CN106564866B - It is a kind of to utilize metal ion control method in slag acid caused by mid low grade phosphate rock production ammonium phosphate salt - Google Patents
It is a kind of to utilize metal ion control method in slag acid caused by mid low grade phosphate rock production ammonium phosphate salt Download PDFInfo
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- CN106564866B CN106564866B CN201610936085.3A CN201610936085A CN106564866B CN 106564866 B CN106564866 B CN 106564866B CN 201610936085 A CN201610936085 A CN 201610936085A CN 106564866 B CN106564866 B CN 106564866B
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- slag acid
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- 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
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/28—Ammonium phosphates
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- 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 kind of methods that efficient removal comes from metal ion in slag acid caused by mid low grade phosphate rock production monoammonium phosphate and Diammonium phosphate (DAP), belong to inorganic technical field of phosphorous chemical industry.Monoammonium phosphate and Diammonium phosphate (DAP) are produced using mid low grade phosphate rock, phosphate rock resource utilization rate can be improved, but has a large amount of slag acid in production and generates, because metal ion potassium, sodium, iron, aluminium equal size are high in slag acid, causes slag acid recovering rate low.Therefore the present invention is for the low problem of slag acid recovering rate, it is determined that a kind of slag acid impurity metal ion efficiently removes technique, realizes the efficient reuse of slag acid, greatly reduces production cost, improve the nutrient of monoammonium phosphate and Diammonium phosphate (DAP).This method is simple, easy to operate, and the slag acid recovery that mid low grade phosphate rock production monoammonium phosphate and Diammonium phosphate (DAP) is greatly improved recycles efficiency, has important theory significance and application value for the recycling of mid low grade phosphate rock.
Description
Technical field
The present invention relates to a kind of slag acid recovery utilization is improved using mid low grade phosphate rock production monoammonium phosphate and Diammonium phosphate (DAP)
The method of rate belongs to the relevant chemical technology field of the utilization of resources of mid low grade phosphate rock.
Background technology
Phosphate rock resource have it is indispensable, cannot substitute, cannot recycle, unrenewable characteristic, and be related to China's agriculture
Industry produces, and belongs to strategic resource.In recent years the scarcity of rock phosphate in powder gradually shows, at present about 50,000,000,000 tons of world phosphate stone gross reserves,
And economic reserve, less than 18,000,000,000 tons, by current exploitation rate, the useful life of global phosphate rock resource was less than 50 years.China is more
To be serious, according to annual 100000000 tons or more at present of phosphorus ore consumption, even if using economic reserve, 40 also can only be at most utilized
Year.And phosphorus is one of indispensable element of crop growth, the protection of phosphor resource is related to the safety in production of national food, closes
It is the stabilization to society and development.But China is becoming tight high-quality phosphate rock resource day, phosphate rock resource quality is gradually reduced, and kind becomes
In complexity, price differs greatly, and large effect is brought to the production and product quality of production of ammonium phosphate producer of China, serious to make
The further development of Yue Liao enterprises.It is becoming tight with the day of phosphate rock resource, the decline increasingly of phosphorus ore quality, the ripe wet method of script
Phosphoric acid technology is faced with more and more difficulties.
The extensive utilization of sulphur dioxide of phosphor chemical industry is obtained using the method that middle-low grade produces monoammonium phosphate and Diammonium phosphate (DAP), still
Since slag acid iterates through filtration washing system, increased phosphorus loses, while also because of a large amount of metal impurities Returning reacting systems,
Cause requirement of the reaction system to impurity content in concentrate high, constrains the technological development using more low-grade phosphate ore.Therefore,
The removal and effectively control for setting about phosphoric acid slag acid metal ion become the research hotspot that mid low grade phosphate rock efficiently uses.Such as pomace
Acid obtains effective recycling, can not only improve the utilization rate of phosphorus and the added value of phosphorus, while can also reduce phosphoric acid and use phosphorus
The impurity requirement of mine, to use more low-grade phosphate ore to pave the way, will bring huge economic benefit to enterprise.
Since there are the metallic elements such as Fe, Al, Mg, Na, K in slag acid, impurity content is high, is unable to meet production qualified phosphorus
The needs of sour diammonium and monoammonium phosphate, therefore the present invention is for there are the metallic elements such as Fe, Al, Mg, Na, K in slag acid composition
Chemical characteristic, using Chemistry-physics method realize effectively to metal ion total content control, make slag acid-utilising rate reach 99% with
On, it is efficiently utilized for middle-low grade phosphor resource, improves enterprise competitiveness and established solid foundation.The invention of this respect in patent or
It is not reported in document.
Invention content
The technical problem to be solved by the present invention is to utilizing mid low grade phosphate rock production monoammonium phosphate and Diammonium phosphate (DAP) mistake
Fe, Al, Mg, Na, K of slag acid in journey are effectively removed, control total metal ion content 7% hereinafter, wherein potassium, sodium from
Sub- content is less than 0.8%, improves slag acid-utilising rate, reduces monoammonium phosphate and features of DAP production cost.
In order to which the control and removal, the technical solution adopted by the present invention that solve the problems, such as metal ion in above-mentioned slag acid are as follows：
1, the precipitating reagent of the metal ion sodium, potassium that are most difficult to removal is found, it is effective by neutralization precipitation method using chemical method
Remove metallic sodium, potassium ion, while part removal magnesium ion.
In conjunction with sulphur dioxide of phosphor chemical industry own characteristic, fluosilicic acid self-produced in Wet-process Phosphoric Acid Production is selected, carries out many experiments.Profit
Small feature is accumulated with the content of prodan, potassium fluosilicate, achievees the purpose that the more sodium potassium ions of removal.
Experiment finds that fluosilicic acid and slag acid mass ratio are 1:200-1:Sodium potassium ion is removed than more significant between 50.It can
So that sodium and potassium content are less than 0.8%（Mass ratio）, the influence to follow-up workshop section is smaller.
2, settling agent is found, the sinking speed of fluosilicate is improved, meets the requirement of technique.
Many experiments find, aryl sulfonic acid, such as benzene sulfonic acid and naphthalene sulfonic acids, especially naphthalene sulfonic acids best results, dosing with
It is not added with dregs of a decoction acid to compare, initial sinking speed differs more than ten times, and dosing slag acid can understand after stopping stirring several seconds
Tell solution boundary layer, floccule rapid subsidence, the clarified solution in entire infall process is transparent.Select aryl sulfonic acid
Concentration is advisable in 5-100ppm, can average settlement speed be improved 1-3 times.
3, ventilating and cooling reduces subsider temperature, by forced ventilation circulation temperature lowering, realizes effectively crystallization, further removes
Metal ion in slag acid.
Experiment finds that between subsider is spent at 80-90 DEG C, each metal ion species can reach saturation state, directly cools down
Need a large amount of cooling waters.We can form whirlpool in a liquid using the method for directly leading to cold wind, one side air stream, effectively
Disperse sediment and liquid, on the other hand can be energy saving, when by temperature reduction to 30-70 DEG C, 50% or more can be removed
Aluminium ion and iron ion.Experiment shows that 15-25 DEG C of air temperature general control is advisable, and blast velocity control is in 0.2-2 L/min, gold
The removal effect for belonging to ion is preferable.
Figure of description
Fig. 1 is the relationship of the concentration and sinking speed of different naphthalene sulfonic acids.
Specific implementation mode：
Embodiment 1
Take the P of 28% grade2O5% produces 1 ton of slag acid caused by monoammonium phosphate, and under stirring condition, fluorine silicon is added at 70 DEG C
Benzene sulfonic acid 10ppm is added fully after reaction in sour 10kg, mixes 30 minutes, stands 15 minutes, obtains supernatant liquid and lower fleece
Clear liquid is warming up to 75 DEG C by condensate after filtering, and 20 DEG C of air are passed through with 1L/min, and after cooling 30 minutes, temperature can be with
Reach 50-55 DEG C, it is seen that many flocculates generate, and quiescent setting is after 50 minutes, filtering, obtain clear slag acid 995kg, metal from
Sub- total content 6.2%, wherein sodium and potassium content are 0.7%, and the rate of recovery reaches 99.5%.
Embodiment 2
Take the P of 30% grade2O5% produces 2 tons of slag acid caused by Diammonium phosphate (DAP), and after stirring, fluosilicic acid is added at 75 DEG C
Naphthalene sulfonic acids 20ppm is added fully after reaction in 30kg, mixes 30 minutes, stands 15 minutes, obtains supernatant liquid and lower layer's flocculation
Object after filtering, is passed through 25 DEG C of air with 1.5 L/min, after cooling down 30 minutes, temperature is made to reach 50 DEG C hereinafter, static layering 50
After minute, filtering obtains clear 1998 tons of slag acid, and metal ion total content 5.1%, wherein sodium and potassium content are 0.5%, slag acid
Recovery utilization rate is 99.9%.
Claims (3)
1. a kind of using metal ion control method in slag acid caused by mid low grade phosphate rock production ammonium phosphate salt, feature exists
In being using precipitating reagent removal sodium, potassium and magnesium metal ion first；Then settling agent is used to improve the rate of settling；Finally use
Cooling means removes aluminium, iron ion；
The precipitating reagent is fluosilicic acid, and fluosilicic acid is with slag acid weight ratio 1:200-1:50；
The settling agent is aryl sulfonic acid, a concentration of 5-100ppm of aryl sulfonic acid；
The cooling means is to be reduced to crystallization temperature by the way of air-cooled direct heat transfer to be crystallized, specifically will reaction
Bath temperature degree is controlled at 80-90 DEG C, then that temperature is air-cooled to 30-70 DEG C.
2. according to the method described in claim 1, it is characterized in that, the method for reducing temperature is using cold air cooling, wind speed
Control is in 0.2-2 L/min, 15-25 DEG C of temperature.
3. according to the method described in claim 1, it is characterized in that, slag acid metal ion total content control is for 5-7%.
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| CN105366654B (en) * | 2015-12-02 | 2017-07-28 | 云南磷化集团有限公司 | A kind of nonphosphate precipitates wet phosphoric acid purifying method |
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