CN1003369B - Method and equipment of manganese dioxide prodn. by pyrolyzing manganese carbonate - Google Patents
Method and equipment of manganese dioxide prodn. by pyrolyzing manganese carbonate Download PDFInfo
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- CN1003369B CN1003369B CN87100333.3A CN87100333A CN1003369B CN 1003369 B CN1003369 B CN 1003369B CN 87100333 A CN87100333 A CN 87100333A CN 1003369 B CN1003369 B CN 1003369B
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- kiln
- rotary kiln
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Abstract
The present invention relates to a method and device for preparing manganese dioxide by pyrolyzing synthesized manganese carbonate as a raw material. The pyrolyzing oxidation reaction of the manganese carbonate in a rotary kiln adopts indirect heating and continuous calcination, and materials and gas taking part in the reaction and a heating medium flow in the same direction; by controlling water in the materials entering the kiln, steam can be generated by the water in the preheating section of the kiln, and simultaneously, the reaction gas containing moisture and oxygen are formed by regulating the quantity of air entering the kiln; therefore, the steam and the oxygen do not need to be led by the conventional method. The designed rotary kiln is a barrel body with a double-layer jacket structure, and adopts a sealed-cycle low-temperature heating method by using the hot air passing through jackets as a calcining and heating medium. Therefore, the present invention has the advantages of high thermal efficiency, low energy consumption and simple device. In addition, the prepared gamma-type manganese dioxide with good activity has the conversion rate of 80% to 85%.
Description
The invention belongs to a kind of method and apparatus of producing Manganse Dioxide with manganese carbonate pyrolysis.
Producing the method for Manganse Dioxide with the manganese carbonate pyrolysis oxidation, when being used for industrial production at first, is that manganous carbonate is placed various types of stoves, carries out roasting in air, its bearing reaction weak effect, and the Manganse Dioxide transformation efficiency is low.If when being controlled at temperature below 300 ℃, react insufficient, transformation efficiency has only 20%; If when temperature was increased to 300～400 ℃, transformation efficiency also just reached about 60%.But the crystal formation of above two kinds of prepared Manganse Dioxide of situation is all the r type, and is active good.If temperature is raise, when surpassing 400 ℃, though transformation efficiency increases to some extent, crystal formation begins to change into the β type again, and active decline influences quality product.When temperature reached 500 ℃, crystal formation changed the β type fully into, and activity is poorer.For this reason, past attempts successively adopts the whole bag of tricks to be improved.For example, in the manganous carbonate roasting process, feed steam or feed steam and oxygen, the pyrolysis oxidizing reaction is carried out containing wet or contain in the wet rich oxygen.And for example, after the manganous carbonate thermal degradation, add water roasting again again; Or roasting in vapoury air, roasting in vapoury oxygen more earlier; Carry out two sections pyrolysis oxidation reaction process.
The clear 50-21995 of Japanese Patent number, proposing at maturing temperature is 280 °～400 ℃, and airborne steam content is in 10～80% scopes, and manganous carbonate is through long time treatment, and Manganse Dioxide content can reach 80%, and crystal formation is the γ type.
Deutsches Reichs-Patent DE-3036962 number, the Manganse Dioxide manufacture method of being narrated, be characterized in manganous carbonate earlier 275 °～375 ℃ of temperature and contain roasting in the air of quantity of steam 15～85%, and then in the oxygen that contains steam 15～85%, carry out roasting, it is active good to make, and content is 80% or higher Manganse Dioxide.
Above the whole bag of tricks though all improved the transformation efficiency of Manganse Dioxide, must add steam and oxygen, has therefore correspondingly increased cost of equipment and production cost.In addition, the maturing temperature of above-mentioned manganese carbonate pyrolysis oxidation must be controlled between 300 °～400 ℃.Therefore, temperature required low, and available having a narrow range of temperature, if take common burning coal or oil firing direct heating mode, temperature of combustion height then, and the temperature of practical application is low, and the UTILIZATION OF VESIDUAL HEAT IN difficulty.So that thermo-efficiency is low, and energy consumption is big, the also difficult control of temperature.
The objective of the invention is to overcome the shortcoming in the above-mentioned production technique, propose a kind ofly to make it in the pyrolysis oxidation reaction process, need not add steam and oxygen, can reach higher Manganse Dioxide transformation efficiency equally, and in the baking heat process, adopt low-temperature heat source, make full use of waste heat simultaneously, improve thermo-efficiency, cut down the consumption of energy.
The present invention is to be raw material with synthetic aqueous carbonic acid manganese, places rotary kiln to carry out roasting, after the pyrolysis oxidation, obtains quality height, active good γ type Manganse Dioxide.
Processing method of the present invention is characterized in: (1) takes indirect roasting mode, will be used for the heated air of roasting and the gas of participation pyrolysis oxidizing reaction and separate, and both do not contact mutually, take their own roads, and become independently closed circulation system.(2) take all same direction of heated air, reactant gases and heated material to flow, make it in roasting process, form preheating, reaction, dry three phases.(3) the roasting material adopts aqueous carbonic acid manganese, makes it be evaporated to water vapor at preheating section, and the water content of regulating manganous carbonate is in 10～50% scopes, with required steam content in the control reactant gases.(4) required oxygen level is about 120～140% of stoichiometric quantity in the reactant gases, takes to regulate the furnace air soakage and controls.
In roasting process, the temperature in of rotary kiln is controlled at about 400 ℃.To guarantee the temperature higher (400～375 ℃) of beginning kiln hood preheating section, make that water content can be evaporated to water vapor quickly in the manganous carbonate, form rapidly reaction required contain humid gas; And the temperature moderate (375～325 ℃) of middle part conversion zone in the kiln accords with the temperature required of manganese carbonate pyrolysis oxidation; The temperature lower (325～300 ℃) of last kiln tail dryer section both can satisfy dehydrating, and the reason temperature is too high and make established γ type Manganse Dioxide change crystal formation again, thereby has guaranteed quality product.More than demonstrated fully in the rotary kiln baking reaction process, taked the material that participates in reacting and the superiority of gas and heating medium three coflow.
Novel rotary kiln of the present invention is characterized in: (1) kiln body is a double layer jacket structure, is made up of shell and inner core, and shell is welded with steel plate, and inner core is made by stainless steel.The roasting material reacts in inner core, and the chuck between shell and the inner core is the circulation passage of heating medium.Form indirect heating roasting mode thus.(2) in order to satisfy the requirement of technological process to heating medium, reactant gases and material three coflow.Kiln hood at rotary kiln is equipped with heating medium inlet tube (being hot blast blast pipe 16), air intake pipe and feed device; Heating medium outlet pipe (being hot blast air outlet tube 17) smoke exhaust pipe and drawing mechanism (3) are housed in order to adapt to required low-temperature heat source of roasting and abundant recovery waste heat at the kiln tail, adopted air as heating medium, and disposed resistance heater, hot air circulation blower and hot air duct, form the baking heat loop of sealing and circulating thus.
Below in conjunction with accompanying drawing equipment of the present invention is described in detail:
Fig. 1 rotary kiln general arrangement
Fig. 2 rotary structure sectional view
Fig. 3 rotary kiln device corollary system figure
Processing unit of the present invention is made up of rotary kiln body and drive unit, feed and discharge system, air feed and fume exhaust system heating circulation system.
The body of rotary kiln (1) is a double layer jacket structure, is made up of shell (2) and inner core (3).Chuck between shell and the inner core is the circulation passage of baking heat medium, and the roasting material carries out the pyrolysis oxidizing reaction in inner core.Kiln body drive (5) is made up of electric motor, step-down gear and drive pinion.Behind double reduction, by the transmission gear ring (4) on the drive pinion drive kiln body.Kiln body rotating speed is that per minute 0.1～0.25 changes.
Feed and discharge system: material is by the disk feeder (12) of kiln hood feed equably, send into rotary kiln inner core (3) through worm conveyor (13), with cylinder of rotary kiln revolution carrying out roasting, slowly advance along inner tube wall simultaneously, discharge from the discharge port (10) of kiln tail then, transport through worm conveyor (13).
Air feed and fume exhaust system: the air that the manganese carbonate pyrolysis oxidation is required, air intake pipe (9) suction by kiln hood enters kiln body inner core (3) through worm conveyor (13) with material then.The air inlet adjustment valve is housed on the air suction pipe.The waste gas that material produces in the roasting reaction is discharged from the smoke exhaust pipe (11) on kiln tail top, after water dust scrubber (9) gathers dust, enters atmosphere through induced draft fan (20) and chimney (21) again.The induced draft fan inlet is equipped with the smoke regulating valve (not shown).
The baking heat recycle system: the baking heat medium adopts air, is heated to 400～450 ℃ in resistance heater (15).Hot-air inlet pipe (16) through kiln hood enters the rotary kiln chuck, material in the inner core is carried out indirect baking heat, when heating medium flow to the kiln tail, (this moment, temperature was reduced to 300～350 ℃), entering hot air circulation blower (14) through hot blast air outlet tube (17) hot-blast conduit (18) again pressurizes, deliver to resistance heater (15) again and heat up, return rotary kiln then.Form sealing and circulating thus, go round and begin again.
Embodiment
Processing method of the present invention and equipment thereof through repetition test repeatedly with after revising, have been determined comparatively reasonably rotary structure and corollary apparatus (referring to Fig. 1 and Fig. 2,3) thereof.
The rotary kiln of the present invention's design and the major technique of corollary apparatus thereof are characterized as:
Rotary kiln external diameter 1000mm
Rotary kiln effective diameter 760mm
Rotary kiln length overall 14000mm
Rotary kiln useful length 12000mm
1～2 ° at rotary kiln pitch angle
Rotary kiln rotating speed 0.1～0.25r/min
Resistance heater voltage 380V
Resistance heater power 140KW
Hot air circulation blower air quantity 5000m
3/ h
Hot air circulation blower blast 1471Pa
The major technique condition of present embodiment is:
Material is gone into kiln amount 80～100kg/h
Material moisture 10～30%
Air imbibed quantity 50～100m
3/ h
Roasting reaction times 4～8h
Go into 400～450 ℃ of kiln hot blast temperatures
300～350 ℃ of kiln discharge hot blast temperatures
According to the prepared Manganse Dioxide of present embodiment, its transformation efficiency can reach 80～85%, and crystal formation is the γ type.
Description of drawings
Fig. 1 rotary kiln general arrangement
Fig. 2 rotary structure sectional view
Fig. 3 rotary kiln device corollary system figure
Sequence number among Fig. 1 and Fig. 2,3 is as follows:
1. rotary kiln
2. kiln body case
3. kiln body inner core
4. kiln body transmission gear ring
5. kiln body drive
6. the kiln body supports backing ring
7. support roller
8. support roller and position-limited wheel
9. air intake pipe
10. discharge port
11. smoke exhaust pipe
12. disk feeder
13. worm conveyor
14. hot air circulation blower
15. resistance heater
16. hot-air inlet pipe
17. hot blast air outlet tube
18. hot-blast conduit
19. water dust scrubber
20. induced draft fan
21. chimney
Claims (5)
1, a kind of method of producing Manganse Dioxide with manganese carbonate pyrolysis, it is characterized in that with synthetic aqueous carbonic acid manganese be raw material, put in the rotary kiln, take indirect heating to connect the roasting mode that continues and carry out the pyrolysis oxidizing reaction, participate in material and the gas and the baking heat medium of reaction, the three connects the roasting that continues in flowing along same direction.
2, method according to claim 1, the gas that it is characterized in that the roasting material and participate in reacting does not mix mutually with the baking heat medium, and heating medium adopts warm air.
3, method according to claim 2 is characterized in that: the required water capacity in the reactant gases, take to regulate the moisture in the material, be controlled in 10～50% scopes, make its preheating section in connecting the roasting process that continues produce steam, required oxygen level is stoichiometrical 120～140% in the reactant gases, and the method for taking to regulate the free air soakage is controlled.
4, the rotary kiln of Manganse Dioxide is produced in a kind of pyrolysis, by motor, and deceleration device, the supporting backing ring, cylindrical shell, feeding device, compositions such as discharge device is characterized in that, the kiln body is the bilayer structure that shell and inner core are formed, and forms hollow jacket between shell and the inner core.
5, the feature of rotary kiln heating unit according to claim 4 is: the sealing and circulating heating circuit of being made up of airheater hot air duct etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87100333.3A CN1003369B (en) | 1987-01-12 | 1987-01-12 | Method and equipment of manganese dioxide prodn. by pyrolyzing manganese carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87100333.3A CN1003369B (en) | 1987-01-12 | 1987-01-12 | Method and equipment of manganese dioxide prodn. by pyrolyzing manganese carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87100333A CN87100333A (en) | 1987-11-04 |
| CN1003369B true CN1003369B (en) | 1989-02-22 |
Family
ID=4812823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87100333.3A Expired CN1003369B (en) | 1987-01-12 | 1987-01-12 | Method and equipment of manganese dioxide prodn. by pyrolyzing manganese carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1003369B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4077647B2 (en) * | 2002-04-08 | 2008-04-16 | 日鉱金属株式会社 | Method for producing manganese oxide |
| CN102040247B (en) * | 2010-11-20 | 2012-10-24 | 湖北开元化工科技股份有限公司 | Method and device for producing chemical manganese dioxide |
-
1987
- 1987-01-12 CN CN87100333.3A patent/CN1003369B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN87100333A (en) | 1987-11-04 |
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| C10 | Entry into substantive examination | ||
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| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| CI01 | Publication of corrected invention patent application |
Correction item: Inventor Name Correct: Chen Shuyong False: Zhan Shuyong Number: 8 Volume: 6 |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ERR | Gazette correction |
Free format text: CORRECT FROM: NAME OF THE INVENTOR ZHAN SHUYONG TO: CHEN SHUYONG |
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| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |