CN102849703B - Method for preparing fine calcium phosphate by using phosphogypsum desulfurization residue - Google Patents
Method for preparing fine calcium phosphate by using phosphogypsum desulfurization residue Download PDFInfo
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- CN102849703B CN102849703B CN201210330185.3A CN201210330185A CN102849703B CN 102849703 B CN102849703 B CN 102849703B CN 201210330185 A CN201210330185 A CN 201210330185A CN 102849703 B CN102849703 B CN 102849703B
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- calcium phosphate
- fine calcium
- lime
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- phosphate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The present invention discloses a method for preparing fine calcium phosphate by using phosphogypsum desulfurization residue. The method is characterized in that phosphogypsum desulfurization residue is added with deionized water to prepare lime milk; the resulting refined lime milk is adopted to carry out pre-neutralization and purification on wet-process phosphoric acid, wherein a reaction is performed for 0.5-6.0 hours at a temperature of 45-85 DEG C, and the wet-process phosphoric acid pre-neutralization pH value is 1.0-3.0; the pre-neutralized slurry is filtered, wherein the filter cake is used for production of fertilizer phosphate products; the resulting filtrate is subjected to neutralization by using the lime milk; filtration is performed; the resulting filter cake is dried to obtain the fine calcium phosphate, wherein the end point pH value is 5.5-9.5, and the pH value is controlled to obtain different fine calcium phosphate; after neutralization, the mother liquor returns to emulsification to prepare the lime milk so as to achieve recycle.
Description
Technical field
The present invention relates to prepare with ardealite desulfurization residue the method for fine calcium phosphate, belong to the preparation field of phosphorus chemical product.
Background technology
The annual emissions of China's ardealite has reached 6,000 ten thousand tons at present, and accumulative total volume of cargo in storage is over 400,000,000 tons.The stacking of ardealite and comprehensive utilization are global problems.A large amount of ardealites store up not only land occupation resource, and bring environmental protection pressure and potential safety hazard.Although Discussion on technology for production of SA with joint product cement from phosphogypsum is ripe, its production cost is too high, causes engineering application difficulty large.Utilize ardealite desulfurization residue to prepare the production cost that fine calcium phosphate not only can reduce ardealite acid-making process, can also make full use of the calcium resource in ardealite, the good ardealite of can yet be regarded as utilizes approach.And utilize ardealite desulfurization residue to prepare fine calcium phosphate, can also avoid the exploitation of natural limestone and because of calcination of calcium carbonate institute energy requirement, and the discharge of greenhouse gases carbon dioxide.
The production of fine calcium phosphate is at present substantially all to adopt phosphoric acid by wet process or thermal phosphoric acid to produce.The fine calcium phosphate quality that adopts thermal phosphoric acid to produce is good, and purity is high, but its production cost is higher; Adopt Wet-process Phosphoric Acid Production fine calcium phosphate to carry out impurity and purification to phosphoric acid, just can produce qualified product.The preparation method > > that Chinese patent 200810058508.1 is entitled as a < < calcium hydrophosphate fodder discloses a kind of preparation method of calcium hydrophosphate fodder: first adopt phosphoric acid and milk of lime after calcium carbonate and the defluorinate of milk of lime two-stage purify to carry out acid-base neutralization, gained slip, through sedimentation, isolated by filtration, obtains product after filtration cakes torrefaction.
Chinese patent CN1107661A, CN1048015A, CN1049403C, CN1063157C etc. are the improvement to calcium hydrophosphate fodder production technology, but there are no utilizing ardealite desulfurization residue for the calcium source production patented technology of fine calcium phosphate and the bibliographical information of non-patent technology.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of method of preparing fine calcium phosphate with ardealite desulfurization residue is provided, be characterized in utilizing calcium oxide in above-mentioned residue to make fine calcium phosphate for calcium source, this method has been avoided exploitation and the lime burning carbon dioxide in process gas purging of natural limestone, thereby realizes the object of energy-saving and emission-reduction.The method adopts the mother liquor digestion desulfurization residue of producing fine calcium phosphate, prepares milk of lime after separation, and residue is for the production of cement; Postdigestive milk of lime is produced fine calcium phosphate product with phosphoric acid by wet process in two sections.
Object of the present invention is realized by following technical measures, and wherein said raw material umber, except specified otherwise, is parts by weight.
The method of preparing fine calcium phosphate with ardealite desulfurization residue comprises the following steps:
(1) preparation of milk of lime
To in ardealite desulfurization residue, add deionized water to prepare thick milk of lime, control liquid-solid ratio and be 5.0 ~ 20 and carry out emulsification, in 90 ~ 100 ℃ of emulsification 0.5 ~ 10h of temperature, then by cyclonic separation, sieve number be that 100 ~ 600 mesh sieves divide, and sloughs indissoluble thing SiO in residue
2, CaSO
4, Ca
3(PO
4)
2, CaHPO
4, CaF
2and other insoluble matter, cross filter residue for manufacture of cement, the refining milk of lime of gained is used for and phosphoric acid by wet process;
(2) preneutralization purifies
Above-mentioned refining milk of lime is carried out to preneutralization purification to phosphoric acid by wet process, in 45 ~ 85 ℃ of reaction 0.5 ~ 6.0h of temperature, phosphoric acid by wet process preneutralization pH is 1.0 ~ 3.0, and the slip after preneutralization filters, filter cake is for the production of fertilizer phosphate product, and filtrate is for the preparation of fine calcium phosphate;
(3) preparation of fine calcium phosphate
Filtrate after filtering with the further neutralization procedure of above-mentioned milk of lime (2), in 45 ~ 85 ℃ of reaction 0.5 ~ 6.0h of temperature, reaction finishes rear filtration, and filter cake drying obtains fine calcium phosphate; Its endpoint pH is 5.5-9.5, controls the size of pH value, obtains different fine calcium phosphates; The rear mother liquor of neutralization returns to emulsification and prepares milk of lime, and realization recycles.
The fine calcium phosphate that the described method of preparing fine calcium phosphate prepares is calcium monohydrogen phosphate and tricalcium phosphate.
Performance test:
1, adopt method shown in GB/T 22549-2008 to measure total phosphorus, citric acid soluble phosphorus, calcium, fluorine, arsenic, the cadmium in calcium hydrophosphate fodder.
2, adopt method shown in GB 1889-2004 to measure heavy metal, lead, arsenic, fluorine, the hydrochloric acid insoluble substance in food-grade calcium hydrogen phosphate.
3, adopt method shown in GB 24568-2009 to measure calcium oxide, phosphorus pentoxide, arsenic, iron, fluorine, carbonate, the sulfide in toothpaste grade calcium hydrophosphate.
4, adopt method shown in GB 25558-2010 to measure food additives tricalcium phosphate.
The present invention compared with prior art tool has the following advantages:
1, make full use of the calcium constituent in ardealite desulfurization residue, improve resource utilization;
2, effectively reduce the production cost of ardealite comprehensive utilization acid-making process, for enterprise obtains economic benefit;
3, avoid the required energy consumption of calcined limestone and release of carbon dioxide to environment, have the meaning of good environmental protection;
4, for enterprise, increase the kind of fine calcium phosphate, the variation of product, the ability of raising enterprise market competition;
5, technique is simple, and cost is low, and mother liquor reusable edible provides technical support for creating economizing type production.
The specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
With 500 grams of ardealite residues (containing calcium oxide 65%), add boiling water and carry out emulsification, liquid-solid ratio is 5.0, in 100 ℃ of emulsification 0.5h of temperature, then sieve, screen cloth number is 100 orders, milk of lime after screening carries out preneutralization with phosphoric acid by wet process and reacts, at temperature 45 C reaction 2.0h, control terminal pH 3.0, slip filters, filter cake is fertilizer grade calcium monohydrogen phosphate, clear liquid carries out main neutralization, at temperature 45 C reaction 3h, terminal pH 6.0, slip filters after completion of the reaction, filter cake is calcium hydrophosphate fodder product after drying, its quality reaches GB/T 22549-2008 requirement.
Embodiment 2
With 1000 grams of ardealite residues (containing calcium oxide 70%), add boiling water and carry out emulsification, liquid-solid ratio is 8.0, in 90 ℃ of reaction 10.0h of temperature, then carry out cyclonic separation, by the milk of lime after separation and food grade phosphoric acid neutralization reaction, at temperature 45 C reaction 2.0h, control terminal pH 5.5, filter after completion of the reaction, filter cake is food-grade calcium hydrogen phosphate product after drying, and its quality reaches GB 1889-2004 requirement.
Embodiment 3
With 800 grams of ardealite residues (containing calcium oxide 68%), add boiling water and carry out emulsification, liquid-solid ratio is 12.0, in 95 ℃ of temperature, reaction 3.0h, then carry out cyclonic separation, milk of lime after separation and phosphoric acid are carried out to preneutralization to react, at 85 ℃ of reaction 0.5h of temperature, control terminal pH 3.0, slip filters, after filtering, filter cake is fertilizer grade calcium monohydrogen phosphate, clear liquid carries out main neutralization, at temperature 50 C reaction 2.5h, control terminal pH 6.2, slip filters after completion of the reaction, filter cake is toothpaste grade calcium hydrophosphate product after drying, its quality reaches GB 24568-2009 requirement.
Embodiment 4
With 1000 grams of ardealite residues (containing calcium oxide 65%), add the mother liquor of producing calcium monohydrogen phosphate and carry out emulsification, liquid-solid ratio is 14.0, in 95 ℃ of reaction 3.0h of temperature, then sieve, screen cloth number is 300 orders, milk of lime after screening is carried out to preneutralization with phosphoric acid by wet process to react, at temperature 50 C reaction 3.0h, control terminal pH 2.5, slip filters, filter cake is fertilizer grade calcium monohydrogen phosphate, clear liquid carries out main neutralization, at 85 ℃ of reaction 0.5h of temperature, terminal pH 6.5, slip filters after completion of the reaction, filter cake is calcium hydrophosphate fodder product after drying, its quality reaches GB/T 22549-2008 requirement.
Embodiment 5
With 1000 grams of ardealite residues (containing calcium oxide 68%), add the mother liquor of producing tricalcium phosphate and carry out emulsification, liquid-solid ratio is 16.0, in 90 ℃ of temperature, reaction 6.0h, then sieve, screen cloth number is 400 orders, milk of lime after screening is carried out to preneutralization with phosphoric acid by wet process to react, at temperature 45 C reaction 4.5h, control terminal pH 3.0, slip filters, filter cake is fertilizer grade calcium phosphate, clear liquid carries out main neutralization, at 75 ℃ of reaction 1.0h of temperature, terminal pH 9.5, slip filters after completion of the reaction, filter cake is food additives tricalcium phosphate product after drying, its quality reaches GB 25558-2010 requirement.
Embodiment 6
With 800 grams of ardealite residues (containing calcium oxide 75%), add the mother liquor of producing calcium monohydrogen phosphate and carry out emulsification, liquid-solid ratio is 20.0, in 90 ℃ of reaction 9.0h of temperature, then sieve, screen cloth number is 240 orders, milk of lime after screening is carried out to preneutralization with phosphoric acid by wet process to react, at temperature 45 C reaction 6.0h, control terminal pH 1.0, slip filters, filter cake is fertilizer grade calcium monohydrogen phosphate, clear liquid carries out main neutralization, at temperature 45 C reaction 6.0h, terminal pH 5.5, slip filters after completion of the reaction, filter cake is calcium hydrophosphate fodder product after drying, its quality reaches GB/T 22549-2008 requirement.
Embodiment 7
With 1000 grams of ardealite residues (containing calcium oxide 75%), add the mother liquor of producing calcium monohydrogen phosphate and carry out emulsification, liquid-solid ratio is 10.0, in 94 ℃ of temperature, reaction 5.0h, then sieve, screen cloth number is 600 orders, milk of lime after screening is carried out to preneutralization with phosphoric acid by wet process to react, at temperature 50 C reaction 3.5h, control terminal pH 3.0, slip filters, filter cake is fertilizer grade calcium monohydrogen phosphate, clear liquid carries out main neutralization, at temperature 50 C reaction 1.5h, terminal pH 6.0, slip filters after completion of the reaction, filter cake is food-grade calcium hydrogen phosphate product after drying, its quality reaches GB 25559-2010 requirement.
Claims (2)
1. with ardealite desulfurization residue, prepare the method for fine calcium phosphate, it is characterized in that the method comprises the following steps:
(1) preparation of milk of lime
To in ardealite desulfurization residue, add deionized water to prepare thick milk of lime, control liquid-solid ratio and be 5.0～20 and carry out emulsification, in 90～100 ℃ of emulsification 0.5～10h of temperature, then by cyclonic separation, sieve number be that 100～600 mesh sieves divide, and sloughs indissoluble thing SiO in residue
2, CaSO
4, Ca
3(PO
4)
2, CaHPO
4, CaF
2and other insoluble matter, cross filter residue for manufacture of cement, the refining milk of lime of gained is used for and phosphoric acid by wet process;
(2) preneutralization purifies
Above-mentioned refining milk of lime is carried out to preneutralization purification to phosphoric acid by wet process, in 45～85 ℃ of reaction 0.5～6.0h of temperature, phosphoric acid by wet process preneutralization pH is 1.0～3.0, and the slip after preneutralization filters, filter cake is for the production of fertilizer phosphate product, and filtrate is for the preparation of fine calcium phosphate;
(3) preparation of fine calcium phosphate
Filtrate after filtering with the further neutralization procedure of above-mentioned milk of lime (2), in 45～85 ℃ of reaction 0.5～6.0h of temperature, reaction finishes rear filtration, and filter cake drying obtains fine calcium phosphate; Its endpoint pH is 5.5-9.5, controls the size of pH value, obtains different fine calcium phosphates; The rear mother liquor of neutralization returns to emulsification and prepares milk of lime, and realization recycles.
2. prepare according to claim 1 the method for fine calcium phosphate, it is characterized in that the fine calcium phosphate preparing is calcium monohydrogen phosphate or tricalcium phosphate.
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| CN201210330185.3A CN102849703B (en) | 2012-09-07 | 2012-09-07 | Method for preparing fine calcium phosphate by using phosphogypsum desulfurization residue |
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| CN201210330185.3A CN102849703B (en) | 2012-09-07 | 2012-09-07 | Method for preparing fine calcium phosphate by using phosphogypsum desulfurization residue |
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| CN102849703B true CN102849703B (en) | 2014-03-19 |
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| CN103213962B (en) * | 2013-04-19 | 2015-05-06 | 武汉工程大学 | Method for preparing feed-grade calcium hydrophosphate from phosphoric acid-containing mixed acid etching waste liquid |
| CN105621379A (en) * | 2016-04-13 | 2016-06-01 | 四川绵竹市盘龙矿物质有限责任公司 | Improved three-stage neutralization crystallization method in feed-grade calcium hydrogen phosphate production technique |
| CN106186601B (en) * | 2016-07-26 | 2019-02-26 | 四川高绿平环境科技有限公司 | A kind of processing method of sludge |
| CN106241851B (en) * | 2016-07-26 | 2018-01-05 | 四川高绿平环境科技有限公司 | A kind of processing method of useless phosphoric acid,diluted |
| CN113233438B (en) * | 2021-06-15 | 2022-11-01 | 瓮福（集团）有限责任公司 | Method for controlling arsenic and increasing yield of calcium hydrophosphate product |
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| CN1045423C (en) * | 1995-10-20 | 1999-10-06 | 四川联合大学 | Method for producing feed calcium hydrogen phosphate |
| CN1204044C (en) * | 2003-05-12 | 2005-06-01 | 四川大学 | Method for preparing industrial grade and food grade phosphoric acid by wet method phosphoric acid |
| WO2005087661A1 (en) * | 2004-03-16 | 2005-09-22 | Abburi Visweswara Rao | A cyclic process for the continuous production of dicalcium phosphate |
| CN100494051C (en) * | 2006-12-21 | 2009-06-03 | 四川大学 | Technology for preparing fine calcium phosphate using phosphor-gypsum backwater and its wash liquid |
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