CN100519425C - Process for Extracting Vanadium Pentoxide from Stone Coal Mine - Google Patents
Process for Extracting Vanadium Pentoxide from Stone Coal Mine Download PDFInfo
- Publication number
- CN100519425C CN100519425C CNB2007100491709A CN200710049170A CN100519425C CN 100519425 C CN100519425 C CN 100519425C CN B2007100491709 A CNB2007100491709 A CN B2007100491709A CN 200710049170 A CN200710049170 A CN 200710049170A CN 100519425 C CN100519425 C CN 100519425C
- Authority
- CN
- China
- Prior art keywords
- ball
- vanadium pentoxide
- precipitation
- exchange
- vanadium
- 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.)
- Expired - Fee Related
Links
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003245 coal Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000004575 stone Substances 0.000 title claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 42
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 29
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005342 ion exchange Methods 0.000 claims abstract description 23
- 238000002386 leaching Methods 0.000 claims abstract description 17
- 230000009615 deamination Effects 0.000 claims abstract description 5
- 238000006481 deamination reaction Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 25
- 210000000988 bone and bone Anatomy 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 239000000292 calcium oxide Substances 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 19
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 13
- 239000001110 calcium chloride Substances 0.000 claims description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000001117 sulphuric acid Substances 0.000 claims description 12
- 235000011149 sulphuric acid Nutrition 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 230000002308 calcification Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 241001234523 Velamen Species 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 229920001429 chelating resin Polymers 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 9
- 239000003456 ion exchange resin Substances 0.000 description 9
- 229920003303 ion-exchange polymer Polymers 0.000 description 9
- -1 phosphate radical Chemical class 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 235000011194 food seasoning agent Nutrition 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910001456 vanadium ion Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for extracting vanadium pentoxide from stone coal ores, which comprises the following steps: calcifying roasting, acid leaching, ion exchange, vanadium precipitation and roasting deamination. The method has the advantages that: short production period, simple process, easy operation, high purity of vanadium pentoxide product which can reach more than 99.0 percent, low production cost and suitability for large-scale production.
Description
Technical field
The present invention relates to the Vanadium Pentoxide in FLAKES production method, especially from the production method of extracting vanadium pentoxide from stone coal.
Background technology
Provinces and regions such as China Hunan, Hubei Province, Zhejiang, Anhui contain carbon shale (being called for short the bone coal ore deposit), and proven reserve are 618.8 * 10
8T, it is many between 0.3%～1.0% that it contains the Vanadium Pentoxide in FLAKES grade, the total reserves 117690kt of Vanadium Pentoxide in FLAKES, account for more than 85% of China's vanadium total reserves, vanadium in the regional bone coal of the overwhelming majority ore deposit all is based on the insoluble trivalent of stable soda acid, so it is bigger to put forward the Vanadium Pentoxide in FLAKES technical difficulty.
Application number is that CN90105503.4 has reported the method for extracting Vanadium Pentoxide in FLAKES from navajoite stone, and this method vanadium leachate adopts abstraction technique, method more complicated.Application number is that CN91102560.X has reported that hydrofluoric acid decomposes the method that the bone coal ore deposit produces Vanadium Pentoxide in FLAKES, and this preparation method's shortcoming is a hydrofluoric acid cost height, and human body is had bigger toxicity, and is extremely strong to the corrodibility of equipment.
In order to overcome the problems referred to above, application number is that CN200510032012.3 has reported the method for extracting Vanadium Pentoxide in FLAKES from navajoite stone, and this method comprises that calcification baking, dilute sulfuric acid, the purification of vanadium liquid, ion-exchange, pyrolysis deamination make V
2O
5Purify although this technical scheme before entering ion exchange column, has been carried out vanadium liquid, and regulate the pH value, free liquid and adopted sodium hydroxide, gained V to 2.0-3.0
2O
5Purity is still not high enough.
Summary of the invention
Technical problem solved by the invention is to provide a kind of production method from extracting vanadium pentoxide from stone coal.The Vanadium Pentoxide in FLAKES purity that this method is with short production cycle, production method simple, extract can be up to more than 99.0%.
The production method of extraction Vanadium Pentoxide in FLAKES provided by the invention comprises that calcification baking, acidleach, ion-exchange, precipitation, roasting deamination make V
2O
5Specifically may further comprise the steps:
A, calcification baking: bone coal ore deposit, calcium oxide and coal-fired ground and mixed is even, add water and make ball, and be 800 ℃～980 ℃ having under the oxygen atmosphere in temperature, promptly got ripe ball in roasting 1h～6h hour;
Wherein, the consumption of calcium oxide is 4%～15% of a bone coal mineral amount, and coal-fired consumption is 5%～40% of a bone coal mineral amount;
B, acidleach: the ripe ball that a step is obtained add concentration be 10%～25% sulphuric acid soln soak leach liquor, reach at 1.5～5.0 o'clock in pH of leaching solution, leach liquor is filtered, to remove solid impurity or suspended substance is standby;
C, ion-exchange: the filtrate that the b step obtains is carried out ion-exchange by macropore weak base type ion exchange resin, and the metavanadic acid velamen is adsorbed on the ion exchange resin, and other ion enters exchange liquid;
Mixed solution with 1～5mol/L ammonium chloride and 0.1～3mol/L ammoniacal liquor is a strippant, and the ion exchange resin that is adsorbed with the metavanadic acid root is carried out desorb, obtains stripping liquid;
D, precipitation: in the stripping liquid that the c step obtains, add precipitation agent precipitation, filter the thick vanadium that obtains;
E, smart vanadium: the thick vanadium of d step gained with the dissolving of 1～10% sodium hydroxide solution, is added calcium chloride and stirs, filter, in filtrate, add precipitation agent precipitation, filter and collect filter cake;
F, roasting deamination: in 450 ℃～600 ℃ roastings, obtain Vanadium Pentoxide in FLAKES behind the filtration cakes torrefaction that step e is obtained.Particular flow sheet such as Fig. 1.
If powder size is excessive, then mixing of materials is inhomogeneous among the technique scheme step a; Undersized is then to the equipment requirements height.If the spherolite footpath of making behind the ball is excessive, then reaction is not exclusively leached difficulty in roasting process; If particle diameter is too small, then makes the ball difficulty and increase calcination operation difficulty in flat kiln.Through experiment showed, that repeatedly powder size is preferably 74 μ m～250 μ m, make the particle diameter 0.1mm～20mm preferably behind the ball.The roasting optimum temps is 920 ℃～960 ℃, and the time is 3h～5h.
If it is low excessively to be used to soak the sulphuric acid soln concentration of ripe ball among the step b, then leaching effect is bad, if excessive concentration, meeting acidolysis such as a large amount of impurity elements such as Fe, Al, Ni, Si in the mineral and consume sulfuric acid, the amount of impurity element can increase greatly in the leach liquor simultaneously, purifies difficulty and increases.If pH of leaching solution is lower than 1.5, then do not reach the requirement of ion exchange resin to exchange liquid pH value, can not directly enter ion exchange column and carry out ion-exchange, this leach liquor is repeated to soak other ripe ball, between being in 1.5～5.0, leach liquor pH carries out ion-exchange step, so promptly improve the vitriolic utilization ratio, regulated the pH value of leach liquor again.
Vanadium exists with the anionic group form in the leach liquor, and particle diameter is bigger, so need to adopt macroporous type anionite-exchange resin.When pH of leaching solution 1.5 when following, vanadium exists with the form of cation group.In order to adopt anionite-exchange resin absorption vanadium negatively charged ion, the pH value of leach liquor need be adjusted to more than 1.5.Different resins requires different to the height of exchange liquid sour environment pH value, if the pH value that requires leach liquor is more than 2.0, just need adjust the pH value of leach liquor, and pH of leaching solution is being carried out adjustment process, the part metals positively charged ion can generate with sedimentary form, have a large amount of precipitation of silica simultaneously and generate, the vanadium negatively charged ion can be adsorbed by these precipitations, thereby the loss of vanadium occurs.Under 1.5 condition, carry out ion-exchange and resin of the present invention can satisfy pH of leaching solution fully, therefore, can adjust the pH value of leach liquor.In addition, at the ion-exchange initial stage, the pH value of leach liquor rises gradually, has partly precipitated and produces and rest in the resin, might influence resin to the anionic absorption of vanadium.And ion exchange resin AMBERLITE IRA96RF of the present invention, AMBERLITE IRA96CRF are macropore weak base type, are produced by Rhom and Hass.Its precursor structure is vinylbenzene/divinylbenzene copolymer, the functional group is a tertiary amine, has the reversibility rate of expansion of stable structure body and limitation, because the structure of resin itself, the precipitation that the duct of resin is difficult for being produced is stopped up, and water also is easy to precipitation is cleared out from resin.
In actual production, can adopt the mode of continuous-flow type to soak ripe ball: promptly the sulphuric acid soln of new preparation is used for the immersion once more of ripe ball, and the leach liquor behind the immersion certain hour is used to soak new ripe ball.Adopt such immersion way, compare, can significantly improve leaching effect, reduce acid consumption with immersion way repeatedly.
Ammonium meta-vanadate in the thick vanadium that steps d obtains contains a lot of impurity such as SiO
2, phosphoric acid salt etc.Smart vanadium step: the ammonium meta-vanadate precipitation is dissolved with 1～10% sodium hydroxide solution, adds calcium chloride and stirs impurity such as solids removed by filtration silicon and phosphorus.The amount that adds calcium chloride is determined according to the amount of phosphate radical.
If phosphorus content is too high in the vanadium product, quality does not conform to the GB requirement, and phosphorus can seriously influence the quality of product when then using in metallurgical industry.The present invention to the vanadium crude product refining that obtains after, the purity height is up to state standards fully.In soaking operation, impurity such as silicate in the ripe ball and phosphoric acid salt enter leach liquor.Because anionite-exchange resin has the absorption of selectivity and priority to anionic group, during ion-exchange, the selected ion exchange resin of the present invention is with preferentially adsorbed vanadium anionic group.Therefore, have only the silicate of minute quantity and phosphate anion to be adsorbed on the resin, when desorb and precipitation, enter in the ammonium meta-vanadate precipitation.In the smart vanadium step, when adding sodium hydroxide and calcium chloride dephosphorization, SiO
2Precipitation is not reacted with sodium hydroxide, can remove with insoluble phosphate when filtering.
In order to save production cost, the exchange liquid among the technique scheme step c can add sulfuric acid and turn back to acidleach operation b and soak ripe ball.Above-mentioned steps d filters gained filtrate and can add ammonium chloride and ammoniacal liquor and return step c and make strippant and use.
The inventive method advantage:
(1) uses the inventive method, three-waste free discharge;
(2) because the ion exchange resin of the inventive method has been selected AMBERLITE IRA96RF or AMBERLITE IRA96CRF for use, so just saved the step of purification of vanadium liquid and adjustment pH value, operation is simplified;
(3) the inventive method is in the step of precipitation, adopted first heavy thick vanadium, dissolve thick vanadium after, the method for heavy smart vanadium again is so the Vanadium Pentoxide in FLAKES product purity height of producing can reach more than 99.0%;
(4) raffinate behind exchange liquid and the heavy Vanadium Pentoxide in FLAKES can recycle, and production cost is low, is suitable for very much scale operation.
Description of drawings
Fig. 1 carries the Vanadium Pentoxide in FLAKES method flow diagram for the bone coal ore deposit.
Embodiment
The hard coal of the calcium oxide of exsiccant bone coal ore deposit and bone coal mineral amount 4%～15%, bone coal mineral amount 5%～40% is mixed together grinding, and evenly to make granularity be 74 μ m～250 μ m powder, and it is 0.1mm～20mm pellet after drying that the water that adds mixture quality 10%～20% in compound is made diameter; Dried pellet is placed flat kiln or rotary kiln, have under the oxygen atmosphere, 800 ℃～1000 ℃ roasting 1h～6h of temperature get ripe ball.Low price vanadium ion in the mineral (mainly being trivalent vanadium ion) is oxidized to the high price vanadium ion, high price vanadium ion and calcium oxide effect generate metavanadic acid calcium, place air to be cooled to room temperature in the ripe ball of roasting, add sulphuric acid soln soak leach liquor, its main chemical reactions formula is as follows:
Ca(VO
3)
2+SO
4 2-＝CaSO
4↓+VO
3 2-
When pH of leaching solution is in 1.5～5.0, to filter, filtrate enters ion exchange resin and carries out ion-exchange, obtains exchanging liquid; The resin that is adsorbed with the metavanadic acid root as the strippant desorb, obtains stripping liquid with 1～5mol/L ammonia chloride and 0.1～3mol/L ammonia water mixture.In the ion exchange resin desorption process, the ammonium root can react with the metavanadic acid radical ion of separating sucking-off and generate the ammonium meta-vanadate precipitation, but this can not influence the desorb of resin, and this precipitation can together flow out ion exchange column along with stripping liquid, enters heavy Vanadium Pentoxide in FLAKES groove.In stripping liquid, add the precipitation agent precipitation that contains the ammonium root, filter and obtain filtrate I and filter cake I; Filtrate I adding ammonium chloride and ammoniacal liquor return makes strippant usefulness, filter cake I dissolves with sodium hydroxide solution, add calcium chloride, stir, filter, obtain filtrate II and enter heavy Vanadium Pentoxide in FLAKES groove, in filtrate II, add the precipitation agent precipitation that contains the ammonium root, as in ammoniacal liquor, ammonium chloride, the ammonium sulfate etc. one or more, filter and obtain filter cake II; With filter cake II drying, be 400 ℃～600 ℃ roasting 20min～90min in temperature, obtain the Vanadium Pentoxide in FLAKES of purity 〉=99.0%, the main chemical reactions formula is as follows:
3Ca
2++2PO
3 3-＝Ca
3(PO
3)
2↓ NH
4 ++VO
3 -＝NH
4VO
3↓
2NH
4VO
3=V
2O
5+ 2NH
3Individual+H
2O
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
In 2000g exsiccant bone coal ore deposit, add 120g calcium oxide (CaO 〉=90%), 100g hard coal (C 〉=80%), grinding mixes, add 200g water and make ball, spherical diameter is about 20mm, puts into the high temperature kiln roasting that communicates with air, 980 ℃ of maturing temperatures after placing the air seasoning, roasting time 3h gets ripe ball, place air to be cooled to room temperature ripe ball taking-up, be equally divided into two parts, be designated as ripe ball I and ripe ball II respectively.With 1060g concentration is that 10% sulphuric acid soln soaks ripe ball I, soak 48h after, again the leach liquor that obtains is soaked ripe ball II, reach 1.5 up to pH of leaching solution, filter, filtrate is carried out ion-exchange with AMBERLITE IRA96RF anionite-exchange resin, after resin absorption is saturated, use 1.5mol/L NH
4The NH of Cl and 0.2mol/L
3H
2The O mixing solutions carries out desorb.In stripping liquid, add the ammoniacal liquor precipitation, filter, with the filter cake dissolving that obtains, add calcium chloride 5g again with sodium hydroxide solution, stir, filter, filtrate is used ammoniacal liquor precipitation, filtration cakes torrefaction again, at 450 ℃ of following calcination 30min, obtain the powdery Vanadium Pentoxide in FLAKES, purity is 99.1%, and the yield of omnidistance vanadium is 55.2%.
Embodiment 2
In 2000g exsiccant bone coal ore deposit, add 160g calcium oxide (CaO 〉=90%), 200g hard coal (C 〉=80%), grinding mixes, add 260g water and make ball, spherical diameter is about 15mm, puts into the high temperature kiln roasting that communicates with air, 950 ℃ of maturing temperatures after placing the air seasoning, roasting time 4h gets ripe ball, place air to be cooled to room temperature ripe ball taking-up, be equally divided into two parts, be designated as ripe ball I and ripe ball II respectively.With 1060g concentration is that 15% sulphuric acid soln is when soaking ripe ball I, after soaking 48h, again the leach liquor that obtains is soaked ripe ball II, reach 2.0 up to pH of leaching solution, filter, filtrate is carried out ion-exchange with AMBERLITE IRA96CRF anionite-exchange resin, after resin absorption is saturated, uses 2mol/L NH
4The NH of Cl and 0.5mol/L
3H
2The O mixing solutions carries out desorb.The mixed solution precipitation precipitation that in stripping liquid, adds ammoniacal liquor and ammonium chloride, filter, with the filter cake dissolving that obtains, add calcium chloride 4g again with sodium hydroxide solution, stir, filter, filtrate is used the mixed solution precipitation of ammoniacal liquor and ammonium chloride, filtration cakes torrefaction again, at 500 ℃ of following calcination 40min, obtain the powdery Vanadium Pentoxide in FLAKES, purity is 99.2%, and the yield of omnidistance Vanadium Pentoxide in FLAKES is 56.5%.
Embodiment 3
In 3000g exsiccant bone coal ore deposit, add 300g calcium oxide (CaO 〉=90%), 450g hard coal (C 〉=80%), grinding mixes, add 450g water and make ball, spherical diameter is about 12mm, puts into the high temperature kiln roasting that communicates with air, 960 ℃ of maturing temperatures after placing the air seasoning, roasting time 5h gets ripe ball, place air to be cooled to room temperature ripe ball taking-up, be equally divided into three parts, be designated as ripe ball I, ripe ball II and ripe ball III respectively.With 2000g concentration is that 20% sulphuric acid soln soaks ripe ball I, soak 48h, again the leach liquor that obtains is soaked ripe ball II, behind the 24h, soak ripe ball III again, reach 3.0 up to pH of leaching solution, filter, filtrate is carried out ion-exchange with AMBERLITE IRA96RF anionite-exchange resin, after resin absorption is saturated, uses 2.5mol/L NH
4The NH of Cl and 0.8mol/L
3H
2The O mixing solutions carries out desorb.The mixed solution precipitation that in stripping liquid, adds ammoniacal liquor and ammonium sulfate, filter, with the filter cake dissolving that obtains, add calcium chloride 6g again with sodium hydroxide solution, stir, filter, filtrate is used the mixed solution precipitation of ammoniacal liquor and ammonium sulfate, filtration cakes torrefaction again, at 550 ℃ of following calcination 50min, obtain the powdery Vanadium Pentoxide in FLAKES, purity is 98.6%, and the yield of omnidistance Vanadium Pentoxide in FLAKES is 56.7%.
Embodiment 4
In 3000g exsiccant bone coal ore deposit, add 450g calcium oxide (CaO 〉=90%), 150g hard coal (C 〉=80%), grinding mixes, add 450g water and make ball, spherical diameter is about 8mm, puts into the high temperature kiln roasting that communicates with air, 800 ℃ of maturing temperatures after placing the air seasoning, roasting time 6h gets ripe ball, place air to be cooled to room temperature ripe ball taking-up, be equally divided into three parts, be designated as ripe ball I, ripe ball II and ripe ball III respectively.With 3200g concentration is that 20% sulphuric acid soln soaks ripe ball I, soak 48h, again the leach liquor that obtains is soaked ripe ball II, behind the 24h, soak ripe ball III again, reach 4.0 up to pH of leaching solution, filter, filtrate is carried out ion-exchange with AMBERLITE IRA96RF anionite-exchange resin, after resin absorption is saturated, uses 3mol/L NH
4The NH of Cl and 0.9mol/L
3H
2The O mixing solutions carries out desorb.In stripping liquid, add the ammoniacal liquor precipitation, filter, with the filter cake dissolving that obtains, add calcium chloride 8g again with sodium hydroxide solution, stir, filter, filtrate is used ammoniacal liquor precipitation, filtration cakes torrefaction, at 550 ℃ of following calcination 40min, obtain the powdery Vanadium Pentoxide in FLAKES, purity is 99.0%, and the yield of omnidistance Vanadium Pentoxide in FLAKES is 46.2%.
Embodiment 5
In 3000g exsiccant bone coal ore deposit, add 240g calcium oxide (CaO 〉=90%), 900g hard coal (C 〉=80%), grinding mixes, add 450g water and make ball, spherical diameter is about 5mm, puts into the high temperature kiln roasting that communicates with air, 850 ℃ of maturing temperatures after placing the air seasoning, roasting time 4h gets ripe ball, place air to be cooled to room temperature ripe ball taking-up, be equally divided into three parts, be designated as ripe ball I, ripe ball II and ripe ball III respectively.With 4000g concentration is that 25% sulphuric acid soln soaks ripe ball I, after soaking 48h, again the leach liquor that obtains is soaked ripe ball II, behind the 24h, soak ripe ball III again, reach 3.0 up to pH of leaching solution, filter, filtrate is carried out ion-exchange with AMBERLITE IRA96RF anionite-exchange resin, after resin absorption is saturated, uses 4mol/L NH
4The NH of Cl and 1.0mol/L
3H
2The O mixing solutions carries out desorb.In stripping liquid, add the ammoniacal liquor precipitation, filter, with the filter cake dissolving that obtains, add calcium chloride 10g again with sodium hydroxide solution, stir, filter, filtrate is used ammoniacal liquor precipitation, filtration cakes torrefaction again, at 550 ℃ of following calcination 40min, obtain the powdery Vanadium Pentoxide in FLAKES, purity is 99.5%, and the yield of omnidistance Vanadium Pentoxide in FLAKES is 48.5%.
Embodiment 6
In 3000g exsiccant bone coal ore deposit, add 240g calcium oxide (CaO 〉=90%), 1200g hard coal (C 〉=80%), grinding mixes, add 360g water and make ball, spherical diameter is about 2mm, puts into the high temperature kiln roasting that communicates with air, 900 ℃ of maturing temperatures after placing the air seasoning, roasting time 3.5h gets ripe ball, place air to be cooled to room temperature ripe ball taking-up, be equally divided into three parts, be designated as ripe ball I, ripe ball II and ripe ball III respectively.With 3200g concentration is that 15% sulphuric acid soln soaks ripe ball I, soak 48h, again the leach liquor that obtains is used to soak ripe ball II, behind the 48h, soak ripe ball III again, reach 5.0 up to pH of leaching solution, filter, filtrate is carried out ion-exchange with AMBERLITE IRA96CRF anionite-exchange resin, after resin absorption is saturated, uses 4.5mol/L NH
4The NH of CI and 0.8mol/L
3H
2The O mixing solutions carries out desorb.In stripping liquid, add ammoniacal liquor and ammonium chloride precipitation, filter, with the filter cake dissolving that obtains, add calcium chloride 8g again with sodium hydroxide solution, stir, filter, filtrate is used ammoniacal liquor and ammonium chloride precipitation, filtration cakes torrefaction again, at 550 ℃ of following calcination 30min, obtain the powdery Vanadium Pentoxide in FLAKES, purity is 99.1%, and the yield of omnidistance Vanadium Pentoxide in FLAKES is 57.3%.
Embodiment 7
In 2000g exsiccant bone coal ore deposit, add 80g calcium oxide (CaO 〉=90%), 800g hard coal (C 〉=80%), grinding mixes, add 360g water and make ball, spherical diameter is about 0.5mm, puts into the high temperature kiln roasting that communicates with air, 920 ℃ of maturing temperatures after placing the air seasoning, roasting time 3h gets ripe ball, place air to be cooled to room temperature ripe ball taking-up, be equally divided into two parts, be designated as ripe ball I and ripe ball II respectively.With 2200g concentration is that 15% sulphuric acid soln soaks ripe ball I, soaks 24h, and the leach liquor that obtains soaks ripe ball II again, after pH of leaching solution reaches 1.5, to filter, filtrate is carried out ion-exchange with AMBERLITE IRA96RF anionite-exchange resin, after resin absorption is saturated, use 3.5mol/L NH
4The NH of Cl and 0.5mol/L
3H
2The O mixing solutions carries out desorb.In stripping liquid, add the ammoniacal liquor precipitation, filter, with the filter cake dissolving that obtains, add calcium chloride 15g again with sodium hydroxide solution, stir, filter, filtrate is used ammoniacal liquor precipitation, filtration cakes torrefaction again, at 600 ℃ of following calcination 30min, obtain the powdery Vanadium Pentoxide in FLAKES, purity is 99.6%, and the yield of omnidistance Vanadium Pentoxide in FLAKES is 56.4%.
Claims (4)
1, from the method for extracting vanadium pentoxide from stone coal, may further comprise the steps:
A, calcification baking: it is 74 μ m～250 μ m that bone coal ore deposit, calcium oxide and fire coal are ground to powder size, mix, add water and make ball, make that the particle diameter of ball is 0.1mm～20mm behind the ball, and be 800 ℃～980 ℃ having under the oxygen atmosphere in temperature, promptly got ripe ball in roasting 1h～6h hour;
Wherein, the consumption of calcium oxide is 4%～15% of a bone coal mineral amount, and coal-fired consumption is 5%～40% of a bone coal mineral amount;
B, acidleach: the ripe ball that a step is obtained add concentration be 10%～25% sulphuric acid soln soak leach liquor, reach at 1.5～5.0 o'clock in pH of leaching solution, filter and obtain filtrate for later use;
C, ion-exchange: the filtrate that the b step obtains is carried out ion-exchange by macropore weak base type anionite-exchange resin, and the metavanadic acid velamen is adsorbed on the anionite-exchange resin, and other ion enters exchange liquid;
Adopting the mixed solution of 1～5mol/L ammonium chloride and 0.1～3mol/L ammoniacal liquor is strippant, and the anionite-exchange resin that is adsorbed with the metavanadic acid root is carried out desorb, obtains stripping liquid;
D, precipitation: in the stripping liquid that the c step obtains, add precipitation agent precipitation, filter and obtain thick vanadium;
E, smart vanadium: the thick vanadium of d step gained dissolves with 1～10% sodium hydroxide solution, adds calcium chloride and stirs, and filters, and adds precipitation agent precipitation in filtrate, and filter cake is collected in filtration;
F, roasting deamination: in 450 ℃～600 ℃ roastings, obtain Vanadium Pentoxide in FLAKES behind the filtration cakes torrefaction that step e is obtained.
2, the method from extracting vanadium pentoxide from stone coal according to claim 1 is characterized in that: maturing temperature is 920 ℃～960 ℃ among the step a, and roasting time is 3h～5h.
3, the method from extracting vanadium pentoxide from stone coal according to claim 1 is characterized in that: the acidleach among the step b adopts continuous-flow type to soak.
4, the method from extracting vanadium pentoxide from stone coal according to claim 1 is characterized in that: the exchange liquid among the step c adds sulfuric acid and turns back to the acidleach operation and soak ripe ball.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100491709A CN100519425C (en) | 2007-05-25 | 2007-05-25 | Process for Extracting Vanadium Pentoxide from Stone Coal Mine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100491709A CN100519425C (en) | 2007-05-25 | 2007-05-25 | Process for Extracting Vanadium Pentoxide from Stone Coal Mine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101066778A CN101066778A (en) | 2007-11-07 |
| CN100519425C true CN100519425C (en) | 2009-07-29 |
Family
ID=38879500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100491709A Expired - Fee Related CN100519425C (en) | 2007-05-25 | 2007-05-25 | Process for Extracting Vanadium Pentoxide from Stone Coal Mine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100519425C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194611A (en) * | 2013-04-01 | 2013-07-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing vanadium oxide |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265524B (en) * | 2008-04-17 | 2010-10-06 | 武汉科技大学 | Method for extracting V2O5 from stone coal |
| CN101586196B (en) * | 2008-05-23 | 2010-11-17 | 湖南金大地材料股份有限公司 | Vanadium-extracting process by blank roasting alkali leaching ion exchange method |
| CN101412539B (en) * | 2008-11-18 | 2010-12-08 | 攀钢集团研究院有限公司 | Clean production process for vanadium oxide |
| CN101402470B (en) * | 2008-11-18 | 2010-06-09 | 攀钢集团研究院有限公司 | Process for producing vanadium oxide for implementing wastewater circulation with ionic exchange |
| CN101532086B (en) * | 2009-03-13 | 2011-03-23 | 攀钢集团研究院有限公司 | A vanadium-containing resin desorption method |
| CN101597697B (en) * | 2009-06-29 | 2011-06-15 | 湘潭大学 | Clean manufacturing technique of extracting vanadium pentoxide from vanadium-contained stone coal |
| CN102828019A (en) * | 2012-08-21 | 2012-12-19 | 攀钢集团研究院有限公司 | Method for oxygen-enriched calcification calcination of high-grade vanadium slag |
| CN105331832A (en) * | 2015-11-27 | 2016-02-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Acid-leaching washing method for vanadium-containing roasting clinker |
| CN106755957A (en) * | 2016-11-30 | 2017-05-31 | 武汉科技大学 | A kind of method that utilization calcium additive extracts vanadium from Rock coal containing alum |
| CN109706329A (en) * | 2018-12-27 | 2019-05-03 | 大连博融新材料有限公司 | A kind of method that extracting vanadium from stone coal prepares ammonium metavanadate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039582A (en) * | 1975-12-29 | 1977-08-02 | Gakif Zakirovich Nasyrov | Method of preparing vanadium pentoxide |
| CN1184162A (en) * | 1996-12-06 | 1998-06-10 | 湖南省安化县东坪钒冶炼厂 | Vanadium pentoxide extracting method from stone coal vanadium ore |
| CN1724387A (en) * | 2005-06-22 | 2006-01-25 | 株洲市湘麒科技开发有限公司 | Process for extracting vanadium pentoxide from stone coal vanadium mining |
| CN1752022A (en) * | 2005-08-12 | 2006-03-29 | 岳阳市中湘实业有限公司 | Method of extracting vanadium pentoxide from vanadium ore |
-
2007
- 2007-05-25 CN CNB2007100491709A patent/CN100519425C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039582A (en) * | 1975-12-29 | 1977-08-02 | Gakif Zakirovich Nasyrov | Method of preparing vanadium pentoxide |
| CN1184162A (en) * | 1996-12-06 | 1998-06-10 | 湖南省安化县东坪钒冶炼厂 | Vanadium pentoxide extracting method from stone coal vanadium ore |
| CN1724387A (en) * | 2005-06-22 | 2006-01-25 | 株洲市湘麒科技开发有限公司 | Process for extracting vanadium pentoxide from stone coal vanadium mining |
| CN1752022A (en) * | 2005-08-12 | 2006-03-29 | 岳阳市中湘实业有限公司 | Method of extracting vanadium pentoxide from vanadium ore |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194611A (en) * | 2013-04-01 | 2013-07-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing vanadium oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101066778A (en) | 2007-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100519425C (en) | Process for Extracting Vanadium Pentoxide from Stone Coal Mine | |
| CN103667710B (en) | Technology for clean production of vanadium pentoxide employing high-calcium vanadium slag | |
| CN102080157B (en) | Method for decomposing scheelite | |
| CN100560757C (en) | A kind of process for extracting vanadium by stone coal wet method | |
| CN102534187B (en) | Method for treating pyrite cinder by combining acidic leaching with alkaline dissolving | |
| CN102828025B (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN104152687B (en) | Aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale | |
| CN100392124C (en) | Method of retrieving magnesium from high magnesium phosphorus ore | |
| CN102021329B (en) | Method for extracting tungsten from scheelite and producing high-quality calcined gypsum | |
| CN102432071B (en) | Method for integrally utilizing high-iron-content bauxite | |
| CN101597688A (en) | From phosphogypsum, reclaim a kind of method of rare earth | |
| CN103395796B (en) | Comprehensive utilization method of serpentine and device used by method | |
| CN107352524A (en) | A kind of recovery method of waste lithium iron phosphate positive electrode | |
| CN102992284B (en) | High-magnesium phosphorite de-magging method with by-product magnesium ammonium phosphate | |
| CN101386909A (en) | Method for extracting rare-earth from ardealite | |
| CN105132696A (en) | Method for extracting vanadium and removing phosphorus from high-calcium high-phosphorus vanadium slag | |
| CN107814370B (en) | Circulating environment-friendly process method for preparing phosphate concentrate, product and application thereof | |
| CN101440430A (en) | Method for recycling rare earth from phosphogypsum leaching solution by fluoride precipitation method | |
| CN103073034B (en) | Method for removing magnesium from ultralow-quality phosphate rock and producing magnesium hydroxide | |
| CN110002421B (en) | Method for preparing battery-grade iron phosphate by using sulfuric acid residues | |
| CN101186284A (en) | Method for preparing phosphoric acid from phosphorus block ore by wet method and extracting rare earth from phosphorus block ore | |
| CN105039746A (en) | Method for directly extracting high-purity vanadium pentoxide from stone coal vanadium ore | |
| CN105154689A (en) | Method for separation and enrichment of rare earth in phosphorite | |
| CN102828034B (en) | Method for producing high-purity zinc oxide through decarbonization on low-grade zinc oxide ore by adopting ammonia process | |
| CN101597687A (en) | The sulfuric acid rare earth that goes out from the phosphogypsum leaching solution crystallization is converted into the method for rare earth chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090729 Termination date: 20160525 |