CN1070167A - Preparing potassium manganate by three-phase pressurization continuous oxidation - Google Patents

Preparing potassium manganate by three-phase pressurization continuous oxidation Download PDF

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Publication number
CN1070167A
CN1070167A CN92108224A CN92108224A CN1070167A CN 1070167 A CN1070167 A CN 1070167A CN 92108224 A CN92108224 A CN 92108224A CN 92108224 A CN92108224 A CN 92108224A CN 1070167 A CN1070167 A CN 1070167A
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preheating
reaction
potassium manganate
temperature
continuous oxidation
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CN1031256C (en
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李守昌
陈维举
何天民
傅尤谋
邹果
饶晓东
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JIALING CHEMICAL PLANT CHONGQING
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JIALING CHEMICAL PLANT CHONGQING
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
    • C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
    • 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
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The three-phase pressurization continuous oxidation preparing potassium manganate new technology that the present invention is is raw material with common manganese ore powder, comprise the preheating that is mixed of material, the reaction that feeds intake, sedimentation and four technological processs of press filtration, wherein reaction is in one custom-designed " multicompartment fluidized bed continuous oxidation reaction tower ".At 0.1-0.5MPa pressure, carry out under 194-260 ℃ of temperature condition.It has production serialization, low, the MnO of energy consumption material consumption 2The transformation efficiency height, environmental pollution is little and the quality product advantages of higher.

Description

Preparing potassium manganate by three-phase pressurization continuous oxidation
The invention belongs to the compound of manganese in the inorganic chemistry, be specifically related to the preparation method of potassium manganate.
Potassium manganate is normally with potassium hydroxide and manganese ore powder (MnO 2) carry out oxidizing reaction and the product that obtains.
Potassium manganate is unstable, generally how it further is oxidized to potassium permanganate as commodity.Therefore it is the important intermediate of producing potassium permanganate.
Potassium manganate also can directly be used as sterilizing agent, mordant and refining oils etc. as a kind of strong oxidizer.
In the prior art, the domestic open hearth roasting methods (solid phase method) that adopt more, external more advanced technology is to produce potassium manganate with liquid phase oxidation.Japanese kokai publication sho 55-85425 is arranged, open on June 27th, 1980.It is at 0.5-9.5MPa pressure, 150-310 ℃ of temperature, MnO 2With KOH weight ratio (be called for short manganese alkali than) be 1: under the condition of 38-52, adopt high-pressure oxidizing kettle to produce potassium manganate.Its advantage is, material reacts under the liquid phase condition of high voltage, can overcome the dust and the noise pollution problem of solid state reaction, corresponding shortening reaction time in 6-8 hour, MnO 2Transformation efficiency also higher.But because of its required pressure is too high, it is big that equipment adapts to difficulty, generally can only can not adapt to big production requirement with less reactor; Simultaneously, it is to the specification of quality strictness of manganese ore powder raw material, if the low slightly MnO that then has a strong impact on of powdered ore quality 2Than the change rate; In addition, the super potassium amount of its material proportion is too high, and the utilization ratio of oxygen is low, and thermosteresis is big.
The objective of the invention is to use common low-grade manganese powder to be raw material, adopt the material proportion, device structure and the technological process that are different from prior art, overcome the defective of above-mentioned prior art, the reaction of continuously feeding under low pressure further improves MnO 2Transformation efficiency and reduce environmental pollution, produce and consume the potassium manganate low, that product are of fine quality.
Realize the object of the invention by following four step process processes.
One, material be mixed, preheating:
1, be the KOH solution of 47-49 weight % with concentration, concentrating and preheating to 225 ℃ temperature (abbreviation concentrated base) in concentrating pan;
2, with manganese ore powder (MnO 2〉=65 weight %), with the KOH solution of 47-49 weight %, with 0.6-1.2: 1 weight ratio, be mixed (abbreviation mixed ingredients) 15-35 ℃ of temperature, be preheating to 140-180 ℃ of temperature then;
3, will compress, the preheating of air of purification and impurity removal matter is to 210-230 ℃ of temperature.
Two, the reaction that feeds intake:
Manganese ore powder (MnO 2) oxidation reaction process in one custom-designed " multicompartment fluidized bed continuous oxidation reaction tower " (abbreviation reaction tower), finish.Reaction tower is made up of three phase separation section (I), conversion zone (II) and enricher (III) three parts, and the diameter of three phase separation section (I) and conversion zone (II) is than (d 1/ d 2)=1.3-1.7: 1, at conversion zone (II) uniform multilayer sieve aperture division board (1), every layer of division board is provided with a upflow tube (2).In the concentrated base of preheating and mixed ingredients, add 2-6%Mn + 6The oxidation initiator drops into the same opening for feed of three phase separation section (I) (A) then and is mixed in the tower, and making the compound manganese alkali ratio into tower is 1: 12-30; Pressurized air through preheating is introduced from enricher (III) inlet mouth (B), makes reaction tower remain on the pressure range of 0.1-0.5MPa; From the in good time make up water steam of same inlet mouth (B), to keep in the reaction tower water content at 25-34% scope degree of being; Utilize pre-thermal material with the dust separating stack gas of thermal source, introduce the heating medium that reaction tower heating jacket (3) is made reaction mass, make reaction tower be controlled at 194-260 ℃ of temperature range.In the reaction tower of above-mentioned process structure, manganese ore powder and KOH mixture be uniform distribution rationally, can adverse current fully contact with air, carries out oxidizing reaction continuously.In cat head first responding layer, manganese ore powder (MnO 2) and KOH at Mn + 6Become pentavalent manganese by tetravalence manganese very soon under the initiator effect, the very fast again oxidation under air effect of pentavalent manganese generates potassium manganate; Responseless MnO in a last responding layer 2With the KOH compound, overflow to next responding layer through upflow tube and react equally, generate potassium manganate; So by that analogy, successively reacting equally continuously, making MnO until last responding layer 290% of total amount is converted into till the potassium manganate.The potassium manganate crude product that generates is dirty through sieve aperture, all is enriched in the enricher (III), extracts out from discharge port (C) at last and send settling vessel.Waste gas is from cat head blow-down pipe (D) emptying.From initially feeding intake after reaction in 2-4 hour can begin discharging and realize continuous dosing steady running.Temperature, pressure, reaction bed liquid level and manganese alkali compare etc. in the tower, and all available electrical instrumentation is realized chain automatic control.
Three, settlement separate:
The potassium manganate crude product of extracting out at the bottom of the reaction tower is sent in the settling vessel, left standstill 2-3 hour 150-200 ℃ of insulation, the settlement separate supernatant liquid that goes out is KOH and a small amount of K 2CO 3Mixing solutions returns the feed circuit recycling; The lower sediment thing is sent to press filtration.
Four, press filtration:
Through the settlement separate throw out that goes out, the electrolysis mother liquor of producing potassium permanganate with the potassium manganate electrolytic oxidation is diluted to 50 weight % concentration, carries out press filtration then and separates, and filtrate is the KOH solution of 45-48 weight %, returns the feed circuit recycling; Filter cake is the potassium manganate product of 〉=70 weight %.
Fig. 1 is the square block diagram of technology of the present invention.
Fig. 2 is the structural representation of multicompartment fluidized bed continuous oxidation reaction tower.
Among Fig. 2, I-three phase separation section, II-conversion zone, III-enricher; 1-sieve aperture division board, 2-upflow tube, 3-heating jacket; A-concentrated base and mixed ingredients import, B-pressurized air and water vapor import, the outlet of C-potassium manganate crude product, D-blow-down pipe, F 1The import of-stack gas, F 2-flue gas outlet.
Compared with the prior art the present invention owing to adopted custom-designed under low pressure " multicompartment fluidized bed continuous oxidation reaction tower " replacement " high-pressure oxidizing kettle " of operation, has realized the production serialization, and production capacity is significantly improved; Simultaneously with common low-grade manganese powder (MnO2When the 65-75 % by weight) being raw material, MnO2Conversion ratio also can reach 90%, and the manganese ore powder that Japan Patent (JP 55-85425) uses equal quality is during as raw material, MnO2Conversion ratio only has 75%; Because MnO2The high corresponding bed drain purge that reduced of conversion ratio has not only reduced breeze consumption but also further improved the industrial environment quality; Material drops into a small amount of Mn before reaction+6The oxidation initator has significantly reduced MnO2The priming reaction temperature and shortened the reaction time; Can react more than two times greater than still than in same time, throwing the powder amount with the still reaction with tower reaction, greatly dwindled manganese alkali than (the present invention is 1: 12-30, Japan Patent are 1: 38-52), thereby the heat consumption of greatly reducing and material consumption amount; The present invention makes the heat medium of reaction tower with flue gas used heat, and heat energy is fully utilized to greatest extent; Comprehensive energy consumption reduction amplitude of the present invention reaches more than 50%. No matter the present invention improves production capacity and product quality each side improving the work operating condition, reducing consumption and pollution, all is that the domestic open hearth roasting method that generally adopts is unrivaled.
Embodiment:
Be preheating to 225 ℃ 13.6 tons of concentrated bases and be preheating to 170 ℃ 3.8 tons of mixed ingredients (wherein containing 1.6 tons in common manganese ore powder) from reaction tower top opening for feed input first, add 3%Mn simultaneously + 6The oxidation initiator; Opening for feed is introduced and is preheating to 220 ℃ clean pressurized air at the bottom of the reaction tower, makes the tower internal pressure reach 0.2MPa; Stack gas after the dedusting is fed the reaction tower heating jacket, make conversion zone remain on 220 ℃ of temperature.React and begin the continuous discharging of drain hole at the bottom of the tower after 4 hours, by average 4.2 tons of concentrated bases and 0.6 ton of mixed ingredients that per hour in tower, drops into continuously through preheating, constantly introduce pre-hot compressed air simultaneously, keep the reaction tower pressure and temperature, realize the continous-stable operation.The material that drain hole is emitted at the bottom of the tower is formed (weight percent):
K 2MnO 430-40，KOH28-35，K 2CO 310-13
The crude product of above-mentioned composition is through sedimentation, press filtration, and the filter cake of acquisition is 〉=70% potassium manganate, sends to electrolytic oxidation and produces potassium permanganate (KMnO 4).

Claims (4)

1, a kind of method of preparing potassium manganate by three-phase pressurization continuous oxidation, comprise the preheating that is mixed of material, the reaction that feeds intake, sedimentation and four technological processs of press filtration, it is characterized in that: the said reaction process that feeds intake is that first manganese alkali ratio in preheating is 1: 12～30 manganese ore powder (MnO 2〉=65 weight %) and in the KOH compound add 2-6%Mn + 6The oxidation initiator drops in the custom-designed multicompartment fluidized bed continuous oxidation reaction tower then, with pressurized air under 0.1-0.5MPa pressure, 194-260 ℃ temperature condition, the continuous oxidation of counter current contact realizes.
2, according to the described method for preparing potassium manganate of claim 1, it is characterized in that: said multicompartment fluidized bed continuous oxidation reaction tower is made up of three phase separation section (I), conversion zone (II) and enricher (III) three parts, and the diameter of three phase separation section and conversion zone is than (d 1/ d 2)=1.3-1.7: 1, at the uniform multilayer sieve aperture of conversion zone division board (1), every layer of division board is provided with a upflow tube (2).
3, according to the described method for preparing potassium manganate of claim 1, it is characterized in that: the said preheating that is mixed is the KOH solution with 47-49 weight %, concentrating and preheating to 225 ℃ temperature; With manganese ore powder (MnO 2〉=65 weight %) with the KOH solution of 47-49 weight %, with 0.6-1.2: 1 weight ratio, be mixed 15-35 ℃ of temperature, be preheating to 140-180 ℃ of temperature; The pressurized air that purifies is preheating to 200-220 ℃ of temperature.
4, according to the described method for preparing potassium manganate of claim 1, it is characterized in that: said 194-260 ℃ temperature of reaction is the stack gas after the dedusting to be introduced reaction tower heating jacket (3) realize as heating medium.
CN92108224A 1992-07-23 1992-07-23 Process of continuous oxidation to prepare potassium manganate by three-phase pressuring Expired - Lifetime CN1031256C (en)

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CN92108224A CN1031256C (en) 1992-07-23 1992-07-23 Process of continuous oxidation to prepare potassium manganate by three-phase pressuring

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CN1031256C CN1031256C (en) 1996-03-13

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101492182B (en) * 2008-01-22 2011-01-19 遵义双源化工（集团）有限责任公司 Method and equipment for manufacturing potassium manganate
CN101746831B (en) * 2009-12-29 2011-12-28 重庆昌元化工有限公司 Heating system of potassium manganate production technology
CN103570075A (en) * 2013-11-22 2014-02-12 云南建水锰矿有限责任公司 Reactor and system for preparing potassium manganate
CN103570076A (en) * 2013-11-22 2014-02-12 云南建水锰矿有限责任公司 Method for preparing potassium manganate
CN111905682A (en) * 2020-08-18 2020-11-10 萍乡市利升科技有限公司 Oxidation tower and molten salt method continuous oxidation process for producing potassium permanganate by using same
CN116040684A (en) * 2023-02-22 2023-05-02 贵州大学 Method for preparing potassium manganate by using pyrolusite

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101492182B (en) * 2008-01-22 2011-01-19 遵义双源化工（集团）有限责任公司 Method and equipment for manufacturing potassium manganate
CN101746831B (en) * 2009-12-29 2011-12-28 重庆昌元化工有限公司 Heating system of potassium manganate production technology
CN103570075A (en) * 2013-11-22 2014-02-12 云南建水锰矿有限责任公司 Reactor and system for preparing potassium manganate
CN103570076A (en) * 2013-11-22 2014-02-12 云南建水锰矿有限责任公司 Method for preparing potassium manganate
CN103570076B (en) * 2013-11-22 2015-09-30 云南建水锰矿有限责任公司 Prepare the method for potassium manganate
CN103570075B (en) * 2013-11-22 2015-10-28 云南建水锰矿有限责任公司 Prepare reactor and the system of potassium manganate
CN111905682A (en) * 2020-08-18 2020-11-10 萍乡市利升科技有限公司 Oxidation tower and molten salt method continuous oxidation process for producing potassium permanganate by using same
CN116040684A (en) * 2023-02-22 2023-05-02 贵州大学 Method for preparing potassium manganate by using pyrolusite

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Expiration termination date: 20120723

Granted publication date: 19960313