CN1054953A - Method for producing phosphoric acid by special-shaped rotary kiln - Google Patents
Method for producing phosphoric acid by special-shaped rotary kiln Download PDFInfo
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- CN1054953A CN1054953A CN 90105433 CN90105433A CN1054953A CN 1054953 A CN1054953 A CN 1054953A CN 90105433 CN90105433 CN 90105433 CN 90105433 A CN90105433 A CN 90105433A CN 1054953 A CN1054953 A CN 1054953A
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Abstract
A method for producing phosphoric acid by using a rotary kiln is characterized by comprising the following steps: adding three organic binders during pelletizing and batching; drying and solidifying the pellets; throwing a solid reducing agent into the kiln head of the rotary kiln; the kiln body is provided with a plurality of fans and air pipes, and air is introduced above the material layer in the kiln along the central axis. The invention can effectively solve the problems of pellet strength, temperature in the kiln and atmosphere control. By controlling the air supply quantity of a fan on the kiln body, the temperature fluctuation of the material bed in the area with the length of more than 50 percent of the rotary kiln is kept not to exceed +/-50 ℃.
Description
The present invention relates to the manufacture method of the semi-graphited cathode carbon pieces that the manufacture method of cathod carbon block used in aluminium electrolytic bath, particularly resistivity are low, electrolyte-resistant solution etch performance is good.
As everyone knows, the cathode portion of aluminium cell constitutes with carbonaceous material with aluminium liquid and ionogen contact site.Particularly bottom of electrolytic tank all is to constitute with the charcoal piece.In the electrolysis operation process, this charcoal piece Chang Yin is subjected to thermal stresses and chemical etching effect and damages and cause shut-down, and in addition, in the electrolysis operation, the volts lost of cathode carbon pieces also can influence the energy consumption of electrolysis process.For this reason, require cathode carbon pieces to have good resistance to compression, tensile strength, resistance to sudden heating, electrolyte-resistant solution etch performance and electroconductibility and wear resistance.
The cathode carbon pieces that the aluminum current electrolyzer uses has common anthracite-base cathode carbon pieces, semi-graphite cathode carbon block, semi-graphited cathode carbon pieces and graphitized cathode carbon block etc. several.
Common anthracite-base cathode carbon pieces is that to use the hard coal after 1250～1350 ℃ of calcinings be aggregate, is binding agent with the coal-tar pitch, behind kneading and compacting, forms through 1300 ℃ of left and right sides roastings again.The carbon back that constitutes it originally belongs to amorphous carbon, the aluminium electrolytic cell cathode of building by laying bricks or stones with this charcoal piece, in aluminium electrolysis process, be subjected to sodium ion etch rate of expansion big (linear expansivity reaches 1.5%), physical strength greatly reduces after the etch, so work-ing life is short, in addition, its resistivity is bigger, is generally (50～60) * 10
-6Ω m, thereby the electric tank cathode pressure drop that is built into this charcoal piece is big, the power consumption height.The knot effect is not strong.(2). be difficult to keep good reducing atmosphere in the bed of material in the kiln, therefore occur the oxidation and generate calcium phosphate in the bed of material of phosphorus steam easily, reduced the evaporation rate of phosphorus in the pelletizing with calcium oxide reaction in the pelletizing.(3). kiln body air feed system complex structure, and be difficult to make the interior oxidation zone of kiln to be separated well with the reduction zone.Reason is that 8 rows totally 96 wind holes are set around the rotary kiln body, and bubbling air destroys the reducing atmosphere in the bed of material when avoiding the wind hole to go to bed of material below, and air feed has to adopt periodical operation, thereby has made complex system.Though and this footpath aweather can effectively utilize the combustion space in the hole, the air that feeds directly arrives bed of material surface easily, makes the mass transfer quickening between oxidation zone and the reduction zone, and oxidation zone just is difficult to separate well with the reduction zone.
The objective of the invention is to: by improving pellet strength, kiln hood is thrown into solid reductant and adopts new kiln body air feed system so that the KPA method is improved.
Technical solution of the present invention is: Rock Phosphate (72Min BPL) and silica, carbonaceous reducing agent are through grinding, making ball after the batching, mixing, need add organic binder bond when making the ball batching, pelletizing adopts drying and consolidating, pelletizing after fixed reduction volatilization and bubbling air in rotary kiln make phosphorus steam and carbon monoxide oxidizing fire, rotary kiln end is thrown into solid reductant, the kiln body is provided with some blower fans and airduct, and air is that bed of material top feeds along the axis in the kiln.
In the technical solution of the present invention, the organic binder bond of interpolation has three kinds: i.e. Sodium salts humic acids, calcium lignin sulphonate, cellulose lye.When using fulvo acid content to account for 30～70% Sodium salts humic acids, addition is 0.5～4.5%(butt); When using calcium lignin sulphonate, addition is 0.3～3.0%(butt); When to use proportion be 1.20～1.30 cellulose lye, addition was 2.0～5.0%.
In the technical solution of the present invention, pelletizing adopts drying and consolidating, and consolidation temperature is 100～400 ℃, and consolidation time is 10～60 minutes.Upper and lower temperature difference is bigger, causes the performance difference of charcoal piece top and the bottom bigger, and whole charcoal piece physical and chemical performance uniformity coefficient is poor.
The objective of the invention is to overcome the deficiencies in the prior art, a kind of raw material that the source is wide, price is low that adopts is provided, produce that resistivity is low, the potential resistance to electrolyte contamination erosion is good, the suitable method of making cathod carbon block used in aluminium electrolytic bath of physical and chemical performance homogeneous.
The manufacture method of cathod carbon block used in aluminium electrolytic bath of the present invention comprises batching and kneading and compacting, roasting and semi-graphited three-procedure.
Raw materials usedly be: the hard coal after 1250～1300 ℃ of calcinings, metallurgical coke, few grey Jiao and graphite broken (or scale graphite), binding agent is a pitch.Each proportion of raw materials (weight percentage) is respectively 40～50,0～30, and 0～35,0～10 and 15～25, the granularity (mm) of raw material (except that pitch) is distributed as :+12:＜2% ,-12～+ 4:25 ± 4% ,-0.5:40 ± 4% ,-0.075:29 ± 3%.
With above-mentioned raw materials through routine mix pinch after, with extruding or vibratory compaction, usually making the cross section is that 420mm * 420mm length is the piece of predetermined length, then in stoving oven, heated up through 280～360 hours and insulation to 1100～1380 ℃ (optimum value is 1250～1350 ℃), according to circumstances with condition, roasting can be carried out in circular furnace or ground kiln or down-draft kiln.Subsequently whole immigration of the charcoal piece after the roasting carried out the semi-graphited processing in the resistance furnace, semi-graphited is everlasting and is carried out in Acheson's resistance furnace, its processing condition are: 2000～3000 kilowatt-hours of energising amounts, 30～45 hours conduction time, top temperature is controlled at 1800～2300 ℃ (optimum value is 1900～2150 ℃) in the stove.Make the graphite state before the charcoal piece reaches complete greying.At last product processing is built into by laying bricks or stones the finished product of required cathode shape.
Cathode carbon pieces with method manufacturing of the present invention has following advantage and effect:
Wide, the low price of raw material sources, be easy to apply;
2. product performance obviously are better than common anthracite-base cathode carbon pieces and semi-graphite cathode carbon block, Jiao who burns till because of its feed particles and pitch, all reach semi-graphited, so performance is even, intensity height, good toughness, its main performance index is: greying index＞0.8, ash＜7%, resistivity 3 * 10
-6Ω m, ultimate compression strength＞17MPa, true density＞2.06g/cm
3, volume density 1.52g/cm
3, electrolytic expansivity 0.5%.
The aluminium electrolytic cell cathode of building by laying bricks or stones with the semi-graphited charcoal piece of method manufacturing of the present invention is low because of the rate of expansion that produced by the sodium ion etch in electrolytic process, therefore reduce fracture because of upwards arching upward and produced, so can prolong the work-ing life of cathode carbon pieces, simultaneously owing to having reduced the volts lost of negative electrode, so reduced the power consumption in the electrolytic process.
The embodiment of cathod carbon block used in aluminium electrolytic bath manufacture method of the present invention lists in table 1, and the physical and chemical performance of product is shown in table 2.
The manufacturing process of table 1 cathode carbon pieces
The physical and chemical performance of table 2 cathode carbon pieces
| Sequence number | 1 | 2 | 3 | 4 | 5 |
| The greying index | 0.8 | 0.8 | 0.82 | 0.80 | 0.80 |
| Porosity (%) | 26.42 | 25.95 | 26.31 | 26.23 | 26.49 |
| Resistivity (10 Ω m) | 23-28 | 21-45 | 18-23 | 22-26 | 20-25 |
| Ultimate compression strength (MPa) | 20-23 | 20-25 | 21-23 | 21.3 | 20.8 |
| Volume density (g/cm) | 1.55 | 1.56 | 1.57 | 1.56 | 1.55 |
| Bending strength (MPa) | 10-12 | 10-12 | 11 | 9.7 | 10.3 |
| True density (g/cm) | 2.12 | 2.14 | 2.14 | 2.12 | 2.12 |
| The swollen rate that rises of electrolysis (%) | 0.44 | 0.42 | 0.40 | 0.45 | 0.47 |
| Ash (%) | 6.06 | 3.96 | 3.87 | 4.22 | 4.30 |
Claims (3)
1, a kind of manufacture method of cathod carbon block used in aluminium electrolytic bath comprises batching and kneading and compacting, roasting and semi-graphited operation, it is characterized in that:
A) raw material and proportioning (weight percentage): the hard coal 45～50 after 1250～1300 ℃ of calcinings, metallurgical coke 0～30, few ash Jiao 0～35, broken (or the scale graphite) 0～10 of graphite, pitch 15～25;
B) raw material (except that pitch) granularity (mm) distributes :+12:＜2% ,-12～+ 4:25 ± 4%;-0.5:40 ± 4%;-0.075:29 ± 3%;
C) sinter process condition: intensification and soaking time 280～360 hours, 1100～1380 ℃ of top temperatures;
D) semi-graphited processing condition: 30～45 hours conduction time, 2000～3000 kilowatt-hours of energising amounts, 1800～2300 ℃ of top temperatures.
2, method according to claim 1 is characterized in that roasting at circular furnace, carries out in ground kiln or the down-draft kiln.
3, method according to claim 1, the top temperature that it is characterized in that calcining process the best is 1250～1350 ℃, the top temperature of semi-graphited operation the best is 1900～2150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105433 CN1026403C (en) | 1990-03-22 | 1990-03-22 | Method for producing phosphoric acid by special-shaped rotary kiln |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105433 CN1026403C (en) | 1990-03-22 | 1990-03-22 | Method for producing phosphoric acid by special-shaped rotary kiln |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1054953A true CN1054953A (en) | 1991-10-02 |
| CN1026403C CN1026403C (en) | 1994-11-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90105433 Expired - Fee Related CN1026403C (en) | 1990-03-22 | 1990-03-22 | Method for producing phosphoric acid by special-shaped rotary kiln |
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| Country | Link |
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| CN (1) | CN1026403C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040199C (en) * | 1993-06-11 | 1998-10-14 | 冶金工业部长沙矿冶研究院 | Method for producing phosphoric acid by directly reducing phosphate ore |
| WO2014194563A1 (en) * | 2013-06-04 | 2014-12-11 | 四川玖长科技有限公司 | Improved method for mass production of phosphoric acid with rotary kiln |
| WO2014194567A1 (en) * | 2013-06-04 | 2014-12-11 | 四川玖长科技有限公司 | Rotary kiln for reducing phosphate ore in kiln process for production of phosphoric acid and method for solving ring forming in kiln tail in kiln process for production of phosphoric acid |
| 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 |
| US9776868B2 (en) | 2013-06-04 | 2017-10-03 | Sichuan Ko Chang Technology Co., Ltd. | Apparatus for preparing phosphoric acid from fume exiting the kiln in a kiln phosphoric acid process |
| 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 |
| US10232312B2 (en) | 2013-06-04 | 2019-03-19 | Sichuan Ko Chang Technology Co., Ltd | Device and process for fluorine recovery from smoke after phosphorus absorption by hydration in kiln process for production of phosphoric acid |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125646B (en) * | 2007-09-26 | 2010-12-29 | 云南常青树化工有限公司 | Method for preparing high concentration phosphoric acid by directly reducing low and middle grade phosphorus ore |
| CN104211425B (en) | 2013-06-04 | 2015-12-02 | 四川玖长科技有限公司 | Method of comprehensive utilization and the process system thereof of rotary kiln high temperature sludge ball is gone out in kiln-process phosphoric acid technique |
-
1990
- 1990-03-22 CN CN 90105433 patent/CN1026403C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040199C (en) * | 1993-06-11 | 1998-10-14 | 冶金工业部长沙矿冶研究院 | Method for producing phosphoric acid by directly reducing phosphate ore |
| WO2014194563A1 (en) * | 2013-06-04 | 2014-12-11 | 四川玖长科技有限公司 | Improved method for mass production of phosphoric acid with rotary kiln |
| WO2014194567A1 (en) * | 2013-06-04 | 2014-12-11 | 四川玖长科技有限公司 | Rotary kiln for reducing phosphate ore in kiln process for production of phosphoric acid and method for solving ring forming in kiln tail in kiln process for production of phosphoric acid |
| 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 |
| CN104211030B (en) * | 2013-06-04 | 2016-03-09 | 四川玖长科技有限公司 | The method of follow-on rotary kiln large-scale production phosphoric acid |
| US9776868B2 (en) | 2013-06-04 | 2017-10-03 | Sichuan Ko Chang Technology Co., Ltd. | Apparatus for preparing phosphoric acid from fume exiting the kiln in a kiln phosphoric acid process |
| RU2640069C2 (en) * | 2013-06-04 | 2017-12-26 | Сычуань Ко Чанг Технолоджи Ко., Лтд | Rotary furnace used for reduction of phosphorus-containing ore during sintering process in furnace for producing phosphoric acid and method to keep ring-shaped moulding in rear part of furnace in during sintering process for producing phosphoric acid |
| RU2642651C2 (en) * | 2013-06-04 | 2018-01-25 | Сычуань Ко Чанг Технолоджи Ко., Лтд | Improved method of mass production of phosphoric acid with application of rotation furnaces |
| RU2650162C2 (en) * | 2013-06-04 | 2018-04-09 | Сычуань Ко Чанг Технолоджи Ко., Лтд | Raw material of composite pellets used in kiln phosphoric acid process and forming method therefor |
| 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 |
| US10005669B2 (en) | 2013-06-04 | 2018-06-26 | Sichuan Ko Chang Technology Co., Ltd. | Method for mass production of phosphoric acid with rotary kiln |
| US10232312B2 (en) | 2013-06-04 | 2019-03-19 | Sichuan Ko Chang Technology Co., Ltd | Device and process for fluorine recovery from smoke after phosphorus absorption by hydration in kiln process for production of phosphoric acid |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1026403C (en) | 1994-11-02 |
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