CN101428775A - Method and equipment for producing phosphoric acid with vertical flaming kiln - Google Patents
Method and equipment for producing phosphoric acid with vertical flaming kiln Download PDFInfo
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- CN101428775A CN101428775A CNA2008102367043A CN200810236704A CN101428775A CN 101428775 A CN101428775 A CN 101428775A CN A2008102367043 A CNA2008102367043 A CN A2008102367043A CN 200810236704 A CN200810236704 A CN 200810236704A CN 101428775 A CN101428775 A CN 101428775A
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Abstract
The invention relates to a method for generating phosphoric acid by using a vertical open flame furnace and a device thereof. The method comprises the following steps: adding prepared ball materials and grainy solid fuels in the vertical open flame furnace from the upper part; causing the ball materials and the fuels to move downwards according to self-gravity during the continuous discharging process at the lower part of the furnace; burning the fuels to add the ball materials, so that the ball materials is gradually warmed up to 1200 to 1550 DEG C; oxidizing phosphoric vapor generated by reaction and carbon monoxide after being emitted into phosphorus pentoxide and carbon dioxide in the weak oxidation atmosphere in a material channel; and spraying and absorbing with circulating acid to obtain the high concentration phosphoric acid. The method for generating the phosphoric acid by using the vertical open flame furnace is another feasible route except for tunnel kiln-method phosphoric acid and revolving kiln-method phosphoric acid. The heat generated by oxidizing and burning phosphoric simple substances and the carbon monoxide is immediately conducted to the ball materials in the material channel to supply heat energy required for reduction reaction, so that the energy consumption is greatly saved.
Description
Technical field
The present invention relates to a kind of method with producing phosphoric acid with vertical flaming kiln.
Background technology
The development of phosphoric acid reparation technology so far, its main technique has two kinds: (1) wet method: the higher-grade Rock Phosphate (72Min BPL) is produced phosphoric acid in decomposing with sulfuric acid, this method needs a large amount of high-quality Rock Phosphate (72Min BPL) and sulfuric acid, producing a large amount of phosphogypsum slags simultaneously is difficult to utilize, phosphoric acid by wet process foreign matter content height, purification process complexity, cost height, and present domestic sulphur price continues to occupy high-order, causes the phosphoric acid by wet process cost also to sharp rise; (2) hot method: reduce Rock Phosphate (72Min BPL) to produce simple substance yellow phosphorus with electric furnace process, absorb in the combustion tower internal combustion then and produce phosphoric acid, this method needs a large amount of electric energy (to produce yellow phosphorus power consumption 15000-16000kwh) per ton and middle higher-grade phosphorus ore lump ore, and environmental pollution is serious, this also almost is the unique method of present produced worldwide yellow phosphorus, but the restriction of many developed countries uses hot method to produce yellow phosphorus.
Kiln-process phosphoric acid is the third method that is different from wet method and Re Fa, its reaction principle is similar to thermal phosphoric acid, but compound carries out solid state reaction, and the reduction and the oxidising process of phosphorus simple substance are placed an equipment, the heat of the CO burning of phosphorus simple substance and by-product release can be used to provide the required heat of phosphorus simple substance reduction like this, save energy consumption greatly, can utilize P simultaneously
2O
5〉=10% mid low grade phosphate rock stone, having widened phosphorus ore greatly is the grade scope of directly utilizing.Yet this technology is also failed the ten minutes successful Application in large-scale industrial is produced.
The thinking of kiln-process phosphoric acid just was suggested the thirties in 20th century, and the Occidental Petroleum Corporation of the U.S. once dropped into a large amount of energy and studies, but owing to the through engineering approaches difficulty is abandoned greatly and finally very much.
Kiln-process phosphoric acid has two study routes for a long time: the one, and kiln process phosphoric acid, the 2nd, tunnel furnace method phosphoric acid mainly is to distinguish with the different of main reactor at oxidising process place with the phosphorus reduction.(1) rotary kiln: be a kind of heavy duty, high pulling torque, many fulcrums, tubular hollow kiln operational system; Spherical material moves along with the rotation of kiln body in kiln, and the reduction of phosphorus is carried out in the reduction zone, and the oxidation of phosphorus is carried out in oxidation zone, and reduction zone and oxidation zone are all in the kiln body; Fuel is at kiln internal combustion direct heating; (2) tunnel furnace: generally be a long linear pattern tunnel, fixed wall and vault are arranged at its both sides and top, are moving kiln car on the track that lay the bottom, and combustion equipment is located at the both sides, middle part of tunnel furnace; Employing is burnt till every cigarette or flaming, and material is placed on the kiln car, through preheating zone, thermal zone and cooling zone.
The main difficulty of rotary kiln is the kiln hood ring formation, and air outlet temperature is too high, and dust is big and the chemoproection cost is big; The main difficult problem of tunnel furnace is that heatproof requirement for anticorrosion height, the tunnel furnace thermo-efficiency of base substrate protecting materials is lower etc.
Summary of the invention
The development course that the purpose of this invention is to provide another kind of kiln-process phosphoric acid: a kind of method with producing phosphoric acid with vertical flaming kiln, thus overcome a rotary kiln and a tunnel furnace part difficult problem, realize the industrialized target of kiln-process phosphoric acid preferably.
The object of the present invention is achieved like this: a kind of method with producing phosphoric acid with vertical flaming kiln, with Rock Phosphate (72Min BPL), carbonaceous reducing agent and other batchings are made globular material, globular material adds from vertical flaming kiln top, material relies on gravity to move downwards, globular material reacted under solid state shape when the fuel combustion temperature of vertical flaming kiln rose to 1250-1500 ℃, reduction generates phosphorous vapor and CO (carbon monoxide converter) gas, in the weak oxide atmosphere in material gap, be oxidized to Vanadium Pentoxide in FLAKES and carbonic acid gas immediately, hydration absorbs and makes phosphoric acid then, and reacted solid materials residue draws off from kiln bottom or bottom through heat exchange cooling back.
Material is finished the reduction reaction of phosphorus under the solid phase condition, the puddle when material at high temperature reacts is the 0-30% of material total amount.
P in the Rock Phosphate (72Min BPL) of selecting for use
2O
5〉=6%, carbonaceous reducing agent is coke, coal or coal gangue, and Rock Phosphate (72Min BPL) and carbonaceous reducing agent according to the effective constituent mol ratio are: P
2O
5: C=1:5-15, other batchings are for silica or lime or Wingdale, in the globular material calcium silicon mol ratio be Ca:Si＜0.4 or 3.5.
Add caking agent in compound balling-up process, the concentration that caking agent used water, phosphoric acid collocation form is 10%-30% dilute phosphoric acid, and the add-on of tackiness agent is 0.1-3% of a compound butt.
Fuel is the particulate solid carbonaceous fuel, as coal dust, coke or coal gangue etc.
A kind of vertical flaming kiln with directly preparing phosphoric acid with phosphate ore, comprise that the cooling hopper of reinforced hopper, bottom on top and dumping device, gas inlet, kiln body are installed on the brace foundation, be provided with one or more material channels in the kiln, the kiln gas relief outlet is all arranged at the top of each material channel.Gas inlet is opened at cooling feed hopper bottom or sidepiece.
Method with producing phosphoric acid with vertical flaming kiln provided by the present invention is another the feasible route except that tunnel furnace method phosphoric acid and kiln process phosphoric acid.The heat that the oxidized burning of phosphorus simple substance that restores and by product carbon monoxide back produces conducts immediately to the ball material in the material channel, with the required heat energy of supply reduction reaction, has saved energy consumption in a large number.
The contrast of the present invention and tunnel furnace method phosphoric acid and kiln process phosphoric acid:
1, a large amount of frictional impact between the ball material when rotary kiln rotates uses vertical furnace can effectively reduce friction between the ball material, has greatly reduced the generation of dust, thereby has improved phosphoric acid quality.
2, do not need kiln car than tunnel furnace, take hear rate out of, reduced energy consumption thereby significantly reduced kiln furnitures.
3, the hopper of vertical flaming kiln upper and lower can guarantee the sealing that vertical flaming kiln is interior effectively with the ball material stock column of interior several meters high of cooling hopper, prevent that effectively extraneous gas from entering in the kiln, thereby the weak oxide atmosphere in the assurance material channel makes the carbonaceous reducing agent in the temperature-rise period be shifted to an earlier date oxidation to the greatest extent less.
Description of drawings
Fig. 1 is the structural representation of vertical flame kiln.
Fig. 2 is the A-A side-view of Fig. 1.
Fig. 3 is the process blocks synoptic diagram that the present invention makes phosphoric acid.
Embodiment
Principle of work of the present invention is described below:
The present invention is reduction and an oxidising process of finishing phosphorus ore with the vertical flaming kiln for principal reaction equipment, and the phosphorous vapor that reduction generates and by product carbon monoxide can make phosphoric acid by the absorption of recycle acid spray after by the weak oxide ambient oxidation in the material channel again.
Embodiments of the present invention are: earlier the dumping device of vertical flaming kiln bottom cuts out, material channel in the kiln is all filled up with waste residue material and particulate solid carbonaceous fuel, form the stock column that enriches.Kiln makes the solid carbonaceous fuel burning from the bottom bubbling air, heat up gradually, after waiting to reach the requirement temperature, the mixing ball material hopper at kiln top and the dumping device of bottom are opened, along with bottom discharging lentamente, ball material and particulate solid fuel in the hopper of top enter material channel gradually automatically under action of gravity, through heating up, reacting, finish production process.
Production technique of the present invention is: Rock Phosphate (72Min BPL), coke powder, silica is levigate to-100 orders after according to certain mixed〉80%, in the process of pan-pelletizer balling-up, spray into a small amount of 10% dilute phosphoric acid as tackiness agent, to strengthen the intensity of ball material, form
The ball material of 30mm.P in the Rock Phosphate (72Min BPL) of selecting for use
2O
5〉=6%, carbonaceous reducing agent is coke, coal or coal gangue, and Rock Phosphate (72Min BPL) and carbonaceous reducing agent according to the effective constituent mol ratio are: P
2O
5: C=1:5-15, other batchings are for silica or lime or Wingdale, in the globular material calcium silicon mol ratio be Ca:Si＜0.4 or 3.5.
Add caking agent in compound balling-up process, the concentration that caking agent water, phosphoric acid collocation form is 10%-30% dilute phosphoric acid, and the add-on of tackiness agent is 0.1-3% of a compound butt.
Fuel is the particulate solid carbonaceous fuel, as coal dust, coke or coal gangue etc.
The ball material is admitted to vertical flaming kiln top loading hopper 3 at roller-way oven dry kiln drying after moisture content is lower than 2%, along with vertical flaming kiln bottom discharge, ball material and particulate solid fuel in the top hopper 3 progress in the vertical flaming kiln material channel 4, the upward motion of air that charges into from gas inlet 8, heat exchange also burns solid fuel gradually, liberated heat adds thermal material, make it to be warming up to when temperature rises to 1250-1500 ℃ and react, material is finished the reduction reaction of phosphorus under the solid phase condition, puddle when material at high temperature reacts is the 0-30% of material total amount, behind the elemental phosphorous steam and carbon monoxide effusion ball material that reduction reaction generates, at once by the weak oxide ambient oxidation in the material channel, generate Vanadium Pentoxide in FLAKES and carbonic acid gas, the heat that oxidation discharges conducts at once to material, in order to support the required heat of reduction of phosphorus in the part kiln, kiln gas is extracted out from kiln gas outlet 5, use the recycle acid spray to absorb and can obtain high-concentration phosphoric acid.After the ball material reacts completely, enter vertical flaming kiln bottom cooling section hopper 6, by charging into cold air and hot-bulb material countercurrent flow, cooled ball material is discharged, and can be used as filtering material after the cooling of ball slag and uses.
Attached Fig. 1 and 2 is a vertical flaming kiln system phosphoric acid synoptic diagram, comprise that the cooling hopper 6 of reinforced hopper 3, bottom on top and dumping device 7, gas inlet 8, kiln body 1 are installed on the brace foundation 2, be provided with one or more material channels 4 in the kiln, kiln gas relief outlet 5 is all arranged at the top of each material channel 4.Gas inlet 8 is opened at cooling feed hopper bottom or sidepiece.
This device is middle high temp, vertical kiln, and material channel can be selected circle or square in the kiln, and the circular passage diameter exists
100-3000mm, the square duct edge lengths is 600-3000mm, height is 3-30m, can establish any number passage; The kiln height overall comprises that the reinforced hopper in top is 15-50m.Its material firing temperature of material channel is at 1100-1550 ℃, and firing period is 2-6 hours.
Each integral part is described below
Kiln body 1: adopt heavy refractory materials, light heat insulation material, insulating cotton or mould material from the inside to the outside successively, guarantee good heat insulation effect, save energy;
Brace foundation 2: adopt the cement pedestal, play the effect of supporting whole kiln body;
Reinforced hopper 3: in order to bear the hopper of green-ball material, the ball material is stacked into the stock column of certain height naturally to guarantee the stopping property in the kiln in reinforced hopper, and the stock column height is about 800-2000mm;
Material channel 4: the passage that the ball material heats up in kiln, reacts; Material adds from top in this passage, relies on gravity to draw off from the bottom.Finish in this passage and heat up and reduction reaction, material channel 4 is one or more in kiln body 1.
Kiln gas relief outlet 5:200-800 ℃ kiln gas is mouthful discharge from then on, enters the absorption tower after heat exchange;
The cooling hopper 6: the ball material that reacts completely in this hopper with the freezing air heat exchange, cool off;
Dumping device 7: cooled ball material (100-200 ℃) is discharged with certain speed under the control of dumping device;
Gas inlet 8: freezing air by fill into here the cooling hopper in 6;
Under the situation of at the uniform velocity blanking, the ball material in the whole kiln is the state that slowly moves downward.After the ball material enters the interior material channel 4 of kiln, with the Vanadium Pentoxide in FLAKES steam and the carbon dioxide heat exchange of rising, simultaneously under the heating of solid fuel ignition, be warming up to 1200-1550 ℃ gradually, thereby react and generate phosphorous vapor and carbon monoxide, be oxidized to Vanadium Pentoxide in FLAKES and carbonic acid gas in the weak oxide environment behind the gas evolution ball material in material channel and discharge a large amount of heats, for reduction reaction provides heat, mixed gas is drawn out of the back from kiln gas relief outlet 5 and uses the absorption of recycle acid spray can make phosphoric acid.The ball material relies on deadweight to enter cooling hopper 6 downwards, and with the freezing air heat exchange that charges into, discharge the cooling back.
Claims (7)
1, a kind of method with producing phosphoric acid with vertical flaming kiln, it is characterized in that: with Rock Phosphate (72Min BPL), carbonaceous reducing agent and other batchings are made globular material, globular material adds from vertical flaming kiln top, material relies on gravity to move downwards, globular material reacted under solid state shape when the fuel combustion temperature of vertical flaming kiln rose to 1250-1500 ℃, reduction generates phosphorous vapor and CO (carbon monoxide converter) gas, in the weak oxide atmosphere in material gap, be oxidized to Vanadium Pentoxide in FLAKES and carbonic acid gas immediately, hydration absorbs and makes phosphoric acid then, and reacted solid materials residue draws off from kiln bottom or bottom through heat exchange cooling back.
2, a kind of method according to claim 1 with producing phosphoric acid with vertical flaming kiln, it is characterized in that: material is finished the reduction reaction of phosphorus under the solid phase condition, and the puddle when material at high temperature reacts is the 0-30% of material total amount.
3, a kind of method with producing phosphoric acid with vertical flaming kiln according to claim 1 is characterized in that: P in the Rock Phosphate (72Min BPL) of selecting for use
2O
5〉=6%, carbonaceous reducing agent is coke, coal or coal gangue, and Rock Phosphate (72Min BPL) and carbonaceous reducing agent according to the effective constituent mol ratio are: P
2O
5: C=1:5-15, other batchings are for silica or lime or Wingdale, in the globular material calcium silicon mol ratio be Ca:Si＜0.4 or 3.5.
4, a kind of method according to claim 1 with producing phosphoric acid with vertical flaming kiln, it is characterized in that: in compound balling-up process, add caking agent, the concentration that caking agent used water, phosphoric acid collocation form is 10%-30% dilute phosphoric acid, and the add-on of tackiness agent is 0.1-3% of a compound butt.
5, a kind of method with producing phosphoric acid with vertical flaming kiln according to claim 1, it is characterized in that: fuel is the particulate solid carbonaceous fuel, as coal dust, coke or coal gangue etc.
6, a kind of vertical flaming kiln with directly preparing phosphoric acid with phosphate ore, comprise that the cooling hopper (6) of reinforced hopper (3), bottom on top and dumping device (7), gas inlet (8), kiln body (1) are installed on the brace foundation (2), it is characterized in that: be provided with one or more material channels (4) in the kiln, kiln gas relief outlet (5) is all arranged at the top of each material channel (4).
7, a kind of vertical flaming kiln with directly preparing phosphoric acid with phosphate ore according to claim 6, it is characterized in that: gas inlet (8) is opened at cooling feed hopper bottom or sidepiece.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102367043A CN101428775B (en) | 2008-12-06 | 2008-12-06 | Method for producing phosphoric acid with vertical flaming kiln |
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| CN2008102367043A CN101428775B (en) | 2008-12-06 | 2008-12-06 | Method for producing phosphoric acid with vertical flaming kiln |
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| CN101428775A true CN101428775A (en) | 2009-05-13 |
| CN101428775B CN101428775B (en) | 2012-02-29 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010025620A1 (en) * | 2008-09-03 | 2010-03-11 | 湖北三新磷酸有限公司 | Method and device for producing yellow phosphorus or phosphoric acid by vertical airtight smoke-baffle kiln |
| CN104211028A (en) * | 2013-06-04 | 2014-12-17 | 四川玖长科技有限公司 | Composite pellet material used for kiln method phosphoric acid technology and molding method thereof |
| CN104211032A (en) * | 2013-06-04 | 2014-12-17 | 四川玖长科技有限公司 | Rotary kiln for reducing phosphate rock in kiln method phosphoric acid technology and method for solving ring forming of kiln tail of kiln method phosphoric acid technology |
| CN104697358A (en) * | 2013-12-05 | 2015-06-10 | 北新集团建材股份有限公司 | Vertical-type powder cooler |
| CN107055498A (en) * | 2017-04-28 | 2017-08-18 | 北京迈未科技有限公司 | The apparatus and method for producing yellow phosphorus and phosphoric acid simultaneously |
| CN107238290A (en) * | 2017-04-28 | 2017-10-10 | 北京迈未科技有限公司 | Integral type vertical furnace and the method that phosphoric acid is prepared by it |
| US9982947B2 (en) | 2013-06-04 | 2018-05-29 | Sichuan Ko Chang Technology Co., Ltd. | Rotary kiln for reducing phosphate ore in kiln phosphoric acid process and method for solving ring forming in kiln tail in kiln phosphoric acid process |
-
2008
- 2008-12-06 CN CN2008102367043A patent/CN101428775B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010025620A1 (en) * | 2008-09-03 | 2010-03-11 | 湖北三新磷酸有限公司 | Method and device for producing yellow phosphorus or phosphoric acid by vertical airtight smoke-baffle kiln |
| CN104211028A (en) * | 2013-06-04 | 2014-12-17 | 四川玖长科技有限公司 | Composite pellet material used for kiln method phosphoric acid technology and molding method thereof |
| CN104211032A (en) * | 2013-06-04 | 2014-12-17 | 四川玖长科技有限公司 | Rotary kiln for reducing phosphate rock in kiln method phosphoric acid technology and method for solving ring forming of kiln tail of kiln method phosphoric acid technology |
| US9982947B2 (en) | 2013-06-04 | 2018-05-29 | Sichuan Ko Chang Technology Co., Ltd. | Rotary kiln for reducing phosphate ore in kiln phosphoric acid process and method for solving ring forming in kiln tail in kiln phosphoric acid process |
| US10435300B2 (en) | 2013-06-04 | 2019-10-08 | Sichuan Ko Chang Technology Co., Ltd. | Raw material of composite pellets used in kiln phosphoric acid process, and forming method therefor |
| CN104697358A (en) * | 2013-12-05 | 2015-06-10 | 北新集团建材股份有限公司 | Vertical-type powder cooler |
| CN107055498A (en) * | 2017-04-28 | 2017-08-18 | 北京迈未科技有限公司 | The apparatus and method for producing yellow phosphorus and phosphoric acid simultaneously |
| CN107238290A (en) * | 2017-04-28 | 2017-10-10 | 北京迈未科技有限公司 | Integral type vertical furnace and the method that phosphoric acid is prepared by it |
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| CN101428775B (en) | 2012-02-29 |
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