CN100486888C - Process for preparing high concentration phosphoric acid from middle-and low-grade phosphorus ore - Google Patents
Process for preparing high concentration phosphoric acid from middle-and low-grade phosphorus ore Download PDFInfo
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- CN100486888C CN100486888C CNB2006100225621A CN200610022562A CN100486888C CN 100486888 C CN100486888 C CN 100486888C CN B2006100225621 A CNB2006100225621 A CN B2006100225621A CN 200610022562 A CN200610022562 A CN 200610022562A CN 100486888 C CN100486888 C CN 100486888C
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- phosphoric acid
- low grade
- concentration
- phosphogypsum
- washing
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Abstract
The invention discloses a making method of high-density phosphic acid based on middle or low grade phosphoric ore, which comprises the following steps: separating extracted phosphic acid system from washing quantity of phosphogypsum; manufacturing sediment phosphate; avoiding the unflavored effect due to increasing present system; using partial phosphor element to manufacture refined sediment phosphoric acid salt; reducing the loss of phosphor; circulating mother liquid of phosphate into grinding system or washing water of phosphogypsum.
Description
One, technical field
The technical field that the present invention uses is phosphatic production.
Two, background technology
China is phosphate rock resource big country, and the phosphorus ore production and consumption is all at the forefront in the world, and the retained reserve of phosphorus ore is 151.58 hundred million tons.China's phosphorus ore based in low-grade, soaring along with domestic and international phosphate fertilizer consumption, the production of phosphate fertilizer enterprise higher-grade phosphorus ore that uses of relying is also quickening exhaustion.At present, all production of phosphate fertilizer enterprises all can not use mid low grade phosphate rock to produce 25% (P both at home and abroad
2O
5) above high-concentration phosphoric acid.
In the world, in order to obtain business economic benefit preferably, and can guarantee factory normally, operation stably, phosphoric acid by wet process factory is very tight to the specification of quality of raw material phosphorus ore, typical phosphorus ore P
2O
5Grade and foreign matter content generally have following regulation:
Table 1-1 is in the world to being used for the phosphorus ore requirement of phosphoric acid by wet process processing
Be about 10～15 years the working life of higher-grade phosphorus ore, and in order to delay the working life of higher-grade phosphorus ore, it is particularly urgent that the development and use of mid low grade phosphate rock seem.Impurity height in the mid low grade phosphate rock, phosphorous many below 25%, 1 ton of P of every production
2O
5The amount of gypsum that produces is (with 20%P about 7.5 tons
2O
5Count), and the higher-grade phosphorus ore is ((with 30%P
2O
5Meter)) produce 1 ton of P
2O
5The amount of gypsum that produces is about 5.3 tons.In order to guarantee certain washing rate, utilize low-grade phosphate ore to produce in the process phosphoric acid, just need more washing water, like this, the phosphoric acid by wet process concentration of being produced is just lower, and this also is the major cause that low product phosphorus ore was produced high-concentration phosphoric acid during Wet-process Phosphoric Acid Production enterprise can not utilize both at home and abroad at present.
In existing technology, patent CN1151959C has related to a kind of method that adopts mid low grade phosphate rock to produce calcium hydrophosphate fodder, its essence is and adopt traditional phosphorus ore decomposition method, the phosphoric acid by wet process of mid low grade phosphate rock and sulfuric acid reaction production and the reaction of a part of ore pulp are generated saturated biphosphate calcium solution, utilize this solution further to produce secondary calcium phosphate, or this solution is further produced phosphoric acid by wet process with sulfuric acid reaction, this technology only is that the conventional production methods of present China secondary calcium phosphate has been extended to mid low grade phosphate rock, patent is not described its phosphoric acid concentration of producing, generally speaking, the phosphoric acid concentration that technological line under adopting in the patent is produced also only has 15～22%, 25～32% the concentration that can not reach that domestic and international large-scale phosphoric acid plant at present produces.Patent CN1683239A has described a kind of method that adopts mid low grade phosphate rock to produce phosphoric acid, its operational path also is that the operational path that adopts patent CN1151959C to produce secondary calcium phosphate is produced phosphoric acid, only this patent is described the detailed process that adopts mid low grade phosphate rock to prepare phosphoric acid in detail, it is 18～22% product that but this patent can be produced phosphoric acid concentration only, can not reach 25～32%.A kind of method that adopts mid low grade phosphate rock to produce phosphoric acid has also been described among the patent CN1792776A, the cardinal principle of this method also is to adopt the phosphorolytic cleavage phosphorus ore, mainly the saturated solution of monocalcium phosphate in the decomposed solution, further decompose this saturated solution with sulfuric acid, obtain phosphoric acid, its resulting phosphoric acid concentration is also 20～24%.In sum, the something in common of these three patents mainly is to make an issue of on the monocalcium phosphate saturated solution, under the bigger situation of laboratory dingus steam output, prepared phosphoric acid concentration also is no more than 24%, if the phosphoric acid by wet process device adopts mid low grade phosphate rock to produce phosphoric acid by wet process both at home and abroad at present, need do a large amount of transformations, invest greatlyyer, not have an operability.
The present invention utilizes mid low grade phosphate rock direct production high-concentration phosphoric acid, can save to concentrate the steam that needs, thereby save production cost, and then can prepare fine water-soluble phosphoric acid product salt.The mid low grade phosphate rock that the present invention utilized need not phosphorus ore is carried out enrichment before using, but directly use mid low grade phosphate rock and sulfuric acid reaction, the product phosphoric acid concentration that obtains is between 25～32%, this not only saves the expense of concentrating for enterprise, also provides technical guarantee for creating conservation-minded society simultaneously.300,000 tons phosphoric acid production device of a cover for example, if phosphoric acid concentration is brought up to 27% from 22%, one ton of phosphoric acid of so every production is saved steam (0.2MPa) 1.1 tons, annual steam (0.2MPa) 330,000 tons that save amounts to 60,000 tons of mark coals.
Three, summary of the invention
The objective of the invention is a kind of technology of directly utilizing mid low grade phosphate rock to prepare high-concentration phosphoric acid of proposing at the deficiencies in the prior art.Be characterized on the basis of existing phosphoric acid extraction device, utilize the direct decomposing medium and low grade of sulfuric acid, slurry solution after the decomposing medium and low grade, through separating, adopt a certain amount of wash water thorough washing solid phosphogypsum, the water-soluble phosphorus in the phosphogypsum is reached and the P that uses in the high-quality phosphorus ore generation phosphogypsum
2O
5The same level has guaranteed that simultaneously institute's production concentration of phosphoric acid is constant.
One ton of P of every production
2O
5Need 20% P
2O
5About 5.3 tons of phosphorus ore, produce about about 7.5 tons of phosphogypsum, be mark ore deposit (30%P
2O
5) produce 1.415 times of phosphogypsum amount.Equally, in order to guarantee to adopt the water-soluble P in mid low grade phosphate rock production phosphogypsum that high-concentration phosphoric acid produced
2O
5Less than 0.3%, the wash water consumption that adopts mid low grade phosphate rock to produce the phosphogypsum of phosphoric acid generation also should be 1.415 times of mark ore deposit leaching requirement.Because the wash water of phosphoric acid extraction system all returns extraction tank, adopt the traditional technology route to utilize the prepared phosphoric acid concentration of mid low grade phosphate rock just can not surpass 20% like this.The present invention utilizes the water balance of phosphoric acid extraction system just, has ingeniously solved present phosphoric acid production device and can not utilize mid low grade phosphate rock to produce the problem of high-concentration phosphoric acid.Some chemical equation that the present invention relates to are as follows:
Ca
5F(PO
3)
3+5H
2SO
4+10H
2O＝＝3H
3PO
4+5CaSO
4·2H
2O↓+HF↑
CaCO
3+H
2SO
4＝＝CaSO
4·2H
2O↓+CO
2↑
MgCO
3+H
2SO
4＝＝MgSO
4+CO
2↑+H
2O
The present invention can be applied directly on the present wet-process phosphoric acid production plant, promptly with the direct decomposing medium and low grade of sulfuric acid.Because the amount of gypsum that mid low grade phosphate rock produces is bigger than the phosphogypsum amount that adopts the high-quality phosphorus ore to produce, in order to reach same washing effect, the wash water consumption is also bigger.But, if use conventional methods, promptly wash water is all returned the phosphoric acid extraction system, just can't effectively guarantee phosphoric acid concentration, the present invention extracts the part washing lotion out the phosphoric acid extraction system, because this part washing lotion contains P
2O
5Have only about 10%, can only prepare precipitate phosphoric acid salt, water-insoluble phosphoric acid salt such as calcium phosphate salt, phosphoric acid zinc salt and phosphoric acid magnesium salts for example, so not only can effectively utilize the phosphorus in the mid low grade phosphate rock, simultaneously also can guarantee higher phosphoric acid concentration, the phosphoric acid of this part higher concentration just can adopt spissated method to produce water miscible phosphate product, for example ammonium phosphate salt, sodium phosphate salt and potassium phosphate salt etc.The part washing lotion of extraction system is after producing precipitate phosphoric acid salt, and the wash water that the mother liquor of generation can all or part ofly turn back to ore grinding or do phosphogypsum recycles, and has so just finished the water balance problem of mid low grade phosphate rock.
If according to traditional operational path, directly utilize mid low grade phosphate rock and sulfuric acid reaction to produce phosphoric acid by wet process, all washing lotions all turn back to the phosphoric acid extraction system, adopt such wet method phosphoric acid manufacture process can produce a lot of problems so, are embodied in following several aspect:
(1) if the production high concentrations of phosphoric acid, leaching requirement must reduce, so the water-soluble P in the phosphogypsum
2O
5Will be 1～2%, the washing rate of phosphogypsum will be lower than 95%, and the stacking of phosphogypsum can cause serious environmental pollution.
(2) if phosphogypsum washing rate will reach more than 99%, the phosphoric acid concentration of production is lower, the inefficiency of extraction tank.
(3) adopt low concentration phosphoric acid production water-soluble phosphate, need spissated expense to improve greatly, to concentrate one ton of P
2O
5Be example, if 20% phosphoric acid extraction is concentrated to 48%, steam (0.2MPa) amount that needs is about 3.8 tons, if 28% phosphoric acid extraction is concentrated to 48%, steam (0.2MPa) amount that needs is about 1.93 tons, promptly be concentrated to same concentration, concentrate high-concentration phosphoric acid (28%) and lack than lower concentration phosphoric acid (20%) and consume 1.87 tons of steam, with 300,000 tons of phosphoric acid (P
2O
5) device is for example, adopts mid low grade phosphate rock to produce high-concentration phosphoric acid (28%) and lacks every year than production lower concentration phosphoric acid (20%) and consume 56.1 ten thousand tons of quantity of steams, steam per ton is reduced expenses 44,880,000 yuan every year according to 80 yuan of calculating.
Core technology of the present invention is: directly utilize mid low grade phosphate rock to produce high-concentration phosphoric acid.In producing the high-concentration phosphoric acid process, the leaching requirement that increases phosphogypsum is isolated the phosphoric acid extraction system, this part washing lotion is used for producing precipitate phosphoric acid salt, avoid the water yield to increase the disadvantageous effect that original system is produced, the part phosphoric is used to produce meticulous precipitate phosphoric acid salt in this process, thereby the loss that can make phosphorus reaches minimum, and the mother liquor of producing the precipitation fine phosphate is recycled to grinding system or as the in addition recycle of the wash water of phosphogypsum.
In existing business-like technology, the utilization of mid low grade phosphate rock is adopted more the method for first ore dressing post-treatment.Wherein if adopt the physical concentration investment quite big, beneficiation cost is also quite high, and the concentrate cost that adopts this method to obtain for some difficult " collophanites " that select is also quite high.
Purpose of the present invention by following technical measures realize, wherein said raw material umber except that specified otherwise, be parts by weight.
Utilize mid low grade phosphate rock directly to prepare the method for high-concentration phosphoric acid:
The reaction conditions that adopts with sulfuric acid decomposing medium and low grade phosphoric acid extraction is: temperature is 60～90 ℃, and the time is 2～7 hours, and liquid-solid ratio is: 1.5～4:1, SO
3Span of control is 1～7%; It is characterized in that: strengthen the wash water consumption of washing phosphogypsum, the water-soluble P in the control gypsum
2O
5Less than 0.3%, the washing rate of phosphogypsum is washed the washing lotion of phosphogypsum generation simultaneously and is only partly returned the phosphoric acid extraction system more than 99%, and remaining washing lotion is isolated described system, and the phosphoric acid concentration of producing with control is 25～32%.
The reaction conditions that decomposing medium and low grade adopts is preferably: 75～85 ℃ of temperature, liquid-solid ratio are 2.0～3.0:1, and the time is 2.5～7 hours, SO
3Span of control is 2.5～6.0%.
The ratio that the washing lotion of isolating described system accounts for total washing lotion amount is 1～70%, is used to produce fine phosphate, the mother liquor of generation return grinding system or as the wash water of phosphogypsum or again pulp-water recycle.
The present invention has following advantage:
The present invention compares its superiority and is with conventional art: can directly utilize mid low grade phosphate rock to produce high-concentration phosphoric acid, simultaneously the meticulous precipitate phosphoric acid salt of by-product; Utilize mid low grade phosphate rock to produce the processing costs in early stage that high-concentration phosphoric acid has not only been saved mid low grade phosphate rock, also reduced the gross investment of design library part editor and reuse; Can produce following positively effect to existing phosphoric acid production device after utilizing the present invention:
(1) not needing that existing phosphoric acid production device is done big change can use mid low grade phosphate rock to produce high-concentration phosphoric acid.
(2) use the high-concentration phosphoric acid of mid low grade phosphate rock production can be used for direct production water-soluble phosphoric acid product salt, save a large amount of expenses that concentrate.To concentrate one ton of P
2O
5Be example, if 20% phosphoric acid extraction is concentrated to 48%, steam (0.2MPa) amount that needs is about 3.8 tons, if 28% phosphoric acid extraction is concentrated to 48%, steam (0.2MPa) amount that needs is about 1.93 tons, promptly be concentrated to same concentration, concentrate high-concentration phosphoric acid (28%) and lack than lower concentration phosphoric acid (20%) and consume 1.87 tons of steam, with 300,000 tons of phosphoric acid (P
2O
5) device is for example, adopts mid low grade phosphate rock to produce high-concentration phosphoric acid (28%) and lacks every year than production lower concentration phosphoric acid (20%) and consume 56.1 ten thousand tons of quantity of steams, steam per ton is reduced expenses 44,880,000 yuan every year according to 80 yuan of calculating.
(3) utilize mid low grade phosphate rock to produce high-concentration phosphoric acid, can effectively improve the extraction efficiency of extraction tank.For example adopt 20% phosphorus ore to produce 20% phosphoric acid and 26% phosphoric acid, the latter is than 1.3 times of the former efficient raisings.
(4) utilize this technology, under investment situation seldom, can the needed meticulous precipitate phosphoric acid product salt in production market.
(5) present, the used phosphorus ore grade of some large-scale phosphoric acid production equipments is about～29%, but water-soluble P in the gypsum that it produced
2O
5All greater than 0.7%, and the mid low grade phosphate rock that the present invention adopts can reduce the water-soluble P in the phosphogypsum significantly under the situation that does not reduce phosphoric acid concentration
2O
5
Four, description of drawings
Fig. 1 utilizes mid low grade phosphate rock to prepare the high-concentration phosphoric acid flow diagram
Five, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can improve and adjust according to some nonessential contents in the invention described above.
Example 1
1.1 the preparation of end acid
Take by weighing ground phosphate rock 12000g (P
2O
5%20.6), method according to traditional extraction phosphoric acid, phosphoric acid is carried dense being divided into six times, each use ground phosphate rock 2000g, extraction for the first time adopts tap water to regulate liquid-solid ratio, reacts the after-filtration that finishes, through three clear water washings, filtrate and primary wash liquor are as the end acid of the phosphoric acid extraction second time, and secondary cleaning water and three washing lotions are respectively as a wash water and two wash waters of collection acidleach next time cake, and three wash the employing tap water.Adopt and finish the 3rd to the 6th collection acid test in the same way.The reaction conditions of control is: SO
3Be～3.5%; Temperature of reaction is :～80 ℃; The extraction time is 6 hours; Liquid-solid ratio is 2.5:1.After the acid of the 6th collection, the phosphoric acid amount of filtrate that obtains after the filtration is 5800.0g, contains P
2O
527.1%, a washing lotion amount that obtains is 1960g, contains P
2O
520.7%, two washing lotion (P
2O
513.0%) amount contains P for 1828g
2O
513.0%, three washing lotion amount is 1630g, contains P
2O
52.7%.
1.2 low-grade phosphate ore relieving haperacidity
Take by weighing ground phosphate rock 2000g (P
2O
5%20.6), add water and make it become moisture 35% ore pulp, according to top extraction conditions, an end acid that utilization prepares above and a washing lotion progressively liquid-solid ratio of conditioned reaction slip are 2.5.The phosphoric acid amount that tradition phosphoric acid plant actual needs is isolated system is 1475g, and the actual amount of filtrate of returning is 4325g in the device, for the liquid-solid ratio that guarantees slip is 2.5, reacts the shared washing lotion amount 1730g that goes.After reaction finishes, filter, utilize two washing lotions that prepare end acid as first washing water, the shared 1500g that goes, all as second washing water of this collection acid, the 3rd washing water all adopt clear water washing, the shared clear water 1700g that goes to three washing lotions of preparation end acid.Filtrate that Chan Shengs and washing lotion by analysis, its data such as following table:
Example 2
2.1 the method according to example 1 prepares end acid, the phosphorus ore gross weight is 18000g, and the reaction conditions of control is: SO
3Be～3.0%; Temperature of reaction is :～75 ℃; The extraction time is 4 hours; Liquid-solid ratio is 3:1.The data of extraction end acid see the following form.
2.2 low-grade phosphate ore relieving haperacidity
Take by weighing ground phosphate rock 3000g (P
2O
5%24.2), add water and make it become moisture 35% ore pulp, according to the reaction conditions of preparation end acid, an end acid that utilization prepares above and a washing lotion progressively liquid-solid ratio of conditioned reaction slip are 3.0.Use amount of filtrate 7970g, a washing lotion amount 3760g.After reaction finishes, filter, utilize two washing lotions that prepare end acid as first washing water, the shared 3000g that goes, all as second washing water of this collection acid, the 3rd washing water all adopt clear water washing, the shared clear water 3000g that goes to three washing lotions of preparation end acid.Filtrate that Chan Shengs and washing lotion by analysis, its data such as following table:
Example 3
3.1 the method according to example 1 prepares end acid, the phosphorus ore gross weight is 6000g, and the reaction conditions of control is: SO
3Be～3.0%, temperature of reaction is :～80 ℃; The extraction time is 5 hours; Liquid-solid ratio is 2.5:1.The end acid number of extraction is according to seeing the following form.
3.2 low-grade phosphate ore relieving haperacidity
Take by weighing ground phosphate rock 1000g (P
2O
5% 22.1), add water and make it become moisture 35% ore pulp, according to the reaction conditions of preparation end acid, an end acid that utilization prepares above and a washing lotion progressively liquid-solid ratio of conditioned reaction slip are 2.5.Use amount of filtrate 1950g, a washing lotion amount 1150g, two washing lotion 150g.After reaction finishes, filter, utilize two washing lotions that prepare end acid as first washing water, the shared 950g that goes, all as second washing water of this collection acid, the 3rd washing water all adopt clear water washing, the shared clear water 990g that goes to three washing lotions of preparation end acid.Filtrate that Chan Shengs and washing lotion by analysis, its data such as following table:
Claims (4)
1. method of utilizing mid low grade phosphate rock to prepare high-concentration phosphoric acid, the reaction conditions that adopts with sulfuric acid decomposing medium and low grade phosphoric acid extraction is: temperature is 60～90 ℃, and the time is 2～7 hours, and liquid-solid ratio is: 1.5～4:1, SO
3Span of control is 1～7%; It is characterized in that: strengthen the wash water consumption of washing phosphogypsum, the water-soluble P in the control gypsum
2O
5Less than 0.3%, the washing rate of phosphogypsum is washed the washing lotion of phosphogypsum generation simultaneously and is only partly returned the phosphoric acid extraction system more than 99%, and remaining washing lotion is isolated described system, and the phosphoric acid concentration of producing with control is 25～32%.
2. according to the described method of utilizing mid low grade phosphate rock to prepare high-concentration phosphoric acid of claim 1, the reaction conditions that wherein said decomposing medium and low grade adopts is: 75～85 ℃ of temperature, liquid-solid ratio are 2.0～3.0:1, and the time is 2.5～7 hours, SO
3Span of control is 2.5～6.0%.
3. according to claim 1 or the 2 described methods of utilizing mid low grade phosphate rock to prepare high-concentration phosphoric acid, the ratio that the washing lotion of wherein isolating described system accounts for total washing lotion amount is 1～70%, is used to produce fine phosphate.
4. according to the described method of utilizing mid low grade phosphate rock to prepare high-concentration phosphoric acid of claim 3, wherein produce the mother liquor that produces behind the fine phosphate return grinding system or as the wash water of phosphogypsum or again pulp-water recycle.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001636B (en) * | 2010-09-26 | 2012-07-25 | 四川大学 | Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process |
| CN105502320A (en) * | 2015-12-30 | 2016-04-20 | 昆明川金诺化工股份有限公司 | Method for producing hemihydrated phosphoric acid from medium/low-grade phosphorite |
| CN106145075B (en) * | 2016-06-30 | 2018-08-21 | 四川大学 | Produce the combined extraction method of high-quality phosphoric acid |
| CN107628596A (en) * | 2017-11-13 | 2018-01-26 | 贵阳开磷化肥有限公司 | A kind of apparatus and method using waste water regulation phosphate ore pulp extraction production phosphoric acid |
| CN111732086A (en) * | 2020-07-31 | 2020-10-02 | 天宝动物营养科技股份有限公司 | Process for preparing phosphoric acid and co-producing high-purity gypsum by semi-water-dihydrate method |
| CN115535976B (en) * | 2022-10-13 | 2024-02-23 | 中国科学院过程工程研究所 | Device system and method for recycling potassium-containing phosphorite |
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Non-Patent Citations (2)
| Title |
|---|
| 磷酸 磷铵 重钙技术与设计手册. 化学工业部建设协调司，化工部硫酸和磷肥设计技术足以组织编写，877，化学工业出版社. 1997 |
| 磷酸 磷铵 重钙技术与设计手册. 化学工业部建设协调司，化工部硫酸和磷肥设计技术足以组织编写，877，化学工业出版社. 1997 * |
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