CN102115819A - Method for recycling magnesium from middle-low grade high-magnesium phosphate rock - Google Patents
Method for recycling magnesium from middle-low grade high-magnesium phosphate rock Download PDFInfo
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- CN102115819A CN102115819A CN2011100287366A CN201110028736A CN102115819A CN 102115819 A CN102115819 A CN 102115819A CN 2011100287366 A CN2011100287366 A CN 2011100287366A CN 201110028736 A CN201110028736 A CN 201110028736A CN 102115819 A CN102115819 A CN 102115819A
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- Prior art keywords
- magnesium
- phosphorus ore
- grade high
- phosphate
- reaction
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- 239000011777 magnesium Substances 0.000 title claims abstract description 64
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 55
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000004137 magnesium phosphate Substances 0.000 title abstract 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 title abstract 3
- 238000004064 recycling Methods 0.000 title abstract 3
- 239000011435 rock Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 238000001556 precipitation Methods 0.000 claims abstract description 30
- MXZRMHIULZDAKC-UHFFFAOYSA-L magnesium;azane;hydrogen phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims abstract description 19
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 17
- 239000002367 phosphate rock Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 239000012141 concentrate Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000003337 fertilizer Substances 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims description 62
- 229910052698 phosphorus Inorganic materials 0.000 claims description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- LFVGISIMTYGQHF-UHFFFAOYSA-N Ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 17
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 17
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 17
- 239000006012 monoammonium phosphate Substances 0.000 claims description 17
- 229910052567 struvite Inorganic materials 0.000 claims description 17
- 238000003828 vacuum filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 230000005591 charge neutralization Effects 0.000 claims description 10
- FXBYOMANNHFNQV-UHFFFAOYSA-L magnesium;hydrogen sulfate Chemical compound [Mg+2].OS([O-])(=O)=O.OS([O-])(=O)=O FXBYOMANNHFNQV-UHFFFAOYSA-L 0.000 claims description 10
- 230000001264 neutralization Effects 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 235000015076 Shorea robusta Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N azanium;hydron;carbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 6
- MXZRMHIULZDAKC-UHFFFAOYSA-O [NH4+].[Mg+2].P(O)(O)(O)=O Chemical compound [NH4+].[Mg+2].P(O)(O)(O)=O MXZRMHIULZDAKC-UHFFFAOYSA-O 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 46
- 238000000034 method Methods 0.000 abstract description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000000706 filtrate Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract 1
- 235000011130 ammonium sulphate Nutrition 0.000 abstract 1
- 230000003472 neutralizing Effects 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 40
- 239000003921 oil Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 235000012970 cakes Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- OHORFAFFMDIQRR-UHFFFAOYSA-P Hexafluorosilicic acid Chemical compound [H+].[H+].F[Si-2](F)(F)(F)(F)F OHORFAFFMDIQRR-UHFFFAOYSA-P 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- -1 phosphorus ammonium Chemical compound 0.000 description 2
- 230000001105 regulatory Effects 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- 229910017625 MgSiO Inorganic materials 0.000 description 1
- MSKSOBAQMWJYTJ-UHFFFAOYSA-N [Mg].OP(O)(O)=O Chemical compound [Mg].OP(O)(O)=O MSKSOBAQMWJYTJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recycling magnesium from middle-low grade high-magnesium phosphate rock, which is used for pretreating phosphate rock serving as a raw material and recycling magnesium during wet phosphoric acid production. The method comprises the following steps of: removing magnesium from the middle-low grade high-magnesium phosphate rock with a magnesium removing agent by using a chemical method and dissolving most magnesium in the phosphate rock out of phosphate rock pulp; after a magnesium removing reaction is finished, performing solid-liquid separation on the formed pulp, wherein an obtained solid filter cake is magnesium-removed phosphate concentrate which can be put into the wet production of phosphoric acid; putting filtrate serving as magnesium-removed pulp into a next precipitation reaction procedure, adding an appropriate amount of neutralizing precipitant to adjust the pH value to 7.5-9.0 and undergoing a precipitation reaction; and performing solid-liquid separation after the reaction, and drying the solid precipitate which is ammonium magnesium phosphate with air stream to obtain a finished ammonium magnesium phosphate slow-release fertilizer. The obtained filtrate (containing ammonium sulfate) can be returned to wet phosphoric acid production.
Description
Technical field
The present invention relates to reclaim in a kind of therefrom low-grade high-magnesium-phosphorus ore the method for magnesium, relate to adopt in the preprocessing process of low-grade high-magnesium-phosphorus ore in a kind of raw material of Wet-process Phosphoric Acid Production chemical process to deviate from concretely and reclaims magnesium in the phosphorus ore, the method for Mg content in reduction phosphoric acid by wet process and the derived product thereof.
Background technology
The existence of magnesium to the processing of phosphorus ore particularly wet processes can bring a series of totally unfavorable influences.Because the magnesium salts in the phosphorus ore will all be dissolved in the phosphoric acid solution in Wet-process Phosphoric Acid Production, in Wet-process Phosphoric Acid Production, because magnesium all enters liquid phase and makes H in the phosphoric acid
+Concentration reduces greatly, has influenced the reaction of phosphorus ore, in order to keep certain H
+Concentration, the just necessary sulfate ion concentration that improves liquid phase so just causes crystal of calcium sulfate tiny.Simultaneously, because Mg
2+Existence, crystal of calcium sulfate is grown into elongated needle crystal, when this just makes phosphogypsum separate not only intensity filter descend, detersive efficiency also decreases, the phosphorus yield also just reduces.For the production equipment of identical scale, its actual capacity descends along with the increase of phosphorus ore magnesium content.Moreover, because a large amount of magnesium enters liquid phase, the phosphoric acid magnesium content height of producing, this brings disadvantageous effect also for the following process of phosphoric acid.Such as, produce coarse whiting and can cause that the secondary phosphorus ore resolution ratio reduces; Produce then block system very easily when Phosphoric Acid Concentration of phosphorus ammonium, strengthened system's cleaning frequency, and the water-soluble phosphorus of fertilizer and available phosphorus are descended; Produce phosphoric acid salt then because the existence of magnesium can reduce its product purity, or the load of phosphoric acid purification system is increased greatly.
For deviating from the impurity that comprises magnesium in the phosphorus ore, the popular beneficiation method is physical concentration both at home and abroad at present.So-called physical concentration mainly is to utilize the difference of different substances on physicals and proportion, adopt clean, dense medium is chosen with physical method such as positive reverse flotation phosphorus ore is separated with impurity, reaches the method for enrichment phosphorus ore.But because China contains " collophanite " that the magnesium phosphorus ore belongs to difficult choosing, carbonate content height, gangue mineral often are distributed in wherein with trickle oolith shape particles dispersed embedding, and cost is higher, and initial cost is bigger, and productive expense is also higher, and waste water is difficult to handle.Therefore, only adopt the method ore dressing of physical concentration, its result is also unsatisfactory.
A kind of method of chemical de-magging is disclosed among the Chinese patent CN1924046A, it adopts compound de-magging agent that magnesium is spun off from phosphorus ore, compound de-magging agent is the mixture of the vitriol oil or the vitriol oil and sodium ethylene diamine tetracetate or silicofluoric acid or nitric acid, though compound de-magging agent like this can spin off the magnesium in the phosphorus ore, but because compound de-magging agent is acid strong, cause easily generating phosphoric acid behind the phosphorus reaction in the phosphorus ore and cause the phosphorus loss, reaction mechanism is as follows
Ca
10F
2(PO
4)
6+H
2SO
4+?H
2O→H
3PO
4+?CaSO
4.2H
2O?+HF。
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of both can slough in most of magnesium in the low-grade high-magnesium-phosphorus ore, can also reduce to reclaim in the therefrom low-grade high-magnesium-phosphorus ore of loss of phosphorus in the phosphorus ore method of magnesium.
The object of the present invention is achieved like this, reclaims the method for magnesium in a kind of therefrom low-grade high-magnesium-phosphorus ore, comprises following processing step:
(1) in magniferous ground phosphate rock or phosphorus ore slurry, adds water and be made into the slurries that mass concentration is 25-35%, be warming up to 50 ~ 60 ℃, stir adding de-magging agent in above-mentioned slurries down, and the maintenance pH value be 50 ~ 60 ℃ of 2.0-4.0, temperature, stirring reaction 2-3 hour, deviate from the magnesium in the phosphorus ore; Described de-magging agent is the mixture of magnesium hydrogen sulfate or the vitriol oil and sal epsom;
(2) stop to stir, above-mentioned reaction solution is carried out solid-liquid separation, solid phase is the phosphorus concentrate behind the de-magging, and liquid phase is for containing the magnesium slip;
(3) the magnesium slip that contains that step (2) obtains enters in the neutralization precipitation groove, adds neutralization precipitation agent adjustment pH value to 7.5 ~ 9.0 under stirring and carries out neutralization-precipitation reaction, reacts 20 ~ 60min under 50 ~ 60 ℃ condition, and precipitation is separated out magnesium ammonium phosphate; Described neutralization precipitation agent be monoammonium phosphate or monoammonium phosphate and bicarbonate of ammonia or with ammoniacal liquor or with liquefied ammonia in any mixture.
(4) after precipitin reaction is finished, the precipitation slip is carried out solid-liquid separation obtain solid phosphoric acid ammonium magnesium.
Adopt technique scheme, as the de-magging agent, the reaction product of sulfuric acid and sal epsom also is magnesium hydrogen sulfate Mg (HSO with the mixture of magnesium hydrogen sulfate or the vitriol oil and sal epsom
4)
2), the mechanism of its de-magging is as follows:
CaCO
3＋Mg(HSO
4)
2＋H
2O→CaSO
4 .2H
2O↓+?CO
2↑+?MgSO
4
MgCO
3＋Mg(HSO
4)
2→MgSO
4+H
2O+CO
2↑
CaSiO
3＋Mg(HSO
4)
2＋H
2O→CaSO
4 .2H
2O↓+SiO
2↓+?MgSO
4
MgSiO
3＋Mg(HSO
4)
2→MgSO
4+SiO
2↓+H
2O
At first magnesium is with MgSO
4Form stay in the liquid phase simultaneously lime carbonate and sulfuric acid reaction generation CaSO
4.2H
2O is precipitated out as precipitation, and it is separated with magnesium.Because a little less than the acidity of acidity than the mixture of the vitriol oil or the vitriol oil and sodium ethylene diamine tetracetate or silicofluoric acid or nitric acid of magnesium hydrogen sulfate, according to strong acid system faintly acid principle, magnesium hydrogen sulfate is difficult to Ca
10F
2(PO
4)
6Be reacted into phosphoric acid and cause the phosphorus loss.Magnesium hydrogen sulfate dissolves in slip as salt on the other hand, helps CaSO
4 .2H
2O and Ca
10F
2(PO
4)
6Precipitation, and improved the quality of magnesium ammonium phosphate.Demagnesium rate of the present invention can reach 70%～85%, and the phosphorus loss is less than 3%.
The mechanism that the present invention reclaims magnesium is:
PO
4 3-?+?6H
2O+Mg
2+＋NH
4 +→MgNH
4PO
4·6H
2O↓
Gained filtrate (sulfur acid ammonium) can be returned the Wet-process Phosphoric Acid Production use in the step 4 in addition.This both can make water resources obtain recycle, can avoid again separation and washings discharging are polluted environment.
In order to make reaction more abundant, the fineness of described magniferous ground phosphate rock or phosphorus ore slurry reach 85% contain magnesium ground phosphate rock or phosphorus ore was starched 100 mesh sieve.
In order to reduce the magnesium loss, reduce the Mg content in the phosphorus concentrate: the solid phase after separating in the step (2) washes with water, and the liquid after the washing is incorporated into and contained in the magnesium slip.
In technique scheme: described de-magging agent is a magnesium hydrogen sulfate.
In technique scheme: described de-magging agent is obtained after sal epsom 40-60 part mixes by vitriol oil 40-60 part of 98%.
In technique scheme: after precipitin reaction is finished, the precipitation slip is forced vacuum filtration, filter cake water or phosphorus-containing wastewater washing obtain solid phosphoric acid ammonium magnesium.
In technique scheme: the magnesium ammonium phosphate that obtains in the step (4) directly is used as slow-release fertilizer or does the slow fertile coating agent of controlling/release after adopting air stream drying under the 80-100 ℃ of condition.
In technique scheme, described neutralization precipitation agent is a monoammonium phosphate.Make magnesium be precipitated out with the form of magnesium ammonium phosphate at last, the magnesium ammonium phosphate of generation can be used to produce the magnesium ammonium phosphate slow-release fertilizer.
In technique scheme, described neutralization precipitation agent is any mixture in monoammonium phosphate and bicarbonate of ammonia or ammoniacal liquor or the liquefied ammonia.Stripping quantity (can be drawn by the amount of adding the de-magging agent) according to magnesium in the process of reaction adds monoammonium phosphate, and the interpolation of bicarbonate of ammonia or ammoniacal liquor or liquefied ammonia makes also has enough NH in the reaction solution
4 +, help the formation and the precipitation of magnesium ammonium phosphate.
Beneficial effect: the present invention reclaims the efficient height of magnesium, and the phosphorus loss is little, and simple and reliable process is fit to suitability for industrialized production.
Specific embodiments
The present invention is further illustrated below in conjunction with embodiment
Embodiment 1
(1) get in low-grade high-magnesium-phosphorus ore (P
2O
5Content is 25.2%, and MgO content is 3.14%, MgO/ P
2O
5Be 12.46%) grind to form ground phosphate rock, the ground phosphate rock fineness is 80% mistake, 100 mesh sieve.Get 650 gram breezes in reactive tank, add water 1625g and stir.Warming-in-water to 60 ℃, adding de-magging agent (by obtaining after 50 parts of 98% vitriol oils and 50 parts of mixing of sal epsom) regulates pH value and equals to stop to add the de-magging agent at 3.5 o'clock, add de-magging agent 235.7g altogether, bath temperature constant temperature to 60 ℃, stirring reaction 2h is dissolved the magnesium in the phosphorus ore under the effect of acid.
(2) the de-magnesium reaction slip carries out solid-liquid separation in the mode (can adopt centrifugal treating when equivalent is big) of forcing vacuum filtration, and uses the proper amount of clear water washing leaching cake.Filter cake is a de-magging phosphorus concentrate, the production that can enter phosphoric acid by wet process, and it is composed as follows:
| P 2O 5（%） | MgO（%） | MgO/P 2O 5(%) |
| 25.0 | 0.71 | 2.84 |
(3) filtrate after vacuum filtration enters the neutralization-precipitation reaction groove, adds the pH value to 7.5 that monoammonium phosphate is regulated slip under 55 ℃ of conditions, adds monoammonium phosphate 23g altogether, stirring reaction 60min, and the magnesium ammonium phosphate that reaction is generated is fully separated out.
(4) the precipitation slip after precipitin reaction finishes carries out solid-liquid separation (can adopt centrifugal treating when equivalent is big) with vacuum filtration, and washes with water, and filtrate is returned phosphoric acid by wet process and used.
(5) filter cake behind the filtration washing promptly obtains the magnesium ammonium phosphate product carrying out air stream drying under 90 ℃ about two hours, and it is composed as follows:
| P 2O 5（%） | MgO（%） | N（%） |
| 36.82 | 19.12 | 5.09 |
Embodiment 2
(1) get in low-grade high-magnesium-phosphorus ore (P
2O
5Content is 25.2%, and MgO content is 3.14%, MgO/ P
2O
5Be 12.46%) grind to form ground phosphate rock, the ground phosphate rock fineness is 80% mistake, 100 mesh sieve.Get 600 gram breezes in reactive tank, adding water 1800g stirs, water-bath to 60 ℃, adding de-magging agent magnesium hydrogen sulfate regulates pH value and equals to stop to add the de-magging agent at 4.0 o'clock, add magnesium hydrogen sulfate 220.6g altogether, bath temperature constant temperature to 60 ℃, stirring reaction 120min is dissolved the magnesium in the phosphorus ore under the effect of acid.
(2) the de-magnesium reaction slip carries out solid-liquid separation in the mode of forcing vacuum filtration, and uses the proper amount of clear water washing leaching cake.Filter cake is a de-magging phosphorus concentrate, the production that can enter phosphoric acid by wet process, and it is composed as follows:
| P 2O 5（%） | MgO（%） | MgO/P 2O 5(%) |
| 25.1 | 0.79 | 3.15 |
(3) filtrate after vacuum filtration enters the neutralization-precipitation reaction groove, under 60 ℃ of conditions, add concentration and be the pH value to 8 that 26.5% ammoniacal liquor and monoammonium phosphate are regulated slip, add concentration altogether and be 26.5% ammoniacal liquor 7.2g, monoammonium phosphate 17g, stirring reaction 45min, the magnesium ammonium phosphate that reaction is generated is fully separated out.
(4) the precipitation slip after precipitin reaction finishes carries out solid-liquid separation with vacuum filtration and washes with water, and filtrate is returned phosphoric acid by wet process and used.
(5) filter cake behind the filtration washing promptly obtains the magnesium ammonium phosphate product carrying out air stream drying under 90 ℃ about two hours, and it is composed as follows:
| P 2O 5（%） | MgO（%） | N（%） |
| 35.90 | 20.32 | 5.28 |
Embodiment 3
(1) get in low-grade high-magnesium-phosphorus ore (P
2O
5Content is 25.2%, and MgO content is 3.14%, MgO/ P
2O
5Be 12.46%) grind to form ground phosphate rock, the ground phosphate rock fineness is 80% mistake, 100 mesh sieve.. get 650 gram breezes in reactive tank, add water 1300g and stir water-bath to 60 ℃, adding de-magging agent (by obtaining after 55 parts of 98% vitriol oils and 45 parts of mixing of sal epsom) regulates pH value and equals to stop to add the de-magging agent at 3.0 o'clock, add de-magging agent 212.4g altogether, bath temperature constant temperature to 50 ℃, stirring reaction 120min is dissolved the magnesium in the phosphorus ore under the effect of acid.
(2) the de-magnesium reaction slip carries out solid-liquid separation in the mode of forcing vacuum filtration, and uses the proper amount of clear water washing leaching cake.Filter cake is a de-magging phosphorus concentrate, the production that can enter phosphoric acid by wet process, and it is composed as follows:
| P 2O 5（%） | MgO（%） | MgO/P 2O 5(%) |
| 24.9 | 0.67 | 2.69 |
(3) filtrate after vacuum filtration enters the neutralization-precipitation reaction groove, under 50 ℃ of conditions, add in liquefied ammonia and the monoammonium phosphate and the pH value to 9.0 of adjusting slip, add liquefied ammonia 11.7g altogether, monoammonium phosphate 14.6g, stirring reaction 60min, the magnesium ammonium phosphate that reaction is generated is fully separated out.
(4) the precipitation slip after precipitin reaction finishes carries out solid-liquid separation with vacuum filtration and washes with water, and filtrate is returned phosphoric acid by wet process and used.
(5) filter cake behind the filtration washing promptly obtains the magnesium ammonium phosphate product carrying out air stream drying under 90 ℃ about two hours, and it is composed as follows:
| P 2O 5（%） | MgO（%） | N（%） |
| 37.74 | 20.43 | 5.30 |
Embodiment 4
(1) get in low-grade high-magnesium-phosphorus ore (P
2O
5Content is 25.2%, and MgO content is 3.14%, MgO/ P
2O
5Be 12.46%) grind to form ground phosphate rock, the ground phosphate rock fineness is 80% mistake, 100 mesh sieve.. get 650 gram breezes in reactive tank, add water 1300g and stir water-bath to 50 ℃, adding de-magging agent (by obtaining after 55 parts of 98% vitriol oils and 45 parts of mixing of sal epsom) regulates pH value and equals to stop to add the de-magging agent at 3.0 o'clock, add de-magging agent 212.4g altogether, bath temperature constant temperature to 55 ℃, stirring reaction 120min is dissolved the magnesium in the phosphorus ore under the effect of acid.
(2) the de-magnesium reaction slip carries out solid-liquid separation in the mode of forcing vacuum filtration, and uses the proper amount of clear water washing leaching cake.Filter cake is a de-magging phosphorus concentrate, the production that can enter phosphoric acid by wet process, and it is composed as follows:
| P 2O 5（%） | MgO（%） | MgO/P 2O 5(%) |
| 24.8 | 0.68 | 2.74 |
(3) filtrate after vacuum filtration enters the neutralization-precipitation reaction groove, under 55 ℃ of conditions, add in bicarbonate of ammonia and the monoammonium phosphate and the pH value to 9.0 of adjusting slip, add bicarbonate of ammonia 49g altogether, monoammonium phosphate 14.6g, stirring reaction 60min, the magnesium ammonium phosphate that reaction is generated is fully separated out.
(4) the precipitation slip after precipitin reaction finishes carries out solid-liquid separation with vacuum filtration and washes with water, and filtrate is returned phosphoric acid by wet process and used.
(5) filter cake behind the filtration washing promptly obtains the magnesium ammonium phosphate product carrying out air stream drying under 90 ℃ about two hours, and it is composed as follows:
| P 2O 5（%） | MgO（%） | N（%） |
| 37.63 | 20.34 | 5.28 |
Claims (9)
1. reclaim the method for magnesium in the therefrom low-grade high-magnesium-phosphorus ore, comprise following processing step:
(1) in magniferous ground phosphate rock or phosphorus ore slurry, adds water and be made into the slurries that mass concentration is 25-35%, be warming up to 50 ~ 60 ℃, stir adding de-magging agent in above-mentioned slurries down, and the maintenance pH value be 50 ~ 60 ℃ of 2.0-4.0, temperature, stirring reaction 2-3 hour, deviate from the magnesium in the phosphorus ore; Described de-magging agent is the mixture of magnesium hydrogen sulfate or the vitriol oil and sal epsom;
(2) stop to stir, above-mentioned reaction solution is carried out solid-liquid separation, solid phase is the phosphorus concentrate behind the de-magging, and liquid phase is for containing the magnesium slip;
(3) the magnesium slip that contains that step (2) obtains enters in the neutralization precipitation groove, adds neutralization precipitation agent adjustment pH value to 7.5 ~ 9.0 under stirring and carries out neutralization-precipitation reaction, reacts 20 ~ 60min under 50 ~ 60 ℃ condition,
Separate out magnesium ammonium phosphate; Described neutralization precipitation agent be monoammonium phosphate or monoammonium phosphate and bicarbonate of ammonia or with ammoniacal liquor or with liquefied ammonia in any mixture;
(4) after precipitin reaction is finished, the precipitation slip is carried out solid-liquid separation obtain solid phosphoric acid ammonium magnesium.
2. according to the method that reclaims magnesium in the described therefrom low-grade high-magnesium-phosphorus ore of claim 1, it is characterized in that: the fineness of described magniferous ground phosphate rock or phosphorus ore slurry reaches 85% magniferous ground phosphate rock or phosphorus ore and starched 100 mesh sieves.
3. according to the method that reclaims magnesium in the described therefrom low-grade high-magnesium-phosphorus ore of claim 1, it is characterized in that: the solid phase after separating in the step (2) washes with water, and the liquid after the washing is incorporated into and contained in the magnesium slip.
4. according to the method that reclaims magnesium in the described therefrom low-grade high-magnesium-phosphorus ore of claim 1, it is characterized in that: described de-magging agent is a magnesium hydrogen sulfate.
5. according to the method that reclaims magnesium in the described therefrom low-grade high-magnesium-phosphorus ore of claim 1, it is characterized in that: described de-magging agent is obtained after sal epsom 40-60 part mixes by vitriol oil 40-60 part of 98%.
6. according to the method that reclaims magnesium in the described therefrom low-grade high-magnesium-phosphorus ore of claim 1, it is characterized in that: after precipitin reaction is finished in the step (4), the precipitation slip is forced vacuum filtration, filter cake water or phosphorus-containing wastewater washing obtain solid phosphoric acid ammonium magnesium.
7. according to the method that reclaims magnesium in the described therefrom low-grade high-magnesium-phosphorus ore of claim 1, it is characterized in that: the magnesium ammonium phosphate that obtains in the step (4) directly is used as slow-release fertilizer or does the slow fertile coating agent of controlling/release after adopting air stream drying under the 80-100 ℃ of condition.
8. according to the method that reclaims magnesium in the described therefrom low-grade high-magnesium-phosphorus ore of claim 1, it is characterized in that: described neutralization precipitation agent is a monoammonium phosphate.
9. according to the method that reclaims magnesium in the described therefrom low-grade high-magnesium-phosphorus ore of claim 1, it is characterized in that: described neutralization precipitation agent be monoammonium phosphate and bicarbonate of ammonia or with ammoniacal liquor or with liquefied ammonia in any mixture.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776367A (en) * | 2012-08-14 | 2012-11-14 | 安徽六国化工股份有限公司 | Method for demagging ground phosphorite and preparing MgHPO4.3H2O |
| CN102923684A (en) * | 2012-11-09 | 2013-02-13 | 瓮福（集团）有限责任公司 | Method for utilizing magnesium bicarbonate aqueous solution to produce magnesium ammonium phosphate compound fertilizer |
| CN102992284A (en) * | 2012-12-12 | 2013-03-27 | 贵州开磷（集团）有限责任公司 | High-magnesium phosphorite de-magging method with by-product magnesium ammonium phosphate |
| CN103318867A (en) * | 2013-06-13 | 2013-09-25 | 江苏远东环保工程有限公司 | Method for recovering magnesium ammonium phosphate from magnesia process desulfurization waste liquid and equipment system of method |
| CN103864037A (en) * | 2014-03-21 | 2014-06-18 | 昆明理工大学 | Method for removing magnesium from phosphorite and recycling rare earth element in phosphorite through industrial smoke |
| CN104445120A (en) * | 2014-11-04 | 2015-03-25 | 湖北祥云(集团)化工股份有限公司 | Co-production method and system of ammonium phosphate and magnesium hydrate |
| CN106745105A (en) * | 2016-12-29 | 2017-05-31 | 云南磷化集团有限公司 | A kind of gypsum stack backwater is used for the method that high-magnesium-phosphorus ore drop magnesium carries phosphorus |
| 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 |
| CN109437982A (en) * | 2018-11-12 | 2019-03-08 | 贵州开磷氟硅化工有限责任公司 | A kind of method that phosphorus ore de-magging waste liquid prepares water-soluble ammonium sulphate phosphate fertiliser containing magnesium feed additives |
| CN110697674A (en) * | 2019-12-03 | 2020-01-17 | 中化重庆涪陵化工有限公司 | Method for producing magnesium ammonium phosphate by using high-magnesium phosphate tailings |
| CN111438002A (en) * | 2020-04-20 | 2020-07-24 | 武汉工程大学 | Method for treating silicon-calcium collophanite by 'floating-chemical' coupling |
| CN112758971A (en) * | 2021-01-04 | 2021-05-07 | 贵州芭田生态工程有限公司 | Method for recycling calcium-magnesium-containing leaching solution |
| CN112794346A (en) * | 2021-01-04 | 2021-05-14 | 贵州芭田生态工程有限公司 | Method for simultaneously preparing calcium sulfate, potassium nitrate, potassium magnesium nitrate and magnesium carbonate from calcium magnesium ammonium nitrate liquid |
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| CN102776367A (en) * | 2012-08-14 | 2012-11-14 | 安徽六国化工股份有限公司 | Method for demagging ground phosphorite and preparing MgHPO4.3H2O |
| CN102776367B (en) * | 2012-08-14 | 2013-10-23 | 安徽六国化工股份有限公司 | Method for demagging ground phosphorite and preparing MgHPO4.3H2O |
| CN102923684A (en) * | 2012-11-09 | 2013-02-13 | 瓮福（集团）有限责任公司 | Method for utilizing magnesium bicarbonate aqueous solution to produce magnesium ammonium phosphate compound fertilizer |
| CN102992284A (en) * | 2012-12-12 | 2013-03-27 | 贵州开磷（集团）有限责任公司 | High-magnesium phosphorite de-magging method with by-product magnesium ammonium phosphate |
| CN102992284B (en) * | 2012-12-12 | 2014-10-29 | 贵州开磷（集团）有限责任公司 | High-magnesium phosphorite de-magging method with by-product magnesium ammonium phosphate |
| CN103318867A (en) * | 2013-06-13 | 2013-09-25 | 江苏远东环保工程有限公司 | Method for recovering magnesium ammonium phosphate from magnesia process desulfurization waste liquid and equipment system of method |
| CN103864037A (en) * | 2014-03-21 | 2014-06-18 | 昆明理工大学 | Method for removing magnesium from phosphorite and recycling rare earth element in phosphorite through industrial smoke |
| CN103864037B (en) * | 2014-03-21 | 2016-08-17 | 昆明理工大学 | Industrial smoke is utilized to carry out phosphorus ore de-magging and the method reclaiming phosphorus ore rare earth elements |
| CN104445120B (en) * | 2014-11-04 | 2016-06-15 | 湖北祥云(集团)化工股份有限公司 | A kind of phosphorus ammonium and magnesium hydroxide with coproduction method and system |
| CN104445120A (en) * | 2014-11-04 | 2015-03-25 | 湖北祥云(集团)化工股份有限公司 | Co-production method and system of ammonium phosphate and magnesium hydrate |
| CN106745105A (en) * | 2016-12-29 | 2017-05-31 | 云南磷化集团有限公司 | A kind of gypsum stack backwater is used for the method that high-magnesium-phosphorus ore drop magnesium carries phosphorus |
| 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 |
| CN109437982A (en) * | 2018-11-12 | 2019-03-08 | 贵州开磷氟硅化工有限责任公司 | A kind of method that phosphorus ore de-magging waste liquid prepares water-soluble ammonium sulphate phosphate fertiliser containing magnesium feed additives |
| CN110697674A (en) * | 2019-12-03 | 2020-01-17 | 中化重庆涪陵化工有限公司 | Method for producing magnesium ammonium phosphate by using high-magnesium phosphate tailings |
| CN110697674B (en) * | 2019-12-03 | 2021-03-30 | 中化重庆涪陵化工有限公司 | Method for producing magnesium ammonium phosphate by using high-magnesium phosphate tailings |
| CN111438002A (en) * | 2020-04-20 | 2020-07-24 | 武汉工程大学 | Method for treating silicon-calcium collophanite by 'floating-chemical' coupling |
| CN112758971A (en) * | 2021-01-04 | 2021-05-07 | 贵州芭田生态工程有限公司 | Method for recycling calcium-magnesium-containing leaching solution |
| CN112794346A (en) * | 2021-01-04 | 2021-05-14 | 贵州芭田生态工程有限公司 | Method for simultaneously preparing calcium sulfate, potassium nitrate, potassium magnesium nitrate and magnesium carbonate from calcium magnesium ammonium nitrate liquid |
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