CN102452712A - Oxidation method of flue gas desulphurization waste liquid - Google Patents
Oxidation method of flue gas desulphurization waste liquid Download PDFInfo
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- CN102452712A CN102452712A CN2010105139648A CN201010513964A CN102452712A CN 102452712 A CN102452712 A CN 102452712A CN 2010105139648 A CN2010105139648 A CN 2010105139648A CN 201010513964 A CN201010513964 A CN 201010513964A CN 102452712 A CN102452712 A CN 102452712A
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Abstract
The invention relates to an oxidation method of flue gas desulphurization waste liquid. The method comprises steps that: Mn ore is adopted as a catalyst; a countercurrent catalytic oxidation tower is adopted; the Mn ore is arranged in the catalytic oxidation tower with a fixed bed manner; desulphurization waste liquid enters from the upper part of the catalytic oxidation tower; the desulphurization waste liquid contacts air with a countercurrent manner on the fixed bed Mn ore catalyst bed layer, such that an oxidation COD-removing reaction is carried out; and a desulphurization waste liquid obtained after oxidation is discharged from the catalytic oxidation tower. The method provided by the invention is advantaged in simple process and high efficiency. The method is economic and reasonable. With the method, obstruction can hardly occur. The method satisfies environment protection standards. The method is suitable to be used in a processing process for reducing the COD of flue gas desulphurization waste liquid.
Description
Technical field
The present invention relates to a kind of method for oxidation of wet process of FGD waste liquid, particularly the treatment process of soda method flue gas desulphurization waste solution oxidation removal COD.
Background technology
Flue gas desulphurization waste solution COD content is one of important quality index, like Wingdale-gypsum method desulfurization, the desulfurization of soda method, magnesium oxide method desulfurization, the ammonia process of desulfurization etc.Many wet desulfurizing process all produce the desulfurization waste liquor that contains a certain amount of COD, therefore need suitable method to remove processing.
Flue gas desulphurization waste solution falls the COD method and mainly is divided into two kinds of natural oxidation and forced oxidations.Natural oxidation is in oxidizer unit, through mechanical stirring air to be got in the doctor solution naturally, utilizes airborne O
2Come oxidation sweetening liquid to reach the purpose that reduces COD, owing to influenced by oxygen solubleness in liquid under the natural condition, required oxidation pond is bulky, and oxidation efficiency is low, and draining COD fluctuation of concentration is bigger, stirs the inhomogeneous dead angle problem that exists simultaneously.Forced oxidation is to utilize pump that the oxidation required air is provided, and be used to reduce the COD index of desulfurization waste liquor, but device volume is huge, and investment is big, and working cost is high, O in the air
2Utilization ratio low, COD removes and to receive some parameter (like the fluctuation of waste liquid flow) influenced.Like the disclosed desulfurization intermediate product of CN200410056878.3-calcium sulfite forced oxidation method etc., insert with the air gun side and to hold the liquid bath bottom, with air the calcium sulfite in the desulfurization waste liquor and calcium bisulfite are oxidized to gypsum, and further separate removal.Like the disclosed a kind of non-stirring oxidization device of flue gas desulfurization slurry pool of CN200720188331.8; Be used for oxidation sweetening slurries calcium sulfite; This method provides the oxidation required air through compressor, in bottom, slurries pond the circular arc conduit is set, and the conduit arc section has gas ejector pipe.The disclosed a kind of wet process of FGD jet oxidizer unit of CN200720125180.1; Be used for oxidation sweetening slurries calcium sulfite; This method is that a jet-pump is set on the slurry circulating pump export pipeline; Bring air into through liquid and to carry out the oxidation sweetening slurries in the slurries pond, slurries have whisking appliance in the pond.
Because the wet process of FGD waste liquid contains higher COD, the treatment process that the most often adopts at present is the direct bubbling aeration of air.The deficiency of the direct aeration of air is to exist device pressure to fall greatly, has O in the air
2The problem that utilization ratio is low needs high pressure, atm number Root's blower to mend into surplus air, the waste energy consumption; Simultaneously; In order to guarantee to take place between the gas-liquid mass transfer, oxidizing reaction needed duration of contact, need the tall and big oxidizing tower of design one volumes, facility investment increases.The economy that the COD treating processes falls in the doctor solution oxidation is to realize the important indicator of industrial application.COD in the oxidation sweetening waste liquid can reduce facility investment to greatest extent, but in general, after oxidation ratio reaches certain limit, further increasing oxidation ratio necessary operations expense again will increase greatly, thereby total economy descends; How the requirement of comprehensive qualified discharge confirms that COD treatment process and control condition falls in the doctor solution oxidation, guarantees to reach under the prerequisite of emission standard, realizes maximum economy, is that the required primary study of COD treatment process falls in the doctor solution oxidation.
Summary of the invention
To the deficiency of prior art, the treatment process that the present invention provides that a kind of process is simple, COD falls in economical rationality, the flue gas desulphurization waste solution catalyzed oxidation that can meet environmental protection standard.
Through the flue gas desulphurization waste solution Study on Properties is found; The high COD waste liquid in flue gas desulphurization waste solution and other source has tangible difference, and promptly the waste liquid main ingredient is vitriol, sulphite and the hydrosulphite etc. of sodium or magnesium, and in general the COD of this desulfurization waste liquor is higher; Do not meet emission standard; Utilize the inventive method oxidation to fall COD, can reduce to below the 100mg/L, can reduce equipment volume, improve oxidation efficiency, increase process economy.
The method for oxidation of flue gas desulphurization waste solution of the present invention; Comprise following content: with the Mn ore is catalyzer, adopts adverse current catalyzed oxidation tower, and the Mn ore is contained in the catalyzed oxidation tower with the mode of fixed bed; Desulfurization waste liquor gets into from catalyzed oxidation tower top; Desulfurization waste liquor and air be counter current contact on fixed bed Mn ore beds, carries out oxidationization and takes off the COD reaction, and the desulfurization waste liquor after the oxidation is discharged the catalyzed oxidation tower.
In the flue gas desulphurization waste solution method for oxidation of the present invention, the reaction time of desulfurization waste liquor was generally 10～90 minutes, and the liquid gas volume ratio of desulfurization waste liquor and air is 10～200L/m
3, be preferably 20～100L/m
3In the inventive method, temperature of reaction and pressure can not need be controlled, and natural temperature and pressure during by normal running get final product, and are generally below 60 ℃ during normal running and normal pressure.
In the flue gas desulphurization waste solution method for oxidation of the present invention, Mn ore beds can be provided with 1 layer, also can be provided with 2～5 layers, and the height of every layer of Mn ore beds is 500～1000mm.Desulfurization waste liquor disperses the back to contact with Mn ore catalyzer from top layer Mn ore beds through liquid distributor.Oxidation air disperses the back adverse current to go out the desulfurization waste liquor contact from lowest layer Mn ore beds bottom through gas distributor, and other Mn ore beds bottom also can the supplemental air, and additional oxidation air also disperses through gas distributor.Preferred every layer of Mn ore beds top all is provided with liquid distributor.
In the flue gas desulphurization waste solution method for oxidation of the present invention, the granularity of Mn ore is 0.2～5cm, is preferably 1～2cm.The Mn ore can be the Mn ore of existing any type, as carbonate type manganese ore, oxide type manganese ore etc. all can, specifically can select commercially available powdery Mn ore.
In the flue gas desulphurization waste solution method for oxidation of the present invention, the tail gas after the oxidation of catalyzed oxidation tower causes desulfurizing and purifying exhanst gas outlet or directly discharging.The structure of catalyzed oxidation tower can adopt the conventional structure of this area; Comprise inlet pipe, liquid distributor, beds, gas distributor, liquid discharge pipe etc.; The inlet pipe of oxidizing tower and discharge opeing tube side inverted U structure, inlet pipe import vertex are higher than liquid discharge pipe outlet vertex 300～500mm.
It is catalyzer that flue gas desulphurization waste solution method for oxidation of the present invention adopts Mn ore deposit story story stone with low cost, though catalytic efficiency (a little less than special catalyzer, desulfurization waste liquor still contains a small amount of COD; But meet GB8978-1996 " integrated wastewater discharge standard "; The Mn ore cost is low, does not have the regenerated problem, even process the inventive method exhausted Mn ore does not influence the follow-up normal use of this Mn ore yet; Therefore; The little increase equipment that needs of the inventive method does not increase any process cost yet, and economy is very outstanding.
The inventive method is fallen the characteristics that COD efficient is low, the oxidizing tower volume is big, energy consumption is high to existing wet desulphurization waste liquid oxidation; A kind of catalyzed oxidation tower has been used in design; This oxidizing tower is oxidized to vitriol through suitable beds sum of series Liquid Distribution structure with the sulphite and the hydrosulphite of doctor solution, has improved the gas-to-liquid contact effect greatly, has improved oxidation ratio and turndown ratio; Reduced equipment scale, saved and taken up an area of and investment.
Description of drawings
Fig. 1 proposes the outline flowchart of technology for the present invention.
Wherein: 1 is inlet pipe, and 2 is the air outlet, and 3 is beds, and 4 is fluid inlet, and 5 is leakage fluid dram, and 6 is liquid distributor, and 7 is gas distributor, 8, and oxidation fan
Fig. 2 is liquid distributor structural representation among the present invention.
Fig. 3 is gas distributor structural representation among the present invention.
Embodiment
In the inventive method, air disperses back and desulfurization waste liquor to contact the catalysed oxidn oxidation Na wherein through Mn ore catalyzer in the catalyzed oxidation district through the gas distributor of oxidizing tower
2SO
3And NaHSO
3, gas distributor is that perforated pipe props up the shape structure.Liquid after the oxidation leans on action of gravity to flow downward through beds.
The concrete structure of the catalyzed oxidation tower that the inventive method is used comprises cylindrical shell, liquid distributor, gas distributor and at least one catalyzed oxidation district; According to COD clearance after the oxidation; The catalyzed oxidation district is traditionally arranged to be 1～3 layer; Gas distributor 7 is arranged between cylindrical shell bottom and adjacent two beds, and liquid phase distributor 6 is arranged on cylindrical shell top, and catalyzed oxidation district 3 is arranged between liquid distributor, gas distributor and the cylindrical shell orlop air-distributor; Bottom, catalyzed oxidation district is a gas distributor, and gas distributor is a type structure.Between liquid distributor and beds, the beds, between beds and the gas distributor suitable space is set.
In the oxidizing tower of the present invention, oxidizing tower top is provided with fluid inlet 4 and air outlet 2, and the bottom is provided with inlet mouth 1 and liquid outlet 3, and gas distributor communicates with inlet mouth 1, and liquid distributor communicates with fluid inlet 4.Liquid distributor 6 is made up of ring pipe, adapter and flange; The ring pipe lower surface is offered some apertures.Gas distributor 7 is made up of collecting tubule, some arms and flange; The arm lower surface is offered some apertures.
Catalyzed oxidation tower of the present invention is when work, and liquid phase enters into the liquid distributor that is arranged on cylindrical shell top through inlet and is sprayed onto bed; Gas phase enters into gas distributor from the tower bottom import, offers being distributed in the tower of some apertures from collecting tubule arm lower surface.Liquid phase forms liquid layer in oxidation zone tower beds after liquid distributor disperses, lean on action of gravity in bed, evenly to flow downward, and the liquid re-distributor redistribution back of leaning on that flows to the beds bottom gets into the next stage beds.Gas is distributed in the liquid layer of oxidation zone catalyzer after passing gas distributor and liquid re-distributor, and gas-liquid two-phase is realized fully contact at this, carries out mass transfer and oxidizing reaction.
Liquid phase is fallen under action of gravity and gas phase from bottom to top forms counter current contact, realizes mass transfer and reaction.Said structure organically is combined in two kinds of gas-to-liquid contact mass transfer means of bubbling and spray in the equipment, has made full use of the device space simultaneously, has improved the use properties of equipment.
The catalyzed oxidation tower that the inventive method is used is provided with some inner members according to gas-liquid mass transfer and reaction process characteristics, and during work, liquid phase enters into the liquid phase divider that is arranged on cylindrical shell top through inlet, is sprayed onto beds; The gas phase blast main general import that exposes oneself enters into the one-level gas distributor and is distributed in the tower.Liquid forms liquid layer at the oxidation zone catalyst surface; Form turbulent flow along with gas distributor produces gas phase, bump with the liquid layer of oxidation zone catalyst surface; Gas-liquid two-phase is realized fully contact at this, carries out mass transfer and oxidizing reaction.So far accomplish the contact-mass transfer reaction process of a bed.Liquid leans on flow by gravity to liquid re-distributor, after redistribution, gets into the gas formation counter current contact from bottom to top that next stage bed and secondary gas sparger come out, and realizes another mass transfer and reaction.Above-mentioned mass transfer structure is processed the vertical multi-stage cascaded structure, and gas-liquid two-phase is realized contact-mass transfer-reaction process repeatedly, and realization liquid phase and gas phase are accomplished top-down counter current contact reaction.
Embodiment 1
The laboratory small test.
Adopt oxidizing tower to comprise a beds oxidation zone, oxidation zone catalyst bed floor height is 200mm, and the spray section height is 100mm, service temperature normal temperature.Oxide catalyst is the commercially available carbonate type manganese ore of diameter a 2～3mm powder, and the Mn mass content is 28%.
With compressed air oxidation S-WAT (mass concentration 10%) aqueous solution simulation desulfurization waste liquor, carry out the doctor solution oxidation test, the gas phase inlet pressure is 0.1MPa (gauge pressure), the oxidizing tower outlet is normal pressure, the reaction result tabulation 1 under the different condition.
Table 1 liquid-gas ratio is to the influence (residence time 20min) of COD clearance
| Liquid-gas ratio, L/m 3 | Tower import COD, mg/L | Tower outlet COD, mg/L | COD place to go rate, % |
| 20 | ?976 | 42 | 95.7 |
| 40 | ?1028 | 38 | 96.3 |
| 60 | ?1125 | 37 | 96.7 |
Table 2 liquid residence time is to influence (the liquid-gas ratio 20L/m of COD clearance
3)
| The residence time, min | Tower import COD, mg/L | Tower outlet COD, mg/L | COD place to go rate, % |
| 20 | 976 | 42 | 95.7 |
| 40 | 1028 | 20 | 98.0 |
| 60 | 1125 | 24 | 97.9 |
Embodiment 2
Certain enterprise's flue gas sodium method desulfurization waste liquor, 53 ℃ of fluid temperatures, doctor solution COD content 11083mg/L.Adopt three grades of catalyzed oxidation towers, comprise three catalyzed oxidation districts, a liquid distributor and two liquid re-distributors.Oxidation zone catalyst bed layer height is 350mm, uses oxide type manganese ore (manganese mass content the be 35%) particle of granularity as 1cm,, the spray section height is 250mm.Through atmospheric oxidation, liquid-gas ratio is 20L/m
3, liquid residence time 60min, service temperature is 50～60 ℃, the doctor solution after the oxidation causes the sewage-farm water-in.
After oxide treatment, doctor solution COD content is reduced to 95mg/L, and the COD clearance reaches about 99% (quality), and oxidizing tower is worked off one's feeling vent one's spleen and is normal pressure, the about 50Nm of oxidation air flow
3/ h.Tail gas causes the FGD unit inlet mouth after the oxidation, does not detect SO from venting port
2Doctor solution COD concentration after peroxo-and discharge rate all meet national environmental protection rules GB16297-1996 " integrated wastewater discharge standard ".
Claims (10)
1. the method for oxidation of a flue gas desulphurization waste solution; It is characterized in that comprising following content: with the Mn ore is catalyzer, adopts adverse current catalyzed oxidation tower, and the Mn ore is contained in the catalyzed oxidation tower with the mode of fixed bed; Desulfurization waste liquor gets into from catalyzed oxidation tower top; Desulfurization waste liquor and air be counter current contact on fixed bed Mn ore beds, carries out oxidationization and takes off the COD reaction, and the desulfurization waste liquor after the oxidation is discharged the catalyzed oxidation tower.
2. according to the described method of claim 1, it is characterized in that: the reaction time of desulfurization waste liquor is 10～90 minutes, and the liquid gas volume ratio of desulfurization waste liquor and air is 10～200L/m
3, be preferably 20～100L/m
3
3. according to the described method of claim 1, it is characterized in that: Mn ore beds is provided with 1 layer, perhaps is provided with 2～5 layers.
4. according to the described method of claim 3, it is characterized in that: the height of every layer of Mn ore beds is 500～1000mm.
5. according to claim 1 or 3 described methods; It is characterized in that: desulfurization waste liquor disperses the back contact with Mn ore catalyzer from top layer Mn ore beds through liquid distributor, and adverse current went out desulfurization waste liquor and contacts after oxidation air disperseed through gas distributor from lowest layer Mn ore beds bottom.
6. according to the described method of claim 3, it is characterized in that: every layer of Mn ore beds top all is provided with liquid distributor.
7. according to the described method of claim 1, it is characterized in that: the granularity of Mn ore is 0.2～5cm, is preferably 1～2cm.
8. according to claim 1 or 7 described methods, it is characterized in that: the Mn ore is carbonate type manganese ore or oxide type manganese ore.
9. according to the described method of claim 1, it is characterized in that: the structure of catalyzed oxidation tower comprises inlet pipe, liquid distributor, beds, gas distributor and liquid discharge pipe.
10. according to the described method of claim 9, it is characterized in that: the inlet pipe of oxidizing tower and discharge opeing tube side inverted U structure, inlet pipe import vertex are higher than liquid discharge pipe outlet vertex 300～500mm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030207A (en) * | 2012-12-28 | 2013-04-10 | 安徽工业大学 | Method for treating ammonia desulfurization waste liquid by oxidation method |
| CN104944556A (en) * | 2015-05-28 | 2015-09-30 | 中冶焦耐工程技术有限公司 | Hydrolysis reactor |
| WO2019196247A1 (en) * | 2018-04-13 | 2019-10-17 | Jiangnan Environmental Protection Group Inc. | A method and a device for oxidizing a solution for ammonia desulfurization |
| CN112010471A (en) * | 2019-05-30 | 2020-12-01 | 中国石油化工股份有限公司 | Sewage treatment device and method |
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| CN101116793A (en) * | 2007-09-13 | 2008-02-06 | 大连理工大学 | Method for expelling sulphur dioxide in flue gas and by-producing Fe composite flocculating agent |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101116793A (en) * | 2007-09-13 | 2008-02-06 | 大连理工大学 | Method for expelling sulphur dioxide in flue gas and by-producing Fe composite flocculating agent |
Non-Patent Citations (1)
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| 李英等: "软锰矿液相催化氧化烟气中的SO2副产稀硫酸的工艺", 《矿产综合利用》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030207A (en) * | 2012-12-28 | 2013-04-10 | 安徽工业大学 | Method for treating ammonia desulfurization waste liquid by oxidation method |
| CN103030207B (en) * | 2012-12-28 | 2014-04-09 | 安徽工业大学 | Method for treating ammonia desulfurization waste liquid by oxidation method |
| CN104944556A (en) * | 2015-05-28 | 2015-09-30 | 中冶焦耐工程技术有限公司 | Hydrolysis reactor |
| WO2019196247A1 (en) * | 2018-04-13 | 2019-10-17 | Jiangnan Environmental Protection Group Inc. | A method and a device for oxidizing a solution for ammonia desulfurization |
| CN112010471A (en) * | 2019-05-30 | 2020-12-01 | 中国石油化工股份有限公司 | Sewage treatment device and method |
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Application publication date: 20120516 |