CN1196332A - High-temp hydrolytic delluorinating method and device for producing feed-grade calcium hydrogen phosphate from phosphoric acid by using wet process. - Google Patents
High-temp hydrolytic delluorinating method and device for producing feed-grade calcium hydrogen phosphate from phosphoric acid by using wet process. Download PDFInfo
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- CN1196332A CN1196332A CN 98107233 CN98107233A CN1196332A CN 1196332 A CN1196332 A CN 1196332A CN 98107233 CN98107233 CN 98107233 CN 98107233 A CN98107233 A CN 98107233A CN 1196332 A CN1196332 A CN 1196332A
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Abstract
A high-temp hydrolysis process for removing fluorine in order to produce feed-grade feed-grade calcium hydrogen phosphate using wet phosphoric acid process features that such apparatuses as reactor, heat-conducting oil boiler, heater, drop separator and washing tower, and such technological steps as phosphoric acid step, heat-conducting oil step, and steam and dried hot wind step are used to reduce the fluorine conten in phospheric acid medium to minimum. Its advantages are no loss of P2O5, recovery nearly 100% deeply removing fluorine (0.05-0.1% of fluorine content).
Description
The present invention relates to chemical technology field, is a kind of method and apparatus that utilizes the pyrohydrolysis defluorination process to produce calcium hydrophosphate fodder.
In all feed phosphates, calcium hydrophosphate fodder is that a kind of raising imitated chemical combination material additive preferably at present, because fluorine is harmful to animal and human's body, so calcium hydrophosphate fodder has the requirement of strictness to the content of fluorine.It is the precipitator method of defluorinating agent that prior art wet defluorination of phosphoric acid method generally adopts the sylvite or the salt of receiving, or uses milk of lime neutralization, sedimentation and filtration method, but this class methods defluorinate rate is not high, P
2O
5Loss is big, as " development of fodder additives secondary calcium phosphate " of the 21st volume third phase of Central China Normal University's journal (1987) report.Use decomposing phosphate rock by chlorhydric acid, add the saturated aqueous common salt defluorinate, carry out one section neutralization and further defluorinate again, carry out two sections neutralizations thereafter and obtain calcium hydrophosphate fodder, feed P
2O
5The rate of recovery the highlyest can only reach 57.4%." feedstuff calcium hydrogen phosphate production by defluorination with gravity floatation " of Chinese patent Granted publication CN1022556C and for example, this method defluorinate P
2O
5The rate of recovery also can only reach 80%, also have 20% P
2O
5Can not reclaim, can only make at a low price fertilizer, as do degree of depth defluorinate and will further increase product cost and difficulty.
The objective of the invention is to overcome above-mentioned shortcoming, provide a kind of and need not add any defluorinating agent, just can obtain to reach the quality products of super GB.
Defluorinate scheme of the present invention realizes by phosphoric acid flow process, thermal oil flow process, steam flow process, hot dry wind flow process and waste gas flow process.In the phosphoric acid flow process, with sour pump phosphoric acid to be sent into reactor and heat concentrated and the defluorinate of feeding steam, reactor is a microscler tank body, is shaped on heating coil in the still, and skin is provided with heating jacket, and steam pipeline and bubbler are equipped with in the centre.Thermal oil is sent thermal oil into the reactor coil heater by geared oil pump after coil heater improves oily temperature once more after the heating boiler heating, after the acid medium heat exchange, flow into heat-conducting oil heating boiler circulation heating more again in reacting kettle jacketing and reactor.The back survey that is positioned at the heat conduction oil cauldron is provided with steam and divides gas bag, in the heat conduction oil cauldron, be provided with the steam helical pipe, the rear side of heat conduction oil cauldron is provided with coil pipe type well heater and tube still heater successively, vapour pipe is through the steam helical pipe, tube still heater is installed on the pipe core of reactor, and bubbler is equipped with in the bottom of pipe core.Divide steam that gas bag sends here through the helical pipe heat temperature raising by boiler, enter the reactor bubbler after heating up once more by tube still heater again and carry out the steam bubbling, make that medium heats up in the still, concentrate, stir defluorinate.Trailing plants thatch gas blower is housed on the pipeline of steam, before reactor medium temperature 100-105 degree, can advances heated dry air,, accelerate to concentrate so that to the evaporation of stirring, heat up of acid medium bubbling in the still by trailing plants thatch blower fan drum.Right side at reactor is provided with droplet separator, induced draft fan and washing tower.Phosphoric acid after the reactor defluorinate is put into clean sour storage tank, and waste gas is discharged behind droplet separator, washing tower isolation of purified outside the tower, and waste liquid is put into storage tank and reclaimed to be processed pair of product.
Advantage of the present invention is that 1. design is scientific and reasonable, and process safety is reliable; 2. rate of recovery height can make the P in the calcium hydrophosphate fodder
2O
5The rate of recovery will reach 100%; 3. fluorine content is low, makes that fluorine content in the secondary calcium phosphate is minimum to reach (GB is 0.18%) below 0.05%; 4. defluorinate expense is low, only accounts for about 4% of product cost; 5. the recyclable product of paying of fluorochemical.
Be described further below in conjunction with accompanying drawing
The pyrohydrolysis defluorinate device of producing calcium hydrophosphate fodder has been shown in the accompanying drawing, and it is made up of reactor and heat conducting oil boiler, geared oil pump, coil pipe type well heater, tube still heater, droplet separator, washing tower etc.Feed-pipe 15 is equipped with in tank body upper end at reactor, and sour pump 19 is housed on the feed pipe, and the suction pipe of sour pump is installed in the phosphoric acid storage tank 20.The bottom of tank body is equipped with that discharging cuts down 18, discharge nozzle 29, and discharge nozzle feeds in the clean sour storage tank 27.Be provided with heat-conducting oil heating coiled pipe 12 in the microscler tank body of reactor, the oil-in 13 of heating coil connects heat-conducting oil pipes 5, and heat-conducting oil pipes leads in heat conduction oil cauldron 1 through coil pipe type well heater 8, geared oil pump 7.Thermal oil the bottom of a pan bogie side frame is located on the burner hearth, and rear side is a combustion flue 28, and burner hearth is provided with gas blower 26 outward.Coil pipe type well heater 8, tube still heater 9 are installed in the combustion flue, and the rear side of combustion flue is equipped with chimney 10, and the other end of heating coil 12 is connected on the heating jacket 16 of reactor, and used oil pipe 11 is equipped with in the bottom of chuck.Heat conducting oil pipe is provided with pays line 6, in order to reconcile reactor oil temperature.Steam pipeline 4 from minute gas bag is connected on the helical pipe 2, and helical pipe is installed in the heat conduction oil cauldron, is installed on the tube still heater 9 by pipe connecting 4a, is connected on the pipe core of anti-still through steam pipeline 4b again, and bubbler 17 is equipped with in the bottom of pipe core.Steam pipeline is provided with pays line 31, in order to reconcile the reactor vapour temperature.Trailing plants thatch gas blower 3 is equipped with in the left side that is positioned at steam pipeline 4, and the blowing pipeline of gas blower is connected on the steam pipeline.The upper end of reactor is provided with waste gas outlet 14, and pipeline is housed in the outlet, and the other end of pipeline is installed on the droplet separator 21, and induced draft fan 22 is equipped with on the right side of droplet separator, washing tower 23, and the top of washing tower is provided with air outlet 24, and waste gas is discharged thus.The lower end is provided with sewage draining exit 25.Washing water are following to the top of tower spray through 32 dozens of pumps, discharged by sewage draining exit 25.
Technical process of the present invention is: A, phosphoric acid flow process: with the f content 1-3% in the phosphoric acid storage tank 20, the liquid extraction phosphoric acid of acid concentration 35-40% is extracted into the concentrated and feeding steam defluorinate of heating in the anti-still by sour pump 19.B, thermal oil flow process: be to be that thermal barrier comes the indirect heating medium with the thermal oil, realize the purpose of medium high temperature defluorinate.Thermal oil is extracted out by geared oil pump 7 from oil cauldron 1 heating back, enter coil pipe type well heater 8 by heat-conducting oil pipes 5 and carry out second-heating, make oily temperature reach the 200-250 degree and enter reactor heating coil 12 internal heating again, thermal oil flows into heating kettle circulation heating through reacting kettle jacketing 16, used oil pipe 11 again.C, steam flow process: be to make phosphoric acid medium lead to the purpose that superheated vapo(u)r into or saturated vapo(u)r are realized the defluorinate of medium pyrohydrolysis.From minute gas bag pressure is 1-1.5kg/cm
2Steam is sent into helical pipe 2 heat temperature raisings in the oil cauldron by pipeline 4, sending into tube still heater 9 through pipe connecting 4a more further heats up, making vapour temperature bring up to 200-250 sends into reactor pipe core bubbler 17 through steam pipeline 4b again and carries out the steam bubbling, make medium intensification in the still, concentrate, stir defluorinate, when acid medium temperature in the still is raised to 120-125 and spends, when the steam total flow is about the 0.5-0.8T/T of medium-weight ratio, after sample examination is up to standard, put into clean sour storage tank 27 by bleeder valve 18.D, hot dry wind flow process: before reactor acid medium temperature 100-105 degree, can advance heated dry air by trailing plants thatch gas blower 3 drums, so that, accelerate to concentrate to acid medium bubbling, stirring, intensification evaporation in the reactor, logical again steam after the 100-105 degree, hot dry wind walks steam pipeline and steam hockets.E waste gas flow process: the upper end of reactor is provided with waste gas outlet 14, and waste gas is sent into washing tower 23 washings, purified by induced draft fan 22 through droplet separator 21.Acid mist drop through droplet separator is separated cuts down 30 by discharging and puts into storage tank.Purified gas has absorbed the hydrogen fluoride gas washings and has put into the storage pond by sewage draining exit 25 by outside the 24 discharging towers of washing tower air outlet.
Claims (8)
1, a kind of pyrohydrolysis defluorination method of Wet-process Phosphoric Acid Production calcium hydrophosphate fodder is realized by phosphoric acid flow process, thermal oil flow process, steam flow process, hot dry wind flow process and waste gas flow process, it is characterized in that:
A, phosphoric acid flow process: by sour pump (19) phosphoric acid extraction is sent into reactor and heat concentrated and the defluorinate of feeding steam; Phosphoric acid after the defluorinate cuts down (18) through discharging and puts into clean sour storage tank;
B, thermal oil flow process: be to be that thermal barrier comes the indirect heating medium with the thermal oil, realize the purpose of medium high temperature defluorinate, thermal oil is after heating oil cauldron (1) heating, after sending coil heater (8) to carry out second-heating heated oil by geared oil pump (7), send into reactor coiled pipe (12) again, reacting kettle jacketing (16) comes heating medium, flows into heating kettle circulation heat temperature raising through used oil pipe (11) again;
C, steam flow process: be to make phosphoric acid medium lead to the purpose that superheated vapo(u)r into or saturated vapo(u)r are realized the defluorinate of medium pyrohydrolysis, from a minute gas bag 1-1.5kg/cm
2Steam send into helical pipe (2) heat temperature raising by steam pipeline (4), after heating up once more by tube still heater (9) again, enter reactor bubbler (17) and carry out the steam bubbling, make that medium heats up in the still, concentrate, stirring, defluorinate;
D, hot dry wind flow process: before reactor medium temperature 100-105 degree, advance heated dry air, so that acid medium bubbling, stirring, intensification evaporation, quickening in the still are concentrated by trailing plants thatch gas blower (3) drum;
E, waste gas flow process: waste gas is discharged by the cat head air outlet behind droplet separator (21), washing tower (23) absorption cleaning, and the washings that contains fluorochemical flows into storage tank and reclaims to be produced pair of product.
2, the pyrohydrolysis defluorination method of Wet-process Phosphoric Acid Production calcium hydrophosphate fodder according to claim 1, it is characterized in that: utilize the thermal oil indirect heating, thermal oil enters the coil pipe type well heater and carries out second-heating, make oily temperature bring up to 200~250 degree, enter the coiled pipe and the chuck of reactor again, make its indirect heating medium.
3, the pyrohydrolysis defluorination method of Wet-process Phosphoric Acid Production calcium hydrophosphate fodder according to claim 1, it is characterized in that: feed vapor water and separate defluorinate, when acid medium temperature in the still rises to 120-125 and spends, sample examination when the steam total flow is the 0.5-0.8T/T of medium-weight ratio is put into storage tank (27) with clean acid after qualified.
4, the pyrohydrolysis defluorination method of Wet-process Phosphoric Acid Production calcium hydrophosphate fodder according to claim 1, it is characterized in that: heating up earlier concentrates, before reactor acid medium 100-105 degree, advance heated dry air by trailing plants thatch gas blower (3) drum, logical again steam after acid medium 100-105 degree, hot dry wind and steam hocket.
5, a kind of pyrohydrolysis device of Wet-process Phosphoric Acid Production calcium hydrophosphate fodder, by reactor, heat conducting oil boiler, geared oil pump, the coil pipe type well heater, tube still heater, composition such as droplet separator and washing tower, it is characterized in that: feed-pipe (15) is equipped with in the tank body upper end of reactor, sour pump (19) is housed on the feed pipe, the suction pipe of acid pump is installed in the phosphoric acid storage tank (20), the bottom of tank body is equipped with discharging and is cut down (18), discharge nozzle (29), discharge nozzle leads in the clean sour storage tank (27), in the tank body of reactor, be provided with heat-conducting oil heating coiled pipe (12), skin is provided with heating jacket (16), steam pipe core and bubbler (17) are equipped with in the centre, and used oil pipe (11) is equipped with in the bottom of chuck.
6, the pyrohydrolysis defluorinate device of Wet-process Phosphoric Acid Production calcium hydrophosphate fodder according to claim 5, it is characterized in that: the oil inlet pipe of reactor heating coil (13) is equipped with heat-conducting oil pipes (5), heat-conducting oil pipes is installed in the heat conduction oil cauldron (1) through coil heater (8), geared oil pump (7), the bottom of heat conduction oil cauldron is provided with burner hearth, the rear portion is provided with combustion flue (28), burner hearth is provided with gas blower (26) outward, coil pipe type well heater (8), tube still heater (9) are housed in the combustion flue, chimney (10) is equipped with at the rear portion of combustion flue, is equipped with on the heat conducting oil pipe to pay line (6).
7, the pyrohydrolysis defluorinate device of Wet-process Phosphoric Acid Production calcium hydrophosphate fodder according to claim 5, it is characterized in that: the steam pipeline (4) from minute gas bag is connected on the helical pipe (2), helical pipe is installed in the heat conduction oil cauldron, be installed on the tube still heater (9) by pipe connecting 4a, be installed on the pipe core of reactor through steam pipeline 4b again, trailing plants thatch gas blower (3) is equipped with in the left side that is positioned at steam pipeline (4), the blowpipe of gas blower is connected on the steam pipeline, is equipped with on the steam pipeline to pay line (31).
8, the pyrohydrolysis defluorinate device of Wet-process Phosphoric Acid Production calcium hydrophosphate fodder according to claim 5, it is characterized in that: droplet separator (21) is equipped with at the rear portion of reactor, the upper end of reactor is provided with waste gas outlet (14), the other end of outlet conduit is connected on the droplet separator, induced draft fan (22) is equipped with at the rear portion of droplet separator, washing tower (23), the upper end of washing tower are provided with air outlet (24), and the lower end is provided with sewage draining exit (25).
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CN98107233A CN1059640C (en) | 1998-04-12 | 1998-04-12 | High-temp hydrolytic delluorinating method and device for producing feed-grade calcium hydrogen phosphate from phosphoric acid by using wet process. |
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CN98107233A CN1059640C (en) | 1998-04-12 | 1998-04-12 | High-temp hydrolytic delluorinating method and device for producing feed-grade calcium hydrogen phosphate from phosphoric acid by using wet process. |
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CN1059640C CN1059640C (en) | 2000-12-20 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106145075A (en) * | 2016-06-30 | 2016-11-23 | 四川大学 | Produce the combined extraction method of high-quality phosphoric acid |
CN109384209A (en) * | 2017-08-08 | 2019-02-26 | 川恒生态科技有限公司 | A method of utilizing hydrochloric acid and Phosphate Rock acid calcium salt |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3427125A (en) * | 1966-04-06 | 1969-02-11 | Central Glass Co Ltd | Process for preparing highly pure calcium hydrogen phosphate dihydrate |
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 |
CN1170517A (en) * | 1996-07-13 | 1998-01-21 | 晏明朗 | Method for producing feed calcium by acid-saving decalcification and defluorination |
-
1998
- 1998-04-12 CN CN98107233A patent/CN1059640C/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106145075A (en) * | 2016-06-30 | 2016-11-23 | 四川大学 | Produce the combined extraction method of high-quality phosphoric acid |
CN106145075B (en) * | 2016-06-30 | 2018-08-21 | 四川大学 | Produce the combined extraction method of high-quality phosphoric acid |
CN109384209A (en) * | 2017-08-08 | 2019-02-26 | 川恒生态科技有限公司 | A method of utilizing hydrochloric acid and Phosphate Rock acid calcium salt |
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