CN1183378A - Method for producing feed calcium hydrogen phosphate - Google Patents
Method for producing feed calcium hydrogen phosphate Download PDFInfo
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- CN1183378A CN1183378A CN95113038A CN95113038A CN1183378A CN 1183378 A CN1183378 A CN 1183378A CN 95113038 A CN95113038 A CN 95113038A CN 95113038 A CN95113038 A CN 95113038A CN 1183378 A CN1183378 A CN 1183378A
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- neutralization
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- slip
- hydrogen phosphate
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Abstract
A process for producing calcium hydrogen phosphate feed features that before reaction of phosphorus ore and sulfuric acid, the phosphorus ore is pre-treated by wet phosphoric acid for removing impurities and reducing consumption of sulfuric acid, the pre-neutralizing step is divided into two steps, and the thick slurry separated out in the second pre-neutralizing is returned to the point before the first pre-neutralizing for being dissolved by used wet phosphoric acid. Its advantages are high output rate increased from 60:40 to 85:15 or 90:10.
Description
The present invention relates to a kind ofly produce earlier dihydrate wet phosphoric acid take the high mid low grade phosphate rock of impurity content and sulfuric acid as raw material, carry out the production method that calcium hydrogen phosphate fodder is produced in two sections neutralizations with milk of lime again.
Press of Chengdu Univ. of Science ﹠ Technology in 1989 publishes, and Chen Jiafu, Tan Guang smoke etc. that to have introduced with mid low grade phosphate rock and sulfuric acid in " phosphatic production and application " book of writing be the processing method that raw material is produced calcium hydrogen phosphate fodder.The step of this process is earlier rock phosphate in powder to be ground into moisture 30% phosphate ore pulp with ball mill, again with phosphate ore pulp and sulfuric acid extractive reaction, the extraction slurry filtration that generates is obtained phosphoric acid by wet process, is residue phosphogypsum behind the residue washing.Phosphoric acid by wet process carries out preneutralization (one section neutralization) with milk of lime after clarifying, control pH value 2.9～3.2, the filter residue that the preneutralization slip obtains after filtration is for white fertile, and filtrate is carried out two sections neutralizations (main neutralization) after sinking clearly, and pH values 6.2～6.5 are controlled in two sections neutralizations.The solid drying that obtains with slurry filtration in two sections is the finished product feedstuff secondary calcium phosphate.
Because mid low grade phosphate rock impurity content height, extraction process sulfuric acid consumption height, and the difficult filtration of extraction slip make filter plant huge, and production capacity is little, and the phosphoric acid by wet process impurity content that obtains is also high, and the defluorinate difficulty is big, and technical indicator falls behind, P
2O
5Fodder/ fertilizer ratio be generally 60: 40, enter the P of feed phosphate
2O
5Measure very low, norm quota of consumption height, calcium hydrogen phosphate fodder per ton consumes 2.4～2.8 tons of rocks phosphate in powder, 1.9～2.3 tons in sulfuric acid.
1992 the 3rd periodicals of " phosphate fertilizer and multiple fertilizer " magazine have carried people's such as professor Wang Lisheng paper, and exercise question is " the application foundation theoretical investigation that phosphoric acid by wet process is produced calcium hydrophosphate fodder ".This paper improves above-mentioned traditional calcium hydrogen phosphate fodder production technology.Carry out defluorinate with sodium salt in that preneutralization (one section neutralization) is front, the by-product fluosilicic acid sodium salt, and two kinds of conditioners have been added at extraction process, a kind of conditioner can reduce the impurity that enters in the phosphoric acid by wet process, another kind of conditioner can change various impurity occurrence status in phosphoric acid, thereby is conducive to defluorinate.Through above technological improvement, technical indicator P
2O
5Fodder/ fertilizer ratio can reach 75: 25.In the paper with no specific disclosure of the content of conditioner.
At the deficiency of existing calcium hydrogen phosphate fodder production technology, main purpose of the present invention is to reduce impurity such as calcium contained in vitriolic consumption and the phosphorus ore, magnesium, iron, aluminium, improves the strainability of extraction slip, improves the throughput of equipment.
Another main purpose of the present invention is to improve P
2O
5Fodder/ fertilizer ratio, thereby further reduce the unit calcium hydrogen phosphate fodder produce in the consumption of sulfuric acid and rock phosphate in powder.
In order to realize above-mentioned first goal of the invention, the present invention has taked following technical measures: with the fresh phosphoric of producing phosphorus ore is carried out predecomposition, add then flocculant, carry out again sedimentation separation, isolated phosphate ore pulp prepares phosphoric acid by wet process with sulfuric acid extractive reaction, filtration again, isolated phosphoric acid and milk of lime carry out preneutralization, the preneutralization slip is through separating, solid is as white fertile, isolated liquid is led neutralization with milk of lime again, among the master with slip through separating, the solid drying is the finished product feedstuff calcium monohydrogen phosphate, mother liquor can be recycled.
Hydrogen ion in the fresh phosphoric is neutralized in the pre-neutralization of phosphoric acid and milk of lime and main neutral reaction process, production to calcium hydrogen phosphate fodder does not produce any effect, with fresh phosphoric phosphorus ore is carried out predecomposition, can utilize the hydrogen ion in the phosphoric acid to remove impurity such as part calcium, iron, aluminium, magnesium, carbonic acid gas, thereby reduced the consumption that phosphorus ore is carried out extractive reaction with sulfuric acid, impurity such as magnesium contained in the phosphoric acid extraction, iron, aluminium have also been reduced, also improve simultaneously the strainability of extraction slip, improved equipment capacity.
For second purpose of the present invention, the present invention can realize by taking following technical measures: preneutralization is divided into twice finishes, for the first time preneutralization control pH value is 2.40～2.70, in with slip through separating, solid is as white fertile, liquid carries out the preneutralization second time, the control pH value is 3.00～3.20, for the second time preneutralization slip is through separating, thick slurry turns back to before for the first time preneutralization, dissolve with the phosphoric acid of processing phosphorus ore, lysate enters for the first time preneutralization groove and participates in preneutralization, and isolated thin liquid is led neutralization again.Preneutralization is divided into twice finishes, by the pH value of control secondary preneutralization, and the isolated thick slurry of preneutralization slip turns back to before for the first time preneutralization for the second time, dissolves with the phosphoric acid of processing phosphorus ore, can greatly reduce P in the white fertilizer
2O
5Content improves P in the calcium hydrogen phosphate fodder
2O
5Content can improve P
2O
5Fodder/ fertilizer ratio.
In order to realize purpose of the present invention better, the present invention has also taked following technical measures: the flocculation agent that is added in the pretreated phosphorus ore slurry of phosphorolytic cleavage is a polyacrylamide, the concentration of flocculation agent is 5～15ppm, and the phosphorus ore slurry carries out settlement separate, and the settling time is 1.5～2.5 hours.
Filtering separation is adopted in the separation of the slip of pre-neutralization for the first time, and the slip of pre-neutralization for the second time adopts settlement separate, and the settled time is 1.5～2.0 hours.
Compared with the prior art the effect of industrial production experiment of the present invention has significant technical progress.The phosphorus ore preconditioning technique that the present invention invented reduces the extraction process sulfuric acid consumption greatly, compare with conventional feed secondary calcium phosphate production technology, the sulfuric acid consumption of product per ton directly reduces 150kg to 200kg, and extraction slurry filtration performance has also obtained large increase, make the throughput of equipment increase more than 30%, make also simultaneously that impurity such as contained magnesium, iron, aluminium greatly reduce in the extraction phosphoric acid by wet process, enlarged application prospect.Another key technology of the present invention is preneutralization to be divided into twice finish, and the phosphoric acid dissolving of processing phosphorus ore of the thick slurry of for the second time preneutralization separation, and circulation neutralization decomposition is carried out defluorinate, thereby technical indicator is improved greatly, P
2O
5Fodder/ fertilizer ratio reach 85: 15 to 90: 10, again widely improved a step at 75: 25 than the highest fodder/ fertilizer ratio of second prior art document record, improved the calcium hydrogen phosphate fodder productive rate, further greatly reduce again the consumption of unit product sulfuric acid and phosphorus ore simultaneously.
Provide below one embodiment of the present of invention, by embodiment invention is described in further detail.
With in low-grade rock phosphate in powder be ground into moisture 30% phosphate ore pulp with ball mill, produce phosphoric acid by wet process with phosphate ore pulp and sulfuric acid extractive reaction earlier, with the phosphoric acid produced phosphate ore pulp is decomposed preliminary treatment thereupon, utilize hydrogen ion in the phosphoric acid to remove the impurity such as part calcium in the phosphate ore pulp, iron, aluminium, magnesium, carbon dioxide.Pre-treatment controlling reaction time 1.8 hours adds the 15ppm polyacrylamide flocculant in the pretreated mixed slurry, carry out settlement separately then, and the settling time is 2.2 hours.Separating obtained phosphoric acid enters the secondary calcium phosphate production system, and ore pulp carries out extractive reaction with sulfuric acid again, and the extraction slip obtains phosphoric acid by wet process after filtration, is residue phosphogypsum behind the residue washing.Calcium hydrogen phosphate fodder is that phosphoric acid is produced by the once main neutralization of twice pre-neutralization with milk of lime.Process the separating obtained phosphoric acid of phosphate ore pulp and be used for earlier the isolated thick slurry of the preneutralization second time is dissolved, then this lysate was carried out the preneutralization first time.For the first time preneutralization control pH value is 2: 4, and neutralization reaction was filtered with filter after neutralization is finished about one hour time, and work is white fertile behind the residue washing, and filtrate and washings carry out the preneutralization second time.Secondary pre-neutralization control pH value is 3.10,1 hour reaction times, after neutralization reaction is finished end, to carry out settlement separately, and the settling time is about 1.5 hours.Sedimentation finishes, and clear liquid is led neutralization, and thick slurry turns back to before for the first time preneutralization, is dissolved the circulation neutralization by the phosphoric acid of processing phosphate ore pulp.Main neutralization control pH value is 6.3, and the neutralization reaction time is 1.5 hours.Neutralization reaction finishes, and filters with filter, and the solid oven dry namely obtains the finished product feedstuff calcium monohydrogen phosphate, and mother liquor can return use.The actual effect that reaches is compared with traditional production technique, and product per ton consumes 1.40 tons in sulfuric acid, 1.85 tons of phosphorus ores, and the throughput of filter plant improves 30%.
Claims (4)
1, a kind of calcium hydrogen phosphate fodder production method, prepare phosphoric acid by wet process with sulfuric acid and phosphorus ore extractive reaction, carry out the pre-neutralization reaction with milk of lime and phosphoric acid, the pre-neutralization slip is separated, solid can be used as white fertilizer, with milk of lime liquid is carried out main neutralization reaction again, separate with slip in will leading, mother liquor can be recycled, and the solid drying is prepared into calcium hydrogen phosphate fodder, it is characterized in that before phosphorus ore and sulfuric acid extractive reaction, with the fresh phosphoric of producing phosphorus ore is carried out predecomposition, add flocculation agent then, separate, isolated phosphorus ore slurry prepares phosphoric acid with the sulfuric acid extractive reaction again.
2, calcium hydrogen phosphate fodder production method according to claim 1, it is characterized in that pre-neutralization is divided into twice to be finished, the control of pre-neutralization for the first time pH value is 2.40～2.70, in and slip through separating, solid is as fertilizer in vain, liquid carries out the pre-neutralization second time, the control pH value is 3.00～3.20, and the slip of pre-neutralization for the second time is through separating, and thick slurry returns before the pre-neutralization for the first time, dissolve with the phosphoric acid of handling phosphorus ore, isolated thin liquid is led neutralization again.
3, calcium hydrogen phosphate fodder production method according to claim 1 and 2 is characterized in that flocculation agent is a polyacrylamide, and the concentration of flocculation agent is 5-15ppm, and the phosphorus ore slurry carries out settlement separate, and the settling time is 1.5～2.5 hours.
4, calcium hydrogen phosphate fodder production method according to claim 2 is characterized in that filtering separation is adopted in the separation of the slip of pre-neutralization for the first time, and the separation of the slip of pre-neutralization is for the second time adopted settlement separate, and the settled time is 1.5～2.0 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113038A CN1045423C (en) | 1995-10-20 | 1995-10-20 | Method for producing feed calcium hydrogen phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113038A CN1045423C (en) | 1995-10-20 | 1995-10-20 | Method for producing feed calcium hydrogen phosphate |
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| CN1183378A true CN1183378A (en) | 1998-06-03 |
| CN1045423C CN1045423C (en) | 1999-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95113038A Expired - Fee Related CN1045423C (en) | 1995-10-20 | 1995-10-20 | Method for producing feed calcium hydrogen phosphate |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343200B (en) * | 2008-09-09 | 2011-05-04 | 中国-阿拉伯化肥有限公司 | Method for preparing sulphur based compound fertilizer by decomposing rock phosphate with hydrogen nitrate and system thereof |
| CN101613229B (en) * | 2009-08-05 | 2012-09-19 | 中国-阿拉伯化肥有限公司 | Improved method for preparing sulfur base fertilizer |
| CN102849703A (en) * | 2012-09-07 | 2013-01-02 | 四川大学 | Method for preparing fine calcium phosphate by using phosphogypsum desulfurization residue |
| CN102897736A (en) * | 2012-11-12 | 2013-01-30 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing calcium hydrophosphate by utilizing wastewater of gelatin production |
| WO2013174061A1 (en) * | 2012-05-25 | 2013-11-28 | 四川龙蟒磷化工有限公司 | Method for preparing high quality feed grade calcium hydrogen phosphate using by-product waste acid from titanium dioxide production |
| CN103803520A (en) * | 2014-02-27 | 2014-05-21 | 武汉工程大学 | Production method for feed-grade calcium monohydrogenphosphate |
| CN105905878A (en) * | 2016-05-30 | 2016-08-31 | 禄丰天宝磷化工有限公司 | Process for producing food-grade calcium hydrophosphate |
| CN106006595A (en) * | 2016-05-30 | 2016-10-12 | 禄丰天宝磷化工有限公司 | Method for making calcium hydrogen phosphate and phosphorus-containing fertilizer by comprehensively utilizing phosphate ore |
| CN106044733A (en) * | 2016-06-05 | 2016-10-26 | 禄丰天宝磷化工有限公司 | Novel method for removing arsenic in phosphorite-produced calcium hydrophosphate |
| CN106044732A (en) * | 2016-06-05 | 2016-10-26 | 禄丰天宝磷化工有限公司 | Method for preparing calcium hydrophosphate through double-acidolysis of phosphorite |
| CN106115641A (en) * | 2016-05-23 | 2016-11-16 | 禄丰天宝磷化工有限公司 | A kind of remove the technique of impurity in calcium hydrogen phosphate |
| CN107128889A (en) * | 2017-05-12 | 2017-09-05 | 湖北三宁化工股份有限公司 | A kind of decomposing phosphate rock by chlorhydric acid produces the system and technique of calcium hydrophosphate fodder |
| CN107188145A (en) * | 2016-03-14 | 2017-09-22 | 姚鼎文 | The method that one kind makes industrial potassium dihydrogen phosphate with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system |
| CN108328590A (en) * | 2018-03-29 | 2018-07-27 | 中化化肥有限公司成都研发中心 | The method for preparing synthos co-production industrial monoammonium phosphate |
| CN113233438A (en) * | 2021-06-15 | 2021-08-10 | 瓮福（集团）有限责任公司 | Method for controlling arsenic and increasing yield of calcium hydrophosphate product |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2372118A1 (en) * | 1976-11-30 | 1978-06-23 | Prod Chimique Montagne Noire | NEW METHODS OF MANUFACTURING PHOSPHORIC ACIDS BY WET METHODS |
| CN1038251A (en) * | 1988-06-02 | 1989-12-27 | 哈尔滨市化工十三厂 | Produce the method for calcium hydrogen phosphate fodder with ground phosphate rock |
| SU1692934A1 (en) * | 1988-08-15 | 1991-11-23 | Самаркандский Химический Завод Им.Хху Съезда Кпсс | Method of producing phosphoric acid |
| CN1048015A (en) * | 1990-02-17 | 1990-12-26 | 云南易门矿务局 | Low ratio acid wet method is produced calcium hydrophosphate fodder |
| CN1091392A (en) * | 1993-02-25 | 1994-08-31 | 张小平 | A kind of method of producing calcium hydrogen phosphate fodder |
-
1995
- 1995-10-20 CN CN95113038A patent/CN1045423C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343200B (en) * | 2008-09-09 | 2011-05-04 | 中国-阿拉伯化肥有限公司 | Method for preparing sulphur based compound fertilizer by decomposing rock phosphate with hydrogen nitrate and system thereof |
| CN101613229B (en) * | 2009-08-05 | 2012-09-19 | 中国-阿拉伯化肥有限公司 | Improved method for preparing sulfur base fertilizer |
| WO2013174061A1 (en) * | 2012-05-25 | 2013-11-28 | 四川龙蟒磷化工有限公司 | Method for preparing high quality feed grade calcium hydrogen phosphate using by-product waste acid from titanium dioxide production |
| CN102849703A (en) * | 2012-09-07 | 2013-01-02 | 四川大学 | Method for preparing fine calcium phosphate by using phosphogypsum desulfurization residue |
| CN102897736A (en) * | 2012-11-12 | 2013-01-30 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing calcium hydrophosphate by utilizing wastewater of gelatin production |
| CN103803520A (en) * | 2014-02-27 | 2014-05-21 | 武汉工程大学 | Production method for feed-grade calcium monohydrogenphosphate |
| CN103803520B (en) * | 2014-02-27 | 2015-06-24 | 武汉工程大学 | Production method for feed-grade calcium monohydrogenphosphate |
| CN107188145A (en) * | 2016-03-14 | 2017-09-22 | 姚鼎文 | The method that one kind makes industrial potassium dihydrogen phosphate with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system |
| CN106115641A (en) * | 2016-05-23 | 2016-11-16 | 禄丰天宝磷化工有限公司 | A kind of remove the technique of impurity in calcium hydrogen phosphate |
| CN106006595A (en) * | 2016-05-30 | 2016-10-12 | 禄丰天宝磷化工有限公司 | Method for making calcium hydrogen phosphate and phosphorus-containing fertilizer by comprehensively utilizing phosphate ore |
| CN105905878A (en) * | 2016-05-30 | 2016-08-31 | 禄丰天宝磷化工有限公司 | Process for producing food-grade calcium hydrophosphate |
| CN106044732A (en) * | 2016-06-05 | 2016-10-26 | 禄丰天宝磷化工有限公司 | Method for preparing calcium hydrophosphate through double-acidolysis of phosphorite |
| CN106044733A (en) * | 2016-06-05 | 2016-10-26 | 禄丰天宝磷化工有限公司 | Novel method for removing arsenic in phosphorite-produced calcium hydrophosphate |
| CN106044732B (en) * | 2016-06-05 | 2018-06-08 | 禄丰天宝磷化工有限公司 | A kind of method that double phosphate rock-sulfuric acids make calcium monohydrogen phosphate |
| CN107128889A (en) * | 2017-05-12 | 2017-09-05 | 湖北三宁化工股份有限公司 | A kind of decomposing phosphate rock by chlorhydric acid produces the system and technique of calcium hydrophosphate fodder |
| CN107128889B (en) * | 2017-05-12 | 2019-09-24 | 湖北三宁化工股份有限公司 | A kind of decomposing phosphate rock by chlorhydric acid produces the system and technique of calcium hydrophosphate fodder |
| CN108328590A (en) * | 2018-03-29 | 2018-07-27 | 中化化肥有限公司成都研发中心 | The method for preparing synthos co-production industrial monoammonium phosphate |
| CN113233438A (en) * | 2021-06-15 | 2021-08-10 | 瓮福（集团）有限责任公司 | Method for controlling arsenic and increasing yield of calcium hydrophosphate product |
| CN113233438B (en) * | 2021-06-15 | 2022-11-01 | 瓮福（集团）有限责任公司 | Method for controlling arsenic and increasing yield of calcium hydrophosphate product |
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| Publication number | Publication date |
|---|---|
| CN1045423C (en) | 1999-10-06 |
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