CN1178733C - Method for eliminating sulphuric acid mist and its device - Google Patents
Method for eliminating sulphuric acid mist and its device Download PDFInfo
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- CN1178733C CN1178733C CNB011242558A CN01124255A CN1178733C CN 1178733 C CN1178733 C CN 1178733C CN B011242558 A CNB011242558 A CN B011242558A CN 01124255 A CN01124255 A CN 01124255A CN 1178733 C CN1178733 C CN 1178733C
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- sulfuric acid
- acid fog
- gas
- absorbent solution
- gaseous diffuser
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Abstract
The present invention provides a method for eliminating sulphuric acid mist. The mist containing sulphuric acid enters to a absorbent solution by passing through a gas diffuser which has pores with average aperture of 1000 micron or less. This method for eliminating sulpheric acid mist is simple and effective.
Description
Technical field
The present invention relates to a kind of sulfuric acid fog cancellation element of eliminating the method for the sulfuric acid fog in the gas and using this method.
Background technology
Sulfuric acid fog is created in the process with the dry wet gas of the concentrated sulfuric acid usually, or is created in water and concentrates SO in the waste gas
3In the desulphurization plant of composition, also may be in other multiple chemical process, to produce.
At known removal sulfur oxide (SO
x) method in, commonly be furnished with washer (scrubber), and use alkaline solution or water cleaning system as absorbent solution.With regard to this system, can remove 90% or more SO
2, but can only remove 50% SO usually
3
When product was polluted by sulfuric acid fog, quality will reduce; And when the employed gas of chemical technology is polluted by sulfuric acid fog, then can suppress its chemical reaction; Simultaneously, sulfuric acid fog also can cause the corrosion of equipment.In addition, the gas discharging that contains sulfuric acid fog also can cause environmental pollution afterwards.Therefore, the sulfuric acid fog in the gas must be removed as much as possible.
In the method for removing sulfuric acid fog, known comprising is the filter (JP-A-6-171907) of sulfuric acid fog by mineral wool (glass wool) and so on; Use and sulfuric acid fog have affinity, as the absorbent of titanium dioxide and so on; And use electrostatic precipitator methods such as (electrostaticprecipitator).
Yet in the method for using filters such as mineral wool, the seizure amount of sulfuric acid fog has its limit.That is when comprising particle diameter 1 μ m or more the sulfuric acid fog of small particle is handled with the method, even if be to use high efficiency filter, the sulfuric acid fog of 1 ~ 2ppm volume of still can having an appointment can not be removed.
Owing to absorb in the method for sulfuric acid fog, must carry out the regeneration of absorbent and refill processing, so comparatively complicated in the process management at above-mentioned use absorbent.On the other hand, use the method for electrostatic precipitator that problem on the high side is then arranged.
Summary of the invention
Purpose of the present invention just be to provide a kind of can be simply and very remove the method and the employed device of sulfuric acid fog effectively.
For addressing the above problem, the inventor finds the method for a kind of not only simple but also highly effective elimination sulfuric acid fog after research, it is that the gas that contains sulfuric acid fog feeds in the absorbent solution through a gaseous diffuser (gas diffuser), and wherein to have average pore size be 1000 microns or following hole to gaseous diffuser.
That is to say, the invention provides a kind of method of eliminating sulfuric acid fog, the gas that contains sulfuric acid fog is fed in the absorbent solution through a gaseous diffuser, wherein to have average pore size be 1000 microns or following hole to gaseous diffuser.
In other words, because the present invention is to be 1000 microns or following gaseous diffuser by average pore size, the gas that will comprise sulfuric acid fog turns small bubble into and feeds in the absorbent solution, so the solution-air contact area is increased, and can remove sulfuric acid fog effectively.
For increasing the removal efficient of sulfuric acid fog, gaseous diffuser material of the present invention is preferably the about 500 μ m or following of average pore size, and porosity (porosity) about 30% or above porous material.In addition, blister-type (bubble-cap type) gaseous diffuser also is to be fit to use, and wherein has about 1000 μ m of average pore size or following hole on the bubble-cap.
The device of removal sulfuric acid fog of the present invention comprises several sinks, wherein has an absorbent solution, and is equipped with about 1000 μ m of average pore size or following gaseous diffuser, and it is that the gas that is used for containing sulfuric acid fog feeds in the absorbent solution.Wherein, each sink all is connected, and makes the gas that contains sulfuric acid fog can pass through each sink in regular turn.
Sulfuric acid fog removal device preferably of the present invention comprises a scrubbing tower, wherein be to be separated out several washing rank with a plurality of tower trays (tray), these tower trays have at least a part to have gaseous diffuser, the cleaning solution cleaning fluid then is to be filled on the tower tray on each washing rank, thereby forms many sinks.One inlet is arranged at the bottom of this scrubbing tower, and a gas vent is arranged at top, for the gas turnover that comprises sulfuric acid fog.
When use had the device of said structure, the gas that contains sulfuric acid fog was to be fed by the inlet of scrubbing tower bottom, and turned micro-bubble into and accept purification in each washing rank, so sulfuric acid fog wherein can removal very effectively.
Description of drawings
Fig. 1 is the generalized section of the sulfuric acid fog removal device of preferred embodiment of the present invention;
Fig. 2 is in the preferred embodiment of the present invention, a kind of generalized section of sulfuric acid fog removal device of bubble-cap tower;
Fig. 3 is the generalized section of comparative example 1 employed packed column (packed column).
The specific embodiment
The porous mass that continuous hole is arranged in gaseous diffuser used in the present invention for example comprises is so that gas passes through.The example of this porous mass comprises that the sintering be made up of synthetic resin presses polymers (sintered compacts), is that the sintering of principal component is pressed polymers (pottery) with aluminium oxide or similar material, and materials similar, wherein synthetic resin for example is polypropylene, polyvinyl chloride, polystyrene, ABS resin or similar material.
Herein, porous material be about 1000 μ m with average pore size or following person preferable, and average pore size is about 500 μ m or following, and porosity be about 30% or above person better.When average pore size surpassed 1000 μ m, the size of bubble was excessive, made solution-air contact area deficiency, and speed is removed in the absorption that can reduce sulfuric acid fog.When porosity approximately less than 30% the time, the bubbles number that unit are produced is very few, can reduce the speed of removal equally.
Except that above-mentioned each example, the used porous material of the present invention also comprises thin-film material, filtering material and similar material, and it has about 1000 μ m of average pore size or following small hole, passes with supplied gas.
In the method for the invention, the gas that contains sulfuric acid fog is through the above-mentioned gas diffuser and feed in the absorbent solution.
Herein, as every square metre of diffusion area with gaseous diffuser, the flow that contains the gas of sulfuric acid fog is about 100 ~ 5000m
3/ hour is preferably 500 ~ 2000m
3/ hour, better then is 1000 ~ 1500m
3/ hour.When the flow of every square metre of diffusion area greater than 5000m
3During/hour, the solution-air contact area will increase, but the pressure fall also will increase.
In addition, the degree of depth of absorbent solution is about 0.1 ~ 2m, is preferably 0.1 ~ 1m, is more preferred from 0.2 ~ 0.5m.If the degree of depth of absorbent solution is greater than 2m, though then can increase removal efficient, the height of sink or scrubbing tower is with excessive.
As shown in Figure 1, be the generalized section of the sulfuric acid fog removal device of preferred embodiment of the present invention.As shown in Figure 1, this device comprises a scrubbing tower 4 that is made of three washing rank cylinders, wherein a tower tray is all arranged at the bottom of each layer, is that the gaseous diffuser 5,6 and 7 by porous material constitutes, and so promptly forms the sink 1,2 and 3 that is used for purifying the gas that contains sulfuric acid fog.In addition, overflow pipe 8 and 9 penetrates the gaseous diffuser 7 that is positioned at the first washing rank by the top respectively, and the gaseous diffuser 6 that is positioned at the second washing rank.In addition, the inlet 10 that contains the gas of sulfuric acid fog is arranged under the undermost gaseous diffuser 5, and gas vent 11 is positioned at the top of scrubbing tower.The tower tray of separating sink 1,2 and 3 only some to be made of gaseous diffuser 5,6 and 7 also be feasible.
In addition, secure bond sink 1,2 and 3 o'clock, be to get up by the support portion double team of its flange part (flange part) separately with gaseous diffuser 5,6 and 7.
In addition, also has a feed nozzle 12 on the sink 3 of the superiors.The absorbent solution 50 (for example being water, alkaline solution or fellow) that enters the superiors' sink 3 by feed nozzle 12 arrives when a certain amount of, can be overflowed in the sink 2 of below by overflow pipe 8, and be flow in the sink 1 by overflow pipe 9 according to same mechanism.Absorbent solution in the sink 1 should use pump 13 to extract out, so that maintain a fixing amount.
For removing the sulfuric acid fog in the gas, the gas 55 that contains sulfuric acid fog in the present embodiment is under certain pressure, is passed gaseous diffuser 5 and is arrived in the undermost sink 1 by inlet 10.This moment, gas promptly entered in the absorbent solution because of the effect of gaseous diffuser 5 is the micro-bubble shape, the promoting the circulation of qi of going forward side by side-liquid contact.The gas that rises in the absorbent solution by sink 1 is begun by the upper space of sink 1, enters in the sink 2 through gaseous diffuser 6, and it is the micro-bubble shape equally and carries out the solution-air contact.Repeat this process, gas is promptly discharged by sink 3 and by gas vent 11.Wherein, behind the pressure of deduction liquid, the pressure drop that each gaseous diffuser caused is about 0 ~ 200mmAq.
Then, please refer to Fig. 2, with the explanation another embodiment of the present invention.As shown in Figure 2, using the device that removes sulfuric acid mist gas in the present embodiment is the bubble column that a branch is done many washings rank, wherein each washs the bubble cap tray that rank all have pattern, and forms sink 25,26 and 27, and wherein bubble cap tray is equipped with bubble-cap 28,29 and 30.Be installed with average pore size 1000 μ m or following hole on the bubble-cap 28,29 and 30, its quantity is according to device size or other factors and decide, so no particular restriction.In this bubble column and dispose overflow pipe 31 and 32, so that absorbent solution 50 is directed at orlop by the superiors, its mechanism is similar to last embodiment, makes that so the solution in each sink 25,26 and 27 can remain on a fixed amount, and can guarantee enough solution-air times of contact.In addition, other member is similar to last embodiment.
For removing sulfuric acid fog, the gas 55 that contains sulfuric acid fog in the present embodiment is the bottom feedings by orlop sink 27, as last embodiment.The inner face that the gas 55 that contains sulfuric acid fog this moment penetrates bubble-cap 30 blows out, and is the micro-bubble shape and enters in the absorbent solution.The gas that rises in the absorbent solution by sink 27, the hole by next bubble-cap 29 of sink 27 tops blows out again, and it is the micro-bubble shape equally and carries out the solution-air contact.Repeat this process, gas is promptly got rid of by sink 25 and by gas vent.Wherein, after the pressure of deduction liquid, the pressure drop that each gaseous diffuser caused is about 0 ~ 200mmAq.
Though all with the example that is designed to of three layers of sink (1,2,3 or 25,26,27), the number on these washing rank can change according to the required removal speed or the concentration of sulfuric acid fog the foregoing description.In addition, when using scrubbing tower or bubble column, also can link to each other between each sink, so that gas can pass through each sink in regular turn with gas piping.Pressure drop or throughput in indivedual sinks can determine that there is no particular restriction according to practical situation.
The method of removal sulfuric acid fog of the present invention and the concrete application of device comprise: (i) remove the sulfuric acid fog that is contained in the waste gas; (ii) remove the sulfuric acid fog that produces in the chemical technology; (iii) remove the sulfuric acid fog that is produced in the step with the dry wet gas of the concentrated sulfuric acid, and other fellow.
With the technology of the dry wet gas of the concentrated sulfuric acid, for example be to be applied in hydrogen chloride oxidation reaction to produce in the processing procedure of chlorine.The method be with hydrogen chloride and oxygen-containing gas as raw material, exist at catalyst and to carry out hydrogen chloride oxidation reaction under the situation.Then remove aqueous vapor in the gas of generation, separate in the mode of compression cooling again and reclaim chlorine with sulfuric acid.
After separating and reclaiming chlorine, the residual gas that with oxygen is main component is again as the part of reaction raw materials.If contain a large amount of sulfuric acid fog in the residual gas this moment, the catalytic poison (catalyst poison) that just has the sulphur compound composition is deposited on the surface of catalyst, makes activity of such catalysts reduce, and is difficult to react long-term and stably.Therefore, when sulfuric acid fog removal device of the present invention and method are applied in the technology of above-mentioned generation chlorine, sulfuric acid fog content in the residual gas after chlorine reclaims must be reduced to 0.01ppm volume or lower, can prevent that so activity of such catalysts from reducing, and can keep long-time stable reaction.
Example one:
Sulfuric acid fog is to remove with device shown in Figure 1 in this example, and each sink 1,2,3 of wherein forming scrubbing tower 4 all is made of the cylinder of a length (L) 0.5m, internal diameter 0.1m.Bottom on each washing rank is connected with gaseous diffuser 5,6,7 respectively, and it is to be made by the polyvinyl chloride porous material of average pore size 100 μ m, porosity 35%.In this example, the diffusion area of each diffuser is 7.5 * 10
-3m
2
, contain the lowest part injection of the gas 55 of sulfuric acid fog by scrubbing tower 4 herein, wherein the content of sulfuric acid fog is with SO
4 2-Equivalent conversion is the 4ppm volume.The production process of this gas is as follows: with 10m
3The air of/hour feeds in the 98% about 15 liters concentrated sulfuric acid, feeds to be filled with in the fog separator of filter (Raschig rings) again.When gas arrived scrubbing tower 4, the gas flow of every square metre gaseous diffuser diffusion area was about 1300m
3/ hour.
The gas that will contain sulfuric acid fog feeds after scrubbing tower 4 processing, and the sulfuric acid fog content in the gas at cat head place is the 0.005ppm volume, and clearance is 99.9%.The pressure drop that the using gases diffuser is caused is about 450mmAq, then is 150mmAq after the deduction fluid pressure.
Example two:
Be to use a bubble column to remove sulfuric acid fog in this example.In brief, please refer to Fig. 2, this bubble column is made up of three washing rank sinks 25,26,27, and its internal diameter separately is 0.1m, and affix has the bubble-cap 28,29,30 of 160 holes respectively, and wherein the diffusion area of each is all 3.7 * 10
-3m
2Degree of depth (t) of absorbent solution all is adjusted to 300mm with overflow pipe 31 and 32 in each washing rank, and the spacing of each layer (L) is 500mm, and is 10kg/hour by the cat head injection with the flow as the water of absorbent solution 50.
The gas that contains sulfuric acid fog that produces when the mode with similar example one is with 10m
3The flow of/hour is fashionable from the tower rising pouring, and the flow of gaseous diffuser (bubble-cap) diffusion area of every side's rice is about 2600m
3/ hour.The sulfuric acid fog concentration at cat head place is the 0.04ppm volume, and clearance is 99%.The pressure drop on each washing rank is about 450mmAq in addition.
Comparative example one:
This example is to use filling column washing tower 20 to remove sulfuric acid fog, and the Raschig ring that wherein is of a size of at 1/2 o'clock is filled in the filling tower of length 1.5m and internal diameter 100mm, and the external form of this filling tower as shown in Figure 3.With the gas that contains sulfuric acid fog 55 that the mode of similar example one produces, be with 10m
3The flow of/hour is gone into from the tower rising pouring.Cat head also disposes a spray nozzle 21 improving the diffusivity of water, and be sprayed in the tower by spray nozzle 21 as the water of absorbent solution, and by discharging at the bottom of the tower, the water yield of input is between 10 to 200kg/hour in addition.As a result, the sulfuric acid fog content in the gas at cat head place is 1.2 to 2.0ppm volumes, and clearance is 50% to 70%.
This shows that the removal method of sulfuric acid fog of the present invention or the advantage of device exactly can be simply and remove sulfuric acid fog expeditiously.
Though the present invention with a preferred embodiment openly as above; but it is not in order to limit the present invention; any personnel that are familiar with this technology; various changes and the retouching done without departing from the spirit and scope of the present invention; all belong to protection scope of the present invention, be as the criterion and protection scope of the present invention claims limit.
Claims (11)
1. method of removing sulfuric acid fog, it is characterized in that: its step comprises a gas that contains sulfuric acid fog fed in the absorbent solution via a gaseous diffuser, and wherein this gaseous diffuser has a plurality of average pore sizes and is about 1000 μ m or following hole.
2. the method for removal sulfuric acid fog according to claim 1 is characterized in that: wherein see it with regard to the diffusion area of this gaseous diffuser of every square metre, this flow that contains the gas of sulfuric acid fog is about 100 to 5000m
3/ hour.
3. the method for removal sulfuric acid fog according to claim 1 is characterized in that: this absorbent solution places a container, and the degree of depth of this absorbent solution in this container is approximately between between the 0.1m to 2m.
4. the method for removal sulfuric acid fog according to claim 1 is characterized in that: this gaseous diffuser is a porous material, and the average pore size of this porous material is about 500 μ m or following, and its porosity be about 30% or more than.
5. the method for removal sulfuric acid fog according to claim 1 is characterized in that: this gaseous diffuser is one to have the blister-type gaseous diffuser of bubble-cap, and this bubble-cap has a plurality of average pore sizes and is about 1000 μ m or following hole.
6. the method for removal sulfuric acid fog according to claim 1 is characterized in that: the process that this gas that contains sulfuric acid fog is fed this absorbent solution repeats plural number in regular turn.
7. device of removing sulfuric acid fog, comprise a plurality of sinks, it is characterized in that: have an absorbent solution in these a plurality of sinks, and be equipped with a gaseous diffuser so that a gas that contains sulfuric acid fog is fed in this absorbent solution, wherein an average pore size of this gaseous diffuser is about 1000 μ m or following, and respectively this sink links together, and makes this gas can pass through those sinks in regular turn.
8. the device of removal sulfuric acid fog according to claim 7, it is characterized in that: comprising a scrubbing tower, the inner space of this scrubbing tower is separated into a plurality of washings rank with a plurality of tower trays, those tower trays have at least a part to have this gaseous diffuser, and this cleaning solution waters on those tower trays that are filled in each washing rank to form a plurality of sinks, an inlet that supplies this gas that contains sulfuric acid fog to enter is arranged at the bottom of this scrubbing tower in addition, and a gas vent is arranged at top.
9. the device of removal sulfuric acid fog according to claim 8, it is characterized in that: this gaseous diffuser is a porous material, the average pore size of this porous material is about 500 μ m or following, and its porosity be about 30% or more than, and all or part of of those tower trays is made up of this porous material.
10. the device of removal sulfuric acid fog according to claim 8 is characterized in that: those tower trays are a plurality of blister-type tower trays with bubble-cap, and this bubble-cap has about 1000 μ m of a plurality of average pore sizes or following hole.
11. the device of removal sulfuric acid fog according to claim 8, it is characterized in that: wherein have an absorbent solution inlet to be disposed at the top of this gaseous diffuser of going up the washing rank most, this absorbent solution is entered by this absorbent solution inlet, and is orderly sent in next washing rank by an overflow mechanism this absorbent solution with overflow.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000025038 | 2000-08-21 | ||
JP200025038 | 2000-08-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1340371A CN1340371A (en) | 2002-03-20 |
CN1178733C true CN1178733C (en) | 2004-12-08 |
Family
ID=18550956
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---|---|---|---|
CNB011242558A Expired - Lifetime CN1178733C (en) | 2000-08-21 | 2001-08-20 | Method for eliminating sulphuric acid mist and its device |
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CN (1) | CN1178733C (en) |
-
2001
- 2001-08-20 CN CNB011242558A patent/CN1178733C/en not_active Expired - Lifetime
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CN1340371A (en) | 2002-03-20 |
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