CN102942166A - Method for preparing toothpaste/food/medicine grade calcium hydrophosphate from phosphoric acid by wet process - Google Patents
Method for preparing toothpaste/food/medicine grade calcium hydrophosphate from phosphoric acid by wet process Download PDFInfo
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- CN102942166A CN102942166A CN2012104568058A CN201210456805A CN102942166A CN 102942166 A CN102942166 A CN 102942166A CN 2012104568058 A CN2012104568058 A CN 2012104568058A CN 201210456805 A CN201210456805 A CN 201210456805A CN 102942166 A CN102942166 A CN 102942166A
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Abstract
The invention discloses a method for preparing toothpaste/food/medicine grade calcium hydrophosphate from phosphoric acid by wet process. The method comprises the following steps of: I, reacting phosphoric acid by wet process with powdered rock phosphate, removing most SO4<2->, then reacting with sodium carbonate, filtering most SiF6<2->, and filtering waste residues; II, neutralizing treated diluted phosphoric acid with ammonia till the pH is 5-7 to form ammonium phosphate slurry; filtering the slurry in a hot state, returning filter residues into an ammonium acid phosphate fertilizer device, mixing with phosphoric acid to produce a fertilizer; and performing conventional concentration, crystallization and filtration on a filtrate in vacuum, crystalizing and purifying to obtain an ammonium phosphate crystal; and III, dissolving the purified ammonium phosphate crystal into water, mixing with a purified calcium chloride solution, reacting to generate a calcium hydrophosphate precipitate; and filtering calcium hydrophosphate out, and drying to obtain a product. Due to the adoption of the method disclosed by the invention, toothpaste/food/medicine grade calcium hydrophosphate can be prepared directly from phosphoric acid by wet process. The method is suitable for phosphorous chemical industry enterprises.
Description
Technical field
The present invention relates to phosphoric acid salt, furthermore, relate to secondary calcium phosphate, in particular to the production method of toothpaste/food/pharmaceutical calcium hydrophosphate.
Background technology
There are strict requirements to foreign matter contents such as fluorine, arsenic, heavy metals for toothpaste/food/pharmaceutical calcium hydrophosphate, according to the purposes difference physical indexs such as whiteness, granularity, water regain also had certain requirement.Its traditional production method mainly contains bone black salt acid system, double decomposition and direct 3 kinds of neutralisations.But hydrochloric acid bone black method will consume a large amount of soda ash. hydrochloric acid decomposition bone black temperature height, time length, equipment corrosion and environmental pollution are serious, and industrial scale is little, and cost is high, is replaced by additive method gradually.SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic mixing solutions can be made with soda ash neutralization, purification by worker's phosphoric acid or phosphoric acid by wet process in the double decomposition, the former raw materials cost is high, the alkaline residue of latter's by-product is difficult to process, and will consume a large amount of soda ash, and the sodium-chlor of by-product, carbonic acid gas are difficult to reclaim.Although directly neutralisation technique is simple, investment is little, owing to use food grade phosphoric acid, simultaneously calcium carbonate and unslaked lime is also had more restriction, production cost is also higher.
Through retrieval, in the Chinese patent database, the technical scheme that relates to food-grade calcium hydrogen phosphate production only has " preparation technology of large grained food-grade calcium hydrogen phosphate " 201010102842.X number at present, and this scheme also belongs to the directly technique of neutralization of thermal phosphoric acid.There is no at present and adopting phosphoric acid by wet process is the patent application of raw material production food-grade calcium hydrogen phosphate.
Summary of the invention
Purpose of the present invention just is to provide a kind of method with wet process phosphoric acid for preparing toothpaste/food/pharmaceutical calcium hydrophosphate, to overcome the various shortcomings of conventional production methods.
The method with wet process phosphoric acid for preparing toothpaste/food/pharmaceutical calcium hydrophosphate that the contriver provides may further comprise the steps:
The first step: with phosphoric acid by wet process and ground phosphate rock reaction, remove most of SO
4 2-, afterwards with the yellow soda ash reaction, and remove by filter most of SiF
6 2-And remove by filter waste residue;
P in the used phosphoric acid by wet process
2O
5Massfraction be 20%～30%, the ground phosphate rock amount is 1.0～1.2 times of Theoretical Calculation amount;
Used yellow soda ash is technical grade product, and the amount of yellow soda ash is 1.0～1.05 times of Theoretical Calculation amount;
Second step, it is 5～7 that the dilute phosphoric acid after above-mentioned processing is neutralized to pH with ammonia, this moment, nearly all metal ion all can Precipitation forms the slip of ammonium phosphate in the acid; Filtered while hot slip, filter residue return the ammophos device and mix the rear fertilizer of producing with phosphoric acid; Filtrate is through concentrated, crystallization, the filtration of vacuum routine, and crystal is the ammonium phosphate crystallization, purifies through recrystallize, obtains the ammonium phosphate crystal;
The 3rd step, the ammonium phosphate crystal after purifying is water-soluble, mix with the calcium chloride solution that purifies, generate the secondary calcium phosphate precipitation by replacement(metathesis)reaction; Again after filtration, leach secondary calcium phosphate, dry according to ordinary method, obtain product;
The massfraction of used calcium chloride is 10%～25%; The molar ratio of used ammonium phosphate crystal and calcium chloride is (1.0～1.1): 1;
The main containing ammonium chloride of mother liquor and a small amount of calcium chloride, this mother liquor and unslaked lime hybrid reaction generate calcium chloride and ammonia, and logical steam steams ammonia, and reclaims with pretreated phosphoric acid by wet process; The calcium chloride mother liquor that steams behind the ammonia recycles after purifying.
The contriver points out: according to conventional production method, in above-mentioned the 3rd step, control different processing condition and can produce respectively toothpaste level, food grade and pharmaceutical grade secondary calcium phosphate.
Reaction described in the above-mentioned the first step is in anterior reactor, and temperature is 50 ℃～70 ℃, have under the condition of stirring and carry out.
Reaction with ammonia neutralization described in the above-mentioned second step is in neutralizing well, and temperature is 90 ℃～110 ℃, have under the condition of stirring and carry out; Described filtration in vacuum filter, the insulation vacuum condition carry out.
In above-mentioned the 3rd step, described replacement(metathesis)reaction is carried out in the metathesis groove.
Adopt method provided by the invention can directly use Wet-process Phosphoric Acid Production toothpaste level or food grade or pharmaceutical grade secondary calcium phosphate.Be applicable to phosphorus ammonium manufacturing enterprise.
Description of drawings
Accompanying drawing is the schematic flow sheet of the inventive method.
Embodiment
Drive the testing apparatus that Wet-process Phosphoric Acid Production toothpaste/food/pharmaceutical calcium hydrophosphate is applied mechanically by phosphorus (group) limited liability company one
Specific practice is: be first that 25% phosphoric acid by wet process and ground phosphate rock react in anterior reactor with massfraction, remove most of SO
4 2-, afterwards with technical grade yellow soda ash reaction, reaction is is 60 ℃ in temperature, have under the condition of stirring and carry out; Remove by filter most of SiF after the reaction
6 2-And remove by filter waste residue; Used ground phosphate rock amount is 1.1 times of Theoretical Calculation amount, and the amount of yellow soda ash is 1.05 times of Theoretical Calculation amount;
Then, the dilute phosphoric acid after processing is neutralized to pH with ammonia in neutralizing well be 5～7, and the processing condition temperature of neutralization is 100 ℃, stirring is arranged; This moment, nearly all metal ion all can Precipitation forms the slip of ammonium phosphate in the acid; Filtered while hot slip in vacuum filter, filter residue return the ammophos device and mix the rear fertilizer of producing with phosphoric acid; Filtrate is through vacuum concentration, crystallization, filtration, and crystal is the ammonium phosphate crystallization, purifies through recrystallize, obtains the ammonium phosphate crystal;
At last, the ammonium phosphate crystal after purifying is water-soluble, in the metathesis groove, be that 20% purification calcium chloride solution mixes with massfraction, generate secondary calcium phosphate by replacement(metathesis)reaction and precipitate; The molar ratio of used ammonium phosphate crystal and calcium chloride is 1.1: 1; Again after filtration, leach secondary calcium phosphate, dry according to ordinary method, obtain product; The main containing ammonium chloride of mother liquor and a small amount of calcium chloride, this mother liquor and unslaked lime hybrid reaction generate calcium chloride and ammonia, and logical steam steams ammonia, and reclaims with pretreated phosphoric acid by wet process; The calcium chloride mother liquor that steams behind the ammonia recycles after purifying.
Claims (4)
1. method with wet process phosphoric acid for preparing toothpaste/food/pharmaceutical calcium hydrophosphate, its feature may further comprise the steps:
The first step: with phosphoric acid by wet process and ground phosphate rock reaction, remove most of SO
4 2-, afterwards with the yellow soda ash reaction, and remove by filter most of SiF
6 2-And remove by filter waste residue;
P in the used phosphoric acid by wet process
2O
5Massfraction be 20%～30%, the ground phosphate rock amount is 1.0～1.2 times of Theoretical Calculation amount;
Used yellow soda ash is technical grade product, and the amount of yellow soda ash is 1.0～1.05 times of Theoretical Calculation amount;
Second step, it is 5～7 that the dilute phosphoric acid after above-mentioned processing is neutralized to pH with ammonia, this moment, nearly all metal ion all can Precipitation forms the slip of ammonium phosphate in the acid; Filtered while hot slip, filter residue return the ammophos device and mix the rear fertilizer of producing with phosphoric acid; Filtrate is through concentrated, crystallization, the filtration of vacuum routine, and crystal is the ammonium phosphate crystallization, purifies through recrystallize, obtains the ammonium phosphate crystal;
The 3rd step, the ammonium phosphate crystal after purifying is water-soluble, mix with the calcium chloride solution that purifies, generate the secondary calcium phosphate precipitation by replacement(metathesis)reaction; Again after filtration, leach secondary calcium phosphate, dry according to ordinary method, obtain product;
The massfraction of used calcium chloride is 10%～25%; The molar ratio of used ammonium phosphate crystal and calcium chloride is (1.0～1.1): 1;
Mother liquor and the unslaked lime hybrid reaction of filtering are generated calcium chloride and ammonia, and logical steam steams ammonia, and reclaims with pretreated phosphoric acid by wet process; The calcium chloride mother liquor that steams behind the ammonia recycles after purifying.
2. the method for claim 1 is characterized in that the reaction described in the first step is in anterior reactor, and temperature is 50 ℃～70 ℃, have under the condition of stirring and carry out.
3. the method for claim 1 is characterized in that the reaction with the ammonia neutralization is in neutralizing well described in the second step, and temperature is 90 ℃～110 ℃, have under the condition of stirring and carry out; Described filtration in vacuum filter, the insulation vacuum condition carry out.
4. the method for claim 1 is characterized in that described replacement(metathesis)reaction is carried out in the 3rd step in the metathesis groove.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174238A (en) * | 2015-09-22 | 2015-12-23 | 贵州开磷集团股份有限公司 | Method for preparing dipotassium phosphate by means of phosphoric acid obtained by wet process |
| CN105174239A (en) * | 2015-09-22 | 2015-12-23 | 贵州开磷集团股份有限公司 | Method for preparing disodium hydrogen phosphate by means of phosphoric acid obtained by wet process |
| CN113353905A (en) * | 2021-06-29 | 2021-09-07 | 湖北兴发化工集团股份有限公司 | Process for preparing medicinal coarse granular anhydrous calcium hydrogen phosphate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1685867A1 (en) * | 1989-07-07 | 1991-10-23 | Предприятие П/Я А-1997 | Method for obtaining dicalcium phosphate |
| CN1174812A (en) * | 1996-08-26 | 1998-03-04 | 四川联合大学 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
| CN102070159A (en) * | 2010-11-19 | 2011-05-25 | 浙江海虹控股集团有限公司 | Method for recovering ammonia from solid-state inorganic strong acid ammonium salt by utilizing quick lime |
| CN102181288A (en) * | 2011-03-08 | 2011-09-14 | 营口市荣兴达科技实业有限公司 | Method for preparing fluorescent powder from leftovers obtained by producing organosilicon |
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2012
- 2012-11-14 CN CN2012104568058A patent/CN102942166A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1685867A1 (en) * | 1989-07-07 | 1991-10-23 | Предприятие П/Я А-1997 | Method for obtaining dicalcium phosphate |
| CN1174812A (en) * | 1996-08-26 | 1998-03-04 | 四川联合大学 | Industrial monoammonium phosphate and productive method for industrial monoammunium phosphate and calcium hydrogen phosphate fodder |
| CN102070159A (en) * | 2010-11-19 | 2011-05-25 | 浙江海虹控股集团有限公司 | Method for recovering ammonia from solid-state inorganic strong acid ammonium salt by utilizing quick lime |
| CN102181288A (en) * | 2011-03-08 | 2011-09-14 | 营口市荣兴达科技实业有限公司 | Method for preparing fluorescent powder from leftovers obtained by producing organosilicon |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174238A (en) * | 2015-09-22 | 2015-12-23 | 贵州开磷集团股份有限公司 | Method for preparing dipotassium phosphate by means of phosphoric acid obtained by wet process |
| CN105174239A (en) * | 2015-09-22 | 2015-12-23 | 贵州开磷集团股份有限公司 | Method for preparing disodium hydrogen phosphate by means of phosphoric acid obtained by wet process |
| CN105174239B (en) * | 2015-09-22 | 2018-03-13 | 贵州开磷集团股份有限公司 | A kind of phosphoric acid by wet process prepares disodium hydrogen phosphate method |
| CN113353905A (en) * | 2021-06-29 | 2021-09-07 | 湖北兴发化工集团股份有限公司 | Process for preparing medicinal coarse granular anhydrous calcium hydrogen phosphate |
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Application publication date: 20130227 |