CN108642308A - A kind of method that high tin tungsten ore is decomposed in mixture of sulfuric phosphoric acid pressurization - Google Patents
A kind of method that high tin tungsten ore is decomposed in mixture of sulfuric phosphoric acid pressurization Download PDFInfo
- Publication number
- CN108642308A CN108642308A CN201810332892.3A CN201810332892A CN108642308A CN 108642308 A CN108642308 A CN 108642308A CN 201810332892 A CN201810332892 A CN 201810332892A CN 108642308 A CN108642308 A CN 108642308A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- wolframite
- tin
- acid
- high tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 89
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000010937 tungsten Substances 0.000 claims abstract description 84
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 83
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 74
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 238000000605 extraction Methods 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims abstract description 9
- 239000000284 extract Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 27
- 239000000706 filtrate Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 239000012141 concentrate Substances 0.000 abstract description 12
- 239000002893 slag Substances 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical group OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 abstract 1
- 239000003350 kerosene Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000002386 leaching Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 4
- -1 sec-octyl alcohols Chemical class 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910004829 CaWO4 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to the methods that high tin tungsten ore is decomposed in a kind of pressurization of mixture of sulfuric phosphoric acid, it is theed improvement is that, during extracting tungsten from the composite ore of high tin wolframite or high tin black and white tungsten with the mixed acid of phosphoric acid and sulfuric acid, pressurized treatments are carried out to reaction system, it is 110~250 DEG C to make its temperature.Decomposition slag after extraction tungsten can obtain Tin concentrate directly or through beneficiating process.The present invention passes through pressurization, the compound that calcic need not be extraly added during extracting tungsten converts wolframite, you can directly extracts the tungsten in the composite ore of wolframite or black and white tungsten, while obtaining Tin concentrate, production process is simplified, production cost is reduced.
Description
Technical field
The invention belongs to the extractions of field of hydrometallurgy tungsten, and in particular to a kind of to decompose high tin tungsten ore by pressurizeing
Method.
Background technology
In China, stanniferous tungsten ore is a kind of important tungsten ore resource, but also the tin containing high value.General tin be all with
The form of cassiterite and wolframite or Scheelite-Wolframite Mixed Mine association.Traditional ore dressing and Tungsten smelting method can not all efficiently separate back
Receive tin therein.Chinese invention is special 201010605095.1,201010605107.0,201010605103.2,
201010605110.2,201010605094.7 propose the new method that Decomposition of Tungsten is cooperateed with using sulfuric-phosphoric, it is efficient real
The decomposition of scheelite is showed, a kind of completely new smelting process is provided for scheelite.But when using sulfuric-phosphoric collaboration point
When solution technology directly leaches wolframite and Scheelite-Wolframite Mixed Mine, the leaching rate of tungsten is but difficult to reach the discomposing effect of scheelite.This
It is primarily due to wolframite (Fe/MnWO4) structure is compared to scheelite (CaWO4) more stablize, it is difficult to it is directly decomposed by acid, i.e.,
Make the strong complexing agent for having phosphoric acid as tungstate radicle.Thus Chinese patent 201510243382.5,201510241154.4,
201510242275.0,201710313207.8 various methods are proposed to realize that mixture of sulfuric phosphoric acid decomposes wolframite or black and white tungsten
Composite ore.In these patents, some methods are by the way that calcium containing compound to be added in wolframite or Scheelite-Wolframite Mixed Mine
So that wolframite is converted into scheelite by mechanical ball mill, also there is method to contain by being added into wolframite or Scheelite-Wolframite Mixed Mine
Calcium compound progress high temperature is burnt or melting is to realize that wolframite changes to scheelite, while being carried out tin volatilization by blowing
Recycling.After changing by above-mentioned measure, the decomposition that mixture of sulfuric phosphoric acid carries out wolframite or Scheelite-Wolframite Mixed Mine is then added.From
From the point of view of the data reported, these measures can effectively realize the decomposition for promoting wolframite or Scheelite-Wolframite Mixed Mine really.
But the measure that above-mentioned patent is taken undoubtedly both increases process and production equipment that tungsten ore is handled, is also increased by tungsten
The disaggregated cost of mine.The technology of wolframite or black and white tungsten ore composite ore is directly decomposed therefore, it is necessary to develop new mixture of sulfuric phosphoric acid,
In favor of the recycling of tungsten and tin.
Mixture of sulfuric phosphoric acid has several advantages when handling scheelite：First is that tungsten ore resolution ratio is high；Second is not generate dangerous waste
Decompose slag；Third is to decompose to use cheap sulfuric acid, disaggregated cost low；4th is to decompose only to need in atmospheric conditions just
It can realize.All the time, this seminar is all based on this several big advantage and removes Decomposition of Tungsten, including wolframite, Scheelite-Wolframite Mixed Mine.
But but occurs the problem of can not directly decomposing when decomposing the mineral containing black tungsten.
Invention content
The object of the present invention is to provide the methods that high tin tungsten ore is decomposed in a kind of pressurization of mixture of sulfuric phosphoric acid, are mainly improved to,
During extracting tungsten from the composite ore of high tin wolframite or high tin black and white tungsten with the mixed acid of phosphoric acid and sulfuric acid, pass through pressurization
It is 110~250 DEG C to make the temperature of reaction system.
The method of the present invention can be realized directly logical by carrying out pressurized treatments to system in the case where not adding calcified material
The tungsten in phosphorus sulphur method extraction wolframite or Scheelite-Wolframite Mixed Mine is crossed, additional treatment process need not be increased, decomposing slag can be straight
It connects or Tin concentrate can be obtained by beneficiating process, simplify operation, reduce the decomposition of wolframite and the cost recovery of tin.
Preferably, WO in the composite ore of the high tin wolframite or high tin black and white tungsten3Grade be 10~70%.
Preferably, the grade of tin is 0.5~20% in the composite ore of the high tin wolframite or high tin black and white tungsten.
Preferably, in the mixed acid, phosphoric acid concentration is 20~250g/L；
Preferably, raw material is the high tin wolframite, then a concentration of 60~200g/L of phosphoric acid, and raw material is the Gao Xihei
The composite ore of white tungsten, then a concentration of 30~160g/L of phosphoric acid；
It is further preferred that raw material is the high tin wolframite, then a concentration of 120~175g/L of phosphoric acid, raw material are institute
The composite ore of high tin black and white tungsten is stated, then a concentration of 100~160g/L of phosphoric acid；
Preferably, in the mixed acid, a concentration of 50~500g/L of sulfuric acid；
Preferably, raw material is the high tin wolframite, then a concentration of 100~250g/L of sulfuric acid, and raw material is the high tin
The composite ore of black and white tungsten, then a concentration of 60~220g/L of sulfuric acid；
It is further preferred that raw material is the high tin wolframite, then a concentration of 180~240g/L of sulfuric acid, raw material are institute
The composite ore of high tin black and white tungsten is stated, then a concentration of 180~200g/L of sulfuric acid；
Preferably, raw material is the high tin wolframite, then the temperature of the reaction system is 130~230 DEG C, and raw material is institute
The composite ore of high tin black and white tungsten is stated, then the temperature of the reaction system is 120~200 DEG C.
It is further preferred that raw material is the high tin wolframite, then the temperature of the reaction system is 200~230 DEG C, former
Material is the composite ore of the high tin black and white tungsten, then the temperature of the reaction system is 150~200 DEG C.
Preferably, raw material is the wolframite, then the pressure of the reaction system is 0.54~3.0Mpa, and raw material is described
The composite ore of black and white tungsten, then the pressure of the reaction system is 0.21~1.85Mpa.
Preferably, the mass volume ratio of the composite ore and the mixed acid of high Sillim's wolframite or high tin black and white tungsten is
1:3~10.
Preferably, the granularity of the composite ore of the high tin wolframite or high tin black and white tungsten is less than 300 μm.
Preferably, reaction system is filtered after completion of the reaction, by esters extractant, alcohol kind of extractants or it is cloudy from
One or more of sub- extractant extracts the tungsten in filtrate.
It is further preferred that the extractant is 25%TBP+10% sec-octyl alcohols+kerosene, 40% sec-octyl alcohol+kerosene, 30%
N235+ kerosene or 30%N235+ kerosene.
Percentage in above-mentioned extractant is percentage by volume, as 25%TBP+10% sec-octyl alcohols+kerosene indicates the body of TBP
Fraction is 25%, and the volume fraction of sec-octyl alcohol is 10%, remaining as kerosene.
Filtrate can be recycled after filling into consumed phosphoric acid and sulfuric acid again after having extracted.
The present invention after the tungsten in extract extract liquor, Ruo Gaoxi tungsten ores be wolframite, decompose slag then be Tin concentrate, can
Raw material as extraction tin；If high tin tungsten ore is Scheelite-Wolframite Mixed Mine, filter residue if is gypsum and stannic oxide, passes through dresser
Tin is extracted into Tin concentrate by skill.
As a preferred option, the method for the present invention includes following steps：
During extracting tungsten from high tin wolframite with the mixed acid of phosphoric acid and sulfuric acid, select granularity for 50~
The high tin wolframite of 250um, the wherein grade of tin are 0.5~20%, add the mixed acid of phosphoric acid and sulfuric acid and make it to wolframite
It is fully dissolved, pressurized treatments is carried out to reaction system, it is 200~230 DEG C to make system temperature, and phosphorus is adjusted during extraction
A concentration of 120~175g/L of acid, adjusts a concentration of 180~240g/L of sulfuric acid.
During extracting tungsten from wolframite with the mixed acid of phosphoric acid and sulfuric acid, select granularity for 50~150um's
The composite ore of high tin black and white tungsten is raw material, and wherein the grade of tin is 0.5~20%, adds the mixed acid of phosphoric acid and sulfuric acid and keeps its right
Wolframite is fully dissolved, and carries out pressurized treatments to reaction system, it is 150~200 DEG C to make system temperature, during extraction
A concentration of 100~the 160g/L for adjusting phosphoric acid, adjusts a concentration of 180~200g/L of sulfuric acid.
The present invention has the advantages that：
1) present invention need not extraly add the compound of calcic to wolframite by pressurization during extracting tungsten
It is converted, you can it realizes the tungsten in the composite ore for directly extracting rich tin wolframite or rich tin black and white tungsten, simplifies production process,
Reduce production cost.
2) tin that can be recycled in the form of Tin concentrate directly or by beneficiating process in slag in tungsten ore is decomposed from tungsten ore.
3) method of the invention still has resolution ratio is high, does not generate dangerous waste to divide compared with existing non-pressurized method
The low advantage of slag, disaggregated cost is solved, and reaction speed can be accelerated after the pressurizing.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
The unit of involved mass volume ratio is that the quality such as g/mL or kg/L are opposite with the order of magnitude of volume in embodiment
The unit answered.
Embodiment 1
The present embodiment is related to a kind of method for extracting tungsten from rich tin wolframite, includes the following steps：
1) it is 100 μm by granularity, WO3Grade be 62%, the grade of tin is 1.2%, wolframite powder and phosphoric acid and sulphur
The mixed acid of acid is with mass volume ratio 1:5 mix, a concentration of 175g/L, a concentration of 240g/ of sulfuric acid of phosphoric acid in mix acid liquor
L pressurizes to system after stirring evenly reaction system, is forced into 2.6MPa, and it is 230 DEG C to maintain the temperature of reaction system,
Stop pressurization after reacting 4.0h, reaction system is down to room temperature；
2) system after reaction is filtered, obtains filtrate, using 25%TBP+10% sec-octyl alcohols+kerosene as organic phase
Extraction 10 minutes is carried out to filtrate at 40 DEG C, extraction obtains the tungsten in filtrate, and surplus solution liquid after extraction, which fills into, to be consumed
Return to step 1 after phosphoric acid and sulfuric acid) in reuse.It is computed, the leaching rate of tungsten is 99.3%, and gained Tin concentrate grade is
12%.
Embodiment 2
The present embodiment is related to a kind of method for extracting tungsten from rich tin wolframite, includes the following steps：
1) it is 150 μm by granularity, WO3Grade be 50%, the grade of tin is 3.2%, wolframite powder and phosphoric acid and sulphur
The mixed acid of acid is with quality system than 1：6 mix, a concentration of 160g/L, a concentration of 220g/ of sulfuric acid of phosphoric acid in mix acid liquor
L pressurizes to system after stirring evenly reaction system, is forced into 2.2MPa, and it is 220 DEG C to maintain the temperature of reaction system,
Stop pressurization after reacting 4.0h, reaction system is down to room temperature；
2) system after reaction is filtered, obtains filtrate, it is right at 40 DEG C as organic phase using 40% sec-octyl alcohol+kerosene
Filtrate carries out extraction 10 minutes, and extraction obtains the tungsten in filtrate, and the surplus solution liquid after extraction fills into consumed phosphoric acid and sulphur
Return to step 1 after acid) in reuse.It is computed, the leaching rate of tungsten is 99.3%, and gained Tin concentrate grade is 26.5%.
Embodiment 3
The present embodiment is related to a kind of method for extracting tungsten from rich tin wolframite, includes the following steps：
1) it is 60 μm by granularity, WO3Grade be 34%, the grade of tin is 16.5%, wolframite powder and phosphoric acid and sulphur
The mixed acid of acid is with quality system than 1：8 mix, a concentration of 120g/L, a concentration of 180g/ of sulfuric acid of phosphoric acid in mix acid liquor
L pressurizes to system after stirring evenly reaction system, is forced into 1.85MPa, and it is 200 DEG C to maintain the temperature of reaction system,
Stop pressurization after reacting 6.0h, reaction system is down to room temperature；
2) system after reaction is filtered, obtains filtrate, using 30%N235+ kerosene as organic phase 50 DEG C to filter
Liquid carries out extraction 10 minutes, and extraction obtains the tungsten in filtrate, after the surplus solution after extraction fills into consumed phosphoric acid and sulfuric acid
Return to step 1) in reuse.It is computed, the leaching rate of tungsten is 99.2%, and gained Tin concentrate grade is 55%.
Embodiment 4
The present embodiment is related to a kind of method for extracting tungsten from rich tin Scheelite-Wolframite Mixed Mine, includes the following steps：
Raw material in the present embodiment is rich tin Scheelite-Wolframite Mixed Mine powder, and the wherein mass percent of wolframite powder is 30%.
1) it is 100 μm by granularity, WO3Grade be 52%, the mixing tungsten ore powder that the grade of tin is 6.5% and phosphoric acid and sulphur
The mixed acid of acid presses mass volume ratio 1：6 mix, a concentration of 160g/L, a concentration of 200g/ of sulfuric acid of phosphoric acid in mix acid liquor
L pressurizes to system after stirring evenly reaction system, is forced into 1.85MPa, and it is 200 DEG C to maintain the temperature of reaction system,
Stop pressurization after reaction 4.0, reaction system is down to room temperature；
2) system after reaction is filtered, obtains filtrate, using 25%TBP+10% sec-octyl alcohols+kerosene as organic phase
Extraction 10 minutes is carried out to filtrate at 40 DEG C, extraction obtains the tungsten in filtrate, and surplus solution liquid after extraction, which fills into, to be consumed
Return to step 1 after phosphoric acid and sulfuric acid) in reuse.It is computed, the leaching rate of tungsten is 99.6%, and Tin concentrate is obtained through ore-dressing technique
Grade is 45.8%.
Embodiment 5
The present embodiment is related to a kind of method for extracting tungsten from rich tin Scheelite-Wolframite Mixed Mine, includes the following steps：
Raw material in the present embodiment is rich tin Scheelite-Wolframite Mixed Mine powder, and the wherein mass percent of wolframite powder is 10%.
1) it is 150 μm by granularity, WO3Grade be 45%, the mixing tungsten ore powder that the grade of tin is 18.5% and phosphoric acid and
The mixed acid of sulfuric acid presses mass volume ratio 1：4 mixing, a concentration of 100g/L of phosphoric acid in mix acid liquor, sulfuric acid it is a concentration of
180g/L pressurizes to system after stirring evenly reaction system, is forced into 1.25MPa, maintains the temperature of reaction system to be
180 DEG C, stops pressurization after reacting 4.0h, reaction system is down to room temperature；
2) system after reaction is filtered, obtains filtrate, it is right at 40 DEG C as organic phase using 30%N1923+ kerosene
Filtrate carries out extraction 10 minutes, and extraction obtains the tungsten in filtrate, and the surplus solution liquid after extraction fills into consumed phosphoric acid and sulphur
Return to step 1 after acid) in reuse.It is computed, the leaching rate of tungsten is 99.4%, and obtaining Tin concentrate grade through ore-dressing technique is
62.6%.
Embodiment 6
The present embodiment is related to a kind of method for extracting tungsten from rich tin Scheelite-Wolframite Mixed Mine, includes the following steps：
Raw material in the present embodiment is rich tin Scheelite-Wolframite Mixed Mine powder, and the wherein mass percent of wolframite powder is 55%.
1) it is 50 μm by granularity, WO3Grade be 39.6%, the mixing tungsten ore powder that the grade of tin is 1.5% and phosphoric acid and
The mixed acid of sulfuric acid presses mass volume ratio 1：8 mixing, a concentration of 140g/L of phosphoric acid in mix acid liquor, sulfuric acid it is a concentration of
200g/L pressurizes to system after stirring evenly reaction system, is forced into 0.56MPa, maintains the temperature of reaction system to be
150 DEG C, stops pressurization after reacting 6.0h, reaction system is down to room temperature；
2) system after reaction is filtered, obtains filtrate, it is right at 40 DEG C as organic phase using 40% sec-octyl alcohol+kerosene
Filtrate carries out extraction 10 minutes, and extraction obtains the tungsten in filtrate, and the surplus solution liquid after extraction fills into consumed phosphoric acid and sulphur
Return to step 1 after acid) in reuse.It is computed, the leaching rate of tungsten is 99.2%, and obtaining Tin concentrate grade through ore-dressing technique is
43.6%.
Comparative example 1
Compared with Example 1, difference lies in do not carry out pressurized treatments, reaction temperature is 90 DEG C, reaction to reaction system
After the completion, the leaching rate of tungsten is 80.6%, and it is tungsten tin composite ore that gained, which decomposes slag, and the grade of tin is 4.5%.
Comparative example 2
Compared with Example 2, difference lies in carry out pressurized treatments, the temperature for controlling reaction system is 106 to system
DEG C, after the completion of reaction, the leaching rate of tungsten is 91.5%, and it is tungsten tin composite ore that gained, which decomposes slag, and the grade of tin is 8.5%.
Comparative example 3
Compared with Example 2, difference lies in, a concentration of 50g/L of phosphoric acid in control system, sulfuric acid it is a concentration of
100g/L, after the completion of reaction, the leaching rate of tungsten is 86.5%, and it is tungsten tin composite ore that gained, which decomposes slag, and the grade of tin is 6.6%.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. the method that high tin tungsten ore is decomposed in a kind of pressurization of mixture of sulfuric phosphoric acid, which is characterized in that with the mixed acid of phosphoric acid and sulfuric acid from
During extracting tungsten in the composite ore of high tin wolframite or high tin black and white tungsten, the temperature of reaction system is set to be 110 by pressurization
~250 DEG C.
2. according to the method described in claim 1, it is characterized in that, in the composite ore of the high tin wolframite or high tin black and white tungsten
WO3Grade be 10~70%.
3. method according to claim 1 or 2, which is characterized in that the mixing of the high tin wolframite or high tin black and white tungsten
The grade of tin is 0.5~20% in mine.
4. according to claims 1 to 3 any one of them method, which is characterized in that in the mixed acid, phosphoric acid concentration be 20~
250g/L, it is preferred that raw material is the high tin wolframite, then a concentration of 60~200g/L of phosphoric acid, and raw material is the Gao Xihei
The composite ore of white tungsten, then a concentration of 30~160g/L of phosphoric acid.
5. according to Claims 1 to 4 any one of them method, which is characterized in that in the mixed acid, a concentration of the 50 of sulfuric acid
~500g/L, it is preferred that raw material is the high tin wolframite, then a concentration of 100~250g/L of sulfuric acid, and raw material is the high tin
The composite ore of black and white tungsten, then a concentration of 60~220g/L of sulfuric acid.
6. according to Claims 1 to 5 any one of them method, which is characterized in that raw material is the high tin wolframite, then described
The temperature of reaction system is 130~230 DEG C, and raw material is the composite ore of the high tin black and white tungsten, then the temperature of the reaction system
It is 120~200 DEG C.
7. according to claim 1~6 any one of them method, which is characterized in that raw material is the wolframite, the then reaction
The pressure of system is 0.54~3.0Mpa, and raw material is the composite ore of the black and white tungsten, then the pressure of the reaction system is 0.21
~1.85Mpa.
8. making the method described in one according to claim 1~7, which is characterized in that high Sillim's wolframite or high tin black and white
The mass volume ratio of the composite ore of tungsten and the mixed acid is 1:3~10；And/or the high tin wolframite or high tin black and white tungsten
Composite ore granularity be less than 300 μm.
9. according to claim 1~8 any one of them method, which is characterized in that carried out after completion of the reaction to reaction system
Filter, by esters extractant, one or more of alcohol kind of extractants or amine extractant extract the tungsten in filtrate.
10. according to claim 1~9 any one of them method, which is characterized in that include the following steps：
During extracting tungsten from high tin wolframite with the mixed acid of phosphoric acid and sulfuric acid, select granularity for 50~250um's
High tin wolframite, the wherein grade of tin are 0.5~20%, add the mixed acid of phosphoric acid and sulfuric acid and it is made to carry out fully wolframite
Dissolving carries out pressurized treatments to reaction system, and it is 200~230 DEG C to make system temperature, and the concentration of phosphoric acid is adjusted during extraction
For 120~175g/L, a concentration of 180~240g/L of sulfuric acid is adjusted；
During extracting tungsten from wolframite with the mixed acid of phosphoric acid and sulfuric acid, select granularity for the high tin of 50~150um
The composite ore of black and white tungsten is raw material, and wherein the grade of tin is 0.5~20%, adds the mixed acid of phosphoric acid and sulfuric acid and makes it to black tungsten
Mine is fully dissolved, and carries out pressurized treatments to reaction system, it is 150~200 DEG C to make system temperature, is adjusted during extraction
A concentration of 100~160g/L of phosphoric acid adjusts a concentration of 180~200g/L of sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810332892.3A CN108642308B (en) | 2018-04-13 | 2018-04-13 | Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810332892.3A CN108642308B (en) | 2018-04-13 | 2018-04-13 | Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108642308A true CN108642308A (en) | 2018-10-12 |
| CN108642308B CN108642308B (en) | 2020-11-10 |
Family
ID=63746086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810332892.3A Expired - Fee Related CN108642308B (en) | 2018-04-13 | 2018-04-13 | Method for decomposing high-tin tungsten ore under pressure by using sulfur-phosphorus mixed acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108642308B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112899502A (en) * | 2021-01-20 | 2021-06-04 | 中南大学 | Method for treating high-calcium black-white tungsten mixed ore |
| CN113106251A (en) * | 2021-03-10 | 2021-07-13 | 湖南柿竹园有色金属有限责任公司 | Chemical beneficiation method for producing tin middling from high-tin wolframite or wolframite and wolframite mixed ore |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414120A (en) * | 2002-11-15 | 2003-04-30 | 自贡硬质合金有限责任公司 | Method of producing tungstic acid by closed type hydrochloric acid decompose tunstite |
| CN101608257A (en) * | 2009-04-09 | 2009-12-23 | 厦门钨业股份有限公司 | Technology for far infrared thermocompression decomposition of tungsten mineral raw material |
| CN102021329A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
| JP2013204068A (en) * | 2012-03-27 | 2013-10-07 | Cmc Gijutsu Kaihatsu Kk | Method for recovering tungsten or cobalt from cemented carbide powder |
| CN104805314A (en) * | 2015-05-13 | 2015-07-29 | 中南大学 | Method for extracting tungsten from raw materials containing wolframite |
| CN106282608A (en) * | 2016-08-29 | 2017-01-04 | 中南大学 | A kind of method decomposing Scheelite-Wolframite Mixed Mine |
| JP2018062691A (en) * | 2016-10-13 | 2018-04-19 | Ｊｘ金属株式会社 | Method for collecting tungsten concentrate from cobalt-tungsten raw material |
-
2018
- 2018-04-13 CN CN201810332892.3A patent/CN108642308B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414120A (en) * | 2002-11-15 | 2003-04-30 | 自贡硬质合金有限责任公司 | Method of producing tungstic acid by closed type hydrochloric acid decompose tunstite |
| CN101608257A (en) * | 2009-04-09 | 2009-12-23 | 厦门钨业股份有限公司 | Technology for far infrared thermocompression decomposition of tungsten mineral raw material |
| CN102021329A (en) * | 2010-12-24 | 2011-04-20 | 中南大学 | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum |
| JP2013204068A (en) * | 2012-03-27 | 2013-10-07 | Cmc Gijutsu Kaihatsu Kk | Method for recovering tungsten or cobalt from cemented carbide powder |
| CN104805314A (en) * | 2015-05-13 | 2015-07-29 | 中南大学 | Method for extracting tungsten from raw materials containing wolframite |
| CN106282608A (en) * | 2016-08-29 | 2017-01-04 | 中南大学 | A kind of method decomposing Scheelite-Wolframite Mixed Mine |
| JP2018062691A (en) * | 2016-10-13 | 2018-04-19 | Ｊｘ金属株式会社 | Method for collecting tungsten concentrate from cobalt-tungsten raw material |
Non-Patent Citations (2)
| Title |
|---|
| 刘珍等: "《化验员读本 上 化学分析 第3版》", 30 September 1989, 化学工业出版社 * |
| 杨凯华等: "硫磷混酸浸出黑钨矿动力学", 《中国有色金属学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112899502A (en) * | 2021-01-20 | 2021-06-04 | 中南大学 | Method for treating high-calcium black-white tungsten mixed ore |
| CN112899502B (en) * | 2021-01-20 | 2021-12-28 | 中南大学 | Method for treating high-calcium black-white tungsten mixed ore |
| CN113106251A (en) * | 2021-03-10 | 2021-07-13 | 湖南柿竹园有色金属有限责任公司 | Chemical beneficiation method for producing tin middling from high-tin wolframite or wolframite and wolframite mixed ore |
| CN113106251B (en) * | 2021-03-10 | 2023-03-10 | 湖南柿竹园有色金属有限责任公司 | Chemical beneficiation method for producing tin middling from high-tin wolframite or wolframite and wolframite mixed ore |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108642308B (en) | 2020-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105886798B (en) | The method that phosphorus and rare earth are recycled from containing rare earth phosphate rock | |
| US11384410B2 (en) | Method for decomposing medium-/low-grade scheelite | |
| CN108707765A (en) | A kind of method that scheelite is decomposed in the pressurization of phosphorus sulphur nitration mixture | |
| CN108642278A (en) | A kind of method that mixture of sulfuric phosphoric acid pressurization decomposes wolframite or Scheelite-Wolframite Mixed Mine to extract tungsten | |
| CN106282608B (en) | A method of decomposing Scheelite-Wolframite Mixed Mine | |
| CN101736153B (en) | Method for extracting ammonium molybdate from molybdenum concentrate by pressure ammonia leaching | |
| CN103073061A (en) | Method for extracting tungsten and molybdenum in high molybdenum scheelite | |
| CN108642307A (en) | A kind of method that wolframite or Scheelite-Wolframite Mixed Mine extraction tungsten are decomposed in hydrochloric acid-phosphoric acid pressurization | |
| US11530465B2 (en) | Method for decomposing mixed wolframite and scheelite ore in alkaline system | |
| CN108642279A (en) | A kind of method that mixture of sulfuric phosphoric acid pressurization adverse current decomposes wolframite | |
| CN107641724A (en) | One kind improves WO in scheelite3The method of leaching rate | |
| Wan et al. | Synthesis of scheelite with wolframite and calcium carbonate by a direct solid-state synthesis route | |
| CN108642308A (en) | A kind of method that high tin tungsten ore is decomposed in mixture of sulfuric phosphoric acid pressurization | |
| CN102925670B (en) | Method for comprehensively recovering fluorine and tungsten from tungsten-containing fluorite mineral | |
| CN105331812A (en) | Method for comprehensively recycling phosphorus and rare earth from rare earth phosphorite containing monazite | |
| CN101709386A (en) | Method for producing zinc by use of high-silicon zinc oxide ore | |
| CN107502740A (en) | One kind reclaims iron resource method from pyrolusite leached mud | |
| CN107012342B (en) | A method of the low-grade ion type rareearth raw ore rare earth elements of extraction | |
| CN105441674B (en) | From the method for synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite | |
| CN111100996B (en) | Method for preparing vanadium oxide from acidic low-concentration vanadium liquid | |
| CN100480404C (en) | Method for leaching vanadium from stone-like coal by oxidation transformation | |
| CN108642277A (en) | A kind of preprocess method containing tungsten mineral | |
| CN106882838A (en) | Method for producing titanium dioxide by using waste acid self-circulation non-blast furnace titanium slag sulfuric acid method | |
| CN108070717B (en) | The adverse current tandem for controlling liquid-solid ratio simultaneously and embathing completion liquid concentration embathes method and system | |
| CN106882839A (en) | Method for comprehensively utilizing titanium white waste acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201110 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |