CN1463917A - Process for increasing fodder/ fertilizer ratio of fodder level calcium hydrogen phosphate - Google Patents
Process for increasing fodder/ fertilizer ratio of fodder level calcium hydrogen phosphate Download PDFInfo
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- CN1463917A CN1463917A CN02133380A CN02133380A CN1463917A CN 1463917 A CN1463917 A CN 1463917A CN 02133380 A CN02133380 A CN 02133380A CN 02133380 A CN02133380 A CN 02133380A CN 1463917 A CN1463917 A CN 1463917A
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- Prior art keywords
- calcium
- feed
- phosphoric acid
- hydrogen phosphate
- calcium hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003337 fertilizer Substances 0.000 title claims abstract description 12
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 title claims description 24
- 235000019700 dicalcium phosphate Nutrition 0.000 title claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011575 calcium Substances 0.000 claims abstract description 41
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- 239000011574 phosphorus Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 18
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 17
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 17
- 239000004571 lime Substances 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 14
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 11
- 239000008267 milk Substances 0.000 claims abstract description 11
- 235000019691 monocalcium phosphate Nutrition 0.000 claims abstract description 11
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 11
- 235000013336 milk Nutrition 0.000 claims abstract description 10
- 210000004080 milk Anatomy 0.000 claims abstract description 10
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229960005069 calcium Drugs 0.000 claims description 37
- 239000012452 mother liquor Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 238000006115 defluorination reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 229960001714 calcium phosphate Drugs 0.000 claims description 6
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000003483 aging Methods 0.000 claims 2
- 230000032683 aging Effects 0.000 claims 2
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 claims 2
- 238000007873 sieving Methods 0.000 claims 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 6
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 244000144972 livestock Species 0.000 description 6
- 244000144977 poultry Species 0.000 description 6
- 235000013594 poultry meat Nutrition 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 206010061762 Chondropathy Diseases 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000019735 Meat-and-bone meal Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 241001482237 Pica Species 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 208000015100 cartilage disease Diseases 0.000 description 1
- 235000013330 chicken meat Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Fertilizers (AREA)
Abstract
The method of raising the ratio between feed level calcium biphosphate and fertilizer level calcium biphosphate during calcium biphosphate producing process features that the neutralized mother liquid after producing feed level calcium biphosphate, stoved tail gas washing liquid and centrifugal calcium biphosphate solution are mixed, neutralized with lime milk, centrifugated and filtered, and the filter cake is mixed with phosphoric acid or wet process phosphoric acid, small amount of lime may be added to regulate calcium content, and the mixture is matured, dried and sieved to obtain feed level calcium biphosphate or rich feed level calcium phosphate. The said process raises the ratio and phosphorus recovering rate, reduces the phosphorus content in exhausted mother liquid and reduces environmental pollution.
Description
Technical Field
The invention relates to a method for improving the feed-fertilizer ratio of feed-grade calcium hydrophosphate, in particular to a method for neutralizing a phosphorus-containing mother liquor in a feed-grade calcium hydrophosphate production system to pH7.0-7.5 by using lime milk, then mixing and reacting the obtained solid material with phosphoric acid or a wet-process phosphoric acid defluorination liquid, and obtaining the feed-grade calcium hydrophosphate or calcium rich phosphate through curing and drying.
Background
The feed-grade calcium hydrophosphate is a high-quality livestock and poultry feed additive, provides indispensable phosphorus and calcium elements for the growth and development of livestock and poultry, can enhance the pestilence-resistant and disease-resistant capability of livestock and poultry, prevents chondropathy, paralysis and pullorum disease of the livestock and poultry, prevents pica of pigs and chickens, and improves the mating rate, fetus protection rate and survival rate of the livestock and poultry. In recent years, with the banning of meat and bone meal in livestock and poultry feed, the production of calcium hydrogen phosphate has increased dramatically with the increase of the demand. The production method of calcium hydrophosphate is mostly prepared by reacting wet-process phosphoric acid with calcium carbonate or lime milk for defluorination and then neutralizing with lime milk, the popularization rate of the method is very high, and a plurality of manufacturers improve the production process from different ways so as to improve the feed-fertilizer ratio (the ratio of phosphorus entering a feed-grade product to phosphorus entering a fertilizer-grade calcium hydrophosphate in the production process of the feed-grade calcium hydrophosphate), reduce the production cost of the feed-grade calcium hydrophosphate and reduce or eliminate the pollution of production wastewater to the nature, but the pollution of the production wastewater to the nature is not reported until now.
The invention content is as follows:
the invention aims to provide a method for improving the feed ratio of feed-grade calcium hydrophosphate on the feed fertilizer, which not only improves the utilization rate of phosphorus and reduces the resource waste, but also reduces the pollution of phosphorus in the wastewater discharged by a production system to the nature, and has more obvious economic benefit and social benefit.
The purpose of the invention is realized as follows: neutralizing phosphorus-containing turbid liquid such as neutralized mother liquor, dried tail gas washing liquid, centrifugal mother liquor and the like in a calcium hydrophosphate production system by using lime milk, controlling the pH of a neutralization end point to be 7.0-7.5, then putting the neutralized slurry into a plate-and-frame filter press for filter pressing, adding phosphoric acid or wet-process phosphoric acid defluorination liquid into an obtained filter cake, adding a small amount of quicklime powder to adjust calcium if necessary, curing, drying and screening the mixed material to obtain feed-grade calcium hydrophosphate or calcium phosphate-rich material.
The slaking refers to that the mixed materials are placed for a certain time, so that tricalcium phosphate and calcium hydrophosphate in the mixed materials react with free phosphoric acid to generate calcium hydrophosphate or calcium dihydrogen phosphate, and lime reacts with surplus free phosphoric acid and calcium dihydrogen phosphate to generate calcium hydrophosphate.
The phosphorus-containing mother liquor can be any one or a mixture of two or a mixture of three of a neutralization mother liquor, a drying tail gas washing liquid and a neutralization centrifugal mother liquor which are generated in the process of producing feed-grade calcium hydrophosphate, wherein the content of P2O5 is more than 0.3 g/l.
The reaction mechanism of the production process is as follows:
the neutralization process of the phosphorus-containing mother liquor is to precipitate phosphorus in the form of calcium dihydrogen phosphate in the mother liquor by converting the phosphorus into calcium hydrogen phosphate or tricalcium phosphate through reaction with lime milk:
the filter cake obtained by filter pressing the reaction slurry mainly contains calcium hydrophosphate, tricalcium phosphate, lime which is wrapped by the reaction and is not available, and a small amount of magnesium hydrophosphate is generated. After the material is dried, the phosphorus content (calculated by P) is about 14-16%, the calcium content is about 20-22%, the phosphorus and calcium content of the feed grade calcium hydrophosphate is not up to the standard, and manufacturers add the material into white fertilizer to improve the phosphorus content of the white fertilizer, so that the use value of the white fertilizer is reduced. Through long-term research and discussion, we invent a method for producing feed-grade calcium hydrogen phosphate or calcium phosphate-rich by using the material, namely, phosphoric acid or wet-process phosphoric acid defluorination liquid is added into the material, or dry calcium hydrogen phosphate or tail powder generated in the drying process is added into the material, mixed and dried, then phosphoric acid or wet-process phosphoric acid defluorination liquid is added, a small amount of quicklime powder is added if necessary, after uniform mixing, curing, drying and screening are carried out, and the feed-grade calcium hydrogen phosphate or calcium phosphate-rich is obtained. The process mainly comprises the following reactions:
the main process steps of the invention are characterized in that:
pumping all the phosphorus-containing mother liquor and a small amount of calcium hydrophosphate suspended matters into a neutralization reaction tank by a pump, slowly adding lime milk (the specific gravity is 1.03-1.06g/l) with relatively thin concentration while stirring, neutralizing to the pH value of 7.0-7.5, pumping the slurry into a plate-and-frame filter press for filter pressing, and performing the obtained filter cake according to the following steps 2-4 or 5-6.
2, mixing the filter cake with dry calcium hydrophosphate or tail powder generated in the drying process to make the filter cake in a quicksand shape, and then drying the filter cake in an airflow drying system to obtain a dry material.
3, adding the dried materials into a mixing reactor after metering, adding a proper amount of thermal phosphoric acid or wet phosphoric acid defluorination liquid, adding a proper amount of quicklime powder after uniformly stirring, uniformly stirring and discharging, and delivering the materials to a semi-finished product storage yard for curing for more than 4 hours.
And 4, conveying the cured material to an airflow dryingsystem for drying, and then screening and packaging to obtain the feed-grade calcium hydrophosphate.
And 5, adding the filter cake into a mixing reactor, adding a proper amount of thermal phosphoric acid or wet phosphoric acid defluorination liquid, uniformly stirring, adding a proper amount of quicklime powder, and stirring for about 1 hour.
And 6, feeding the cured material to a spray drying system for drying, and then screening and packaging to obtain the feed-grade calcium phosphate.
The realization of the process can not only improve the feed-fertilizer ratio of the feed-grade calcium hydrophosphate production, improve the phosphorus recovery rate and reduce the production cost of the feed-grade calcium hydrophosphate, but also effectively control the phosphorus content in the mother liquor discharged by a calcium hydrophosphate production system, reduce the pollution to the environment and create the social benefit while creating the economic benefit.
Description of the drawings:
FIG. 1 is a schematic view of the process of the present invention:
the specific implementation mode is as follows:
the technical scheme of the invention is further illustrated by the following examples in combination with a process flow schematic diagram.
Example 1:
pumping phosphorus-containing mother liquor (including calcium hydrophosphate neutralization mother liquor, centrifugal mother liquor and tail gas washing liquor) with the height of 2/3 into a neutralization reaction tank with the stirring diameter of 2500 multiplied by 2800 by apump, slowly adding lime milk (the specific gravity is 1.05) to the pH value of 7.5 while stirring, keeping stirring for 30 minutes, conveying the reacted slurry to a plate-and-frame filter press by the pump for filtering, and directly discharging the filtered clear liquid with the pH value of 7.3 and the phosphorus content (measured by P) of 0.15 g/l; 315Kg of filter cake (55% water, P7.22%, Ca9.81%) was obtained, which was mixed with 400Kg of dry calcium hydrogen phosphate and dried in a pneumatic dryer to obtain 536Kg of dry material (P16.2%, Ca20.75%, F0.169%). 150Kg of the material and 8Kg of 85% thermal phosphoric acid (diluted) are added into a mixing reactor, and after being stirred uniformly, 2.8Kg of quicklime powder is added, and the mixture is stirred uniformly, sent to a storage yard for curing for 5 hours, dried and screened to obtain 155.5Kg of calcium hydrophosphate, wherein the quality indexes are as follows:
phosphorus content (calculated as P) 17.08%, calcium content (calculated as Ca) 21.15%,
the fluorine content (counted by F) is 0.16 percent, and the indexes of arsenic and lead are qualified.
Example 2:
adding 150Kg of the dried filter cake material into a mixing reactor, and simultaneously adding wet-process phosphoric acid defluorination liquid (containing P)2O514.2 percent of calcium hydrogen phosphate and 0.06 percent of F), stirring uniformly, adding 2.5Kg of quicklime powder, stirring uniformly, curing for 5 hours, drying and screening to obtain 157Kg of calcium hydrophosphate with the following quality indexes:
phosphorus content (calculated as P) 17.15%, calcium content (calculated as Ca) 21.32%,
the fluorine content (counted by F) is 0.16 percent, and the indexes of arsenic and lead are qualified.
Example 3:
pumping into phosphorus-containing mother liquor (including calcium hydrogen phosphate neutralized mother liquor, centrifugal mother liquor and tail gas washing liquor) with 2/3-degree height into a stirred neutralization reaction tank with phi 2500X 2800, slowly adding lime milk (specific gravity 1.05) to pH7.5 under stirring, stirring for 30 min, pumping the reacted slurry to plate-frame pressFiltering with a filter, wherein the pH of the filtered clear solution is 7.3, and the clear solution contains 0.13g/l of phosphorus (calculated as P) and can be directly discharged; 380Kg of filter cake (containing 58% of water, P7.03% and Ca9.72%) is obtained by charging the filter cake into a mixing reactor, and adding 15Kg of 85% thermal phosphoric acid and 100Kg of wet phosphoric acid defluorination solution (containing P)2O514.2 percent and F0.06 percent) and stirring for 2 hours, then sending the mixture to a spray dryer for drying and screening to obtain 204Kg of calcium phosphate rich, wherein the quality indexes are as follows:
phosphorus content (calculated as P) 19.57%, calcium content (calculated as Ca) 21.05%,
water soluble phosphorus (calculated by P) 3.46%, fluorine content (calculated by F) 0.16%, and qualified arsenic and lead indexes
Claims (7)
1. A process for increasing the feed-fertilizer ratio of feed-class calcium hydrogen phosphate includes such steps as neutralizing the mother liquid containing phosphorus in feed-class calcium hydrogen phosphate production system to pH7.0-7.5 with lime milk, press filtering, mixing the filter cake with phosphoric acid or defluorinating liquid of wet phosphoric acid, adding a small amount of calcium lime powder, regulating calcium content, ageing, drying, sieving and preparing feed-class calcium hydrogen phosphate or rich calcium phosphate.
2. A process for increasing the feed-fertilizer ratio of feed-class calcium hydrogen phosphate includes such steps as filtering the mother liquid containing phosphorus in calcium hydrogen phosphate system to pH7.0-7.5, filter pressing, mixing the filter cake with dry calcium hydrogen phosphate or the tail powder generated in baking, mixing the dried material with phosphoric acid or the defluorinating liquid of phosphoric acid, adding or not adding lime powder, ageing, drying and sieving.
3. The method for improving the feed ratio of calcium hydrogen phosphate as claimed in claim 1 or 2, wherein the phosphorus-containing mother liquor in the calcium hydrogen phosphate system comprises any one or two or three of the neutralized mother liquor after production of calcium hydrogen phosphate, the drying tail gas washing liquid and the calcium hydrogen phosphate centrifugal mother liquor.
4. The method as claimed in claim 3, wherein each phosphorus-containing mother liquor contains more than 0.3g/l of P2O5。
5. A method for increasing the feed rate of dibasic calcium phosphate according to claim 1 or claim 2 wherein the phosphoric acid is 30-85% hot or wet process phosphoric acid required for production of feed grade products.
6. The method for improving the feed/fertilizer ratio of feed grade dibasic calcium phosphate according to claim 1 or 2, characterized in that the wet phosphoric acid defluorination solution is the treatment of P with calcium carbonate or lime milk2O5The defluorination liquid of the wet-process phosphoric acid is obtained by defluorinatingmore than or equal to 120g/l of the wet-process phosphoric acid.
7. A method as claimed in claim 1 or claim 2 wherein the slaking is performed by holding the feed material containing a quantity of water for a period of time to allow tricalcium phosphate and calcium hydrogen phosphate to react with free phosphoric acid to form calcium hydrogen phosphate and calcium dihydrogen phosphate, respectively, and lime to react with excess free phosphoric acid and calcium dihydrogen phosphate to form calcium hydrogen phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021333807A CN1207184C (en) | 2002-06-28 | 2002-06-28 | Process for increasing fodder/ fertilizer ratio of fodder level calcium hydrogen phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021333807A CN1207184C (en) | 2002-06-28 | 2002-06-28 | Process for increasing fodder/ fertilizer ratio of fodder level calcium hydrogen phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1463917A true CN1463917A (en) | 2003-12-31 |
| CN1207184C CN1207184C (en) | 2005-06-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021333807A Expired - Fee Related CN1207184C (en) | 2002-06-28 | 2002-06-28 | Process for increasing fodder/ fertilizer ratio of fodder level calcium hydrogen phosphate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040206A (en) * | 2010-11-02 | 2011-05-04 | 昆明川金诺化工有限公司 | Method for recycling acid sludge produced by concentrated phosphoric acid |
| 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 |
| CN104291308A (en) * | 2014-09-19 | 2015-01-21 | 贵阳中化开磷化肥有限公司 | Production method for preparing tricalcium phosphate and coproducing special fertilizer for rye |
| CN115108541A (en) * | 2022-07-14 | 2022-09-27 | 瓮福（集团）有限责任公司 | Method for recycling ultralow-concentration phosphorus-containing wastewater |
-
2002
- 2002-06-28 CN CNB021333807A patent/CN1207184C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040206A (en) * | 2010-11-02 | 2011-05-04 | 昆明川金诺化工有限公司 | Method for recycling acid sludge produced by concentrated phosphoric acid |
| 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 |
| CN104291308A (en) * | 2014-09-19 | 2015-01-21 | 贵阳中化开磷化肥有限公司 | Production method for preparing tricalcium phosphate and coproducing special fertilizer for rye |
| CN115108541A (en) * | 2022-07-14 | 2022-09-27 | 瓮福（集团）有限责任公司 | Method for recycling ultralow-concentration phosphorus-containing wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1207184C (en) | 2005-06-22 |
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