CN113909260B - Clean production and resource recycling treatment process for manganese products - Google Patents
Clean production and resource recycling treatment process for manganese products Download PDFInfo
- Publication number
- CN113909260B CN113909260B CN202111333598.2A CN202111333598A CN113909260B CN 113909260 B CN113909260 B CN 113909260B CN 202111333598 A CN202111333598 A CN 202111333598A CN 113909260 B CN113909260 B CN 113909260B
- Authority
- CN
- China
- Prior art keywords
- manganese
- temperature
- gas
- manganese slag
- slag
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 clean production and resource recycling treatment process for manganese products. The invention adopts reasonable technology to carry out resource treatment on acid mist and hydrogen sulfide gas generated in the production process of manganese industry and huge amount of solid waste of manganese slag generated, replaces traditional alkaline substances with commonly abandoned low-grade manganese dioxide, fully absorbs acid mist and harmful gas of hydrogen sulfide generated in the process of preparing the manganese acid leaching to generate manganese sulfate slurry which can be recycled by enterprises in the manganese industry, and the manganese sulfate is dissolved in the slurry to be reused in a manganese product production system through pressure filtration and liquid containing manganese sulfate. The process finds application for the low-grade manganese dioxide which is generally abandoned, realizes the full recovery of pollutants generated in the whole process of manganese production, 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 of manganese products.
Background
The manganese industry is an industry with high resource and energy consumption and large pollutant production amount, although the technical level is improved in recent years and the environmental protection work is enhanced, the pollution to the environment caused by manganese manufacturing enterprises in the production process is still serious, such as acid mist, hydrogen sulfide gas and filter residues generated after the combination of manganese ore in the production process, and the filter residues 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 in raw ores, and generate volatile ammonia gas and leachate in the stacking process to pollute the environment, waste land resources and generate risks of geological disasters such as dam break, debris flow and the like. The fact that sulfuric acid mist and hydrogen sulfide gas generated in the production process of the manganese industry are not in competition 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 severely restricts the rapid development of the manganese industry.
Disclosure of Invention
The invention aims to provide a resource recycling treatment process and device based on a manganese product production system, which are based on reasonable environmental protection treatment of the whole flow in the production of the manganese industry, can convert waste gas and waste residue into byproducts such as manganese sulfate, ammonia water, sulfuric acid and the like for recycling to the manganese industry and form recycling industry on site, and meanwhile, the calcined desulfurization deamination manganese residue has activity after superfine grinding, can become building mixed material micro powder, can be used as clinker to be sold to cement enterprises 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 recycling economic development.
In order to achieve the above purpose, the present invention proposes the following technical scheme: the clean production and resource recycling treatment process of the manganese product comprises the steps of introducing acid mist and hydrogen sulfide generated by a manganese product production system into an acid mist/hydrogen sulfide absorption device, wherein manganese dioxide slurry is arranged in the acid mist/hydrogen sulfide absorption device, and absorbing the acid mist and the hydrogen sulfide through the manganese dioxide slurry to generate manganese sulfate slurry;
the manganese sulfate slurry is filtered by a filtering device to obtain filtrate and manganese slag, the main component of the filtrate is manganese sulfate, the filtrate 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 in the filtering device and the manganese slag produced in the manganese product production system are mixed with water and quicklime in the gas stripping deamination tank to carry out pulping and deamination, ammonium sulfate in the manganese slag and the added quicklime and water carry out exothermic reaction, hot air with pressure from the hot air booster pump is introduced into the gas stripping deamination tank, so that the ammonia gas is promoted to escape in a large amount and fully by stirring the slurry, and the water quantity in the gas stripping deamination tank is not continuously increased due to steam condensation due to the adoption of the hot air instead of steam.
Further, in the invention, the addition 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 generated in the stripping deamination tank enters an ammonia water production device after passing through a zoned dust removal system, and ammonia water produced by the ammonia water production device returns to a manganese product production system;
residual products in the gas stripping deamination tank enter a filter press, filtered water and deamination manganese slag are obtained through the filter press, the filtered water is recycled to the gas stripping deamination tank, the deamination manganese slag enters a high-temperature rotary kiln for desulfurization, and the high-temperature rotary kiln provides pulverized coal as fuel by a pulverized coal mill.
Furthermore, in the invention, the deaminated and desulphurized manganese slag in the high-temperature rotary kiln is led into the cooling cylinder to exchange heat, the normal-temperature air is heated into high-temperature air with the temperature of more than 500 ℃ through the cooling cylinder, and the high-temperature air is led into the high-temperature rotary kiln to support combustion, and the high-temperature air supports combustion of coal dust to form a high-temperature combustion environment; and cooling the deaminated and desulphurized manganese slag, and then feeding the cooled and desulphurized manganese slag into an ultrafine grinding device for ultrafine grinding to obtain manganese slag micro powder.
Further, in the invention, the flue gas generated in the high-temperature rotary kiln is filtered by the high-temperature gas filter, and a large amount of dust in the flue gas is blown to the dust bin by the high-temperature gas filter, and is sent into an ultrafine grinding device together with the dust collected by the partition dust removal system, and all the dust and 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 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 to provide stirring hot air for the stripping deamination tank.
Further, in the invention, hot air is adopted to replace conventional steam for stripping, and stripping is adopted to replace stripping, so that condensed water is not continuously generated in the deamination tank like the stripping process.
Further, in the invention, the flue gas from the first heat exchanger enters the catalytic oxidation device after being purified by the zoned dust removal system, the catalytic oxidation device fully oxidizes sulfur dioxide in the flue gas into sulfur trioxide (exothermic reaction), the 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 forms high-temperature air after heat exchange by utilizing normal-temperature air and the high-temperature sulfur trioxide gas and is introduced into the catalytic oxidation device so as to maintain the temperature required by the catalytic oxidation reaction.
In the invention, the sulfur trioxide gas passing through the heat exchanger II enters a sulfuric acid production system to become sulfuric acid with proper concentration to be recycled to the manganese product production system;
the flue gas escaping from the sulfuric acid production system is absorbed and purified by lime of the flue gas purification system and then discharged after reaching 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 to form circulation.
A clean production and resource recycling treatment process for manganese products comprises the following steps:
the acid mist/hydrogen sulfide absorbing device is internally provided with a manganese dioxide slurry, and the manganese dioxide slurry absorbs the acid mist and the hydrogen sulfide and generates a manganese sulfate slurry to be sent to the filtering device;
the filtering device is used for filtering the manganese sulfate slurry to obtain filtrate and manganese slag, the manganese slag enters a gas stripping deamination tank, and the filtrate is recycled to a manganese product production system;
the gas stripping deamination tank is used for deamination of manganese slag, ammonia gas and deaminated manganese slag are obtained, the ammonia gas is introduced into an ammonia water production device, and the rest products enter a filter press;
the filter press is used for carrying out filter pressing on the deaminated manganese slag to obtain filtered water and dehydrated deaminated manganese slag, and sending the dehydrated deaminated manganese slag into a high-temperature rotary kiln, wherein the filtered water is reused for the stripping deamination tank;
a high-temperature rotary kiln, wherein the high-temperature rotary kiln obtains flue gas and deaminated and desulphurized manganese slag, the flue gas is introduced into a high-temperature gas filter, and the deaminated and desulphurized manganese slag enters a cooling cylinder;
the cooling cylinder is used for cooling the deaminated and desulphurized manganese slag, introducing high-temperature air obtained through heat exchange into the high-temperature rotary kiln for supporting combustion, and allowing the deaminated and desulphurized manganese slag after cooling to enter the superfine grinding device;
the superfine grinding device is used for uniformly mixing the manganese slag and the dust and carrying out superfine processing on the manganese slag and the dust to obtain manganese slag building material micro powder;
the high-temperature gas filter filters the flue gas and enters a first heat exchanger, and filtered dust is introduced into a dust bin;
the first heat exchanger is used for obtaining high-temperature air after heat exchange between normal-temperature air and high-temperature flue gas, pressurizing the high-temperature air through a hot air booster pump, providing stirring hot air for the stripping deamination tank, and introducing the flue gas into a zoned dust removal system;
the zoned dust removing system is used for removing dust from ammonia and sulfur-containing gas in a zoned manner and sending the respectively collected dust into a dust bin;
the ammonia water production device is used for generating ammonia water from ammonia gas and recycling the ammonia water to the manganese product production system;
and the catalytic oxidation device is used for fully oxidizing sulfur dioxide in the flue gas into sulfur trioxide, the catalytic reaction is exothermic, the high-temperature sulfur trioxide gas is introduced into the second heat exchanger to exchange heat with normal-temperature air, and the high-temperature air obtained by heat exchange is introduced into the catalytic oxidation system to maintain the environmental temperature required by catalytic oxidation.
Furthermore, the invention also comprises a sulfuric acid production system and a flue gas purification system, wherein the sulfuric acid production system returns the sulfuric acid with proper concentration after use to the manganese product production system;
the flue gas escaping from the sulfuric acid production system is purified by a flue gas purification system and then discharged after reaching standards, and the calcium sulfate solid waste produced by the flue gas purification system is mixed into manganese slag to enter a treatment program to form circulation.
The beneficial effect, the technical scheme of this application possesses following technical effect:
1. the invention adopts reasonable technology to carry out resource treatment on sulfuric acid mist and hydrogen sulfide gas generated in the production process of the manganese industry and huge amount of solid waste of manganese slag generated, uses waste low-grade manganese dioxide to replace traditional alkali substances, fully absorbs acid mist and harmful gas of hydrogen sulfide, reacts to generate a manganese sulfate slurry product which can be directly recycled by the enterprises of the manganese industry, the manganese sulfate is dissolved in the slurry, the manganese sulfate solution can be recycled to a manganese product production system through solid-liquid separation, the filter residues are calcined to become the manganese slag building material micro powder product for sale, ammonia gas generated by stripping and sulfur dioxide gas generated during calcination are respectively recycled to the manganese product production system as ammonia water and sulfuric acid, and dust collected in flue gas dust collection is doped into the building material micro powder for sale. The process method realizes the full recovery of pollutants generated in the manganese industry and industrial circulation.
2. The invention designs an advanced heat energy recovery system, including but 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 heat source is not needed for the gas stripping deamination tank and the catalytic oxidation device, and the heat pollution is eliminated.
It should be understood that all combinations of the foregoing concepts, as well as additional concepts described in more detail below, may be considered a part of the inventive subject matter of the present disclosure as long as such concepts are not mutually inconsistent.
The foregoing and other aspects, embodiments, and features of the present teachings will be more fully understood from the following description, taken together with the accompanying drawings. Other additional aspects of the invention, such as features and/or advantages of the exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the embodiments according to the teachings of the 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 invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic flow chart of the process of the present invention.
FIG. 2 is a schematic diagram of the detection of manganese slag micropowder according to the invention.
In the drawings, the meanings of the reference numerals are as follows: 1. a manganese product production system; 2. an acid mist/hydrogen sulfide absorption device; 3. a filtering device; 4. a stripping deamination tank; 5. a filter press; 6. a high-temperature rotary kiln; 7. a cooling cylinder; 8. an ultra-fine grinding device; 9. grinding 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 device; 15. a hot air booster pump; 16. a second heat exchanger; 17. a sulfuric acid production system; 18. a flue gas purification system; 19. and a dust bin.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Aspects of the invention are described in this disclosure with reference to the drawings, in which are shown a number of illustrative embodiments. The embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be understood that the various concepts and embodiments described above, as well as those described in more detail below, may be implemented in any of a number of ways, as the disclosed concepts and embodiments are not limited to any implementation. Additionally, some aspects of the disclosure may be used alone or in any suitable combination with other aspects of the 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 water or alkali absorption method 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-pressed slag is a relatively special waste slag, has high viscosity and high water content, basically belongs to inert materials, and has no effective utilization mode. From the analysis of the existing data, the research results on the comprehensive utilization of the manganese press filtration residues are not more, and the basic research on the comprehensive utilization of the manganese press filtration residues comprises the following aspects:
(1) Using manganese filter pressing slag to replace gypsum as cement retarder
The manganese filter pressing slag contains about 40% of sulfate, wherein most of sulfate exists in the form of calcium sulfate, and the manganese filter pressing slag can be used for replacing (or partially replacing) natural gypsum as a cement retarder, so that the manganese filter pressing slag has the characteristics of simple treatment process, less investment in fixed asset, low treatment cost and the like. However, in practical application, as the manganese press residues contain harmful substances such as soluble ammonium salt and the like, and the influence rule of siliceous minerals on the cement clinker hydration process is unknown, the manganese press residues have low doping amount in cement production, and further intensive research is needed in theory for a large amount of piled manganese press residues.
(2) Production of building materials
The manganese filter pressing slag has low activity and no hydration activity, and has poor effect of directly replacing cement to prepare cementing materials. Researches show that the manganese filter pressing slag is calcined to show a certain activity, the optimal calcining temperature is 750 ℃, the cementing material with good effect can be prepared, and the strength of the material is obviously reduced due to the too high calcining temperature. However, the research results are only preliminary attempts for recycling the manganese filter pressing slag, and because the manganese filter pressing slag has various compositions and forms, the manganese filter pressing slag needs to be subjected to deep system research to realize large-scale recycling, and meanwhile, the investment of the process fixed asset is increased, and the treatment cost is limited by energy supply.
(3) Manganese press filtration residues as wall materials
The comprehensive utilization of the manganese press filter residues adopts a scheme that firstly, manganese minerals are recovered by a mineral separation process, then, baking-free bricks are prepared by tailings, and wastewater is recycled after being treated. However, the phenomena of salt precipitation, whitening, pulverization and the like of the baking-free bricks in the service process are caused by the fact that the baking-free bricks contain more water-soluble sulfate in the brick manufacturing process, and the failure mechanism of the baking-free bricks needs to be further researched in the application field, so that a proper solution is found.
(4) Other utilization modes
In addition to the above utilization, there are studies on the use of ultrasonic-assisted acid extraction of manganese from manganese press residues for other purposes and the use of manganese press residues instead of anthracite and clay, plus sulfur fixationThe agent has dual functions of carbonization and gypsum formation of quicklime, and can be used for producing civil honeycomb briquette; however, honeycomb briquette is high in sulfur content and is liable to generate SO when burned in a reducing atmosphere 2 And harmful gases, life threatening safety and environmental pollution.
In summary, at present, the technology for developing the combination of clean production of the manganese industry and zero emission recycling of filter pressing slag is basically not available in China, and a technology method capable of fully utilizing solid waste resources of the manganese slag is not available.
Based on the above, as shown in fig. 1, the invention provides a clean production and resource recycling treatment process of manganese products, which comprises the following steps:
the manganese ore is subjected to acid leaching treatment to obtain manganese sulfate, during which the manganese product production system 1 generates pungent and toxic sulfuric acid or hydrogen sulfide acid mist to pollute the environment, and no good solution exists, because the commonly used alkaline method is used for absorbing and treating hydrogen sulfide gas, secondary solid waste (such as sodium sulfate, calcium sulfate and the like) is generated, the embodiment provides that low-grade and widely-sourced manganese dioxide pulping liquid is used in the acid mist/hydrogen sulfide absorption device 2 to absorb acid mist/hydrogen sulfide, the generated manganese sulfate pulping liquid passes through the filtering device 3, the main component of the filtering liquid is manganese sulfate, the main component of the filtering liquid can be directly recycled to the manganese product production system 1, and filter residues enter manganese residues for subsequent treatment. The method solves the problems of low-grade manganese dioxide outlet, acid mist or hydrogen sulfide gas absorption, sulfur resource recovery and pollution and secondary pollution.
Filtering manganese slag in a gas stripping deamination tank 4, adding water and quicklime for pulping, carrying out exothermic reaction between ammonium sulfate in the manganese slag and the added quicklime and water, adding the stirring action of hot air with pressure in the slurry, which is discharged from a hot air booster pump 15, and allowing ammonia to escape largely and fully, wherein the quicklime, which is added in an amount of 5-35% by weight of the manganese slag, can promote the escape (exothermic reaction) of ammonia in the manganese slag: caO+H 2 O+(NH 4 ) 2 SO 4 ＝CaSO 4 +2NH 3 ↑+2H 2 O, and the manganese slag-lime slurry is stirred by using hot air with the temperature of 50-220 ℃ to replace the traditional steam so as to ensure that the reaction is complete but excessive water is not generated and accumulated, thereby changing into "The stripping is '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. As the water content of the manganese slag is about 21%, the quicklime absorbs water and releases heat after being mixed with the quicklime, which is favorable for the escape of ammonia gas, the drying of the manganese slag and the energy consumption. Ammonia gas generated by the stripping deamination tank 4 is purified by the zoned dust removal system 12 and then enters the ammonia water production device 13, and is absorbed by water to be changed into ammonia water to be returned to the manganese product production system 1. The dust from the zoned dust removing system 12 enters a dust bin 19 and then enters an ultra-fine grinding device 8 to be mixed and stirred uniformly with manganese slag, and the mixture is ground into building material micro powder products for sale.
In addition, the method utilizes the normal temperature air to exchange heat with the high Wen Tuoan desulfurization manganese slag just coming out of the kiln in the cooling cylinder 7, the obtained high temperature air with the temperature of more than 600 ℃ enters the high temperature rotary kiln to support combustion, and meanwhile, the deamination desulfurization manganese slag is cooled. As 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 when entering the high-temperature rotary kiln 6, and compared with the normal-temperature air combustion supporting, the high-temperature air combustion supporting can reduce the energy consumption by more than 35 percent and reduce the generation of nitrogen oxides by 70 percent. The temperature of deaminated and desulphurized manganese slag is reduced through heat exchange, so that heat energy recovery is realized, the heat pollution of a working site is avoided, and the manganese slag is also beneficial to being subjected to superfine processing into manganese slag micro powder after being cooled in the superfine grinding device 8.
The working temperature of the high-temperature rotary kiln 6 is 700-1300 ℃, and the generated high-temperature flue gas (containing SO) 2 +SO 3 And dust, etc.) enters a high-temperature gas filter 10, and the filter effectively filters a large amount of dust in the flue gas, and then the dust is blown to a dust bin 19 and is sent to an ultra-fine grinding device 8 together with the dust collected by a zoned dust removal system 12 to be uniformly mixed with the sintered manganese slag and ground into a final product (ultra-fine manganese slag building material mineral powder); the high-temperature clean sulfur-containing gas enters a first heat exchanger 11, the heat exchanger exchanges heat with the high-temperature sulfur-containing flue gas by utilizing normal-temperature air, the obtained high-temperature air is pressurized by a hot air booster pump 15 to provide stirring hot air for the stripping deamination tank 4, and the working temperature of the stripping deamination tank 4 is about 200 ℃.
Coming out of heat exchanger one 11SO 2 +SO 3 The mixed gas enters the catalytic oxidation device 14 after being purified by the zoned dust removal system 12, and the working temperature of the catalytic oxidation device 14 is more than 500 ℃ so as to maintain
Forward progress of this reversible reaction will bring about SO 2 All oxidation to SO 3 . The hot air required for the temperature field of the catalytic reaction device is provided by the second heat exchanger 16.
SO from the catalytic oxidation device 14 3 The cooled water enters a sulfuric acid production system 17 after passing through a second heat exchanger 16 to become a sulfuric acid recycling and manganese product production system 1 with proper concentration.
The flue gas escaping from the sulfuric acid production system 17 is purified by the flue gas purification system 18 and then discharged after reaching standards, 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.
In this embodiment, since the heat energy recovery system is comprehensively used, the heat energy recovery system includes the cooling cylinder 7, the first heat exchanger 11, the hot air booster pump 15, and the second heat exchanger 16, no additional heat source or heating device is needed for the stripping deamination tank 4 and the catalytic oxidation device 14 in the system, and energy is saved.
The system adopts the prior invention patent product of the inventor of rotary mortar mill (invention patent number: ZL 200910042947.8) to bear the grinding work of the pulverized coal and manganese slag building material micropowder of the system: the coal is prepared into pulverized coal, the combustion speed of the coal is increased, the combustion is more complete, the combustion efficiency is higher and the generated nitrogen oxides are lower under the high-temperature air combustion-supporting condition; after the calcined manganese slag is subjected to superfine grinding, the manganese slag fine powder has stronger activity, can directly replace part of cement clinker, and improves the economic benefit of the environmental protection project. Harmful substances contained in the manganese slag are all oxidized or carbonized at high positions after high-temperature calcination, so that the nature is not endangered.
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, acid manganese slag and the like generated in the treatment process after eating, drying and squeezing completely, and the produced partial 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 waste low-grade manganese dioxide is used for replacing the traditional alkali substances (such as sodium hydroxide and the like), so that not only is the waste utilized, but also the acid mist and the harmful gas of hydrogen sulfide are fully absorbed, the emptying reaches the standard, and the manganese sulfate slurry product which can be directly recycled by manganese industry enterprises is produced.
The quicklime powder is utilized to promote the escape of ammonia in the manganese slag, and meanwhile, the first heat exchanger 11 and the hot air booster pump 15 are utilized to provide hot air flow for disturbing the manganese slag-lime slurry for the gas stripping deamination tank 4, the high-temperature air flow replaces steam used in traditional stripping, the steam stripping is changed into gas stripping, excessive water is not formed after disturbance (the steam becomes water after cooling), the working temperature of the gas stripping deamination tank 4 is below 200 ℃, the possibility of escaping gas of sulfate contained in the manganese slag is avoided, and the sufficient escape of ammonia is ensured, but the escaping of sulfur-containing gas is not caused due to low temperature (the escaping of sulfur-containing gas is started until the temperature of the sulfur-containing gas is above 300 ℃).
Advanced heat energy recovery systems are 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 an external heat source is not needed any more for the stripping deamination tank 4 and the catalytic oxidation device 14, and heat pollution is eliminated.
The high-temperature gas filter 10 can filter dust in high-temperature gas through the ceramic fiber pipe, clean the high-temperature gas, ensure that the content of the discharged gas dust is lower than 5ppm, ensure that the first heat exchanger 11 works normally for a long time, and prevent the problems of function reduction or failure and the like caused by scaling phenomenon of the first heat exchanger caused by dust;
the manganese slag superfine grinding device 8 ensures that the specific surface area of the active micro powder of the final product is smaller, the activity is stronger and the market acceptance is higher.
The coal powder grinding 9 ensures that the particle size of the coal powder finished product is smaller, the combustion is more sufficient, the generated nitrogen oxides are less, and the combustion efficiency is higher under the combustion supporting of high-temperature air.
In the test, the manganese slag is added with active materials for mixing and calcining, 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 summary, the invention is based on the reasonable environmental protection treatment of the whole flow in the production of the manganese industry, the waste gas and the waste residue can be converted into byproducts such as manganese sulfate, ammonia water, sulfuric acid and the like for recycling to prepare the manganese industry, the circulating industry is formed on site, and meanwhile, the calcined desulfurization deamination manganese slag has activity after being subjected to superfine grinding, can be used as building mixed material micro powder, can be sold as clinker to cement enterprises 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 circular economy development.
Each device or system mentioned in the present invention is a device or system existing in the prior art. Such as manganese product production systems, acid mist/hydrogen sulfide absorption devices, filtration devices, superfine grinding devices, coal grinding, zoned dust removal systems, ammonia water production devices, catalytic oxidation devices, sulfuric acid production systems, flue gas purification systems and the like. The invention is focused on the combination application and system innovation of the route.
While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (9)
1. A clean production and resource recycling treatment process for manganese products 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 a manganese dioxide slurry is arranged in the acid mist/hydrogen sulfide absorption device (2), and absorbing the acid mist and the hydrogen sulfide through the manganese dioxide slurry to generate manganese sulfate slurry;
the manganese sulfate slurry is filtered by a filter device (3) to obtain filtrate and manganese slag, the main component of the filtrate is manganese sulfate, the filtrate can be directly recycled to a manganese product production system (1), and the manganese slag can be subjected to subsequent recycling process treatment;
the manganese slag is produced by the manganese product production system (1), the manganese slag obtained by the filtering device (3) and the manganese slag produced by the manganese product production system (1) are mixed with water and quicklime in the gas stripping deamination tank (4) to prepare slurry, the solid content of the slurry is 10% -50%, ammonium sulfate in the manganese slag, the added quicklime and the water are subjected to exothermic reaction, and ammonia gas escapes; the pressurized hot air from the hot air booster pump (15) is introduced into the stripping deamination tank (4) instead of steam, and the slurry is stirred to promote deamination reaction, so that a large amount of ammonia gas can fully escape.
2. The clean production and resource recycling process of manganese products according to claim 1, wherein: the dosage of the quicklime is 5-35% of the manganese slag, and the temperature of the hot air with pressure is 50-220 ℃.
3. The clean production and resource recycling process of manganese products according to claim 1, wherein: ammonia generated in the stripping deamination tank (4) enters an ammonia water production device (13) after being subjected to zone dust removal through a zone dust removal system (12), and ammonia water produced by the ammonia water production device (13) is recycled into the manganese product production system (1);
the solid-liquid mixture from the gas stripping deamination tank (4) enters a filter press (5), filtered water and deamination manganese slag are obtained through the filter press (5), the filtered water returns to the gas stripping deamination tank (4) for pulping, the deamination manganese slag enters a high-temperature rotary kiln (6) for calcination and desulfurization, and a pulverized coal mill (9) provides pulverized coal fuel for the high-temperature rotary kiln (6).
4. A process for the clean production and recycling treatment of manganese products according to claim 3, characterized in that: feeding the deaminated and desulphurized manganese slag in the high-temperature rotary kiln (6) into a cooling cylinder (7) for heat exchange and cooling, enabling normal-temperature air to be heated into high-temperature air with the temperature of more than 500 ℃ through the cooling cylinder (7), and enabling the high-temperature air to enter the high-temperature rotary kiln (6) for combustion supporting, wherein the temperature of the high-temperature air reaches the ignition point of coal, so that coal dust entering the high-temperature rotary kiln (6) from a coal dust mill (9) is instantaneously combusted; the deaminated and desulphurized manganese slag is cooled and then enters an ultrafine grinding device (8) for ultrafine grinding to obtain manganese slag building material micro powder.
5. The clean production and resource recycling process of manganese products according to claim 4, wherein: the flue gas generated in the high-temperature rotary kiln (6) passes through a high-temperature gas filter (10), a large amount of dust in the high-temperature flue gas is effectively filtered by the high-temperature gas filter (10), and then is blown to a dust bin (19), and is sent into an superfine grinding device (8) together with the dust collected by the 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 the first heat exchanger (11), the first heat exchanger (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 the hot air booster pump (15) to provide pressurized stirring hot air for the stripping deamination tank (4).
6. The clean production and resource recycling process of manganese products according to claim 5, wherein: the high-temperature flue gas from the first heat exchanger (11) enters the catalytic oxidation device (14) after being purified by the zoned dust removal system (12), sulfur dioxide in the high-temperature flue gas is completely converted into sulfur trioxide by the catalytic oxidation device (14), sulfur trioxide gas is introduced into the second heat exchanger (16) for heat exchange, and the second heat exchanger (16) forms high-temperature air after heat exchange by utilizing normal-temperature air and the high-temperature sulfur trioxide gas and is introduced into the catalytic oxidation device (14) so as to maintain the required environmental temperature for catalytic oxidation.
7. The clean production and resource recycling process of manganese products according to claim 1, wherein: 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 to be recycled to the manganese product production system (1);
the acid mist and the flue gas which escape from the sulfuric acid production system (17) are absorbed and purified by lime through the flue gas purification system (18) and then discharged after reaching standards, 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 to form circulation.
8. A clean production and resource recycling treatment process for manganese products is characterized in that: comprising the following steps:
an acid mist/hydrogen sulfide absorbing device (2), wherein the hydrogen sulfide absorbing device (2) is provided with a manganese dioxide slurry, and the manganese dioxide slurry absorbs the acid mist and the hydrogen sulfide and generates a manganese sulfate slurry which is sent to a filtering device (3);
the filtering device (3), the manganese sulfate slurry of filtering device (3) gets filtrate and manganese slag, the manganese slag enters the stripping deamination tank (4), the main ingredient of filtrate is manganese sulfate, reuse to manganese product production system (1);
the gas stripping deamination tank (4), the gas stripping deamination tank (4) is used for deamination of manganese slag, ammonia gas and deamination manganese slag slurry are obtained, the ammonia gas is introduced into an ammonia water production device (13), and the deamination manganese slag slurry enters a filter press (5);
the filter press (5) is used for carrying out filter pressing on the deaminated manganese slag slurry to obtain filtered water and dehydrated deaminated manganese slag, the filtered water is recycled to the stripping deamination tank (4), and the dehydrated deaminated manganese slag is sent to the high-temperature rotary kiln (6);
a high-temperature rotary kiln (6), wherein the high-temperature rotary kiln (6) obtains flue gas and deaminated and desulphurized manganese slag, the flue gas is introduced into a high-temperature gas filter (10), and the deaminated and desulphurized manganese slag enters a cooling cylinder (7);
the cooling cylinder (7) is used for cooling deaminated and desulphurized manganese slag through heat exchange, introducing heat exchanged high-temperature air into the high-temperature rotary kiln (6) for supporting combustion, and allowing the deaminated and desulphurized manganese slag after cooling to enter the superfine grinding device (8);
the superfine grinding device (8), the superfine grinding device (8) uniformly mixes the manganese slag and the dedusting and filtering dust and performs superfine processing to produce manganese slag building material micropowder;
a high-temperature gas filter (10), wherein the high-temperature gas filter (10) filters the flue gas and enters a first heat exchanger (11), and the filtered dust is introduced into a dust bin (19);
the first heat exchanger (11), the first heat exchanger (11) uses the normal temperature air to exchange heat with the high temperature flue gas to obtain the high temperature air, the high temperature air is pressurized by the hot air booster pump (15) to provide stirring hot air for the stripping deamination tank (4), and the flue gas after heat exchange and cooling is introduced into the partitioned dust removal system (12);
the zoned dust removing system (12) is used for respectively removing dust from ammonia and sulfur-containing gas in a zoned manner and sending the dust into a dust bin;
an ammonia water production device (13), wherein the ammonia water production device (13) absorbs ammonia gas through water to generate ammonia water;
the catalytic oxidation device (14) is used for oxidizing all sulfur dioxide in the flue gas from the partitioned dust removal system (12) into sulfur trioxide, and high-temperature sulfur trioxide gas is introduced into the second heat exchanger (16) for heat exchange because the catalytic oxidation is an exothermic reaction;
and the second heat exchanger (16) is used for forming high-temperature air after the heat exchange between the normal-temperature air and the high-temperature sulfur trioxide gas and introducing the high-temperature air into the catalytic oxidation device (14) so as to maintain the required environmental temperature for catalytic oxidation.
9. The clean production and resource recycling process of manganese products according to claim 8, wherein: also comprises a sulfuric acid production system (17) and a flue gas purification system (18), wherein the sulfuric acid production system (17) is used for converting SO 3 The gas is prepared into sulfuric acid with proper concentration to be recycled to the manganese product production system (1);
the fume escaping from the sulfuric acid production system (17) is absorbed and purified by lime through a fume purification system (18) and then discharged after reaching the standard, and the calcium sulfate solid waste produced by the fume purification system (18) is mixed into the manganese slag to enter a treatment procedure to form circulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111333598.2A CN113909260B (en) | 2021-11-11 | 2021-11-11 | Clean production and resource recycling treatment process for manganese products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111333598.2A CN113909260B (en) | 2021-11-11 | 2021-11-11 | Clean production and resource recycling treatment process for manganese products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113909260A CN113909260A (en) | 2022-01-11 |
| CN113909260B true CN113909260B (en) | 2023-05-05 |
Family
ID=79246220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111333598.2A Active CN113909260B (en) | 2021-11-11 | 2021-11-11 | Clean production and resource recycling treatment process for manganese products |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113909260B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114632801B (en) * | 2022-03-10 | 2023-07-14 | 湖南博一环保科技有限公司 | Method for deaminizing and desulfurizing manganese slag by using rotary kiln |
| CN114871240B (en) * | 2022-03-30 | 2023-05-30 | 湖南博一环保科技有限公司 | Electrolytic manganese filter pressing slag for ammonia nitrogen removal and desulfurization as well as preparation method and application thereof |
| CN115058724B (en) * | 2022-06-17 | 2024-01-05 | 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 |
| CN115432714B (en) * | 2022-11-03 | 2023-02-28 | 中科镁基（北京）科技有限公司 | Comprehensive utilization method of electrolytic manganese slag and demanganization building material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127726A (en) * | 1995-05-19 | 1996-07-31 | 赵培岭 | Method for producing manganese sulfate using waste residue from production of potassium permanganate |
| CN101920998A (en) * | 2010-08-05 | 2010-12-22 | 蓝星化工新材料股份有限公司广西分公司 | Method for preparing manganese sulfate from waste byproducts obtained in the production of titanium white and low-grade pyrolusite |
| CN101928041A (en) * | 2010-08-31 | 2010-12-29 | 湖北省通山县通力镁业有限责任公司 | Production technique of manganese sulfate |
| CN104726702A (en) * | 2015-03-13 | 2015-06-24 | 四川会理铅锌股份有限公司 | Method for preparing manganese sulfate from high-sulfur manganese carbonate ores and manganese peroxide ores |
| RU2734205C1 (en) * | 2020-04-27 | 2020-10-13 | Пётр Александрович Зимовец | Method of utilizing used chemical sources of current of manganese-zinc system |
-
2021
- 2021-11-11 CN CN202111333598.2A patent/CN113909260B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113909260A (en) | 2022-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113909260B (en) | Clean production and resource recycling treatment process for manganese products | |
| CN101343047B (en) | Improved preparation technique for preparing sulphuric acid and cement with gypsum | |
| CN107352819B (en) | Method for producing calcium fluoroaluminate clinker by using aluminum cell carbon waste | |
| CN106904849A (en) | The system and method that a kind of utilization Industrial Solid Waste produces sulphate aluminium cement co-producing sulfuric acid | |
| CN106830722B (en) | Organic wastewater cooperates with the system and method for Industrial Solid Waste preparation ultrahigh water filler | |
| CN111410446B (en) | Method and production system for recycling solid waste in aluminum industry by rotary kiln | |
| CN102311136A (en) | Method for producing low iron aluminum sulfate by utilization of coal gangue | |
| CN101353233B (en) | Radiation protection cement and sulphuric acid production method | |
| CN101623592A (en) | Process for comprehensively treating waste acid and desulphurized ash | |
| CN110465177B (en) | Comprehensive utilization and treatment method for red mud | |
| Han et al. | Comprehensive utilization of carbide slag | |
| CN107324288A (en) | A kind of acid waste gypsum integrated treatment and the technique recycled | |
| CN111116224B (en) | Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof | |
| CN107363074B (en) | A kind of aluminium cell carbonaceous materials recycling is the method for alternative fire coal | |
| CN106810094B (en) | The system and method for cement joint production sulphur is prepared using municipal waste and Industrial Solid Waste | |
| WO2018166221A1 (en) | System and method for co-treating organic wastewater and industrial solid waste | |
| CN110844888A (en) | Reduction-oxidation two-stage treatment method for desulfurized fly ash | |
| CN204685646U (en) | The treating apparatus of aluminium electroloysis waste lining | |
| CN107159688B (en) | A kind of aluminium cell carbonaceous materials recycling is made a living the method for producing electricity stone raw material | |
| CN103013613A (en) | Clean fuelization system and fuelization method for urban sludge | |
| CN107200488B (en) | Method for producing fluoroaluminate cement by using carbon waste of aluminum electrolytic cell in dry-process rotary kiln plant | |
| CN104147917B (en) | Fume desulphurization method | |
| CN103143251B (en) | Purification method for industrial emission gas | |
| CN104176752B (en) | A kind of method of use producing metallurgical-grade aluminum oxide by coal ash | |
| CN102795701A (en) | Method for treating acidic waste water from titanium dioxide preparation by sulfuric acid method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |