CN101747107B - Method for extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid - Google Patents
Method for extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid Download PDFInfo
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- CN101747107B CN101747107B CN200910231188A CN200910231188A CN101747107B CN 101747107 B CN101747107 B CN 101747107B CN 200910231188 A CN200910231188 A CN 200910231188A CN 200910231188 A CN200910231188 A CN 200910231188A CN 101747107 B CN101747107 B CN 101747107B
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- sulfuric acid
- soluble sulphate
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Abstract
The invention relates to a method for extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid. In the method, in the reaction for generating the phosphoric acid by phosphorite pulp in the phosphoric acid extraction process, the soluble sulphate is added for partly replacing the sulfuric acid. The invention has the advantages that the amount of the generated heat is small, the subsequent processing is simple, and the cost is greatly lowered.
Description
Technical field
The present invention relates to a kind of method of phosphoric acid extraction, particularly a kind of in composite fertilizer produces with the method for extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid.
Background technology
The working method of well-known wet method phosphorus ore phosphoric acid extraction; Be to utilize phosphorus ore slurry and sulfuric acid to add extraction tank after metering; The light phosphoric acid of simultaneously the diafiltration post being carried adds extraction tank, and the material after chemical reaction obtains the extraction slip; Slip to after the maturation is transported to filter by shurry pump, through filtering phosphoric acid.This traditional production process receives the restriction of the single extraction agent of sulfuric acid, particularly when the sulfuric acid cost value is higher, can increase the production cost of composite fertilizer.
Simultaneously; The core reaction that sulfuric acid decomposes the technology in phosphoric acid ore deposit is a thermopositive reaction; Under the situation of not setting up cooling system, the interior temperature of reaction tank is usually near 100 degrees centigrade, and the design temperature of the extraction tank of phosphate fertilizer industry generally all is less than or equal to 90 degrees centigrade; Just the main reaction process temperature in the production technique will surpass the Equipment Design temperature, and the high temperature extractive reaction can bring bigger safety in production hidden danger.Therefore, in above-mentioned reaction process, for the temperature that makes extraction tank is lower than design temperature; Have on extraction tank, set up the flash distillation cooling system, this equipment at least more than 300 ten thousand, and be furnished with a large-size machine; Increased the total installation of generating capacity of whole plant; Be unfavorable for safety and economic operation, and existing scheme not only increases facility investment, also increased the complicacy of system.
Summary of the invention
The method cost that the objective of the invention is in order to overcome existing Wet-process Phosphoric Acid Production composite fertilizer is high; And control extraction tank temperature of reaction defect of high cost; And a kind of composite fertilizer's production cost that can significantly reduce is provided, and be easy to control the method for the extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid of extraction tank temperature of reaction.
The present invention adopts following technical scheme:
The method of extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid, the phosphorus ore ore pulp in the phosphoric acid extraction process generate in the reaction of phosphoric acid, add soluble sulphate and partly replace sulfuric acid.
Described vitriolic replacement amount is greater than 0 and be not more than 30% of required sulfuric acid quality before the replacement.
Described vitriolic replacement amount before said reaction is preferably replacement the starting stage required sulfuric acid quality 20%.
Described soluble sulphate preferably sulfuric acid ammonium.
Adjust said replacement amount according to the extraction tank temperature, if temperature greater than preset temperature, increases said replacement amount, if temperature less than preset temperature, reduces said replacement amount.
The adding point selection slime dam of described soluble sulphate, return in acid tank and the thick stock tank a bit, or said soluble sulphate sneaked in three wash waters, perhaps said soluble sulphate is directly added at extraction tank.
For said vitriol be in the mode that extraction tank adds, be provided with one be used to dissolve said vitriol lixator, this lixator flows into extraction tank through dashpot through the overflow mode.
After adding said vitriol, detect SO in the extraction tank in real time
3Index if be higher than preset value, reduce vitriolic and adds.
Said phosphoric acid takes every two hours to observe at least in the process crystal habit of a phosphogypsum, if crystal habit is unusual, reduces said phosphatic add-on.
Following formula according to the embodiment of the invention:
Ca
5F(PO
4)
3+3.5H
2SO
4+1.5(NH
4)
2SO
4+5nH
2O＝3NH
4H
2PO
4+5CaSO
4·nH
2O+HF?↑
Can know; The needed hydrogen ion of phosphoric acid extraction needs to guarantee; Obviously, under the situation with two position parameters of sulfate radical, soluble sulphate substitutes the vitriolic amount can not be greater than 30%; And this reaction also shows, uses soluble sulphate in the method for liquid extraction phosphoric acid, to substitute sulfuric acid feasibility in theory.
Experiment showed, and use sulphate moiety ground to replace the vitriolic phosphoric acid by wet process, said basically replacement amount all reaches suitable reaction temperature about 20%, and therefore, said replacement amount is preferably 20% in the said reaction starting stage, is convenient to the adjustment of its consumption.In addition, in the case, can guarantee the basic demand of excess sulfuric acid.
In order to reduce the cost of subsequent disposal, said vitriol is preferably ammonium sulfate, and the monoammonium phosphate that is generated itself also is a kind of chemical fertilizer commonly used at present, and the by product of this reaction can not influence the production of composite fertilizer.Therefore,, in selecting the process of vitriol, preferably consider the production of composite fertilizer, such as vitriolate of tartar etc. based on this.
Because adding opportunity of vitriol, the influence to this programme was not very big; Mainly optimum before extraction work is carried out; Therefore the adding point selection slime dam of said vitriol, return in acid tank and the thick stock tank a bit; Or said vitriol sneaked in three wash waters, or to add at extraction tank all be suitable.
Further, for the ease of said temperature regulation, the adding of vitriol obtains the handiness of control more easily the closer to extraction tank, therefore add at extraction tank proper, to the response speed of adjustment temperature than very fast.Therefore, said vitriol in the mode that extraction tank adds is, be provided with one be used to dissolve said vitriol lixator, this lixator flows into extraction tank through dashpot through the overflow mode, adopt overflow mode ratio to be easier to adjust liquid flow rate, and flow is steady.Said dashpot is actual to be exactly the groove that further improves the flow stationarity, and its concrete structure does not have particular restriction, adopts conventional dashpot just can.
After adding said vitriol, detect SO in the extraction tank in real time
3Index if be higher than preset value, reduce vitriolic and adds, to obtain reasonable phosphogypsum crystal form.
Said phosphoric acid takes every two hours to observe at least in the process crystal habit of a phosphogypsum, if crystal habit is unusual, reduces said phosphatic add-on.The crystal habit of phosphogypsum is a kind of more typical form, just can observe through reading lens, and is different if crystal habit has, and regulates through the amount that reduces said vitriol.
The invention has the beneficial effects as follows:
Heat is very little because soluble sulphate is given birth in above-mentioned reaction, and pyrogenic reaction mainly is the reaction of sulfuric acid and phosphorus ore slurry, therefore, under the situation that satisfies the said replacement amount upper limit, according to predetermined temperature, the amount of the vitriol that adjustment is added.In experiment, the said use adjustment difficulty that partly substitutes the vitriolic situation postrun part period that only is to drive thereafter just can steady running, does not need adjustment basically, adjusts the method that is not difficult and adopts the flash distillation cooling system in existing.And obvious a bit is, the cost of the filing provision of said vitriol is far below the cost of flash distillation cooling system, and the whole cost of equipment can reduce greatly, and, can reduce the total installation of generating capacity of system greatly, be convenient to the safety and economic operation of system.
On the other hand, adopting vitriol to substitute sulfuric acid can reduce production costs, and the cost of general soluble sulphate is lower than sulfuric acid.Certainly; Even if consider the subsequent disposal of using soluble sulphate, promptly how to separate basic metal or other positive ions introduced, its whole cost does not increase; For the adding of some vitriol, the whole cost of this method still reduces significantly.
Embodiment
Do to describe more specifically in the face of technical scheme of the present invention down, make the clearer the present invention of understanding of those skilled in the art, the method for this preferred embodiment extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid; After the phosphoric acid production line was driven operation, the phosphorus ore ore pulp in the phosphoric acid extraction process generated the reaction of phosphoric acid, partly replaces sulfuric acid with soluble sulphate; Satisfying the replacement amount is not more than under 30% the situation; Adjust said replacement amount according to the extraction tank temperature, if temperature greater than preset temperature, increases said replacement amount; If temperature less than preset temperature, reduces said replacement amount.Certainly; Said preset temperature is a TR, can adopt the TR of those skilled in the art's normal needs control of adopting in phosphoric acid by wet process, correspondingly; Be said greater than to as if the upper limit of said TR, less than to as if the lower limit of said TR.
Embodiment 1:
Replace the vitriolic amount to add ammonium sulfate for 30% of required sulfuric acid quality before replacing according to ammonium sulfate, per hour add-on is 5 bags, uses dilture acid to carry out the dilute sulphuric acid ammonium, per hour amount of dilution 0.4m
3, survey dilture acid SO
3Concentration is 0.020-0.025g/ml, SO behind the adding ammonium sulfate
3Concentration is that 0.4g/ml becomes redness, adds point in extraction tank two districts, adds the first two district and differs 0.3m with three district's sulfuric acid amount
3/ hour, add the back according to survey SO
3Concentration and gypsum crystallization situation reduce by two district's sulfuric acid add-ons gradually, add the vitriolic amount between two districts and differ 1m
3/ hour, temperature of reaction decline 1 degree in two districts is observed crystallization and filtration washing effect and is not had big variation.
Embodiment 2:
Replace the vitriolic amount to add ammonium sulfate according to ammonium sulfate for 20% of required sulfuric acid quality before replacing; The ammonium sulfate add-on is adjusted to 7 bags/hour; Crystallization has the parcel phenomenon, has adjusted to add sulfuric acid amount, reduces by two district's sulfuric acid add-ons; Add point in extraction tank two districts, add the first two district and differ 0.3m with three district's sulfuric acid amount
3/ hour, add the back according to survey SO
3Concentration and gypsum crystallization situation reduce by two district's sulfuric acid add-ons gradually, and two districts and three district's sulfuric acid add-ons differ 1.4m
3/ hour, it is general that effect is blotted in filtration, and residual phosphorus has the rising phenomenon.One district, two district's temperature descend, more 0.5 degree of two districts decline.
Embodiment 3:
Replace the vitriolic amount to add ammonium sulfate according to ammonium sulfate for 5% of required sulfuric acid quality before replacing; The ammonium sulfate add-on is adjusted to 8 bags/hour, and crystal has the thickening phenomenon, and the parcel phenomenon is more; Add point in extraction tank two districts, add the first two district and differ 0.3m with three district's sulfuric acid amount
3/ hour, add the back according to survey SO
3Concentration and gypsum crystallization situation reduce by two district's sulfuric acid add-ons gradually, and two districts and three district's sulfuric acid amount differ 1.8m
3/ hour, SO
3Concentration control lower bound, 0.025-0.030g/ml is on the low side, after drop to 0.020-0.025g/ml gradually, insoluble phosphorus is about 0.67%, it is general to blot effect.After take to add half a hour 4 bag of one groove dilture acid, the dilture acid add-on is many, dissolving is fast, residual phosphorus changes little.Sulfuric acid amount does not add 0.4m than adding per hour to lack before the ammonium sulfate
3/ hour about, 0.67 ton in sulfuric acid of folding.
Claims (5)
1. the method for extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid; It is characterized in that; Phosphorus ore ore pulp in the phosphoric acid extraction process generates in the reaction of phosphoric acid; Add soluble sulphate and partly replace sulfuric acid, described vitriolic by the amount of replacement greater than 0 and be not more than 30% of required sulfuric acid quality before the replacement.
2. according to the method for the described extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid of claim 1, it is characterized in that described vitriolic is 20% of required sulfuric acid quality before replacing by the amount of replacement.
3. according to the method for claim 1 or 2 described extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid, it is characterized in that described soluble sulphate is an ammonium sulfate.
4. according to the method for the described extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid of claim 1; It is characterized in that; The adding point selection slime dam of described soluble sulphate, return in acid tank and the thick stock tank a bit; Or said soluble sulphate sneaked in three wash waters, perhaps said soluble sulphate is directly added at extraction tank.
5. according to the method for the described extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid of claim 4; It is characterized in that; Said vitriol in the mode that extraction tank adds is, be provided with one be used to dissolve said vitriol lixator, this lixator flows into extraction tank through dashpot through the overflow mode.
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| CN200910231188A CN101747107B (en) | 2009-12-17 | 2009-12-17 | Method for extracting phosphoric acid by soluble sulphate instead of part of sulfuric acid |
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| CN101747107B true CN101747107B (en) | 2012-10-03 |
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| CN102431981A (en) * | 2011-09-01 | 2012-05-02 | 贵州开磷（集团）有限责任公司 | Reduction of SO in dilute phosphoric acid3Method of concentration |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1398331A (en) * | 1971-08-03 | 1975-06-18 | Montedison Spa | Preparation of phosphoric acid by the wet process |
| ES2013211A6 (en) * | 1989-07-11 | 1990-04-16 | Ercros Sa | Process for obtaining phosphoric acid from phosphorus- bearing rock via a wet route |
| CN1113880A (en) * | 1994-06-01 | 1995-12-27 | 龚家竹 | Method for extracting phosphoric acid and solution containing phosphate by sulfuric acid method |
| CN1460635A (en) * | 2003-06-17 | 2003-12-10 | 东华工程科技股份有限公司 | Method for producing phosphoric acid by using 93%-98% concentrated sulfuric acid to extract phosphate rock and its equipment |
-
2009
- 2009-12-17 CN CN200910231188A patent/CN101747107B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1398331A (en) * | 1971-08-03 | 1975-06-18 | Montedison Spa | Preparation of phosphoric acid by the wet process |
| ES2013211A6 (en) * | 1989-07-11 | 1990-04-16 | Ercros Sa | Process for obtaining phosphoric acid from phosphorus- bearing rock via a wet route |
| CN1113880A (en) * | 1994-06-01 | 1995-12-27 | 龚家竹 | Method for extracting phosphoric acid and solution containing phosphate by sulfuric acid method |
| CN1460635A (en) * | 2003-06-17 | 2003-12-10 | 东华工程科技股份有限公司 | Method for producing phosphoric acid by using 93%-98% concentrated sulfuric acid to extract phosphate rock and its equipment |
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Address after: 252300 No. 13 Han Qiao Road, Chengxi, Yanggu County, Shandong, Liaocheng Patentee after: Shandong Liaocheng Luxi Chemical Fifth Fertilizer Co.,Ltd. Address before: 252300 No. 13 Han Qiao Road, Chengxi, Yanggu County, Shandong, Liaocheng Patentee before: Liaocheng Luxi Chemical No.5 Chemical Fertilizer Plant |