CN102826530A - Method for co-producing calcium hydrogen phosphate and calcium superphosphate by using high calcium siliceous low-graded phosphate ore - Google Patents
Method for co-producing calcium hydrogen phosphate and calcium superphosphate by using high calcium siliceous low-graded phosphate ore Download PDFInfo
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- CN102826530A CN102826530A CN2012103599044A CN201210359904A CN102826530A CN 102826530 A CN102826530 A CN 102826530A CN 2012103599044 A CN2012103599044 A CN 2012103599044A CN 201210359904 A CN201210359904 A CN 201210359904A CN 102826530 A CN102826530 A CN 102826530A
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Abstract
A method for co-producing calcium hydrogen phosphate and calcium superphosphate by using high calcium siliceous low-graded phosphate ore comprises the following steps of: (1), milling the high calcium siliceous low-graded phosphate ore to be ore pulp; directly conducting phosphoric acid to react with the low-graded ore pulp; after a second-stage clarificator is full, leading overflow wet-method phosphoric acid in a third-stage reaction tank, leading underflow low-graded phosphate ore thick slurry in the third-stage reaction tank, enabling a phosphoric acid leaching low-graded phosphate ore system to run continuously according to a technique process; shunting the third-stage clarified clear solution after the system runs stably, wherein 60% of clear solution enters a calcium hydrogen phosphate system and 40% of clear solution is returned to a dihydrate process phosphoric acid system as dilute acid; then, subjecting the phosphoric acid entering the calcium hydrogen phosphate system to P2O5 concentration adjustment, and carrying out a traditional phosphoric acid purification technique by using lime milk; conducting solid-liquid separation to the purified thick pulp, directly conducting the filtrate to a neutralization reaction for calcium hydrogen phosphate, so as to produce feed-level calcium hydrogen phosphate; leading the filter cake in a phosphatic fertilizer system; conducting solid-liquid separation on the thick pulp after the first-stage clarification, returning the filtrate back to the first-stage clarificator, and leading the filter cake in the phosphatic fertilizer system; mixing the two filter cakes, and producing common calcium superphosphate according to a traditional technology.
Description
Technical field
The present invention relates to a kind of phosphate production technology, specifically is a kind of method of utilizing high calcium siliceous low-grade phosphate ore coproduction secondary calcium phosphate and superphosphate of lime.
Background technology
China is phosphor resource big country, is only second to Morocco, occupies the second in the world, but the P of phosphor resource economic reserve
2O
5Whole grade only 17%.China's mid low grade phosphate rock is main with the siliceous phosphorus ore of high calcium, and economic worth is low, is difficult to direct utilization.At present, the utilization that is directed to low-grade phosphate ore is main with ore dressing basically, and must be the compound ore-dressing practice of positive and negative flotation for the siliceous phosphorus ore of high calcium, and plant investment is big, and beneficiation cost is high.Domestic each research institutions, technical community have been launched the development research of mid low grade phosphate rock one after another, have obtained gratifying technical know-how achievement.Such as: the research of kiln-process phosphoric acid, phosphoric acid leaching low-grade phosphate ore technology or the like, but all be difficult to suitability for industrialized production because of a variety of causes.
Existing 19 places, the phosphorus ore place of production of resource reserve are possessed in the area, Guangxi, have verified nearly hundred million tons of retained reserves, its P
2O
5Average out to 12～16% belongs to the siliceous mid low grade phosphate rock of high calcium, is difficult to utilize.In the production technology of current Wet-process Phosphoric Acid Production calcium hydrophosphate fodder, basically all adopted technology with phosphoric acid extraction predecomposition phosphorus ore, be intended to through free sulfuric acid in the phosphoric acid extraction and phosphorolytic cleavage phosphorus ore, in the hope of improving Ca in the phosphoric acid
+Concentration, thus vitriolic consumption reduced.But because the existence of free sulfuric acid, its rapidly and the carbonate in the phosphorus ore react, cause the H in the phosphoric acid
+Activity sharply descends, and the reaction of phosphoric acid and phosphorus ore is faint, the Ca in the phosphoric acid of reaction back
+Concentration is in 1.5%.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing high calcium siliceous low-grade phosphate ore coproduction secondary calcium phosphate and superphosphate of lime, can and make it with calcium in the low-grade phosphate ore and silicon branch, it is sharp changing fraud, turns waste into wealth.
The present invention achieves the above object through following technical scheme: a kind of method of utilizing high calcium siliceous low-grade phosphate ore coproduction secondary calcium phosphate and superphosphate of lime comprises the following steps:
1, the siliceous low-grade wet ball grinding of high calcium is processed contained moisture, contain P 25～30%
2O
5Be 14%～18%, slurry fineness: the ore pulp of-200 orders>=90%.
With P
2O
5Concentration is 20%～25%; Directly reactive tank reacts by the technology controlling and process index high-quality phosphoric acid of SO3:40～60g/l in the second stage with the low-grade phosphate ore slurry, second order reaction controlling index: temperature: 50 ℃～55 ℃, liquid-solid ratio: 5:1, react mean residence time: 30 minutes, P
2O
5: SO 16%～18%,
3: 3～5g/l.
2, after the secondary settler is full; The overflow phosphoric acid by wet process is imported third stage reactive tank, and underflow low-grade phosphate ore slurry imports first step reactive tank, and switch to high-quality phosphoric acid and get into the first order reaction groove this moment from the second order reaction groove; One-level settler overflow phosphoric acid gets into the second order reaction groove; The thick slurry of its underflow is behind vertical filter press, and filtrating is returned the one-level settler, and filter cake gets into the phosphate fertilizer system.Strict CONTROL PROCESS index lets phosphoric acid leaching low-grade phosphate ore system move continuously by said technical process.
First order reaction CONTROL PROCESS index: temperature: 55 ℃～65 ℃, liquid-solid ratio: 5:1, reaction mean residence time: 30 minutes, P
2O
5: SO 18%～20%,
3: 8～10g/l.
Third order reaction CONTROL PROCESS index: temperature: 45 ℃～50 ℃, liquid-solid ratio: 5:1, reaction mean residence time: 40 minutes, P
2O
5: 16%～18%.
4, after this system operates steadily, the shunting third stage clarification stillness of night, strict control fractional flow, wherein: what get into the secondary calcium phosphate system is 60%, what return two water law phosphoric acid systems as dilture acid is 40%.Secondly, the phosphoric acid that gets into the secondary calcium phosphate system is through regulating P
2O
5Concentration adopts CaO behind 10-12% be that the milk of lime of 5-6% carries out traditional phosphoric acid purification technological operation,
5, the thick slurry after the purification adopts vertical plate-and-frame filter press to carry out continuous solid-liquid separation, and filtrating is directly gone the secondary calcium phosphate neutralization reaction, produces calcium hydrophosphate fodder.
6, filter cake is controlled moisture 20%～25%, and gets into the phosphate fertilizer system.
7, the thick slurry after the one-level clarification adopts vertical plate-and-frame filter press to carry out continuous solid-liquid separation, and filtrating is returned the one-level settler, and filter cake control moisture is 15%～20%, and entering phosphate fertilizer system.
8, last, in tempering tank, two kinds of filter cakes are mixed, the control mixture moisture is 28%～30%.Mixed slip carries out normal superphosphate production by traditional technology.
Outstanding substantive distinguishing features of the present invention and substantial effect are:
1, through the fractional order reaction of phosphoric acid extraction and low-grade phosphate ore,, strengthened the reaction between the carbonate in phosphoric acid and the phosphorus ore, Ca in the phosphoric acid of reaction back with phosphoric acid that removes free sulfuric acid and low-grade phosphate ore reaction
+Concentration reaches 2.5%.Phosphoric acid purification workshop section purifies consumption of raw materials in the secondary calcium phosphate production process thereby reduced on the one hand, and also because phosphoric acid purification workshop section purifies the reduction of raw material unit's consumption, phosphoric acid purification co-precipitation phosphorus reduces on the one hand, and phosphoric acid purification phosphorus yield improves about 2%.
2, through the fractional order reaction of liquid extraction phosphoric acid and low-grade phosphate ore, with phosphoric acid extraction that is rich in free sulfuric acid and the low-grade phosphate ore reaction that removes carbonate, because the existence of high activity H+ in free sulfuric acid and the phosphoric acid, the phosphorus ore decomposition reaction aggravates, and phosphoric acid is to phosphorus ore P
2O
5Average rate of decomposition reaches 15%.Relatively improved about 10% with the parallel laboratory test of traditional technology.
3, in industrialized large-scale production plant, lower concentration phosphoric acid is incomplete to the decomposition of phosphorus ore, P in the filtration of slip and the filtration back filter cake
2O
5Recycling be whether this technology can industrialized key.The present invention mixes and is aided with the A material with the thick slurry behind the phosphorolytic cleavage phosphorus ore with the high phosphorus slag slurry of secondary calcium phosphate purification section and carry out normal superphosphate production through secondary calcium phosphate and normal superphosphate coproduction mode, and the product rerum natura is good, and quality is up to state standards.As everyone knows, produce and reach GB phosphate fertilizer, the total phosphorus that gets into the phosphate fertilizer system need be guaranteed.
4, the slag behind the use phosphoric acid leaching low-grade phosphate ore divides four steps to guarantee to get into the total phosphorus content of phosphate fertilizer system.One, phosphoric acid is to the decomposition of carbonate in the low-grade phosphate ore, P in the undecomposed low-grade phosphate ore
2O
5Improve about 2%; Two, free vitriolic amount in the control phosphoric acid; And then the rate of decomposition of control phosphorus ore is at optimal balance point, that is: about 25%, three, system introduces a certain amount of phosphoric acid by wet process; The high phosphorus slag slurry that in producing the calcium hydrophosphate fodder process, produces replenishes the phosphate fertilizer system, and four, the A material (staple of A material: NH
4F), with the activated silica reaction in the low-grade phosphate ore, silicon is with SiF
4Form overflow from gas phase, guaranteed on the one hand to get into the total phosphorus content of phosphate fertilizer system, install by-product gas phase SiO on the other hand
2Turn waste into wealth.
Description of drawings
Fig. 1 is high calcium siliceous phosphorus ore coproduction secondary calcium phosphate and the superphosphate of lime process flow diagram of utilizing of the present invention.
Embodiment
Below through specific embodiment technical scheme of the present invention is further described.
Embodiment 1
The method of utilizing high calcium siliceous phosphorus ore coproduction secondary calcium phosphate and superphosphate of lime of the present invention comprises the following steps:
Raw material: high calcium siliceous low grade rock phosphate-200 order>=90%, total analysis result: P
2O
516.25%, CaO32.68%, MgO0.22%, R
2O
33.52%, SiO
227.64%, F1.63%, CO
213.89%, H
2O1.5%.
Two water law phosphate compsns are: P
2O
522.45%, CaO0.23%, MgO0.38%, R
2O
32.05%, F1.85%, SO
348g/l.
Concrete steps are:
1, take by weighing sample phosphoric acid 5000g for twice, place two 5000ml beakers respectively, the beaker that phosphoric acid is housed is placed water-bath, the weighing apparatus temperature slowly adds ground phosphate rock respectively to 55 ℃ in beaker, and control reaction end slip liquid phase SO is stirred in startup
3After 5-8g/l, question response accomplish, will react afterwards slip and carry out vacuum and take out rate.Obtain phosphoric acid filtrating 8000g (I).Its analytical results: P
2O
523.85%, CaO1.32%, MgO0.41%, SO
36g/l.
2, take by weighing appearance (I) 4000g, place the 3#5000ml beaker, the 3# beaker is placed water-bath; The weighing apparatus temperature in beaker, slowly add 812g ground phosphate rock, and startup is stirred to 55 ℃; Controlling reaction time 40 minutes after question response is accomplished, will be reacted the back slip and carry out vacuum filtration; Filtrating is poured in the 4#5000ml beaker, and filter cake is put into the 1#5000ml beaker.
3, the 1# beaker is placed water-bath, the weighing apparatus temperature adds 3000g sample phosphoric acid to 55 ℃; And starting stirring, controlling reaction time 30 minutes is after question response is accomplished; To react the back slip and carry out vacuum filtration, filtrating is poured in the 2#3000ml beaker, and filter cake is put into the 5#5000ml beaker.
4, repeating step 3,4 once.
5, utilize vertical plate-and-frame filter press (model machine) to carry out press filtration filter cake in the 5# beaker, obtain filter cake, weight: 1906.5g filtrating, weight: 316.2g wherein: filter cake analytical results: P
2O
520.56%, CaO28.60%, MgO0.01%, SiO
232.03%, H
2O16.5%.Filtrate analysis result: P
2O
523.85%, CaO1.35%.
6, filtrating in the 4# beaker is weighed altogether its analytical results: P
2O
524.52%, CaO2.26%, MgO0.43%.
7, take by weighing phosphatase 11 000g in the 4# beaker, pour in the 6# beaker, the 6# beaker is placed water-bath, the weighing apparatus temperature starts and stirs to 45 ℃, in beaker, slowly adds milk of lime, control terminal point pH value 2.8.After question response is accomplished, will react the back slip and adopt vertical plate-and-frame filter press to carry out press filtration.Obtain the 3541.2g that filtrates, filter cake 86.75g.Wherein: filter cake analytical results: P
2O
535.45%, CaO26.46%, MgO1.42%, H
2O22.38%.Filtrate analysis result: P
2O
56.25%, CaO1.28%.
8, get the filtrating and the milk of lime reaction of step 8; Control reaction temperature is at 50 ℃, and in 45 minutes reaction times, the reaction end pH value is 6.5; After question response is accomplished; To react the back slip and carry out the vacuum press filtration, after gained filter cake (calcium hydrophosphate fodder) dries by the fire to 2 hours in 90 ℃ of constant temperature ovens, sampling analysis.Analytical results: P17.25%, Ca21.68%, MgO1.26%, F0.132%, H
2O0.84%.
9, get step 6 filter cake 240g, get step 8 filter cake 80g, add A material 3.2g;, and adding clear water 54.8g mixes adjusting slurry moisture to 30% in the 7# beaker; Start and stir; In the 7# beaker, add 98% sulfuric acid 78g again, question response placed 65 ℃ of constant temperature of water-bath 4 hours with the 7# beaker after accomplishing.Sampling analysis result: effective P
2O
5Be 12.45%, H
2O14.23%.
10, get the filter cake 100g of step 6, respectively with behind the 100ml clear water washing suction filtration three times, filter cake analytical results: P
2O
517.86%, CaO30.72%, MgO0.008%, SiO
231.03%, H
2O28.5%.
Experimental result shows:
(1) utilize the high-quality phosphorus ore to carry out 75% the Wet-process Phosphoric Acid Production that calcium hydrophosphate fodder needs total phosphorus, this part phosphoric acid has improved H in the acid
+Reactive behavior, strengthen the activity of phosphoric acid and phosphorus ore reaction, phosphoric acid reaches 15% to the rate of decomposition of phosphorus ore, controls SO in the phosphoric acid by wet process
3At 40～60g/l, control the total rate of decomposition of low-grade phosphate ore about 25%.
(2) utilize low-grade phosphate ore to belong to the characteristics that high calcium silicon is phosphorus ore, strengthen the reaction of calcium salt material in phosphoric acid and the phosphorus ore, reached the purpose of phosphoric acid neutralization reaction preliminary cleaning.In the secondary calcium phosphate production process, directly adopt milk of lime to carry out deep purifying and remove fluorine, phosphoric acid purification phosphorus yield reaches 90%
(3) returning of phosphoric acid purification slag slurry M (white fertile) mixed with the slag slurry N of first order reaction in the phosphoric acid leaching low-grade phosphate ore process, and control M:N is 1:3, has adjusted and has produced phosphate fertilizer with the demand of ore pulp to phosphorus, and the ore pulp total phosphorus reaches 24%.
(4) the A material (staple of A material: NH
4F), with the activated silica reaction in the low-grade phosphate ore, silicon is with SiF
4Form overflow from gas phase, further improve the total phosphorus content that gets into the phosphate fertilizer system, its butt mass percent is greater than 25%.Install by-product gas phase SiO simultaneously
2, turn waste into wealth.
Claims (1)
1. a method of utilizing high calcium siliceous low-grade phosphate ore coproduction secondary calcium phosphate and superphosphate of lime is characterized in that, comprises the following steps:
(1) the siliceous low-grade wet ball grinding of high calcium is processed contained moisture, contain P 25%～30%
2O
5Be 14%～18%, slurry fineness is the ore pulp of-200 orders>=90%;
(2) with containing P
2O
5Concentration is 20%～25%; SO
3: directly reactive tank reacts by the technology controlling and process index phosphoric acid of 40～60g/l in the second stage with the low-grade phosphate ore slurry, second order reaction controlling index: temperature: 50 ℃～55 ℃, liquid-solid ratio: 5:1, react mean residence time: 30 minutes, P
2O
5: SO 16%～18%,
3: 3～5g/l;
(3) after the secondary settler is full, the overflow phosphoric acid by wet process is imported third stage reactive tank, the thick slurry of underflow low-grade phosphate ore imports third stage reactive tank, and strict CONTROL PROCESS index lets phosphoric acid leaching low-grade phosphate ore system move continuously by said technical process;
First order reaction CONTROL PROCESS index: temperature: 55 ℃～65 ℃, liquid-solid ratio: 5:1, reaction mean residence time: 30 minutes, P
2O
5: SO 18%～20%,
3: 8～10g/l;
Third order reaction CONTROL PROCESS index: temperature: 45 ℃～50 ℃, liquid-solid ratio: 5:1, reaction mean residence time: 40 minutes, P
2O
5: 16%～18%;
(4) after this system operates steadily, the shunting third stage clarification stillness of night, strict control fractional flow, wherein: what get into the secondary calcium phosphate system is 60%, what return two water law phosphoric acid systems as dilture acid is 40%.Secondly, the phosphoric acid that gets into the secondary calcium phosphate system is through regulating P
2O
5Concentration adopts CaO behind 10-12% be that the milk of lime of 5-6% carries out traditional phosphoric acid purification technological operation;
(5) the thick slurry after the purification adopts vertical plate-and-frame filter press to carry out continuous solid-liquid separation, and filtrating is directly gone the secondary calcium phosphate neutralization reaction, produces calcium hydrophosphate fodder;
(6) filter cake is controlled moisture 20%～25%, and gets into the phosphate fertilizer system;
(7) after the one-level clarification, overflow phosphoric acid gets into the second order reaction groove, and the thick slurry of underflow adopts vertical plate-and-frame filter press to carry out continuous solid-liquid separation, and filtrating is returned the one-level settler, and filter cake control moisture is 15%～20%, and entering phosphate fertilizer system;
(8) last, in tempering tank, two kinds of filter cakes are mixed, the control mixture moisture is 28%～30%.Mixed slip carries out normal superphosphate production by traditional technology.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104671225A (en) * | 2014-10-22 | 2015-06-03 | 昆明川金诺化工股份有限公司 | Method for preparing high-quality calcium superphosphate in producing process of feed-grade calcium hydrogen phosphate |
| CN106744753A (en) * | 2016-12-30 | 2017-05-31 | 贵州开磷集团股份有限公司 | A kind of method of phosphorus ore stagewise de-magging |
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2012
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Patent Citations (3)
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|---|---|---|---|---|
| EP0253414A2 (en) * | 1984-04-24 | 1988-01-20 | AUTE Gesellschaft für autogene Technik mbH | Flame-cutting machine with principal and sliding clamping and cutting frameworks |
| FR2687657A1 (en) * | 1992-02-07 | 1993-08-27 | Cerphos | Process for manufacture of commercial-grade phosphoric acid containing a very low cadmium content |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104671225A (en) * | 2014-10-22 | 2015-06-03 | 昆明川金诺化工股份有限公司 | Method for preparing high-quality calcium superphosphate in producing process of feed-grade calcium hydrogen phosphate |
| CN104671225B (en) * | 2014-10-22 | 2016-06-29 | 昆明川金诺化工股份有限公司 | A kind of produce the method producing high-quality calcium superphosphate in calcium hydrophosphate fodder process |
| CN106744753A (en) * | 2016-12-30 | 2017-05-31 | 贵州开磷集团股份有限公司 | A kind of method of phosphorus ore stagewise de-magging |
| CN106744753B (en) * | 2016-12-30 | 2019-03-05 | 贵州开磷集团矿肥有限责任公司 | A kind of method of phosphorus ore stagewise de-magging |
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Application publication date: 20121219 |