CN101293640B - Method for preparing ammonium phosphate salt with hydrochloric acid leaching deficient phosphorus ore - Google Patents
Method for preparing ammonium phosphate salt with hydrochloric acid leaching deficient phosphorus ore Download PDFInfo
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- CN101293640B CN101293640B CN2008100315472A CN200810031547A CN101293640B CN 101293640 B CN101293640 B CN 101293640B CN 2008100315472 A CN2008100315472 A CN 2008100315472A CN 200810031547 A CN200810031547 A CN 200810031547A CN 101293640 B CN101293640 B CN 101293640B
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- phosphoric acid
- phosphate
- hydrochloric acid
- trimeric cyanamide
- phosphorus ore
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Abstract
The invention discloses a method for preparing ammonium phosphates by using hydrochloric acid to leach poor phosphate rocks, and the technology of the method comprises (1) the acidolysis of the poor phosphate rocks; (2) pretreatment; (3) the precipitation of the phosphoric acid; (4) washing; (5) amination reaction; and (6) concentration and crystallization, the ammonium phosphates is obtained. The method of the invention has the following advantages: firstly, low-grade phosphate rock powder leached by using the hydrochloric acid has high reactivity, and P2O5 is completely leached without appearing any coating phenomena of mineral powder coated by calcium sulfate generated by using a sulfuric acid method; secondly, by the precipitation of melamine weak base to the phosphoric acid, the separation of the phosphoric acid and calcium chloride in leaching solution is realized, which is especially suitable for the further treatment of crude phosphoric acid which is leached by the poor phosphate rocks and has a low concentration; thirdly, the precipitant of melamine has low solubility, can be used in a recycling way, and has small loss quantity in the process; and fourthly, the technology of the technical method has mild condition, low energy consumption, the easy realization of operating equipments, and the complete separation of solid and liquid, thus avoiding the coprecipitation interference of sulfate radical, furthermore, the by-products of the calcium chloride can be utilized.
Description
Technical field
The present invention relates to the method that a kind of phosphoric acid by wet process prepares ammonium phosphate salt, specially refer to the technology of producing Wet-process Phosphoric Acid Production monoammonium phosphate and diammonium phosphate with the hydrochloric acid leaching deficient phosphorus ore.
Background technology
The development and use of poor phosphorus ore are the important topics during phosphorous chemical industry is produced always, and the poor phosphate rock resource of China is very abundant, but because P
2O
5Standard that content is lower than 24.0%, its Rock Phosphate (72Min BPL) does not reach HG/T 2673-1995 " acid system processing Rock Phosphate (72Min BPL) ", the acid consumption is big, gained raw phosphoric acid concentration is low and impurity how etc. shortcoming cause practical application to be restricted.Wet-process Phosphoric Acid Production is to handle the effective ways of Rock Phosphate (72Min BPL), compare with thermal phosphoric acid to have advantages such as the little and production cost of energy consumption is low, but technical process is long, product separation purification techniques complexity.Phosphoric acid by wet process can be divided into sulfuric acid process, nitrate method and salt acid system etc. by the difference of its used mineral acid.Sulfuric acid process is the predominant methods of phosphoric acid by wet process, but produces a large amount of phosphogypsums, consumes a large amount of sulphur resources, produces 1 ton of phosphoric acid and will produce 4～6 tons of phosphogypsums, does not meet the long-range requirement of Green Chemistry development.Nitrate method uses the solid calcium of ammonium sulfate, can obtain fine nitric nitrogen binary compound fertilizer, but uses few in the actual production.And the salt acid system can utilize industrial by-product hydrochloric acid, wide material sources, though the IMI company of Israel as far back as the beginning of the sixties in last century just with salt acid system preparation of industrialization phosphoric acid, but this process using Di Iso Propyl Ether etc. is an extraction agent, hydrochloric acid separates not exclusively with phosphoric acid, need further evaporative removal, equipment material requires high, does not see so far in China and adopts.
Ammonium phosphate salt is the first Chemicals of phosphorus, accounted for 49.3% in 2006 in the phosphate fertilizer product structure, the main ammonium phosphate of slurry concentration process technology that adopts is produced, but the utilization of grade phosphorus mine during this technology can only solve, requiring the phosphorus ore grade is 26.5%～28%, as " design of sulphur phosphorus and powder technology ", 2004, (5): described in the 1-2.In the Chinese patent 92108090.5 usefulness ammonia and P
2O
5Content is 20% Wet-process Phosphoric Acid Production pure phosphoric acid one ammonium, and wherein the colloidal state contamination precipitation of Xing Chenging is by settlement separate, and slurry and mother liquor part can only be used as the fertilizer grade product.People such as Dang Jiexiu are raw material with the sulfuric acid process raw phosphoric acid, having studied with trimeric cyanamide is that the reaction medium is produced phosphatic technology, as " inorganic chemicals industry ", 1999,31 (2): described in the 18-20, but adopt salt acid system and melamine phosphate precipitation bonded processing technology routine to yet there are no report at poor phosphorus ore.
Summary of the invention
The purpose of this invention is to provide a kind of method with preparing ammonium phosphate salt with hydrochloric acid leaching deficient phosphorus ore.
The objective of the invention is to realize in the following way: a kind of method with preparing ammonium phosphate salt with hydrochloric acid leaching deficient phosphorus ore:
1), the poor phosphorus ore of acidolysis: is 1.0 with poor ground phosphate rock and hydrochloric acid by the mol ratio of calcium oxide in the ground phosphate rock and hydrochloric acid: 1.8-2.4 feeds intake, in 50 ℃ of stirring reaction 1-4h to the boiling state, filter leach liquor; Described poor phosphorus ore is P
2O
5Content is lower than 24.0% low-grade phosphate ore;
2), pre-treatment: in the gained leach liquor, add activated carbon, organic matter is removed in absorption; Add yellow soda ash, remove by filter F
-Add tributyl phosphate again, the separation organic phase is removed the ferric iron in the solution; Get the preprocessing solution of phosphoric acid and calcium chloride;
3), precipitate phosphoric acid: join in the preprocessing solution of phosphoric acid and calcium chloride at following precipitation agent trimeric cyanamide of quick stirring, the trimeric cyanamide add-on is 1 by the mol ratio of phosphoric acid in the preprocessing solution and trimeric cyanamide: 1-3 determines, temperature of reaction is 10-80 ℃, reaction times is 0.5-2h, filter, repeating the precipitate and separate number of times is 1-3 time, gets the melamine phosphate throw out;
4), washing: wash the melamine phosphate throw out with water, water and melamine phosphate throw out quality are than being 3-7: 1, temperature is 20-80 ℃, churning time is 0.2-2h, filtering separation is removed the calcium chloride of wherein carrying secretly then, and continuous washing 2-5 time gets melamine phosphate;
5), aminating reaction: the ammoniacal liquor of amount such as in melamine phosphate, add, stir reaction 0.2-1h down, from throw out, displace trimeric cyanamide, filter and obtain ammonium phosphate salt solution;
6), condensing crystal: with ammonium phosphate salt solution concentrate, crystallisation by cooling, make ammonium phosphate salt.
The trimeric cyanamide that displaces in the aminating reaction recycles.
The present invention has following beneficial effect, and the one, with hydrochloric acid leaching low grade rock phosphate reactive behavior height, P
2O
5Leach fully, the calcium sulfate that generates in the no sulfuric acid process is to the coating phenomenon of breeze; The 2nd, by the precipitation of trimeric cyanamide weak base, realized separating of phosphoric acid and calcium chloride in the leach liquor to phosphoric acid, be particularly suitable for the further processing of the lower concentration raw phosphoric acid that poor phosphorus ore leaches; The 3rd, precipitation agent trimeric cyanamide solubleness is little, can recycle, and the process loss amount is little; The 4th, present technique method processing condition gentleness, energy expenditure is low, operating equipment is realized easily, solid-liquid separation is thorough, has avoided the co-precipitation of sulfate radical to disturb, and the calcium chloride byproduct can be utilized.
Description of drawings
Fig. 1 is the process flow sheet with preparing ammonium phosphate salt with hydrochloric acid leaching deficient phosphorus ore of the present invention.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Monoammonium phosphate prepares embodiment:
Take by weighing P
2O
5Content is 15.84% the poor phosphorus ore 100g in Liuyang, presses the theoretical consumption of calcium oxide content calculating hydrochloric acid in the ground phosphate rock, gets 1: the 1 hydrochloric acid 133mL that surpasses theoretical consumption 5%, under 75 ℃, stir with ground phosphate rock, and reaction 3h final vacuum suction filtration, it is light yellow that filtrate is.Filter cake is carried out repetitive scrubbing, must contain the leach liquor 170.6mL of phosphoric acid and calcium chloride, wherein P
2O
5Content is 7.23%, density is 1.2762g/cm
3, P
2O
5Leaching yield is 99.37%.Substep adds activated carbon, yellow soda ash and tributyl phosphate and removes organic matter, F-and ferric iron in the solution respectively then, phosphoric acid and calcium chloride preprocessing solution.
Equal to take by weighing trimeric cyanamide 13.3107g at 1: 2 by the mol ratio of phosphoric acid and precipitation agent trimeric cyanamide, be divided into equal two parts.Stir following the 1st part of trimeric cyanamide fast and join 50.0mL preprocessing solution (P
2O
56.17%, 1.2145g/cm
3) in, in 25 ℃ of continuously stirring 1h, filter; Add the 2nd part of trimeric cyanamide under stirring fast in filtrate, uniform temp stirs 1h, filtering separation down; Be total to such an extent that have the solid of melamine phosphate to filter excess 21.4930g.The phosphoric acid precipitates rate is 99.68%.
In having the solid filter excess of melamine phosphate, gained adds the solid-liquid mass ratio and is 1: 5 distilled water, wash the calcium chloride of wherein carrying secretly in 40 ℃ of continuously stirring 1h, continuous washing is 3 times under the same water yield, and the clearance of calcium chloride is 99.45%, must remain insolubles 18.0364g at last.Add 1.0mol/L ammoniacal liquor 52.6mL in remaining insolubles, stirring reaction 0.5h after-filtration gets trimeric cyanamide solid 12.6279g behind the washing filter excess fast.Concentrating filter liquor, crystallisation by cooling make monoammonium phosphate, and quality product reaches GB 10205-2001 standard.
Diammonium phosphate prepares embodiment:
Take by weighing P
2O
5Content is 15.84% the poor phosphorus ore 100g in Liuyang, presses the theoretical consumption of calcium oxide content calculating hydrochloric acid in the ground phosphate rock, gets 1: the 1 hydrochloric acid 133mL that surpasses theoretical consumption 5%, under 75 ℃, stir with ground phosphate rock, and reaction 3h final vacuum suction filtration, it is light yellow that filtrate is.Filter cake is carried out repetitive scrubbing, must contain the leach liquor 170.6mL of phosphoric acid and calcium chloride, wherein P
2O
5Content is 7.23%, density is 1.2762g/cm
3, P
2O
5Leaching yield is 99.37%.Substep adds activated carbon, yellow soda ash and tributyl phosphate and removes organic matter, F in the solution respectively then
-And ferric iron, get phosphoric acid and calcium chloride preprocessing solution.
Equal to take by weighing trimeric cyanamide 7.9859g at 1: 2 by the mol ratio of phosphoric acid and precipitation agent trimeric cyanamide, be divided into equal two parts.Stir following the 1st part of trimeric cyanamide fast and join 30.0mL preprocessing solution (P
2O
56.17%, 1.2145g/cm
3) in, in 25 ℃ of continuously stirring 1h, filter; Add the 2nd part of trimeric cyanamide under stirring fast in filtrate, uniform temp stirs 1h, filtering separation down; Be total to such an extent that have the solid of melamine phosphate to filter excess 12.8922g.The phosphoric acid precipitates rate is 99.52%.
In having the solid filter excess of melamine phosphate, gained adds the solid-liquid mass ratio and is 1: 5 distilled water, wash the calcium chloride of wherein carrying secretly in 40 ℃ of continuously stirring 1h, continuous washing is 3 times under the same water yield, and the clearance of calcium chloride is 99.29%, must remain insolubles 10.7091g at last.Add 1.0mol/L ammoniacal liquor 63.0mL in remaining insolubles, stirring reaction 0.5h after-filtration gets trimeric cyanamide solid 7.5837g behind the washing filter excess fast.Concentrating filter liquor, crystallisation by cooling make diammonium phosphate, and quality product reaches GB 10205-2001 standard.
Claims (2)
1. method with preparing ammonium phosphate salt with hydrochloric acid leaching deficient phosphorus ore is characterized in that:
1), the poor phosphorus ore of acidolysis: is 1.0 with poor ground phosphate rock and hydrochloric acid by the mol ratio of calcium oxide in the ground phosphate rock and hydrochloric acid: 1.8-2.4 feeds intake, in 50 ℃ of stirring reaction 1-4h to the boiling state, filter leach liquor; Described poor phosphorus ore is P
2O
5Content is lower than 24.0% low-grade phosphate ore;
2), pre-treatment: in the gained leach liquor, add activated carbon, organic matter is removed in absorption; Add yellow soda ash, remove by filter F
-Add tributyl phosphate again, the separation organic phase is removed the ferric iron in the solution; Get the preprocessing solution of phosphoric acid and calcium chloride;
3), precipitate phosphoric acid: join in the preprocessing solution of phosphoric acid and calcium chloride at following precipitation agent trimeric cyanamide of quick stirring, the trimeric cyanamide add-on is 1 by the mol ratio of phosphoric acid in the preprocessing solution and trimeric cyanamide: 1-3 determines, temperature of reaction is 10-80 ℃, reaction times is 0.5-2h, filter, repeating the precipitate and separate number of times is 1-3 time, gets the melamine phosphate throw out;
4), washing: wash the melamine phosphate throw out with water, water and melamine phosphate throw out quality are than being 3-7: 1, temperature is 20-80 ℃, churning time is 0.2-2h, filtering separation is removed the calcium chloride of wherein carrying secretly then, and continuous washing 2-5 time gets melamine phosphate;
5), aminating reaction: the ammoniacal liquor of amount such as in melamine phosphate, add, stir reaction 0.2-1h down, from throw out, displace trimeric cyanamide, filter and obtain ammonium phosphate salt solution;
6), condensing crystal: with ammonium phosphate salt solution concentrate, crystallisation by cooling, make ammonium phosphate salt.
2. a kind of method with preparing ammonium phosphate salt with hydrochloric acid leaching deficient phosphorus ore according to claim 1, it is characterized in that: the trimeric cyanamide that displaces in the aminating reaction recycles.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073743A (en) * | 2013-01-11 | 2013-05-01 | 贵州合众拓源磷资源综合利用技术股份有限公司 | Method for preparing flame retardant with phosphate rock |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992291B (en) * | 2012-12-12 | 2014-12-17 | 贵州开磷（集团）有限责任公司 | Method for preparing feed grade calcium hydrophosphate by phosphorite decomposition by hydrochloric acid |
| CN103723697B (en) * | 2013-12-27 | 2016-03-09 | 安徽六国化工股份有限公司 | Improve the method for quality of acid for diammonium phosphate |
| CN107089909A (en) * | 2016-02-18 | 2017-08-25 | 姚鼎文 | The method that melamine complex salt crystal method directly manufactures sodium citrate, potassium citrate and ammonium citrate from citric acid fermentation broth |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073743A (en) * | 2013-01-11 | 2013-05-01 | 贵州合众拓源磷资源综合利用技术股份有限公司 | Method for preparing flame retardant with phosphate rock |
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