CN109987636A - A kind of energy-saving new technology of manganese sulphate - Google Patents
A kind of energy-saving new technology of manganese sulphate Download PDFInfo
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- CN109987636A CN109987636A CN201910367930.3A CN201910367930A CN109987636A CN 109987636 A CN109987636 A CN 109987636A CN 201910367930 A CN201910367930 A CN 201910367930A CN 109987636 A CN109987636 A CN 109987636A
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- sulfur
- manganese
- sulfur dioxide
- waste heat
- flammable
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/54—Preparation of sulfur dioxide by burning elemental sulfur
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- 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
-
- 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
Abstract
A kind of energy-saving new technology of manganese sulphate, it is related to chemical industry and hydrometallurgical production technical field.It, which is comprised the steps of:, generates sulfur dioxide through burning for flammable sulfide containing material, introduced after residual heat boiler for exchanging heat equipped with after being reacted in manganese dioxide ore pulp reacting sucting collector through filtering, filter residue enters washing kettle and adds water, acid adding tune pH value=2 and liquid-solid ratio=3:1, filtrate Returning reactor after filtering, it is filtered through impurity removal and purification, filtrate returns to impurity removal and purification system after being evaporated to a certain concentration into evaporation and crystallization system, the product after centrifugal dehydration through drying, screening, pack to obtain product.Advantage of the invention is: producing manganese sulfate using the sulfur dioxide generated during the cheap flammable sulfur-bearing object of commercial recovery and nonferrous smelting industry sulfur-bearing mine desulfurization with roasting technique, flammable sulfur-bearing object burning generates a large amount of heat, manganese sulfate solution evaporative crystallization heat supply in this technique is directly used in after waste heat boiler recycles, the heat demand for substantially meeting this technique, has saved production cost.
Description
Technical field
The present invention relates to the production technical fields of manganese sulfate, and in particular to a kind of energy-saving new work of manganese sulfate production
Skill.
Background technique
Manganese sulfate physical property: manganese sulfate (chemical formula MnSO4, formula weight 151.00), monohydrate are blush rhomboidal crystal,
Relative density is 3.50, and fusing point is 700 DEG C, soluble easily in water, does not dissolve in ethyl alcohol.It exists in the form of a variety of hydrates.
Manganese sulfate starts to decompose at 850 DEG C, because of heating degree difference, can release SO3, SO2 or oxygen, residue has titanium dioxide
Manganese or mangano-manganic oxide.When the crystalline hydrate of manganese sulfate is heated to 280 DEG C, the crystallization water of itself can be lost and become nothing
Water object.
Manganese sulfate is the microelement that the crop of synthetic fatty acid needs, therefore manganese sulfate can be applied as fertilizer into soil
Earth can increase production.Manganese sulfate is added in animal feed, there is the effect of fattening.Manganese sulfate be also prepare other manganese salts raw material and
Analytical reagent.Manganese sulfate is also used in the industrial productions such as electrolytic manganese, dyestuff, papermaking and ceramics.
The production technology of manganese sulfate is more at present, there is two mine acid adding lixiviation process, coal reduction roasting method, ferrous sulfate reduction
A variety of production technologies such as lixiviation process, by-product method, sulfur dioxide flue gas reduction method, but all there are a little insufficient and defects in these techniques,
If two mine acid adding lixiviation process are reduced directly acidleach using pyrolusite, troilite, sulfuric acid, this process flow is short, and equipment is simple,
It is easy to control, but the quantity of slag generated in technical process is very big, the whereabouts of slag is difficult to handle, and filter plant investment is big, occupied area
Greatly, manganese recovery ratio is low, besides due in technique use troilite make acidleach reducing agent, brought contents of many kinds of heavy metal ion into, after
The treatment process of phase is more complex；Although coal reduction roasting method simple process, the quantity of slag is few, and energy consumption is high, and environment influences more serious；
Ferrous sulfate reduction method filtration difficulty, the quantity of slag are big；By-product method is although at low cost, but impurity is difficult, of poor quality, and low output etc. lacks
Point；The present technology of sulfur dioxide flue gas reduction method is more mature, and simple process, the quantity of slag is small, system easy to control the quality, due to sulfur dioxide
It is both reducing agent and leaching agent, so acting on the selective leaching of manganese, process flow is controlled and shortened convenient for quality, is value
The method that must be promoted, but the problems such as there is also production capacities to be restricted, and energy consumption is higher.
Summary of the invention
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of energy-saving manganese sulfate productions
New process, the sulfur dioxide flue gas which uses flammable sulfur-bearing object burning to generate are reacted for raw material with pyrolusite pulp, are being reacted
Not only make reducing agent in the process but also makees leaching agent use.The reducing agent of traditional handicraft is eliminated in this way and has saved sulfuric acid dosage.Together
When sulfur-bearing object burning after, generate a large amount of thermal energy, by waste heat boiler recycling be used for this technique manganese sulfate solution evaporative crystallization.Base
This meets the thermal requirement of technique, is not necessarily to additional heat, and raw materials for production and energy consumption cost, later period removal of impurities processing work is greatly saved
Sequence is simple, and expense is low, and product quality is high, practical, has very high market popularization value.
To achieve the above object, the present invention is using following technical scheme: it is comprised the steps of:
A burns flammable sulfide containing material as raw material through combustion furnace generates sulfur dioxide gas；
The sulfur dioxide gas of high temperature obtained by step a in residual heat boiler for exchanging heat, is obtained low temperature sulfur dioxide flue gas by b；
C introduces the low temperature sulfur dioxide flue gas of step b equipped with manganese dioxide ore pulp and certain density iron ion and pH value=2
Reacting sucting collector in carry out redox reaction, object slurry is obtained after redox reaction and is sent to lower workshop section, exhaust gas is sent to alkalinity
Emptying after desulfurizing tower desulfurization is up to standard；
Through filtering, filter residue enters washing kettle and adds water, acid adding tune pH value=2 and liquid-solid ratio=3 material of d after step c fully reacting:
1, filtering, filtrate returns to reacting sucting collector, and filter residue sends brick field or cement plant outside；
Filtrate of e after step d slurry filtration through impurity removal and purification filter (including oxidation removal dithionic acid radical ion, iron ion,
Heavy metal ion, calcium ions and magnesium ions etc.), filter residue sends brick field outside, and filtrate is into evaporation and crystallization system, and centrifugation is de- after being evaporated to a certain concentration
Water, centrifugal dehydration post mother liquor return to impurity removal and purification system；
Product of f after step e centrifugal dehydration through drying, screening, pack to obtain product.
The flammable sulfide containing material is industrial sulphur, commercial recovery sulfur-bearing waste residue and all flammable containing sulfur minerals.Such as: coking
Sulfur waste sulphur, troilite, zinc sulfide ore, galena, antimony sulfide ore that factory recycles etc..
The sedimentation slag of the waste heat boiler of the combustion furnace and step b of the step a send brick field, cement plant or smeltery's disposition.
Steaming of waste heat for supplying medium of the 1 step b high temperature sulfur dioxide gas after residual heat boiler for exchanging heat for this technique
It sends out crystal system to use, the waste heat heat transfer medium after use returns again to waste heat boiler recycling.
The working principle of the invention: flammable industrial sulphur, commercial recovery sulfur-bearing waste residue and all flammable containing sulfur minerals are utilized
Make raw material and generate sulfur dioxide gas through combustion furnace burning, sulfur dioxide gas is introduced into the reaction equipped with manganese dioxide ore pulp and is set
In standby, redox reaction is carried out, tail gas after the reaction was completed is again through alkaline desulfurizing tower desulfurization to qualified discharge.Object after reaction
Expect through filtering, removal of impurities, evaporative crystallization, centrifugal dehydration, drying, screening, pack to obtain sulfuric acid product.Flammable sulfur-bearing object is fired in combustion furnace
After burning, high-temperature gas residual heat boiler for exchanging heat again makes sulfur dioxide temperature be down to the temperature of suitable manganese dioxide ore pulp reaction.Heat exchange
Heat transfer medium afterwards is used as the heating medium of evaporation and crystallization system, and entire process system is made not need external additional heat.
After adopting the above technical scheme, the present invention has two big effects: 1, using the cheap flammable sulfur-bearing object of commercial recovery and coloured
The sulfur dioxide that generates during smelting industry sulfur-bearing mine desulfurization with roasting technique produces manganese sulfate, since raw material is inherently cheap, then
Be exactly sulfur dioxide it is both reducing agent and leaching agent, eliminates reducing agent and sulfuric acid in traditional handicraft, and institute in this technique
The sulfuric acid of addition only adjusts pH value to use, dosage very little, so realizing simultaneously present invention saves the raw materials for production cost of manganese sulfate
Scale, continuous production, it is such to be different from sulfur dioxide FGD method production manganese sulfate, low output, cannot on a large scale
Disadvantage.2, since the burning of flammable sulfur-bearing object generates a large amount of heat, sulfuric acid in this technique is directly used in after waste heat boiler recycles
Manganese solution evaporation and crystallization system heat supply, the heat demand that can meet in this technique substantially have saved manganese sulfate using multiple-effect evaporation
The cost of energy of production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other drawings based on these drawings.
Fig. 1 is process flow diagram of the invention.
Specific embodiment
Referring to shown in Fig. 1, present embodiment the technical solution adopted is that: it is comprised the steps of:
1, burning generates high temperature sulfur dioxide flue gas:
A burns flammable sulfide containing material as raw material through combustion furnace generates sulfur dioxide gas；
The sulfur dioxide gas of high temperature obtained by step a in residual heat boiler for exchanging heat, is obtained low temperature sulfur dioxide flue gas by b, heat exchange
Heat transfer medium afterwards is used as the heating medium of evaporation and crystallization system, and entire process system is made not need external additional heat,
Achieve the purpose that energy-saving；
C introduces the low temperature sulfur dioxide flue gas of step b equipped with manganese dioxide ore pulp and certain density iron ion and pH value=2
Reacting sucting collector in carry out redox reaction, tail gas and slurry are obtained after redox reaction, in process due to using
Sulfur dioxide had not only made reducing agent but also had made leaching agent, thus to manganese Selectively leaching effect with higher, other impurity leaching rates
Low feature.Later period removal of impurities treatment process is simple in this way, and expense is low, and product quality is high, especially for LITHIUM BATTERY high-purity sulphuric acid
For manganese, quality is more secure；
Through filtering, filter residue enters washing kettle and adds water, acid adding tune pH value=2 and liquid-solid ratio=3 slurry of d after step c fully reacting:
1, it filters after mixing evenly, filtrate returns to reacting sucting collector, and filter residue sends brick field or cement plant outside；
Filtrate of e after step d slurry filtration through impurity removal and purification filter (including oxidation removal dithionic acid radical ion, iron ion,
Heavy metal ion, calcium ions and magnesium ions etc.), filter residue sends brick field or cement plant outside, and filtrate is evaporated to a certain concentration into evaporation and crystallization system
Centrifugal dehydration afterwards, centrifugal dehydration post mother liquor return to impurity removal and purification system；
Product of f after step e centrifugal dehydration through drying, screening, pack to obtain product.
The sulfide containing material is industrial sulphur, commercial recovery sulfur-bearing waste residue and all containing sulfur minerals, in production manganese sulfate original
The feature of the selection of material above mainly selects cheap commercial recovery sulfur-bearing object, such as the sulfur residue and smelting of coke-oven plant's recycling
Containing sulfur minerals roast the sulfur dioxide generated and waste heat to generate manganese sulfate, such sulfur dioxide substitution in industry, relieving haperacidity industry
Sulfuric acid uses, and has saved the use cost of sulfuric acid.
The sedimentation slag of the waste heat boiler of the combustion furnace and step b of the step a send brick field, cement plant or smeltery's disposition.
2, waste heat recycles:
Evaporative crystallization of waste heat for supplying medium of the step b high temperature sulfur dioxide flue gas after residual heat boiler for exchanging heat for this technique
System uses, and the waste heat heat transfer medium after use returns again to waste heat boiler recycling, and the combustion furnace and waste heat boiler are not
The combustion furnace or waste heat boiler for being confined to a certain form may be any type of combustion furnace or waste heat recovery furnace, combustion furnace and
Waste heat boiler can also be integrated use.
The step c exhaust gas is again through alkaline desulfurizing tower desulfurization to qualified discharge.
The working principle of the invention: made using industrial sulphur, commercial recovery sulfur-bearing waste residue and all flammable containing sulfur minerals former
Material burns through combustion furnace generates sulfur dioxide gas, and sulfur dioxide gas is introduced to the consersion unit that manganese dioxide ore pulp is housed
In, redox reaction is carried out, exhaust gas after the reaction was completed is again through alkaline desulfurizing tower desulfurization to qualified discharge.Material after reaction
Through filtering, removal of impurities, evaporative crystallization, centrifugal dehydration, drying, screening, pack to obtain sulfuric acid product.Sulfur-bearing object combustion furnace burning after,
High-temperature gas residual heat boiler for exchanging heat again makes sulfur dioxide temperature be down to the temperature of suitable manganese dioxide ore pulp reaction.After heat exchange
Heat transfer medium is used as the heating medium of evaporation and crystallization system, so that entire process system is not needed external additional heat, is reached
Energy-saving purpose.
After adopting the above technical scheme, the present invention has two big effects: 1, using the cheap flammable sulfur-bearing object of commercial recovery and
The sulfur dioxide that generates during nonferrous smelting industry sulfur-bearing mine desulfurization with roasting technique produces manganese sulfate, conveniently due to raw material itself
Preferably, besides sulfur dioxide is both reducing agent and leaching agent, eliminates reducing agent and sulfuric acid in traditional handicraft, and this technique
In added sulfuric acid only adjust pH value use, dosage very little, so present invention saves the raw materials for production costs of manganese sulfate, simultaneously
Scale, continuous production are realized, such different from sulfur dioxide FGD method production manganese sulfate, low output is unable to established practice
The shortcomings that mould.2, it since the burning of flammable sulfur-bearing object generates a large amount of heat, is directly used in this technique after waste heat boiler recycles
Manganese sulfate solution evaporation and crystallization system heat supply can meet the heat demand (using multiple-effect evaporation) in this technique substantially, save
The cost of energy of manganese sulfate production.
The above is only used to illustrate the technical scheme of the present invention and not to limit it, and those of ordinary skill in the art are to this hair
The other modifications or equivalent replacement that bright technical solution is made, as long as it does not depart from the spirit and scope of the technical scheme of the present invention,
It is intended to be within the scope of the claims of the invention, meanwhile, this patent is also applied for the manganese such as electrolytic manganese, electrolytic manganese dioxide
The technique application of product industry.
Claims (3)
1. a kind of energy-saving new technology of manganese sulphate, it is characterised in that the titanium dioxide generated using the burning of flammable sulfur-bearing object
As reducing agent and leaching agent in production of manganese sulfate as, it is comprised the steps of: sulphur gas
A is burnt as raw material through combustion furnace using flammable sulfide containing material generates sulfur dioxide gas；
The sulfur dioxide gas of high temperature obtained by step a in residual heat boiler for exchanging heat, is obtained low temperature sulfur dioxide flue gas by b；
C introduces the low temperature sulfur dioxide flue gas of step b equipped with manganese dioxide ore pulp and certain density iron ion and pH value=2
Reacting sucting collector in carry out redox reaction, tail gas and slurry are obtained after the completion of redox reaction；
Through filtering, filter residue enters washing kettle and adds water, acid adding tune pH value=2 and liquid-solid ratio=3 slurry of d after step c fully reacting:
1, filtering, filtrate Returning reactor, filter residue sends brick field or cement plant outside；
Filtrate of e after step d slurry filtration through impurity removal and purification filter (including oxidation removal dithionic acid radical ion, iron ion,
Heavy metal ion, calcium ions and magnesium ions etc.), filter residue sends brick field or cement plant outside, and filtrate is evaporated to a certain concentration into evaporation and crystallization system
Centrifugal dehydration afterwards, centrifugal dehydration post mother liquor return to impurity removal and purification system；
Product of f after step e centrifugal dehydration through drying, screening, pack to obtain product.
2. the energy-saving new technology of manganese sulphate of one kind according to claim 1, it is characterised in that: the sulfur-bearing object
Material is industrial sulphur, commercial recovery sulfur-bearing waste residue and all flammable containing sulfur minerals.
3. the energy-saving new technology of manganese sulphate of one kind according to claim 1, it is characterised in that: the step b
Waste heat for supplying medium of the high temperature sulfur dioxide flue gas after residual heat boiler for exchanging heat is used for the evaporation and crystallization system of this technique, is used
Waste heat heat transfer medium afterwards returns again to waste heat boiler recycling, and the combustion furnace and waste heat boiler are not limited to a certain shape
The combustion furnace or waste heat boiler of formula may be any type of combustion furnace or waste heat recovery furnace, and combustion furnace and waste heat boiler can also
It is used with being integrated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910367930.3A CN109987636A (en) | 2019-05-05 | 2019-05-05 | A kind of energy-saving new technology of manganese sulphate |
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| CN201910367930.3A CN109987636A (en) | 2019-05-05 | 2019-05-05 | A kind of energy-saving new technology of manganese sulphate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010180A (en) * | 2022-07-26 | 2022-09-06 | 贵州金瑞新材料有限责任公司 | Preparation method of high-purity manganese sulfate |
| CN115058724A (en) * | 2022-06-17 | 2022-09-16 | 贵州能矿锰业集团有限公司 | Energy-saving and consumption-reducing process of coal-electricity-manganese comprehensive utilization system |
| CN115159470A (en) * | 2022-08-02 | 2022-10-11 | 广西埃索凯新材料科技有限公司 | Method for preparing sulfuric acid and manganese sulfate in linkage manner by adopting sulfur |
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