CN108193047B - With the method for the manganese sulfate solution of anolyte manganous dithionate low with slurries desulfurization system prepared by manganese ore - Google Patents
With the method for the manganese sulfate solution of anolyte manganous dithionate low with slurries desulfurization system prepared by manganese ore Download PDFInfo
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- CN108193047B CN108193047B CN201711470455.XA CN201711470455A CN108193047B CN 108193047 B CN108193047 B CN 108193047B CN 201711470455 A CN201711470455 A CN 201711470455A CN 108193047 B CN108193047 B CN 108193047B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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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 discloses with electrolytic manganese produce in anolyte manganous dithionate low with slurries desulfurization system prepared by manganese ore manganese sulfate solution method, belong to electrolytic manganese production field.In the present invention, using anolyte and the slurries of manganese ore configuration as desulfurizing agent, the multistage spray scrubber with sieve plate is added simultaneously and carries out flue gas desulfurization and leaching manganese, after the filtering of obtained slurries, liquid phase is added oxidant and cuts down manganous dithionate therein, to be conducive to the production of electrolytic manganese and/or manganese sulfate.The solid formation being obtained by filtration can further improve the leaching rate of manganese after secondary acidolysis.Using this technique and method, the leaching rate of manganese can be made up to 94.3% or more, while the sulfur dioxide of flue gas middle and high concentration is down to 100mg/m3Hereinafter, desulfuration efficiency can achieve 99% or more.Desulfurization obtained leaching manganese liquid of the invention is sent into the production that electrolysis workshop section carries out electrolytic manganese, average veneer yield rises to 3.1kg~3.2kg by 2.5kg~2.6kg that the prior art is handled.When the manganese sulfate solution of low manganous dithionate prepared by the present invention is produced for electrolytic manganese, the upper plate rate of manganese can be improved, the quality and yield of manganese is promoted, reduces energy consumption and production costs.
Description
Technical field
The present invention relates to electrolytic manganese production fields, specially with anolyte company low with slurries desulfurization leaching manganese system prepared by manganese ore
The method of the manganese sulfate solution of two manganese sulfates, i.e., with electrolytic manganese anolyte two sulphur of company low with slurries desulfurization leaching manganese system prepared by manganese ore
The method of the manganese sulfate solution of sour manganese.The present invention can be used in the environmental pollution improvements such as metallurgy and resource utilization field, realize
The removing and resource utilization of high-concentration sulfur dioxide flue gas；The manganese sulfate solution of prepared low manganous dithionate is for being electrolysed
When manganese produces, the upper plate rate of manganese can be significantly improved, the quality and yield of manganese is promoted, reduces energy consumption and production costs, had higher
Application value.
Background technique
When nonferrous metallurgy is smelted and some containing sulfur minerals are in the flue gas of the generations such as calcining, roasting, dioxy in flue gas
It is often dense to change sulphur, even as high as 8%~12%.This flue gas direct emission, will cause ambient enviroment and seriously affects,
Serious environmental pollution is caused, according to the pollutant emission standard of relevant industries, it is necessary to handle flue gas.This high concentration
Sulfur dioxide flue gas, more commonly used processing mode is for preparing sulfur dioxide liquid or Sulphuric acid.Chinese patent is announced
Number CN102614765A is disclosed a kind of removes SO from industrial waste gas2New process.It is mutually being gone here and there using pyrolusite pulp
Processing sulfur-bearing industrial waste gas is absorbed in the reaction kettle of connection, exhaust gas is handled by multistage, removes the SO in industrial waste gas2After discharge.
Chinese patent publication No. CN105198000B discloses a kind of utilization high concentration SO2The manganese that flue gas leaches in manganese ore produces manganese product
Process.
In existing pyrolusite desulfurization technology, using reaction autoclave desulphurization plant, flue gas is in sweetening process, cigarette to be processed
Gas need to be bubbled across the slurries area that water and pyrolusite are prepared.In order to reach higher desulfuration efficiency, extend connecing for flue gas and slurries
The time is touched, on the one hand needs to be inserted into gas phase pipe under deeper liquid level, on the other hand, in order to reach emission request, also needs to add
The desulfurizing tower of more series, when this has resulted in system operation, desulphurization system resistance is big, and energy consumption is high, operating cost is high, but soft manganese
The extraction rate of manganese is not high in mine.It is soft there are the mutual adverse current of liquid phase during soaking manganese using the desulfurization of tandem desulfuration spray tower
Manganese ore slurry is to enter desulphurization system from afterbody desulfurization spray scrubber.Sulfur-containing smoke gas is in sweetening process, due to desulfurization
The reaction of agent consumes, and the mass transfer force of every first grade desulfurizing is smaller, in order to reach higher desulfuration efficiency, needs multistage desulfurization
Spray scrubber, and during desulfurization leaching manganese, the manganous dithionate of generation is not cut down.
Summary of the invention
Goal of the invention of the invention is: in view of the above problems, provide it is a kind of with electrolytic manganese produce in anode
The method of the manganese sulfate solution of liquid manganous dithionate low with slurries desulfurization leaching manganese system prepared by manganese ore.Another invention of the invention
Purpose is, provides the reaction unit for preceding method.In the present invention, using electrolytic manganese produce in anolyte configure manganese ore
Slurries, and change the feed way of manganese ore slurries, control effectively to reaction condition, and to the slurries filtering of desulfurization leaching manganese after
Manganous dithionate in gained filtrate is degraded, and the manganese sulfate solution of low manganous dithionate is obtained, for electrolytic manganese production and/
Or the production of manganese sulfate, high purity manganese sulfate.It is measured through test, using the present invention, the total leaching rate of manganese is up to 94.3% in manganese ore
More than, the concentration of the sulfur dioxide in flue gas can be reduced to 200mg/m3Hereinafter, desulfuration efficiency can achieve 99% or more.Together
When, desulfurization leaching manganese liquid of the invention is sent into the production that electrolysis workshop section carries out electrolytic manganese, average veneer yield is by the prior art
2.5kg~2.6kg of reason rises to 3.1kg~3.2kg, has remarkable progress.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of manganese ore slurries handle the device containing sulfur dioxide flue gas, including the spray scrubber with sieve plate, booster fan,
Wet chimney, Sprayer Circulation pump, spray tube, with stock tank, the manganese ore powder cabin being connected with stock tank, slurries delivery pipe, setting in slurries
Manganese ore slurry feeding pump, anolyte storage tank in delivery pipe, anolyte delivery pipe, the anolyte being arranged in anolyte delivery pipe
Delivery pump, oxidation fan, oxidation air pipe, discharge pipe, the discharge pump being arranged on discharge pipe, filter, gas-liquid separator, company
Two manganese sulfate degradation grooves, the spray scrubber be it is N number of, the N is natural number, and N >=3；
Booster fan for being connected with containing sulfur dioxide flue gas passes through the middle and lower part of flue and first spray scrubber
Connection；In two neighboring spray scrubber, the tower top exhanst gas outlet of previous spray scrubber passes through flue and next spray
The middle and lower part of scrubbing tower is connected to and capable of entering through flue containing sulfur dioxide flue gas of handling in previous spray scrubber is next
Spray scrubber is handled, and the tower top exhanst gas outlet of n-th spray scrubber is connected with Wet chimney and flue gas after processing
It can be discharged through Wet chimney；
It is provided with sieve plate in the spray scrubber, spraying layer is set above sieve plate, the sieve plate is 1~2 layer and sieve plate
On be provided with non-homogeneous aperture, the spraying layer is 3~6 layers, and spray scrubber lower slurry pond passes through spray tube and spray
Drenching layer is connected, and the Sprayer Circulation pump is arranged on spray tube and Sprayer Circulation pump can be by spray scrubber lower part by spray tube
Manganese ore slurries in slurry pool are delivered in spraying layer；
The both ends of the slurries delivery pipe are connected respectively with stock tank, spray scrubber and slurries delivery pipe can will match stock tank
The manganese ore slurries of interior same concentrations are delivered to the 1st in N number of spray scrubber respectively；
The anolyte storage tank by anolyte delivery pipe with match that stock tank is connected and anolyte in anolyte storage tank can be through
Anolyte delivery pipe is sent into in stock tank；
The oxidation fan is connected by oxidation air pipe with spray scrubber and oxidation fan can pump air into spray
In the slurry pool of scrubbing tower lower inside；
The spray scrubber, discharge pipe, filter, gas-liquid separator, manganous dithionate degradation groove are connected and spray is washed
Washing the slurries in tower after desulfurization leaching manganese can enter in manganous dithionate degradation groove through discharge pipe, filter, gas-liquid separator.
Further include the demister being arranged in spray scrubber, process water pond, technique water pipe, be arranged on technique water pipe
Technique water pump, the demister are located above spraying layer, and the process water pond is connected by technique water pipe with demister and technique
Process water in process water pond can be sent into demister by technique water pipe by water pump, and wash tub pipe is rinsed demister.
The spray scrubber is 3~6.
It further include the vacuum pump being connected with gas-liquid separator, the discharge pipe is through filter, gas-liquid separator and connects two sulphur
Sour manganese degradation groove is connected, and having heaters is arranged in the manganous dithionate degradation groove.
It further include the secondary acidolysis slot being connected with filter, the sulfuric acid storage tank for storing sulfuric acid, sulfuric acid delivery pump, secondary
Acid hydrolysis solution delivery pump, plate and frame filter press, having heaters is arranged on the secondary acidolysis slot, and the sulfuric acid storage tank passes through sulfuric acid and conveys
Pump is connected with secondary acidolysis slot and sulfuric acid can be added into secondary acidolysis slot by sulfuric acid delivery pump, and the secondary acidolysis slot passes through
Secondary acid hydrolysis solution delivery pump, plate and frame filter press are matched with manganous dithionate degradation groove.
Further include secondary acidolysis filtrate pump, secondary acidolysis filtrate receiver, the secondary acid hydrolysis solution delivery pump, plate and frame filter press,
Secondary acidolysis filtrate pump, secondary acidolysis filtrate receiver are connected with manganous dithionate degradation groove.
It further include the dioxygen water storage tank, hydrogen peroxide delivery pump, the oxidant for storing oxidant for storing hydrogen peroxide
Storage tank, oxidant delivery pump, the dioxygen water storage tank are connected with manganous dithionate degradation groove and can be led to by hydrogen peroxide delivery pump
Cross hydrogen peroxide delivery pump and add hydrogen peroxide into manganous dithionate degradation groove, the oxidant storage tank by oxidant delivery pump with
Manganous dithionate degradation groove is connected and can add oxidant into manganous dithionate degradation groove by oxidant delivery pump.
It is provided with non-homogeneous aperture on the sieve plate, in the range of the 0.5 beta diameter of sieve plate center, percent opening is
45%~55%, the aperture of aperture is 30mm~45mm；In 0.50~0.75 beta diameter range of sieve plate center, percent opening is
50%~60%, the aperture of aperture is 50mm~60mm；In 0.75~0.95 beta diameter range of sieve plate center, percent opening is
50%~65%, aperture is 60mm~80mm；
The sieve plate is located at 1.0~1.5m of adsorption tower smoke entrance top, and supporting beam is equipped with below the sieve plate；Sieve plate
Edge is weldingly connected with tower body, and the sieve plate edge and tower wall are at 30 °~45 °；
If two pieces of sieve plates are arranged, the spacing of sieve plate is 1.8~2.5m.
With the method for the manganese sulfate solution of anolyte manganous dithionate low with slurries desulfurization system prepared by manganese ore, including it is as follows
Step:
(1) manganese ore slurry feeding pump will be delivered to the 1st to N with the manganese ore slurries in stock tank respectively by slurries delivery pipe
In a spray scrubber with sieve plate, thus respectively to the 1st to N number of spray scrubber input manganese ore slurries；
(2) the manganese ore slurries of spray scrubber lower part are delivered in spraying layer by Sprayer Circulation pump by spray tube, and are passed through
Spraying layer discharge, and the counter current contacting containing sulfur dioxide flue gas with entrance, and then washed to containing sulfur dioxide flue gas, it washs
Manganese ore slurries afterwards are back to the lower part of spray scrubber after sieve plate；
(3) first spray scrubber is entered by first spray scrubber middle and lower part with flue containing sulfur dioxide flue gas
It is interior, flue gas is uniformly distributed through sieve plate, with after spray to the slurries initial contact on sieve plate, then in spray scrubber from top to bottom
Manganese ore serous adverse flow washing after, into next spray scrubber；Repeat aforementioned process, until containing sulfur dioxide flue gas into
Enter in n-th spray scrubber, after manganese ore serous adverse flow washing wherein from top to bottom, is emptied through Wet chimney；
(4) oxidation fan is connected by oxidation air pipe with spray scrubber, oxidation fan air is pumped into respectively the 1st to
In the slurry pool of N number of spray scrubber lower inside, for being aoxidized to the solution containing sulphite；
(5) carry out step (1) to step (4), realize to containing sulfur dioxide flue gas continuous desulfurization and manganese ore soak manganese；
(6) when desulfurization leaching manganese reaction reaches the residence time in spray scrubber, pump startup is discharged, after manganese is soaked in desulfurization
Slurries are sent into filter by discharge pipe, respectively obtain filtrate, filter residue；
(7) manganous dithionate degradation groove is admitted to after gas-liquid separator separates go out gas through the resulting filtrate of filter
In, it is separately added into pH adjusting agent, oxidant into manganous dithionate degradation groove, and be warming up to 60~90 DEG C, aoxidize anti-
It answers, reduces the manganous dithionate in solution, obtain the manganese sulfate solution of low manganous dithionate；
(8) enter in secondary acidolysis slot through the resulting filter residue of filter, and sulfuric acid is added thereto, and be warming up to 60~90
DEG C, secondary acidolysis is carried out to filter residue, the mixture after acidolysis respectively obtains secondary filtrate and secondary filter residue after secondary filter；
The secondary filtrate of gained is sent into manganous dithionate degradation groove.
In the step (1), the solid content of manganese ore slurries is 8wt%~20wt%；
In the step (2), the concentration 5000mg/m containing sulfur dioxide in sulfur dioxide flue gas3~300000mg/m3。
In the step (2), (3), manganese ore slurries and the liquid-gas ratio containing sulfur dioxide flue gas are 10~35l/m3。
In the step (3), sulfur dioxide flue gas will be contained with flue by first spray scrubber by booster fan
Lower part is sent into first spray scrubber.
Residence time of the manganese ore slurries in spray scrubber is 60min~900min.
Manganese mineral powder for configuring manganese ore slurries is the manganese mineral powder containing manganese dioxide, and in the manganese mineral powder, tetravalence manganese content
>=15wt%, full manganese content >=35wt%.
The raw material that the slurries after desulfurization leaching manganese in the manganous dithionate degradation groove are re-used as electrolytic manganese is sent into electrolysis work
Duan Zhong, anolyte storage tank, which is connected with electrolysis workshop section and is electrolysed the anolyte that workshop section generates, can enter in anolyte storage tank.
In the step (8), the secondary filter residue of gained carries out calcination processing after concentrating.
In existing pyrolusite desulfurization technology, existing such as using reaction autoclave desulphurization plant, flue gas is in sweetening process
In, flue gas to be processed need to be bubbled across slurries area.In this method, in order to reach higher desulfuration efficiency, flue gas and slurries are improved
Time of contact, on the one hand need for be inserted under deeper liquid level gas phase pipe, on the other hand, also need the desulfurization for adding more series
Tower, when this has resulted in system operation, desulphurization system resistance is big, and energy consumption is high, operating cost is high, but the extraction rate of pyrolusite is not
It is high.During manganese is soaked in the desulfurization of tandem desulfuration spray tower, pyrolusite pulp is entered from afterbody desulfurization spray scrubber
Desulphurization system, desulfurization slurry subsequently into penultimate stage ... until the second level, the first order.When pyrolusite slurries stop
Between it is long, the extraction rate of pyrolusite is higher, can achieve 90% or more.But in this method, sulfur-containing smoke gas is each in sweetening process
The mass transfer force of grade desulfurization is smaller, in order to reach higher desulfuration efficiency, needs multistage desulfurization spray scrubber, and desulfurization
During soaking manganese, the manganous dithionate of generation can not be cut down.The purpose of the present invention is directed to a kind of new be suitable for height
Concentration is combined containing sulfur dioxide FGD and resource utilization, desulfuration efficiency height, leaching manganese ore rate are high, manganese liquid is soaked in desulfurization
The concentration of middle manganous dithionate can be with the device and method of suitable control.More specifically, the benefit being made up of following technical proposals
The device and method of manganese ore extracting sulfuric acid manganese slurries are leached with high-concentration sulfur dioxide flue gas to realize.
In the present invention, the manganese ore slurries prepared using the anolyte in electrolytic manganese production process are washed in the spray with sieve plate
Wash the flue gas for the sulfur dioxide that countercurrent washing in tower contains high concentration.Wherein, the manganese mineral powder for preparing manganese ore slurries was 100 mesh manganese
Miberal powder, sieving rate are not less than 90%.The manganese mineral powder for preparing manganese ore slurries is to mainly contain the manganese mineral powder of manganese dioxide, in miberal powder
Tetravalence manganese content is advisable not less than 15%, and full manganese content is advisable not less than 35%.Sulfur-containing smoke gas is with flue by the first tower middle and lower part
Into the first spray scrubber, in tower from bottom to top after countercurrent washing, and from the middle and lower part of the second spray scrubber into
Enter the second spray scrubber, from bottom to top after slurry wash, into third tower ... ..., until the 5th tower, the 6th
Tower ..., N tower.It is added and is supplemented at every grade by the manganese ore slurries that anolyte is prepared, meanwhile, slurries are in towers at different levels
Circulated sprinkling.In spray washing tower bottoms at different levels, device is blasted equipped with oxidation air, to guarantee the oxidation of sulphite.Each
Bottom outside grade spray scrubber, is equipped with slurry discharge pump, and the slurries obtained Jing Guo redox reaction are sent into filter.
Desulfurization soaks manganese slurries after filtering, and filtrate enters manganous dithionate degradation groove.In degradation groove, by heating and being added oxidation
Agent adjusts the pH of control solution, so that the manganous dithionate in solution is cut down and is reduced, be conducive to the production of subsequent handling,
The especially production of electrolytic manganese.Meanwhile the solids being obtained by filtration, it falls into secondary acidolysis slot and carries out further acid with sulfuric acid
Solution leaching, to improve the manganese leaching rate of manganese ore.Secondary acidolysis is soaked into manganese rear slurry after filtering, secondary acid hydrolysis solution is by being pumped into
Manganous dithionate degradation groove；The remaining solid formation of acidolysis sends to calcining.
In the present invention, the spray scrubber used can be the spray scrubber of 1~2 layer of band non-homogeneous aperture sieve plate.To
Handle flue gas from spray scrubber, lower part enter spray scrubber, in tower from bottom to top, by sieve plate, spraying layer and
Demister is moved to tower top, is washed with top-down manganese ore slurry loop slurry counter current contacting, the sulfur dioxide in flue gas
Equal substances react with the manganese dioxide etc. in manganese ore slurry.In the top of spray scrubber sieve plate, the top of spray scrubber
Equipped with 3~6 layers of loop slurry spraying layer, recycle slurry liquid pool is equipped in the bottom of spray scrubber.Meanwhile the present invention is spraying
The top of layer is equipped with demister, to remove most of droplet in flue gas；It is exhanst gas outlet above demister.In exhanst gas outlet
Section, sample point and/or detection mouth equipped with gas analysis monitoring device.To prevent solid precipitation, in spray washing tower bottom
The outside of recycle slurry liquid pool is additionally provided with 3~5 side-feeding mixers.To promote recycling for slurries, outside spray scrubber
3~5 Sprayer Circulation pumps are provided with, the slurries in serum recycle pond are extracted out from tower bottom, by pump energy supply, are sent into each spraying layer,
Circulated sprinkling washs flue gas.For the lasting progress for promoting redox reaction, oxidation air is additionally provided in recycle slurry liquid pool and is added
Pipe and spray gun, blast air for sulphite and are oxidized to sulfate in time.According to the sieve of the non-homogeneous aperture of sulfur content in flue gas
Plate can be set to 1~2 layer, and the setting of spraying layer is to meet liquid-gas ratio for 15~35l/m3.Each fresh manganese of spray scrubber
The additional amount of pulp slurry is depending on the desulfurization load of setting.The slurries amount of each spray scrubber discharge, and according to setting
Desulfurization load, depending on slurries residence time and the manganese ore slurry liquid measure of addition.
Wherein, it into the flue-gas temperature of flue gas desulfurization washing system, preferably controls at 80 DEG C~250 DEG C, when the first tower flue gas
When inlet temperature is higher than 200 DEG C, spraying cooling section is preferably arranged in spray scrubber entrance.The wash temperature of flue gas is preferably controlled at 40 DEG C
Between~80 DEG C, slurries are 60min~900min in the residence time that each tower recycles, and the running temperature of loop slurry maintains 40
DEG C~75 DEG C between.The pH value of each tower operation control controls between 2~6.In addition, what manganese ore slurries used contains in the present invention
Gu amount is 8%~20%；When the sulfuric acid manganese content that need to be prepared is higher, the solid content of fresh manganese ore slurries is preferably high；When needing to prepare
The solid content of the lower manganese sulfate slurries of sulfuric acid manganese content, the fresh manganese ore slurries that can be used at this time is preferably lower.It is surveyed through test
Fixed, the concentration for the sulfur dioxide in flue gas that the present invention is capable of handling is 5000mg/m3~300000mg/m3。
Further, in manganous dithionate degradation groove, it is equipped with blender, pipe is added in sulfuric acid, pipe is added in oxidant and adds
Thermal etc. is degraded with guaranteeing that the slurries being discharged by each spray scrubber are filtered by filter device into manganous dithionate
After slot, slurries by be added sulfuric acid content in sulphur acid for adjusting pH value and slurries, by heat, be added the operation such as other oxidants and
Control, cuts down the manganous dithionate in slurries.Temperature in manganous dithionate degradation groove maintains 40 DEG C~90 DEG C.Slurry
After liquid persistently stays for some time in its manganous dithionate degradation groove, make sulfuric acid manganese content therein, manganous dithionate, sulfurous
The content of hydrochlorate and sulfuric acid is in and requires within control range, meets needed for the production and operation of subsequent processing.Dithionic acid
The quantity of manganese degradation groove is arranged 1~3 according to residence time and produce load requirement.In the present invention, manganous dithionate degradation groove
The oxidant of addition be the concentrated sulfuric acid, hydrogen peroxide, potassium permanganate, manganese dioxide, ozone, chlorine dioxide, potassium bichromate, potassium chlorate,
The mixture of one or more of Fenton reagent etc..The amount (volume) that oxidant is added is 0.5 ‰~the 30 ‰ of amount of solution.
Further, the position 1.0~1.5m is arranged above smoke inlet in sieve plate；If two pieces of sieve plates, the spacing of sieve plate is arranged
For 1.8~2.5m.Supporting beam, sieve plate edge and tower body welding or flanged joint, and sieve plate edge and tower wall are equipped with below sieve plate
At 30 °~45 °.At sieve plate center in the range of 0.5 beta diameter, percent opening is 45%~55%, and the aperture of aperture is 30mm
~45mm；In 0.50~0.75 beta diameter range of sieve plate center, percent opening is 50%~60%, and the aperture of aperture is 50mm
~60mm；In 0.75~0.95 beta diameter range of sieve plate center, percent opening is 50%~65%, and the aperture of aperture is 60mm
~80mm.
In the present invention, desulfurization is prepared using the anolyte generated in electrolytic manganese production process and the manganese ore containing manganese dioxide
Slurries, the solid content of slurries are 8%~20%.Using the manganese ore slurries of preparation as desulfurizing agent, spray scrubber is squeezed into.Contain height
The middle and lower part of the first order tower of spray scrubber of the sulfur dioxide flue gas of concentration from multistage with sieve plate enters, first order desulfurization spray
The slurries of leaching scrubbing tower take the mode of circulated sprinkling, spray the flue gas that countercurrent washing is flowed from the bottom to top from top to bottom.Washing
The liquid-gas ratio that sulfur-containing smoke gas uses is 15~35l/m3.The flue gas come out from first order spray washing column overhead, enters with flue
The middle and lower part of second level desulfurization spray scrubber carries out second and washs.Fresh washing slurries are still to squeeze into from stock tank
Second level spray scrubber, manganese ore slurry wash flue gas ... ... in second level spray scrubber still in the form of circulated sprinkling,
Similar, the SO 2 from fume after N grades, desulfurization reaches corresponding discharge standard.
After the leaching manganese slurries of desulfurization made from each spray scrubber are filtered out the residue in slurries by filter, filtrate is sent into
Manganous dithionate degradation groove.In manganous dithionate solution slot, the temperature of solution is adjusted by heating device, uses sulfuric acid regulation solution
PH, be added oxidant, carry out solution in manganous dithionate decomposition reduce.Manganous dithionate in solution is by reducing disposition
Afterwards, solution is re-fed into electrolysis workshop section and carries out impurity removal and purification, carries out the production of electrolytic manganese.Segment anode liquid after electrolysis returns to desulfurization
Soak the anolyte storage tank of manganese systems system, the preparation for manganese ore slurries.Desulfurization leaching manganese slurries by filter be obtained by filtration it is residual
Slag further leaches manganese slag with sulfuric acid in case of heating.Slurries after leaching are sent in manganous dithionate degradation groove；
Undegradable residue is sent into manganese slag calcining workshop section after concentration and is calcined.After these step process, manganese in manganese ore is converted
Leaching rate is up to 93% or more.
In conclusion the present invention contains high-concentration sulfur dioxide flue gas using the manganese ore processing containing manganese dioxide, produce
Manganese sulfate.Wherein, the manganese mineral powder that tetravalence manganese content is not less than 15%100 mesh can be used in manganese ore slurry；It is adopted for anolyte with slurry
With the anolyte generated in electrolytic manganese metal production process, in anolyte, 10~20g/l sulfuric acid, 10~18g/l bis- are typically contained
Valence manganese, ammonium sulfate of 40~90g/l etc..Flue gas containing high-concentration sulfur dioxide is sieved by manganese ore slurry multistage with non-homogeneous aperture
After the countercurrent washing of the spray scrubber of plate, desulfuration efficiency can achieve 99% or more.Meanwhile the manganese ore slurry containing manganese dioxide
Liquid during washing sulfur dioxide, occur catalytic reduction reaction, become manganese sulfate solution, by be added oxidant eliminate and
Manganous dithionate in degraded solutions, the manganous dithionate in solution further decrease, are conducive to subsequent handling, are especially electrolysed
The production of manganese.The manganese sulfate solution can be used for the manganese sulfate of high-purity after impurity removal and purification.
After measured, it is washed by multi-stage spray scrubbing tower, the concentration of the sulfur dioxide in flue gas can be fallen too low, generally
In 200mg/m3Hereinafter, even 100mg/m3Below；And the total desulfurization degree of sulfur dioxide in flue gas can achieve 99% or more.It is de-
Sulphur soaks manganese liquid by the way that after the degradation of manganous dithionate degradation groove, the manganous dithionate in solution can be down to by 5100mg/l
2000mg/l hereinafter, even 800mg/l hereinafter, have remarkable progress.Meanwhile desulfurization slurry is dropped by manganous dithionate
After solving slot disposition, the sulfuric acid manganese content in slurries can achieve 35~70g/l.Manganese liquid is soaked into the desulfurization for degrading manganous dithionate
It is sent into the production that electrolysis workshop section carries out electrolytic manganese, average veneer yield is risen to by 2.5kg~2.6kg that the prior art is handled
3.1kg~3.2kg.
Compared with traditional production of manganese sulfate as either electrolytic manganese metal production, the present invention can be suitble to industrial sulphuric acid
The production of manganese and high-purity manganese sulphate and the production preparation of electrolytic manganese metal, have lower production cost and advantage, recycling
Utilization rate is more preferable.
Detailed description of the invention
Examples of the present invention will be described by way of reference to the accompanying drawings, in which:
Fig. 1 is structural schematic diagram upper left in embodiment 1.
Fig. 2 is structural schematic diagram upper right portion in embodiment 1.
Fig. 3 is structural schematic diagram bottom left section in embodiment 1.
Fig. 4 is structural schematic diagram lower right-most portion in embodiment 1.
Fig. 5 is the spray scrubber with sieve plate.
Fig. 6 is the structural schematic diagram of non-homogeneous aperture sieve plate.
Fig. 7 is the partial enlargement diagram of I in Fig. 5.
Appended drawing reference: 1 is booster fan, and 2,9,13,17,21,25 be spray scrubber, and 3,10,14,18,22,26 be slurry
Liquid pool, 4,11,15,19,23,27 be discharge pump, and 5,12,16,20,24,28 pump for Sprayer Circulation, and 6 be spraying layer, and 8 be demisting
Device, 29 be Wet chimney, and 30 be anolyte storage tank, and 31 be anolyte delivery pump, and 32 be manganese ore powder cabin, and 33 is, with stock tank, 34 are manganese
Pulp slurry delivery pump, 35 be oxidant storage tank, and 36 be oxidant delivery pump, and 37,39 be manganous dithionate degradation groove, and 41 be technique
Water pump, 42 be process water pond, and 43,49,59 be heater, and 44 be oxidation fan, and 45 be dioxygen water storage tank, and 46 convey for hydrogen peroxide
Pump, 47 be sulfuric acid storage tank, and 48 be sulfuric acid delivery pump, and 50 be secondary acidolysis slot, and 51 be secondary acid hydrolysis solution delivery pump, and 52 be filtering
Device, 53 be gas-liquid separator, and 54 be vacuum pump, and 55 be plate and frame filter press, and 56 be secondary acidolysis filtrate pump, and 57 filter for secondary acidolysis
Liquid bath, 58 be sieve plate.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
Any feature disclosed in this specification unless specifically stated can be equivalent or with similar purpose by other
Alternative features are replaced.That is, unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
?.
The present invention is specifically described below by embodiment, but it is necessary to it is again noted that embodiment is served only for
The present invention is further detailed, should not be understood as limiting the scope of the invention, person skilled in art, root
It according to the content of aforementioned present invention, makes some nonessential modifications and adaptations and is embodied, be to be not required to pay creative labor
Dynamic, protection scope of the present invention should be still fallen within.
Embodiment 1
The temperature that flue gas to be processed enters flue gas desulphurization system is 185 DEG C, exhaust gas volumn 199000m3/ h, the ingredient of flue gas
As shown in table 1 below.
1 smoke components of table
| Component | N2 | CO2 | H2O | O2 | SO2 |
| Content, v% | 65.28 | 16.00 | 11.18 | 2.78 | 4.75 |
Constituent analysis in manganese ore powder cabin 32 is as shown in table 2 below.
2 manganese ore meal component of table
The ingredient of anolyte for electrolytic manganese with slurry is as shown in table 3 below.
Table 3 is used to configure the anolyte of manganese ore slurries
| Component | Full Mn | Divalent Mn | H+ | pH |
| Content g/l | 14.19 | 13.41 | 14.74 | 0.35 |
Concrete operations are as follows.
1, the anolyte in anolyte storage tank 30 is sent through anolyte delivery pump 31 to in stock tank 33, and will be from manganese ore powder cabin
Manganese mineral powder and anolyte in 32 are mixed according to the ratio of solid content 13%, in stock tank 33, are configured to manganese ore slurries.
2, prepared manganese ore slurries are squeezed into the spray washing that diameter is 4.3m through manganese ore slurry feeding pump 34 respectively
In the slurry pool 3,10,14,18,22,26 of tower 2,9,13,17,21,25, and the side-feeding mixer of slurry pool institute band is opened, opened
The Sprayer Circulation pump 5,12,16,20,24,28 for opening each tower, carries out serum recycle spray.In the present embodiment, spray scrubber is used
Liquid-gas ratio be 20.
3, gas inlet baffle is opened, starts booster fan 1, flue gas is successively introduced to first spray scrubber 2, second
A spray scrubber 9 ... until the 5th spray scrubber 21 and the 6th spray scrubber 25.Adjust each spray washing
Tower fresh slurry inlet controls the pH value of each spray scrubber 2~5.
4, dioxy of the flue gas after the processing of continuous six spray scrubbers, in the exiting flue gas of the 6th spray scrubber
Change sulphur concentration and is reduced to 113mg/m3。
5, manganese ore slurries are washed by circulation desulfurization, and the filtrate that desulfurization leaching manganese slurries are obtained by filtration through filter 52 is passed through
After gas-liquid separator 53 separates gas, liquid is discharged into the manganous dithionate degradation groove 37,39 of diameter 12m.The solid being obtained by filtration
Object is discharged into the secondary acidolysis slot 50 with heater 59；Meanwhile the sulfuric acid in sulfuric acid storage tank 47 being conveyed by sulfuric acid delivery pump 48
Secondary response leaching is carried out to secondary acidolysis slot 50, the slurries after leaching are transported to sheet frame pressure by secondary acid hydrolysis solution delivery pump 51
Filter carries out filters pressing, and the filtrate that filters pressing obtains is stored in secondary acidolysis filtrate receiver 57, is conveyed by secondary acidolysis filtrate delivery pump 56
To manganous dithionate degradation groove 37.After the solid that plate and frame filter press filters pressing obtains is concentrated, manganese slag calcining workshop section is sent to be calcined.
It is separately turned on heater 43,49 in manganous dithionate degradation groove 37,39, the temperature of solution is made to rise to 80 DEG C；Together
When, the sulfuric acid come from sulfuric acid storage tank 47 and the conveying of sulfuric acid delivery pump 48 is added, is added and comes from dioxygen water storage tank 45 and hydrogen peroxide
The hydrogen peroxide that the conveying of delivery pump 46 comes, the manganese dioxide slurry that addition carrys out autoxidator storage tank 35 and the conveying of oxidant delivery pump 36 comes
Liquid etc. cuts down the dithionic acid manganese content in slurries, and the oxidant overall control of addition is in 20 ‰,.Desulfurization is soaked in manganese slurries
Manganous dithionate is after cutting down, and dithionic acid manganese content is reduced to 1827mg/l by 4623mg/l, the divalent manganese content in slurries
For 43.53g/l.
6, gained slurries are transported to electrolytic manganese process, the production after further cleaning and deploying, for electrolytic manganese.
The veneer yield average out to 3.1kg of electrolytic manganese.Gained slurries can also be transported to manganese sulfate refining step, by further cleaning
Afterwards, production prepares high-purity manganese sulphate.
By detection, the desulfurization degree of the first spray scrubber 2 is 24%, and the desulfurization degree of the second spray scrubber 9 is 33%,
The desulfurization degree of third spray scrubber 13 is 53%, and the desulfurization degree of the 4th spray scrubber 17 is 78%, the 5th spray scrubber
21 desulfurization degree is 86%, and the desulfurization degree of the 6th spray scrubber 25 is 90%, and total desulfurization degree is 99.9%.Manganese in manganese ore
Total extraction rate is 94.3%.
Embodiment 2
The temperature that flue gas to be processed enters flue gas desulphurization system is 200 DEG C, exhaust gas volumn 158000m3/ h, the ingredient of flue gas
As shown in table 4 below.
4 smoke components of table
| Component | N2 | CO2 | H2O | O2 | SO2 |
| Content, v% | 67.5 | 14.9 | 10.6 | 3.2 | 3.8 |
Constituent analysis in manganese ore powder cabin 32 is as shown in table 5 below.
5 manganese ore meal component of table
| Component | Full Mn | Tetravalence Mn | Divalent Mn |
| Content, wt% | 37.48 | 16.90 | 4.52 |
The ingredient of anolyte for electrolytic manganese with slurry is as shown in table 6 below.
Table 6 is used to configure the anolyte of manganese ore slurries
| Component | Full Mn | Divalent Mn | H+ | pH |
| Content g/l | 14.19 | 13.41 | 14.74 | 0.35 |
Concrete operations are as follows.
1, the anolyte in anolyte storage tank 30 is sent through anolyte delivery pump 31 to in stock tank 33, and will be from manganese ore powder cabin
Manganese mineral powder and anolyte in 32 are mixed according to the ratio of solid content 12%, in stock tank 33, are configured to manganese ore slurries.
2, prepared manganese ore slurries are squeezed into the spray washing that diameter is 4.0m through manganese ore slurry feeding pump 34 respectively
In the slurry pool 3,10,14,18,22,26 of tower 2,9,13,17,21,25, and the side-feeding mixer of slurry pool institute band is opened, opened
The Sprayer Circulation pump 5,12,16,20,24,28 for opening each tower, carries out serum recycle spray.In the present embodiment, spray scrubber is used
Liquid-gas ratio be 20.
3, gas inlet baffle is opened, starts booster fan 1, flue gas is successively introduced to first spray scrubber 2, second
A spray scrubber 9, third spray scrubber 13, the 4th spray scrubber 17, until the 5th 21 He of spray scrubber
6th spray scrubber 25.Each spray scrubber fresh slurry inlet is adjusted, controls the pH value of each spray scrubber 2
~5.
4, dioxy of the flue gas after the processing of continuous six spray scrubbers, in the exiting flue gas of the 6th spray scrubber
Change sulphur concentration and is reduced to 195mg/m3。
5, manganese ore slurries are washed by circulation desulfurization, and the filtrate that desulfurization leaching manganese slurries are obtained by filtration through filter 52 is passed through
After gas-liquid separator 53 separates gas, liquid is discharged into the manganous dithionate degradation groove 37,39 of diameter 10m.In manganous dithionate
In degradation groove 37,39, the sulfuric acid come from sulfuric acid storage tank 47 and the conveying of sulfuric acid delivery pump 48 is added, is added and comes from dioxygen water storage tank
45 and hydrogen peroxide delivery pump 46 conveying come hydrogen peroxide, be added come autoxidator storage tank 35 and oxidant delivery pump 36 conveying come
Fenton oxidation agent, cuts down the dithionic acid manganese content in slurries, and the oxidant total amount of addition is 18 ‰, of slurries amount.Abatement
After dithionic acid manganese content in slurries, the dithionic acid manganese content in slurries is reduced to 2253mg/l, slurries by 5138mg/l
In divalent manganese content be 40.78g/l.
6, gained slurries are transported to electrolytic manganese process, the production after further cleaning and deploying, for electrolytic manganese.
The veneer yield average out to 3.0kg of electrolytic manganese.Gained slurries can also be transported to manganese sulfate refining step, by further cleaning
Afterwards, production prepares high-purity manganese sulphate.
By detection, the desulfurization degree of the first spray scrubber 2 is 22%, and the desulfurization degree of the second spray scrubber 9 is 31%,
The desulfurization degree of third spray scrubber 13 is 45%, and the desulfurization degree of the 4th spray scrubber 17 is 75%, the 5th spray scrubber
21 desulfurization degree is 83%, and the desulfurization degree of the 6th spray scrubber 25 is 86%, and total desulfurization degree is 99.8%.Manganese in manganese ore
Extraction rate is 93.8%.
Through calculating, when being produced using manganese sulfate prepared by the present invention for electrolytic manganese, compared with traditional electrolyte manganese production technology energy
800~1000 yuan/ton are reduced, there is significant economic benefit.
The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (9)
1. a kind of manganese ore slurries handle the device containing sulfur dioxide flue gas, which is characterized in that including the spray scrubber with sieve plate,
Booster fan, Wet chimney, Sprayer Circulation pump, spray tube, with stock tank, the manganese ore powder cabin being connected with stock tank, slurries delivery pipe, set
Set in slurries delivery pipe manganese ore slurry feeding pump, anolyte storage tank, anolyte delivery pipe, be arranged in anolyte delivery pipe
Anolyte delivery pump, oxidation fan, oxidation air pipe, discharge pipe, the discharge pump being arranged on discharge pipe, filter, gas-liquid
Separator, manganous dithionate degradation groove, the spray scrubber be it is N number of, the N is natural number, and N >=3；
Booster fan for being connected with containing sulfur dioxide flue gas is connected to by flue with the middle and lower part of first spray scrubber；
In two neighboring spray scrubber, the tower top exhanst gas outlet of previous spray scrubber passes through flue and next spray scrubber
Middle and lower part connection and previous spray scrubber in handle containing sulfur dioxide flue gas can through flue enter it is next spray wash
It washs tower to be handled, the tower top exhanst gas outlet of n-th spray scrubber is connected with Wet chimney and flue gas after processing can be through wet
Chimney discharge；
It is provided with sieve plate in the spray scrubber, spraying layer is set above sieve plate, the sieve plate is to set on 1~2 layer and sieve plate
It is equipped with non-homogeneous aperture, the spraying layer is 3~6 layers, and spray scrubber lower slurry pond passes through spray tube and spraying layer
It is connected, the Sprayer Circulation pump is arranged on spray tube and Sprayer Circulation pump can be by spray scrubber lower slurry by spray tube
Manganese ore slurries in pond are delivered in spraying layer；Non-homogeneous aperture is provided on the sieve plate, 0.5 beta of sieve plate center is straight
In the range of diameter, percent opening is 45%~55%, and the aperture of aperture is 30mm~45mm；In 0.50~0.75 beta of sieve plate center
In diameter range, percent opening is 50%~60%, and the aperture of aperture is 50mm~60mm；In 0.75~0.95 beta of sieve plate center
In diameter range, percent opening is 50%~65%, and aperture is 60mm~80mm；The sieve plate is located at adsorption tower smoke entrance top
At 1.0~1.5m, supporting beam is equipped with below the sieve plate；Sieve plate edge is weldingly connected with tower body, and the sieve plate edge and tower
Wall is at 30 °~45 °；
The both ends of the slurries delivery pipe are connected respectively with stock tank, spray scrubber and slurries delivery pipe can will match phase in stock tank
Manganese ore slurries with concentration are delivered to the 1st in N number of spray scrubber respectively；
The anolyte storage tank is connected by anolyte delivery pipe with stock tank and the anolyte in anolyte storage tank can be through anode
Liquid delivery pipe is sent into in stock tank；
The oxidation fan is connected by oxidation air pipe with spray scrubber and oxidation fan can pump air into spray washing
In the slurry pool of tower lower inside；
The spray scrubber, discharge pipe, filter, gas-liquid separator, manganous dithionate degradation groove is connected and spray scrubber
Slurries after interior desulfurization leaching manganese can enter in manganous dithionate degradation groove through discharge pipe, filter, gas-liquid separator；
Further include for store the dioxygen water storage tank of hydrogen peroxide, hydrogen peroxide delivery pump, the oxidant storage tank for storing oxidant,
Oxidant delivery pump, the dioxygen water storage tank are connected with manganous dithionate degradation groove by hydrogen peroxide delivery pump and can pass through dioxygen
Water delivery pump adds hydrogen peroxide into manganous dithionate degradation groove, and the oxidant storage tank is by oxidant delivery pump and connects two sulphur
Sour manganese degradation groove is connected and can add oxidant into manganous dithionate degradation groove by oxidant delivery pump.
2. the apparatus according to claim 1, which is characterized in that it further include the vacuum pump being connected with gas-liquid separator, it is described
Discharge pipe is connected through filter, gas-liquid separator with manganous dithionate degradation groove, is provided in the manganous dithionate degradation groove
Heater, the manganous dithionate degradation groove are 1~3.
3. the apparatus of claim 2, which is characterized in that further include the secondary acidolysis slot matched with filter, use
In on sulfuric acid storage tank, sulfuric acid delivery pump, the secondary acid hydrolysis solution delivery pump, plate and frame filter press of storage sulfuric acid, the secondary acidolysis slot
Having heaters is set, and the sulfuric acid storage tank is connected with secondary acidolysis slot by sulfuric acid delivery pump and can pass through sulfuric acid delivery pump to two
Sulfuric acid is added in secondary acidolysis slot, the secondary acidolysis slot passes through secondary acid hydrolysis solution delivery pump, plate and frame filter press and manganous dithionate
Degradation groove matches.
4. device according to claim 3, which is characterized in that it further include secondary acidolysis filtrate pump, secondary acidolysis filtrate receiver,
The secondary acid hydrolysis solution delivery pump, plate and frame filter press, secondary acidolysis filtrate pump, secondary acidolysis filtrate receiver and manganous dithionate are degraded
Slot is connected.
5. the apparatus according to claim 1, it is characterised in that: two pieces of sieve plates of setting, the spacing of sieve plate are 1.8~2.5m.
6. the method for the manganese sulfate solution with anolyte manganous dithionate low with slurries desulfurization system prepared by manganese ore, feature exist
In including the following steps:
(1) manganese ore slurry feeding pump will be delivered to the 1st to n-th band with the manganese ore slurries in stock tank respectively by slurries delivery pipe
In the spray scrubber of sieve plate, thus respectively to the 1st to N number of spray scrubber input manganese ore slurries；
(2) the manganese ore slurries of spray scrubber lower part are delivered in spraying layer by Sprayer Circulation pump by spray tube, and through spraying
Layer discharge, and the counter current contacting containing sulfur dioxide flue gas with entrance, and then washed to containing sulfur dioxide flue gas, after washing
Manganese ore slurries are back to the lower part of spray scrubber after sieve plate；
(3) entered in first spray scrubber with flue by first spray scrubber middle and lower part containing sulfur dioxide flue gas, cigarette
Gas is uniformly distributed through sieve plate, with after spray to the slurries initial contact on sieve plate, then with the manganese in spray scrubber from top to bottom
After pulp slurry countercurrent washing, into next spray scrubber；Aforementioned process is repeated, until entering the containing sulfur dioxide flue gas
In N number of spray scrubber, after manganese ore serous adverse flow washing wherein from top to bottom, emptied through Wet chimney；
(4) oxidation fan is connected by oxidation air pipe with spray scrubber, and air is pumped into the 1st to N number of by oxidation fan respectively
In the slurry pool of spray scrubber lower inside, for being aoxidized to the solution containing sulphite；
(5) carry out step (1) to step (4), realize to containing sulfur dioxide flue gas continuous desulfurization and manganese ore soak manganese；
(6) when desulfurization leaching manganese reaction reaches the residence time in spray scrubber, pump startup is discharged, the slurries after desulfurization to be soaked to manganese
It is sent into filter by discharge pipe, respectively obtains filtrate, filter residue；
(7) it is admitted in manganous dithionate degradation groove after gas-liquid separator separates go out gas through the resulting filtrate of filter, to
It is separately added into pH adjusting agent, oxidant in manganous dithionate degradation groove, and is warming up to 60~90 DEG C, carries out oxidation reaction, drop
Manganous dithionate in low solution obtains the manganese sulfate solution of low manganous dithionate；
(8) enter in secondary acidolysis slot through the resulting filter residue of filter, and sulfuric acid be added thereto, and be warming up to 60~90 DEG C,
Secondary acidolysis is carried out to filter residue, the mixture after acidolysis respectively obtains secondary filtrate and secondary filter residue after secondary filter；Gained
Secondary filtrate is sent into manganous dithionate degradation groove.
7. according to the method described in claim 6, it is characterized in that, in the step (1), the solid content of manganese ore slurries is
8wt%~20wt%；
In the step (2), the concentration 5000mg/m containing sulfur dioxide in sulfur dioxide flue gas3~300000mg/m3。
8. according to the method described in claim 6, it is characterized in that, residence time of the manganese ore slurries in spray scrubber be
60min~900min.
9. according to the described in any item methods of claim 6-8, which is characterized in that the desulfurization in the manganous dithionate degradation groove
The raw material that slurries after leaching manganese are re-used as electrolytic manganese is sent into electrolysis workshop section, and anolyte storage tank is connected with electrolysis workshop section and is electrolysed work
The anolyte that section generates can enter in anolyte storage tank.
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| CN109133179A (en) * | 2018-09-26 | 2019-01-04 | 昆明理工大学 | A method of inhibiting pyrolusite pulp desulfurizing byproduct manganous dithionate |
| CN110102170B (en) * | 2019-04-16 | 2021-01-05 | 四川大学 | Short-process manganese oxide ore slurry desulfurization method based on micro cyclone separation, desulfurization absorption tower and manganese-sulfur resource recovery system |
| CN110396595B (en) * | 2019-08-29 | 2020-08-04 | 四川大学 | Efficient decomposition method of manganese dithionate in manganese ore sulfur dioxide leaching solution |
| CN115418476A (en) * | 2022-07-26 | 2022-12-02 | 株洲精卓科技有限公司 | Method for treating low-manganese ore containing tin and product thereof |
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