CN103387246A - Treatment process suitable for rapidly oxidizing magnesium sulfite to magnesium sulfate - Google Patents
Treatment process suitable for rapidly oxidizing magnesium sulfite to magnesium sulfate Download PDFInfo
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- CN103387246A CN103387246A CN2012101411844A CN201210141184A CN103387246A CN 103387246 A CN103387246 A CN 103387246A CN 2012101411844 A CN2012101411844 A CN 2012101411844A CN 201210141184 A CN201210141184 A CN 201210141184A CN 103387246 A CN103387246 A CN 103387246A
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Abstract
The invention relates to a treatment process suitable for rapidly oxidizing magnesium sulfite to magnesium sulfate. The process is characterized by comprising the steps of pumping a magnesium sulfite slurry with a certain concentration into an efficient oxidizer; adding a catalyst (copper-cobalt-aluminum composite salt) with a concentration of 0.001-0.003 mol/L in the efficient oxidizer; oxidizing for one hour, and thus magnesium sulfite solid in a desulfurated slurry is almost oxidized completely; transferring the oxidized magnesium sulfite into a condensation reactor; adding a coagulant and coagulant aid so that solid impurities in the slurry are condensed into easily settled large particles; introducing the slurry into a purifier to carry out two-phase separation so as to remove the solid impurities from the solution; overflowing a supernatant liquid to a buffer tank for use by an evaporation and concentration system; and crystallizing the solution in the buffer tank by evaporation and concentration to produce magnesium sulfate heptahydrate. The treatment process has the beneficial effects that by adding the catalyst, oxidation rate is shortened to one hour and power consumption and operation cost are reduced; reuse rate of the catalyst reaches 75%; catalyst cost is reduced; and environmental waste can be treated harmlessly and recycled efficiently.
Description
Technical field
The present invention relates to coordinate the use of catalyzer, promote the waste water reclaiming technology of oxidation effectiveness, specifically, is the technique that is applicable to the oxidation of wet-type magnesium method desulfurization by product magnesium sulfite quick catalysis is generated sal epsom.Be applied to the environment-protective circulating economic field.
Background technology
Can produce the mixed state slurries that contain in a large number magnesium sulfite in the process of wet-type magnesium method desulfurization, slurries are directly discarded after discarded or solid-liquid separation, all can produce a large amount of pollutents, cause secondary pollution, and discarded desulfurization product can lose a large amount of element sulphurs and magnesium elements, and conventional end treatment technology has difficult effectively sedimentation and the high problem of working cost.As adopt effective technique that it is reclaimed, and processed, make the magnesium sulfite in desulfurization product be converted into sal epsom, can produce higher economic worth, reduced simultaneously the running cost that end is processed.Therefore the oxide treatment for magnesium method desulfurization product magnesium sulfite has larger meaning.Carry out the oxidation magnesium sulfite with traditional oxidizing process, not only oxidation is insufficient, and rate of oxidation is low, has working cost high, the problem that process efficiency is low.By inventing suitable catalyzer and efficient oxidizing process, to improve the oxidation efficiency of magnesium sulfite, and then realize reducing equipment volume, fast reaction speed, improve oxidation rear slurry quality, the purpose of manufacture level magnesium sulfate heptahydrate.
Chinese patent CN1565709A discloses a kind of catalytic oxidation technique of desulfurization product of flue gas, directly can reach the standard of national discharge water add appropriate soluble salts catalyzer in the desulfurization absorption liquid after, this method is applied in desulfurizing adsorption system, and also inapplicable in desulphurization system liquid effluent system, be mainly that pH value, the reaction oxygen supply ratio of two kinds of systems is different with reaction conditions.Administer the content that can reduce dissolving sulphite in slurries with this technique, but can not reduce the content of slightly soluble salt magnesium sulfite, and can't recycle production sal epsom.Chinese patent CN101244360A discloses the catalytic oxidation technique of calcium sulfite, to add soluble ferrite, manganese salt catalyst in desulfurization slurry, promoted the absorption of sulfur dioxide in flue gas, reduce the possibility of scaling, but can, fully with sulfite oxidation, also be suitable for the catalyzed oxidation of magnesium sulfite.
Summary of the invention
The object of the invention is to the characteristics for magnesium method desulfurization slurry, propose a kind of magnesium sulfite Quick Oxidation that is applicable to and become the treatment process of sal epsom, can be fast, abundant oxidation magnesium sulfite, make it by the microsolubility solid, be converted into solubility sal epsom, solve the emission problem of desulfurizing byproduct, can produce qualified Adlerika again, produce economic benefit preferably.
Technical scheme of the present invention is following realization, a kind of magnesium sulfite Quick Oxidation that is applicable to generates the treatment unit of sal epsom, comprise catalyzer supplying tank, apparatus of oxygen supply, efficient oxidation device, flocculation agent feedway, coagulant aids feedway, coagulum reactor, cleaner, baffle-box, evaporation concentration system, its processing step comprises oxidation, cohesion, purification, evaporation concentration, and concrete technical characterictic is as follows:
(1) the magnesium sulfite slurries of 50 degrees centigrade of temperature after desulfurization, solids concn 15-20% are squeezed in the efficient oxidation device, the catalyzer that adds 0.001-0.003mol/L in the efficient oxidation device, introduce simultaneously oxygen, after oxidation 1 hour, the basic complete oxidation of magnesium sulfite solid in desulfurization slurry, become the mixed serum that contains magnesium sulfite, sal epsom and other impurity;
(2) send into coagulum reactor, add flocculation agent and coagulant aids, coagulum reactor is provided with agitator, make silicon-dioxide in unoxidized magnesium sulfite and desulfurization slurry etc. not the impurity of free settling be condensed into the more macrobead solid of free settling;
(3) enter in cleaner and carry out two and be separated, remove the solid impurity in solution, as not oxidation magnesium sulfite and silicon-dioxide; The overflow of cleaner supernatant liquid is to baffle-box, as the stoste of further production magnesium sulfate heptahydrate;
(4) the evaporative crystallization reaction of solution by evaporation concentration system in baffle-box, the output magnesium sulfate heptahydrate.
Efficient oxidation device as above, for semienclosed container, top is provided with catalyzer and adds mouth, material relief outlet, all the other positions, top are provided with cover plate, inside is provided with multi-functional sieve plate and apparatus of oxygen supply, multi-functional sieve plate can in case in grouting liquid deposition of solids on aerating pore, avoid the oxygen supply blockage of the micro orifice, oxygenous bubble can also be carried out effective fragmentation, improve oxidation, can also effectively avoid the oxidizer bottom to form dead band simultaneously, the precipitation fouling.
The catalyzer that adds in efficient oxidation device as above is cobalt salt, aluminium salt, and the composite compound of mantoquita, and the total amount that adds catalyzer is 0.001-0.003mol/L.
Coagulum reactor as above, be semienclosed container, is provided with vertical agitator, and flocculation agent is 1-2 ‰ iron(ic) chloride, and coagulant aids is 1-2 ‰ polyacrylamide.
Cleaner as above, be closed container, and the slurries after oxidation enter water distributor by the water-in on top, and water distributor is vertical the layout, and the water distributor water outlet is apart from cleaner bottom 600mm, and slurries are undertaken two by sedimentation and are separated in cleaner.Solution after purification passes through the overflow weir overflow at cleaner top to baffle-box.
Baffle-box as above, be conventional closed container, and storage solutions is for evaporation concentration system.
Evaporation concentration system as above is comprised of conventional equipments such as triple-effect evaporator, cooling crystallizer, whizzer and wrapping machines.
Catalyzer can reuse, and major part all exists in the underflow of cleaner bottom, and the underflow of clarifying in cleaner is back in the efficient oxidation device.
Beneficial effect of the present invention: add catalyzer and make rate of oxidation greatly increase, by conventional oxidation 48 hours, taper to 1 hour, reduced the power consumption of oxygen system, reduced working cost.The reclamation rate of catalyzer reaches 75%, greatly reduces the catalyzer cost.The magnesium sulfate heptahydrate product that obtains simultaneously can reach national industrial level standard, has increased certain economic benefit.Effectively solve the processing problem of magnesium method flue gas desulphurization by product magnesium sulfite, avoided secondary pollution, can realize the harmlessness disposing of refuse, can realize the recycling resource utilization of refuse.
Description of drawings
The invention will be further described below in conjunction with accompanying drawing and specific examples.
Fig. 1 is that a kind of magnesium sulfite Quick Oxidation that is applicable to generates the treatment process schematic diagram of sal epsom
Fig. 2 is efficient oxidation device organigram
In figure, 1-catalyzer supplying tank; The 2-apparatus of oxygen supply; 3-efficient oxidation device; 4-flocculation agent feedway; 5-coagulant aids feedway; The 6-coagulum reactor; The 7-cleaner; The 8-baffle-box; The 9-evaporation concentration system; The 11-catalyzer adds mouth; 12-material relief outlet; The multi-functional sieve plate of 13-; 14-apparatus of oxygen supply (by the access of the apparatus of oxygen supply in Fig. 1)
Embodiment
As shown in Figure 1, treatment unit of the present invention, comprise catalyzer supplying tank 1, oxygen system 2, efficient oxidation device 3, flocculation agent feedway 4, coagulant aids feedway 5, coagulum reactor 6, cleaner 7, baffle-box 8, evaporation concentration system 9.Its treatment process steps comprises oxidation, cohesion, purification, evaporation concentration, is specially:
(1) certain density magnesium sulfite slurries are squeezed in the efficient oxidation device, the catalyzer that adds 0.001-0.003mol/L in the efficient oxidation device, introduce oxygen simultaneously, and oxidation is after 1 hour, the basic complete oxidation of magnesium sulfite solid in desulfurization slurry, become magnesium sulfite and sal epsom slurries;
(2) send into coagulum reactor, add flocculation agent and coagulant aids, stir, make silicon-dioxide in unoxidized magnesium sulfite and desulfurization slurry etc. not the impurity of free settling be condensed into the more macrobead solid of free settling.
(3) enter in cleaner and carry out two and be separated, remove the solid impurity in solution, as silicon-dioxide; The overflow of cleaner supernatant liquid is to baffle-box, as the solution of further production sal epsom;
(4) the evaporative crystallization effect of solution by evaporation concentration system in baffle-box, the output magnesium sulfate heptahydrate.
Catalyzer is cobalt salt, aluminium salt, and the composite compound of mantoquita, and the total amount that adds catalyzer is 0.001-0.003mol/L,
Flocculation agent is 1-2 ‰ iron(ic) chloride, and consumption is 7g/L; Coagulant aids is 1-2 ‰ polyacrylamide, and consumption is 5g/L.
As shown in Figure 2, efficient oxidation device 3 is semienclosed container, top is provided with catalyzer and adds mouth 11, material relief outlet 12, and inside is provided with multi-functional sieve plate 13 and apparatus of oxygen supply 14, multi-functional sieve plate 13 can in case in grouting liquid deposition of solids on aerating pore, avoid the oxygen supply blockage of the micro orifice, oxygenous bubble can also be carried out effective fragmentation, improve oxidation, can also effectively avoid simultaneously the oxidizer bottom to form dead band, the precipitation fouling.Apparatus of oxygen supply 14 is by apparatus of oxygen supply 2 accesses in Fig. 1.
Claims (4)
1. a treatment process that is applicable to magnesium sulfite Quick Oxidation generation sal epsom, comprise oxidation, cohesion, purification, evaporation concentration, and its processing step technical characterictic is:
(1) certain density magnesium sulfite slurries are squeezed in the efficient oxidation device, added the catalyzer of 0.001-0.003mol/L in the efficient oxidation device, oxidation is after 1 hour, the basic complete oxidation of magnesium sulfite solid in desulfurization slurry;
(2) send into coagulum reactor, add flocculation agent and coagulant aids, stir, make silicon-dioxide in unoxidized magnesium sulfite and desulfurization slurry etc. not the impurity of free settling be condensed into the more macrobead solid of free settling;
(3) enter in cleaner and carry out two and be separated, remove the solid impurity in solution, the overflow of cleaner supernatant liquid is to baffle-box, as the solution of further production sal epsom;
(4) the evaporative crystallization effect of solution by evaporation concentration system in baffle-box, the output magnesium sulfate heptahydrate.
2. a kind of magnesium sulfite Quick Oxidation that is applicable to according to claim 1 generates the treatment process of sal epsom, it is characterized in that: the catalyzer that adds in the efficient oxidation device is cobalt salt, aluminium salt, and the composite compound of mantoquita, and to add the total amount of catalyzer be 0.001-0.003mol/L.
3. a kind of magnesium sulfite Quick Oxidation that is applicable to according to claim 1 generates the treatment process of sal epsom, it is characterized in that: coagulum reactor is semienclosed container, be provided with vertical agitator, flocculation agent is 1-2 ‰ iron(ic) chloride, and coagulant aids is 1-2 ‰ polyacrylamide.
4. a kind of magnesium sulfite Quick Oxidation that is applicable to according to claim 1 generates the treatment process of sal epsom, it is characterized in that: in the inside of efficient oxidation device, be provided with multi-functional sieve plate, prevent the oxygen supply blockage of the micro orifice, avoid the oxidizer bottom to form dead band, the precipitation fouling.
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| CN2012101411844A CN103387246A (en) | 2012-05-09 | 2012-05-09 | Treatment process suitable for rapidly oxidizing magnesium sulfite to magnesium sulfate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977832A (en) * | 2014-04-28 | 2014-08-13 | 华北电力大学（保定） | Loaded solid phase metal catalyst for magnesium desulfurization process, and preparation method thereof |
| CN109772427A (en) * | 2019-02-22 | 2019-05-21 | 浙江大学 | It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application |
| CN110420659A (en) * | 2019-08-15 | 2019-11-08 | 华北电力大学（保定） | A kind of device and method of catalysis oxidation magnesium sulfite, a kind of cobalt nitrate/ZSM-5 molecular sieve catalyst and preparation method thereof |
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| US5614158A (en) * | 1995-10-20 | 1997-03-25 | Dravo Lime Company | Process for removing sulfur dioxide from gases and producing gypsum and purified magnesium hydroxide |
| CN1481926A (en) * | 2003-04-11 | 2004-03-17 | 清华大学 | Technology for magnesia wet method stack gas desulfurization and recovering the products |
| CN1727055A (en) * | 2005-07-26 | 2006-02-01 | 六合天融（北京）环保科技有限公司 | Method for carrying out flue gas desulfurization by using mineral powder of magnesite |
| CN1733656A (en) * | 2005-08-01 | 2006-02-15 | 六合天融（北京）环保科技有限公司 | Method for manufacturing magnesium sulphate hepta hydrate fertilizer using boiler flue gas |
| CN101035616A (en) * | 2004-08-25 | 2007-09-12 | 约翰森·马瑟公开有限公司 | High cobalt content , high cobalt surface area catalysts, preparation and use thereof |
| CN201280436Y (en) * | 2008-09-27 | 2009-07-29 | 六合天融（北京）环保科技有限公司 | Aeration stirring reaction still for magnesium sulfate preparation |
| CN101618331A (en) * | 2009-07-28 | 2010-01-06 | 清华大学 | Composite metallic catalyst for desulfurization by magnesium and preparation method thereof |
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2012
- 2012-05-09 CN CN2012101411844A patent/CN103387246A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5614158A (en) * | 1995-10-20 | 1997-03-25 | Dravo Lime Company | Process for removing sulfur dioxide from gases and producing gypsum and purified magnesium hydroxide |
| CN1481926A (en) * | 2003-04-11 | 2004-03-17 | 清华大学 | Technology for magnesia wet method stack gas desulfurization and recovering the products |
| CN101035616A (en) * | 2004-08-25 | 2007-09-12 | 约翰森·马瑟公开有限公司 | High cobalt content , high cobalt surface area catalysts, preparation and use thereof |
| CN1727055A (en) * | 2005-07-26 | 2006-02-01 | 六合天融（北京）环保科技有限公司 | Method for carrying out flue gas desulfurization by using mineral powder of magnesite |
| CN1733656A (en) * | 2005-08-01 | 2006-02-15 | 六合天融（北京）环保科技有限公司 | Method for manufacturing magnesium sulphate hepta hydrate fertilizer using boiler flue gas |
| CN201280436Y (en) * | 2008-09-27 | 2009-07-29 | 六合天融（北京）环保科技有限公司 | Aeration stirring reaction still for magnesium sulfate preparation |
| CN101618331A (en) * | 2009-07-28 | 2010-01-06 | 清华大学 | Composite metallic catalyst for desulfurization by magnesium and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977832A (en) * | 2014-04-28 | 2014-08-13 | 华北电力大学（保定） | Loaded solid phase metal catalyst for magnesium desulfurization process, and preparation method thereof |
| CN109772427A (en) * | 2019-02-22 | 2019-05-21 | 浙江大学 | It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application |
| CN110420659A (en) * | 2019-08-15 | 2019-11-08 | 华北电力大学（保定） | A kind of device and method of catalysis oxidation magnesium sulfite, a kind of cobalt nitrate/ZSM-5 molecular sieve catalyst and preparation method thereof |
| CN110420659B (en) * | 2019-08-15 | 2022-10-14 | 华北电力大学（保定） | Device and method for catalytic oxidation of magnesium sulfite, cobalt nitrate/ZSM-5 molecular sieve catalyst and preparation method thereof |
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Application publication date: 20131113 |