CN105256135B - Method for recovering phosphorus resource in high-phosphorus iron ore through ball-milling acid leaching-biological adsorption - Google Patents
Method for recovering phosphorus resource in high-phosphorus iron ore through ball-milling acid leaching-biological adsorption Download PDFInfo
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- CN105256135B CN105256135B CN201410265113.4A CN201410265113A CN105256135B CN 105256135 B CN105256135 B CN 105256135B CN 201410265113 A CN201410265113 A CN 201410265113A CN 105256135 B CN105256135 B CN 105256135B
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Abstract
The invention provides a method for recovering the phosphorus resource in high-phosphorus iron ore through ball-milling acid leaching-biological adsorption and belongs to the field of hydrometallurgy dephosphorization of the high-phosphorus iron ore. The method comprises the steps that biomass adsorbent materials are prepared by using biomass containing active functional group such as -COOH and -SH as raw materials, and the obtained biomass adsorbent materials are mixed with a zirconium oxychloride solution or a zirconium sulfate solution or a zirconium propoxide solution, so that corresponding negative zirconium absorbent materials are prepared; and high-phosphorus iron ore powder is added into a high-phosphorus iron ore acid leaching solution and mixed with acid-resistant steel balls to be subjected to ball milling after the pH value is adjusted, filtering is conducted after ball milling, iron ore powder is added in obtained filter liquor, filtering is conducted after the pH value is adjusted, the biomass adsorbent materials are added in the obtained filter liquor, stirring and filtering are conducted, the negative zirconium absorbent materials are added into the obtained filter liquor again, stirring and filtering are conducted, a high-concentration phosphate radical solution is condensed through evaporation after desorption, and thus crystalloid phosphate particles are obtained. According to the method, phosphorus is directly extracted from the acid leaching solution through selective adsorption by using the negative zirconium absorbent materials, and thus the grade of the extracted phosphorus is improved.
Description
Technical field
The present invention relates to high-phosphorus iron ore hydrometallurgy dephosphorization field, particularly relates to a kind of ball milling acidleach-biological adsorption and reclaims
The method of phosphor resource in high-phosphorus iron ore.
Background technology
In recent years, the drop phosphorus technical study of high-phosphorus iron ore becomes a hot subject of ferrous metallurgical industry.How economical,
Efficiently the phosphorus element content in iron ore is reduced, so as to reasonably using the high-phosphorus iron ore resource of flood tide, for iron and steel smelting
The sustainable development of metal working industry has great importance.
At present, the method for reducing phosphorus of the high-phosphorus iron ore studied has magnetic separation, flotation, pyrolytic semlting, wet-leaching and biology
The method of leaching.Magnetic separation and method for floating have the shortcomings that dephosphorization efficiency is low, the qualified iron mine response rate is low, not generally applicable
Process in the drop phosphorus of all kinds of high-phosphorus iron ores.Pyrolytic semlting rule is that dephosphorization under oxidizing atmosphere is carried out during steel-making, exist energy consumption compared with
The high, quantity of slag is larger, high cost shortcoming.And Bioleaching rule has the advantage of low cost, but drop phosphorus depth is limited, expends
Time it is longer, generally so that drop phosphorus efficiency it is low.Comparatively speaking, wet-leaching rule has obvious comprehensive advantage：
Acidleach drop phosphorus efficiency high, the short time, advantage of lower cost, process is simple, it is easily extensive implement, to the drop phosphorus of high-phosphorus iron ore at
The advantages of strong adaptability of reason, and become and study a kind of more method at present.
The ultimate principle of wet-method for leaching is, using the aqueous solution of acid reagent come the phosphoric acid in molten leaching high-phosphorus iron ore
Salt, so as to reduce the content of phosphorus in iron ore.According to it has been reported that acid reagent have nitric acid, hydrochloric acid and sulphuric acid, wherein nitric acid and
There is the shortcomings of price is high, readily volatilized, equipment corrosion is serious in hydrochloric acid, therefore acid most with practical value should be sulphuric acid.
At present about the research of the phosphorus in the molten leaching removing high-phosphorus iron ore of sulphuric acid, there are many reports, related leaching technology condition
Parameters optimization also determines that many experiments all confirm that dilute sulfuric acid solvent extraction method is a kind of the very effective of high-phosphorus iron ore drop phosphorus substantially
Process choice.Such as, Cheng Chuyong etc. is processed through preroast-acidleach to the high-phosphorus iron ore of Western Australia, can be by high-phosphorus iron ore
In phosphorus content be reduced significantly to qualified level, and the consumption acid cost of ore deposit per ton only about several Australian Dollars；Yu Jintao etc. is to west place in Hubei
High-phosphor oolitic Iron Ore Powder has carried out sulfuric acid leaching experiment, is 1 or so in pH, can show in the case where keeping the molten damage of ferrum relatively low
Writing reduces the content of phosphorus in iron mine.Phosphorus technique is dropped around this wet method acid immersion, the design of various optimizations has continuously emerged.Such as,
By the acid solution after molten leaching dephosphorization through mending after acid, the molten leaching dephosphorization treatment of iron ore is used further to, it is expected to fully improve the profit of acid
Use efficiency.After sufficient number of multistage acidleach is processed, high-phosphorus iron ore can reach the phosphorous requirement of Iron industry, but produce
A large amount of acid solution containing phosphate also always need to be processed, phosphorus especially therein needs open circuit to process.At present, around this problem
Solution, main method is that acid dip solution alkali (such as Calx) neutralization is changed into corresponding synthos for agriculturally
Fertilizer application, and the waste water after neutralizing then is arranged outward.This neutralization method is for the P elements reclaimed in pickle liquor, although method has
Effect, but there is also obvious shortcoming：1) substantial amounts of alkali to be expended, increased the cost of whole technique；2) neutralization precipitation is obtained
Synthos can contain substantial amounts of ferrum and other gangue contents, the content of phosphorus is often very low, can not sell high price, it is also possible to meeting
Side effect is produced during to which as Fertilizer application；3) pickle liquor does not obtain repeatedly utilizing as far as possible, so as to increased whole work
The cost of skill.
To solve problem above, the wet method acid immersion drop phosphorus totle drilling cost of high-phosphorus iron ore is significantly reduced, the invention discloses a kind of
Novel technical method, i.e.,：The acid leaching solution that high-phosphorus iron ore is obtained after the molten leaching drop phosphorus of dilute sulfuric acid is processed, through biological suction
Attached method directly in acid condition, is carried out adsorbing, is enriched with and obtains higher degree through desorbing to phosphate radical therein
Phosphate, and acid solution can direct Returning utilization, continue the phosphorus in molten leaching high-phosphorus iron ore.In order to accelerate and promote high-phosphorus iron ore
In phosphorus it is fully molten be dipped in acid solution, the invention also discloses a kind of technology of ball milling acidleach, can be by advance roasting
The high-phosphorus iron ore managed, or directly by high-phosphorus iron ore material, insert in special acidproof ball mill, after mixing with acid solution
Wet grinding mill leaching a period of time, suitably can also heat as needed, this method is different from traditional by ball milling and acidleach tandem
The effect of operation, but ball milling and acidleach are carried out simultaneously, molten leaching effect can be obviously improved.The enforcement of the new technique, it is expected to aobvious
Writing reduces the cost of existing wet method acid immersion dephosphorization method, lifts the technology of the phosphorus technique in whole wet method acid immersion removing high-phosphorus iron ore
Economic benefit and the market competitiveness.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of ball milling acidleach-biological adsorption and reclaims phosphor resource in high-phosphorus iron ore
Method.
The method is comprised the following steps that：
High-phosphorus iron ore is crushed to 80～200 mesh by step one, according to mass ratio 1:1～10 ratio is by high-phosphorus iron ore
Powder and high-phosphorus iron ore acidic leaching solution are mixed, and Deca dilute sulfuric acid makes pH value of solution maintain 0.5～1.2, by solution with it is resistance to
Sour steel ball is according to 5～25:1 mass ratio mixing, load ball grinder in ball milling, in mechanical milling process can room temperature, can also heat, ball milling
After 30～500min, filter, high-phosphorus iron ore powder added in clear filtrate A of gained, the pH of filtrate A is adjusted to 2.0～2.5,
Filter again, obtain Iron Ore Powder and clear filtrate B, gained Iron Ore Powder returns to next stage acidleach, by biomass absorbent agent material
According to 1:During 10～1000 mass ratio adds gained liquor B；
Step 2, adds the liquor B of biomass absorbent material to be stirred 200～1200min of reaction, by biomass absorbent
Agent material is filtered, and obtains reacted biomass absorbent agent material and clear filtrate C；
Step 3, will filter gained biomass absorbent agent material and washs after 3 times, according to 1 in step 2:1～100 quality
Mix than the sodium hydroxide or ammonia spirit with 0.1～1mol/L, filter after 50～1000min of air stirring or mechanical agitation,
Biomass adsorbent filtration of material collection after desorbing dephosphorization, water purification are washed after 3 times, the acidic leaching for being transferred to upper level is stirred
The phosphorus gone in mixing reactive tank in continuation adsorbing and extracting high-phosphorus iron ore acidic leaching solution, and the phosphate radical of the higher concentration after desorbing
Solution obtains crystalloid phosphate particle by evaporation and concentration；
Step 4, will add negative zirconium sorbent material, wherein negative zirconium adsorbs in clear filtrate C of filtration gained in step 2
Agent material is 1 with filtrate quality ratio:10～1000,200～1500min of stirring reaction, negative zirconium sorbent material are filtered, are obtained
Reacted negative zirconium sorbent material processed according to the method for step 3, the negative zirconium sorbent material after desorbing dephosphorization turn
Go to continue the phosphorus in adsorbing and extracting high-phosphorus iron ore acidic leaching solution in the acidic leaching stirred tank for moving on to upper level, and solve
The phosphate radical solution of the higher concentration after suction obtains crystalloid phosphate particle by evaporation and concentration.
Wherein, biomass absorbent agent material is according to patent No. ZL：201210019530.1 disclosed in method prepare, will
After washing containing-COOH ,-SH ,-NH2,-(phenol) OH isoreactivity functional groups biomass, such as garlic residue, Garcinia mangostana slag, Sargassum,
Distiller grains, Fructus Citri tangerinae slag, Pericarpium Mali pumilae, pomelo peel etc. and alkali, water are according to 1：0.05-0.2：The mass ratio of 0.5-2 is stirred hybrid reaction,
Stirring 12～24 hours, filters, obtains solid product, wherein, the alkali is lithium, sodium, potassium, calcium, the oxide of magnesium, hydroxide
Thing, carbonate, bicarbonate or ammonium carbonate, ammonium hydrogen carbonate, carbamide, one or two or more kinds mixing in ammonia；It is solid by more than
Body products in water is washed up to neutral, feeding vacuum drying oven, is 60～120 DEG C of dryings in temperature, drying object is smashed, is sieved, and 40
The following powder collection of mesh obtains biomass absorbent agent material.
The preparation method of negative zirconium sorbent material is as follows：It is 1 according to mass ratio:10～1000 ratio, biomass are inhaled
Attached agent material is mixed with the basic zirconium chloride or Disulfatozirconic acid. or zirconium-n-propylate solution of 0.01～1mol/L, adjusts the pH value range of solution
For 2～6, after 5～1200min of mechanical agitation or air stirring, by absorbent powder through filtering, water purification cyclic washing 2～3
After secondary, dry in the hot bellows of room temperature or 80 DEG C, born zirconium sorbent material accordingly.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
In such scheme, the phosphorus content after high-phosphorus iron ore ball milling acidleach substantially reduces ([P]<0.025%)；Alkali need not be expended
Reagent is neutralizing pickle liquor；If tangible need, the method for addition Iron Ore Powder can be adopted to increase the pH value of pickle liquor to appropriate
Scope, the consumption of alkali can be greatly reduced；Using the biomass absorbent agent material for having loaded zirconium ion, can be from acid leaching solution
Directly selecting property ground adsorbing and extracting phosphorus, and the phosphorus being adsorbed up come desorbing and concentration by alkali, so as to substantially increase extraction
Phosphorus grade, while the adsorbent after desorbing can return prime technique to go to continue in multiple adsorbing and extracting pickle liquor again
Phosphorus.
Description of the drawings
Fig. 1 is that the negative zirconium adsorbent of the present invention is repeatedly more to phosphate anion in west place in Hubei high-phosphorus iron ore powder dilute sulfuric acid leaching solution
The design sketch of secondary absorption-desorption.
Specific embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool
Body embodiment is described in detail.
The present invention is big for existing high-phosphorus iron ore wet-leaching alkali charge, and phosphorus cannot get efficient recovery, acidleach
Liquid can not obtain the problem of good recycling, there is provided a kind of ball milling acidleach-biological adsorption reclaims phosphor resource in high-phosphorus iron ore
Method.
As shown in figure 1, be 60mg/L phosphorous in immersion, quantity of sorbent 16.7g/L, pH=2.50, adsorption time 24h, solution
Vapor adopts 0.2M sodium hydroxide solutions, and desorption time is under the experiment condition of 24 hours, using negative zirconium adsorbent to west place in Hubei height
The design sketch of the repeated multiple times absorption-desorption of phosphate anion in ferrophosphorus breeze dilute sulfuric acid leaching solution, it is known that its adsorption effect is good,
Below specific embodiment is described.
Embodiment 1
The preparation of negative zirconium Garcinia mangostana slag adsorbent：It is 10 according to mass ratio:1：50 ratio, will be broken into 80 mesh sizes
Garcinia mangostana ground-slag end is uniformly mixed with sodium hydrate solid, water, and stirring reaction by Garcinia mangostana slag powder filter, was washed after 48 hours
And dry, that is, obtain Garcinia mangostana slag adsorbent；Take the zirconium oxychloride solution of Garcinia mangostana solid impurity particle sorbent material 1kg and 0.1mol/L
10L mixes, and the pH value range for regulating solution is 3, after mechanical agitation 1200min, absorbent powder filtration, water purification is washed repeatedly
After washing 2～3 times, dry in the hot bellows of room temperature or 80 DEG C, born zirconium Garcinia mangostana slag adsorbent material accordingly.
Absorption in ball milling acidleach and filtrate carries phosphorus：By high-phosphorus iron ore (phosphorous 0.7%) breeze and the 10L high phosphorus of 1Kg80 mesh
Iron mine acidic leaching solution is sized mixing, is stirred, and slowly Deca dilution heat of sulfuric acid maintains 1.2 to solution ph, by this solution with
The acidproof steel ball mixing of 0.5Kg, loads in the ball grinder of 20L, starts mechanical milling process, and ball milling speed is 30 turns per minute, heating
Temperature is 60 DEG C, after so reaction 120min, filters, adds 200g iron mine powder and adjust its pH in the filtrate of resulting clarification
Value filters gained Iron Ore Powder and can return to next stage acidleach, add Garcinia mangostana slag biological adsorption agent material 467g in filtrate 2.3,
After stirring makes its adsorption reaction 1200min, by absorbent filtering, reacted biomass absorbent agent material and clarification filter are obtained
Liquid.
Gained reacted adsorbent water purification is washed after 3 times, is mixed with the sodium hydroxide solution 0.1L of 1mol/L, air
Stirring 100min after filter, the sorbent material after desorbing dephosphorization is collected by filtration, water purification wash 3 times after, be transferred to upper level
Acidic leaching stirred tank in go to continue the phosphorus in the pickle liquor of the molten leaching high-phosphorus iron ore of adsorbing and extracting, it is and higher after desorbing
The phosphate radical solution of concentration then by evaporation and concentration, is obtained crystalloid phosphate particle.
The Garcinia mangostana slag biomaterial adsorption agent 733g of negative zirconium, stirring will be added in gained clear filtrate to make its adsorption reaction
After 1440min, absorbent filtering, gained adsorbent can be mixed with the sodium hydroxide solution 2L of 1mol/L after washing 3 times
Close, after air stirring 100min filter, the sorbent material after desorbing dephosphorization is collected by filtration, water purification wash 3 times after, be transferred to
Go to continue the phosphorus in the pickle liquor of the molten leaching high-phosphorus iron ore of adsorbing and extracting in the acidic leaching stirred tank of upper level, and after desorbing
Higher concentration phosphate radical solution then by evaporation and concentration, and obtain crystalloid sodium phosphate granule.
Embodiment 2
The preparation of negative zirconium garlic waste adsorbent：It is 10 according to mass ratio:1：80 ratio, will be broken into 150 mesh
The garlic waste powder of size is uniformly mixed with calcium hydroxide solid, water, and stirring reaction is after 96 hours, by garlic waste
Powder filter, wash and dry, obtain garlic waste adsorbent；Take the garlic waste particulate adsorbent material 1kg with
The sulphuric acid zirconium solution 5L mixing of 0.2mol/L, the pH value range for regulating solution is 2, after mechanical agitation 2400min, by adsorbent
Powder is through filtering, after water purification cyclic washing 2-3 time, zirconium is born in the drying in the hot bellows of room temperature or 80 DEG C accordingly
Garlic waste sorbent material.
Absorption in ball milling acidleach and filtrate carries phosphorus：By the 200 height of eye fosfosiderites of 1Kg (phosphorous 0.7%) breeze, it is high with 10L
Fosfosiderite acidic leaching solution is sized mixing, is stirred, and slowly Deca dilution heat of sulfuric acid maintains 0.8 to solution ph, by this solution with
The acidproof steel ball mixing of 1Kg, loads in the ball grinder of 20L, starts mechanical milling process, and ball milling speed is 30 turns per minute, so anti-
After answering 120min, filter, 300g iron mine powder is added in obtaining clear filtrate and its pH value is adjusted 2.5, filter gained iron mine
Powder returns to next stage acidleach.Add garlic residue biological adsorption agent material 400g in filtrate, stirring makes its adsorption reaction 240min
Afterwards, by absorbent filtering, reacted biomass absorbent agent material and clear filtrate are obtained.
The reacted garlic residue biological adsorption agent material of gained is after water purification washs 3 times, molten with the ammonia of 2mol/L
Liquid 1L mix, after air stirring 60min filter, the sorbent material after desorbing is collected by filtration, water purification wash 3 times after, transfer
Phosphorus in the acidic leaching stirred tank of upper level in the pickle liquor of the molten leaching high-phosphorus iron ore of continuation adsorbing and extracting, and desorbing
The phosphate anion solution containing higher concentration for getting off then can be concentrated to give ammonium phosphate crystal grain solid through evaporative crystallization.
The garlic waste biomaterial adsorption agent 533g of negative zirconium is added in gained clear filtrate, makes its stirring and adsorbing anti-
After answering 240min, can be after washing 3 times by absorbent filtering, gained adsorbent, the sodium hydroxide solution 0.2L with 1mol/L
Mixing, after air stirring 100min filter, by desorbing dephosphorization after negative zirconium garlic waste sorbent material be collected by filtration, water purification
After washing 3 times, go to continue the acidleach of the molten leaching high-phosphorus iron ore of adsorbing and extracting in being transferred to the acidic leaching stirred tank of upper level
Phosphorus in liquid, and the phosphate radical solution of the higher concentration after desorbing then passes through evaporation and concentration, and obtain crystalloid phosphate
Grain.
Embodiment 3
The preparation of negative zirconium shaddock peel adsorbent：It is 10 according to mass ratio:2：100 ratio, will be broken into 200 mesh sizes
Pomelo peel garbage powder uniformly mix with magnesium hydroxide solid, water, stirring reaction is after 30 hours, by pomelo peel powder mistake
Filter, wash and dry, obtain shaddock peel adsorbent；Take the normal propyl alcohol of the pomelo peel particulate adsorbent material 1kg and 0.15mol/L
Zirconium solution 2L mixes, and the pH value range for regulating solution is 2, after mechanical agitation 2400min, by absorbent powder filtration, water purification
After cyclic washing 2-3 time, dry in the hot bellows of room temperature or 80 DEG C, born zirconium shaddock peel adsorbent material accordingly.
Absorption in ball milling acidleach and filtrate carries phosphorus：By the 100 height of eye fosfosiderites of 1Kg (phosphorous 0.7%) breeze, it is high with 10L
Fosfosiderite acidic leaching solution is sized mixing, is stirred, and slowly Deca dilution heat of sulfuric acid maintains 0.75 to solution ph, by this solution with
The acidproof steel ball mixing of 1.5Kg, loads in the ball grinder of 20L, starts mechanical milling process, and ball milling speed is 45 turns per minute, so
After reaction 180min, filter, 500g iron mine powder is added in obtaining the filtrate clarified and adjust its pH value 2.5.Filter gained
Iron Ore Powder returns to next stage acidleach.Add shaddock peel adsorbent material 667g in filtrate, stirring makes its adsorption reaction 1200min
Afterwards, by absorbent filtering, reacted biomass absorbent agent material and clear filtrate are obtained.
Gained reacted pomelo peel biological adsorption agent material through water purification wash 3 times after, the hydroxide with 1mol/L
Sodium solution 2L mix, after air stirring 600min filter, desorbing sorbent material is collected by filtration, water purification wash 3 times after, transfer
Phosphorus in the acidic leaching stirred tank of upper level in the pickle liquor of the molten leaching high-phosphorus iron ore of continuation adsorbing and extracting, and desorbing
The phosphate anion solution containing higher concentration for getting off then can be concentrated to give sodium phosphate crystal grain solid through evaporative crystallization.
The pomelo peel biomaterial adsorption agent 800g of negative zirconium is added in gained clear filtrate, makes its stirring and adsorbing react
After 1500min, can be after water purification wash 3 times by absorbent filtering, gained adsorbent, the sodium hydroxide solution with 1mol/L
0.25L mix, after air stirring 600min filter, sorbent material after desorbing dephosphorization is collected by filtration, water purification wash 3 times after,
Go to continue the phosphorus in the pickle liquor of the molten leaching high-phosphorus iron ore of adsorbing and extracting in being transferred to the acidic leaching stirred tank of upper level, and
The phosphate radical solution of the higher concentration after desorbing is then by evaporation and concentration, and obtains crystalloid phosphate particle.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of without departing from principle of the present invention, some improvements and modifications can also be made, these improvements and modifications
Should be regarded as protection scope of the present invention.
Claims (3)
1. the method that a kind of ball milling acidleach-biological adsorption reclaims phosphor resource in high-phosphorus iron ore, it is characterised in that：
High-phosphorus iron ore is crushed to 80～200 mesh by step one, according to mass ratio 1:1～10 ratio by high-phosphorus iron ore powder with
High-phosphorus iron ore acidic leaching solution is mixed, and Deca dilute sulfuric acid makes pH value of solution maintain 0.5～1.2, by the solution after stirring
With acidproof steel ball according to 5～25:1 mass ratio mixing, loads ball milling in ball grinder, after 30～500min of ball milling, filters, to institute
High-phosphorus iron ore powder is continuously added in clear filtrate A for obtaining, the pH to 2.0～2.5 of filtrate A is adjusted, is filtered again, obtain Iron Ore Powder
With clear filtrate B, gained Iron Ore Powder returns to next stage acidleach, by biomass absorbent agent material according to 1:10～1000 quality
Than adding in gained clear filtrate B；
Step 2, adds clear filtrate B of biomass absorbent agent material to be stirred 200～1200min of reaction, biomass is inhaled
Attached agent material is filtered, and obtains reacted biomass absorbent agent material and clear filtrate C；
Step 3, will filter gained biomass absorbent agent material and washs after 3 times, according to 1 in step 2:1～100 mass ratio with
The sodium hydroxide of 0.1～1mol/L or ammonia spirit mixing, filter after 50～1000min of air stirring or mechanical agitation, will solution
After biomass adsorbent filtration of material collection after suction dephosphorization, water purification wash 3 times, the acidic leaching stirring for being transferred to upper level is anti-
The phosphorus gone in answering groove in continuation adsorbing and extracting high-phosphorus iron ore acidic leaching solution, and the phosphate radical solution of the higher concentration after desorbing
By evaporation and concentration, crystalloid phosphate particle is obtained；
Step 4, will add negative zirconium sorbent material, wherein negative zirconium adsorbent material in clear filtrate C of filtration gained in step 2
Material is 1 with filtrate quality ratio:10～1000,200～1500min of stirring reaction, negative zirconium sorbent material is filtered, and what is obtained is anti-
Negative zirconium sorbent material after answering is processed according to the method for step 3, and the negative zirconium sorbent material after desorbing dephosphorization is transferred to
Go to continue the phosphorus in adsorbing and extracting high-phosphorus iron ore acidic leaching solution in the acidic leaching stirred tank of upper level, and after desorbing
Higher concentration phosphate radical solution by evaporation and concentration, obtain crystalloid phosphate particle.
2. the method that a kind of ball milling acidleach according to claim 1-biological adsorption reclaims phosphor resource in high-phosphorus iron ore, which is special
Levy and be：The preparation method of negative zirconium sorbent material is as follows：It is 1 according to mass ratio:10～1000 ratio, by biomass absorbent
Agent material is mixed with the basic zirconium chloride or Disulfatozirconic acid. or zirconium-n-propylate solution of 0.01～1mol/L, and the pH value range for adjusting solution is
2～6, after 5～1200min of mechanical agitation or air stirring, by absorbent powder through filtering, water purification cyclic washing 2～3 times
Afterwards, dry in the hot bellows of room temperature or 80 DEG C, born zirconium sorbent material accordingly.
3. the method that a kind of ball milling acidleach according to claim 1-biological adsorption reclaims phosphor resource in high-phosphorus iron ore, which is special
Levy and be：The preparation method of the biomass absorbent agent material is：After by washing containing-COOH ,-SH ,-NH2,-(phenol) OH
Biomass and the alkali of active function group, water are according to 1：0.05‐0.2：The mass ratio of 0.5-2 is stirred hybrid reaction, stirring 12
～24 hours, filter, obtain solid product, wherein, it is described containing-COOH ,-SH ,-NH2,-(phenol) OH active functions group life
Material is garlic residue, Garcinia mangostana slag, Sargassum, distiller grains, Fructus Citri tangerinae slag, Pericarpium Mali pumilae, one or more in pomelo peel, the alkali be lithium, sodium,
One kind in potassium, calcium, the oxide of magnesium, hydroxide, carbonate, bicarbonate or ammonium carbonate, ammonium hydrogen carbonate, carbamide, ammonia
Or two kinds mixed above；Above solid product is washed with water until neutral, feeding vacuum drying oven, dry for 60～120 DEG C in temperature
It is dry, drying object to be smashed, is sieved, the following powder collection of 40 mesh obtains biomass absorbent agent material.
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| CN108866354B (en) * | 2018-06-20 | 2020-12-04 | 吉首大学 | Method for efficiently extracting vanadium from vanadium-containing ore |
| CN109701749A (en) * | 2019-01-22 | 2019-05-03 | 云南磷化集团有限公司 | A kind of method of nitric acid pretreatment direct flotation phosphorus concentrate |
| CN109722264B (en) * | 2019-03-05 | 2021-03-30 | 重庆大学 | Method for recovering phosphorus by hydrothermal carbonization of livestock and poultry manure |
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