CN103288056B - A kind of decomposing phosphogypsum prepares SO 2method - Google Patents
A kind of decomposing phosphogypsum prepares SO 2method Download PDFInfo
- Publication number
- CN103288056B CN103288056B CN201310034399.0A CN201310034399A CN103288056B CN 103288056 B CN103288056 B CN 103288056B CN 201310034399 A CN201310034399 A CN 201310034399A CN 103288056 B CN103288056 B CN 103288056B
- Authority
- CN
- China
- Prior art keywords
- phosphogypsum
- mineralizer
- raw material
- perpendicular tank
- decomposing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010792 warming Methods 0.000 claims abstract description 11
- 239000004568 cement Substances 0.000 claims abstract description 10
- 239000000571 coke Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000003034 coal gas Substances 0.000 claims abstract description 4
- 239000000428 dust Substances 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005453 pelletization Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 abstract description 10
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 7
- -1 homogenizing Substances 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to phosphogypsum Sulphuric acid jointly producing cement technical field, disclose a kind of decomposing phosphogypsum and prepare SO
2method.Be intended to solve prior art decomposing phosphogypsum energy consumption excessive, Sulphuric acid high cost, restriction phosphogypsum develops and industrialized technical barrier.The present invention for producing primary device with perpendicular tank, adds mineralizer in proportion, and mixes by 22.67:1 weight ratio with coke, through abrasive dust, homogenizing, ball processed, and dry in phosphogypsum.Dry bulb group adds perpendicular tank, with coal gas as fuel, to the mode that perpendicular tank heats with muffle, is preheated to 600 DEG C ~ 700 DEG C and enters reduction section, be warming up to 820 DEG C, is incubated 1 hour 20 points, and furnace gas drawn by induced draft fan, through two sections of dedustings, and obtained desired product SO
2.Its energy consumption is only existing process energy consumption 45% ~ 50%.For subsequent production sulfuric acid, jointly producing cement play a role in energy conservation.
Description
The present invention relates to the technical field of phosphogypsum Sulphuric acid jointly producing cement, more particularly, the present invention relates to and adopt phosphogypsum to be raw material, decomposite SO
2method.
Background technology
The solid industrial waste residue produced when phosphogypsum is Wet-process phosphoric acid (WPPA), main chemical compositions is CaSO altogether
42H
2o.And containing a small amount of SIO
2, AL
2o
3, Fe
2o
3, C
athe metal ion of O, MgO, trace and radioelement, and undecomposed ground phosphate rock, P
2o
5, F
-with impurity such as free acids.In the technique of two water law phosphoric acid by wet processes, often produce 1t phosphoric acid and produce 4-5t phosphogypsum.The phosphogypsum of the annual discharge of China reaches more than 20,000,000 tons, and utilization ratio is less than 10%, undressed phosphogypsum is stacked and is not only taken a large amount of soils, fund, wastes the Sulphur ressource that a large amount of soils, fund, waste are a large amount of, and serious soil can be caused, water body, topsoil.
Up to now, phosphogypsum only for Sulphuric acid cement, cement setting retarder, gypsum sheet material etc.Consumption is few.Phosphogypsum Sulphuric acid jointly producing cement is the direction of process phosphogypsum.Traditional technique is using rotary kiln as reactor, adopts the reductive agents such as coke.By decomposing phosphogypsum, produce SO
2, enter " two turns " " two inhale " operation and obtain sulfuric acid.Residue is used as cement processed.In this technological process, the SO produced
2gas is Sulphuric acid main raw material.But decomposing phosphogypsum prepares SO
2be carry out at temperatures as high 1250 DEG C ~ 1300 DEG C, this high energy consumption is the major cause that follow-up Sulphuric acid cost is high.So more domestic producers, the device set up, owing to holding the pressure that can't stand high cost, when operation, namely becomes the day of bankruptcy.Reduce the temperature of decomposing ardealite, realize real energy-saving and emission-reduction, comprehensive utilization phosphogypsum just can reach existing good social benefit, and benefit future generations offspring, has again good economic benefit.This is technical barrier anxious to be resolved in this area.
Summary of the invention
Object of the present invention, is that energy consumption is too high in existing decomposing ardealite, causes phosphogypsum Sulphuric acid high cost, provide a kind of decomposing ardealite method.
Object of the present invention, by following technical proposals, is achieved.
Except as otherwise noted, the percentage ratio adopted in the present invention is weight percentage.
The invention provides a kind of decomposing phosphogypsum and prepare SO
2method, the method comprises the following steps:
1, the perpendicular tank in use metallurgical industry is as production unit;
2, using phosphogypsum as raw material;
3, the mineralizer of 2% ~ 10% is added in the feed.Described mineralizer is selected from the one in F or CI, or their mixture;
4, by step (3) gains, coke presses the proportion mixing of 22.67:1, abrasive dust to 200 order, and homogenizing, adds binding agent, makes oval spherical raw material pelletizing, and dries;
5, with lift, step (4) gains are added in perpendicular tank, utilize coal gas, adopt muffle type of heating, be preheated to 600 DEG C ~ 700 DEG C, enter reduction section, be warming up to 820 DEG C of insulations, furnace gas is drawn with induced draft fan, after gravity settling dedusting and electric precipitation two sections of dedustings, obtained SO
2.Enter " two turns " and " two inhale " Sulphuric acid operation, residue cement operation.
Binding agent wherein described in (4) is selected from tonerde or wilkinite.Described ellipsoid shape raw material pelletizing size: 50mm × 30mm × 20mm.
Chemical principle of the present invention:
CaSO
4+2C=CaS+2CO
2↑
CaS+3CaSO
4=4CaO+4SO
2↑
Net reaction:
2CaSO
4+C=2CaO+2SO
2+CO
2↑
Compared with prior art, the present invention has following outstanding advantages:
1, technique advantages of simple---owing to adopting perpendicular tank as production unit, the basic structure of perpendicular tank is high temperature resistant, corrosion-resistant, and the refractory materials good by thermal conductivity is constructed, and good seal performance, can form good reducing environment, be conducive to decomposing ardealite, SO simultaneously
2reduction ratio reach more than 98.50%;
2, energy-conservation.Using rotary kiln as production unit, decomposing phosphogypsum temperature 1250 DEG C ~ 1300 DEG C.And adopting the present invention, during preparation raw material, add mineralizer, decomposing phosphogypsum temperature 796 DEG C ~ 820 DEG C in proportion, its energy consumption is only 45% ~ 50% of conventional art;
3, because energy consumption significantly reduces, phosphogypsum Sulphuric acid jointly producing cement produces positive benefit.Thus promote comprehensive utilization phosphogypsum, there is extremely far-reaching influence to China environmental protection.
Embodiment
By providing specific embodiment below, the present invention can be understood further.But they are not limiting the scope of the present invention.
Embodiment 1
take phosphogypsum as raw material, add 3%CL mixture in the feed as mineralizer, then the material prepared, coke are mixed by 22.67:1 weight ratio, abrasive dust to 200 order, homogenizing, adds tonerde and makes binding agent, make ellipsoid shape raw material pelletizing, pelletizing size: 50mm × 30mm × 20mm, and dry, with lift, the raw material pelletizing of oven dry is added perpendicular tank, muffle type of heating is adopted with coal gas, be preheated to 680 DEG C and enter reduction section, be warming up to 796 DEG C and start reduction, have SO
2gas overflowing, 820 DEG C are incubated 1 hour 10 points, and furnace gas drawn by induced draft fan, through gravity settling dedusting, after electric precipitation, obtains SO
2, reduction ratio 98.93%.
Embodiment 2
repeat embodiment 1, have following difference: add 3%F mixture in the feed as mineralizer.Be preheated to 680 DEG C, enter reduction section, be warming up to 800 DEG C and start reduction, have SO
2overflow, 820 DEG C are incubated 1 hour 10 points, and reduction ratio reaches 98.86%.
Embodiment 3
Repeat embodiment 1, have following difference: add composite mineralizer in the feed.Composite mineralizer forms 1.2%CL mixture, 1.8%F mixture.Be preheated to 650 DEG C, enter reduction section, being warming up to 798 DEG C has SO
2overflow, 820 DEG C are incubated 1 hour 10 points, reduction ratio 99.00%.
Embodiment 4
repeat embodiment 1, have following difference: add 5%CL mixture in the feed as mineralizer.Be preheated to 660 DEG C and enter reduction section, be warming up to 796 DEG C and start reduction, 810 DEG C are incubated 1 hour, reduction ratio 98.10%.
Embodiment 5
Repeat embodiment 1, have following difference: add 5%F mixture in the feed as mineralizer.Preheating 660 DEG C, enters reduction section, is warming up to 799 DEG C and starts reduction, and 810 DEG C are incubated 1 hour, reduction ratio 98.30%.
Embodiment 6
Repeat embodiment 1, have following difference, add 2%C1 mixture mineralizer in the feed, be preheated to 700 DEG C and enter reduction section, be warming up to 796 DEG C and start reduction.820 DEG C are incubated 1 hour 10 points, reduction ratio 82.10%.
Embodiment 7
Repeat embodiment 1, have following difference: add 2%F mixture mineralizer in the feed.Be preheated to 700 DEG C and enter reduction section, be warming up to 799 DEG C.Start to reduce 820 DEG C of insulations 1 hour 10 points, reduction ratio 80.50%.
Embodiment 8
repeat embodiment 1, have following difference: do not add any mineralizer in the feed.Be preheated to 700 DEG C and enter reduction section, be warming up to 1050 DEG C.Be incubated 2 hours 30 points, reduction ratio 31%.。
Claims (3)
1. a decomposing phosphogypsum prepares SO
2method, it is characterized in that: the method comprises the following steps:
(1) perpendicular tank is used to be production unit;
(2) take phosphogypsum as raw material;
(3) add the mineralizer of 2% ~ 10% in the feed, described mineralizer, be selected from fluorine or chlorine a kind of, or their mixture;
(4) step (3) gains, coke are pressed the weight ratio mixing of 22.67:1, abrasive dust to 200 order, homogenizing, adds binding agent, makes ellipsoid shape raw material pelletizing, and dries;
(5) with lift, step (4) gains are added perpendicular tank, coal gas is utilized to make fuel, muffle type of heating, be preheated to 600 DEG C ~ 700 DEG C, enter reduction section, be incubated 1 hour 20 points when being warming up to 820 DEG C, furnace gas drawn by induced draft fan, through gravity settling dedusting, electric precipitation is obtained SO later
2;
Obtained SO
2, through " two turns ", " two inhale " obtained sulfuric acid, residue is for cement processed.
2. method according to claim 1, is characterized in that: the binding agent described in step (4), is selected from clay or wilkinite.
3. method according to claim 1, is characterized in that: the ellipsoid shape raw material pelletizing described in step (4) is of a size of 50mm × 30mm × 20mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310034399.0A CN103288056B (en) | 2013-01-30 | 2013-01-30 | A kind of decomposing phosphogypsum prepares SO 2method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310034399.0A CN103288056B (en) | 2013-01-30 | 2013-01-30 | A kind of decomposing phosphogypsum prepares SO 2method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103288056A CN103288056A (en) | 2013-09-11 |
| CN103288056B true CN103288056B (en) | 2015-10-14 |
Family
ID=49089671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310034399.0A Expired - Fee Related CN103288056B (en) | 2013-01-30 | 2013-01-30 | A kind of decomposing phosphogypsum prepares SO 2method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103288056B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244811A (en) * | 2008-03-17 | 2008-08-20 | 云南云天化国际化工股份有限公司 | Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate |
| CN101602518A (en) * | 2009-07-21 | 2009-12-16 | 中国石化集团南京设计院 | A kind of production technique of utilizing phosphogypsum to decompose preparation calcium oxide and sulfurous gas |
-
2013
- 2013-01-30 CN CN201310034399.0A patent/CN103288056B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244811A (en) * | 2008-03-17 | 2008-08-20 | 云南云天化国际化工股份有限公司 | Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate |
| CN101602518A (en) * | 2009-07-21 | 2009-12-16 | 中国石化集团南京设计院 | A kind of production technique of utilizing phosphogypsum to decompose preparation calcium oxide and sulfurous gas |
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| Publication number | Publication date |
|---|---|
| CN103288056A (en) | 2013-09-11 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zeng Fanduan Inventor after: Ning Ping Inventor after: Che Jianqing Inventor after: Liu Shugen Inventor before: Che Jianqing Inventor before: Zeng Fanduan |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: CHE JIANQING CENG FANDUAN TO: CENG FANDUAN NING PING CHE JIANQING LIU SHUGEN |
|
| C10 | Entry into substantive examination | ||
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Effective date of registration: 20190621 Granted publication date: 20151014 |
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Date of cancellation: 20220621 Granted publication date: 20151014 |
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Granted publication date: 20151014 Termination date: 20190130 |