CN100548875C - Adopt the method for Production By Sulfuric Acid Process calcium hydrogen phosphate fodder - Google Patents
Adopt the method for Production By Sulfuric Acid Process calcium hydrogen phosphate fodder Download PDFInfo
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- CN100548875C CN100548875C CNB2004100815028A CN200410081502A CN100548875C CN 100548875 C CN100548875 C CN 100548875C CN B2004100815028 A CNB2004100815028 A CN B2004100815028A CN 200410081502 A CN200410081502 A CN 200410081502A CN 100548875 C CN100548875 C CN 100548875C
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- sulfuric acid
- liquid
- calcium hydrogen
- milk
- lime
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Abstract
This invention belongs to the method that adopts the Production By Sulfuric Acid Process calcium hydrogen phosphate fodder.Comprise once, reextraction, again through one section, two sections, three sections neutralizing treatment, filtration, drying and mother liquor reclaim.This method is because on routine extraction basis, the ground phosphate rock that has increased adding is not for the second time adding under the corresponding vitriolic condition, utilize that first hydrogen ion and residual vitriolic effect extract it in the raw phosphoric acid, and to the recycling of the mother liquor after three sections neutralizing treatment back Returning utilization.Thereby have and to reduce sulfuric acid consumption 15～20% respectively than background technology, milk of lime consumption about 20%, P
2O
5Yield improves about 10%, and production cost descends 10～20%, and has avoided characteristics such as mother liquor exhaust emission environment.Overcome background technology and must adopt the excess sulfuric acid extraction, consumptions such as sulfuric acid, milk of lime are big, P
2O
5Disadvantages such as yield is lower, and mother liquor exhaust emission environment, production cost are high.
Description
Technical field
The invention belongs in the Chemical Manufacture with ground phosphate rock is raw material, the method that adopts the Production By Sulfuric Acid Process calcium hydrogen phosphate fodder.
Background technology
Tradition adopts the method for Production By Sulfuric Acid Process calcium hydrogen phosphate fodder, be by the direct decomposing rock phosphate with hydrogen of sulfuric acid, through sedimentation, filter obtain raw phosphoric acid after a neutralizing treatment defluorinate, defluorinate liquid again through the secondary neutralizing treatment, filter, be drying to obtain the calcium hydrogen phosphate fodder product.Though this method has characteristics such as technical process is short, owing to must extract, otherwise will cause the ground phosphate rock rate of decomposition to descend with excess sulfuric acid, adverse consequences such as gypsum crystallization is little, filtration difficulty, phosphorus yield are low, thereby have raw material consumption height, P such as sulfuric acid
2O
5Yield is low, disadvantages such as production cost height.At these disadvantages, in the patent No. is that ZL94111776, name are called in the patent documentation of " a kind of method of producing phosphoric acid extraction and solution containing phosphate with sulfuric acid process ", disclose a kind of phosphoric acid extraction that at first adopts production process to obtain raw material ground phosphate rock has been carried out pre-treatment, with remove carbonate in the raw material and the free sulfuric acid in the phosphoric acid extraction, again after settlement separate, supernatant liquid is phosphoric acid, the thick slurry of lower floor carries out acidolysis to obtain phosphoric acid extraction with sulfuric acid again, and this phosphoric acid extraction returns and is used for the pre-treating phosphorite powder.The phosphoric acid that is obtained again routinely technology carry out defluorinate, add calcium hydroxide or lime carbonate, after precipitation, drying get final product the calcium hydrogen phosphate fodder product.Though this technology has reduced the vitriolic consumption to a certain extent, improved the throughput of the intensity filter and the equipment of solution; But still there are material consumption quantity height such as sulfuric acid, milk of lime, P
2O
5Yield is lower, the more high disadvantage of production cost.
Summary of the invention
The objective of the invention is the disadvantage that exists at the above-mentioned background technology, improve a kind of method that adopts the Production By Sulfuric Acid Process calcium hydrogen phosphate fodder of design,, improve P to reach raw-material consumption such as effective reduction sulfuric acid
2O
5Yield, the waste water reclamation utilization, reduce purposes such as exhaust emission and production cost.
Solution of the present invention is on the common process basis, to carry out in two steps the extraction of ground phosphate rock, the first step component and proportioning routinely feeds intake, after obtaining raw phosphoric acid, under the condition of heating, drop into the ground phosphate rock of original ore powder weight 15～20% and the filter cake after the secondary neutralizing treatment again, utilize first hydrogen ion and residual sulfuric acid in the phosphoric acid to carry out the extraction second time, extraction for the second time no longer adds sulfuric acid, carry out one section (inferior) neutralization and two sections (inferior) neutralizing treatment then, filter cake after two sections neutralizations returns the reextraction groove, after filtrate (defluorinate liquid) is then carried out three sections (inferior) neutralization again, filter, the filter cake drying is handled and is promptly obtained the finished product feedstuff calcium hydrophosphate, and waste water (mother liquor) is again after neutralizing treatment, the clear water Returning utilization; The present invention promptly realizes its goal of the invention with this.Therefore, the present invention includes:
A, single extraction: is that 1: 1.015～1.03 ratio drops into extraction tank with ground phosphate rock or ore pulp and sulfuric acid by CaO in the ground phosphate rock and vitriolic mol ratio, under agitation extract according to a conventional method, filtration, residue washing, tail gas recycle or purify the back discharging; Filter residue phosphogypsum after washing uses it for anything else in addition, and filtrate and washings are sent into reactor;
B, reextraction: the filtrate in the reactor is heated to 80～110 ℃, the ground phosphate rock or the ore pulp that add the ground phosphate rock weight 15～20% of A operation input again, powerful stirring reaction 20～60 minutes to the abundant acidolysis of ground phosphate rock, stop heating, the filter residue, the continuation stirring reaction that add then after two sections neutralizing treatment of last a circulation D operation were sent into neutralizing well after 3～15 minutes;
C, one section neutralization: above-mentioned feed liquid under whipped state, slowly add milk of lime and carry out neutralizing treatment to material liquid pH value 1.8～2.5, put into settling pond cooling, clarification; Supernatant liquid is extracted out, and lower floor's concentrated solution is through press filtration, and filter cake is incorporated supernatant liquid into as fertilizer, filtrate and sent into two sections neutralizing wells as just taking off liquid;
D, two sections neutralizations: under whipped state, reach at 100 o'clock only to just taking off milk of lime to the phosphorus fluorine ratio in the feed liquid that slow adding concentration is 10～15wt% in the liquid, the feed liquid endpoint pH is 2.8～3.1, after filtration, filter cake returns the B operation, the filtrate input neutralizing well after defluorinate is handled;
E, three sections neutralizations: the filtrate of handling through defluorinate, slowly to add concentration under whipped state be the milk of lime of 5～10wt%, and the feed liquid neutralizing treatment is ended to pH6.0～6.3;
F, filtration, drying: E gained feed liquid is filtered, and mother liquor is sent into the neutralizing well recycling, and filter cake promptly gets the calcium hydrogen phosphate fodder finished product through≤100 ℃ of temperature dryings;
G, mother liquor reclaim: filter mother liquid obtainedly through the F operation, the milk of lime, neutralization reaction that add concentration≤5wt% under whipped state are put into the settling pond clarification to pH8～8.5, and throw out is through press filtration, oven dry, and the gained calcium hydrogen phosphate fodder is incorporated in the operation finished product; The upper strata clear water returns and is used to prepare ore pulp and washing gypsum.
Being heated to 80～110 ℃ described in the reextraction, is to heat in confined conditions, and its type of heating is a steam heating.And described powerful the stirring, its stirring velocity is 11～13m/ second.Neutralizing treatment agent in one section and two sections neutralizing treatment also comprises CaCO
3
The present invention is owing to increased reextraction operation, conventional first hydrogen ion and the residual vitriolic effect that extracts in the gained raw phosphoric acid of utilization, the ground phosphate rock that adds is for the second time carried out acidolysis to extract phosphorus wherein not adding in addition under the vitriolic condition, both improved the content of phosphorus in the raw phosphoric acid, again since in the feed liquid reduction of acidity contamination precipitations such as part iron, aluminium, fluorine are separated out, in the corresponding shortening and removal of impurities and the defluorinate time of handling and the consumption of milk of lime; Portioned product had both been reclaimed in mother liquor recycling after three sections neutralizations, clear liquid was returned be used to prepare ore pulp and washing gypsum, efficiently solved problem of environmental pollution.Thereby the present invention has under the same conditions and can reduce sulfuric acid consumption 15～20% than background technology, reduction milk of lime consumption about 20%, raising P
2O
5About yield 10%, production cost descends 10～20%, and has characteristics such as steady quality.
Embodiment
The ground phosphate rock that present embodiment adopts is for containing P
2O
534wt%, CaO 45.5wt%, F 3.3wt%, granularity 100 purpose breezes, sulfuric acid concentration is 98%.
A, single extraction: with 850g ground phosphate rock add that water 2200ml furnishing ore pulp and 705.5g sulfuric acid are gone in the reactor of 5000ml altogether, stirring reaction is after 5 hours, adopt B that slip is carried out vacuum filtration, also divides the washing filter residue 3 times with the 1250ml clear water, get the about 1700g of phosphogypsum filter residue, use it for anything else in addition; Filtrate and washings 3000ml are altogether sent into reactor as raw phosphoric acid;
B, reextraction: after in reactor, feeding steam, raw phosphoric acid being heated to 95 ℃, the ore pulp that adding is made into 150g ground phosphate rock and 390ml water, under 12m/ speed second stirring reaction 30 minutes, stop the heating, add a last circulation D operation gained filter cake 283g then, continue stirring reaction after 5 minutes, feed liquid is put into the open type neutralization reactor;
Among the C, one section and removal of impurities: slowly adding concentration under agitation condition in feed liquid is the milk of lime 65ml of 15wt%, material liquid pH value is transferred to 2.0 postcooling, clarification, supernatant liquid sucks two sections neutralizing treatment devices, lower floor's concentrated solution is used as fertilizer through press filtration, filter cake 230g, and filtrate is also sent into two sections neutralizing treatment devices and mixed with supernatant liquid, is total to such an extent that 3100ml just takes off liquid;
Among the D, two sections and defluorinate: will through first after one section neutralization take off liquid slowly add under the whipped state concentration be the milk of lime 1100ml of 12wt% to feed liquid endpoint pH 3.0, centrifuging, filter cake 290g, defluorinate filtrate 3950ml;
E, three sections neutralizations: above-mentioned defluorinate liquid slowly adds concentration under whipped state be the milk of lime 1000ml of 8wt%, reacts to material liquid pH value 6.2 and end;
F, filtration, drying: the feed liquid after three sections neutralizations is sent into centrifuging, get mother liquor 4400ml and send into the neutralization reactor recycling, filter cake is sent into thermostatic drying chamber, is dried to water ratio≤3% back under 90 ℃ of temperature, gets calcium hydrogen phosphate fodder finished product 700g;
G, mother liquor reclaim: the mother liquor of sending into the neutralizing treatment device under agitation slowly adds the milk of lime 150ml that concentration is 4wt%, and neutralizing treatment is to material liquid pH 8 back clarifications, and clear water about 4500ml in upper strata extracts out, returns to be used to modulate ore pulp and washing gypsum; The lower sediment thing is filtered to such an extent that thing also send thermostat container dry under 90 ℃ of temperature behind the pressurization suction filtration, gets calcium hydrogen phosphate fodder 17g.
Present embodiment altogether calcium hydrogen phosphate fodder finished product 717g, wherein contain after testing: P 16.83%, F 0.11%, Ca 21.3%.
Claims (3)
1, a kind of method that adopts the Production By Sulfuric Acid Process calcium hydrogen phosphate fodder, this method comprises:
A, single extraction: is that 1: 1.015～1.03 ratio drops into extraction tank with ground phosphate rock or ore pulp and sulfuric acid by CaO in the ground phosphate rock and vitriolic mol ratio, under agitation extract according to a conventional method, filtration, residue washing, tail gas recycle or purify the back discharging; Filter residue phosphogypsum after washing uses it for anything else in addition, and filtrate and washings are sent into reactor;
B, reextraction: the filtrate in the reactor is heated to 80～110 ℃, the ground phosphate rock or the ore pulp that add the ground phosphate rock weight 15～20% of A operation input again, powerful stirring reaction 20～60 minutes to the abundant acidolysis of ground phosphate rock, stop heating, the filter residue, the continuation stirring reaction that add then after two sections neutralizing treatment of last a circulation D operation were sent into neutralizing well after 3～15 minutes;
C, one section neutralization: above-mentioned feed liquid under whipped state, slowly add milk of lime and carry out neutralizing treatment to material liquid pH value 1.8～2.5, put into settling pond cooling, clarification; Supernatant liquid is extracted out, and lower floor's concentrated solution is through press filtration, and filter cake is incorporated supernatant liquid into as fertilizer, filtrate and sent into the secondary neutralizing well as just taking off liquid;
D, two sections neutralizations: under whipped state, reach at 100 o'clock only to just taking off milk of lime to the phosphorus fluorine ratio in the feed liquid that slow adding concentration is 10～15WT% in the liquid, the feed liquid endpoint pH be 2.8～3.1 after filtration, filter cake returns the B operation, the filtrate input neutralizing well that defluorinate is handled;
E, three sections neutralizations: the filtrate of handling through defluorinate, slowly to add concentration under whipped state be the milk of lime of 5～10WT%, and the feed liquid neutralizing treatment is ended to pH6.0～6.3;
F, filtration, drying: E gained feed liquid is filtered, and mother liquor is sent into neutralizing well; Recycling, filter cake are dry under≤100 ℃ of temperature, promptly get the calcium hydrogen phosphate fodder finished product;
G, mother liquor reclaim: filter mother liquid obtained through the F operation, the milk of lime, neutralization reaction that add concentration≤5WT% under whipped state are to pH8～8.5, put into the settling pond clarification, throw out is through press filtration, oven dry, and gained calcium hydrogen phosphate fodder finished product is incorporated in the operation finished product; The upper strata clear water returns and is used to prepare ore pulp and washing gypsum.
2, by the method for the described Production By Sulfuric Acid Process calcium hydrogen phosphate fodder of claim 1, wherein saidly in reextraction, be heated to 80～110 ℃, be to heat in confined conditions, its type of heating is a steam heating.
3, by the method for the described Production By Sulfuric Acid Process calcium hydrogen phosphate fodder of claim 1, wherein powerful stirring the described in the reextraction, its stirring velocity is 11～13m/ second.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100815028A CN100548875C (en) | 2004-12-17 | 2004-12-17 | Adopt the method for Production By Sulfuric Acid Process calcium hydrogen phosphate fodder |
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| CNB2004100815028A CN100548875C (en) | 2004-12-17 | 2004-12-17 | Adopt the method for Production By Sulfuric Acid Process calcium hydrogen phosphate fodder |
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| CN1789118A CN1789118A (en) | 2006-06-21 |
| CN100548875C true CN100548875C (en) | 2009-10-14 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030318B (en) * | 2010-11-02 | 2012-10-10 | 昆明川金诺化工股份有限公司 | Sulfur-economizing method for extracting phosphoric acid |
| CN102001637A (en) * | 2010-12-07 | 2011-04-06 | 昆明川金诺化工有限公司 | Feed-grade calcium hydrophosphate P2O5 yield improvement method |
| CN102674286B (en) * | 2012-05-25 | 2013-11-13 | 四川龙蟒磷化工有限公司 | Method for preparing high-quality feed-grade calcium hydrophosphate by by-product waste acid of titanium dioxide |
| 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 |
| CN106829905A (en) * | 2017-03-30 | 2017-06-13 | 四川龙蟒磷化工有限公司 | The method that silicon phosphorus ore high produces calcium hydrophosphate fodder |
| CN108658085B (en) * | 2018-05-29 | 2021-06-08 | 西南科技大学 | Method for preparing silicon micropowder and gypsum powder by leaching quartz processing sludge with sulfuric acid |
| CN111717904A (en) * | 2019-03-22 | 2020-09-29 | 云南善施化工有限公司 | Production method of calcium hydrogen phosphate |
| CN110510589A (en) * | 2019-09-10 | 2019-11-29 | 湖北祥云(集团)化工股份有限公司 | A kind of Wet-process Phosphoric Acid Production method and production system |
| CN115092900A (en) * | 2022-06-28 | 2022-09-23 | 新希望化工投资有限公司 | Process for producing potassium dihydrogen phosphate and calcium sulfate whiskers by adopting phosphorite |
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