CN1283584A - Process for preparing calcium hydrogen phosphate from middle-and low-grade phosphorus ore - Google Patents
Process for preparing calcium hydrogen phosphate from middle-and low-grade phosphorus ore Download PDFInfo
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- CN1283584A CN1283584A CN 99115057 CN99115057A CN1283584A CN 1283584 A CN1283584 A CN 1283584A CN 99115057 CN99115057 CN 99115057 CN 99115057 A CN99115057 A CN 99115057A CN 1283584 A CN1283584 A CN 1283584A
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- phosphoric acid
- hydrogen phosphate
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Abstract
A precess for preparing calcium hydrogen phosphate from middle-or low-grade phosphorus ore indudes acidolyzing the phosphorus ore with phosphoric acid as intermediate product to obtain suspension of calcium dihydrogen phosphate, and direct neutralizing reaction on lime milk to obtain calcium hydrogen phosphate while removing impurities and mud. Its advantages include high utilization rate of phosphorus, low consumption of lime and energy, long service life of equipment.
Description
The invention relates to the technical field of producing calcium hydrophosphate by using medium and low grade phosphorite, in particular to a process method for preparing calcium hydrophosphate by carrying out acidolysis reaction on the phosphorite and finally carrying out neutralization reaction on lime milk.
Calcium hydrogen phosphate has wide application and large market demand. The existing technology for producing calcium hydrogen phosphate is mainly a wet-process two-stage phosphoric acid sedimentation process, i.e. high-grade phosphate ore is used to prepare phosphoric acid, phosphogypsum waste residue is separated and removed, and lime milk and phosphoric acid are used to perform neutralization reaction to prepare calcium hydrogen phosphate. The deficiency of the prior art is that calcium contained in phosphate ore is removed firstly, and then calcium required by calcium hydrophosphate production is provided by adding lime milk, which not only does not fully utilize calcium in phosphate ore, but also increases the consumption of sulfuric acid and lime milk, increases energy consumption and process burden, andp in phosphate ore2O5The utilization rate is low.
The invention aims to avoid the defects of the prior art and provide people with a method for taking middle-low grade phosphorite as a raw material and fully utilizing calcium and P in the phosphorite2O5The utilization rate of the calcium hydrophosphate is high, the consumption of sulfuric acid, lime milk and energy is low, and the process is simple.
Aiming at the aim, the invention adopts the following technical measures, and the process steps are as follows:
1. the intermediate product phosphoric acid in the production process and the middle-low grade phosphorite are subjected to acidolysis reaction to generate suspension with the main component of monocalcium phosphate, and coarse sand impurities in the suspension are removed.
2. Adding flocculant, defluorinating agent and other treating agents into the calcium dihydrogen phosphate suspension without coarse sand impurities, separating to remove sludge which can be used as coarse fertilizer, performing crystallization reaction on one part of the suspension and sulfuric acid, and performing neutralization reaction on the rest part of the suspension and lime milk.
3. And (3) reacting with sulfuric acid crystallization to generate slurry with a solid phase of calcium sulfate and a liquid phase of phosphoric acid, and performing solid-liquid separation to obtain a solid of calcium sulfate and a liquid of phosphoric acid, wherein the phosphoric acid is returned to the acidolysis unit to be recycled as acidolysis acid.
4. And the calcium hydrogen phosphate is neutralized and reacted with lime milk to generate slurry of which the solid phase is calcium hydrogen phosphate, and the solid obtained is the calcium hydrogen phosphate to be produced through liquid-solid separation.
In the process method for producing calcium hydrophosphate by using medium and low grade phosphate ore, the main chemical reaction in the acidolysis reaction process is as follows:
the main chemical reaction of the neutralization reaction of calcium dihydrogen phosphate and lime milk is as follows:
the main chemical reactions of the crystallization reaction of calcium dihydrogen phosphate and sulfuric acid are:
the above-mentioned technological process can also be used for simultaneously producing calcium hydrogen phosphate and phosphoric acid, and only proper technological regulation is required. I.e. the separated, sludge-removed suspension of monocalcium phosphate, the major part of which is used for the crystallization reaction with sulfuric acid, and the remaining part of which is used for the neutralization reaction with milk of lime. Most of the phosphoric acid generated by the reaction with the sulfuric acid crystals is mixed with washing water and then returned to the acidolysis unit as acidolysis reaction phosphoric acid, and the rest phosphoric acid is concentrated into finished phosphoric acid.
The above process may be adjusted to produce only phosphoric acid. Namely, the suspension of the calcium dihydrogen phosphate after removing the sludge is completely used for carrying out crystallization reaction with sulfuric acid, a part of the phosphoric acid generated by the reaction is used as circulating phosphoric acid and returned to an acidolysis unit, and the rest part is concentrated into finished acid.
The invention further adopts the following technical measures.
The weight ratio of the part of the calcium dihydrogen phosphate suspension subjected to the sludge removal and used for the crystallization reaction with sulfuric acid to the part of the calcium dihydrogen phosphate suspension subjected to the neutralization reaction with lime milk is 6-18.
P of phosphorus ore2O5The content is not lower than 24 percent (wt), (the weight percentage is expressed by wt), when the acidolysis is carried out by using 10-20 percent (wt) phosphoric acid, the liquid-solid ratio of the phosphoric acid to the phosphorite is 2.5-5.0, the acidolysis reaction temperature is 70-80 ℃, the crystallization reaction temperature is 60-70 ℃, and the neutralization reaction temperature is 40-50 ℃.
P of phosphorus ore2O5The content of the phosphoric acid is 10-24% (wt), when 10-20% (wt) phosphoric acid is used for acidolysis, the liquid-solid ratio of the phosphoric acid to the phosphorite is 5-12, the acidolysis reaction temperature is 70-80 ℃, the crystallization reaction temperature is 55-65 ℃, and the neutralization reaction temperature is 40-50 ℃.
The raw material phosphate rock is crushed into particles with the particle size of not more than 5mm before the acidolysis reaction with the phosphoric acid.
The invention also adopts other technical measures.
Compared with the prior art, the invention has the following outstanding advantages:
1. the investment is low, and the waste of phosphorus resources is reduced. The calcium hydrophosphate is produced by using high-impurity low-grade phosphate rock, and if the existing process technology is adopted, the ore dressing investment is large, and the removal of impurities is difficult to reach the industrial use level. Most seriously, the loss of phosphorus is large and can reach 50%. Because the process method of the invention adopts phosphoric acid to leach the phosphorite, the phosphorus in the phosphorite can be effectively resolved, thus the mineral separation process can be cancelled, the phosphorus loss is greatly reduced, the phosphorus loss can be reduced to 3 percent, and compared with the prior art, the service time of the phosphorite resource can be doubled under the condition of the same yield. Annual capacity of 10 ten thousand tons P2O5For example, for a phosphoric acid production plant, the investment in the phosphoric acid plant in the conventional dihydrate process requires 11253 ten thousand yuan renowned coins, if P is to be added2O5Lean ore with content of about 15% is obtained by mineral separation30 percent, the beneficiation investment is approximately equal to that of a phosphoric acid system, the phosphorus loss can reach 50 percent, a large amount of fields are required to be opened up to be used as the stacking places of beneficiation sludge, and the time-effective period of the sludge is 10-15 years. The total investment is about 22500 ten thousand yuan. If the process of the invention is adopted, a mineral separation system can be omitted, although the investment of a phosphoric acid system is increased by about 1/3, the total investment is only 15000 ten thousand yuan, and the mining time of the mine is prolonged due to the reduction of phosphorus loss, so that the process is equivalent to the picking of a new mine.
2. P in phosphate ore2O5The conversion rate is high and can reach more than 95 percent. The acidolysis of phosphorite with the mixed acid of sulfuric acid and phosphoric acid is the most common prior art, but calcium sulfate will be simultaneously separated out in the acidolysis reaction process, and a calcium sulfate film is formed on the surface of phosphorite particles by deposition. The membrane is generally incomplete permeable, but when the process conditions are not well controlled, a dense membrane is formed, the further decomposition of the phosphorite is influenced to different degrees, and the insoluble membrane particularly hinders the reaction for the decomposition of the low-grade phosphorite. The invention adopts phosphoric acid to extract phosphorite, does not generate compact film, and performs acidolysis in a special reactor because phosphorite particles violently react with each otherCollision strengthens the mass transfer effect, thus having high phosphorus conversion rate.
3. Can greatly reduce the consumption of sulfuric acid and lime milk. The calcium hydrophosphate is produced by the process method of the invention, after the calcium hydrophosphate suspension liquid from the acidolysis reactor is pretreated, a part of the calcium hydrophosphate suspension liquiddirectly enters a neutralization reaction tank, and the pH value is properly adjusted, so that part of the calcium hydrophosphate can be directly obtained. Because the part of calcium separated out from the suspension slurry does not need to be reacted by sulfuric acid, part of sulfuric acid and most of lime milk can be saved, and thus, the raw material consumption and the energy consumption are reduced. Compared with the production process of calcium hydrophosphate in the prior art, the production process can save 3-30% of sulfuric acid and 17-100% of lime milk (calculated by calcium oxide).
4. Effectively remove impurities in time and reduce the consumption of sulfuric acid. The Russian Condrania ore is measured and calculated, and P in the Ore2O5The content is reduced from 28 percent to 24.5 percent, and the consumption of the sulfuric acid is increased by 0.54 ton/ton P2O5I.e. the content of impurities in the phosphate rock influences the consumption of sulfuric acid. Because the acidolysis process is carried out in a special reactor and the negative temperature effect of iron and aluminum impurities is skillfully utilized, phosphorite particles are continuously and hierarchically elutriated in the reactor, most of impurities are left in silt and are discharged, sedimentation separation is carried out before crystallization reaction, sludge and waste residues are removed, and meanwhile, a large amount of circulating acid returns to an acidolysis unit, so that the reaction activity of the residual sulfuric acid and the first hydrogen ions in the phosphoric acid is fully utilized, the consumption of the sulfuric acid is further reduced, and compared with the common secondary water flow, the consumption of the sulfuric acid can be reduced by 1-3%.
5. Relatively pure phosphoric acid and gypsum can be obtained. Most of silt and sludge are effectively removed in time, so that the filtering strength of theequipment is improved, and the liquid filtering strength of the vacuum filtering device adopted in experiments is 763-1032 kgP2O5/h·m2And the purity of the product can be improved, the obtained phosphogypsum is white and clean, has the same color as snow, and provides a high-quality raw material for manufacturing a high-strength gypsum board.
6. The production of calcium hydrogen phosphate and phosphoric acid can be adjusted according to the market demand. Due to the process method, calcium hydrogen phosphate and phosphoric acid can be simultaneously produced, calcium hydrogen phosphate and phosphoric acid can be respectively produced, and the yield of the two products can be conveniently adjusted. Therefore, the yield of the two products can be adjusted according to the market demand, and the method is very convenient.
The figure is a process flow block diagram of one embodiment of the present invention.
The following examples are given and the present invention will be described in further detail by way of examples.
The technological process for producing calcium hydrophosphate from low-grade phosphate ore is shown in the attached figure. Takes the phosphorite of Xiaofeng in Sichuan province as the raw material, and the phosphorite mainly comprises the following components: p2O510.11％，CaO 15.68％，Al2O32.02％，Mg2O30.658％，Fe2O32.22 percent, A.I 59.99 percent, the particle size range of phosphorite is 2.5-4 mm, and phosphoric acid with the concentration of 14 percent and the phosphorite are added into the acidolysis reactor 1 according to the liquid-solid ratio of 10. The reactoris a multi-bin jet flow reactor with a grading function. The inlet A of the reactor is an inlet for acidolysis circulating phosphoric acid, and the inlet B is a phosphorite material inlet. The reaction temperature of the phosphorite and the phosphoric acid is controlled to be about 78 ℃, and the reaction time is about 2 hours. Coarse sand impurities containing a small amount of liquid are discharged from the outlet C, and the monocalcium phosphate suspension enters the static mixer 2 from the outlet D. Adding a polyacrylamide flocculant with the concentration of about 5ppm and a defluorination agent of a mixture of mirabilite and perovskite with the concentration of about 12% into a static mixer, uniformly mixing the calcium dihydrogen phosphate suspension with the added flocculant and defluorination agent, and then feeding into a settler 3. After full sedimentation, the thick slurry is discharged from an outlet E and enters a filter 4, filter residues are sludge and can be used as fertilizer, after the filtrate is combined with clear liquid, one part of the mixture is discharged from an outlet F and enters a crystallization reactor 5, and the other part of the mixture is discharged from an outlet G and enters a neutralization sedimentation tank 8. The weight ratio of the suspension entering the crystallization reactor to the suspension entering the neutralization reactor was about 10. Sulfuric acid with a concentration of 98% was added to the crystallization reactor. The addition amount of the sulfuric acid is determined by SO in the solution3The concentration of (2) is controlled,SO3the concentration of (A) is generally less than 3%. The crystallization reaction temperature is about 60 ℃, the reaction time is about 4 hours, so that the sulfuric acid and the calcium dihydrogen phosphate fully react to generate solid-phase CaSO4And the liquid phase is phosphoric acid slurry. The slurry from the crystallization reactor 5 enters a settler 6, after the slurry is fully settled inthe settler, the supernatant phosphoric acid is directly discharged and contains CaSO4The thick liquid layer phosphoric acid enters a filter 7 for filtration and separation, and filter residue is washed and dried to obtain the finished product calcium sulfate gypsum which is white like snow. Phosphoric acid and filter residue washing water are returned to the acidolysis reactor 1 as acidolysis phosphoric acid. The calcium dihydrogen phosphate suspension entering the neutralization reactor 9 is subjected to neutralization reaction with lime milk in the neutralization reactor, and the reaction product is calcium hydrogen phosphate. The addition amount of lime milk is controlled by pH value. The pH value is 5-7.2. The neutralization reaction temperature is controlled to be about 45 ℃, and the reaction curing time is about 2.5 hours. And the slurry after the neutralization reaction enters a vacuum filter 9 for solid-liquid separation. And washing and drying the filter residue to obtain the finished product of calcium hydrophosphate. The process water such as the filtrate can be used as washing water in the filtration of calcium sulfate. The implementation results of this example: p in phosphate ore2O5The decomposition rate of the calcium hydrogen phosphate reaches 97 percent, the utilization rate of phosphorus reaches 85 percent, 1.16 tons of sulfuric acid are consumed by each ton of calcium hydrogen phosphate, 29 percent can be saved, 0.354 ton of lime milk is consumed, and 45.9 percent can be saved.
Claims (5)
1. The method for producing calcium hydrophosphate by using medium-low grade phosphate ore is characterized by comprising the following steps:
(1) performing acidolysis reaction on an intermediate product phosphoric acid and middle-low grade phosphate ores in the production process to generate a suspension with the main component of monocalcium phosphate, and removing coarse sand impurities in the suspension;
(2) adding a flocculating agent and a defluorinating agent into the calcium dihydrogen phosphate suspension, removing sludge which can be used as crude fertilizer, then using one part of the sludge for the crystallization reaction with sulfuric acid, and using the rest part of the sludge for the neutralization reaction with lime milk;
(3) the solid phase is calcium sulfate and the liquid phase is phosphoric acid slurry, the solid-liquid separation is carried out to obtain the solid calcium sulfate phosphogypsum, and the liquid is phosphoric acid which is returned to the acidolysis unit to be used as acidolysis phosphoric acid for recycling;
(4) and the calcium hydrogen phosphate is neutralized and reacted with lime milk to generate slurry of which the solid phase is calcium hydrogen phosphate, and the solid obtained is the calcium hydrogen phosphate to be produced through solid-liquid separation.
2. The method for producing calcium hydrogen phosphate by using middle-low grade phosphorus ore according to claim 1, wherein the weight ratio of the part for the reaction with sulfuric acid crystallization and the part for the neutralization reaction with lime milk of the calcium hydrogen phosphate suspension from which the sludge is removed is 6-18.
3. The method for producing calcium hydrogen phosphate from middle and low grade phosphorus ore according to claim 1 or 2, wherein P of phosphorus ore2O5The content is not lower than 24 percent (wt), when 10-20 percent (wt) phosphoric acid is used for acidolysis, the liquid-solid ratio of the phosphoric acid to the phosphorite is 2.5-5, the acidolysis reaction temperature is 70-80 ℃, the crystallization reaction temperature is 60-70 ℃, and the neutralization reaction temperature is 40-50 ℃.
4. The method for producing calcium hydrogen phosphate from middle and low grade phosphorus ore according to claim 1 or 2, wherein P of phosphorus ore2O5The content of the phosphoric acid is 10-24% (wt), when 10-20% (wt) phosphoric acid is used for acidolysis, the liquid-solid ratio of the phosphoric acid to the phosphorite is 5-12, the acidolysis reaction temperature is 70-80 ℃, the crystallization reaction temperature is 55-65 ℃, and the neutralization reaction temperature is 40-50 ℃.
5. The method for producing calcium hydrogen phosphate from middle and low grade phosphorus ore according to claim 1 or 2, wherein the phosphorus ore is crushed into particles with a particle size of not more than 5mm, and then the particles are subjected to acidolysis reaction with phosphoric acid.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008061473A1 (en) * | 2006-11-19 | 2008-05-29 | Shandong Wu | Phosphorite acidolysis method |
| CN102001636A (en) * | 2010-09-26 | 2011-04-06 | 四川大学 | Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process |
| CN102030318A (en) * | 2010-11-02 | 2011-04-27 | 昆明川金诺化工有限公司 | Sulfur-economizing method for extracting phosphoric acid |
| CN102583290A (en) * | 2012-02-18 | 2012-07-18 | 张黔生 | Low-grade phosphorite mineral dressing technology and method for producing by-product high-purity gypsum powder |
| CN103359699A (en) * | 2013-07-24 | 2013-10-23 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Wet-process phosphoric acid dissolving technology |
| CN103553722A (en) * | 2013-10-24 | 2014-02-05 | 瓮福（集团）有限责任公司 | Method for preparing super phosphate by use of ardealite slag site sewage |
| CN103613181A (en) * | 2013-11-29 | 2014-03-05 | 瓮福（集团）有限责任公司 | Method for treating phosphogypsum slag dump pool water by using low-grade lime |
| CN104591109A (en) * | 2013-10-31 | 2015-05-06 | 贵州川恒化工有限责任公司 | A producing method of a phosphorus-calcium highly-water-soluble fertilizer |
| CN105731513A (en) * | 2016-01-22 | 2016-07-06 | 贵州能矿织金磷化工有限公司 | Method for preparing rare earth oxide by leaching rare earth-containing phosphorite from regenerated phosphoric acid |
| CN105921259A (en) * | 2016-05-09 | 2016-09-07 | 贵州省冶金化工研究所 | Method for producing feed grade monocalcium phosphate through medium and low grade mixed phosphate ore |
| CN106800285A (en) * | 2017-01-10 | 2017-06-06 | 四川龙蟒磷化工有限公司 | The production method of calcium hydrophosphate fodder |
| CN106800286A (en) * | 2017-01-10 | 2017-06-06 | 四川龙蟒磷化工有限公司 | The method that phosphorus ore de-magging produces calcium hydrophosphate fodder |
| CN108840417A (en) * | 2018-07-06 | 2018-11-20 | 佛山市陵谐环保科技有限公司 | A kind of preparation method of food and drink waste water flocculant |
| CN115340074A (en) * | 2022-08-16 | 2022-11-15 | 四川大学 | Method and system for preparing phosphoric acid by using titanium white waste acid |
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| CN108557791A (en) * | 2018-06-08 | 2018-09-21 | 武汉工程大学 | The method for preparing calcium dihydrogen phosphate using low-grade phosphate ore |
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1999
- 1999-08-04 CN CNB991150570A patent/CN1151959C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008061473A1 (en) * | 2006-11-19 | 2008-05-29 | Shandong Wu | Phosphorite acidolysis method |
| CN102001636A (en) * | 2010-09-26 | 2011-04-06 | 四川大学 | Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process |
| CN102001636B (en) * | 2010-09-26 | 2012-07-25 | 四川大学 | Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process |
| CN102030318A (en) * | 2010-11-02 | 2011-04-27 | 昆明川金诺化工有限公司 | Sulfur-economizing method for extracting phosphoric acid |
| CN102030318B (en) * | 2010-11-02 | 2012-10-10 | 昆明川金诺化工股份有限公司 | Sulfur-economizing method for extracting phosphoric acid |
| CN102583290A (en) * | 2012-02-18 | 2012-07-18 | 张黔生 | Low-grade phosphorite mineral dressing technology and method for producing by-product high-purity gypsum powder |
| CN103359699A (en) * | 2013-07-24 | 2013-10-23 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Wet-process phosphoric acid dissolving technology |
| CN103359699B (en) * | 2013-07-24 | 2015-03-04 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Wet-process phosphoric acid dissolving technology |
| CN103553722A (en) * | 2013-10-24 | 2014-02-05 | 瓮福（集团）有限责任公司 | Method for preparing super phosphate by use of ardealite slag site sewage |
| CN104591109B (en) * | 2013-10-31 | 2017-05-10 | 贵州川恒化工股份有限公司 | A producing method of a phosphorus-calcium highly-water-soluble fertilizer |
| CN104591109A (en) * | 2013-10-31 | 2015-05-06 | 贵州川恒化工有限责任公司 | A producing method of a phosphorus-calcium highly-water-soluble fertilizer |
| CN103613181A (en) * | 2013-11-29 | 2014-03-05 | 瓮福（集团）有限责任公司 | Method for treating phosphogypsum slag dump pool water by using low-grade lime |
| CN105731513A (en) * | 2016-01-22 | 2016-07-06 | 贵州能矿织金磷化工有限公司 | Method for preparing rare earth oxide by leaching rare earth-containing phosphorite from regenerated phosphoric acid |
| CN105921259A (en) * | 2016-05-09 | 2016-09-07 | 贵州省冶金化工研究所 | Method for producing feed grade monocalcium phosphate through medium and low grade mixed phosphate ore |
| CN105921259B (en) * | 2016-05-09 | 2018-07-31 | 贵州省冶金化工研究所 | The method for producing feed-level calcium biphosphate using middle-low grade mixing rock phosphate in powder |
| CN106800285A (en) * | 2017-01-10 | 2017-06-06 | 四川龙蟒磷化工有限公司 | The production method of calcium hydrophosphate fodder |
| CN106800286A (en) * | 2017-01-10 | 2017-06-06 | 四川龙蟒磷化工有限公司 | The method that phosphorus ore de-magging produces calcium hydrophosphate fodder |
| CN108840417A (en) * | 2018-07-06 | 2018-11-20 | 佛山市陵谐环保科技有限公司 | A kind of preparation method of food and drink waste water flocculant |
| CN115340074A (en) * | 2022-08-16 | 2022-11-15 | 四川大学 | Method and system for preparing phosphoric acid by using titanium white waste acid |
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