CN103848408B - A kind of method utilizing shell to prepare secondary calcium phosphate - Google Patents
A kind of method utilizing shell to prepare secondary calcium phosphate Download PDFInfo
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- CN103848408B CN103848408B CN201210494701.6A CN201210494701A CN103848408B CN 103848408 B CN103848408 B CN 103848408B CN 201210494701 A CN201210494701 A CN 201210494701A CN 103848408 B CN103848408 B CN 103848408B
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- calcium phosphate
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- secondary calcium
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- shell whiting
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Abstract
The present invention relates to the preparation method of secondary calcium phosphate, be specifically related to utilize oyster shell whiting to replace lime, Rock Phosphate (72Min BPL) etc. to prepare the method for secondary calcium phosphate.Phosphoric acid is added pretreated oyster shell whiting to carry out processing namely obtaining secondary calcium phosphate.Show through X-ray diffraction and electronic microscope photos, secondary calcium phosphate purity prepared by the present invention is very high.Shell is turned waste into wealth by the present invention, takes full advantage of seashells resource, improves Business Economic Benefit, decrease environmental pollution.
Description
Technical field
The present invention relates to the preparation method of secondary calcium phosphate, be specifically related to utilize oyster shell whiting to replace lime, Rock Phosphate (72Min BPL) etc. to prepare the method for secondary calcium phosphate.
Background technology
China is aquaculture big country, and shellfish annual production occupies first place in the world, and within 2007, shellfish output reaches 1,073 ten thousand tons, accounts for more than 60% of world's shellfish culture total amount.But shellfish is after processing, the shell Chang Zuowei processing waste accounting for shellfish body weight more than 50% abandons or the starting material of production, shellwork etc. for low value feed, and resource utilization is low, seriously polluted.In fact, in shell, calcium carbonate content can reach more than 95%, is a kind of extraordinary substitute replacing the raw materials such as raw material production calcium chloride, secondary calcium phosphate such as Rock Phosphate (72Min BPL).Secondary calcium phosphate, as fine chemical product, is mainly used as foodstuff additive, toothpaste abrasives, medical calsium supplement etc.Calcium and phosphorus are the mineral elements very important to poultry vital movement, but must proportional competence exertion beneficial effect.The poultry disease that the low-phosphorous feed of high calcium causes has chicken urinary calculus, duckling paralysed disease etc. and high phosphorus low calcium feed causes chicken to produce soft shelled egg, shell egg. and pure secondary calcium phosphate is the excellent poultry and livestock feed additive containing phosphorus, calcium 2 kinds of nutritive elements.Because its ratio of calcium and phosphorus is 1.29:1, more close than with the phosphorus calcium in animal skeleton, and can all be dissolved in the hydrochloric acid in gastric juice of animal again, so easily to enter in animal body and to participate in metabolism, required hormone, enzyme and VITAMIN in composition body, keep the phosphorus calcium ratio in bone, thus prevent animal because of scarce phosphorus, calcium and the various diseases that cause, promote the quick growth of animal body simultaneously.Usually in feed, add the calcium hydrophosphate fodder (calcium raised in abbreviation) of 1% ~ 3% of total amount, then meat, eggs and milk on average increases production 15% ~ 20%, and its economic benefit and social benefit are all very considerable.Calcium hydrogen phosphate fodder is applied widely in the world, and its annual production and consumption are all more than 5,000,000 tons.In recent years, along with developing rapidly of China's husbandry, extensive, intensive animal husbandry, aquaculture and feed processing industry develop at a speed unheard of before, and the demand of domestic market to calcium hydrophosphate fodder is increasing.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing shell to prepare secondary calcium phosphate.
For achieving the above object, the technical solution used in the present invention is:
Utilize shell to prepare a method for secondary calcium phosphate, phosphoric acid is added pretreated oyster shell whiting and carry out processing namely obtaining secondary calcium phosphate.
Described shell is the shell of scallop shell, oyster shells, clam loudspeaker shell or other seashells.
The amount that the described phosphoric acid volume added is 0.5-1.1:1 by the mol ratio of phosphorus in calcium in pretreated oyster shell whiting and phosphoric acid adds.
Concrete steps are:
(1) pre-treatment of oyster shell whiting
1) employing mass concentration is the acid solution immersion shell 1-5 hour of 1-4%, and pure water cleans the acid of shell surface, other impurity of outwash shell surface, dries, is ground into 100-200 object oyster shell whiting and namely obtains pretreated oyster shell whiting; Main component is calcium carbonate.
Or 700-1200 DEG C of calcined shell 2-6 hour, be ground into 100-200 object oyster shell whiting after calcining and namely obtained pretreated oyster shell whiting; Main component is calcium oxide.
(2) preparation of calcium carbonate or calcium oxide suspension
Pretreated for above-mentioned gained oyster shell whiting is added water at normal temperatures and is mixed with 20-35% oyster shell whiting suspension;
(3) under normal temperature, in oyster shell whiting suspension, dropwise add the phosphoric acid that concentration is 40-60% while stirring in proportion, after dropwising, continue to stir 30-60min, make it fully react;
(4) after completion of the reaction, reaction solution is left standstill 30-60min, remove supernatant liquor for subsequent use, stirred evenly by throw out, vacuum filtration, the supernatant liquor of filtrate and removal merges, and then washing and precipitating is constant to washing lotion pH, and precipitation is secondary calcium phosphate.
The secondary calcium phosphate precipitated filter cakes that above-mentioned (4) step obtains is obtained calcium hydrophosphate fodder after 80-100 DEG C of drying, and wherein containing P >=20%, Ca >=27%, F≤0.15%, detects secondary calcium phosphate content through X-ray and reaches more than 98%.
Continued in the supernatant liquor for subsequent use that above-mentioned (4) step is obtained to add pretreated oyster shell whiting and constantly stir, stop adding oyster shell whiting when the pH to 7.2-7.5 of supernatant liquor, collect filter cake, dry, prepare secondary calcium phosphate, wherein P >=20%, Ca >=27%, F≤0.15%, detects secondary calcium phosphate content through X-ray and reaches more than 98%.
Described step 1) mass concentration is the acid solution of 1-4% is inorganic or organic acid.
Described step 1) mass concentration is the acid solution of 1-4% is hydrochloric acid, acid or glacial acetic acid.
Advantage of the present invention
1. the present invention adopts waste shell/phosphoric acid Wet Method Reaction system, obtains the secondary calcium phosphate of the ratio of calcium and phosphorus 1.29:1 as fodder additives the best, shows that secondary calcium phosphate purity reaches more than 98% through X-ray diffraction.
2. the processing condition of the present invention's employing, are raw material with waste shell, have saved the materials such as a large amount of lime, Rock Phosphate (72Min BPL).The mineral products such as lime, Rock Phosphate (72Min BPL) are first resource product, therefore waste shell are replaced lime etc., have both saved Mineral resources, have taken full advantage of Mollusca Resource again, and decrease destruction and the pollution of environment, economic and social profit is huge.
3. the processing condition of the present invention's employing, without using hydrochloric acid and Two-step neutralization, enormously simplify technical process, have both saved the energy and facility investment, turn improve the rate of recovery and the purity of secondary calcium phosphate, reduce production cost.
4. China is aquaculture big country, and the annual production of sea farming shellfish occupies first place in the world, but accounts for the shell of shellfish gross weight more than 50% except minority low value utilizes, and as shellwork etc., substantially not processed utilization, causes the wasting of resources and environmental pollution.In shell, calcium carbonate content can reach more than 95%, and therefore the present invention utilizes marine products processing waste shell, prepares secondary calcium phosphate after pretreatment with phosphoric acid direct reaction.Show through X-ray diffraction and electronic microscope photos, secondary calcium phosphate purity prepared by the present invention is very high.Shell is turned waste into wealth by the present invention, takes full advantage of seashells resource, improves Business Economic Benefit, decrease environmental pollution.
Accompanying drawing explanation
Fig. 1 provides the Electronic Speculum figure of calcium monophosphate product for the embodiment of the present invention.
The X-ray diffractogram of the calcium monophosphate product that Fig. 2 provides for the embodiment of the present invention.
Specific embodiment
Below in conjunction with Figure of description, the invention will be further described, and protection scope of the present invention is not only confined to following examples.
The method utilizing shell to prepare secondary calcium phosphate comprises the following steps:
(1) pre-treatment of oyster shell whiting
Soak shell 1-5 hour with 1-4% acid solution, pure water cleans the acid of shell surface, other impurity of outwash shell surface, dries, is ground into 100-200 object oyster shell whiting and namely obtains pretreated oyster shell whiting.Main component is that calcium carbonate content can reach more than 95%.
Or 700-1200 DEG C of calcination processing shell 2-6 hour, be ground into 100-200 object oyster shell whiting and namely obtained pretreated oyster shell whiting.Main component is that calcium oxide content can reach more than 95%.
(2) preparation of calcium carbonate or calcium oxide suspension
The pretreated oyster shell whiting of step (1) gained is added water at normal temperatures and is mixed with 20-35% oyster shell whiting suspension;
(3) under normal temperature, in oyster shell whiting suspension, dropwise add 40-60% phosphoric acid while stirring in proportion, after dropwising, continue to stir 30-60min, make it fully react.
(4) after completion of the reaction, reaction solution is left standstill 30-60min, remove supernatant liquor for subsequent use, stirred evenly by throw out, vacuum filtration, the supernatant liquor of filtrate and removal merges, and then washing and precipitating is constant to washing lotion pH, and precipitation is secondary calcium phosphate.
(5) the secondary calcium phosphate filter cake that (4) step obtains is obtained calcium hydrophosphate fodder after 80-100 DEG C of drying, containing P >=20% in product, Ca >=27%, F≤0.15%.Detect secondary calcium phosphate content through X-ray and reach more than 98%.
(6) the filtrate continuation that (4) step obtains added pretreated oyster shell whiting and constantly stir, stopping adding oyster shell whiting when the pH to 7.2-7.5 of supernatant liquor, collect filter cake, dry, prepare secondary calcium phosphate, P >=20% in product, Ca >=27%, F≤0.15%.Detect secondary calcium phosphate content through X-ray and reach more than 98%.
Shell described in above-mentioned experiment is the shell of the seashells such as scallop shell, oyster shells, clam loudspeaker shell; The acid of described immersion shell is the common inorganic or organic acid such as hydrochloric acid, acetic acid, formic acid; The volume of described phosphoric acid adds according to the amount that the mol ratio of phosphorus in calcium in oyster shell whiting suspension and phosphoric acid is 0.5 ~ 1.1:1.
Embodiment 1
1) be that 1-4% acid solution soaks shell 1-5 hour by mass concentration, pure water cleans the acid of shell surface, other impurity of outwash shell surface, dries and gets shell 2000g, be ground into 100-200 object oyster shell whiting and namely obtain pretreated oyster shell whiting, for subsequent use;
Described acid solution can be hydrochloric acid, acid or glacial acetic acid.
2) get above-mentioned oyster shell whiting 20g, add 5ml water, stir, make 25% oyster shell whiting suspension;
3) in 100ml beaker, add 15ml85% phosphoric acid, add the pure water of 10.5ml, be i.e. the phosphoric acid solution of 50%;
4) to step 2) dropwise add 50% phosphoric acid solution 25.5ml prepared by step 3) in the oyster shell whiting suspension prepared while stirring, make it fully react, after 50% phosphoric acid solution has added, continue to stir 30min;
5) above-mentioned reaction solution is left standstill 30min, suction filtration, supernatant liquor is for subsequent use;
6) precipitation step 5) prepared is constantly constant to washing lotion pH with the cleaning of pure water suction filtration, and precipitation is secondary calcium phosphate;
7) the supernatant liquor inner edge prepared to step 5) slowly adds step 1) gained oyster shell whiting limit and stirs, and the pH to 7.2 of assaying reaction liquid, react complete, reaction solution is left standstill 30min, suction filtration, washing and precipitating is constant to washing lotion pH, and precipitation is secondary calcium phosphate;
8) by two step gained secondary calcium phosphate filter cakes, dry, control temperature is 80-100 DEG C, after 2 hours, obtains secondary calcium phosphate dry product.Detect the oven dry sample of gained, examination criteria and result are if following table 1 is simultaneously see Fig. 1 and Fig. 2.
Table 1: the detected result of embodiment
Step 1) mass concentration described above is the acid solution of 1-4% is hydrochloric acid, acid or glacial acetic acid
Embodiment 2
Difference from Example 1 is that the processing condition aspects such as ratio of calcium and phosphorus change, specifically see table 2.
Table 2 utilizes different oyster shell whiting to prepare the condition of secondary calcium phosphate
Embodiment 3
Difference from Example 1 is to utilize different oyster shell whiting to prepare the experimental result of secondary calcium phosphate see table 3
Table 3 utilizes different oyster shell whiting to prepare the result of secondary calcium phosphate
From table 2, table 3, the wider calcium monophosphate product of ratio of calcium and phosphorus can be obtained by this technique, and obtain the processing condition of the ratio of calcium and phosphorus 1.29:1 as fodder additives the best, for theoretical basis has been established in the utilization of sea-food tankage waste shell.
Claims (7)
1. utilize shell to prepare a method for secondary calcium phosphate, it is characterized in that: phosphoric acid is added pretreated oyster shell whiting and carry out processing namely obtaining secondary calcium phosphate;
Concrete steps are:
(1) pre-treatment of oyster shell whiting
1) employing mass concentration is the acid solution immersion shell 1-5 hour of 1-4%, and pure water cleans the acid of shell surface, other impurity of outwash shell surface, dries, is ground into 100-200 object oyster shell whiting and namely obtains pretreated oyster shell whiting;
Or 700-1200 DEG C of calcined shell 2-6 hour, be ground into 100-200 object oyster shell whiting after calcining and namely obtained pretreated oyster shell whiting;
(2) preparation of calcium carbonate or calcium oxide suspension
Pretreated for above-mentioned gained oyster shell whiting is added water at normal temperatures and is mixed with 20-35% oyster shell whiting suspension;
(3) under normal temperature, in oyster shell whiting suspension, dropwise add the phosphoric acid that concentration is 40-60% while stirring in proportion, after dropwising, continue to stir 30-60min, make it fully react;
(4) after completion of the reaction, reaction solution is left standstill 30-60min, remove supernatant liquor for subsequent use, stirred evenly by throw out, vacuum filtration, the supernatant liquor of filtrate and removal merges, and then washing and precipitating is constant to washing lotion pH, and precipitation is secondary calcium phosphate.
2. by the method utilizing shell to prepare secondary calcium phosphate described in claim 1, it is characterized in that: described shell is the shell of scallop shell, oyster shells, clam loudspeaker shell or other seashells.
3., by the method utilizing shell to prepare secondary calcium phosphate described in claim 1, it is characterized in that: described in the phosphoric acid volume that adds add by the amount that the mol ratio of phosphorus in calcium in pretreated oyster shell whiting and phosphoric acid is 0.5-1.1:1.
4. by the method utilizing shell to prepare secondary calcium phosphate described in claim 1, it is characterized in that: the secondary calcium phosphate precipitated filter cakes that above-mentioned (4) step obtains is obtained calcium hydrophosphate fodder after 80-100 DEG C of drying, wherein containing P >=20%, Ca >=27%, F≤0.15%, detects secondary calcium phosphate content through X-ray and reaches more than 98%.
5. by the method utilizing shell to prepare secondary calcium phosphate described in claim 1, it is characterized in that: continued in the supernatant liquor for subsequent use that above-mentioned (4) step is obtained to add pretreated oyster shell whiting and constantly stir, stop adding oyster shell whiting when the pH to 7.2-7.5 of supernatant liquor, collect filter cake, dry, prepare secondary calcium phosphate, wherein P >=20%, Ca >=27%, F≤0.15%, detects secondary calcium phosphate content through X-ray and reaches more than 98%.
6. by the method utilizing shell to prepare secondary calcium phosphate described in claim 1, it is characterized in that: described step 1) mass concentration be the acid solution of 1-4% is inorganic or organic acid.
7. by the method utilizing shell to prepare secondary calcium phosphate described in claim 6, it is characterized in that: described step 1) mass concentration be the acid solution of 1-4% is hydrochloric acid, acid or glacial acetic acid.
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| CN104448936A (en) * | 2014-11-17 | 2015-03-25 | 浙江大学舟山海洋研究中心 | Method for preparing phosphoric acid-modified biological calcium carbonate |
| CN110074417A (en) * | 2019-05-09 | 2019-08-02 | 五邑大学 | A kind of calcium tartrate agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292353A (en) * | 1999-09-23 | 2001-04-25 | 化学工业部上海化工研究院 | Production method of feed-level calcium hydrogen phosphate |
| CN1927803A (en) * | 2006-09-13 | 2007-03-14 | 陕西今日生物化工科技发展有限责任公司 | Method of preparing calcium propionate and calcium lactate with oyster shell as calcium source |
| CN101215231A (en) * | 2007-12-26 | 2008-07-09 | 仲恺农业技术学院 | Method for preparing calcium salt by using shell as raw material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292353A (en) * | 1999-09-23 | 2001-04-25 | 化学工业部上海化工研究院 | Production method of feed-level calcium hydrogen phosphate |
| CN1927803A (en) * | 2006-09-13 | 2007-03-14 | 陕西今日生物化工科技发展有限责任公司 | Method of preparing calcium propionate and calcium lactate with oyster shell as calcium source |
| CN101215231A (en) * | 2007-12-26 | 2008-07-09 | 仲恺农业技术学院 | Method for preparing calcium salt by using shell as raw material |
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