CN103073041A - Method for producing water-soluble calcium nitrate dihydrate and phosphoric acid by decomposing phosphorite through nitric acid - Google Patents
Method for producing water-soluble calcium nitrate dihydrate and phosphoric acid by decomposing phosphorite through nitric acid Download PDFInfo
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- CN103073041A CN103073041A CN2012105157217A CN201210515721A CN103073041A CN 103073041 A CN103073041 A CN 103073041A CN 2012105157217 A CN2012105157217 A CN 2012105157217A CN 201210515721 A CN201210515721 A CN 201210515721A CN 103073041 A CN103073041 A CN 103073041A
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Abstract
The invention relates to a water-soluble calcium nitrate production method, and especially relates to a method for producing water-soluble calcium nitrate dihydrate and phosphoric acid by decomposing phosphorite through nitric acid. The method comprises the following steps: decomposing phosphorite by nitric acid to prepare an acidolysis liquid, carrying out freezing crystallization of the acidolysis liquid to separate a calcium nitrate crystal and phosphoric acid, dissolving the calcium nitrate crystal, carrying out deep impurity removal of the obtained calcium nitrate solution, carrying out evaporative concentration of the calcium nitrate solution, removing water from the obtained crystal, and carrying out ammonium nitrate wrapping granulation to prepare calcium nitrate dihydrate having a water solubility of not less than 99.9%. The method avoids the insufficient utilization of sulfate radicals residual in phosphogypsum of sulfuric acid methods when wet phosphoric acid is simultaneously produced, and the production of the high-added-value calcium nitrate dihydrate through the combination of nitrate radicals with calcium ions has the advantages of widening of the product chains of phosphoric acid or nitric phosphate enterprises, economic utilization of the nitrogen element in nitric acid, and improvement of the competition advantages of the enterprises.
Description
Technical field
The present invention relates to a kind of production method of water-soluble nitrocalcite, particularly relate to the method that a kind of decomposing phosphorite by using nitric acid is produced water-soluble two water nitrocalcite coproduction phosphoric acid.
Background technology
At present, phosphoric acid by wet process mainly adopts sulfuric acid to come decomposing phosphate rock, can produce a large amount of phosphogypsums when obtaining phosphoric acid.Nitric acid also can be used to dissolve phosphorus ore, and nitric acid is widely used in acidic phosphorus mine and makes nitrophosphate fertilizer, with the ammonification of acidifying material and dried bath, obtains a kind of solid nitric acid phosphate fertilizer product in such method, wherein comprises part or all of calcium.There is (in souring soln) in phosphoric acid in some stages like this, and is used for producing phosphate fertilizer.Can say that from this respect nitric acid is used for making phosphoric acid.But, when ammonification and calcium react and generate insoluble phosphoric acid calcium, rather than as the phosphoric acid ammonification, generate the water-soluble phosphoric acid ammonium.
Adopt decomposing phosphorite by using nitric acid for the preparation of the phosphoric acid of phosphorus ammonium production and comparatively pure nitrocalcite product, because nitric acid wide material sources, need not to use sulphur, by-product gypsum does not have certain directive function to solving the multiple fertile product restructuring of producing phosphorus ammonium and by-product phosphogypsum of existing phosphorus.Use decomposing phosphorite by using nitric acid, not only decomposition rate is fast, leaching rate is high, and nitrate radical obtains utilizing, and the nitrocalcite that generating value is higher to the abundant China of sulphur resource, replaces the sulfuric acid decomposing phosphate rock more meaningful with nitric acid.
Decomposing phosphorite by using nitric acid, then producing nitrophosphate fertilizer by cold method or mixed acid process has been the technology of comparative maturity.Tradition nitrophosphate fertilizer adopts cold method to use in ammonia and remaining liquid fabrication portion soluble nitrophosphate fertilizer after with the form fractionation of four water-calcium nitrate crystallization calcium in the acid hydrolysis solution again.Patent " decomposing phosphorite by using nitric acid nitrocalcite cold method is produced the method for high-water solubility nitrophosphate fertilizer " (application number CN201110199681.5), and " decomposing phosphorite by using nitric acid ammonium sulfate circulation method is produced the method for high-water solubility nitrophosphate fertilizer " (application number CN201110201294.0), all introduced a kind of decomposing phosphorite by using nitric acid, then defluorinate, freezing and crystallizing crystallize out most nitrocalcite in the phosphoric acid, add again the decalcification of the ammonium sulfate degree of depth, last in and removal of impurities obtain the nitrophosphate fertilizer of highly water-soluble.Tianjimei Chemical Group Co.,Ltd is at patent " utilizing nitrophosphate fertilizer by-product nitrocalcite to produce method and the device thereof of calcium ammonium nitrate " (application number: introduced a kind of method that generates calcium ammonium nitrate of being reacted by thick calcium nitrate filtrate and gas ammonia CN200510012494.6) in tubular reactor; Patent " a kind of processing method of producing high concentration nitric-phosphate fertilizer " (application number: adopt decomposing phosphorite by using nitric acid 200910009223.3), the nitrocalcite freezing and crystallizing, the deliming of the phosphoric acid degree of depth prepares high concentration nitric-phosphate fertilizer.Up to now, there is no decomposing phosphorite by using nitric acid and produce phosphoric acid, nitrocalcite carries out deep impurity-removing, revaporization is concentrated, the degree of depth is concentrated, the technique report of the water-soluble two water nitrocalcite of granulation parcel preparation, also without related application.
Summary of the invention
The object of the present invention is to provide a kind of decomposing phosphorite by using nitric acid to produce the method for water-soluble two water nitrocalcite coproduction phosphoric acid, to widen the product chain of phosphoric acid or nitrophosphate fertilizer enterprise, utilize nitrogen element in the nitric acid, the method that the decomposing phosphorite by using nitric acid of the competitive edge of raising enterprise is produced water-soluble two water nitrocalcite coproduction phosphoric acid more economically.
Decomposing phosphorite by using nitric acid of the present invention is produced the method for water-soluble two water nitrocalcite coproduction phosphoric acid, the steps include:
A) preparation of thick nitrocalcite: the acid hydrolysis solution of decomposing phosphorite by using nitric acid preparation obtains thick nitrocalcite crystal by the freezing and crystallizing separation under 0～-12 ℃ and coproduction Vanadium Pentoxide in FLAKES mass concentration is the phosphoric acid solution of 18-28%.
B) nitrocalcite dissolution of crystals deep impurity-removing: adding lime milk solution regulator solution pH value in the thick nitrocalcite crystal is 5-7, and sedimentation and filtration separates, and removes phosphate radical and metal ion, the ca nitrate soln that obtains making with extra care.
C) ca nitrate soln evaporation concentration: refining one section evaporation concentration of ca nitrate soln is removed free-water, and two sections degree of depth concentrate and remove crystal water, obtain containing the nitrocalcite of 1～2 crystal water;
D) granulating and forming: with two water nitrocalcite melt pelletization, wrap up moulding with ammonium nitrate again, obtain at last two water nitrocalcite of water-soluble rate 〉=99.9%.
In the aforesaid method, the freezing and crystallizing of acid hydrolysis solution is 0～-12 ℃ in the step a), also contain part nitrocalcite in the phosphoric acid of coproduction, obtain to prepare the required phosphoric acid of high-water solubility nitrophosphate fertilizer, can by mature method, under agitation condition, add tertiary sodium phosphate or SODIUMNITRATE defluorinate, under agitation condition, add ammonium sulfate again, remove by filter terra alba, thereby obtain the very low phosphoric acid of calcium contents, Vanadium Pentoxide in FLAKES concentration is 18-28% in the phosphoric acid solution
Step B) in, owing to the nitrate of meeting wrapping portion phosphoric acid and iron, aluminium, magnesium etc. in the nitrocalcite crystal of crystallization gained, in order to obtain the high nitrocalcite product of water-soluble rate, needs these impurity are wherein removed.Adopting the pH value of milk of lime regulator solution be 5-7, and neutralization phosphoric acid wherein with other nitrate reaction, generates nitrocalcite and accordingly precipitation of hydroxide simultaneously, removes by filter precipitation, obtains the high ca nitrate soln of water-soluble rate.
Step C) in, nitrocalcite contains a large amount of water through behind the deep impurity-removing in the solution, and employing evaporation concentration mode removes free-water wherein, and thickening temperature is 40～100 ℃.Research is found, when the crystal water in the nitrocalcite is 3～4, also is difficult to moulding after the reduction temperature; When the crystal water in the nitrocalcite during less than 1, nitrocalcite itself will foam and solidify, and also is unfavorable for forming process, in order to obtain preferably nitrocalcite product of molding effect, preferably is removed to 1～2 crystal water, and thickening temperature is 120～220 ℃.
Step D) in, the two water nitrocalcite that melt pelletization obtains adopt ammonium nitrate to wrap up moulding, and the mass percent consumption of ammonium nitrate is 1～12%, and the content of its water-soluble two water nitrocalcite mass percents is 82～98.5%.
Method provided by the invention can make two water nitrocalcite of water-soluble rate 〉=99.9%, and the Application Areas of nitrocalcite has been widened in the increase of water-soluble rate, can be used as that foliar nutrient uses and blocking pipe not, be easy to Crop, and utilization ratio is high.Present method does not produce a large amount of phosphogypsums with respect to Production By Sulfuric Acid Process phosphoric acid, only has a small amount of acid non-soluble substance to discharge, and the acid non-soluble substance main component is silicon-dioxide, and then effluent discharge is few, greatly reduces and stores up the space, with environmental friendliness; And, when producing phosphoric acid by wet process, remain in the phosphogypsum unlike the sulfate radical in the sulfuric acid process and be not fully utilized, nitrate radical and calcium binding, two water nitrocalcite of production high added value, can widen the product chain of phosphoric acid or nitrophosphate fertilizer enterprise, utilize nitrogen element in the nitric acid more economically, improve the competitive edge of enterprise.And to the not abundant China of sulphur resource, replace the sulfuric acid decomposing phosphate rock more meaningful with nitric acid.
Description of drawings
Fig. 1 is that decomposing phosphorite by using nitric acid of the present invention is produced water-soluble two water nitrocalcite coproduction phosphoric acid process schemas.
Specific implementation method
Below in conjunction with embodiment the present invention is done further invention name, but be not limited to embodiment.Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Embodiment:
Adopt decomposing phosphorite by using nitric acid of the present invention to produce water-soluble two water nitrocalcite coproduction phosphoric acid, concrete operations are:
Table 1 ground phosphate rock forms
| Project | The ore particle degree | P 2O 5 | SiO 2 | Al 2O 3 | Fe 2O 3 | MgO | CaO | F |
| Content/% | 80%≤-200 order | 28.21 | 17.10 | 1.70 | 1.94 | 1.98 | 43.0 | 2.41 |
A), acidolysis
Concentration is that 60%～66% the nitric acid washings when filtering with acid non-soluble substance mixes, concentration of nitric acid is 50%～55%, this salpeter solution is added the acidolysis groove, under agitation add ground phosphate rock and carry out acidolysis reaction, nitric acid dosage is 95%～110 % of theoretical amount, the temperature of acidolysis reaction is 50 ℃～70 ℃, the residence time 0.5～4h of acidolysis reaction.Then filter slip, filter residue (acid non-soluble substance) washs with clear water, and washings returns the acidolysis groove, with nitric acid mixed decomposition ground phosphate rock.
Table 2 acid hydrolysis solution forms
| Project | P 2O 5 | CaO | Fe 2O 3 | MgO | Al 2O 3 | SiO 2 | F |
| Content/% | 7.45 | 11.62 | 0.10 | 0.55 | 0.06 | 0.28 | 0.86 |
Filter residue forms: P
2O
5The %=1.23%(butt)
B), nitrocalcite freezing and crystallizing
Acid hydrolysis solution is added in the freezing and crystallizing device of band stirring, Tc is 0～-12 ℃, crystallization 1.5～4h, and the crystallization of filtering separation nitrocalcite, with freezing nitric acid liquid washing nitrocalcite crystal, washings returns the acidolysis groove, with nitric acid mixed decomposition ground phosphate rock.
Table 3 filtrate (phosphoric acid solution) forms
| Project | Proportion | Ca/% | P 2O 5/% | N% | F/% | Fe/% | Al/% | Mg/% |
| Content/% | 1.28 | 3.72 | 18.89 | 6.35 | 0.84 | 0.2 | 0.11 | 0.85 |
The thick nitrocalcite crystal composition of table 4
| Project | Ca/% | P 2O 5/% | N% | Fe/% | Al/% | Mg/% |
| Content/% | 14.98 | 2.25 | 11.41 | 0.02 | 0.11 | 0.10 |
C), defluorinate
The filtrate that Crystallization Separation is gone out adds in the defluorinate groove, adds tertiary sodium phosphate or SODIUMNITRATE defluorinate under agitation condition, and the defluorinate temperature is 20～50 ℃, and the defluorinate time is 0.5～3h, isolates defluorination residues after reaction product is filtered, and the filter residue main component is Sodium Silicofluoride.
D), phosphoric acid degree of depth decalcification
Filtrate after the defluorinate is added in the degree of depth decalcification groove, under agitation condition, add ammonium sulfate, the ammonium sulfate consumption is 100%～110% of theoretical consumption, treatment temp is 30～60 ℃, treatment time is 1～3h, then remove by filter terra alba, with the clear water washing, mainly contain phosphoric acid and ammonium nitrate in the filtrate.
Composition after the decalcification of the table 5 phosphoric acid degree of depth
| Project | P 2O 5 | Ca | Al | Fe | Mg |
| Content/% | 24.81 | 0.48 | 0.11 | 0.21 | 0.91 |
E), nitrocalcite deep impurity-removing
The isolated nitrocalcite dissolution of crystals of freezing and crystallizing adds milk of lime, and temperature is 20～45 ℃, and regulating the pH value is 5～7, then filters, and washs filter residue with clear water, and washings is used for configuration milk of lime.
F), evaporation concentration
With the filtrate evaporation concentration behind the nitrocalcite deep impurity-removing, remove wherein most free-water;
Composition after table 6 nitrocalcite deep impurity-removing is concentrated
| Project | P 2O 5 | Ca | Al | Fe | Mg | Water-insoluble |
| Content/% | —— | 19.84 | —— | —— | 0.08 | 0.01 |
G), the degree of depth is concentrated
The nitrocalcite degree of depth that removes free-water is concentrated, remove crystal water to 1 wherein～2 crystal water, treatment temp is 120 ℃～220 ℃.；
H), granulating and forming
To contain the calcium nitrate melt granulation of 1～2 crystal water, the nitrocalcite of making grain wraps up moulding with ammonium nitrate, and the ammonium nitrate consumption is 1～12% of final product quality.
Table 7 two water nitrocalcite products form
| Project | Ca(NO 3) 2·2H 2O | Ca | N | Water-insoluble | PH value (50g/L) |
| Content/% | 93 | 18.6% | 15.2 | 0.01% | 6.5 |
Claims (3)
1. method that decomposing phosphorite by using nitric acid is produced water-soluble two water nitrocalcite coproduction phosphoric acid, it is characterized in that, it mainly be the acid hydrolysis solution that utilizes decomposing phosphorite by using nitric acid preparation by freezing and crystallizing separate the removing of nitrocalcite crystal and phosphoric acid, nitrocalcite dissolution of crystals deep impurity-removing, ca nitrate soln evaporation concentration, crystal water, ammonium nitrate wraps up granulation, make two water nitrocalcite of water-soluble rate 〉=99.9%, and coproduction phosphoric acid, concrete production technique comprises:
A) preparation of thick nitrocalcite: the acid hydrolysis solution of decomposing phosphorite by using nitric acid preparation obtains thick nitrocalcite crystal by the freezing and crystallizing separation under 0～-12 ℃ and coproduction Vanadium Pentoxide in FLAKES mass concentration is the phosphoric acid solution of 18-28%;
B) nitrocalcite dissolution of crystals deep impurity-removing: adding lime milk solution regulator solution pH value in the thick nitrocalcite crystal is 5-7, and sedimentation and filtration separates, and removes phosphate radical and metal ion, the ca nitrate soln that obtains making with extra care;
C) ca nitrate soln evaporation concentration: refining one section evaporation concentration of ca nitrate soln is removed free-water, and two sections degree of depth concentrate and remove crystal water, obtain containing the nitrocalcite of 1～2 crystal water;
D) granulating and forming: with two water nitrocalcite melt pelletization, wrap up moulding with ammonium nitrate again, obtain at last two water nitrocalcite of water-soluble rate 〉=99.9%.
2. decomposing phosphorite by using nitric acid according to claim 1 is produced the method for water-soluble two water nitrocalcite coproduction phosphoric acid, it is characterized in that ca nitrate soln removes free-water by evaporation concentration among the step C, and thickening temperature is 40～100 ℃; Two sections degree of depth concentrate and remove partial crystallization water, and thickening temperature is 120～220 ℃.
3. decomposing phosphorite by using nitric acid according to claim 1 is produced the method for water-soluble two water nitrocalcite coproduction phosphoric acid, it is characterized in that among the step D, the two water nitrocalcite that melt pelletization obtains adopt ammonium nitrate to wrap up moulding, the consumption of ammonium nitrate is mass percent 1～12%, and the content of its water-soluble two water nitrocalcite mass percents is 82～98.5%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936466A (en) * | 2014-04-29 | 2014-07-23 | 天脊煤化工集团股份有限公司 | Method and device for producing calcium ammonium nitrate |
| CN108083877A (en) * | 2017-12-20 | 2018-05-29 | 贵州芭田生态工程有限公司 | A kind of method that calcium nitrate using Phosphate Fertilizer Nitrate with Frozen Method process by-product produces calcium nitrate-urea as raw material |
| CN108502861A (en) * | 2018-06-25 | 2018-09-07 | 中化重庆涪陵化工有限公司 | Method and the crystallization in motion agent of concentrated phosphoric acid coproduction semi-hydrated gypsum whisker are produced using low-grade phosphate ore |
| CN108975374A (en) * | 2018-09-20 | 2018-12-11 | 秦皇岛天鼎化工有限公司 | The method and calcium nitrate of calcium nitrate are prepared using ardealite |
| CN109399688A (en) * | 2018-10-17 | 2019-03-01 | 贵州芭田生态工程有限公司 | The method of phosphate fertilizer mother liquor low temperature decalcification and decalcification filtrate and phosphate fertilizer preparation method |
| CN111498892A (en) * | 2020-04-21 | 2020-08-07 | 贵州大学 | Method for preparing α high-strength gypsum from byproduct calcium nitrate tetrahydrate of nitrophosphate fertilizer by freezing method |
| CN114085100A (en) * | 2021-12-16 | 2022-02-25 | 贵州芭田生态工程有限公司 | Method for preparing calcium-magnesium-sulfur secondary element water-soluble fertilizer and product |
| CN114436230A (en) * | 2022-01-29 | 2022-05-06 | 贵州芭田生态工程有限公司 | Process for preparing ammonium phosphate to improve quality of lithium iron phosphate by denitrifying phosphoric acid |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936466A (en) * | 2014-04-29 | 2014-07-23 | 天脊煤化工集团股份有限公司 | Method and device for producing calcium ammonium nitrate |
| CN108083877A (en) * | 2017-12-20 | 2018-05-29 | 贵州芭田生态工程有限公司 | A kind of method that calcium nitrate using Phosphate Fertilizer Nitrate with Frozen Method process by-product produces calcium nitrate-urea as raw material |
| CN108502861A (en) * | 2018-06-25 | 2018-09-07 | 中化重庆涪陵化工有限公司 | Method and the crystallization in motion agent of concentrated phosphoric acid coproduction semi-hydrated gypsum whisker are produced using low-grade phosphate ore |
| CN108975374A (en) * | 2018-09-20 | 2018-12-11 | 秦皇岛天鼎化工有限公司 | The method and calcium nitrate of calcium nitrate are prepared using ardealite |
| CN108975374B (en) * | 2018-09-20 | 2020-12-18 | 秦皇岛天鼎化工有限公司 | Method for preparing calcium nitrate by using phosphogypsum and calcium nitrate |
| CN109399688A (en) * | 2018-10-17 | 2019-03-01 | 贵州芭田生态工程有限公司 | The method of phosphate fertilizer mother liquor low temperature decalcification and decalcification filtrate and phosphate fertilizer preparation method |
| CN111498892A (en) * | 2020-04-21 | 2020-08-07 | 贵州大学 | Method for preparing α high-strength gypsum from byproduct calcium nitrate tetrahydrate of nitrophosphate fertilizer by freezing method |
| CN114085100A (en) * | 2021-12-16 | 2022-02-25 | 贵州芭田生态工程有限公司 | Method for preparing calcium-magnesium-sulfur secondary element water-soluble fertilizer and product |
| CN114436230A (en) * | 2022-01-29 | 2022-05-06 | 贵州芭田生态工程有限公司 | Process for preparing ammonium phosphate to improve quality of lithium iron phosphate by denitrifying phosphoric acid |
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