CN101343051A - Method for decomposing phosphorus ore and phosphorus ore containing article with hydrochloric acid to produce phosphoric acid and ammonium phosphate salt - Google Patents
Method for decomposing phosphorus ore and phosphorus ore containing article with hydrochloric acid to produce phosphoric acid and ammonium phosphate salt Download PDFInfo
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- CN101343051A CN101343051A CNA2008101968442A CN200810196844A CN101343051A CN 101343051 A CN101343051 A CN 101343051A CN A2008101968442 A CNA2008101968442 A CN A2008101968442A CN 200810196844 A CN200810196844 A CN 200810196844A CN 101343051 A CN101343051 A CN 101343051A
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- phosphoric acid
- phosphorus ore
- acid
- ore containing
- hydrochloric acid
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Abstract
Disclosed is a method which adopts the hydrochloric acid to decompose the phosphorite and phosphor-containing minerals to produce phosphoric acid and ammonium phosphate salt in the decomposition liquor; the method is characterized in that the lime milk is used to neutralize the decomposition liquor to obtain the sediment calcium hydrogen phosphate, and then the hydrochloric acid is added for re-dissolution; the re-dissolution liquid is processed with organic extraction and aqua pura inverse extraction to obtain purer phosphoric acid which is further ammoniated to prepare the ammonium phosphate salt; the filtered mother liquor and the extraction water phase after the organic extraction are neutralized to recover the calcium chloride after condensation; the calcium chloride is mixed with silicon residue or silica sand to prepare the silicon fertilizer after the intermediate temperature calcination; the generated fume contains HCl is absorbed by water to prepare diluted hydrochloric acid which is returned for system utilization.
Description
Technical field
The invention belongs to chemical mineral processing and chemical processing field, is to decompose any phosphorus ore and phosphorus ore containing with hydrochloric acid---tungsten phosphorus ore, therefrom separation and Extraction phosphoric acid and phosphatic chemical process technology category.
Background material
As everyone knows, producing phosphoric acid by wet process and multiple phosphatic method at present both at home and abroad, all is sulfuric acid decomposed P
2O
5〉=28% phosphorus ore, make raw phosphoric acid earlier, wherein making the phosphorus ammonium is in concentrating ammonification or ammonia and reconcentration is a granulated into product, this method processing unit maturation, for common people can adopt, along with China's phosphorus ore richness of measuring is greatly in decades abandoned poor exploitation, the grade of phosphorus ore constantly descends, and country has classified phosphorus ore as the mineral that no rich ore can be adopted after 10 years.Yet at present a large amount of mid low grade phosphate rocks and some phosphorus ore containings also can't utilize.Decompose these mineral with hydrochloric acid in fact and also can make high-grade phosphoric acid and phosphoric acid salt, the phosphorus ammonium is exactly one of them.Last century 80, the nineties, Hubei Prov. Chemical Research Inst have been made big quantity research in this respect, get permission two Chinese patents already, are to separate out the chlorination monocalcium phosphate earlier (to be called for short calcium chlorophosphate, code name P in the decomposed solution of decomposing phosphate rock by chlorhydric acid as CN100622B
-01), succeeded by P
-01For raw material is made phosphoric acid and multiple phosphoric acid salt.Our company simplifies on this patent basis and innovates, applied for a patent (200810048974.1) of making the method for calcium hydrogen phosphate fodder, innovate again now,, make than products such as pure phosphoric acid and ammonium phosphate salts with hydrochloric acid decomposing medium and low grade and phosphorus ore containing.
Summary of the invention
The present invention makes than products such as pure phosphoric acid and ammonium phosphate salts with hydrochloric acid decomposing medium and low grade and phosphorus ore containing.
Of the present inventionly a kind ofly produce the method for phosphoric acid, it is characterized in that earlier with in the milk of lime and decomposed solution, with the P in the decomposed solution with decomposing phosphate rock by chlorhydric acid and phosphorus ore containing
2O
5Generate precipitate phosphoric acid hydrogen calcium, return molten precipitate phosphoric acid hydrogen calcium with hydrochloric acid again, return the lysate organic solvent extraction, pure water back extraction and make phosphoric acid.Phosphoric acid ammonification then makes ammonium phosphate salt.
Wherein extracting used organic solvent is propyl carbinol, primary isoamyl alcohol, diisopropyl ether or tributyl phosphate etc., the preferably phosphoric acid tri-n-butyl, and with tributyl phosphate and the mixed liquid extraction of boat coal, the tributyl phosphate of this mixed liquid and boat coal volume ratio=1: 1.
Decomposing phosphate rock by chlorhydric acid of the present invention and phosphorus ore containing are produced in the method for phosphoric acid, the raffinate water of filtering mother liquor and organic solvent extraction of neutralizing merges, with membrane sepn and concentrating under reduced pressure, reclaim crystallization calcium chloride, and the calcium chloride that reclaims mixes with white residue or silica sand, produce Calucium Silicate powder 800-900 ℃ of roasting---siliceous fertilizer, the HCl flue gas that contains of generation returns preceding plane system use with the water absorption.
Characteristics of the present invention are earlier with in the milk of lime and decomposed solution, with the P in the decomposed solution
2O
5Generate precipitate phosphoric acid hydrogen calcium, return molten precipitate phosphoric acid hydrogen calcium with hydrochloric acid again, obtain P
2O
5The higher solution of concentration, carry out organic solvent extraction again, can improve extraction efficiency greatly.Such advantage can directly be utilized the mid low grade phosphate rock (mid low grade phosphate rock account for national phosphorus ore 93%) of the huge standing stock of China, changes the critical situation that China does not have the phosphorus ore supply after 10 years.
Material % described in the present invention all is meant the weight percentage of this material.
Description of drawings
Fig. 1 decomposing phosphate rock by chlorhydric acid is made the schema of phosphoric acid and ammonium phosphate salt
Fig. 2 makes the schema of phosphoric acid and ammonium phosphate salt with salt acid treatment phosphorus ore containing (tungsten phosphorus ore)
Main component among Fig. 1 in the decomposed solution is H3PO
4And CaCl2, to pH=6, then phosphorus is all with CaHPO with lime slurry neutralization4·2H
2O separates out, and through diafiltration, again with hydrochloric acid making beating Hui Rong, can produce a P this moment2O
5The concentrated solution of content 〉=100 grams per liters all can effectively extract P with alcohol, ether or ester2O
5Come, our company extracts with TBP, and the pure water back extraction obtains P2O
5〉=50% than pure phosphoric acid. Phosphoric acid just can be made multiple phosphate thus. Thus phosphoric acid ammonification ammonification, slurry-spraying pelletizing, Get ammonium phosphate salt. The filtrate of raffinate water and lime slurry neutralization and wash water contain a large amount of calcium chloride, adopt film to separate and vacuum Concentrate and obtain solid calcium chloride, mix with white residue or silica sand, medium temperature roast makes siliceous fertilizer again, and flue gas absorbs through water makes salt Decomposing phosphate rock is returned in acid.
Salt acid treatment tungsten phosphorus ore among Fig. 2, the main component in the treatment fluid also is H3PO
4And CaCl2, but P2O
5Concentration very low, only have 34 grams per liters, directly extraction efficiency is low, to pH=6, then phosphorus is all with CaHPO with lime slurry neutralization for treatment fluid4·2H
2O separates out, and through diafiltration, again with hydrochloric acid making beating Hui Rong, can produce a P this moment2O
5The concentrated solution of content 〉=100 grams per liters all can effectively extract P with alcohol, ether or ester2O
5Come, our company extracts with TBP, and the pure water back extraction obtains P2O
5〉=50% (weight) than pure phosphoric acid. Phosphoric acid just can be made multiple phosphate thus. Thus phosphoric acid ammonification ammonification, Slurry-spraying pelletizing gets ammonium phosphate salt. The filtrate of raffinate water and lime slurry neutralization and wash water contain a large amount of calcium chloride, adopt film Separation and Vacuum Concentration obtain solid calcium chloride, mix with white residue or silica sand, and medium temperature roast makes siliceous fertilizer again, and flue gas is through water Hydrochloric acid is made in absorption, returns and processes the tungsten phosphorus ore.
Embodiment
Embodiment 1:
Used phosphorus ore (Yicheng, Hubei) weight percent is formed:
P
2O
5 CaO MgO Fe Al
2O
3 F
15.89％ 40.6％ 1.28％ 0.71％ 3.5％ 2.8％
Get 1 kilogram of ground phosphate rock (full mistake 40 orders), slowly join in 1500 milliliter of 30% (weight) technical hydrochloric acid+1500 ml water (about 100 ℃), finished restir 10 minutes, suction filtration while hot, drip washing, white residue 345 grams must wet, decomposed solution+wash water 3645 grams, add milk of lime at 50-60 ℃ and adjust decomposed solution pH=6, the secondary calcium phosphate (heavy calcium) 620 that must wet restrains, and adds 650 milliliter of 30% (weight) hydrochloric acid and returns molten above-mentioned heavy calcium, filters, must treat 1020 milliliters of extraction solutions, with 3000 milliliters of (1500 milliliters of TBP+1500 milliliter boat coals) extractions of extraction agent of 3 times of volumes, extraction temperature 35-40 ℃, with pure water washing three times, each 40 milliliters, with 1/6 volume pure water back extraction three times, each 500 grams, the raffinate water carries out reextraction with these the three times oil phase same steps as that purify of stripping again for the first time, three extractions, altogether 4480 milliliters of strip liquors, concentrating under reduced pressure gets 280 grams, and (weight content is: P than pure phosphoric acid
2O
5=52.8%, Cl=1.8%).Get the ammoniacal liquor 55 gram reactions of 100 gram phosphoric acid and 23% concentration, oven dry, (weight content is: P to obtain 100 gram phosphorus ammoniums
2O
5=52.1%, N=12.2%, Cl=1.5%).With milk of lime neutralization filtrate and raffinate water for the third time, concentrating under reduced pressure is separated out the wet calcium chloride of 1780 grams, is combined in 850 ± 5 ℃ of electric tube furnaces roasting half an hour with 520 gram white residues companions, siliceous fertilizer 1128 grams (contain active SiO
2=31.5% (weight)), flue gas absorbs with water, gets 4020 grams and contains HCl=14% (weight) dilute hydrochloric acid, and retrieval system is used.
Embodiment 2:
Known waste liquid with the refining tungsten phosphorus ore of dilute hydrochloric acid contains P
2O
5=34.35 grams per liters, get 1 and go up waste liquid, add milk of lime at 50-60 ℃ and adjust waste liquor PH=6, get 129 grams and do heavy calcium, return molten that solution 400 restrains (334 milliliters) with 30% (weight) technical hydrochloric acid, 100 milliliters+170 ml tap waters, with four times of these liquor capacities is that extraction for the first time for 1336 milliliters of organic solvents (668 milliliters of TBP+668 milliliters boat coals), wash oil phase three times with pure water, each 20 milliliters, strip each 260 milliliters three times with the pure water of oil phase 1/5 volume, the oil phase that purifies removes to extract last raffinate water again, totally three extractions so, with the reextraction dilute phosphoric acid, (weight content is concentrating under reduced pressure to 60 gram: P
2O
5=53.5%, Cl=1.6%) than pure phosphoric acid.Get the ammoniacal liquor 27.8 gram reactions of 50 gram phosphoric acid and 23% (weight) concentration, oven dry, (weight content is: P to obtain 51.5 gram phosphorus ammoniums
2O
5=52%, N=12.1%, Cl=1.3%).Will in and mother liquor concentrate and to separate out the wet calcium chloride of 308 grams and close with 90 gram white residues companions, roasting half an hour in 850 ± 5 ℃ of electric tube furnaces, siliceous fertilizer 86.7 restrains and (contains active SiO
2=32.3% (weight)), flue gas water absorbs to such an extent that 690 grams contain HCl=13.5% (weight) dilute hydrochloric acid, and retrieval system is used.
Claims (6)
1, a kind ofly produces the method for phosphoric acid, it is characterized in that earlier with in the milk of lime and decomposed solution, with the P in the decomposed solution with decomposing phosphate rock by chlorhydric acid and phosphorus ore containing
2O
5Generate precipitate phosphoric acid hydrogen calcium, return molten precipitate phosphoric acid hydrogen calcium with hydrochloric acid again, return the lysate organic solvent extraction, pure water back extraction and make phosphoric acid.
2, according to claim 1ly produce the method for phosphoric acid, it is characterized in that the phosphoric acid that the pure water back extraction makes ammonification then makes ammonium phosphate salt with decomposing phosphate rock by chlorhydric acid and phosphorus ore containing.
3, according to claim 1ly produce the method for phosphoric acid with decomposing phosphate rock by chlorhydric acid and phosphorus ore containing, it is characterized in that extracting used organic solvent is propyl carbinol, primary isoamyl alcohol, diisopropyl ether or tributyl phosphate.
4, according to claim 1ly produce the method for phosphoric acid with decomposing phosphate rock by chlorhydric acid and phosphorus ore containing, it is characterized in that extracting used organic solvent is tributyl phosphate and the mixed liquid of boat coal, the tributyl phosphate of this mixed liquid and boat coal volume ratio=and 1: 1.
5, according to claim 1ly produce the method for phosphoric acid, it is characterized in that the raffinate water of neutralize filtering mother liquor and organic solvent extraction merges,, reclaim crystallization calcium chloride with membrane sepn and concentrating under reduced pressure with decomposing phosphate rock by chlorhydric acid and phosphorus ore containing.
6, the method for producing phosphoric acid with decomposing phosphate rock by chlorhydric acid and phosphorus ore containing according to claim 5, it is characterized in that, the calcium chloride that reclaims being mixed with white residue or silica sand, produces Calucium Silicate powder 800-900 ℃ of roasting---siliceous fertilizer, the HCl flue gas that contains of generation returns preceding plane system use with the water absorption.
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|---|---|---|---|
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|---|---|---|---|
| CNA2008101968442A CN101343051A (en) | 2008-09-02 | 2008-09-02 | Method for decomposing phosphorus ore and phosphorus ore containing article with hydrochloric acid to produce phosphoric acid and ammonium phosphate salt |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211956A (en) * | 2010-11-24 | 2011-10-12 | 贵州省冶金化工研究所 | Utilization method of middle-low grade phosphate ore containing rare earth |
| CN101837963B (en) * | 2009-12-01 | 2012-01-25 | 瓮福（集团）有限责任公司 | Stepped utilization method of steam in ammonium phosphate production |
| CN102923681A (en) * | 2012-09-26 | 2013-02-13 | 武汉新协达精细化工研发有限公司 | Method for directly preparing industrial monopotassium phosphate through low-grade phosphate ores by hydrochloric acid process |
| CN105603215A (en) * | 2015-12-30 | 2016-05-25 | 武汉工程大学 | Method using extraction agent and hydrochloric acid acidolysis technology to efficiently leach K, Ca, Mg and P from P and K associated ore |
| CN107188144A (en) * | 2016-03-14 | 2017-09-22 | 姚鼎文 | The method that one kind makes MAP and Diammonium phosphate (DAP) with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system |
| CN109052353A (en) * | 2018-08-30 | 2018-12-21 | 中国科学院过程工程研究所 | A kind of system and method preparing phosphoric acid and silico-calcium potassic-magnesian fertilizer by phosphorus ore |
| CN115180602A (en) * | 2022-07-05 | 2022-10-14 | 生态环境部南京环境科学研究所 | Preparation method for preparing calcium hydrophosphate from phosphorus-containing wastewater |
| CN115475411A (en) * | 2022-09-30 | 2022-12-16 | 武汉工程大学 | Method for extracting and purifying wet-process phosphoric acid by using isopropyl ether-fatty alcohol mixed solution |
-
2008
- 2008-09-02 CN CNA2008101968442A patent/CN101343051A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837963B (en) * | 2009-12-01 | 2012-01-25 | 瓮福（集团）有限责任公司 | Stepped utilization method of steam in ammonium phosphate production |
| CN102211956A (en) * | 2010-11-24 | 2011-10-12 | 贵州省冶金化工研究所 | Utilization method of middle-low grade phosphate ore containing rare earth |
| CN102211956B (en) * | 2010-11-24 | 2013-06-19 | 贵州省冶金化工研究所 | Utilization method of middle-low grade phosphate ore containing rare earth |
| CN102923681A (en) * | 2012-09-26 | 2013-02-13 | 武汉新协达精细化工研发有限公司 | Method for directly preparing industrial monopotassium phosphate through low-grade phosphate ores by hydrochloric acid process |
| CN102923681B (en) * | 2012-09-26 | 2014-12-24 | 武汉新协达精细化工研发有限公司 | Method for directly preparing industrial monopotassium phosphate through low-grade phosphate ores by hydrochloric acid process |
| CN105603215A (en) * | 2015-12-30 | 2016-05-25 | 武汉工程大学 | Method using extraction agent and hydrochloric acid acidolysis technology to efficiently leach K, Ca, Mg and P from P and K associated ore |
| CN107188144A (en) * | 2016-03-14 | 2017-09-22 | 姚鼎文 | The method that one kind makes MAP and Diammonium phosphate (DAP) with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system |
| CN109052353A (en) * | 2018-08-30 | 2018-12-21 | 中国科学院过程工程研究所 | A kind of system and method preparing phosphoric acid and silico-calcium potassic-magnesian fertilizer by phosphorus ore |
| CN115180602A (en) * | 2022-07-05 | 2022-10-14 | 生态环境部南京环境科学研究所 | Preparation method for preparing calcium hydrophosphate from phosphorus-containing wastewater |
| CN115475411A (en) * | 2022-09-30 | 2022-12-16 | 武汉工程大学 | Method for extracting and purifying wet-process phosphoric acid by using isopropyl ether-fatty alcohol mixed solution |
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Open date: 20090114 |