CN1021809C - Industrial manganese sulphate production method - Google Patents
Industrial manganese sulphate production method Download PDFInfo
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- CN1021809C CN1021809C CN 89107720 CN89107720A CN1021809C CN 1021809 C CN1021809 C CN 1021809C CN 89107720 CN89107720 CN 89107720 CN 89107720 A CN89107720 A CN 89107720A CN 1021809 C CN1021809 C CN 1021809C
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- gas
- absorption
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- sulfur dioxide
- pyrolusite
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Abstract
The present invention relates to a novel method for absorbing sulfur dioxide and producing industrial manganese sulfate by using the slurry of pyrolusite, which is a method for eliminating the sulfur dioxide in industrial waste gas and is suitable for environmental protection. More specifically, the sulfur dioxide in the industrial waste gas is absorbed by the slurry of the pyrolusite, and obtained absorption liquid is used for producing the industrial manganese sulfate by a conventional method of trash extraction, filtration and evaporative crystallization; finally, crystals are baked for 1 to 2 hours at 140 to 190 DEG C for decomposing associated manganous dithionate to obtain the industrial manganese sulfate meeting national standards. An apparatus used in the process of absorption is a horizontal type mechanical spray absorber with low resistance reduction, the recovery rate of the sulfur dioxide is over 95%, and the concentration of SO2 in exhausted gas is lower than 200 ppm after the waste gas is treated.
Description
The sulfurous gas that all contains some amount in many industrial gaseous wastees directly is discharged into atmosphere and can causes serious environmental to pollute.Therefore, how removing the sulfurous gas in the industrial gaseous waste, is an important environmental protection problem.It is a lot of to remove in the industrial gaseous waste method of sulfurous gas, the present invention relates to the method and the equipment thereof of aqeous suspension (being pyrolusite pulp) absorption sulfurous gas with pyrolusite, the major ingredient of the resulting absorption liquid of this method is a manganous sulfate, and can be used for the process industry manganous sulfate is Manganous sulfate monohydrate (MnSo
4H
2O)
Absorb the method for the sulfur dioxide to produce sulfuric acid manganese in the industrial gaseous waste with pyrolusite pulp, just there is the people intermittently to study from the fifties, but seldom can adhere to industrialization,, cause this method can't base oneself upon economically mainly due to there being two key problem in technology to fail fine solution.Now situation and the terms of settlement of the present invention with relevant these two key problem in technology is presented below:
(1), the selection issue of absorption technique and absorption equipment.In any production process, equipment all is the means that realize production technique, therefore must adapt to the requirement of technology.When the sulfurous gas that absorbs with pyrolusite pulp in the industrial gaseous waste, should select what kind of absorption equipment for use, at first to see technological process how to organize absorption.In forefathers' work, all take the mode of periodical operation usually with the process of pyrolusite pulp absorption sulfurous gas.This is because after pyrolusite and sulfurous gas react, can be left iron content, silicon, the aluminium of some amount, the residue of calcium.Mix with residue for fear of the ore pulp that advances resorber, can only draw off residue earlier and add fresh ore pulp again, thereby the absorption operation can only be intermittently.For example domestic certain factory set up one not long ago and applied mechanically the packaged unit that pyrolusite pulp absorbs the sulfur dioxide to produce sulfuric acid manganese in the sulfuric acid tail gas, is exactly periodical operation.This situation has reflection the 64th page of " sulfuric acid industry " 1988 the 5th phase.But periodical operation has following shortcoming: must stop when (a) loading and unloading ore pulp, waste gas can only cause environmental pollution to airborne release when drawing.(b) inventor learns through test, and when absorbing sulfurous gas with fresh pyrolusite pulp, the concentration of sulfurous gas can both remain on below the 100ppm in the considerable time inner exhaust gas, rises rapidly then.And when sulfur dioxide concentration reached 300ppm in the tail gas, 1/3rd the manganese of also having an appointment in the ore pulp did not react.If this moment guarantee the discharge quality of tail gas and change fresh ore pulp, will cause the waste of manganese; If improve the rate of recovery of manganese and do not change ore pulp, then sulfurous gas exceeds standard in the tail gas.The sulfur dioxide removal rate of above-mentioned domestic certain factory only reaches 80%, and reason promptly is this.In order to address this problem.Be provided with two resorbers among the present invention, one is equipped with the ore pulp that has reacted half, is called " main resorber ", and another fresh ore pulp of then packing into is called " subabsorber ".The waste gas that contains sulfurous gas is earlier through main resorber, after fully reacting with wherein ore pulp, absorbs concentration through subabsorber with fresh ore pulp general sulfurous gas wherein again and is lower than emission standard and discharges.When the manganese ore in the main resorber has reacted completely, promptly carry out the switching operation of resorber, transform original subabsorber into main resorber together with wherein ore pulp, and the slurry in the original main resorber is drawn off, charge into fresh ore pulp and make subabsorber and use.Switching operation can make the absorption of sulfurous gas become successive processes so in turn, can guarantee that the desulfurization degree of waste gas can improve the utilization ratio of manganese in the ore pulp again.
In order to adapt to above-mentioned two resorbers series connection technology of switching operation in turn, must select corresponding absorption equipment for use, forefathers are when the sulfurous gas that absorbs with pyrolusite in the industrial gaseous waste, and used absorption equipment all belongs to the bubbling absorber category.For example chemical plant, nineteen sixty-five Changsha was once set up one and was applied mechanically the device that pyrolusite pulp absorbs the sulfur dioxide to produce sulfuric acid manganese in vitriol works's tail gas, and used absorption equipment is a foam column.This situation has reflection at Changsha nonferrous metallurgy design institute smelting section of Ministry of Metallurgical Industry in 1975 " flue gas dust collection and the recovery and the utilization that purify design aids (five)-domestic low concentration sulphur dioxide flue gas " the 38th～40 page and the 43rd page that group compiles that gather dust.The packaged unit of aforementioned domestic certain factory, the absorption equipment of selecting for use are the jet blistering devices.The shortcoming of bubbling absorber is that resistance is big, the jet blistering device of domestic certain factory as described above, and the mouth of pipe is imbedded 200～300mm under the liquid, the about 300～400mm-H of systemic resistance
2O.Carry out the result of lab scale according to the inventor with single bubble absorbing tower, in order to remove the sulfurous gas in the waste gas effectively, the static height of liquid layer should be more than 400mm, and corresponding tower resistance is then at 500mm-H
2O is above.And according to the requirement of top said absorption technique, two resorbers series connection must be set use, add scum dredger, even get lower bound by the data of aforementioned domestic certain factory, the total-resistance of absorption system also reaches 700mm-H
2O.And the pressure of industrial gaseous waste itself is very low, and the gas transportation facilities that gas blower and so on is not set pressurizes it.Be to pass through such absorption system.The sulfuric acid tail gas in chemical plant, aforementioned Changsha just enters the sulfurous gas absorption system after pressurizeing by gas blower.Yet because the concentration of sulfurous gas is general also very low in the industrial gaseous waste, for example sulfuric acid tail gas is about 0.4%, smeltery's tail gas is also below 3%, therefore the power overwhelming majority that pressurised exhaust gas consumed is wasted in the void gas of compression except sulfurous gas, even the income of by-product manganous sulfate also is difficult to compensate the expense of this part power.Select the equipment of the horizontal mechanical spray absorber of low resistance for use in order to address this problem the present invention as pyrolusite pulp absorption sulfurous gas.
B.M draws " gas absorption (second edition) " the 378th～379 page of nurse work that the structure of horizontal mechanical spray absorber has been done introduction.It is the container of a hollow, some mechanical sprinkers is installed in interior, and rotating shaft that this sprinker is installed by a level and blade or the disk that is fixed in this rotating shaft are formed.The sub-fraction of blade or disk is immersed in the liquid simplely, can drive liquid during rotation and it be shed away formation conical jet fluid column.This absorption equipment is all only seen the silicon tetrafluoride (S that is used for absorbing calcium superphosphate factory tail gas at present at home and abroad
iF
4) occasion, be called " fluorine absorption chamber ", mechanical sprinker wherein then is commonly referred to as " water-sprinkling wheel " at home.BM draws nurse " gas absorption (second edition) " the 404th page the resistance of various absorption equipments to be contrasted, state in the literary composition: concerning the resistance of the next mass transfer unit of optimum regime, bubble tower is 100～400Pa, and the spray column of band shower nozzle then only has 20～50Pa(to amount to 2～5mm-H
2O).On structure, the resistance of horizontal mechanical spray absorber should be suitable with the spray column of band shower nozzle, should be little more than bubble tower therefore.So the present invention selects this absorption equipment for use, get exactly its resistance little, do not need again the equipment gas transportation facilities with waste gas pressurization and there is not easily advantage such as plug members such as shower nozzle.But domestic used fluorine absorption chamber can not simply be transplanted use at present.Because it is gas one liquid two phase reaction that water absorbs silicon tetrafluoride, absorbing sulfurous gas with pyrolusite pulp then is that gas one liquid one solid phase reaction, particularly manganese ore powder also have proportion very big (4.73～4.86), very easily settled characteristics.According to these characteristics, the present invention is improved the fluorine absorption chamber, makes it become a kind of equipment that is applicable to solution-air one solid phase reaction.
Fig. 1 is an example of resorber of the present invention.This resorber has two structural units, respectively is in a cell (1) cell horizontal mechanical sprinker (2) to be installed, and this sprinker is made up of the rotating shaft (3) of a level installation and several radial flow impellers (4) that are installed in this rotating shaft.The hull bottom shape is made at the end of cell (5), and sprinker is seated in " cabin ".(6), (7) are the waste gas import and exports, (8), (9) are the ore pulp import and exports, (10) be the gas baffling plate, Fig. 2 is the used a kind of radial flow impeller of sprinker, is made up of a flat-disk (11) and 6 wheel blades (12) of being installed on this disk.The wheel blade tip is suitably crooked, and to roll ore pulp be principle to wheel blade when its bending direction rotated with sprinker.Wheel blade can be vertically mounted on the disk, but also slightly inclined, but the angle of wheel blade plane and disk plane should not exceed 70 °～90 ° scope.Half of impeller (4) is immersed in the ore pulp.Two sprinker reverse rotations, in sprinker when rotation,, impeller stirs evenly, is dispersed into fine droplet with ore pulp and offers upward, contacts with sulfurous gas by cell to react.Resorber is not limited to have two unit, can have only a unit, also can be put together by a plurality of unit, decides according to practical situation.Gas can be parallel with the sprinker axle into and out of direction, also can be vertical with the sprinker axle.In the resorber traverse baffle can be set, also can not be provided with.
Resorber of the present invention and fluorine absorption chamber relatively have following advantage: (a) during the rotation of radial flow impeller, can produce powerful centrifugal force in the wheel blade tip on the one hand, produce the vortex that trails consumingly simultaneously again at the wheel blade rear.The hangover vortex has the intensive stirring action to liquid phase, can guarantee that the manganese ore powder is suspended in the liquid phase equably; The suspension that centrifugal force then will stir evenly sprays into drop; In addition, after the impeller rotation reaches certain speed, also have a certain amount of gas and involved in the liquid phase; Thereby reach gas one liquid, one solid triphasic abundant contact and fast reaction speed.(b) the hull bottom shape is made at the end of structural unit, can eliminate stirring less than the dead angle, make whole breezes can both be in good suspended state.
(2), the problem that removes of manganous dithionate.When absorbing sulfurous gas, manganous dithionate (MnS is always arranged inevitably in the absorption liquid with pyrolusite pulp
2O
6) association.Manganous dithionate is difficult to separate with manganous sulfate, causes the purity of manganese sulfate product not reach the industrial manganic sulfate commercial standards.Czech had patent to adopt the secondary spray method to address this problem in 1972.Method is: absorption liquid is arrived pH＜1 with sulfuric acid acidation, then with the together spray evaporation of stoichiometric fresh manganese ore, make the big portion of manganous dithionate change manganous sulfate into, after isolating the manganous sulfate crystallization, again the crystallization and the vitriol oil are together sprayed, make the manganous dithionate that remains in this crystallization be decomposed into manganous sulfate.This situation has reflection at CA78 among the 32202u.This method complicated operation, and need to consume sulfuric acid.The rule of doing in chemical plant, aforementioned Changsha is to add sulfuric acid in the mother liquor and pyrolusite powder makes manganous dithionate be oxidized to manganous sulfate.This method also need consume sulfuric acid.
The present invention adopts solid-phase pyrolysis to address this problem.Some scholars once related to the thermolysis property of manganous dithionate when the character of the various dithionates of research in history, but the saying of having nothing in common with each other.Someone generates Manganous sulfate monohydrate (MnSo when thinking the decomposition of hydration manganous dithionate
4H
2O) and anhydrous manganous dithionate (MnS
2o
6), this situation is at CA28:3327
8In reflection is arranged.Someone thinks and is decomposed into anhydrous manganous dithionate (MnS when the hydration manganous dithionate is heated to 150 ℃ earlier
2o
6), the latter is decomposed into anhydrous manganous sulfate (MnSo again in the time of 190 ℃
4) this situation has reflection in CA76:9993C.Water molecules and sulfur dioxide molecule left simultaneously when someone thought the decomposition of hydration manganous dithionate, and this situation has reflection in CA89:122330r.The inventor learns that through overtesting the decomposition under different condition of hydration manganous dithionate can obtain different products.In view of the above, the method that the present invention takes is that absorption liquid is produced crystallization by the ordinary method of producing manganous sulfate, but the crystallization of gained and ordinary method gained is different, is not manganous sulfate but the mixing salt of anhydrous manganese and hydration manganous dithionate.With this mixing salt 140～190 ℃ the baking 1～2 hour, preferably under water vapour atmosphere in 150～170 ℃ the baking 1～2 hour, the hydration manganous dithionate in the mixing salt promptly is decomposed into Manganous sulfate monohydrate (MnSo
4H
2O) be industrial manganic sulfate.This method does not consume sulfuric acid, and removing with the drying merging of manganous sulfate of manganous dithionate once can be carried out, and does not increase operation link and treatment facility, only need grasp baking condition and just can.
To forefathers' method make as above improve after, method of the present invention is: two placed in-line, serve as in the horizontal mechanical spray absorber of main resorber and subabsorber in turn, absorb sulfurous gas in the industrial gaseous waste with pyrolusite pulp.The absorption liquid of gained carries out removal of impurities, filtration, evaporative crystallization by the ordinary method of manufacture manganous sulfate.At last the crystallization of gained was toasted 1～2 hour under 140～190 ℃ of temperature, preferably toasted 1～2 hour in water vapour atmosphere and under 150～170 ℃ of temperature, the manganous dithionate pyrolysis that makes association is a manganous sulfate.
Embodiment:
Fig. 3, Fig. 4 are the procedure of laboratory that the present invention implements in chemical industry system of Guangxi University.Fig. 3 is the flow process of absorption portion.(13) are the sulfurous gas steel cylinders among the figure, (14) be the nitrogen steel cylinder, (15) be air compressor, (16) be gas mixing bottle, (17) are main resorbers, and (18) are subabsorbers, (19) be wet test meter, (20), (21), (22) are spinner-type flowmeters, (23), (24), (25) are U-tube manometers, (26), (27), (28) they are the gas sampling points.The used gas of absorption test is the composition N of simulation vitriol works tail gas
2, air and SO
2Be mixed with, it consists of: SO
20.4～0.6%, O
26～7%, N
292～93%.Processing tolerance is 221/min.Filling 1.051 ore pulps in each resorber.All gases mixes in hybrid bottle through separately under meter metering back, and the gas mixture of gained exports tail gas emptying after wet test meter measures (this promptly handles gas volume) after fully reacting with pyrolusite pulp through main resorber and subabsorber successively.Ore pulp in main resorber loses and absorbs SO
2Ability the time, this ore pulp (being called " ripe slurry ") is drawn off, carry out removal of impurities by the flow process of Fig. 4 according to the ordinary method of producing manganous sulfate, the final evaporation crystallization obtains the mixing salt of anhydrous manganese and hydration manganous dithionate.With this mixing salt under water vapour atmosphere in 150～170 ℃ the baking 1～2 hour, promptly get industrial manganic sulfate.Through test, simulation vitriol works tail gas discharges SO in the gas after treatment
2Concentration stabilize is controlled at below the 200ppm, is lower than national specified discharge standard (500ppm), sulfur recovery rate＞95%, and the gained manganous sulfate meets the national standard of industrial manganic sulfate.
Test used resorber and have only a structural unit, it is cylindrical to be horizontal, and length is 440mm, and volume is 3.4541.In the rotating shaft of machinery sprinker 6 radial flow impellers are installed equidistantly.With the vertical gas baffling plate of rotating shaft resorber is divided into 6 cells with 7, each impeller is seated in the cell.Gas is entered by an end of resorber, and baffling skims over each cell, with the ore pulp contact reacts that impeller sprays, discharges from the other end of absorption chamber at last.According to test determination, system-wide resistance is about 140mm-H
2O, the resistance of each resorber is about 15mm-H
2O.And employing is had the test that the bubbling absorber of same diameter carries out, and when handling identical tolerance, the liquid layer static height will just can meet the demands more than 400mm, and the proportion of ore pulp is about 1.2, so the resistance of resorber is more than 480mm.
Claims (2)
1, a kind of method of manufacture manganous sulfate, this method comprise with pyrolusite pulp absorb sulfurous gas, with absorption liquid removal of impurities, evaporative crystallization then, it is characterized in that:
(1) pyrolusite pulp carries out in the horizontal mechanical spray absorber; Absorb the sulfurous gas in the waste gas.
(2) resulting crystallization was 140～190 ℃ of bakings 1～2 hour.
2, the method for claim 1 is characterized in that: the gained crystallization was toasted 1～2 hour in water vapour atmosphere and under 150～170 ℃ the temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89107720 CN1021809C (en) | 1989-10-05 | 1989-10-05 | Industrial manganese sulphate production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89107720 CN1021809C (en) | 1989-10-05 | 1989-10-05 | Industrial manganese sulphate production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1043113A CN1043113A (en) | 1990-06-20 |
| CN1021809C true CN1021809C (en) | 1993-08-18 |
Family
ID=4857316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89107720 Expired - Fee Related CN1021809C (en) | 1989-10-05 | 1989-10-05 | Industrial manganese sulphate production method |
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| Country | Link |
|---|---|
| CN (1) | CN1021809C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376698C (en) * | 2003-07-30 | 2008-03-26 | 海特克能源有限公司 | Improved hydrometallurgical processing of manganese containing materials |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055067C (en) * | 1997-02-18 | 2000-08-02 | 周保强 | Method for direct production of manganese sulfate by sulfur dioxide gas |
| US7153345B2 (en) * | 2004-02-04 | 2006-12-26 | Battelle Memorial Institute | Sulfur oxide adsorbents and emissions control |
| CN100411997C (en) * | 2005-02-01 | 2008-08-20 | 桂林市孟泰矿产技术开发有限责任公司 | Method of recovering manganese sulfate from low-grade manganese carbonate and manganese oxide |
| CN101732956B (en) * | 2008-11-21 | 2011-12-14 | 胡海清 | Process for producing manganese salt by using sulfur-containing smoke gas |
| CN106582210B (en) * | 2016-12-22 | 2019-08-02 | 贵州大学 | A kind of tartaric acid is that raw material prepares coal-fired flue gas desulfurization demercuration agent method |
| CN107445209B (en) * | 2017-07-05 | 2020-04-10 | 四川大学 | Method for preparing saturated manganese sulfate slurry and manganese sulfate by removing manganese dithionate in pyrolusite slurry leaching solution |
-
1989
- 1989-10-05 CN CN 89107720 patent/CN1021809C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376698C (en) * | 2003-07-30 | 2008-03-26 | 海特克能源有限公司 | Improved hydrometallurgical processing of manganese containing materials |
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| Publication number | Publication date |
|---|---|
| CN1043113A (en) | 1990-06-20 |
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