CN102674286A - Method for preparing high-quality feed-grade calcium hydrophosphate by by-product waste acid of titanium dioxide - Google Patents
Method for preparing high-quality feed-grade calcium hydrophosphate by by-product waste acid of titanium dioxide Download PDFInfo
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- CN102674286A CN102674286A CN201210164927XA CN201210164927A CN102674286A CN 102674286 A CN102674286 A CN 102674286A CN 201210164927X A CN201210164927X A CN 201210164927XA CN 201210164927 A CN201210164927 A CN 201210164927A CN 102674286 A CN102674286 A CN 102674286A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/322—Preparation by neutralisation of orthophosphoric acid
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Abstract
The invention provides a method for preparing high-quality feed-grade calcium hydrophosphate by by-product waste acid of titanium dioxide, comprising the following steps of: enabling phosphorite slurry to pre-react; mixing with dilute sulphuric acid, concentrated sulfuric acid and water; and performing desulfurating, filtering, removing impurities, neutralizing, depositing and centrifugally drying on the obtained material. The method overcomes the problem that the titanium dioxide waste acid is difficult to recycle due to high impurity content; the quality of the obtained calcium hydrophosphate meets production requirement of the feed additive completely; and due to the waste produced by titanium dioxide, the method solves the pollution problem of waste sulfuric acid produced by titanium dioxide, develops new recycling path of the waste, reduces adding amount of the make-up water in the water balance of a leaching system due to low-concentration sulfuric acid, reduces water consumption for production, saves cost and improves the economic benefit.
Description
Technical field
The present invention relates to the phosphoric acid by wet process technical field, be specifically related to the preparation technology of phosphoric acid by wet process hydrogen calcium.
Background technology
At present, phosphatic production is main with the sulfuric acid process phosphoric acid by wet process, at first through the vitriol oil and Rock Phosphate (72Min BPL) mixing acidleach, generates phosphoric acid, again through producing phosphoric acid salt after the removal of impurities.Mainly have following problem, phosphorus ore quality constantly descends, and makes the phosphate product downgrade; The vitriol oil can discharge a large amount of heat during the phosphoric acid acidleach; Cause the acidleach temperature too high; Influence the crystallization and the filter effect of relieving haperacidity process phosphogypsum, therefore need cooling system to remove a large amount of heat energy, the existing as mode flash distillation of employing low level removes heat energy; Need a large amount of equipment inputs and working cost high, waste a large amount of heat resources simultaneously; Need to consume a large amount of sulfuric acid in the preparation process of phosphoric acid.
And in the process of white titanium pigment, produce a large amount of useless 25% sulfuric acid; Environmental protection is caused sizable pressure; When using Titanium White Production By Sulfuric Acid Process, no matter adopt which kind of technology, the 25% sulfuric acid by-products 6-8 ton that white titanium pigment per ton produced; Because of containing a large amount of impurity in the sulfur waste acid, be used in titanium white production once more and can influence the white titanium pigment quality through directly concentrating; Just present titanium white production industry, making full use of of titanium white waste acid is also not extensive, and major part passes through in the hydrogen calcification calcium and after filtering, the titanium gypsum is selected the stacking of special stockyard for use, the discharging after sinking clearly of filtrating.
When the production of phosphoric acid by wet process hydrogen calcium, the sulfur waste acid that utilizes in the production process of titanium pigment to be produced, the charcoal acid calcium salt of phosphoric acid is removed in the pre-reaction that is used for phosphorus ore; And phosphoric acid is produced in the decomposition reaction that can be used for phosphorus ore; Impurity in the phosphoric acid can be removed impurity excessive in the phosphoric acid through in two sections and removal of impurities, and the hydrogen calcium final product quality of being produced is stable; Reach the national standard requirement of GB/T22549-2008; Therefore make full use of titanium white waste acid and produce calcium hydrophosphate fodder and can not only reach and turn waste into wealth, the purpose of comprehensive utilization of resources, and have great environmental benefit.
Propose sulfur waste acid is used to produce normal superphosphate in " research that normal superphosphate is produced in the acid of titanium white sulfur waste " (phosphate fertilizer and the multiple fertile third phase in 2000, total the 15 volume).But general calcium production and phosphoric acid by wet process hydrogen calcium production technique are different again; General calcium is that anhydrite is done finished product with phosphoric acid salt; Phosphoric acid by wet process hydrogen calcium has then adopted stripping technique, and phosphogypsum is separated earlier with phosphoric acid, passes through impurity removal process again; Phosphoric acid is carried out cleansing operation, and the more general calcium of the purity of hydrogen calcium is higher, operation easier is bigger, the operation fineness is higher.
" acid of a kind of by-product of white titanium pigment sulfur waste is used for the working method of phosphoric acid by wet process " (Sichuan Lomon Group Co., Ltd's 2,002 59 patent No.s 02113711.0) once proposed titanium white waste acid through after concentrating deironing; Reach about 60% back and mix, cool off back and phosphorus ore reaction, extraction phosphoric acid with commodity sulfuric acid; But the present invention is more advanced, and production cost is lower.
" low ratio acid wet method production calcium hydrophosphate fodder " (Yimen Mining Bureau, Yunnan Prov.'s 1,990 12 26 patent No.s 90100845.1) literary composition; This method adopts low ratio sulfuric acid that Rock Phosphate (72Min BPL) is carried out immersion treatment; Leaching rate to Rock Phosphate (72Min BPL) is lower, running period is long, production cost is higher, is unfavorable for the serialization production of factory.
Summary of the invention
Goal of the invention of the present invention is: a kind of method of utilizing the by-product in titanium dioxide powder production spent acid to prepare calcium hydrophosphate fodder is provided; Effective solution by-product in titanium dioxide powder production spent acid, waste utilize again, the problem of environmental pollution; Spent acid can utilize again; The calcium monophosphate product of preparation is pollution-free nuisanceless, can be as fodder additives.
The method of utilizing the by-product in titanium dioxide powder production spent acid to prepare calcium hydrophosphate fodder of the present invention is to be raw material with the phosphorus ore slurry, said phosphorus ore slurry be with behind the Rock Phosphate (72Min BPL) crushing and grinding with the mixture of water mixing gained, specifically comprise the steps:
(1) the phosphorus ore slurry is carried out de-magging and handle, the pH value of regulating the de-magging ore pulp is 2.5-4.5, carries out solid-liquid separation, obtains the phosphorus ore filter cake; In this step, solid-liquid separation can adopt the press filtration mode, also can filter through straining installations such as dish filter, turntable, band filters), gained filter cake moisture massfraction is not more than 30% (wt%);
(2) said phosphorus ore filter cake is mixed with phosphoric acid, making proportion is the slurry of slurry again of 1.60-1.95;
(3) waste sulfuric acid with gained in the production process of titanium pigment mixes with the vitriol oil, must dispose acid, H in the configuration acid
2SO
4Massfraction be 35-80wt%;
(4) get the vitriol oil, configuration acid, slurry and phosphoric acid again, mix also and stirred at least 2 hours, must leach slurry; The massfraction of said phosphoric acid is 5wt%-20wt%; Said configuration acid and the amount ratio of the vitriol oil mix time institute's thermal discharge can be made mixture liquid phase temperature reach 60-90 ℃ to be as the criterion with it; Phosphoric acid is as the criterion can make reaction back leaching slurry liquid-solid ratio reach 1.8-3.0:1 with the consumption of slurry again, configuration acid and total consumption of the vitriol oil and again between slurry amount ratio with the sulfuric acid concentration that can make gained and leach the slurry liquid phase (with SO
3Meter) reaching 20-60g/L is as the criterion
(5) in the leaching slurry, add the phosphorus ore slurry, and stir, treat that sulphur content is (with SO in the material liquid phase
3The content meter) be not more than and stop behind the 20g/L stirring, the desulfurization material; The desulfurization material is carried out through solid-liquid separation, get desulfurization filtrating and desulfurization filter cake; Reaction formula is following:
Ca
5F(PO
4)
3+5H
2SO
4+10H
2O=5CaSO
4·2H
2O↓+3H
3PO
4+HF↑
(6) pH that regulates said desulfurization filtrating is 1.5-1.8, stirs after at least 1 hour, after the pH that filters and regulate filtrating is 2. 2-2.6, stirs at least 1 hour, and then filters and control and filter total phosphorus that gained filtrates once more (with P
2O
5Meter) concentration is that 60-72 g/L, total phosphorus concentration and total fluorine (in F) concentration ratio are 230-350, gets neutralization filtrate;
(7) pH of regulating step (6) gained neutralization filtrate is 6.0-6.5, adds milk of lime then and regulates in the neutralization filtrate total phosphorus concentration (with P
2O
5Meter) is not more than 1g/L;
(8) in step (7) gained liquid, add flocculation agent, after staticly settling, abandon clear liquid, taking precipitate carries out centrifugal treating, dries the solid material of centrifugal gained, gets calcium hydrophosphate fodder.
In technical scheme of the present invention; The water cut of step (1) control filter cake; This is that this step enters into subsequent technique to avoid too much metals ion via filter cake through control phosphorus ore cake moisture owing to can carry a large amount of metals ions in the filter cake contained humidity; Said de-magging is handled can be with reference to existing technology, and the granularity of the above solid material of 50 wt% is not more than 100 orders in the phosphorus ore slurry, concrete de-magging treatment process such as sulfuric acid (the sulfur waste acid that perhaps produces in the production process of titanium pigment) and the reaction of phosphorus ore slurry, and reaction formula is:
MgCO
3+H
2SO
4=MgSO
4+H
2O+CO
2↑
CaCO3+H
2SO
4=CaSO
4+H
2O+CO
2↑
In the step (4) of technical scheme of the present invention, replacement(metathesis)reaction takes place, the Ca in the phosphorus ore with slurry again in the vitriol oil and the mixture (being mixing acid) of configuration acid in whipping process
5F (PO
4)
3React, generate phosphoric acid, the reaction that in this process, is taken place is following:
Ca
5F(PO
4)
3+5H
2SO
4+10H
2O=5CaSO
4·2H
2O↓+3H
3PO
4+HF↑
7H
3PO
4+Ca
5F(PO
4)
3=5Ca(H
2PO
4)
2+HF↑
CaCO
3+H
2SO
4+2H
2O=CaSO
4·2H
2O↓+H
2O+CO
2↑
This step (4) disposes the amount ratio sour and vitriol oil through controlling, and makes that disposing the heat that discharges in sour and the vitriol oil mixing process can make mixture liquid phase temperature reach 60-90 ℃, has made full use of the heat that diluting concentrated sulfuric acid discharges, and cuts down the consumption of energy; Practice thrift cost, on the other hand, the material liquidus temperature has material impact to the crystal habit of phosphorus ore raw material rate of decomposition, reaction gained phosphogypsum; Temperature is too high, and phosphorus ore decomposes too fast, and phosphogypsum generates rapidly; Produce a large amount of nucleus, phosphogypsum crystal is tiny, is difficult for filtering; And temperature is low excessively, and phosphorus ore decomposes slowly, and the reaction times is oversize; Unfavorable to enhancing productivity, as far as this programme, said 60-90 ℃ suits.
In this step (4), also slurry is with respect to the consumption of mixing acid again through control, and the solid-to-liquid ratio that makes the leaching slurry that obtains after the reaction is (1.8-3.0): 1; This is because material is decomposed liquid-solid ratio and the crystalline process has material impact, when liquid-solid ratio is big, though help decomposition course and crystallisation process; But can increase the throughput of the load and the reduction acidolysis groove of filter; But if liquid-solid ratio is low excessively, mean that then solid load is too high in the slip, this not only can make slip viscosity increase; Increase to stir load, and be unfavorable for that the decomposition of ground phosphate rock and crystalline grow up.Liquid-solid ratio of the present invention is comparatively suitable.
The total sulphur concentration of liquid phase that this step (4) is also controlled the leaching slurry simultaneously is (with SO
3Meter), this concentration control can recently realize that as equivalents, the present invention also can be through adding the total sulphur concentration of liquid phase that sulfuric acid is controlled the leaching slurry in reaction back gained leaching slurry through the sour ore deposit before the conditioned reaction; Total sulphur concentration all has very big influence to decomposition, the generation of calcium sulfate nucleus, crystalline growth, crystal boundary and the size of ground phosphate rock, and concerning the present invention program, this total sulphur concentration suits.
Step (5) for the present invention program; In actually operating; Can step (5) gained filter cake repeatedly be washed water; After each time washing, can in the material that contains washing water, add the flocculation agent post precipitation and carry out solid-liquid separation (also can not add the direct press filtration of flocculation agent etc.) again, can get after the solid-liquid separation part of gained and filtrate as the surrogate (promptly returning phosphoric acid) of the used phosphoric acid of step (2).Step (5) adds the phosphorus ore slurry can reduce leaching slip liquid phase SO
3Concentration but can not reduce phosphoric acid concentration can reduce production costs to greatest extent.
The present invention program's step (6) is carried out the pH value to desulfurization filtrating continuously and is regulated and filter; This is because the by product sulfur waste acid of titanium white production contains various heavy metal ion; These ions change various impurity in reaction process of the present invention, some impurity are (like FePO
4H
2O, AlPO
4H
2O, Ca
3(AsO
3)
2, CaF
2And SiO
2Deng) insoluble or slightly soluble under the described pH value of step (6) condition, control pH helps the removal of this type of impurity, guarantees that product can reach the feed grade requirement.
The equation of reaction is following in the step (6):
CaCO
3+H
2SO
4+2H
2O=CaSO
4·2H
2O↓+H
2O+CO
2↑
CaCO
3+2H
3PO
4=Ca(H
2PO
4)
2+?CO
2↑+?H
2O
H
2SiF
6+3Ca(OH)
2=3CaF
2↓+SiO
2↓+3H
2O
2HF+Ca(OH)2=CaF
2↓+H
2O
Fe
3++PO
4 3-+H
2O=FePO
4·H
2O↓
Al3++PO
4 3-+H
2O=AlPO
4·H
2O↓
H
2SO
4+Ca(OH)
2=CaSO
4·2H
2O↓
H
3AsO
3+3Ca(OH)
2=Ca
3(AsO
3)
2↓+6H
2O
2H
3PO
4+Ca(OH)
2=Ca(H
2PO
4)
2↓+2H
2O
Preferably, in the step (3), the H of configuration acid
2SO
4Massfraction is 50-80%, and under this massfraction condition, configuration acid is better with the mixed heat of dilution releasing effect of the vitriol oil, and the consumption of the vitriol oil is minimum.
Preferably, the liquid-solid ratio of leaching slurry is 2.2:1 in the step (4).
Preferably, liquidus temperature is 60-95 ℃ in the step (5).
Preferably, it is to make acid of gained sulfur waste and phosphorus ore slurry hybrid reaction in the production process of titanium pigment that de-magging described in the step (1) is handled, and the pH value of control reaction mass is 2.5-4.5 in the reaction process.In described pH2.5-4.5 scope, acidity is strong more, and de-magnesium reaction is thorough more, and the de-magging effect is good more, but acid above said scope, and is not obvious to the demagnesium rate raising, can cause the phosphorus loss in the de-magging treating processes to increase simultaneously.
Beneficial effect of the present invention:
In sum, than prior art, the invention provides a kind of method of utilizing the by-product in titanium dioxide powder production spent acid to prepare calcium hydrophosphate fodder; Overcome the defective that titanium white waste acid is high because of foreign matter content, be difficult to utilize, the calcium monophosphate product quality of production is superior to the calcium monophosphate product quality that traditional technology is produced, and meets the calcium hydrophosphate fodder production standard of GB/T 22549-2008 fully; Satisfy the fodder additives production requirement; The present invention solves the useless vitriolic problem of environmental pollution of the massfraction 25wt% that titanium white production produced because what add is the titanium white production waste, has developed the new route of producing the Sustainable development that waste utilizes again; Simultaneously because the adding of low-concentration sulfuric acid; Make the add-on of leaching make up water in the systematic water balance reduce, reduced to produce consuming, practiced thrift production cost.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, allly all belong to scope of the present invention based on the technology that content of the present invention realized
Embodiment one:
1) preparation H
2SO
4Massfraction is 35% (wt%) configuration acid
Using massfraction is that (it consists of: H for the industrial sulphuric acid of 98% (wt%)
2SO
498.0% (wt%), proportion 1.84, Fe
2O
30.63% (wt%), Al
2O
30.02% (wt%) and MgO 0.08% (wt%)) in tempering tank with production process of titanium pigment in the acid of gained sulfur waste mix, be mixed with nitration mixture, H in the nitration mixture liquid phase
2SO
4Massfraction be 36% (wt%), after preparing again through filter cleaner, H
2SO
4Massfraction is 35.14% (wt%) configuration acid, its proportion 1.31, Fe
2O
33.23% (wt%), Al
2O
30.28% (wt%) and MgO0.36% (wt%)), subsequent use.
2) preparation of phosphorus ore slurry
(Rock Phosphate (72Min BPL) is formed: P to get the 30t Rock Phosphate (72Min BPL)
2O
531.2% (wt%), CaO 43.66% (wt%), SO
32.98% (wt%), Fe
2O
32.54% (wt%), Al
2O
33.01% (wt%), MgO 2.51% (wt%) and H
2O 8.0% (wt%)) carry out fragmentation through single toggle jaw crusher, the Rock Phosphate (72Min BPL) after the fragmentation is crossed 10 mesh sieves, adds entry to ball mill again; The Rock Phosphate (72Min BPL) of crossing 10 mesh sieves mixes with water and through processing ore pulp just behind the ball milling; Just ore pulp is crossed 100 mesh sieves, finally makes phosphorus ore slurry 43.84t, H in the phosphorus ore slurry
2O content is 35% (wt%).
3) preparation de-magging ore pulp
43.84 tons of phosphorus ore slurries are added anterior reactor continuously, start stirrer simultaneously, the configuration acid that under agitation condition, step 1 is made adds in the anterior reactor, stirs 1.5h simultaneously, and the liquid phase pH that makes ore pulp is 1.5; Ore pulp after will handling again uses and pumps into specification and carry out press filtration as the pressure filter of XMZFG500/1500-V and handle, and obtains filter cake 35.62t (its composition: amount to butt: P
2O
5Be that 31.2% (wt%), CaO are 43.66% (wt%), SO
3Be 3.04% (wt%), Fe
2O
3% is 2.62% (wt%), Al
2O
3Be that 2.86% (wt%), MgO are 1.98% (wt%) and H
2O 20% (wt%)), it is Φ 4000*3000 again in the stock tank that filter cake is sent into specifications and models, and (the phosphoric acid quality mark is (with P to add phosphoric acid 8.22t
2O
5Meter) be 13.2% (wt%)) starch again, being starched amount of slurry again is 43.85t, proportion is 1.89.
4) leaching
With gained 43.85t again slurry to add specifications and models be the leaching groove of φ 1500*300; Be that 35% sulfuric acid 25.06t, massfraction are 98% vitriol oil 11t and return in 45.36 tons of adding leachings of phosphoric acid (massfraction of its phosphoric acid is 15wt%) groove and mix and stirring with the massfraction that configures simultaneously; Stir after 2 hours; Get mixed slurry (promptly leaching slurry); The liquidus temperature of this mixed slurry is 62 ℃, reactivity 96.83%, and mixed slurry contains phosphoric acid liquid 87.7t, and (its liquid phase is formed: P
2O
5For 243.14g/L, Ca are that 1.12g/L, F are 13.75g/L, SO
3Be 28.29 g/L, Fe
2O
3Be 4.55g/L, Al
2O
3Be that 14.25 g/L and MgO are 13.52g/L) and anhydrous phosphogypsum 38.9t.
5) filter
It is HDZP-I 120m that step 4) gained mixed slurry 116.7t is conveyed into specifications and models
2The turntable vacuum filter just filter the district and carry out solid-liquid separation; Get just filtrating and filter cake; Carry out three washing leaching cakes of adverse current with 21.5t water, the washing after-filtration also mixes gained filtrating with just filtrating, and must mix filtrating; Get mix filtrating totally 45.36 tons of conducts return phosphoric acid and send the leaching operation back to and use as phosphoric acid surrogate (promptly returning phosphoric acid), (it consists of remaining mixing filtrating: P
2O
5208.7 g/L, Ca 0.95 g/L, F 10.75 g/L, SO
324.41 g/L, Fe
2O
34.55 g/L, Al
2O
314.25 g/L and MgO g/L 13.52) to send into specification be clarification in the settling tank of Φ 19000*17000 to 50t, gets clear liquid.
6) neutralization, press filtration
Get step 5) gained clear liquid 10t and add in the neutralizing well, add 8.75t water, 5.5t calcium powder slurry (its composition: CaCO simultaneously
3Content 19.5%; Moisture content 20%); Regulate after the pH value to 1.7,, get clear liquor and add 6t milk of lime that to be neutralized to pH be 2.3 through clarifying tank heavy clear (also can adopt other straining installation to carry out solid-liquid separation); Get filter cake and neutralization filtrate through press filtration, heavy 2.4t (its composition (in the butt massfraction): P of filter cake
2O
514.86% (wt%), Ca 9.66% (wt%), SO
36.28% (wt%), Fe
2O
31.99% (wt%), Al
2O
34.59% (wt%), MgO 0.39% (wt%) and H
2O 47.6% (wt%)), heavy 27.85t (its composition (in the butt mass concentration): P of neutralization filtrate
2O
565.10g/L, Ca 2.48 g/L, F 8.12 g/L, SO
311.26 g/L, Fe
2O
32.33 g/L, Al
2O
35.26 g/L and MgO 7.50 g/L), be fertilizer grade secondary calcium phosphate (promptly white fertile) after the filter cake oven dry, weight is 1.22t, it consists of: effective P
2O
525.80% (wt%), Ca 18.57% (wt%), F 0.23% (wt%), SO
38.48% (wt%), Fe
2O
32.48% (wt%), Al
2O
39.01% (wt%), MgO 0.62% (wt%) and H
2O 0.90% (wt%).
7) neutralization, thickening are used for calcium hydrophosphate fodder again
Step 6) gained 27.85t neutralization filtrate is conveyed in the neutralizing well once more, and adding 11t milk of lime adjusting pH simultaneously is 6.2, gets the liquid phase total phosphorus (with P
2O
5Meter) concentration be not more than 1g/L in and slip, the gained slip is delivered in the thickener and adds the flocculation agent sedimentation 15min of 3.11t 3 ‰ (wt%) concentration, obtain thick slurry and clear liquid, thick slurry weight is 22.32t, H in the thick slurry
2The O massfraction is 80.2% (wt%)), clear liquid weight is 5.53t, total phosphorus concentration is (with P in the liquid phase
2O
5Meter) be 0.31 g/L.
8) centrifugal, the oven dry, the packing
Be delivered in the whizzer the thick slurry of step 6) gained 22.32t centrifugal; Obtain centrifugal material 5.5t; Moisture content is 20.45% (wt%) in the centrifugal material; Again centrifugal material being sent into specifications and models continuously is that the rotary kiln of Φ 2500*25000 is dried processing; Obtain 4.4 tons of required calcium hydrophosphate fodders, it forms (the material composition described in the present invention all is meant the composition of representing with element or oxide form) as follows: P17.30% (wt%), solubility in citric acid P17.00% (wt%), Ca 21.04% (wt%), F 0.16% (wt%), SO
31.13% (wt%), Fe
2O
30.18% (wt%), Al
2O
30.19% (wt%), MgO 0.19% (wt%), H
2O 1.67% (wt%), As 8PPm, Pb 9PPm, Cd 3PPm, fineness is crossed the choosing of 100 mesh sieves for the 99wt% product.
Embodiment two:
1) step 1)-3 of repetition embodiment 1) operation; Difference is to dispose the H of acid
2SO
4Massfraction is 55% (wt%)
2) leaching
With gained 43.85t again slurry to add specifications and models be the leaching groove of φ 1500*300; The massfraction that configures simultaneously is that 55% sulfuric acid 15.94t, massfraction are 98% vitriol oil 11t and return 54.46 tons of phosphoric acid (massfraction of its phosphoric acid is 20wt%); Add in the lump in the leaching groove and mix and stirring, stir after 4 hours, get mixed slurry; The liquidus temperature of this mixed slurry is 81.26 ℃, reactivity 97.03%, and mixed slurry contains phosphoric acid liquid 87.7t, and (its liquid phase is formed: P
2O
5For 248g/L, Ca are that 1.32g/L, F are 14.75g/L, SO
3Be 30.29 g/L, Fe
2O
3Be 5.08g/L, Al
2O
3Be that 14.45 g/L and MgO are 14.52g/L) and anhydrous phosphogypsum 38.9t.
3) filter
With step 2) to be conveyed into specifications and models be HDZP-I 120m to gained mixed slurry 116.7t mixed slurry
2The turntable vacuum filter just filter the district and carry out solid-liquid separation; The flocculation agent that adds 2.32t 3 ‰ (wt%) concentration simultaneously; And carrying out adverse current three times washing with 16.45t water, the washing after-filtration also mixes gained filtrating with just filtrating, and must mix filtrating; Get and mix 54.46 tons of mixing of filtrating and return the leaching operation and use remaining mixing filtrating (its composition: P as phosphoric acid surrogate (promptly returning phosphoric acid)
2O
5For 248.5g/L, Ca are that 1.32g/L, F are 14.75g/L, SO
3Be 30.29 g/L, Fe
2O
3Be 5.08g/L, Al
2O
3Be that 14.45 g/L and MgO are 14.52g/L)) to send into specification be clarification in the settling tank of Φ 19000*17000 to 41.15t, gets clear liquid.
5) salify
Press the step 6) of embodiment one again---8) operation; Difference is in the step 6); The pH regulator value is 1.5 for the first time; The pH regulator value is 2.2 for the second time, makes secondary calcium phosphate. gained secondary calcium phosphate finished product, it consists of P17.35% (wt%), solubility in citric acid P17.00% (wt%), Ca 21.24% (wt%), F 0.15% (wt%), SO
31.23% (wt%), Fe
2O
30.20% (wt%), Al
2O
30.18% (wt%), MgO 1.2% (wt%), H
2O 2.3% (wt%), As 8.2PPm, Pb 9.5PPm and Cd 3.5PPm, its fineness is crossed the choosing of 100 mesh sieves for the 99wt% finished product.
Embodiment three:
1) step 1)-3 of repetition embodiment 1) operation; Difference is that disposing sour massfraction is 80% (wt%)
2) leaching
With gained 43.85t again slurry to add specifications and models be the leaching groove of φ 1500*300; The massfraction that configures simultaneously is that 79.52% sulfuric acid 10.96t, massfraction are 98% vitriol oil 11t and return 41.65 tons of phosphoric acid (massfraction of its phosphoric acid is 5wt%); Add in the lump in the leaching groove and mix and stirring; Stir after 3 hours; Get mixed slurry, the liquidus temperature of this mixed slurry is 88 ℃, reactivity 96.83%, and the gained mixed slurry contains phosphoric acid liquid 87.7t, and (its liquid phase is formed: P2O5 is that 248.56g/L, Ca are that 1.32g/L, F are 13.65g/L, SO
3Be 29.29 g/L, Fe
2O
3Be 4.65g/L, Al
2O
3Be that 14.75 g/L and MgO are 13.52g/L) and anhydrous phosphogypsum 38.9t.
3) filter
Get step 2) to be conveyed into specifications and models be HDZP-I 120m to gained mixed slurry 116.7t mixed slurry
2The turntable vacuum filter just filter the district and carry out solid-liquid separation; The flocculation agent that adds 2.32t 3 ‰ (wt%) concentration simultaneously; And carrying out adverse current three times washing with 21.95t water, the washing after-filtration also mixes gained filtrating with just filtrating, and must mix filtrating; Get 59.44 tons of mixing of mixing filtrating and return the leaching operation, remaining mixing filtrating (its composition: P as phosphoric acid surrogate (promptly returning phosphoric acid) use
2O
5245.6 g/L, Ca 1.25 g/L, F 14.75 g/L, SO
327.41 g/L, Fe
2O
35.85 g/L, Al
2O
315.25 g/L and MgO g/L 14.52) to send into specification be clarification in the settling tank of Φ 19000*17000 to 4t, gets clear liquid.
4) salify
Press the step 6) of embodiment one again---8) operation; Difference is in the step 6); The pH regulator value is 1.8 for the first time; The pH regulator value is 2.6 for the second time, makes secondary calcium phosphate. gained secondary calcium phosphate finished product, it forms P17.25% (wt%), solubility in citric acid P17.00% (wt%), Ca 21.08% (wt%), F 0.135% (wt%), SO
31.33% (wt%), Fe
2O
30.18% (wt%), Al
2O
30.19% (wt%), MgO 1.39% (wt%), H
2O 2.2% (wt%), As 8.5PPm, Pb 9.7PPm and Cd 3.3PPm, its fineness is crossed the choosing of 100 mesh sieves for the 99wt% finished product.
The secondary calcium phosphate of technology of the present invention production feed grade simultaneously and fertilizer grade (promptly white fertile), calcium hydrophosphate fodder and fertilizer grade calcium monophosphate product quality all can National standard.
The foregoing description data presentation; The present invention program's gained calcium hydrophosphate fodder quality has raising by a relatively large margin; Calcium monophosphate product phosphorus, calcium, fluorine stable content; Heavy metal content does not have influence far below the prescribed value among the GB GB/T22549-2008 to the citric acid soluble phosphorus of fertilizer grade secondary calcium phosphate, and it is required to satisfy plant growth fully.
The inventive method technology is simple, owing to adopted sulfur waste acid, it is not counted in the phosphate production consumption; Greatly reduce the sulfuric acid consumption in the phosphate production process, improved the phosphogypsum crystal effect in the phosphoric acid leaching process, improved filtration capacity; Reduced production cost,, efficiently solved the environmental problem that useless vitriolic digestive problems of 25% (wt%) that titanium white production produces and titanium white production are brought simultaneously because what add is the titanium white production waste; While because a part of make up water has been brought in the adding of lower concentration acid into, has been reduced the water of productive use amount in phosphatic production process; And utilize sulfuric acid and phosphorus ore reaction in the spent acid to greatest extent; Reduced the production cost of feed phosphate, realized turning waste into wealth, the recycling economy pattern of comprehensive utilization of resources.
Need to prove at last; Above embodiment only is used to explain technical scheme of the present invention and is unrestricted; Although technical scheme of the present invention is specified, it will be appreciated by those skilled in the art that and to make amendment or be equal to replacement technical scheme of the present invention with reference to preferred embodiment; And not breaking away from aim of the present invention and scope, it all should be encompassed in the middle of protection scope of the present invention.
Claims (4)
1. utilizing the by-product in titanium dioxide powder production spent acid to prepare the method for calcium hydrophosphate fodder, is to be raw material with the phosphorus ore slurry, said phosphorus ore slurry be with behind the Rock Phosphate (72Min BPL) crushing and grinding with the mixture of water mixing gained, it is characterized in that: comprise the steps:
(1) phosphorus ore slurry is carried out carrying out solid-liquid separation after de-magging handles, obtain the phosphorus ore filter cake; The massfraction of contained humidity is not more than 30% (wt%) in the phosphorus ore filter cake;
(2) said phosphorus ore filter cake is mixed with phosphoric acid, making proportion is the slurry of slurry again of 1.60-1.95;
(3) waste sulfuric acid with gained in the production process of titanium pigment mixes with the vitriol oil, must dispose acid, H in the configuration acid
2SO
4Massfraction be 35-80wt%;
(4) get the vitriol oil, configuration acid, slurry and phosphoric acid again, mix also and stirred at least 2 hours, must leach slurry;
The massfraction of said phosphoric acid is 5wt%-20wt%; Said configuration acid and the amount ratio of the vitriol oil mix time institute's thermal discharge can be made mixture liquid phase temperature reach 60-90 ℃ to be as the criterion with it; Phosphoric acid is as the criterion can make reaction back leaching slurry liquid-solid ratio reach 1.8-3.0:1 with the consumption of slurry again, configuration acid and total consumption of the vitriol oil and again between slurry amount ratio with the sulfuric acid concentration that can make gained and leach the slurry liquid phase (with SO
3Meter) reaching 20-60g/L is as the criterion;
(5) in the leaching slurry, add the phosphorus ore slurry, and stir, treat that sulphur content is (with SO in the material liquid phase
3The content meter) be not more than and stop behind the 20g/L stirring, the desulfurization material; The desulfurization material is carried out through solid-liquid separation, get desulfurization filtrating and desulfurization filter cake;
(6) pH that regulates said desulfurization filtrating is 1.5-1.8, stirs after at least 1 hour, after the pH that filters and regulate filtrating is 2. 2-2.6, stirs at least 1 hour, and then filters and control and filter total phosphorus that gained filtrates once more (with P
2O
5Meter) concentration is that 60-72 g/L, total phosphorus concentration and total fluorine (in F) concentration ratio are 230-350, gets neutralization filtrate;
(7) pH of regulating step (6) gained neutralization filtrate is 6.0-6.5, adds milk of lime then and regulates in the neutralization filtrate total phosphorus concentration (with P
2O
5Meter) is not more than 1g/L;
(8) in step (7) gained liquid, add flocculation agent, after staticly settling, abandon clear liquid, taking precipitate carries out centrifugal treating, dries the solid material of centrifugal gained, gets calcium hydrophosphate fodder.
2. want 1 described a kind of working method of utilizing the by-product in titanium dioxide powder production spent acid to prepare calcium hydrophosphate fodder according to right, it is characterized in that: in the step (3), the H in the configuration acid
2SO
4Massfraction be 50-80wt%.
3. according to the described a kind of method of utilizing the by-product in titanium dioxide powder production spent acid to prepare calcium hydrophosphate fodder of the arbitrary claim of claim 1 to 2, it is characterized in that: the liquid-solid ratio of mixing the gained material in the step (4) is 2.2:1.
4. the method for utilizing the by-product in titanium dioxide powder production spent acid to prepare calcium hydrophosphate fodder according to claim 3; It is characterized in that: it is to make acid of gained sulfur waste and phosphorus ore slurry hybrid reaction in the production process of titanium pigment that de-magging described in the step (1) is handled, and the pH value of control reaction mass is 2.5-4.5 in the reaction process.
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| PCT/CN2012/078166 WO2013174061A1 (en) | 2012-05-25 | 2012-07-04 | Method for preparing high quality feed grade calcium hydrogen phosphate using by-product waste acid from titanium dioxide production |
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| CN103073034A (en) * | 2013-01-17 | 2013-05-01 | 贵州开磷（集团）有限责任公司 | Method for removing magnesium from ultralow-quality phosphate rock and producing magnesium hydroxide |
| CN107055494A (en) * | 2017-04-13 | 2017-08-18 | 云南胜威化工有限公司 | The method that a kind of spent acid in utilization sulfuric acid method titanium pigment production technology selects phosphorus ore |
| CN107128890A (en) * | 2017-06-20 | 2017-09-05 | 四川龙蟒磷化工有限公司 | Titanium white waste acid is used for the closed circulation process of phosphorus ore de-magging |
| CN109553372A (en) * | 2018-12-26 | 2019-04-02 | 四川绵筑新材料有限公司 | A kind of preparation and application for the ardealite roadbed material that can be recycled |
| CN109941971A (en) * | 2019-04-24 | 2019-06-28 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for biphosphate Calcium treatment waste sulfuric acid solution |
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| CN103950911B (en) * | 2014-05-06 | 2016-03-16 | 云南磷化集团有限公司 | Slag acid and yellow phosphorus furnace slag is utilized to prepare the method for calcium hydrophosphate fodder coproduction water glass |
| CN106115645B (en) * | 2016-06-28 | 2018-08-31 | 四川省汉源化工总厂 | A kind of production method of feed-level calcium biphosphate |
| CN108046228A (en) * | 2017-12-29 | 2018-05-18 | 四川绵竹三佳饲料有限责任公司 | A kind of preparation method of high-purity phosphoric acid hydrogen calcium |
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| CN103073034A (en) * | 2013-01-17 | 2013-05-01 | 贵州开磷（集团）有限责任公司 | Method for removing magnesium from ultralow-quality phosphate rock and producing magnesium hydroxide |
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| CN107055494A (en) * | 2017-04-13 | 2017-08-18 | 云南胜威化工有限公司 | The method that a kind of spent acid in utilization sulfuric acid method titanium pigment production technology selects phosphorus ore |
| CN107128890A (en) * | 2017-06-20 | 2017-09-05 | 四川龙蟒磷化工有限公司 | Titanium white waste acid is used for the closed circulation process of phosphorus ore de-magging |
| CN107128890B (en) * | 2017-06-20 | 2019-08-27 | 四川龙蟒磷化工有限公司 | Titanium white waste acid is used for the closed circulation process of phosphorus ore de-magging |
| CN109553372A (en) * | 2018-12-26 | 2019-04-02 | 四川绵筑新材料有限公司 | A kind of preparation and application for the ardealite roadbed material that can be recycled |
| CN109941971A (en) * | 2019-04-24 | 2019-06-28 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for biphosphate Calcium treatment waste sulfuric acid solution |
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| WO2013174061A1 (en) | 2013-11-28 |
| CN102674286B (en) | 2013-11-13 |
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Effective date of registration: 20230810 Address after: No. 1 to No. 3, Chengguan Bianhe Road, Nanzhang County, Xiangyang City, Hubei Province, 441500 Patentee after: Nanzhang longmang phosphorus products Co.,Ltd. Address before: 618200 Xinshi Industrial Development Zone, Mianzhu City, Deyang City, Sichuan Province (zone a) Patentee before: SICHUAN LOMON PHOSPHOROUS CHEMISTRY Co.,Ltd. |