CN113909260A - Manganese product clean production and resource recycling treatment process - Google Patents
Manganese product clean production and resource recycling treatment process Download PDFInfo
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- CN113909260A CN113909260A CN202111333598.2A CN202111333598A CN113909260A CN 113909260 A CN113909260 A CN 113909260A CN 202111333598 A CN202111333598 A CN 202111333598A CN 113909260 A CN113909260 A CN 113909260A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D25/00—Filters formed by clamping together several filtering elements or parts of such elements
- B01D25/12—Filter presses, i.e. of the plate or plate and frame type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/40—Acidic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a manganese product clean production and resource recycling treatment process. The invention carries out resource treatment on the sulfuric acid mist and hydrogen sulfide gas generated in the production process of the manganese industry and the generated massive manganese slag solid waste by adopting a reasonable process, replaces the traditional alkali substances with the commonly-discarded low-grade manganese dioxide, fully absorbs the harmful gas of the acid mist and the hydrogen sulfide generated in the acid leaching process for preparing manganese, generates the manganese sulfate slurry which can be recycled by enterprises in the manganese industry, manganese sulfate is dissolved in the slurry, and the liquid containing manganese sulfate is reused in a manganese product production system after filter pressing, the filter-pressing manganese slag generated in the production process of the filter-pressing manganese slag and manganese industry is calcined to become manganese slag building material micro powder products for sale, hot air generated in the calcining period is recycled in the deamination process to promote full deamination, ammonia gas is separately recycled to be ammonia water, sulfur dioxide flue gas generated in the calcining period is separately recycled to be sulfuric acid, and the ammonia water and the sulfuric acid are all recycled to a front-end manganese product production system. The process method finds application in the commonly discarded low-grade manganese dioxide, realizes the full recovery of pollutants generated in the whole manganese preparation process, and realizes industrial circulation.
Description
Technical Field
The invention relates to the technical field of manganese industry, in particular to a clean production and resource recycling treatment process for a manganese product.
Background
The manganese industry is an industry with high resource and energy consumption and large pollutant generation amount, although the technical level is improved in recent years and the environmental protection work is enhanced, the environment pollution of manganese manufacturing enterprises in the production process is still serious, for example, the filter pressing residues generated after the sulfuric acid mist generated in the production process is combined with hydrogen sulfide gas and manganese ores contain soluble ammonium sulfate, magnesium sulfate, manganese sulfate, insoluble calcium sulfate and trace heavy metal elements besides siliceous minerals, aluminosilicate minerals and a small amount of iron minerals brought by raw ores, volatile ammonia gas and leachate generated in the stacking process pollute the environment, waste land resources and generate the risks of geological disasters such as dam break and debris flow. The fact that sulfuric acid mist generated in the production process of the manganese industry does not compete with hydrogen sulfide gas is avoided, but no effective zero-emission treatment means exists at present, and a large amount of manganese slag not only seriously affects land resources, biological resources and water resources, but also seriously restricts the rapid development of the manganese industry.
Disclosure of Invention
The invention aims to provide a resource circulation treatment process and a resource circulation treatment device based on a manganese product production system, which are based on the fact that through the reasonable environment-friendly treatment of the whole flow in the manganese industry production, waste gas and waste residues can be converted into byproducts such as manganese sulfate, ammonia water, sulfuric acid and the like to be reused in the manganese manufacturing industry to form the circulation industry in situ, and meanwhile, the calcined desulfurization and deamination manganese residues have activity after being subjected to superfine grinding, can become building mixed material micro powder, can be sold to cement enterprises as clinker or directly sold to enterprises such as concrete, dry mixed mortar and the like to replace part of cement, and meet the aim of sustainable circulation economic development.
In order to achieve the above purpose, the invention provides the following technical scheme: a clean production and resource recycling treatment process for manganese products is characterized in that acid mist and hydrogen sulfide generated by a manganese product production system are introduced into an acid mist/hydrogen sulfide absorption device, manganese dioxide pulping liquid is arranged in the acid mist/hydrogen sulfide absorption device, and the acid mist and the hydrogen sulfide are absorbed by the manganese dioxide pulping liquid to generate manganese sulfate slurry;
and (3) filtering the manganese sulfate slurry through a filtering device to obtain filtrate and manganese slag, wherein the main component of the filtrate is manganese sulfate which can be directly recycled to a manganese product production system, and the manganese slag can be subjected to subsequent process recycling treatment.
Further, in the invention, the manganese slag is also produced by the manganese product production system, the manganese slag obtained from the filtering device and the manganese slag produced in the manganese product production system are mixed with water and quicklime in the gas stripping ammonia removal tank to carry out pulping and ammonia removal, ammonium sulfate in the manganese slag is subjected to exothermic reaction with the added quicklime and water, hot air under pressure from the hot air booster pump is introduced into the gas stripping ammonia removal tank, so that the slurry is stirred to promote the ammonia to escape largely and fully, and the water amount in the gas stripping ammonia removal tank cannot be continuously increased due to steam condensation because the hot air is adopted to replace steam.
Further, in the invention, the adding amount of the quicklime is 5-35% of the amount of the manganese slag, and the temperature of the hot air with pressure is 50-220 ℃.
Further, in the invention, ammonia gas generated in the gas stripping deammoniation tank passes through a partition dedusting system and then enters an ammonia water production device, and ammonia water produced by the ammonia water production device returns to a manganese product production system;
and the residual product in the gas stripping ammonia removal tank enters a filter press, filtered water and deamination manganese slag are obtained through the filter press and recycled to the gas stripping ammonia removal tank, the deamination manganese slag enters a high-temperature rotary kiln for desulfurization, and pulverized coal provided by a pulverized coal mill is used as fuel in the high-temperature rotary kiln.
Further, in the invention, the deamination and desulfurization manganese slag in the high-temperature rotary kiln is introduced into a cooling cylinder for heat exchange, normal-temperature air is heated into high-temperature air with the temperature of more than 500 ℃ through the cooling cylinder and enters the high-temperature rotary kiln for combustion supporting, and the high-temperature air supports the combustion of pulverized coal to form a high-temperature combustion environment; cooling the deaminated and desulfurized manganese slag, and then feeding the deaminated and desulfurized manganese slag into a superfine grinding device for superfine grinding to obtain manganese slag micropowder.
Further, in the invention, the flue gas generated in the high-temperature rotary kiln passes through the high-temperature gas filter, after the high-temperature gas filter effectively filters a large amount of dust in the flue gas, the dust is blown to the dust bin and is sent into the superfine grinding device together with the dust collected by the partition dust removal system, and all the dust and the manganese slag are uniformly mixed and ground;
the high-temperature flue gas filtered by the high-temperature gas filter enters a first heat exchanger, the first heat exchanger utilizes normal-temperature air to exchange heat with the high-temperature flue gas to form high-temperature air, and the high-temperature air is pressurized by a hot air booster pump to provide stirring hot air for the air stripping ammonia removal tank.
Further, in the invention, hot air is used for replacing conventional steam for stripping, and the stripping is replaced by 'air stripping', so that condensed water is not continuously generated in the deamination tank like a stripping process.
Further, in the invention, the flue gas from the first heat exchanger enters the catalytic oxidation device after being purified by the partition dust removal system, sulfur dioxide in the flue gas is completely oxidized into sulfur trioxide (exothermic reaction) by the catalytic oxidation device, high-temperature sulfur trioxide gas generated by the exothermic reaction is introduced into the second heat exchanger for heat exchange, and the second heat exchanger utilizes normal-temperature air and the high-temperature sulfur trioxide gas for heat exchange to form high-temperature air and introduces the high-temperature air into the catalytic oxidation device so as to maintain the temperature required by the catalytic oxidation reaction.
Further, in the invention, sulfur trioxide gas passing through the heat exchanger II enters a sulfuric acid production system to become sulfuric acid with proper concentration for reusing in a manganese product production system;
the flue gas escaped from the sulfuric acid production system is absorbed and purified by lime of the flue gas purification system and then is discharged after reaching standards, and the calcium sulfate solid waste produced by the flue gas purification system is mixed into the manganese slag to enter a treatment procedure, so that circulation is formed.
A manganese product clean production and resource recycling treatment process comprises the following steps:
the acid mist/hydrogen sulfide absorption device is internally provided with manganese dioxide pulping liquid, the manganese dioxide pulping liquid absorbs the acid mist and the hydrogen sulfide and generates manganese sulfate slurry which is sent to the filtering device;
the filtering device filters the manganese sulfate slurry to obtain filtrate and manganese slag, the manganese slag enters the gas stripping ammonia removal tank, and the filtrate is recycled to the manganese product production system;
the gas stripping deamination tank is used for deaminating the manganese slag and obtaining ammonia gas and deaminated manganese slag, the ammonia gas is introduced into an ammonia water production device, and the residual product enters a filter press;
the filter press is used for carrying out filter pressing on the deamination manganese slag to obtain filtered water and deamination manganese slag after being dewatered, the deamination manganese slag after being dewatered is sent to the high-temperature rotary kiln, and the filtered water is reused in the air stripping ammonia removal tank;
the high-temperature rotary kiln obtains flue gas and deamination and desulfurization manganese slag, the flue gas is introduced into a high-temperature gas filter, and the deamination and desulfurization manganese slag enters a cooling cylinder;
the cooling cylinder cools the deamination desulfurization manganese slag, high-temperature air obtained through heat exchange is introduced into the high-temperature rotary kiln for combustion supporting, and the deamination desulfurization manganese slag after being cooled enters the superfine grinding device;
the superfine grinding device is used for uniformly mixing and superfine processing the manganese slag and the dust into manganese slag building material micro powder;
the high-temperature gas filter filters the flue gas, the flue gas enters the first heat exchanger, and filtered dust is introduced into the dust bin;
the first heat exchanger utilizes normal-temperature air to exchange heat with high-temperature flue gas to obtain high-temperature air, the high-temperature air is pressurized by a hot air booster pump to provide stirring hot air for the air stripping and ammonia removing tank, and the flue gas is introduced into a partitioned dust removal system;
the partition dust removal system removes dust of ammonia gas and sulfur-containing gas in a partition manner, and sends the dust collected respectively into the dust bin;
the ammonia water production device generates ammonia water from ammonia gas and returns the ammonia water to the manganese product production system;
the catalytic oxidation device is used for completely oxidizing sulfur dioxide in the flue gas into sulfur trioxide, the catalytic reaction is an exothermic reaction, high-temperature sulfur trioxide gas is introduced into the heat exchanger II to exchange heat with normal-temperature air, and the high-temperature air obtained through heat exchange is introduced into the catalytic oxidation system so as to maintain the required environment temperature of catalytic oxidation.
Further, the invention also comprises a sulfuric acid production system and a flue gas purification system, wherein the sulfuric acid production system prepares sulfuric acid with proper concentration after being used and then the sulfuric acid is reused in the manganese product production system;
the flue gas escaped from the sulfuric acid production system is purified by the flue gas purification system and then discharged up to the standard, and the calcium sulfate solid waste produced by the flue gas purification system is mixed into the manganese slag to enter a treatment procedure, so that circulation is formed.
The beneficial effects are that the technical scheme of this application possesses following technological effect:
1. according to the method, acid mist and hydrogen sulfide gas of sulfuric acid generated in the production process of the manganese industry and a large amount of solid waste of manganese slag are subjected to resource treatment by adopting a reasonable process, waste low-grade manganese dioxide is used for replacing traditional alkali substances, harmful gases of the acid mist and the hydrogen sulfide are fully absorbed, a manganese sulfate slurry product which can be directly recycled by manganese industry enterprises is generated through reaction, manganese sulfate is dissolved in the slurry, the manganese sulfate solution can be recycled to a manganese product production system through solid-liquid separation, filter residues are calcined to form manganese slag building material micro powder for sale, ammonia gas generated by gas stripping and sulfur dioxide gas generated during calcination are respectively recycled to ammonia water and sulfuric acid for reuse to the manganese product production system, and dust collected in flue gas collection is mixed into the building material micro powder for sale. The process method realizes the full recovery of the pollutants generated in the manganese industry and realizes industrial circulation.
2. The invention designs an advanced heat energy recovery system, which comprises but is not limited to a high-temperature rotary kiln, a cooling cylinder, a first heat exchanger, a second heat exchanger, a hot air booster pump and the like, so that an external heating source is not required for the gas stripping deammoniation tank and the catalytic oxidation device, and the heat pollution is eliminated.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic flow diagram of the process of the present invention.
FIG. 2 is a schematic diagram of manganese slag micro powder detection according to the invention.
In the figures, the meaning of the reference numerals is as follows: 1. a manganese product production system; 2. an acid mist/hydrogen sulfide absorption unit; 3. a filtration device; 4. a gas stripping deammoniation tank; 5. a filter press; 6. a high temperature rotary kiln; 7. a cooling cylinder; 8. a superfine grinding device; 9. grinding the coal; 10. a high temperature gas filter; 11. a first heat exchanger; 12. a zoned dust removal system; 13. an ammonia water production device; 14. a catalytic oxidation unit; 15. a hot air booster pump; 16. a second heat exchanger; 17. a sulfuric acid production system; 18. a flue gas purification system; 19. a dust bin.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways, as the disclosed concepts and embodiments are not limited to any one implementation. In addition, some aspects of the present disclosure may be used alone, or in any suitable combination with other aspects of the present disclosure.
At present, sulfuric acid and hydrogen sulfide acid mist generated in the production process of the manganese industry not only corrode field equipment, but also are harmful to human bodies. The industry adopts a method of water or alkali absorption so far, the water absorption efficiency is low, and the absorption effect is not ideal; the alkali absorption cost is high, and secondary pollutants such as sodium sulfate or calcium sulfite are left.
The manganese filter-press residue is relatively special waste residue, has high viscosity and high water content, basically belongs to an inert material, and is always short of an effective utilization mode. From the analysis of the existing data, the research results on the comprehensive utilization of manganese filter-press residues are few, and the basic research on the comprehensive utilization of manganese filter-press residues comprises the following aspects:
(1) cement retarder using manganese filter-pressing residue instead of gypsum
The manganese filter-press residue contains about 40 percent of sulfate, wherein most of the sulfate exists in the form of calcium sulfate, and the manganese filter-press residue can be used for replacing (or partially replacing) natural gypsum as a cement retarder theoretically, and has the characteristics of simple treatment process, less investment in fixed assets, low treatment cost and the like. However, in practical applications, because the manganese filter-press residue contains harmful substances such as soluble ammonium salts and the like, and the influence rule of siliceous minerals on the hydration process of cement clinker is not clear, the doping amount of the manganese filter-press residue in cement production is low, and further intensive research on a large amount of manganese filter-press residue accumulated theoretically is required.
(2) Production of building materials
The manganese filter-pressing residue has low activity and no hydration activity, and the effect of directly replacing cement to prepare the cementing material is poor. Research shows that the manganese filter-press residue shows certain activity after being calcined, the best calcining temperature is 750 ℃, a cementing material with good effect can be prepared, and the strength of the material is obviously reduced due to overhigh calcining temperature. However, these research results are only preliminary attempts to recycle the manganese filter-pressing residues, and because the manganese filter-pressing residues have diverse compositions and forms, extensive system researches on the manganese filter-pressing residues are needed to realize large-scale resource utilization of the manganese filter-pressing residues, and meanwhile, the investment of fixed assets of the process is increased, and the treatment cost is restricted by energy supply.
(3) Wall material using manganese filter-pressing residue
The comprehensive utilization of the manganese press-filtering residues adopts the scheme that firstly, manganese ores are recovered by a mineral separation process, then, the tailings are used for preparing baking-free bricks, and the wastewater is recycled after being treated. However, in the process of brick making, the phenomena of salt precipitation, whitening, pulverization and the like of the baking-free brick in the service process are caused due to the fact that the baking-free brick contains more water-soluble sulfate, and the application field needs to further research on a failure mechanism of the baking-free brick and find a proper solution.
(4) Other ways of utilization
In addition to the utilization modes, researches are carried out to utilize ultrasonic-assisted acid to extract manganese in the manganese filter-press residues for other purposes, utilize the manganese filter-press residues to replace anthracite and clay, and add the dual functions of carbonization and gypsum of sulfur-fixing agent quicklime to produce civil honeycomb briquette; but the sulfur content is high, SO is easily generated when the honeycomb briquette is burnt in a reducing atmosphere2And the like, threaten life safety and pollute the environment.
In conclusion, the process developed by combining the clean production of the manganese industry and the zero emission resource of the filter-pressing residue is basically absent at home, and a process method capable of fully utilizing the solid waste resource of the manganese residue is not available.
Based on this, as shown in fig. 1, the invention provides a manganese product clean production and resource recycling treatment process, which specifically comprises the following steps:
manganese (manganese sulfate or electrolytic manganese) preparation needs to be performed with acid leaching treatment on manganese ore to obtain manganese sulfate, and in the process, a manganese product production system 1 generates harsh and toxic sulfuric acid or hydrogen sulfide acid mist to pollute the environment, and no good solution exists, because the hydrogen sulfide gas is absorbed and treated by a commonly used alkaline method, secondary solid waste (such as sodium sulfate, calcium sulfate and the like) is generated, the embodiment provides that low-grade manganese dioxide slurry with wide sources is used in an acid mist/hydrogen sulfide absorption device 2 to absorb acid mist/hydrogen sulfide, the generated manganese sulfate slurry passes through a filtering device 3, the main component of a filtrate is manganese sulfate, the manganese sulfate can be directly recycled to the manganese product production system 1, and filter residues enter manganese slag to be subjected to subsequent treatment. The method not only solves the problem of the outlet of low-grade manganese dioxide, but also completely absorbs acid mist or hydrogen sulfide gas, recovers sulfur resources and avoids the problems of pollution and secondary pollution.
Filtering manganese slag in a gas stripping ammonia removal tank 4, adding water and quicklime for pulping, carrying out exothermic reaction on ammonium sulfate in the manganese slag and the added quicklime and the water, adding stirring action of hot air with pressure discharged from a hot air booster pump 15 in slurry, allowing a large amount of ammonia to escape sufficiently, and promoting escape (exothermic reaction) of the ammonia in the manganese slag by adding quicklime with the weight of 5-35 percent of that of the manganese slag: CaO + H2O+(NH4)2SO4＝CaSO4+2NH3↑+2H2And O, the hot air at the temperature of 50-220 ℃ is used for replacing the traditional steam to stir the manganese slag-lime slurry so as to ensure that the reaction is complete, but excessive water is not generated and accumulated, stripping is changed into stripping so as to ensure that deamination is sufficient, clean ammonia gas is obtained to produce ammonia water, and the ammonia water is recycled to the manganese product production system 1. Because the moisture content of the manganese slag is about 21 percent, the quicklime is mixed with the manganese slag to absorb water and release heat, thereby being beneficial to the escape of ammonia gas, being beneficial to the drying of the manganese slag and saving energy consumption. The ammonia gas generated by the gas stripping deammoniation tank 4 is purified by the partition dedusting system 12 and then enters the ammonia water production device 13, and is absorbed by water to become ammonia water which is sent back to the manganese product production system 1. The dust from the partition dedusting system 12 enters the powder bin 19 and then enters the superfine grinding device 8 to be mixed with the manganese slag and stirred uniformly, and the mixture is ground into building material micropowder products for sale.
In addition, the method utilizes normal temperature air and the high temperature deamination and desulfurization manganese slag just taken out of the kiln to exchange heat in the cooling cylinder 7, obtains high temperature air above 600 ℃, enters the high temperature rotary kiln to support combustion, and simultaneously cools the deamination and desulfurization manganese slag. Because the temperature of the hot air is higher than the ignition point (600 ℃) of the pulverized coal fuel, the pulverized coal fuel provided by the pulverized coal mill (9) can be rapidly and fully combusted once entering the high-temperature rotary kiln 6, and compared with combustion supporting by normal temperature air, combustion supporting by high-temperature air can reduce the energy consumption by more than 35% and reduce the generation of nitrogen oxides by 70%. The temperature of the deamination desulfurization manganese slag is reduced through heat exchange, heat energy recovery is realized, thermal pollution of a working site is avoided, and the manganese slag is cooled and then enters the superfine grinding powder 8 to be processed into manganese slag micropowder.
The working temperature of the high-temperature rotary kiln 6 is 700-1300 ℃, and the generated high-temperature flue gas (containing SO) is2+SO3Dust and the like) enters a high-temperature gas filter 10, the filter effectively filters a large amount of dust in the flue gas, the dust is blown to a dust bin 19 and sent to an ultrafine grinding device 8 together with the dust collected by a partition dust removal system 12 to be uniformly mixed with the burnt manganese slag to be ground into a final product (ultrafine manganese slag building material mineral powder); the high-temperature clean sulfur-containing gas enters a heat exchanger I11, the heat exchanger utilizes normal-temperature air to exchange heat with high-temperature sulfur-containing flue gas, high-temperature air obtained is pressurized by a hot air booster pump 15 and then provides stirring hot air for the air stripping ammonia removal tank 4, and the working temperature of the air stripping ammonia removal tank 4 is about 200 ℃.
SO coming out of the first heat exchanger 112+SO3The mixed gas enters the catalytic oxidation device 14 after being purified by the subarea dust removing system 12, and the working temperature of the catalytic oxidation device 14 is more than 500 ℃ so as to maintain
In the forward direction of this reversible reaction, SO is reacted2All being oxidized to SO3. The hot air required by the temperature field of the catalytic reaction device is provided by the second heat exchanger 16.
SO from catalytic oxidation unit 143And the temperature is reduced by a second heat exchanger 16 and then enters a sulfuric acid production system 17 to form a sulfuric acid recycling and manganese product production system 1 with proper concentration.
The flue gas escaped from the sulfuric acid production system 17 is purified by the flue gas purification system 18 and then discharged after reaching the standard, and the calcium sulfate solid waste produced by the flue gas purification system 18 is mixed into the manganese slag to enter a treatment procedure, so as to form circulation.
In the embodiment, the heat energy recovery system is fully used and comprises the cooling cylinder 7, the first heat exchanger 11, the hot air booster pump 15 and the second heat exchanger 16, and the gas stripping ammonia removal tank 4 and the catalytic oxidation device 14 in the system do not need additional heat sources or heating devices, so that energy is saved.
The system adopts the rotary mortar mill (patent No. ZL200910042947.8) which is the product of the invention of the inventor, and takes the grinding work of the coal powder and the manganese slag building material micro powder of the system: the coal is made into the coal powder, the combustion speed of the coal is accelerated, the combustion is more sufficient, the combustion efficiency is higher and the generated nitrogen oxides are lower under the high-heat air combustion supporting condition; after the manganese slag after calcination is subjected to superfine grinding processing, the activity of the manganese slag fine powder is stronger, and part of cement clinker can be directly replaced, so that the economic benefit of the environmental protection project is improved. After high-temperature calcination, the harmful substances contained in the manganese slag are all subjected to high-order oxidation or carbonization, so that the manganese slag does not harm the nature any more.
Therefore, the embodiment discloses a process method for clean production and zero emission recycling in the manganese industry, which can realize clean production in the manganese industry, and recycle acid mist, hydrogen sulfide, acidic manganese slag and the like generated in the treatment process through dry squeezing, wherein part of the produced products (ammonia water, sulfuric acid and manganese sulfate) are recycled by manganese manufacturing enterprises, and other products (active micro powder) are building material products with wide application and have no secondary pollutants.
The conventional alkali substances (such as sodium hydroxide and the like) are replaced by the commonly-discarded low-grade manganese dioxide, so that not only is the waste utilized, but also the acid mist and the hydrogen sulfide harmful gas are fully absorbed, the evacuation reaches the standard, and a manganese sulfate slurry product which can be directly recycled by enterprises in the manganese industry is produced.
The quick lime powder is used for promoting the escape of ammonia gas in manganese slag, the heat exchanger 11 and the hot air booster pump 15 are used for providing hot air flow for disturbing manganese slag-lime slurry for the gas stripping ammonia removal tank 4, the high-temperature air flow replaces steam used in the traditional steam stripping, steam stripping is changed into gas stripping, excessive water cannot be formed after disturbance (the steam can be changed into water after being cooled), the working temperature of the gas stripping ammonia removal tank 4 is below 200 ℃, the possibility of escaping gas of sulfate contained in the manganese slag is avoided, and the ammonia gas is ensured to be fully escaped but the sulfur-containing gas cannot escape due to low temperature (the sulfur-containing gas starts to escape when the temperature is above 300 ℃).
An advanced heat energy recovery system is designed, including but not limited to a high-temperature rotary kiln 6, a cooling cylinder 7, a first heat exchanger 11, a hot air booster pump 15 and a second heat exchanger 16, so that the gas stripping deammoniation tank 4 and the catalytic oxidation device 14 do not need an external heating source any more, and the heat pollution is eliminated.
The high-temperature gas filter 10 can filter and clean dust in high-temperature gas through the ceramic fiber pipe, so that the content of the discharged dust is lower than 5ppm, the heat exchanger I11 can be ensured to normally work for a long time, and the problems of function reduction or failure and the like caused by the scaling phenomenon of the heat exchanger caused by the dust are avoided;
the manganese slag superfine grinding device 8 ensures that the specific surface area of the final product active micro powder is smaller, the activity is stronger and the market acceptance is higher.
The coal powder grinding 9 enables the particle size of the finished coal powder product to be smaller, the combustion to be more sufficient, the generated nitrogen oxides to be less, and the combustion efficiency to be higher under the combustion supporting of high-heat air.
In the test, the manganese slag is added with active materials to be mixed and calcined, and then the calcined manganese slag is subjected to superfine grinding to obtain S95 superfine mineral powder, and the detection result is shown in figure 2.
In conclusion, the invention is based on the fact that through reasonable environmental protection treatment of the whole flow in the production of the manganese industry, waste gas and waste residues can be converted into byproducts such as manganese sulfate, ammonia water, sulfuric acid and the like to be recycled in the manganese manufacturing industry to form a circulation industry in situ, and meanwhile, the calcined desulfurization and deamination manganese residues have activity after being subjected to ultrafine grinding, can become building mixed material micro powder, can be sold to cement enterprises as clinker or directly sold to enterprises such as concrete, dry mixed mortar and the like to replace part of cement, and meets the aim of sustainable circulation economic development.
Each of the devices or systems mentioned in the present invention is a device or system existing in the prior art. Such as a manganese product production system, an acid mist/hydrogen sulfide absorption device, a filtering device, an ultra-fine grinding device, coal grinding, a partition dust removal system, an ammonia water production device, a catalytic oxidation device, a sulfuric acid production system, a flue gas purification system and the like. The invention focuses on the combination of the route and the system innovation.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (10)
1. A manganese product clean production and resource recycling treatment process is characterized in that: introducing acid mist and hydrogen sulfide generated by a manganese product production system (1) into an acid mist/hydrogen sulfide absorption device (2), wherein manganese dioxide pulping liquid is arranged in the acid mist/hydrogen sulfide absorption device (2), and the acid mist and the hydrogen sulfide are absorbed by the manganese dioxide pulping liquid to generate manganese sulfate slurry;
and (3) filtering the manganese sulfate slurry through a filtering device (3) to obtain a filtrate and manganese slag, wherein the main component of the filtrate is manganese sulfate and can be directly recycled to a manganese product production system (1), and the manganese slag can be subjected to subsequent recycling process treatment.
2. The manganese product clean production and resource recycling process according to claim 1, characterized in that: manganese slag is also generated in the manganese product production system (1), the manganese slag obtained in the filtering device (3) and the manganese slag generated in the manganese product production system (1) are mixed with water and quicklime in a gas stripping deamination tank (4) to be pulped, the solid content of the slurry is 10% -50%, ammonium sulfate in the manganese slag and the added quicklime and water perform an exothermic reaction, and ammonia gas escapes; pressurized hot air from a hot air booster pump (15) is introduced into an air stripping deamination tank (4) to replace steam, and slurry is stirred to promote deamination reaction, so that a large amount of ammonia gas is fully escaped;
3. the manganese product clean production and resource recycling process according to claim 2, characterized in that: the usage amount of the quicklime is 5-35% of the amount of the manganese slag, and the temperature of the hot air with pressure is 50-220 ℃.
4. The manganese product clean production and resource recycling process according to claim 2, characterized in that: ammonia gas generated in the gas stripping and ammonia removing tank (4) enters an ammonia water production device (13) after being subjected to partition dust removal through a partition dust removal system (12), and ammonia water produced by the ammonia water production device (13) is recycled to the manganese product production system (1);
and the solid-liquid mixture discharged from the gas stripping ammonia removal tank (4) enters a filter press (5), filtered water and deaminated manganese slag are obtained through the filter press (5), the filtered water is returned to the gas stripping ammonia removal tank (4) for pulping, the deaminated manganese slag enters a high-temperature rotary kiln (6) for calcination and desulfurization, and pulverized coal fuel is provided for the high-temperature rotary kiln (6) by the coal pulverizer (9).
5. The manganese product clean production and resource recycling process according to claim 4, wherein: the deamination and desulfurization manganese slag in the high-temperature rotary kiln (6) is sent into a cooling cylinder (7) for heat exchange and cooling, normal-temperature air is heated into high-temperature air with the temperature of more than 500 ℃ through the cooling cylinder (7) and enters the high-temperature rotary kiln (6) for combustion supporting, and the temperature of the high-temperature air reaches the ignition point of coal, so that the coal powder entering the high-temperature rotary kiln (6) from a coal powder mill (9) is instantaneously combusted; the deaminated and desulfurized manganese slag is cooled and then enters a superfine grinding device (8) for superfine grinding processing to obtain manganese slag building material micro powder.
6. The manganese product clean production and resource recycling process according to claim 5, wherein: the flue gas generated in the high-temperature rotary kiln (6) passes through a high-temperature gas filter (10), after a large amount of dust in the high-temperature flue gas is effectively filtered by the high-temperature gas filter (10), the dust is blown to a dust bin (19) and is sent to an ultrafine grinding device (8) together with the dust collected by a partition dust removal system (12), and all the dust and manganese slag are uniformly mixed;
the high-temperature flue gas filtered by the high-temperature gas filter (10) enters a heat exchanger I (11), the heat exchanger I (11) exchanges heat with the high-temperature flue gas by utilizing normal-temperature air to form high-temperature air, and the high-temperature air is pressurized by a hot air booster pump (15) and then provides pressurized stirring hot air for the air stripping ammonia removal tank (4).
7. The manganese product clean production and resource recycling process according to claim 6, wherein: high temperature flue gas that comes out from heat exchanger one (11) enters catalytic oxidation device (14) after subregion dust pelletizing system (12) purifies, sulfur dioxide is all turned into sulfur trioxide in catalytic oxidation device (14) with the high temperature flue gas, sulfur trioxide gas lets in heat exchanger two (16) and carries out the heat transfer, heat exchanger two (16) utilize normal atmospheric temperature air and high temperature sulfur trioxide gas heat transfer after form high temperature air and let in catalytic oxidation device (14) to maintain the required ambient temperature of catalytic oxidation.
8. The manganese product clean production and resource recycling process according to claim 1, characterized in that: the sulfur trioxide gas passing through the second heat exchanger (16) enters a sulfuric acid production system (17) to become sulfuric acid with proper concentration, and the sulfuric acid is reused in the manganese product production system (1);
acid mist and flue gas which escape from a sulfuric acid production system (17) are absorbed and purified by lime of a flue gas purification system (18) and then are discharged after reaching standards, and calcium sulfate solid waste generated by the flue gas purification system (18) is mixed into manganese slag to enter a treatment procedure to form circulation.
9. A manganese product clean production and resource recycling treatment process is characterized in that: the method comprises the following steps:
the acid mist/hydrogen sulfide absorption device (2), manganese dioxide pulping liquid is arranged in the hydrogen sulfide absorption device (2), the acid mist and the hydrogen sulfide are absorbed by the manganese dioxide pulping liquid, and manganese sulfate slurry is generated and sent to the filtering device (3);
the manganese sulfate slurry is filtered by the filtering device (3) to obtain filtrate and manganese slag, the manganese slag enters the gas stripping ammonia removal tank (4), and the main component of the filtrate is manganese sulfate and is recycled to the manganese product production system (1);
the gas stripping ammonia removal tank (4) is used for removing ammonia from the manganese slag to obtain ammonia gas and ammonia-removed manganese slag slurry, the ammonia gas is introduced into an ammonia water production device (13), and the ammonia-removed manganese slag slurry enters a filter press (5);
the filter press (5) is used for carrying out filter pressing on the deamination manganese slag slurry to obtain filtered water and deamination manganese slag after being dewatered, the filtered water is reused in the gas stripping deamination tank (4), and the deamination manganese slag after being dewatered is sent to the high-temperature rotary kiln (6);
the high-temperature rotary kiln (6) obtains flue gas and deamination and desulfurization manganese slag, the flue gas is introduced into a high-temperature gas filter (10), and the deamination and desulfurization manganese slag enters a cooling cylinder (7);
the cooling cylinder (7) cools the deamination desulfurization manganese slag through heat exchange, high-temperature air after heat exchange is introduced into the high-temperature rotary kiln (6) for combustion supporting, and the deamination desulfurization manganese slag after temperature reduction enters the superfine grinding device (8);
the manganese slag and the dust-removing filter dust are uniformly mixed and subjected to superfine processing by the superfine grinding device (8) to produce manganese slag building material micro powder;
the high-temperature gas filter (10), the high-temperature gas filter (10) filters the flue gas and enters the first heat exchanger (11), and the filtered dust is introduced into the dust bin (19);
the heat exchanger I (11) exchanges heat with high-temperature flue gas by utilizing normal-temperature air to obtain high-temperature air, the high-temperature air is pressurized by a hot air booster pump (15) to provide stirring hot air for the air stripping and ammonia removing tank (4), and the flue gas after heat exchange and temperature reduction is introduced into a partition dedusting system (12);
the partition dust removal system (12) is used for respectively removing dust of the ammonia gas and the sulfur-containing gas in a partition manner and sending dust into the dust bin;
the ammonia water production device (13) absorbs ammonia gas through water to generate ammonia water;
the catalytic oxidation device (14) is used for completely oxidizing sulfur dioxide in the flue gas from the partition dust removal system (12) into sulfur trioxide, and the high-temperature sulfur trioxide gas is introduced into the second heat exchanger (16) for heat exchange because the catalytic oxidation is an exothermic reaction;
the heat exchanger II (16) utilizes normal-temperature air to exchange heat with high-temperature sulfur trioxide gas to form high-temperature air, and the high-temperature air is introduced into the catalytic oxidation device (14) to maintain the environmental temperature required by catalytic oxidation;
10. the clean production and resource recycling process for manganese products according to claim 9, wherein: and alsoComprises a sulfuric acid production system (17) and a flue gas purification system (18), wherein the sulfuric acid production system (17) is used for purifying SO3The gas is made into sulfuric acid with proper concentration and is reused in a manganese product production system (1);
the flue gas escaped from the sulfuric acid production system (17) is absorbed and purified by lime in the flue gas purification system (18) and then is discharged after reaching the standard, and the calcium sulfate solid waste produced by the flue gas purification system (18) is mixed into the manganese slag to enter a treatment procedure, so that circulation is formed.
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