CN1239706A - One-step fluidized phosphoric acid spraying process for producing calcium phosphate - Google Patents
One-step fluidized phosphoric acid spraying process for producing calcium phosphate Download PDFInfo
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- CN1239706A CN1239706A CN 98112087 CN98112087A CN1239706A CN 1239706 A CN1239706 A CN 1239706A CN 98112087 CN98112087 CN 98112087 CN 98112087 A CN98112087 A CN 98112087A CN 1239706 A CN1239706 A CN 1239706A
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- calcium phosphate
- phosphoric acid
- fluidized bed
- cahpo
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Abstract
The process of producing calcium phosphate from phosphoric acid and lime or limestone powder has the technological feature that the whole phosphoric acid-spraying and powder fluidizing, mixing and reacting process from feeding to discharging loose granular product is completed inside one full-enclosed vibrating fluid bed. Compared with the prior art, the process eliminates certain technological steps and equipment, e. q. dewatering, drying, crushing, sieving or pelletizing. The present invention makes it possible to produce following products in one identical equipment: CaHPO4.2H2O, CaHPO4, Ca(H2PO4)2.H2O and Ca(H2PO4)2.
Description
The present invention relates to a kind of method of producing calcium phosphate, particularly relate to the dicalcium phosphate dihydrate CaHPO that is used for feed, food, medicine, toothpaste and electronic material
42H
2O, calcium phosphate dibasic anhydrous CaHPO
4, a water monocalcium phosphate Ca (H
2PO
4)
2H
2O and anhydrous dihydro calcium phosphate Ca (H
2PO
4)
2Production Deng calcium phosphate.
Existing dicalcium phosphate dihydrate CaHPO
42H
2The production method of O mainly contains wet method and dry method two classes.Wet method is divided into the two sections precipitator method (Wang Lisheng that the employing phosphoric acid by wet process is raised fertile coproduction again, Wan Xianda, multiple fertilizer of Liao Hua book phosphorus and phosphating processes are learned, press of Chengdu Univ. of Science ﹠ Technology, 1993, p..334～335) and adopt thermal phosphoric acid one section continuous precipitation (И. Н. П о с т н й к о в work, Cai's filial piety is worn and is translated salt and the fertilizer of thermal phosphoric acid for the basis, Chemical Industry Press, 1976, p.232～243), its common feature is to make phosphoric acid and limestone powder suspension or milk of lime reaction generate dicalcium phosphate dihydrate CaHPO
42H
2The O crystallization.Row is dry again after reaction is reached home or behind spraying drying or the filter dehydration, and drying temperature does not allow above 100 ℃.This method time-continuing process is long, and required equipment is many, complicated operation, and the last stage reaction solid particles surface is wrapped up by impervious product crystalline membrane, and speed of response is extremely slow, and the exsiccant energy consumption is also high.Existing dry process mainly is to adopt the thermal phosphoric acid of high density directly to mix afterreaction and ageing with limestone powder or lime powder in intensively stirred mixing machine, needs remix between aging period.Material after the slaking is through rotary kiln drying, and crusher is pulverized, and obtains product (Chen Jiapu, Tan Guang smoke phosphatic production of chief editor and application, press of Chengdu Univ. of Science ﹠ Technology, 1989, p.120～121) after the screening.This method also needs more equipment and production site, the production cycle of growing and higher energy consumption, although feed intake accurately measure control, liquid-solid two-phase is difficult to thorough mixing thereby the thorough product composition complexity of reaction, also may contain more free phosphoric acid.
Existing calcium phosphate dibasic anhydrous CaHPO
4Production method mainly be to obtain exsiccant dicalcium phosphate dihydrate CaHPO
42H
2Sloughing crystal water after the O crystallization under 115～120 ℃ of temperature forms.
An existing water monocalcium phosphate Ca (H
2PO
4)
2H
2The production method of O has wet method and dry method two classes.Wet method (US1818114; Kirk-Othmer, Encyclopedia of Chemical Technology, 3
RdEd., mainly be to adopt phosphoric acid and milk of lime neutral solvent or diluent slurry spraying drying or pasty state slip rotary drying, fragmentation, screening to obtain product Vol.17, p.467～468).This method required equipment is many, the energy consumption for drying height.Dry method (the M.E. ripple is appointed inorganic salt technology, Chemical Industry Press, and 1981, p.181; CN1076592) be under intensive mechanically mixing condition, to make the phosphoric acid of 60% above concentration and lime or limestone powder neutralization, obtain product after the dough drying of generation, levigate, the screening.This method also needs more equipment and production site, long production cycle, although feed intake accurately measure control, liquid-solid two-phase is difficult to thorough mixing thereby reaction is not thorough, and quality product is not easy to control, and contains a certain amount of dicalcium phosphate dihydrate CaHPO usually
42H
2O or free phosphoric acid.
Existing anhydrous dihydro calcium phosphate Ca (H
2PO
4)
4Production method mainly be to obtain exsiccant one water monocalcium phosphate Ca (H
2PO
4)
2H
2Sloughing crystal water after the O crystallization under 125～140 ℃ of temperature forms.
It is the method for the one-step fluidized phosphoric acid spraying production calcium phosphate of raw material that the present invention discloses a kind of phosphoric acid and limestone powder or lime powder of adopting, purpose be make from metering feed intake beginning till product output all production processes all same totally enclosed vibrated fluidized bed serialization carry out, and adjust feed ratio easily and process operation parameter is that available same table apparatus is produced dicalcium phosphate dihydrate CaHPO
42H
2O, calcium phosphate dibasic anhydrous CaHPO
4, a water monocalcium phosphate Ca (H
2PO
4)
2H
2O and anhydrous dihydro calcium phosphate Ca (H
2PO
4)
2Deng the tricalcium orthophosphate product salt, product is even, loose, good fluidity.
Main invention thought of the present invention is the gas-liquid-solid three-phase reaction system of phosphoric acid, lime or limestone powder that constitutes the high dispersive performance.Phosphoric acid spraying that proposes and lime or limestone powder gas-solid fluidization reaction system can be distributed to the almost solid particles surface of each participation reaction to liquid medium equably, and the result of reaction emits CO
2Easily the effusion surface enters gas phase, thereby the porous surface layer of formation comes off easily and makes Surface Renewal, therefore has very high speed of reaction.This system solid phase has good flowability simultaneously, makes that finishing reacted material keeps its fluidized state directly to carry out drying, carries out comminution by gas stream then equally and meets the requirements of granularity under fluidized state.
Principal feature of the present invention is to realize above-mentioned whole invention thoughts in the separate unit vibrated fluidized bed, as accompanying drawing 1.And adjust feed ratio easily and process operation parameter can be produced dicalcium phosphate dihydrate CaHPO in same table apparatus
42H
2O, calcium phosphate dibasic anhydrous CaHPO
4, a water monocalcium phosphate Ca (H
2PO
4)
2H
2O and anhydrous dihydro calcium phosphate Ca (H
2PO
4)
2Deng the tricalcium orthophosphate product salt, product is even, loose, good fluidity.
Technical essential of the present invention is that the full scale production process is all finished in the vibrated fluidized bed of same division operation, as accompanying drawing 1.The phosphoric acid that foreign matter content meets the requirements, measures (55～85%) mixes the back slave unit with lime that measures or limestone powder (20～120 μ m) after two fluid-type nozzle atomizations a end enters bed, finish reaction, dry and pulverizing by bed Nei Ge district continuously successively, the other end of finished product slave unit is discharged continuously, directly carries out metering packing.Divide three the road to enter bed after air heating, the temperature adjustment, cause powder dust separating device through house steward, reach emptying after the environmental requirement by the bed top from the bottom.
Compare with existing wet method or dry technique, technical process of the present invention is short, operation steps and equipment are few, the production process serialization is carried out, the level of automation height, and labour intensity is little, energy consumption and process cost are low, install compact totally-enclosed non-environmental-pollution, to raw material phosphoric acid concentration subject range broadness, 55%～85% concentration all can.Therefore can reduce production costs greatly, facility investment is reduced by at least 1/3.
Provide embodiments of the invention below in conjunction with accompanying drawing 1, and the present invention is described in further detail by embodiment.
Embodiment 1: produce dicalcium phosphate dihydrate CaHPO
42H
2The 55% mud phosphoric acid (fluorine, arsenic and heavy metal content meet food or feed request) that O 1. purifies from storage tank 1 through under meter 2 metering backs with (w: ratio w) enters vibrated fluidized bed 6 behind the pressurized air thorough mixing by 0.2～0.5MPa in spray mixing device 5 (I) distinguished in 180: 100 through the limestone dust (20～120 μ m, fluorine, arsenic and heavy metal content meet food or feed request) of metered charge device 4 from hopper 3; 2. fierce neutralization reaction takes place in (I) district of vibrated fluidized bed 6 in mixture, emits carbonic acid gas, generates dicalcium phosphate dihydrate CaHPO
42H
2The crystallization of O; The warm air of heater via 8 enters (I) district of vibrated fluidized bed 6 by freezing air by-pass temperature adjustment to 100～110 ℃ by the bottom, and superficial gas velocity 0.4～0.8m/s keeps the fluidization in this district; 3. material is finished the reaction back in (I) district and is flowed into (II) district automatically, the warm air of heater via 8 enters (II) district of vibrated fluidized bed 6 by freezing air by-pass temperature adjustment to 90～100 ℃ by the bottom, and superficial gas velocity 0.3～0.6m/s keeps the fluidization in this district and makes dry materials; 4. dried material flows into (III) district automatically by (II) district, freezing air is entered (III) district of vibrated fluidized bed 6 by the bottom, superficial gas velocity 0.2～0.4m/s keeps the fluidization in this district and makes the material cooling, is expelled to metering packing device 7 below compressed air jet comminuting matter to the 100 μ m of introducing 0.5～1.0MPa; 5. the gas that will contain dust by bed top effuser causes separator 9, and gas reaches emptying after the emission standard, and the dust of collecting can be used as product.The product dicalcium phosphate dihydrate CaHPO that obtains
42H
2O is the loose spherical granules of granularity less than 100 μ m, and main content is greater than 98% (butt), and water-content is less than 3%, and fluorine, arsenic and heavy metal content meet food or feed request.Embodiment 2: produce calcium phosphate dibasic anhydrous CaHPO
4
Embodiment 2 produces calcium phosphate dibasic anhydrous CaHPO
4Step and embodiment 1 produce dicalcium phosphate dihydrate CaHPO
42H
2The step of O is identical.The operating parameters of each step removes air that the 3rd step entered vibrated fluidized bed 6 (II) district by the bottom and wants temperature adjustment to 115～120 ℃ to slough dicalcium phosphate dihydrate CaHPO
42H
2Two molecular crystal water among the O make it to be converted into calcium phosphate dibasic anhydrous CaHPO
4Product is and outer, and other is also identical.The product calcium phosphate dibasic anhydrous CaHPO that obtains
4Be the loose spherical granules of granularity less than 100 μ m, main content is greater than 98% (butt), and water-content is less than 3%, and fluorine, arsenic and heavy metal content meet food or feed request.Embodiment 3: produce a water monocalcium phosphate Ca (H
2PO
4)
2H
2O1. 85% thermal phosphoric acid (fluorine, arsenic and heavy metal content meet food or feed request) that purifies from storage tank 1 through under meter 2 metering backs with (w: ratio w) enters vibrated fluidized bed 6 behind the pressurized air thorough mixing by 0.2～0.5MPa in spray mixing device 5 (I) distinguished in 235: 100 through the limestone dust (20～120 μ m, fluorine, arsenic and heavy metal content meet food or feed request) of metered charge device 4 from hopper 3; 2. fierce neutralization reaction takes place in (I) district of vibrated fluidized bed 6 in mixture, emits carbonic acid gas, generates a water monocalcium phosphate Ca (H
2PO
4)
2H
2The crystallization of O; The warm air of heater via 8 enters (I) district of vibrated fluidized bed 6 by freezing air by-pass temperature adjustment to 100～110 ℃ by the bottom, and superficial gas velocity 0.4～0.8m/s keeps the fluidization in this district; 3. material is finished the reaction back in (I) district and is flowed into (II) district automatically, the warm air of heater via 8 enters (II) district of vibrated fluidized bed 6 by freezing air by-pass temperature adjustment to 80～90 ℃ by the bottom, and superficial gas velocity 0.3～0.6m/s keeps the fluidization in this district and makes dry materials; 4. dried material flows into (III) district automatically by (II) district, freezing air is entered (III) district of vibrated fluidized bed 6 by the bottom, superficial gas velocity 0.2～0.4m/s keeps the fluidization in this district and makes the material cooling, is expelled to metering packing device 7 below compressed air jet comminuting matter to the 100 μ m of introducing 0.5～1.0MPa; 5. the gas that will contain dust by bed top effuser causes separator 9, and gas reaches emptying after the emission standard, and the dust of collecting can be used as product.The product one water monocalcium phosphate Ca (H that obtains
2PO
4)
2H
2O is the loose spherical granules of granularity less than 100 μ m, and main content is greater than 98% (butt), and water-content is less than 3%, and fluorine, arsenic and heavy metal content meet food or feed request.Embodiment 4: produce anhydrous dihydro calcium phosphate Ca (H
2PO
4)
2
Embodiment 4 produces anhydrous dihydro calcium phosphate Ca (H
2PO
4)
2Step and embodiment 3 produce a water monocalcium phosphate Ca (H
2PO
4)
2H
2The step of O is identical.The operating parameters of each step removes air that the 3rd step entered vibrated fluidized bed 6 (II) district by the bottom and wants temperature adjustment to 125～135 ℃ to slough a water monocalcium phosphate Ca (H
2PO
4)
2H
2A part crystal water among the O makes it to be converted into anhydrous dihydro calcium phosphate Ca (H
2PO
4)
2Product is and outer, and other is also identical.The product anhydrous dihydro calcium phosphate Ca (H that obtains
2PO
4)
2Be the loose spherical granules of granularity less than 100 μ m, main content is greater than 98% (butt), and water-content is less than 3%, and fluorine, arsenic and heavy metal content meet food or feed request.
Claims (4)
1. method of producing calcium phosphate, product comprises: dicalcium phosphate dihydrate CaHPO
42H
2O, calcium phosphate dibasic anhydrous CaHPO
4, a water monocalcium phosphate Ca (H
2PO
4)
2H
2O and anhydrous dihydro calcium phosphate Ca (H
2PO
4)
2Lime or the direct hybrid reaction of limestone powder of 50～80% hot methods of employing or phosphoric acid by wet process and 20～120 μ m, the mixing, reaction, ageing, drying, the pulverizing that it is characterized in that collecting raw material phosphoric acid and solid-phase material are a step, the full scale production process all in a vibrated fluidized bed serialization carry out, totally-enclosed non-environmental-pollution is installed in no returning charge.
2. the method for production calcium phosphate according to claim 1 is characterized in that realizing phosphoric acid spraying and solid phase powder material uniform mixing, does not lump, the heterogeneous fluidization of sticking wall.
3. the method for production calcium phosphate according to claim 1 and 2 is characterized in that satisfying phosphoric acid and lime or limestone powder neutralization reaction, ageing, drying, the vibrated fluidized bed partitioned method of the required residence time of pulverizing.
4. the method for production calcium phosphate according to claim 1 and 2 is characterized in that introducing comminution by gas stream and makes product reach required fineness in vibrated fluidized bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98112087 CN1117698C (en) | 1998-06-18 | 1998-06-18 | One-step fluidized phosphoric acid spraying process for producing calcium phosphate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98112087 CN1117698C (en) | 1998-06-18 | 1998-06-18 | One-step fluidized phosphoric acid spraying process for producing calcium phosphate |
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| Publication Number | Publication Date |
|---|---|
| CN1239706A true CN1239706A (en) | 1999-12-29 |
| CN1117698C CN1117698C (en) | 2003-08-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98112087 Expired - Fee Related CN1117698C (en) | 1998-06-18 | 1998-06-18 | One-step fluidized phosphoric acid spraying process for producing calcium phosphate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849704A (en) * | 2012-09-14 | 2013-01-02 | 石棉县亿欣钙业有限责任公司 | Method of using calcium carbonate to produce calcium phosphate and monocalcium phosphate |
| CN103449393A (en) * | 2013-08-21 | 2013-12-18 | 瓮福（集团）有限责任公司 | Feed-grade dicalcium phosphate production device |
| CN106395779A (en) * | 2016-08-31 | 2017-02-15 | 连云港东泰食品配料有限公司 | Calcium hydrophosphate preparation method |
| CN110075779A (en) * | 2019-05-31 | 2019-08-02 | 昆明理工大学 | A kind of injection reactor and calcium monohydrogen phosphate, nanometer or micro-powder synthetic method for powder body material synthesis |
| CN113945069A (en) * | 2021-09-15 | 2022-01-18 | 朱双权 | Vibration dryer for bio-pharmaceuticals |
-
1998
- 1998-06-18 CN CN 98112087 patent/CN1117698C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849704A (en) * | 2012-09-14 | 2013-01-02 | 石棉县亿欣钙业有限责任公司 | Method of using calcium carbonate to produce calcium phosphate and monocalcium phosphate |
| CN103449393A (en) * | 2013-08-21 | 2013-12-18 | 瓮福（集团）有限责任公司 | Feed-grade dicalcium phosphate production device |
| CN106395779A (en) * | 2016-08-31 | 2017-02-15 | 连云港东泰食品配料有限公司 | Calcium hydrophosphate preparation method |
| CN110075779A (en) * | 2019-05-31 | 2019-08-02 | 昆明理工大学 | A kind of injection reactor and calcium monohydrogen phosphate, nanometer or micro-powder synthetic method for powder body material synthesis |
| CN110075779B (en) * | 2019-05-31 | 2024-02-09 | 昆明理工大学 | Jet reactor for powder material synthesis and powder synthesis method |
| CN113945069A (en) * | 2021-09-15 | 2022-01-18 | 朱双权 | Vibration dryer for bio-pharmaceuticals |
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| Publication number | Publication date |
|---|---|
| CN1117698C (en) | 2003-08-13 |
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