CN1072186C - Process for producing high effective phosphorus calcium hydrogen phosphate - Google Patents
Process for producing high effective phosphorus calcium hydrogen phosphate Download PDFInfo
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- CN1072186C CN1072186C CN97111341A CN97111341A CN1072186C CN 1072186 C CN1072186 C CN 1072186C CN 97111341 A CN97111341 A CN 97111341A CN 97111341 A CN97111341 A CN 97111341A CN 1072186 C CN1072186 C CN 1072186C
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- phosphate
- dihydrogen phosphate
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- phosphoric acid
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Abstract
The present invention relates to a method for producing calcium hydrophosphate by high available phosphorus, which is characterized in that calcium lime powder and powdery calcium phosphate or calcium hydrophosphate or a mixture of the powdery calcium phosphate and the calcium hydrophosphate are uniformly mixed, and are intensely stirred and mixed with phosphoric acid to react, and thus, calcium dihydrogen phosphate is generated; the calcium dihydrogen phosphate is naturally piled for 8 to 100 hours in rooms, and is pulverized after being dried. The calcium dihydrogen phosphate and the powdery calcium hydroxide are slowly stirred for 1 to 2 hours, and thus, calcium hydrophosphate is prepared. The temperature for the method to prepare the calcium dihydrogen phosphate and the calcium hydrophosphate is lower than the dehydration critical temperature. The calcium dihydrogen phosphate and the calcium hydrophosphate are generated by one step, and are naturally dried, crystal water are not lost, and the content of the available phosphorus is more than 40 % higher than that of the existing products. The method has the advantages of few procedures, short processes, no pollution and low cost, and the capital cost accounts for 1/15 to 1/22 of that of the prior art.
Description
The present invention relates to a production method of calcium phosphate salt, i.e. firstly, calcium dihydrogen phosphate is produced, then calcium hydroxide is reacted with calcium dihydrogen phosphate to obtain calcium hydrogen phosphate.
The existing production method of calcium hydrogen phosphate is mainly characterized by firstly producing wet-process phosphoric acid, then defluorinating the wet-process phosphoric acid, neutralizing the wet-process phosphoric acid with lime milk, and filtering and drying the defluorinated phosphoric acid to obtain the calcium hydrogen phosphate. The first method is to react phosphoric acid with calcium carbonate to generate calcium dihydrogen phosphate, then crystallize, filter and dry to obtain the calcium dihydrogen phosphate; the second method is a one-step no-return method, such as the one-step no-return method 93110806 for producing feed monocalcium phosphate, which is prepared by stirring and reacting phosphoric acid and limestone ore powder, and heating and drying at 110 ℃ under the action of 100-. The above method uses phosphoric acid and calcium carbonate as raw materials, and the product is baked and dried at a higher temperature, especially at a temperature of more than 100 ℃, so that the water loss of the product is high, the water-soluble phosphorus and available phosphorus components are reduced, and the conversion from calcium carbonate to monocalcium phosphate is difficult to complete, and the content of water-soluble phosphorus is lower. In addition, in the prior art, the production of wet-process phosphoric acid is taken as a component, so that the process is multiple, the flow is long, the capital cost is high, the production cost is high, thedischarge amount of three wastes is large, and the environmental pollution is serious.
The invention aims to provide a production method of calcium dihydrogen phosphate and calcium hydrogen phosphate, which has the advantages of short flow, less working procedures, no pollution, no need of drying and high effective phosphorus content, so as to overcome the defects of the prior art.
The production method of the monocalcium phosphate provided by the invention is mainly characterized by comprising the following steps of:
(1) mixing quicklime powder with powdery calcium phosphate, calcium hydrogen phosphate or their mixture;
(2) mixing the mixed material obtained in the step (1) with phosphoric acid, stirring strongly, and reacting to generate calcium dihydrogen phosphate, wherein the liquid-solid ratio of the phosphoric acid to the mixed material is 1: 0.65-0.80, the concentration of the phosphoric acid is 62-85%, and the stirring time is 20-60 seconds;
(3) the generated calcium dihydrogen phosphate is piled up indoors, dried naturally and then crushed.
The stacking time of the calcium dihydrogen phosphate is 8 to 100 hours.
The reaction temperature for producing calcium dihydrogen phosphate is maintained below 80 deg.C.
The production method of calcium hydrophosphate is characterized in that the obtained powdery calcium biphosphate is mixed with powdery calcium hydroxide and is slowly stirred for 1-2 hours to prepare the calcium hydrophosphate, wherein the powdery calcium hydroxide accounts for 10-22% of the total weight of the mixture of the powdery calcium biphosphate and the powdery calcium hydroxide.
The powdery calcium hydroxide is prepared by adding a proper amount of water into quicklime powder.
The chemical reaction principle for preparing the monocalcium phosphate is as follows:
the reaction is not heated, and only strong stirring is carried out for a short time, so that the temperature can be ensured to be below 80 ℃.
The principle of the chemical reaction from calcium dihydrogen phosphate to calcium hydrogen phosphate is as follows:
the reaction is not heated in the same way, only slow stirring is carried out for 1-2 hours, and the temperature generated by the exothermic reaction is below 75 ℃.
The monocalcium phosphate is generally used as aquatic feed, and aquatic animals such as fish and the like cannot absorb water-insoluble phosphate because the aquatic animals do not secrete gastric acid. The above reactions are all below the critical temperature of dehydration of monocalcium phosphate of 80 ℃, so the product has no problem of becoming water-insoluble phosphate due to dehydration.
Calcium hydrogen phosphate is mainly used as feed for livestock and poultry, and whether the product is effective for animals depends on the amount of calcium hydrogen phosphate which can be dissolved by animal gastric acid, in other words, the amount of calcium hydrogen phosphate which is dissolved by 0.4% hydrochloric acid is equivalent to the concentration of animal gastric acid. Calcium hydrogen phosphate (CaHPO)4·2H2O) started to become a monohydrate at 100 c, with only 47% available phosphorus measured as 0.4% hydrochloric acid. The reaction temperature from calcium dihydrogen phosphate to calcium hydrogen phosphate is below 80 deg.c, so that the available phosphorus content in calcium hydrogen phosphate is far over 47%.
The temperature for preparing the monocalcium phosphate and the calcium hydrophosphate is far lower than the dehydration critical temperature of the monocalcium phosphate and the calcium hydrophosphate, the working procedures are few, the monocalcium phosphate and the calcium hydrophosphate are generated in one step, the natural drying is carried out, the water loss is avoided, and the effective phosphorus content of the monocalcium phosphate and the calcium hydrophosphate is higher than that of the conventional products by more than 40 percent. The water-soluble phosphorus of calcium dihydrogen phosphate reaches 80-95%, and the other indexes are phosphorus 22-24%, calcium 14.5-16.5%, fluorine 0.18%, water content is less than 4%, arsenic is less than 0.003%, and lead is less than 0.002%. The available phosphorus of calcium hydrogen phosphate is 70-90%, and the other indexes are that phosphorus is more than 16%, calcium is more than 21% and fluorine is less than 0.18%. The invention has the advantages of less working procedures, short flow, only three steps of mixing, stirring, natural drying and crushing, no waste discharge and no pollution to the environment, thereby having low production cost, less phosphoric acid consumption and capital construction cost which is only 1/15-1/22 in the prior art.
The invention is further illustrated by the following examples.
Example 1
4Kg of quicklime powder and 25Kg of powdered calcium phosphate are mixed uniformly, and 40Kg of phosphoric acid with the concentration of 75 percent is stirred in a strong stirrer for 20 seconds and then discharged, and the mixture is piled indoors, naturally dried for 48 hours and crushed to obtain the calcium dihydrogen phosphate meeting the standard.
Example 2
Mixing calx powder 4Kg and calcium hydrogen phosphate powder 25Kg, stirring with 75% concentration phosphoric acid 40Kg in a strong stirrer for 20 sec, discharging, naturally drying in room for 48 hr, and pulverizing to obtain calcium dihydrogen phosphate product.
Example 3
4Kg of quicklime powder, 25Kg of half-and-half mixture of powdered calcium phosphate and calcium hydrogen phosphate (the mixing ratio of the mixture can be any) and 40Kg of phosphoric acid with the concentration of 75 percent are discharged after being stirred strongly for 20 seconds in a strong stirrer, and the calcium dihydrogen phosphate product with the standard is obtained after being naturally dried in a room for 48 hours and crushed.
Example 4
3Kg of quicklime powder and 26Kg of powdered calcium phosphate are mixed, stirred, dried and crushed with 35Kg of phosphoric acid with the concentration of 85% in the above manner to obtain the same calcium dihydrogen phosphate product.
Example 5
The same product was obtained by replacing 26Kg of powdered calcium phosphate of example 4 with the same weight of powdered calcium hydrogen phosphate, the remaining conditions remaining unchanged.
Example 6
The same product can be obtained by replacing 26Kg of powdered calcium phosphate of example 4 with the same weight of a mixture of powdered calcium phosphate and calcium hydrogen phosphate in any ratio, the remaining conditions remaining unchanged.
Example 7
Mixing 8.25Kg of quicklime powder and 17Kg of powdered calcium phosphate uniformly, stirring the mixture with 33.5Kg of 62% phosphoric acid in a strong stirrer for 20 seconds, stacking indoors for 100 hours, naturally drying, and pulverizing to obtain calcium dihydrogen phosphate. 47Kg of the product was slowly stirred with 9Kg of prepared powdered calcium hydroxide in a mixer for 2 hours to obtain a calcium hydrogen phosphate product meeting the above criteria. The powdery calcium hydroxide can be prepared from quicklime powder and appropriate amount of water.
Example 8
Calcium hydrogen phosphate product was obtained by mixing 61Kg of the calcium dihydrogen phosphate obtained in one of examples 1 to 6 with 17Kg of the prepared powdery calcium hydroxide in a mixer for 1 hour.
Claims (5)
1. The production method of monocalcium phosphate is characterized by comprising the following steps:
(1) mixing quicklime powder with powdery calcium phosphate, calcium hydrogen phosphate or their mixture;
(2) mixing the mixed material obtained in the step (1) with phosphoric acid, stirring strongly, and reacting to generate calcium dihydrogen phosphate, wherein the liquid-solid ratio of the phosphoric acid to the mixed material is 1: 0.65-0.80, the concentration of the phosphoric acid is 62-85%, and the stirring time is 20-60 seconds;
(3) the generated calcium dihydrogen phosphate is piled up indoors, dried naturally and then crushed.
2. The method of claim 1, wherein the calcium dihydrogen phosphateis stacked for a period of 8 to 100 hours.
3. The process of claim 1, wherein the reaction temperature for the formation of monocalcium phosphate is maintained below 80 ℃.
4. A process for producing calcium hydrogen phosphate, characterized in that the powdery calcium dihydrogen phosphate obtained in any one of claims 1 to 3 is mixed with powdery calcium hydroxide and slowly stirred for 1 to 2 hours, wherein the powdery calcium hydroxide accounts for 10 to 22% of the total amount of the mixture of the powdery calcium dihydrogen phosphate and the powdery calcium hydroxide.
5. The method of claim 4, wherein the powdered calcium hydroxide is made from quicklime powder with an appropriate amount of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111341A CN1072186C (en) | 1997-05-22 | 1997-05-22 | Process for producing high effective phosphorus calcium hydrogen phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111341A CN1072186C (en) | 1997-05-22 | 1997-05-22 | Process for producing high effective phosphorus calcium hydrogen phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1220236A CN1220236A (en) | 1999-06-23 |
| CN1072186C true CN1072186C (en) | 2001-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97111341A Expired - Fee Related CN1072186C (en) | 1997-05-22 | 1997-05-22 | Process for producing high effective phosphorus calcium hydrogen phosphate |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864042A (en) * | 2014-02-28 | 2014-06-18 | 昆明川金诺化工股份有限公司 | Method for lowering free acid of feed grade monocalcium phosphate |
| RU2628292C1 (en) | 2016-03-03 | 2017-08-15 | Акционерное общество "Минерально-химическая компания "ЕвроХим" | Phosphor-potassium-nitrogen-containing npk-fertiliser and method of producing granulated phosphor-potassium-nitrogen-containing npk-fertilisers |
| RU2626947C1 (en) | 2016-03-03 | 2017-08-02 | Акционерное общество "Минерально-химическая компания "ЕвроХим" | Phosphorus-potassuim-nitrogen-containing npk-fertiliser and method for producing granulated phosphorus-potassuim-nitrogen-containing npk-fertiliser |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUT59065A (en) * | 1990-03-19 | 1992-04-28 | Csongrad Megyei Gabonaforgalmi | Continuous process for producing solide calcium-phosphates from raw phosphate without adding phosphoric acid and lime |
| CN1110250A (en) * | 1994-12-05 | 1995-10-18 | 乐山市太康工业总公司 | Technology for producing active calcium phosphate |
| CN1118332A (en) * | 1994-09-08 | 1996-03-13 | 陈书香 | Wet process for preparing calcium hydrophosphate fodder from phosphoric acid |
-
1997
- 1997-05-22 CN CN97111341A patent/CN1072186C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUT59065A (en) * | 1990-03-19 | 1992-04-28 | Csongrad Megyei Gabonaforgalmi | Continuous process for producing solide calcium-phosphates from raw phosphate without adding phosphoric acid and lime |
| CN1118332A (en) * | 1994-09-08 | 1996-03-13 | 陈书香 | Wet process for preparing calcium hydrophosphate fodder from phosphoric acid |
| CN1110250A (en) * | 1994-12-05 | 1995-10-18 | 乐山市太康工业总公司 | Technology for producing active calcium phosphate |
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| Publication number | Publication date |
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| CN1220236A (en) | 1999-06-23 |
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Address after: Kaiyuan City Township in Yunnan Province Bureau of supply and marketing company Applicant after: Yintong Feed Factory, Kaiyuan Inventor after: Ran Leiming Inventor after: Zhang Caifeng Address before: Kaiyuan city of Yunnan province No. 74 West Township Bureau of supply and marketing company Applicant before: Ran Leiming Inventor before: Ran Leiming Applicant before: Zhang Caifeng |
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