CN104988337B - The bone coal navajoite extract technology that a kind of spent acid recycles - Google Patents
The bone coal navajoite extract technology that a kind of spent acid recycles Download PDFInfo
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- CN104988337B CN104988337B CN201510310672.7A CN201510310672A CN104988337B CN 104988337 B CN104988337 B CN 104988337B CN 201510310672 A CN201510310672 A CN 201510310672A CN 104988337 B CN104988337 B CN 104988337B
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Abstract
The bone coal navajoite extract technology that a kind of spent acid recycles, recycle, neutralize by broken ore grinding, high acidic oils, separation of solid and liquid, spent acid successively, extract and being stripped and precipitation step, finally giving ammonium metavanadate product；The separation of solid and liquid that mother liquor wherein in precipitation step returns to terminates link circulation and is neutralized, extracted and be stripped and precipitation step；The leached mud of separation of solid and liquid and the extraction water of extraction and back extraction generation enter Tailings Dam after carrying out sewage neutralization；Broken also to include belt type filter and filter cake slurrying between ore grinding and high acidic oils, belt type filter is arranged at before filter cake slurrying；Separation of solid and liquid includes the 1 grade of dense dense washing separation of solid and liquid of separation of solid and liquid and Pyatyi sequentially arranged, and the clear liquid of 1 grade of dense separation of solid and liquid returns to filter cake slurrying and recycled.The present invention greatly reduces the dosage of sulfuric acid, has saved cost, reduce the harm to environment on the premise of leaching rate is ensured.
Description
Technical field
The invention belongs to metallurgical mineral products field, and in particular to the bone coal navajoite extract technology that a kind of spent acid recycles.
Background technology
The main preservation of vanadium in China's overwhelming majority bone coal is in mica-group clay minerals, and the overwhelming majority is with V (III)
Form is present in clay mineral sandwich of layers, and part substitutes Al (III), and this aluminosilicate structure is relatively stable, in usual bone coal
V (III) is difficult to by water, acid or alkali soluble solution；V (IV) is present very few in the primary sample of bone coal.The general principle of extracting vanadium from stone coal is：It is logical
Crossing leaching makes vanadium be entered by solid phase (bone coal or bone coal fired slags) in liquid phase (leachate), using hands such as extraction or ion exchanges
After section makes vanadium enrichment, using precipitation and crystallization technique, make vanadium by liquid-phase conversion be solid phase, vanadic anhydride is obtained after calcining and is produced
Product.From the point of view of technological process, it is related to being calcined, leaches, is enriched with (extraction or ion exchange) and four processing steps of precipitation, this four
The efficiency of individual step determines the height of vanadium overall recovery.Extraction, three processing steps of ion exchange and precipitation technically phase
To more ripe, vanadium loss is little, and therefore, the height of V leaching rate turns into the key determinant of vanadium overall recovery.
Improving the method for V leaching rate at present mainly has two kinds, and one kind is to carry out roasting pretreatment to navajoite, is then carried out
Acidleach or alkali leaching；Another kind is that high temperature peracid directly leaches.The selection of both approaches depends on the presence of vanadium in stone coal mine
Form.Vanadium in bone coal is mainly with class matter in-phase version preservation in roscoelite, hydromica, biotite, muscovite and illite
Deng in mica mineral, next to that with adsorbed state preservation in some organic carbonate minerals.If in stone coal mine vanadium mainly with
When mica mineral is main occurrence form, just roasting pretreatment-extract technology is used；If vanadium mainly using organic carbonaceous as
During main occurrence form, just high temperature peracid direct leaching process is used.
Bone coal roasting pretreatment method mainly has sodium-salt calcination, oxidizing roasting and a calcification baking, and sodium-salt calcination method is main
It is that sodium salt is added in roasting process, the difficult Low Valent Vanadium leached in stone coal mine is changed into the high price sodium vanadate easily leached.Oxidation roasting
Burning is that the Low Valent Vanadium in stone coal mine is changed into the V of high price in roasting process using the oxygen in air2O5.Calcium salt roasting be by
Vanadium is changed into the calcium vanadate of high price.In roasting process, in addition to valence state and the existence form transformation of vanadium, the mica in mineral
The structure of class mineral can also change, and the class matter of vanadium is destroyed with phase structure.
Roasting method is heated using fuel at present, consumes substantial amounts of fuel, while gives off substantial amounts of poisonous fume
And waste residue, environment is caused seriously to pollute.
Bone coal high temperature peracid direct leaching process is primarily adapted for use in the bone coal navajoite using adsorbed state as main occurrence form,
To not applied to substantially with the navajoite mutually for main occurrence status with class matter, this method is poor to the adaptability of mineral.In addition should
Method leaching process acid consumption is higher, and generally acid is consumed in the range of 15-20%, and, it is necessary to be entered with substantial amounts of lime in subsequent handling
Row neutralizes, and production cost is larger.But the technique biggest advantage is：There is no atmosphere pollution, waste water can circulate after treatment
Utilize, environmentally friendly low-carbon, technological process is short.
Bone coal navajoite Whote-wet method sulfuric acid leaching extraction vanadium extraction technology, carried out under conditions of high temperature, peracid, to ensure vanadium
Leaching rate, Leaching Systems must ensure enough acidity, and the dosage of sulfuric acid is very big in technical process, contains after leaching in leachate
Substantial amounts of spent acid, this is the basic reason for causing technique peracid to consume, and process costs are also very high.
The content of the invention
It is an object of the invention to provide the bone coal navajoite extract technology that a kind of spent acid recycles, and it is ensureing leaching rate
On the premise of, the dosage of sulfuric acid is greatly reduced, has saved cost, reduces the harm to environment.
The present invention technical solution be：
The bone coal navajoite extract technology that a kind of spent acid recycles, successively by broken ore grinding, high sulfuric acid leaching, solid-liquid point
Recycle, neutralize from, spent acid, extract with back extraction and precipitation step, finally give ammonium metavanadate product；Wherein precipitation step
In mother liquor return to separation of solid and liquid and terminate link circulation and neutralized, extracted and be stripped and precipitation step；The leaching of separation of solid and liquid
Slag tap and enter Tailings Dam after extracting the extraction water progress sewage neutralization with back extraction generation；It is characterized in that：It is described broken
Also include belt type filter and filter cake slurrying between comminution ore deposit and high sulfuric acid leaching, the belt type filter be arranged at filter cake slurrying it
Before；The separation of solid and liquid includes the 1 grade of dense dense washing separation of solid and liquid of separation of solid and liquid and Pyatyi sequentially arranged, described
The clear liquid of 1 grade of dense separation of solid and liquid returns to filter cake slurrying and recycled.
The milk of lime that above-mentioned neutralization includes sequentially arranging neutralizes to be neutralized with reduction.
The broken ore grinding of filtrate return after above-mentioned belt type filter terminates recycles.
Above-mentioned filter cake slurrying is specifically：It is dehydrated first with hydrocyclone eddy flow, then adds flocculant sedimentation, obtains concentration
More than 75% solid ore pulp, the flocculant are polyacrylamide.
Above-mentioned breakage parameter is that particle diameter is not more than -20mm；Ball mill parameter is that the mesh of particle diameter -80 accounts for more than 60%, ore pulp quality
Percent concentration is 65%.
The mode of above-mentioned separation of solid and liquid is separated using horizontal centrifuge.
Above-mentioned milk of lime neutralizes：After slurry is made in milk of lime, mass percent concentration is between 15%-30%, one
Individual 100m3 Neutralization chamber neutralize, neutralize the time typically in 20-30 minutes；It is described reduction neutralization be specifically：Using sodium thiosulfate
The aqueous solution is reduced, and the general recovery time is in 5-10 minutes.
Extracted during above-mentioned extraction with organic solvent, extraction process is that feed liquid containing vanadium presses certain quality with organic solvent
Than carrying out after being sufficiently mixed stirring, the mass ratio, which should ensure that, is fully transformed into the vanadium ion in feed liquid containing vanadium in organic solvent；
The organic solvent is： P-204+ TBP+ solvent naphthas form.
Carried out during above-mentioned back extraction with dilute sulfuric acid and organic solvent containing vanadium after being sufficiently mixed stirring, by the vanadium in organic solvent
Ion is transferred in dilution heat of sulfuric acid, is as stripped.
It is an advantage of the invention that：
1st, the engineering technology of ore pulp economical and efficient dehydration.
By hydrocyclone-Flocculating Settling Technology, the solid ore pulp of concentration more than 75% is obtained, is realized economical, high
The dehydration technique of effect.
2nd, the Returning utilization of spent acid.
The return of bone coal navajoite spent acid recycles, and cost is greatly lowered, and realizes energy-saving and emission-reduction.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Embodiment
Spent acid is leached it is contemplated that trying to recycle, raw ore is leached acid consumption reduces by 20%, reduces sulfuric acid dosage every year
40000 tons.Applicant is studied in terms of following two respectively：（1）The influence leached when same amount spent acid does not return to vanadium.
Due to containing various foreign ions in spent acid, certain influence will be produced to leaching, therefore, we are by respectively to leaching
Its influence of the return to vanadium extraction yield, and each spent acid back amount of research are studied when liquid directly returns, raffinate water returns to leaching
Influence, to utilize spent acid with it is expected amplitude peak, reduce acid consumption, reduce the generation and discharge of waste residue.（2）Spent acid, which returns, to be leached
The engineering chemistry database of process.As described above, to ensure the leaching rate of vanadium, leach and certain acidity is must assure that in ore pulp, but
In grinding process, because acid is by etching apparatus, so using clear water, spent acid is now directly returned, liquid-solid ratio will be increased, equally
The addition of acid will be increased, to ensure constant liquid-solid ratio, add spent acid again after ore grinding overflow must being carried out to efficient concentration dehydration, by
In mine mass produces the characteristics of, high efficiency, low cost is dehydrated into the key that engineering is implemented.We intend using hydraulic cyclone
Device high-efficiency dehydration, the technology of remaining mud flocculating setting carry out separation of solid and liquid, studies the running parameter and flocculant of hydrocyclone
Selection and settlement parameter.
Referring to Fig. 1, a kind of bone coal navajoite extract technology of spent acid recycling, successively by broken ore grinding, high-sulfur acidleach
Go out, separation of solid and liquid, neutralization, extraction and back extraction and precipitation step, finally give ammonium metavanadate product；Wherein in precipitation step
The separation of solid and liquid that mother liquor returns to terminates link circulation and is neutralized, extracted and be stripped and precipitation step；The leached mud of separation of solid and liquid
Enter Tailings Dam after carrying out sewage neutralization with the extraction water of extraction and back extraction generation；The broken ore grinding and high sulfuric acid leaching it
Between also include belt type filter and filter cake slurrying, the belt type filter is arranged at before filter cake slurrying；The separation of solid and liquid includes pressing
1 grade of dense dense washing separation of solid and liquid of separation of solid and liquid and Pyatyi of sequencing arrangement, the clear liquid of 1 grade of dense separation of solid and liquid
Filter cake slurrying is returned to recycle.
Applicant's research not influence of the same amount leachate spent acid return to leaching process, that is, keeping existing leaching bar
In the case that part is constant, with leach supernatant and by dehydration raw ore mixing it is with slurry leached, crude ore pulp abjection water
Ball mill is returned with raffinate water to use, and is chosen different leachate back amount respectively, is investigated the sulfuric acid under equal leaching condition
Dosage, investigate influence of the back amount to extract technology index.Optimal leachate back amount is determined by testing, determines optimised process
Parameter, on the premise of ensuring to leach index, amplitude peak reduces the dosage of sulfuric acid.By laboratory research, when leaching supernatant
When liquid back amount is 80%, 30% can be reduced by leaching process sulfuric acid dosage.On the basis of laboratory research, scene is proceeded by
Experiment, belt filter and ceramic filter filtering ore pulp is respectively adopted, supernatant is leached using thickening pond solid-liquor separation, from work
From the point of view of industry test situation, 50% leachate is returned to, raw ore per ton reduces by 35 kilograms of acid consumption, and average acid consumption reduces by 20%；Lime consumption
Averagely reduce by 21%；The water consumption of ball mill is by former 0.7m3/ ton ore deposit is reduced to 0.2 m3/ ton ore deposit.
From relatively inexpensive hydrocyclone predrainage technology, more than 85% ore in sand form is concentrated to by hydrocyclone
80% concentration, the sludge of remainder about 15% using flocculant flocculation-high-efficiency pipe chute settler sedimentation technology, sedimentation ore pulp with
Hydrocyclone sand setting merges the ore pulp for obtaining more than 75% solids-enriched and spent acid is combined into leaching operation, and recycle-water enters
Ore grinding system circulates.
The present invention calculates according to the treating capacity of the ton per day of design scale ore 800, five months, reduces by 4200 tons of sulfuric acid dosage；
Reduce by 4500 tons of lime consumption；60000 cubic metres of using water wisely；Reduce 8700 tons of waste sludge discharge.According to sulfuric acid, the current city of lime
Field low price skill is calculated, and is run over five months, is realized more than 4,500,000 yuan of direct economic benefit, and reduces waste residue and waste water row
Put, be advantageous to energy-saving and circulation sustainable development.
Overall leach, which can be achieved, in the present invention reduces acid consumption more than 20%；It can reduce 40,000 tons/year of sulfuric acid dosage, 40,000 tons of lime/
Year, yuan/year of material consumption 44,000,000 is saved, reduces 80,000 tons/year of waste sludge discharge, debris dump is reduced and is saved as this 800,000 yuan/year.
Claims (3)
1. the bone coal navajoite extract technology that a kind of spent acid recycles, successively by broken ore grinding, high acidic oils, separation of solid and liquid,
Neutralization, extraction and back extraction and precipitation step, finally give ammonium metavanadate product；
The separation of solid and liquid that mother liquor wherein in precipitation step returns to terminates link circulation and is neutralized, extracted and be stripped and precipitation step
Suddenly；
The leached mud of separation of solid and liquid and the extraction water of extraction and back extraction generation enter Tailings Dam after carrying out sewage neutralization；
It is characterized in that：Also include belt type filter and filter cake slurrying, the belt mistake between the broken ore grinding and high acidic oils
Filter is arranged at before filter cake slurrying；
The separation of solid and liquid includes the 1 grade of dense dense washing separation of solid and liquid of separation of solid and liquid and Pyatyi sequentially arranged, institute
The clear liquid return filter cake slurrying for stating 1 grade of dense separation of solid and liquid recycles；
The mode of the separation of solid and liquid is to use horizontal centrifuge or other separation equipments；The belt type filter terminate after filtrate
Broken ore grinding is returned to recycle；
The filter cake slurrying is specifically：It is dehydrated first with hydrocyclone eddy flow, then adds flocculant sedimentation, obtains concentration 75%
Solid ore pulp above, the flocculant is polyacrylamide；
Described neutralize neutralizes including the milk of lime neutralization sequentially arranged and reduction；
The milk of lime neutralizes：After slurry is made in milk of lime, mass percent concentration is between 15%-30%, at one
100m3 Neutralization chamber neutralize, the neutralization time is 20-30 minutes；It is described reduction neutralization be specifically：Using sodium thiosulfate solution
Reduced, the recovery time is 5-10 minutes；
The breakage parameter is that particle diameter is not more than -20mm；Ball mill parameter is that the mesh of particle diameter -80 accounts for more than 60%, ore pulp quality percentage
Specific concentration is 65%.
2. the bone coal navajoite extract technology that spent acid recycles according to claim 1, it is characterised in that：Used during the extraction
Organic solvent is extracted, and extraction process is that feed liquid containing vanadium is carried out being sufficiently mixed stirring with organic solvent by certain mass ratio
Afterwards, the mass ratio, which should ensure that, is fully transformed into the vanadium ion in feed liquid containing vanadium in organic solvent；The organic solvent is：
P-204+ TBP+ solvent naphthas form.
3. the bone coal navajoite extract technology that spent acid recycles according to claim 2, it is characterised in that：During the back extraction
Carried out with dilute sulfuric acid and organic solvent containing vanadium after being sufficiently mixed stirring, the vanadium ion in organic solvent is transferred to dilution heat of sulfuric acid
In, as it is stripped.
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| CN114950005A (en) * | 2022-06-29 | 2022-08-30 | 格林爱科(荆门)新能源材料有限公司 | Recovery system and recovery method for ternary positive electrode precursor production regeneration waste liquid |
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| CN101054630B (en) * | 2007-05-28 | 2011-10-19 | 德物华经济信息研究院有限公司 | Integrated treatment method for the three wastes generated form method of extracting vanadium pentoxide from stone-like coal navajoite |
| CN101215636B (en) * | 2008-01-11 | 2011-04-06 | 中南大学 | Stone coal sodication roasting and vanadium-extracting method |
| CN101580902B (en) * | 2008-05-16 | 2010-11-10 | 陕西五洲矿业有限公司 | Lime milk neutralization method acid dipping-extraction vanadium extraction technology |
| CN101323914A (en) * | 2008-07-29 | 2008-12-17 | 旺苍县振华矿业有限公司 | Process for extracting vanadic anhydride by high calcium calcination |
| CN102251103A (en) * | 2011-05-27 | 2011-11-23 | 保靖天瑞钒业有限公司 | Circulating graded leaching method of stone coal acid-leaching vanadium extraction sulfuric acid |
| CN102828025B (en) * | 2012-09-20 | 2014-04-16 | 长沙矿冶研究院有限责任公司 | Method for extracting V2O5 from stone coal navajoite |
| CN104099483A (en) * | 2013-04-11 | 2014-10-15 | 陕西五洲矿业股份有限公司 | Preparation method of highly pure vanadium pentoxide |
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