CN103848408A - Method for preparing calcium hydrogen phosphate by using shells - Google Patents
Method for preparing calcium hydrogen phosphate by using shells Download PDFInfo
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- CN103848408A CN103848408A CN201210494701.6A CN201210494701A CN103848408A CN 103848408 A CN103848408 A CN 103848408A CN 201210494701 A CN201210494701 A CN 201210494701A CN 103848408 A CN103848408 A CN 103848408A
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Abstract
The present invention relates to a calcium hydrogen phosphate preparation method, particularly to a method for preparing calcium hydrogen phosphate by using shell powder to replace lime, phosphate ore and the like, wherein phosphoric acid is added to pre-treated shell powder to carry out a treatment to obtain the calcium hydrogen phosphate. According to the present invention, X-ray diffraction and electron microscope analysis results show that the prepared calcium hydrogen phosphate has high purity; and the shells are changed into treasure from waste so as to completely utilize the marine shellfish resources, improve economic benefits of the enterprise, and reduce 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 the more than 60% of world's shellfish culture total amount.But shellfish is after processing, account for that the more than 50% shell Chang Zuowei processing waste of shellfish body weight abandons or for the starting material of production, the shellwork etc. of low value feed, resource utilization is low, seriously polluted.In fact, in shell, calcium carbonate content can reach more than 95%, is a kind of extraordinary substitute that replaces the raw materials such as raw material production calcium chloride, secondary calcium phosphate such as Rock Phosphate (72Min BPL).Secondary calcium phosphate is as fine chemical product, mainly 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 the low calcium feed of high phosphorus causes that chicken produces soft shelled egg, shell egg. and pure secondary calcium phosphate is the good poultry and livestock feed additive that contains phosphorus, 2 kinds of nutritive elements of calcium.Because its ratio of calcium and phosphorus is 1.29:1, more approaching than with the phosphorus calcium in animal skeleton, and can all be dissolved in again in the hydrochloric acid in gastric juice of animal, so easily enter in animal body and participate in metabolism, required hormone, enzyme and VITAMIN in composition body, keep the phosphorus calcium ratio in bone, thereby prevent that animal from, because of the various diseases that scarce phosphorus, calcium cause, promoting the Fast Growth of animal body simultaneously.Conventionally 1%～3% the calcium hydrophosphate fodder (calcium raised in abbreviation) that adds total amount in feed, 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 domestic market is increasing to the demand of calcium hydrophosphate fodder.
Summary of the invention
The object of the present invention is to provide a kind of method of 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, add pretreated oyster shell whiting to process phosphoric acid and obtain 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 adding is 0.5-1.1:1 by the mol ratio of phosphorus in calcium and phosphoric acid in pretreated oyster shell whiting adds.
Concrete steps are:
(1) pre-treatment of oyster shell whiting
1) adopt the acid solution that mass concentration is 1-4% to soak shell 1-5 hour, pure water is cleaned the acid of shell surface, and other impurity of outwash shell surface is dried, and is ground into 100-200 object oyster shell whiting and obtains pretreated oyster shell whiting; Main component is calcium carbonate.
Or 700-1200 ℃ of calcined shell 2-6 hour, after calcining, be ground into 100-200 object oyster shell whiting and obtained pretreated oyster shell whiting; Main component is calcium oxide.
(2) preparation of calcium carbonate or calcium oxide suspension
Pretreated 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, be the phosphoric acid of 40-60% to dropwise adding concentration in oyster shell whiting suspension while stirring in proportion, after dropwising, continue to stir 30-60min, it is fully reacted;
(4) after completion of the reaction, reaction solution is left standstill to 30-60min, remove supernatant liquor for subsequent use, throw out is stirred evenly, 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 is obtained obtains calcium hydrophosphate fodder at 80-100 ℃ after dry, wherein containing P >=20%, and Ca >=27%, F≤0.15%, detects secondary calcium phosphate content through X ray and reaches more than 98%.
In the supernatant liquor for subsequent use that above-mentioned (4) step is obtained, continue to add pretreated oyster shell whiting and constantly stir, in the time of the pH to 7.2-7.5 of supernatant liquor, stop adding oyster shell whiting, 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%.
The acid solution that described step 1) mass concentration is 1-4% is inorganic or organic acid.
The acid solution that described step 1) mass concentration is 1-4% is hydrochloric acid, acid or glacial acetic acid.
Advantage of the present invention
1. the present invention adopts discarded shell/phosphoric acid Wet Method Reaction system, has obtained the secondary calcium phosphate as the ratio of calcium and phosphorus 1.29:1 of fodder additives the best, shows that through X-ray diffraction secondary calcium phosphate purity reaches more than 98%.
2. the processing condition that the present invention adopts, to discard shell as raw material, have saved a large amount of materials such as lime, Rock Phosphate (72Min BPL).The mineral products such as lime, Rock Phosphate (72Min BPL) are first resource product, therefore will discard shell and replace lime etc., have both saved Mineral resources, take full advantage of again Mollusca Resource, have reduced destruction and the pollution of environment, and economic and social profit is huge.
3. the processing condition that the present invention adopts, without utilizing hydrochloric acid and secondary neutralization, have simplified technical process greatly, have both saved the energy and facility investment, have improved again the rate of recovery and the purity of secondary calcium phosphate, have reduced production cost.
4. China is aquaculture big country, and the annual production of sea farming shellfish occupies first place in the world, and exceedes 50% shell except the utilization of minority low value but account for shellfish gross weight, and as shellwork etc., substantially not processed utilization, has caused 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 in the present invention, takes full advantage of seashells resource, has improved Business Economic Benefit, has reduced 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 of utilizing shell to prepare secondary calcium phosphate comprises the following steps:
(1) pre-treatment of oyster shell whiting
With 1-4% acid solution immersion shell 1-5 hour, pure water is cleaned the acid of shell surface, and other impurity of outwash shell surface is dried, and is ground into 100-200 object oyster shell whiting and obtains pretreated oyster shell whiting.Main component is that calcium carbonate content can reach more than 95%.
Or 700-1200 ℃ of calcination processing shell 2-6 hour, be ground into 100-200 object oyster shell whiting and 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, it is fully reacted.
(4) after completion of the reaction, reaction solution is left standstill to 30-60min, remove supernatant liquor for subsequent use, throw out is stirred evenly, 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 (4) step being obtained obtains calcium hydrophosphate fodder at 80-100 ℃ after dry, in product containing P >=20%, Ca >=27%, F≤0.15%.Detecting secondary calcium phosphate content through X ray reaches more than 98%.
(6) the filtrate continuation (4) step being obtained adds pretreated oyster shell whiting and constantly stirs, and in the time of the pH to 7.2-7.5 of supernatant liquor, stops adding oyster shell whiting, collects filter cake, dry, prepare secondary calcium phosphate, P >=20% in product, Ca >=27%, F≤0.15%.Detecting secondary calcium phosphate content through X ray reaches 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 acids such as hydrochloric acid, acetic acid, formic acid; The amount that the volume of described phosphoric acid is 0.5 ~ 1.1:1 according to the mol ratio of phosphorus in calcium and phosphoric acid in oyster shell whiting suspension adds.
Embodiment 1
1) be that 1-4% acid solution soaks shell 1-5 hour by mass concentration, pure water is cleaned the acid of shell surface, and other impurity of outwash shell surface is dried and got shell 2000g, is ground into 100-200 object oyster shell whiting and obtains 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 15ml 85% phosphoric acid, add the pure water of 10.5ml, i.e. 50% phosphoric acid solution;
4) to step 2) the 50% phosphoric acid solution 25.5ml that dropwise adds while stirring step 3) to prepare in the oyster shell whiting suspension prepared, it is fully reacted, after 50% phosphoric acid solution has added, continue to stir 30min;
5) above-mentioned reaction solution is left standstill to 30min, suction filtration, supernatant liquor is for subsequent use;
6) precipitation of being prepared by step 5) is constantly cleaned to washing lotion pH constant with pure water suction filtration, precipitation is secondary calcium phosphate;
7) the supernatant liquor inner edge of preparing to step 5) slowly adds step 1) gained oyster shell whiting limit to stir, and the pH to 7.2 of assaying reaction liquid, reacts complete, and reaction solution is left standstill to 30min, suction filtration, and 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, to dry, control temperature is 80-100 ℃, after 2 hours, obtains secondary calcium phosphate dry product.Oven dry sample to gained detects, and examination criteria and result are if following table 1 is simultaneously referring to Fig. 1 and Fig. 2.
The detected result of table 1: embodiment
The acid solution that step 1) mass concentration described above is 1-4% is hydrochloric acid, acid or glacial acetic acid
Difference from Example 1 is that the processing condition aspects such as ratio of calcium and phosphorus change, specifically referring to table 2.
Table 2 utilizes different oyster shell whitings to prepare the condition of secondary calcium phosphate
Embodiment 3
Difference from Example 1 is that the experimental result of utilizing different oyster shell whitings to prepare secondary calcium phosphate is referring to table 3
Table 3 utilizes different oyster shell whitings to prepare the result of secondary calcium phosphate
From table 2, table 3, can obtain the wider calcium monophosphate product of ratio of calcium and phosphorus by this technique, and obtain the processing condition as the ratio of calcium and phosphorus 1.29:1 of fodder additives the best, for theoretical basis has been established in the utilization of the discarded shell of sea-food tankage.
Claims (8)
1. utilize shell to prepare a method for secondary calcium phosphate, it is characterized in that: add pretreated oyster shell whiting to process phosphoric acid and obtain secondary calcium phosphate.
2. by utilizing shell to prepare the method for 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 utilizing shell to prepare the method for secondary calcium phosphate described in claim 1, it is characterized in that: described in the phosphoric acid volume that adds be 0.5-1.1:1 by the mol ratio of phosphorus in calcium and phosphoric acid in pretreated oyster shell whiting amount adds.
4. utilize shell to prepare the method for secondary calcium phosphate by described in claim 1,2 or 3, it is characterized in that:
(1) pre-treatment of oyster shell whiting
1) adopt the acid solution that mass concentration is 1-4% to soak shell 1-5 hour, pure water is cleaned the acid of shell surface, and other impurity of outwash shell surface is dried, and is ground into 100-200 object oyster shell whiting and obtains pretreated oyster shell whiting;
Or 700-1200 ℃ of calcined shell 2-6 hour, after calcining, be ground into 100-200 object oyster shell whiting and obtained pretreated oyster shell whiting;
(2) preparation of calcium carbonate or calcium oxide suspension
Pretreated 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, be the phosphoric acid of 40-60% to dropwise adding concentration in oyster shell whiting suspension while stirring in proportion, after dropwising, continue to stir 30-60min, it is fully reacted;
(4) after completion of the reaction, reaction solution is left standstill to 30-60min, remove supernatant liquor for subsequent use, throw out is stirred evenly, 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. by utilizing shell to prepare the method for secondary calcium phosphate described in claim 4, it is characterized in that: the secondary calcium phosphate precipitated filter cakes that above-mentioned (4) step is obtained obtains calcium hydrophosphate fodder at 80-100 ℃ after dry, wherein containing P >=20%, Ca >=27%, F≤0.15%, detects secondary calcium phosphate content through X ray and reaches more than 98%.
6. by utilizing shell to prepare the method for secondary calcium phosphate described in claim 4, it is characterized in that: in the supernatant liquor for subsequent use that above-mentioned (4) step is obtained, continue to add pretreated oyster shell whiting and constantly stir, in the time of the pH to 7.2-7.5 of supernatant liquor, stop adding oyster shell whiting, 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%.
7. by utilizing shell to prepare the method for secondary calcium phosphate described in claim 4, it is characterized in that: the acid solution that described step 1) mass concentration is 1-4% is inorganic or organic acid.
8. by utilizing shell to prepare the method for secondary calcium phosphate described in claim 7, it is characterized in that: the acid solution that described step 1) mass concentration is 1-4% is hydrochloric acid, acid or glacial acetic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-11-28 CN CN201210494701.6A patent/CN103848408B/en active Active
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN103848408B (en) | 2016-04-13 |
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