CN101654236B - Preparation method of food additive grade tricalcium phosphate - Google Patents
Preparation method of food additive grade tricalcium phosphate Download PDFInfo
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- CN101654236B CN101654236B CN2009101921811A CN200910192181A CN101654236B CN 101654236 B CN101654236 B CN 101654236B CN 2009101921811 A CN2009101921811 A CN 2009101921811A CN 200910192181 A CN200910192181 A CN 200910192181A CN 101654236 B CN101654236 B CN 101654236B
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Abstract
The invention provides a preparation method of food additive grade tricalcium phosphate, which comprising the following steps: using an aqueous calcium chloride solution and an aqueous sodium hydroxide solution to prepares fresh lime cream, aging, subsiding, filtering and washing the fresh lime cream to obtain calcium hydroxide precipitates; aging, centrifugalizing, drying and smashing tricalciumphosphate generated during reaction of the calcium hydroxide precipitates and phosphoric acid to obtain the product. The preparation method of the food additive grade tricalcium phosphate is easy to eliminate impurities through washing in such a way that the coacervation and sedimentation effect of calcium hydroxide particles is better than that of the phosphoric acid under the condition of high alkalinity and the calcium hydroxide particles wrap and absorb few impurities. The tricalcium phosphate product prepared by the method accords with China HG 2789-1996 and America FCC food additive standards in quality. The preparation method has extensive material source and easy technology condition control and is especially suitable for large-scaled industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of tricalcium phosphate, relate in particular to a kind of preparation method of the tricalcium phosphate that uses as foodstuff additive.
Background technology
Tricalcium phosphate is a kind of unformed powder of white, and is atomic water-soluble, is insoluble to ethanol, is soluble in dilute hydrochloric acid and nitric acid.Tricalcium phosphate has been widely used, and is used as anticaking agent, buffer reagent, water retention agent, acidity regulator, stablizer and nutrition-fortifying agent etc. in foodstuffs industry; At the binding agent that pharmaceutically is used as antacid and dentistry; On plastics and rubber industry, as dispersion agent, also can be used for making the fodder additives of pottery, opaque glass, syrup finings, poultry etc.
The common preparation method of tricalcium phosphate concludes and mainly contains: (1) Rock Phosphate (72Min BPL) and calcium superphosphate mixed sintering method; (2) white lime and phosphatase reaction method; (3) lime powder (lime carbonate) and phosphatase reaction method; (4) tertiary sodium phosphate and calcium chloride replacement(metathesis)reaction method etc.Method (1) is because the raw material that adopts is coarse, and the quality grade is low, is mainly used in the production of feed grade product; For the production of the tricalcium phosphate of food additive grade, mainly be the method that adopts (2), (3) and (4).At present, domestic white lime is to be fired with coal by natural lime to form substantially, the white lime impurity component that obtains so particularly arsenic and heavy metal content than higher, bring in the finished product easily, therefore, when the tricalcium phosphate of being produced by (2) and (3) method used as foodstuff additive, arsenic and other heavy metals often exceeded standard, have only by selecting high-quality white lime and carrying out strict quality just can obtain qualified product, certainly will increase cost like this to control; The main problem that exists of method (4) is that a large amount of brine waste dischargings are arranged in the production process, and because the tricalcium phosphate that forms is the lightweight fine particle, the flocking settling weak effect, it is not thorough to remove impurity by washing, be easy to generate impurity double team and absorption, influence production efficiency and quality product.
Summary of the invention
For overcoming the problem of above existence, the purpose of this invention is to provide the new preparation method of a kind of tricalcium phosphate, by the product that this method obtains, the purity height, arsenic and other beavy metal impurity content are low, are suitable as foodstuff additive and use.
For realizing above purpose, tricalcium phosphate preparation method of the present invention in turn includes the following steps:
(1) prepare fresh milk of lime by calcium chloride water and aqueous sodium hydroxide solution, through ageing, sedimentation, suction filtration, wash the calcium hydroxide throw out, wherein the pH value of calcium chloride and sodium hydroxide reaction end is controlled at pH 〉=12;
(2) the calcium hydroxide throw out that step (1) is obtained stirs the furnishing pulpous state with an amount of pure water, the phosphoric acid solution that under constantly stirring, adds food grade then with the thread form, through ageing, centrifugal, dry, pulverizing, obtain product, wherein the pH value of calcium hydroxide throw out and phosphatase reaction terminal point is preferably at 6.0-7.5.
Among the above-mentioned preparation method, the calcium chloride of step (1) and the charging capacity of sodium hydroxide in molar ratio 1: 2.01-2.02.
In order to promote sodium-chlor dissolving, also making the better flocking settling of calcium hydroxide, the ageing condition of above-mentioned steps (1) simultaneously is 50-70 ℃ of following insulated and stirred more than 15 minutes, and standing sedimentation is more than 30 minutes then.
In order to make the sodium-chlor dissolving more complete, above-mentioned steps (1) adds 2-3 and doubly to the pure water of calcium chloride solution volume milk of lime is diluted before ageing.
The washing of above-mentioned steps (1) is to stir out with the filter cake of pure water after with the sedimentation suction filtration, again at 50-70 ℃ of insulated and stirred 15-20 minute, standing sedimentation 30-35 minute, extracts suction filtration after the supernatant liquor out.Can carry out 1-2 time washing as required.
In order to save cost, the calcium chloride water of above-mentioned steps (1) is to be dissolved in the pure water, to be added proper amount of active carbon and be incubated 20 minutes down at 50-60 ℃ and filter the clear liquid that obtains by the technical grade Calcium dichloride dihydrate, and wherein the weight ratio of Calcium dichloride dihydrate and water is 1: 1.6-1.7.
The sodium hydroxide solution of above-mentioned steps (1) is the clear liquid that is obtained by weight preparation in about 1: 2, dissolving after-filtration by solid sodium hydroxide and pure water.
For the tricalcium phosphate that makes generation flocking settling better, the calcium hydroxide throw out of above-mentioned steps (2) and the pH value of phosphatase reaction terminal point are 6.5-7.0, and the ageing condition is 55-65 ℃ of following insulated and stirred more than 30 minutes, and standing sedimentation is more than 60 minutes then.
The drying temperature of above-mentioned steps (2) is 110-120 ℃, and be more than 4 hours time of drying.
In order to lower the fierce degree of reaction, the preferred 37-40% of phosphoric acid solution concentration expressed in percentage by weight of above-mentioned steps (2).
Tricalcium phosphate preparation method of the present invention, adopt the calcium chloride and the sodium hydroxide reaction of technical grade to generate calcium hydroxide, utilize calcium hydroxide particle flocking settling good effectiveness under strong alkaline condition, pH value and ageing condition by the control reaction end, make calcium hydroxide double team to impurity in settling process few (according to result's demonstration of test and detection with absorption, calcium hydroxide only is equivalent to the 30-35% of the tricalcium phosphate adsorptive capacity of amount together to the adsorptive capacity of impurity sodium-chlor), thus remove impurity by washing easily; And, making the tricalcium phosphate that obtains better assemble sedimentation by controlling the pH value and the ageing condition of calcium hydroxide and phosphatase reaction terminal point, foreign matter content is lower; The tricalcium phosphate product that is obtained by preparation method of the present invention meets China HG 2789-1996 and U.S. FCC foodstuff additive standard.Preparation method of the present invention, raw material sources are wide, and processing condition are easy to control, are particularly suitable for large-scale industrial production.
Embodiment
Be specific embodiments of the invention below, these embodiment to the specifying of the preparation method of tricalcium phosphate of the present invention, are not in order to restriction protection scope of the present invention just.
Embodiment 1
(1) Calcium dichloride dihydrate 300g is dissolved with pure water 500ml, add spoonful gac, limpid in 2 liters of beakers after stirring evenly at 20 minutes after-filtration of 50-60 ℃ of insulation; The sodium hydroxide 168g of content 96% is dissolved with pure water 350ml, filter limpid standby; With the food grade concentration expressed in percentage by weight is that to add pure water 170ml dilution be that 38% phosphoric acid is standby for 85% phosphoric acid 80ml;
(2) stirring joins above-mentioned sodium hydroxide solution fast by separating funnel down and reacts in the calcium chloride solution, reinforced finishing, control pH value of solution＞12, replenish pure water to 1.5 liters of total amounts, heating and 60-65 ℃ of following insulated and stirred 15 minutes, standing sedimentation 30 minutes, suction filtration after the siphon off supernatant liquor;
(3) filter cake that step (2) is obtained adds pure water to 1.5 liters of total amounts, stirs out the back 60-65 ℃ of insulated and stirred 15 minutes, and standing sedimentation is extracted suction filtration after the supernatant liquor out after 30 minutes;
(4) filter cake that step (3) is obtained adds about 500ml pure water, fully stir the furnishing pulpous state, adding above-mentioned 38% phosphoric acid with the thread form then under constantly stirring reacts, reaction end control pH value is 6.5-7.0 (adopting accurate pH test paper to detect), the phosphoric acid that adds is about 240ml, reaction finishes, heating and 55-65 ℃ of following insulated and stirred 30 minutes, and standing sedimentation is 90 minutes then;
(5) after the siphon off supernatant liquor with the throw out centrifuge dripping, then 110-120 ℃ of drying 4 hours, through grind, sieve tricalcium phosphate 195g, product meets China HG2789-1996 and U.S. FCC foodstuff additive standard through check.
Embodiment 2
(1) Calcium dichloride dihydrate 300g is dissolved with pure water 500ml, add spoonful gac, limpid in 2 liters of beakers after stirring evenly at 20 minutes after-filtration of 50-60 ℃ of insulation; The sodium hydroxide 172g of content 96% is dissolved with pure water 350ml, filter limpid standby; With the food grade concentration expressed in percentage by weight is that to add pure water 170ml dilution be that 38% phosphoric acid is standby for 85% phosphoric acid 80ml;
(2) stirring joins above-mentioned sodium hydroxide solution fast by separating funnel down and reacts in the calcium chloride solution, reinforced finishing, control pH value of solution＞12, replenish pure water to 1.5 liters of total amounts, heating and 55-60 ℃ of following insulated and stirred 30 minutes, standing sedimentation 40 minutes, suction filtration after the siphon off supernatant liquor;
(3) filter cake that step (2) is obtained adds pure water to 1.5 liters of total amounts, stirs out the back 55-60 ℃ of insulated and stirred 20 minutes, and standing sedimentation is extracted suction filtration after the supernatant liquor out after 35 minutes;
(4) filter cake that step (3) is obtained adds about 500ml pure water, fully stir the furnishing pulpous state, adding above-mentioned 38% phosphoric acid with the thread form then under constantly stirring reacts, reaction end control pH value is 6.0-6.5 (adopting accurate pH test paper to detect), the phosphoric acid that adds is about 240ml, reaction finishes, heating and 55-60 ℃ of following insulated and stirred 40 minutes, and standing sedimentation is 80 minutes then;
(5) after the siphon off supernatant liquor with the throw out centrifuge dripping, then 110-120 ℃ of drying 5 hours, through grind, sieve tricalcium phosphate 193g, product meets China HG2789-1996 and U.S. FCC foodstuff additive standard through check.
Claims (10)
1. the preparation method of a food additive grade tricalcium phosphate in turn includes the following steps:
(1) prepare fresh milk of lime by calcium chloride water and aqueous sodium hydroxide solution, through ageing, sedimentation, suction filtration, wash the calcium hydroxide throw out, wherein the pH value of calcium chloride and sodium hydroxide reaction end is controlled at pH 〉=12;
(2) the calcium hydroxide throw out that step (1) is obtained stirs the furnishing pulpous state with an amount of pure water, the phosphoric acid solution that under constantly stirring, adds food grade then with the thread form, through ageing, centrifugal, dry, pulverizing, obtain product, wherein the pH value of calcium hydroxide throw out and phosphatase reaction terminal point is 6.0-7.5.
2. according to the preparation method of the described food additive grade tricalcium phosphate of claim 1, it is characterized in that: the calcium chloride of described step (1) and the charging capacity of sodium hydroxide in molar ratio 1: 2.01-2.02.
3. according to the preparation method of the described food additive grade tricalcium phosphate of claim 2, it is characterized in that: the ageing condition of described step (1) is 50-70 ℃ of following insulated and stirred more than 15 minutes, and standing sedimentation is more than 30 minutes then.
4. according to the preparation method of the described food additive grade tricalcium phosphate of claim 2, it is characterized in that: the washing of described step (1) is to stir out with the filter cake of pure water after with the sedimentation suction filtration, again at 60-65 ℃ of insulated and stirred 15-20 minute, standing sedimentation 30-35 minute, extract suction filtration after the supernatant liquor out.
5. according to the preparation method of claim 3 or 4 described food additive grade tricalcium phosphates, it is characterized in that: described step (1) adds 2-3 and doubly to the pure water of calcium chloride solution volume milk of lime is diluted before ageing.
6. according to the preparation method of claim 3 or 4 described food additive grade tricalcium phosphates, it is characterized in that: the calcium chloride water of described step (1) is to be dissolved in the pure water, to be added proper amount of active carbon and be incubated 20 minutes down at 50-60 ℃ and filter the clear liquid that obtains by Calcium dichloride dihydrate, and wherein the weight ratio of Calcium dichloride dihydrate and water is 1: 1.6-1.7.
7. according to the preparation method of claim 3 or 4 described food additive grade tricalcium phosphates, it is characterized in that: the sodium hydroxide solution of described step (1) is the clear liquid that is obtained by weight preparation in 1: 2, dissolving after-filtration by solid sodium hydroxide and pure water.
8. according to the preparation method of claim 3 or 4 described food additive grade tricalcium phosphates, it is characterized in that: the calcium hydroxide throw out of described step (2) and the pH value of phosphatase reaction terminal point are 6.5-7.0, the ageing condition is 55-65 ℃ of following insulated and stirred more than 30 minutes, and standing sedimentation is more than 60 minutes then.
9. according to the preparation method of claim 3 or 4 described food additive grade tricalcium phosphates, it is characterized in that: the drying temperature of described step (2) is 110-120 ℃, and be more than 4 hours time of drying.
10. according to the preparation method of claim 3 or 4 described food additive grade tricalcium phosphates, it is characterized in that: the preferred 37-40% of phosphoric acid solution concentration expressed in percentage by weight of described step (2).
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| CN103204485B (en) * | 2013-04-25 | 2015-02-11 | 连云港树人科创食品添加剂有限公司 | Production method of food grade tricalcium phosphate |
| CN111232940B (en) * | 2020-03-12 | 2023-05-02 | 连云港树人科创食品添加剂有限公司 | Preparation method of tricalcium phosphate and potassium chloride in co-production |
| CN113735085A (en) * | 2021-09-13 | 2021-12-03 | 奥斯泰克医疗器械（苏州）股份有限公司 | Preparation method of beta-tricalcium phosphate |
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| CN101362594A (en) * | 2008-09-10 | 2009-02-11 | 云南天创科技有限公司 | Method for producing high-quality tricalcium phosphate |
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