CN1273389C - Method of preparing manganese sulphate using gray manganese ore and dialozite to adsorb sulfur dioxide waste gas - Google Patents
Method of preparing manganese sulphate using gray manganese ore and dialozite to adsorb sulfur dioxide waste gas Download PDFInfo
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- CN1273389C CN1273389C CN 03135926 CN03135926A CN1273389C CN 1273389 C CN1273389 C CN 1273389C CN 03135926 CN03135926 CN 03135926 CN 03135926 A CN03135926 A CN 03135926A CN 1273389 C CN1273389 C CN 1273389C
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- pyrolusite
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- manganous sulfate
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Abstract
The present invention relates to a method for absorbing the waste gas of sulfur dioxide and preparing manganese sulfate by using pyrolusite and rhodochrosite, which adopts the mixture of the pyrolusite and the rhodochrosite for absorbing the waste gas of SO2 and preparing MnSO4. The present invention integrates the production of MnSO4 and the treatment of the waste gas of SO2, a reduction roasting procedure in the production of the manganese sulfate is saved, a large quantity of energy resource is saved, the source problem of sulfuric acid is solved, and the waste gas treatment problem of SO2 is solved; the absorption rate of the waste gas of SO2 is over 90%, the standard-reaching exhaustion of the waste gas of SO2 is realized, the waste gas of SO2 is converted into a resource without harm, and the quantity of SO2 is reduced; simultaneously, the prepared product of the manganese sulfate in the technique can be over a second-class product (GB1622-79) after treatment.
Description
Technical field: the present invention a kind ofly absorbs the method that form waste gas of sulfur dioxide is produced manganous sulfate with pyrolusite and rhodochrosite, belongs to technical field metallurgical, environmental protection.
Background technology: manganous sulfate is that a kind of important Chemicals also are main chemical industry, metallurgical raw materials, can be used for the production of medicine, papermaking, pottery, catalyzer, ore floatation, electrolytic manganese and the manufacturing of other manganese salt etc.In herding and raising industry, add the growth that an amount of manganous sulfate can promote the animal skeleton agent; In addition, manganese still is one of important trace element fertilizer, and it is the chlorophyllous catalyzer of phytosynthesis, and the diversified economy crop imposes an amount of manganese sulfate solution, can make to produce well, increases harvest yield.On the one hand, traditional manganous sulfate production method is relatively complicated, and its main method has: 1. pyrolusite method: it will contain MnO
2Mix with 100: 20 quality proportioning with the anthracite powder at the pyrolusite powder more than 65%, in reduction roaster, carry out reducing roasting to produce MnO in 700 ℃-850 ℃, then MnO is cooled to room temperature under the condition of secluding air, cooled MnO is with dissolving in the dilute sulphuric acid, and sulfuric acid concentration is about 15%.The impurity of pyrolusite kind (Ca, Mg, Fe, Al etc.) all generates corresponding vitriol in dissolution process, pass through purification and impurity removal, static, evaporative crystallization, centrifugation then, again through warm air drying and manganous sulfate; This technology is topmost manganous sulfate production method.2. rhodochrosite method: its generates manganese sulfate solution with rhodochrosite and dilute sulphuric acid effect, then through purification and impurity removal, leave standstill, evaporative crystallization, centrifugation, again through warm air drying and manganous sulfate.3. ferrous sulfate method: generate the mixing solutions of manganous sulfate and ferric sulfate by pyrolusite and ferrous sulfate reaction, then through iron purification, leave standstill, evaporative crystallization, centrifugation, again through warm air drying and manganous sulfate.4. two ore deposits add acid system: the mixing solutions that has both adopted pyrolusite and sulfurous iron ore under the condition that sulfuric acid exists, to react to generate manganous sulfate and ferric sulfate then through purification and impurity removal, leave standstill, evaporative crystallization, centrifugation, again through warm air drying and manganous sulfate.On the other hand, traditional sulfur dioxide flue gas is administered technology " lime cream absorption method ", " alkali absorption method ", " S-WAT absorption cycle ", " ammoniacal liquor absorption process ", " the flue gas condensing method of purification ", " soda absorption process " etc., all be to adopt alkaline absorbent to absorb, these methods are to alleviating industrial SO
2Atmospheric pollution aspect is played a role, but there are some problems in these methods aspect the market of the supply of absorption agent and byproduct,
Can only solve SO merely
2Pollution problem, comprehensive benefit is low, has brought the problems such as increase of production cost in the enforcement again.Chinese patent discloses Guangxi University's number of patent application: 89107720.0, name is called: " absorbing the novel method of sulphur dioxide production industrial manganic sulfate with pyrolusite pulp ".The used equipment of this method absorption process is the horizontal mechanical spray absorber that low resistance is fallen, use simple pyrolusite pulp as absorption agent, simpler outwardly, but we found through experiments this method and have the following disadvantages: contain a large amount of oxygen owing in the waste gas when absorbing industrial gaseous waste 1., have a large amount of oxygen dissolutions to participate in reaction simultaneously when spray absorbs in ore pulp and generate sulfuric acid, making the product in the system is manganous sulfate and sulfuric acid; Vitriolic generates and causes pulp PH value to reduce, and can seriously reduce the specific absorption of sulfurous gas after pulp PH value reduces, and can not realize the qualified discharge of form waste gas of sulfur dioxide; 2. the used equipment of clear and definite its technology absorption process is the horizontal mechanical spray absorber that low resistance is fallen in this application file, though the absorption resistance drop of horizontal mechanical spray absorber is very little, but the processing that facts have proved this resorber equipment when industrial production is relatively more difficult, floor space is bigger, specific absorption is lower, cost is high, and enterprise is difficult to accept.The Chinese patent communique also discloses number of patent application: 89104140.0, name is called: " sulfur method of sulfur-containing smoke gas or tail gas ", it is the method that adopts the oxide compound of manganese sulfur-containing smoke gas and industrial tail gas to be carried out desulfurization, it with after sweetening agent contacts, changes sulfurous gas into water miscible manganous sulfate; The oxide compound of its disclosed manganese is the oxide compound of the manganese of insoluble or indissoluble, in fact mainly is Manganse Dioxide; Therefore the technology and the patent 89107720.0 of this patent application are close substantially, can not solve SO equally
2When waste gas absorbs in the system vitriolic form SO
2The influence of waste gas specific absorption can not realize SO
2The qualified discharge of waste gas.
Summary of the invention: the objective of the invention is to: provide a kind of and absorb the method that form waste gas of sulfur dioxide is produced manganous sulfate with pyrolusite and rhodochrosite; Present method adopts pyrolusite and rhodochrosite blended absorbent SO
2Waste gas is produced MnSO
4With MnSO
4Production and SO
2The improvement of waste gas combines, and has not only saved the reducing roasting operation that manganous sulfate is produced, and has saved a large amount of energy, has solved vitriolic and has come source problem; And make SO
2The waste gas pollution control and treatment problem is solved, SO
2The specific absorption of waste gas reaches more than 90%, can realize SO
2The qualified discharge of waste gas has been realized SO
2The resource utilization of waste gas, innoxious and minimizing, the prepared product manganous sulfate of this technology can reach seconds above (GB1622--79) after treatment simultaneously.
The present invention constitutes like this: be mixed with ore pulp with pyrolusite and water earlier, under the effect of recycle pump, enter packed absorber by the jet apparatus in pulp tank, circulating line and the absorption tower, spray downwards from nozzle, contain SO
2Waste gas enter from the bottom, absorption tower, in the absorption tower, contact the SO in the flue gas with pyrolusite pulp
2With the pyrolusite reaction, with SO
2Remove, in pulp tank, add the pH value that rhodochrosite is regulated ore pulp then, in and byproduct sulfuric acid, so the circulation mixture that can obtain forming by pyrolusite, manganous sulfate, impurity and water, flow out from the absorption tower, that can realize water miscible manganous sulfate and slag after filtration separates, obtains water miscible manganous sulfate, then manganese sulfate solution is added the milk of lime hydrolytic purification and adds the barium sulphide removing heavy metals, filter again at last and obtain more purified manganese sulfate solution, solution obtains manganous sulfate through concentrating thermal crystalline, manganous sulfate is carried out drying can obtain the product manganous sulfate.Specifically: the present invention be with contain manganese more than 20% pyrolusite and water to be mixed with liquid-solid ratio be 5: 1 pyrolusite pulp, under the effect of recycle pump, enter packed absorber by the jet apparatus zone of action in pulp tank, circulating line and the absorption tower, spray downwards from nozzle, scatter on top, contain SO
2Waste gas enter from the bottom, absorption tower, in the absorption tower with the pyrolusite pulp counter current contact, SO in the flue gas
2With the pyrolusite reaction, with SO
2Remove, in pulp tank, add chippy rhodochrosite, regulate the pH value of ore pulp, in and byproduct sulfuric acid, obtain by pyrolusite, manganous sulfate, the mixture that impurity and water are formed flows out from the absorption tower, can realize separating of water miscible manganous sulfate and slag after filtration, and obtain water miscible manganous sulfate, then manganese sulfate solution is added the milk of lime hydrolytic purification and adds the barium sulphide removing heavy metals, filter again and obtain more purified manganese sulfate solution, solution obtains manganous sulfate through concentrating thermal crystalline, at last manganous sulfate is carried out under 150 ℃-200 ℃ the condition can obtaining the product manganous sulfate in dry two hours.
Compared with prior art: the present invention had both utilized pyrolusite and SO
2Oxidation, reducing property, in packed absorber, carry out counter-current absorption, use rhodochrosite effectively to control the pH value of ore pulp simultaneously, promptly controlled the system pH value, the specific absorption that realizes sulfurous gas is more than 90%, realize the qualified discharge of form waste gas of sulfur dioxide simultaneously, the sulfuric acid and the rhodochrosite reaction that generate in the system are generated manganous sulfate, can not influence that whole technology is smooth and easy carries out, this method unites two into one two cover technologies, be novel process, the novel method of a kind ofly really accomplishing " comprehensive regulation, turn waste into wealth ", reached the purpose of invention.This method shows through interim test: can make SO
2The specific absorption of waste gas reaches more than 90%, can realize SO
2The qualified discharge of waste gas, the prepared product manganous sulfate of this technology can reach seconds above (GB1622--79) after treatment simultaneously.This technology has the following advantages: 1. employed starting material pyrolusite of this method and rhodochrosite all are natural crystals, and reserves are abundant, and low price, grade requirement not high (containing manganese 20-25% gets final product) only need Mechanical Crushing to 100 order to get final product during use.2. this technology had both been utilized pyrolusite and SO
2Oxidation, reducing property, pyrolusite pulp absorbs SO at the packed absorber internal recycle
2Waste gas uses rhodochrosite effectively to control the pH value of ore pulp simultaneously, and the specific absorption that realizes sulfurous gas realizes the qualified discharge of form waste gas of sulfur dioxide more than 90%, and sulfuric acid and the rhodochrosite reaction that generates in the system generated manganous sulfate.3. this technology can realize SO
2The resource utilization of waste gas, innoxious and minimizing.This method not only can be used for the SO of all coal firing boilers
2Waste gas pollution control and treatment comprises heat power plant's large-sized boiler, small-sized coal firing boiler and steam boiler, can be used for simultaneously
Iron work sintering SO
2The SO in waste gas pollution control and treatment and nonferrous smelting and chemical plant
2Waste gas pollution control and treatment.
Embodiments of the invention 1: with containing 2.5 tons in the pyrolusite 500kg of manganese 22.25% and water, be mixed with liquid-solid ratio and be 5: 1 pyrolusite pulp, under the effect of recycle pump, (absorption tower is the packed absorber of Φ 800 * 4000mm to enter packed absorber by the jet apparatus in pulp tank, circulating line and the absorption tower (zone of action), filler is a square saddle type filler), spray downwards from nozzle, scatter on top; Contain SO
2Waste gas (1000m3/h) enters from the reaction tower bottom, in the absorption tower with the pyrolusite pulp counter current contact, SO in the flue gas
2With the pyrolusite reaction, with SO
2Remove; Be the qualified discharge that guarantees to have higher absorption rate of sulfur dioxide and realize form waste gas of sulfur dioxide, every pH value that will in pulp tank, add rhodochrosite 50kg (containing manganese about 20%) adjusting ore pulp in 6-8 hour later on that absorbs, in and byproduct sulfuric acid, pulp PH value is remained on more than 2.5; So circulation can obtain being flowed out from the absorption tower by the mixture that pyrolusite, manganous sulfate, byproduct and water are formed, can realize obtaining water miscible manganous sulfate and separating of slag water miscible manganous sulfate after filtration, then manganese sulfate solution is added the milk of lime hydrolytic purification and adds the barium sulphide removing heavy metals, and then filter and obtain more purified manganese sulfate solution, solution obtains manganous sulfate through concentrating thermal crystalline, at last manganous sulfate is carried out under 150 ℃-200 ℃ the condition can obtaining the product manganous sulfate in dry two hours; The product manganous sulfate can reach seconds above (GB1622--79) after treatment.
Embodiments of the invention 2: with 5 tons in 1 ton of pyrolusite that contains manganese 20% and water, be mixed with pyrolusite pulp, under the effect of recycle pump, (absorption tower is the packed absorber of Φ 1000 * 5000mm to enter packed absorber by the jet apparatus in pulp tank, circulating line and the absorption tower (zone of action), filler is a square saddle type filler), spray downwards from nozzle, scatter on top; Contain SO
2Waste gas (1000m3/h) enters from the reaction tower bottom, in the absorption tower with the pyrolusite pulp counter current contact, SO in the flue gas
2With the pyrolusite reaction, with SO
2Remove; Be the qualified discharge that guarantees to have higher absorption rate of sulfur dioxide and realize form waste gas of sulfur dioxide, every pH value that will in pulp tank, add rhodochrosite 70-120kg (containing manganese about 20%) adjusting ore pulp in 6-8 hour later on that absorbs, in and byproduct sulfuric acid, pulp PH value is remained on more than 2.5.So circulation can obtain being flowed out from the absorption tower by the mixture that pyrolusite, manganous sulfate, byproduct and water are formed, can realize obtaining water miscible manganous sulfate and separating of slag water miscible manganous sulfate after filtration, then manganese sulfate solution is added the milk of lime hydrolytic purification and adds the barium sulphide removing heavy metals according to ordinary method, and then filter and obtain more purified manganese sulfate solution, solution obtains manganous sulfate through concentrating thermal crystalline, at last manganous sulfate is carried out under 150 ℃=200 ℃ the condition can obtaining the product manganous sulfate in dry two hours.
Concrete absorption data is seen: table one, table two
Adopt the higher-grade pyrolusite to absorb table one
| 1 | Accumulative total is added pyrolusite | 500Kg | Contain manganese 41.9% | |
| 2 | Accumulative total is added manganese carbonate ore | 150Kg | Contain manganese 19.8% | |
| 3 | Add up cycling time | 36 hours | ||
| 4 | Repair time | 0 hour | ||
| 5 | The actual cycle time | 36 hours | ||
| 6 | Maximum value | Minimum value | Mean value | |
| 7 | Air quantity | 946m 3/h | 543m 3/h | 790m 3/h |
| 8 | SO 2Entrance concentration | 11140mg/m 3 | 9500mg/m 3 | 10315mg/m 3 |
| 9 | SO 2Exit concentration | 780mg/m 3 | 290mg/m 3 | 490mg/m 3 |
| 10 | SO 2Specific absorption | 97.40％ | 93.0％ | 95.24％ |
Adopt low-grade pyrolusite to absorb table two
| 1 | Accumulative total is added pyrolusite | 650Kg | Contain manganese 22.25% | |
| 2 | Accumulative total is added manganese carbonate ore | 150Kg | Contain manganese 19.8% | |
| 3 | Add up cycling time | 45 hours | ||
| 4 | Repair time | 3 hours | ||
| 5 | The actual cycle time | 42 hours | ||
| 6 | Maximum value | Minimum value | Mean value | |
| 7 | Air quantity | 940m 3/h | 543m 3/h | 877.56m 3/h |
| 8 | SO 2Entrance concentration | 11550mg/m 3 | 10060mg/m 3 | 10988mg/m 3 |
| 9 | SO 2Exit concentration | 790mg/m 3 | 280mg/m 3 | 410mg/m 3 |
| 10 | SO 2Specific absorption | 97.40％ | 93.16％ | 96.26％ |
Claims (2)
1, a kind of method of producing manganous sulfate with pyrolusite and rhodochrosite absorption form waste gas of sulfur dioxide, it is characterized in that: earlier with contain manganese more than 20% pyrolusite and water to be mixed with liquid-solid ratio be 5: 1 pyrolusite pulp, under the effect of recycle pump, enter packed absorber by the jet apparatus in pulp tank, circulating line and the absorption tower, spray downwards from nozzle, contain SO
2Waste gas enter from the bottom, absorption tower, in the absorption tower, contact the SO in the flue gas with pyrolusite pulp
2With the pyrolusite reaction, with SO
2Remove, in pulp tank, add the pH value that rhodochrosite is regulated ore pulp then, in and byproduct sulfuric acid, so the circulation mixture that can obtain forming by pyrolusite, manganous sulfate, impurity and water, flow out from the absorption tower, that can realize water miscible manganous sulfate and slag after filtration separates, obtains water miscible manganous sulfate, then manganese sulfate solution is added the milk of lime hydrolytic purification and adds the barium sulphide removing heavy metals, filter again at last and obtain more purified manganese sulfate solution, solution obtains manganous sulfate through concentrating thermal crystalline, manganous sulfate is carried out drying can obtain the product manganous sulfate.
2, absorb the method that form waste gas of sulfur dioxide is produced manganous sulfate according to claim 1 is described with pyrolusite and rhodochrosite, it is characterized in that: contain SO
2Waste gas in the absorption tower, be counter current contact with pyrolusite pulp, the rhodochrosite that adds in pulp tank is chippy rhodochrosite, it is to carry out under 150 ℃ of conditions of-200 ℃, two hours that manganous sulfate is carried out drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03135926 CN1273389C (en) | 2003-09-24 | 2003-09-24 | Method of preparing manganese sulphate using gray manganese ore and dialozite to adsorb sulfur dioxide waste gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03135926 CN1273389C (en) | 2003-09-24 | 2003-09-24 | Method of preparing manganese sulphate using gray manganese ore and dialozite to adsorb sulfur dioxide waste gas |
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| Publication Number | Publication Date |
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| CN1537811A CN1537811A (en) | 2004-10-20 |
| CN1273389C true CN1273389C (en) | 2006-09-06 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355485C (en) * | 2005-10-25 | 2007-12-19 | 四川大学 | Waste gas desulfurizing method with composite absorbant comprising pyrolusite and pH buffering agent |
| BRPI0901089A2 (en) * | 2009-02-26 | 2010-11-16 | Mineracao Tabipora Ltda | manganese sulfate production process from the pyrolusite chemical reaction |
| CN104750130A (en) * | 2013-12-25 | 2015-07-01 | 贵州大学 | Method for regulating pH of low-grade pyrolusite sintering flue gas desulfurization slurry |
| CN104740982A (en) * | 2013-12-25 | 2015-07-01 | 贵州大学 | Method and apparatus for processing sulfur-containing flue gas by lean manganese mine and rhodochrosite |
| CN105688671A (en) * | 2016-03-16 | 2016-06-22 | 贵州大学 | Low-grade soft manganese ore sintering flue gas dry desulfurization method |
| CN106377993B (en) * | 2016-10-31 | 2023-05-12 | 昆明理工大学 | SO in pyrolusite slurry desorption flue gas 2 And method and device for recycling thereof |
| CN108117101B (en) * | 2018-02-08 | 2019-06-28 | 四川恒泰环境技术有限责任公司 | Sub-prime multiple feed method removes flue gas middle and high concentration SO2Sulphuric acid manganese method |
| CN110357164B (en) * | 2019-07-08 | 2022-03-15 | 四川大学 | Method for green purification of manganese oxide ore slurry by coupling circulating efficient flue gas desulfurization with manganese sulfate |
| CN115140775A (en) * | 2022-07-26 | 2022-10-04 | 贵州金瑞新材料有限责任公司 | Method for preparing manganese sulfate solution by reduction of pyrolusite |
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- 2003-09-24 CN CN 03135926 patent/CN1273389C/en not_active Expired - Lifetime
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