CN115520843A - Method for improving phosphorus yield of low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite - Google Patents
Method for improving phosphorus yield of low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite Download PDFInfo
- Publication number
- CN115520843A CN115520843A CN202211208881.7A CN202211208881A CN115520843A CN 115520843 A CN115520843 A CN 115520843A CN 202211208881 A CN202211208881 A CN 202211208881A CN 115520843 A CN115520843 A CN 115520843A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- phosphorite
- acid
- mother liquor
- chemical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
Abstract
The invention discloses a method for improving the yield of phosphorus in low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite, which comprises the following steps: preparing magnesium-containing phosphate ore; adding diluted acid into magnesium-containing phosphorite to carry out demagging reaction to obtain reacted slurry; the diluted dilute acid controls the acidity PH to be 1-2, mainly reacts with carbonate and rarely reacts with phosphorite due to low acidity, thereby improving the yield of phosphorus; carrying out solid-liquid separation on the slurry after the reaction to obtain a low-magnesium phosphate cake and a magnesium-removed mother liquor; settling and separating the magnesium-removed mother liquor to remove suspended matters in the magnesium-removed mother liquor to obtain clear mother liquor; part of the obtained clarified mother liquor is returned to an acid mixer to dilute sulfuric acid or phosphoric acid, and part of the clarified mother liquor is sent to a water treatment process for recycling. The method is economical and feasible, and improves the recovery rate of phosphorus in the chemical magnesium removal process of the magnesium-containing phosphorite.
Description
Technical Field
The invention belongs to the technical field of phosphorite processing, and particularly relates to a method for improving the yield of low-magnesium phosphorite phosphorus produced by chemical magnesium removal of magnesium-containing phosphorite.
Background
The storage capacity of phosphorite in China is the second place in the world, most of the phosphorite is refractory medium-low grade collophanite, mineral particles are fine and closely embedded, associated magnesium and other impurities are high, the use of the phosphorite can increase the acid consumption during wet treatment of the phosphorite, and the deep processing process and the product quality of phosphoric acid and phosphate are influenced. Along with the development of social economy, the living standard of people is improved, the demand of the society on phosphorus resources is continuously increased, and the high-grade and low-magnesium resources which can be mined by phosphorite are less and less. The quality of phosphorite is reduced, and the impurity content is higher, which is a problem faced by people. For the utilization of high-magnesium phosphate ore, part of magnesium content needs to be removed firstly, so that the phosphate ore can be used for normal production of wet-process phosphoric acid and can be used for smoothly producing subsequent fine phosphate products.
The prior magnesium-containing phosphorite magnesium removal method mainly comprises flotation magnesium removal and chemical magnesium removal. The comprehensive flotation method has wide application range for magnesium removal. Part of manufacturers adopt concentrated sulfuric acid to carry out chemical magnesium removal pretreatment on magnesium-containing phosphorite, then prepare wet-process phosphoric acid from the magnesium-removed phosphorite, and then carry out wet-process phosphoric acid refining and subsequent production of fine phosphate products. However, concentrated sulfuric acid is strong acid, so that the concentrated sulfuric acid can not be reacted with phosphorite to cause partial phosphorus loss, and the economic index in actual production is difficult to achieve, so that the method can not be popularized.
Disclosure of Invention
The invention aims to provide a method for improving the yield of low-magnesium phosphate rock phosphorus produced by chemical magnesium removal of magnesium-containing phosphate rock so as to meet the normal production requirement of wet-process phosphoric acid, thereby subsequently producing various fine phosphate products with qualified quality and solving the problem caused by the direct chemical magnesium removal of concentrated acid in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a method for improving the yield of phosphorus in low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite comprises the following steps:
step A: preparing magnesium-containing phosphate ore;
and B: adding diluted acid into magnesium-containing phosphorite to perform demagging reaction to obtain reacted slurry; the diluted dilute acid controls the acidity PH to be 1-2, mainly reacts with carbonate and rarely reacts with phosphorite due to low acidity, thereby improving the yield of phosphorus;
step C: carrying out solid-liquid separation on the slurry after the reaction to obtain a low-magnesium phosphate cake and a magnesium-removed mother liquor;
step D: settling and separating the magnesium-removed mother liquor to remove suspended matters in the magnesium-removed mother liquor to obtain clarified mother liquor;
and E, step E: and D, returning part of the clarified mother liquor obtained in the step D to an acid mixer to dilute sulfuric acid or phosphoric acid, and sending part of the clarified mother liquor to a water treatment process for recycling.
Further, in the acid-adding chemical demagging reaction in the step B, the used diluted acid is sulfuric acid or phosphoric acid, and the pH value is 1-2.
Further, in the step B, the addition manner of the diluted acid is: adding the magnesium-containing phosphorite into the magnesium-containing phosphorite while stirring, and adding the magnesium-containing phosphorite into a magnesium removal reaction tank (4 tanks in the invention) in multiple tanks and multiple points for chemical magnesium removal of the magnesium-containing phosphorite, thereby reducing the phosphorus loss of the magnesium-removed phosphorite.
Furthermore, in the step B, the temperature of the magnesium removal reaction is 45-50 ℃, and the temperature is too high, so that diluted acid is added to react with part of phosphorite, and the reaction recovery rate is reduced; the inventor finds out through experiments that the reaction of the diluted acid and the phosphorite can be effectively avoided when the reaction temperature is controlled below 50 ℃.
Further, in the step B, the solid-to-solid ratio of the magnesium removal reaction liquid is controlled to be (2.5-3.0): 1.
further, the diluted acid used in the step B is a diluted acid obtained by diluting (pH 1-2) the partially clarified mother liquor (pH 2.5) obtained in the step D with sulfuric acid or phosphoric acid in an acid mixer, and the diluted acid is added into a demagging reaction tank for use.
In the invention, the main chemical reactions involved in the step B are as follows:
4H 3 PO 4 +(MgCa)(CO 3 ) 2 ＝Mg(H 2 PO 4 ) 2 +Ca(H 2 PO 4 ) 2 +2CO 2 ↑+2H 2 O (1)
2H 2 SO 4 +(MgCa)(CO 3 ) 2 ＝MgSO 4 +CaSO 4 ·2H 2 O↓+2CO 2 ↑ (2)
2H 3 PO 4 +CaCO 3 ＝Ca(H 2 PO 4 ) 2 +CO 2 ↑+H 2 O (3)
H 2 SO 4 +CaCO 3 +H 2 O＝CaSO 4 ·2H 2 O↓+CO 2 ↑ (4)
in addition, a small amount of fluorapatite and H 3 PO 4 The reaction takes place according to the following equation:
Ca 5 (PO 4 ) 3 F+7H 3 PO 4 ＝5Ca(H 2 PO 4 ) 2 +HF↑ (5)
the chemical magnesium removal of magnesium-containing phosphorite is suitable for phosphorite with magnesium oxide content not more than 4%.
Sulfuric acid or phosphoric acid (or mixed acid) is added into an acid mixer to be diluted with returned clarified magnesium-removed mother liquor, and then is added into a magnesium-removed reaction tank in multiple grooves and multiple points, wherein the slow addition in multiple grooves and multiple points is used for preventing the excessive local relative excess of acid addition to cause the excessive reaction of phosphorite and reduce the phosphorus recovery rate; part of the magnesium removal liquid is adopted to dilute the mixed sulfuric-phosphoric acid, so that the consumption of the mixed acid is reduced.
Because the magnesium removal of the magnesium-containing phosphorite by adopting concentrated sulfuric acid or concentrated phosphoric acid has the defects of large phosphorus loss (generally, the phosphorus loss is 3-5%) of the magnesium-removed phosphorite and high acid consumption; the invention adopts dilute acid (sulfuric acid or phosphoric acid) to carry out chemical demagging, firstly, the concentrated acid is diluted, and then, the diluted acid is added into the reaction tank in multiple points and multiple grooves to carry out demagging reaction, thereby reducing the phosphorus loss of the demagging phosphorite and reducing the acid consumption. The method has the characteristics of small loss and low consumption of magnesium and phosphorus removal of the phosphorite, and can be industrially implemented.
The method can effectively avoid phosphorus loss caused by the reaction of the phosphorite and the concentrated acid in a large amount, obtains the filter cake of the demagnetised phosphorite which is low-magnesium phosphorite, reaches the phosphorite standard for processing by the HG/T2673-1995 acid method, and can be directly used as a raw material to normally produce wet-process phosphoric acid and subsequently produce various fine phosphate products.
The traditional concentrated acid is adopted to carry out chemical magnesium removal on magnesium-containing phosphorite, and the phosphorus loss rate is generally about 3-5%; by adopting the chemical magnesium removal method, the phosphorus loss rate is about 1-3 percent, and the phosphorus yield is improved by 1-2 percent. The method is economical and feasible, and improves the recovery rate of phosphorus in the chemical magnesium removal process of magnesium-containing phosphorite.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Embodiments of the present invention will now be described with reference to the accompanying drawings. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention.
The present invention is further illustrated by the following examples.
Description of the drawings: the percentage contents of substances in the following examples are not particularly specified but refer to the mass percentage of substances.
The first embodiment is as follows:
A. magnesium-containing ground phosphate rock (dry basis P) 2 O 5 MgO =30.82% MgO = 2.03%), 100 mesh sieve throughput is greater than 85%, weigh 1000 kg;
B. feeding magnesium-containing phosphorite into a magnesium removal tank, adding diluted acid (PH = 2) while stirring, and controlling the liquid-solid ratio (2.5-3) of the reaction tank: 1. the pH of the slurry is =2.5, and a demagging reaction occurs; during the demagging reaction, detecting the pH of the slurry every 10min, and when the pH is =3, supplementing a diluting acid until the pH of the slurry is =2.5, and reacting for about 40min;
C. filter-pressing the reacted slurry by a plate-and-frame filter press to obtain a de-magnesiated phosphate cake and a de-magnesiated mother liquor, and taking the de-magnesiated phosphate cake as a wet-process phosphoric acid production raw material;
D. settling and separating the magnesium-removed mother liquor to remove suspended matters in the magnesium-removed mother liquor to obtain clarified mother liquor;
E. part of the clarified magnesium-removing liquid is returned to dilute sulfuric acid or phosphoric acid, and part of the clarified magnesium-removing liquid is sent to a water treatment process for recycling.
The obtained low-magnesium phosphate concentrate is 970.2 kg dry basis, P 2 O 5 =31.32%, mgO =0.92%. The phosphorus recovery rate is 98.59 percent, and the magnesium oxide removal rate is 56.03 percent. The loss of chemical magnesium and phosphorus removal is 1.41 percent.
Example two:
A. magnesium-containing ground phosphate rock (dry basis P) 2 O 5 =30.46% = mgo 2%), 100 mesh sieve pass rate > 85%, weigh 1000 kg;
B. feeding magnesium-containing phosphate rock powder into a magnesium removal tank, adding a diluting acid (PH = 1) while stirring, and controlling the acid-mineral ratio (2.5-3) of the reaction tank: 1, the pH of the slurry =1.5, and a demagging reaction occurs; detecting the pH of the slurry every 10min in the process of the magnesium removal reaction, and supplementing a diluting acid until the pH of the slurry is =2.5, and reacting for about 40min;
C. filter-pressing the reacted slurry by a plate-and-frame filter press to obtain a magnesium-removed phosphate rock filter cake and a magnesium-removed mother liquor, and taking the magnesium-removed phosphate rock filter cake as a raw material for producing wet-process phosphoric acid;
D. settling and separating the magnesium-removed mother liquor to remove suspended matters in the magnesium-removed mother liquor to obtain clarified mother liquor;
E. part of the clarified and demagging mother liquor is returned to dilute sulfuric acid or phosphoric acid, and part of the clarified and demagging mother liquor is sent to a water treatment process for treatment and then recycled.
The obtained low-magnesium phosphate concentrate dry basis is 938.6 kg, P 2 O 5 =31.69%, mgO =0.78%. The phosphorus recovery rate is 97.65 percent, and the magnesium oxide removal rate is 63.39 percent. The chemical magnesium and phosphorus removal loss is 2.35 percent.
The magnesium oxide removal rate of the magnesium-containing phosphorite is more than 55 percent, and the phosphorite yield is more than 97.5 percent. Compared with other chemical magnesium removal for producing low-magnesium phosphate ore, the yield of phosphorus is improved by 1-2%, and the method has better economic indexes and can be industrially popularized.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (6)
1. A method for improving the yield of phosphorus in low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite is characterized by comprising the following steps:
step A: preparing magnesium-containing phosphate ore;
and B: adding diluted acid into magnesium-containing phosphorite to perform demagging reaction to obtain reacted slurry;
and C: carrying out solid-liquid separation on the slurry after the reaction to obtain a low-magnesium phosphate cake and a magnesium-removed mother liquor;
step D: settling and separating the magnesium-removed mother liquor to remove suspended matters in the magnesium-removed mother liquor to obtain clear mother liquor;
step E: and D, returning part of the clarified mother liquor obtained in the step D to an acid mixer to dilute sulfuric acid or phosphoric acid, and sending part of the clarified mother liquor to a water treatment process for recycling.
2. The method for improving the phosphorus yield of the low-magnesium phosphorite produced by chemical magnesium removal of the magnesium-containing phosphorite according to claim 1, is characterized in that: in the acid-adding chemical magnesium removal reaction in the step B, the used diluted acid is sulfuric acid or phosphoric acid, and the PH is 1-2.
3. The method for improving the yield of phosphorus in low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite according to claim 1 or 2, characterized in that in the step B, the addition mode of the diluted acid is as follows: adding the magnesium-containing phosphate ore into the magnesium-containing phosphate ore while stirring, and adding the magnesium-containing phosphate ore into the magnesium removal reaction tank in multiple grooves and multiple points.
4. The method for improving the phosphorus yield of the low-magnesium phosphorite produced by chemical magnesium removal of the magnesium-containing phosphorite according to the claim 1 or 2, characterized in that, in the step B, the magnesium removal reaction temperature is 45-50 ℃.
5. The method for improving the phosphorus yield of the low-magnesium phosphorite produced by chemical magnesium removal of the magnesium-containing phosphorite according to the claim 1 or 2, characterized in that in the step B, the solid-to-solid ratio of the magnesium removal reaction liquid is controlled to be (2.5-3.0): 1.
6. the method for improving the yield of phosphorus in low-magnesium phosphorite by chemical demagging of magnesium-containing phosphorite as claimed in claim 1, wherein the diluted acid used in step B is diluted acid obtained by diluting part of the clarified mother liquor obtained in step D with sulfuric acid or phosphoric acid in an acid mixer, and the diluted acid is added into a demagging reaction tank for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211208881.7A CN115520843A (en) | 2022-09-30 | 2022-09-30 | Method for improving phosphorus yield of low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211208881.7A CN115520843A (en) | 2022-09-30 | 2022-09-30 | Method for improving phosphorus yield of low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115520843A true CN115520843A (en) | 2022-12-27 |
Family
ID=84699384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211208881.7A Pending CN115520843A (en) | 2022-09-30 | 2022-09-30 | Method for improving phosphorus yield of low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115520843A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1806089C (en) * | 1991-01-22 | 1993-03-30 | Владимир Григорьевич Богачев | Process of producing phosphoric acid |
| WO2008061473A1 (en) * | 2006-11-19 | 2008-05-29 | Shandong Wu | Phosphorite acidolysis method |
| CN102115819A (en) * | 2011-01-27 | 2011-07-06 | 中化重庆涪陵化工有限公司 | Method for recycling magnesium from middle-low grade high-magnesium phosphate rock |
| CN102674278A (en) * | 2012-05-25 | 2012-09-19 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorus rock by titanium dioxide waste acid |
| CN106744753A (en) * | 2016-12-30 | 2017-05-31 | 贵州开磷集团股份有限公司 | A kind of method of phosphorus ore stagewise de-magging |
| CN106800284A (en) * | 2017-01-10 | 2017-06-06 | 四川龙蟒磷化工有限公司 | A kind of method of the ammonium of phosphorus ore de-magging phosphoric acid byproduct one |
| CN107055495A (en) * | 2017-04-25 | 2017-08-18 | 贵州芭田生态工程有限公司 | A kind of acid phosphorus-containing wastewater is used for the method for phosphorus ore de-magging |
| CN110357054A (en) * | 2019-07-29 | 2019-10-22 | 四川大学 | The pretreated method of phosphorus ore |
-
2022
- 2022-09-30 CN CN202211208881.7A patent/CN115520843A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1806089C (en) * | 1991-01-22 | 1993-03-30 | Владимир Григорьевич Богачев | Process of producing phosphoric acid |
| WO2008061473A1 (en) * | 2006-11-19 | 2008-05-29 | Shandong Wu | Phosphorite acidolysis method |
| CN102115819A (en) * | 2011-01-27 | 2011-07-06 | 中化重庆涪陵化工有限公司 | Method for recycling magnesium from middle-low grade high-magnesium phosphate rock |
| CN102674278A (en) * | 2012-05-25 | 2012-09-19 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorus rock by titanium dioxide waste acid |
| CN106744753A (en) * | 2016-12-30 | 2017-05-31 | 贵州开磷集团股份有限公司 | A kind of method of phosphorus ore stagewise de-magging |
| CN106800284A (en) * | 2017-01-10 | 2017-06-06 | 四川龙蟒磷化工有限公司 | A kind of method of the ammonium of phosphorus ore de-magging phosphoric acid byproduct one |
| CN107055495A (en) * | 2017-04-25 | 2017-08-18 | 贵州芭田生态工程有限公司 | A kind of acid phosphorus-containing wastewater is used for the method for phosphorus ore de-magging |
| CN110357054A (en) * | 2019-07-29 | 2019-10-22 | 四川大学 | The pretreated method of phosphorus ore |
| CN113735081A (en) * | 2019-07-29 | 2021-12-03 | 四川大学 | Method for pretreating phosphorite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103706485B (en) | A kind of beneficiation method of high carbon acid calcium type fluorite ore | |
| CN102992284B (en) | High-magnesium phosphorite de-magging method with by-product magnesium ammonium phosphate | |
| CN104445300A (en) | Method of preparing magnesium hydroxide and calcium carbonate and separating out phosphorus ores by taking phosphate tailings as raw materials through ammonia circulation process | |
| CN109573972B (en) | Method for producing phosphoric acid and low-silicon gypsum from medium-low grade phosphorite | |
| CN103073034B (en) | Method for removing magnesium from ultralow-quality phosphate rock and producing magnesium hydroxide | |
| CN106744753B (en) | A kind of method of phosphorus ore stagewise de-magging | |
| CN110357054A (en) | The pretreated method of phosphorus ore | |
| CN108383094A (en) | The method for preparing calcium monohydrogen phosphate and ammonium chloride using reverse flotation phosphorus tailing | |
| CN107879321B (en) | Method for demagging phosphate rock and co-producing sodium fluosilicate and magnesium sulfate | |
| KR102029195B1 (en) | Manufacturing method for lithium hydroxide from lithium phosphate | |
| CN115520843A (en) | Method for improving phosphorus yield of low-magnesium phosphorite produced by chemical magnesium removal of magnesium-containing phosphorite | |
| US4393032A (en) | Production of phosphoric acid and additional products from phosphate ore | |
| CN107697893A (en) | Improve the method for calcium leaching efficiency and its product and application in phosphorus ore | |
| CN110255591A (en) | The method of phosphorus ore de-magging co-production magnesium carbonate and calcium carbonate | |
| CN113860343B (en) | Comprehensive utilization method of red mud and bauxite | |
| CN112429709B (en) | Method for graded production of wet-process phosphoric acid | |
| US4743438A (en) | Process for producing phosphoric acid from low purity phosphate rock | |
| CN103803517B (en) | The method of the low silicon ardealite of high silicon Phosphate Rock acid by-product | |
| CN106673026A (en) | Process for preparing crystal whisker calcium carbonate through combined production of high-purity magnesium hydrate and by-product | |
| CN113149717A (en) | Method for extracting phosphorus from flotation tailings | |
| CN112439552A (en) | Phosphate rock acid triggering-cyclone demagging method | |
| CN113148968A (en) | Method for producing alpha-semi-hydrated gypsum by wet-process phosphorus processing | |
| US4479923A (en) | Production of phosphoric acid and additional products from phosphate ore | |
| US4393030A (en) | Upgrading of phosphate ore | |
| CN112624074B (en) | Method for producing industrial grade monoammonium phosphate, monopotassium phosphate and fertilizer grade monoammonium phosphate from raffinate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |