleach, leachate is filtered, is measured and is calculated by ICP
The leaching rate of titanium magnalium valuable metal is respectively 96.85%, 93.21%, 97.18% in pickle liquor out.
(3) high-valued Product recycling
1.5 times of dilution waters are added after keeping the temperature 0.7h under fluidized state in the acidleach filtrate that step (2) is obtained, then keep the temperature
1.2h is recrystallized, and canescence hydrolysate occurs, filtrate and filter residue is collected by filtration, and filter residue is washed away with 3.5% dilute sulfuric acid dip
It miscellaneous 5 times, is calcined in 950 DEG C, obtains 98.81% titanium dioxide of purity；The ammonium hydroxide that filtrate added drop-wise step (1) is collected is adjusted to pH=
5.3, there is hydrolysate, filtrate and filter residue is collected by filtration, filter residue is washed with distilled water removal of impurities 6 times, in 1250 DEG C of calcining 2h, is obtained
The alumina product for being 97.26% to purity；The ammonium hydroxide that above-mentioned filtered fluid a dropping step (1) is collected adjusts pH=12.5, occurs
Filtrate and filter residue is collected by filtration in hydrolysate, filter residue is washed with distilled water removal of impurities 5 times, in 700 DEG C of calcining 2h, obtaining purity is
97.59% magnesium oxide product；Remained ammonia is added to above-mentioned filtered fluid, evaporative crystallization obtains ammonia sulfate crystal, realizes it
It recycles.
Embodiment 3
The high titanium slag of He Gang limited liability company, chemical composition analysis are as follows:
3 high titanium slag composition analysis result of table
Sample is derived from the high titanium slag of He Gang limited liability company electro-smelting, chemical composition analysis result such as table 3, main mine
Object is anosovite, silicate glass body and free TiO2。
Step recovery Pd magnalium valuable metal is carried out by the method for Fig. 1, the specific steps are as follows:
(1) ammonium sulfate roasts
By high titanium slag be milled to -0.074mm be 71.63%, dry and break up at 100 DEG C, by above-mentioned powder material with
Ammonium sulfate is mixed in the ratio of 1:4, is pyrolyzed 2.5h in autoclave under the conditions of temperature is 400 DEG C, sample tap is opened in the initial stage
Mouthful, the ammonia of generation is collected, distilled water is passed through and forms ammonium hydroxide, the closed pressurized pyrolysis when sampling gas pH≤7.
(2) Ore Leaching
Fired slags that step (1) obtains are added to the H of mass fraction 12% by liquid-solid ratio 10:12SO4In solution, Yu Wendu
85 DEG C, mixing speed be 355rpm water-bath in acidleach 3.5h, after acidleach, leachate is filtered, is measured and is counted by ICP
The leaching rate for calculating titanium magnalium valuable metal in pickle liquor is respectively 97.38%, 94.62%, 98.57%.
(3) high-valued Product recycling
0.6 times of dilution water is added after keeping the temperature 0.8h under fluidized state in the acidleach filtrate that step (2) is obtained, then keeps the temperature
0.6h is recrystallized, and canescence hydrolysate occurs, filtrate and filter residue is collected by filtration, by 4% dilute sulfuric acid washing impurity-removing of filter residue
It 7 times, is calcined in 960 DEG C, obtains 99.34% titanium dioxide of purity；The ammonium hydroxide that filtrate added drop-wise step (1) is collected is adjusted to pH=5.1,
There is hydrolysate, filtrate and filter residue is collected by filtration, filter residue is washed with distilled water removal of impurities 7 times, in 1150 DEG C of calcining 1.5h, is obtained
The alumina product that purity is 96.44%；The ammonium hydroxide that above-mentioned filtered fluid a dropping step (1) is collected adjusts pH=13.2, water occurs
Object is solved, filtrate and filter residue is collected by filtration, filter residue is washed with distilled water removal of impurities 6 times, in 750 DEG C of calcining 1.5h, obtaining purity is
98.16% magnesium oxide product；Remained ammonia is added to above-mentioned filtered fluid, evaporative crystallization obtains ammonia sulfate crystal, realizes it
It recycles.
Embodiment 4
The kaolin of Fujian company, chemical composition analysis are as follows:
4 kaolin composition analysis result of table
Sample is derived from the kaolin of Zhangzhou, Fujian company, chemical composition analysis result such as table 4, and essential mineral is that more water are high
Ridge soil and illite
Step recovery Pd magnalium valuable metal is carried out by the method for Fig. 1, the specific steps are as follows:
(1) ammonium sulfate roasts
By kaolin be milled to -0.074mm be 82.54%, dry and break up at 105 DEG C, by above-mentioned powder material with
Ammonium sulfate is mixed in the ratio of 1:3.5, is pyrolyzed 2.3h in autoclave under the conditions of temperature is 420 DEG C, sample tap is in the initial stage
Opening, collects the ammonia of generation, is passed through distilled water and forms ammonium hydroxide, the closed pressurized pyrolysis when sampling gas pH≤7.
(2) Ore Leaching
Fired slags that step (1) obtains are added to the H of mass fraction 7% by liquid-solid ratio 12:12SO4In solution, Yu Wendu 93
DEG C, mixing speed be 410rpm water-bath in acidleach 4h, after acidleach, leachate is filtered, is measured and is calculated by ICP
The leaching rate of titanium magnalium valuable metal is respectively 98.38%, 95.62%, 99.17% in pickle liquor.
(3) high-valued Product recycling
1.3 times of dilution waters are added after keeping the temperature 0.4h under fluidized state in the acidleach filtrate that step (2) is obtained, then keep the temperature
1.2h is recrystallized, and canescence hydrolysate occurs, filtrate and filter residue is collected by filtration, and filter residue is washed away with 3.5% dilute sulfuric acid dip
It miscellaneous 6 times, is calcined in 980 DEG C, obtains 98.52% titanium dioxide of purity；The ammonium hydroxide that filtrate added drop-wise step (1) is collected is adjusted to pH=
5.4, there is hydrolysate, filtrate and filter residue is collected by filtration, filter residue is washed with distilled water removal of impurities 8 times, in 1230 DEG C of calcining 1.2h,
Obtain the alumina product that purity is 97.29%；The ammonium hydroxide that above-mentioned filtered fluid a dropping step (1) is collected adjusts pH=13.7, out
Existing hydrolysate, is collected by filtration filtrate and filter residue, and filter residue is washed with distilled water removal of impurities 7 times, in 770 DEG C of calcining 1.8h, is obtained pure
The magnesium oxide product that degree is 97.96%；Remained ammonia is added to above-mentioned filtered fluid, evaporative crystallization, ammonia sulfate crystal is obtained, it is real
Existing its recycles.
Embodiment 5
The titanium-containing blast furnace slag of Pan Gang group, chemical composition analysis are as follows:
5 titanium-containing blast furnace slag composition analysis result of table
Sample is derived from the titanium-containing blast furnace slag after the ironmaking of Pan Gang group, and chemical composition analysis result such as table 2, essential mineral is calcium
Titanium ore, magnesium aluminate spinel and rich titandiopside.
Step recovery Pd magnalium valuable metal is carried out by the method for Fig. 1, the specific steps are as follows:
(1) ammonium chloride roasts
It is 83.67% that titanium-containing blast furnace slag, which is milled to -0.074mm, dries and breaks up at 110 DEG C, by above-mentioned powder object
Material is mixed with ammonium chloride in the ratio of 1:0.8, is pyrolyzed 2.5h in autoclave under the conditions of temperature is 310 DEG C, sample tap is in initial
Stage opening, collects the ammonia of generation, is passed through distilled water and forms ammonium hydroxide, the closed pressurized pyrolysis when sampling gas pH≤7.
(2) acidleach
Fired slags that step (1) obtains are added to by liquid-solid ratio 6:1 in the HCl solution of mass fraction 3.5%, Yu Wendu 73
DEG C, mixing speed be 375rpm water-bath in acidleach 3.6h, after acidleach, leachate is filtered, is measured and is calculated by ICP
The leaching rate of titanium magnalium valuable metal is respectively 99.27%, 94.92%, 98.25% in pickle liquor out.
(3) high-valued Product recycling
1.3 times of dilution waters are added after keeping the temperature 0.9h under fluidized state in the acidleach filtrate that step (2) is obtained, then keep the temperature
1.1h is recrystallized, and canescence hydrolysate occurs, filtrate and filter residue is collected by filtration, and filter residue is washed with 2.4% dilute hydrochloric acid and is removed
It miscellaneous 6 times, is calcined in 960 DEG C, obtains 99.12% titanium dioxide of purity；The ammonium hydroxide that filtrate added drop-wise step (1) is collected is adjusted to pH=
5.6, there is hydrolysate, filtrate and filter residue is collected by filtration, filter residue is washed with distilled water removal of impurities 7 times, in 1280 DEG C of calcining 2h, is obtained
The alumina product for being 98.86% to purity；The ammonium hydroxide that above-mentioned filtered fluid a dropping step (1) is collected adjusts pH=12.6, occurs
Filtrate and filter residue is collected by filtration in hydrolysate, filter residue is washed with distilled water removal of impurities 6 times, in 710 DEG C of calcining 2h, obtaining purity is
98.47% magnesium oxide product；Remained ammonia is added to above-mentioned filtered fluid, evaporative crystallization obtains ammonia chloride crystal, realizes it
It recycles.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (9)
1. a kind of method of the processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral, comprising the following steps:
Step 1: drying and breaing up titanium mineral and metal silicate mineral, powder material is obtained；
Step 2: the powder material that step 1 is obtained and ammonium salt mix, in calciner 250~450 DEG C of roastings 0.5~
2h, calciner sample tap are open in the initial stage, collect the ammonia of generation, and are passed through water and form ammonium hydroxide, when sampling gas
Closed pressurized pyrolysis when pH is in acidity；
Step 3: being filtered after dilute acid soln acidleach is added in the fired slags that step 2 is pyrolyzed；
Step 4: the filtered fluid that step 3 is obtained keeps the temperature 0.5~1h under fluidized state, water is added and is diluted, then at boiling
0.5~2h of heat preservation under state is risen, is then recrystallized, canescence hydrolysate occurs, filtrate and filter residue is collected by filtration, by filter residue
It is calcined after dilute acid wash removal of impurities, obtains titanium dioxide.
2. the method according to claim 1, wherein the method also includes:
Step 5: there is hydrolysate, filtering is received to pH=5~6 in the ammonium hydroxide that the filtrate added drop-wise step 2 that step 4 is obtained is formed
Collect filtrate and filter residue, after filter residue is washed with water removal of impurities and is calcined, obtains alumina product；
Step 6: there is hydrolysate, is collected by filtration to pH >=12 in the ammonium hydroxide that the filtrate added drop-wise step 2 that step 5 is obtained is formed
Filtrate and filter residue are calcined after removal of impurities is washed with water in filter residue, obtain magnesium oxide product；
Step 7: the filtrate obtained to step 6 is added in the ammonium hydroxide that step 2 is formed, evaporative crystallization obtains ammonium salt crystal.
3. according to the method described in claim 2, it is characterized in that, step 5 by residue washing clean 4~8 times after, in 1000
~1300 DEG C of 1~5h of calcining；
Step 6 cleans residue washing 3~6 times, in 400~800 DEG C of 2~4h of calcining.
4. method according to claim 1 to 3, which is characterized in that step 1 is by titanium mineral and metal silicate mineral
It is milled to -0.074mm >=75%, dries and breaks up at 50~110 DEG C, obtains moisture≤2wt% grey powder material.
5. method according to claim 1 to 3, which is characterized in that control sample tap valve opening and closing in step 2 and sentence
Disconnected standard is that sampling gas pH≤7 are detected by pH meter, realizes the abundant salinization of valuable elements in minerals, generates soluble-salt.
6. method according to claim 1 to 3, which is characterized in that powder material and ammonium salt are pressed 1:0.5 by step 2
~1:5 ratio mixes, wherein the ammonium salt is ammonium sulfate and/or ammonium chloride.
7. method according to claim 1 to 3, which is characterized in that fired slags are pressed liquid-solid ratio 10:1~2 by step 3:
1 is added the H that mass fraction is 2%~30%2SO4Or HCl solution, the acidleach under 40~90 DEG C, 100~400rpm mixing speed
0.5~4h.
8. method according to claim 1 to 3, which is characterized in that 0.4~2 times of volume of step 4 addition filtered fluid
The water of score is diluted.
9. method according to claim 1 to 3, which is characterized in that filter residue concentration is 1%~5% by step 4
Weak acid scrubbing cleans 6~10 times, calcines in 850~1000 DEG C, obtains titanium dioxide.
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| CN114716162A (en) * | 2022-04-11 | 2022-07-08 | 四川顺应动力电池材料有限公司 | Method for removing magnesium and calcium from acid-soluble titanium slag |
| CN115466854A (en) * | 2022-10-13 | 2022-12-13 | 江西闪凝科技有限公司 | Comprehensive extraction method for lithium ore |
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