CN1102357A - Flue gas desulfurization method and system - Google Patents
Flue gas desulfurization method and system Download PDFInfo
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- CN1102357A CN1102357A CN94108254A CN94108254A CN1102357A CN 1102357 A CN1102357 A CN 1102357A CN 94108254 A CN94108254 A CN 94108254A CN 94108254 A CN94108254 A CN 94108254A CN 1102357 A CN1102357 A CN 1102357A
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- magnesia
- gas
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- light burned
- mgo
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003546 flue gas Substances 0.000 title claims description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 24
- 238000006477 desulfuration reaction Methods 0.000 title claims description 24
- 230000023556 desulfurization Effects 0.000 title claims description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 302
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 153
- 230000002745 absorbent Effects 0.000 claims abstract description 38
- 239000002250 absorbent Substances 0.000 claims abstract description 38
- 238000010521 absorption reaction Methods 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 230000036571 hydration Effects 0.000 claims abstract description 16
- 238000006703 hydration reaction Methods 0.000 claims abstract description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000003009 desulfurizing effect Effects 0.000 claims description 40
- 239000012530 fluid Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000007921 spray Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 230000000452 restraining effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 31
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 24
- 229910052749 magnesium Inorganic materials 0.000 description 24
- 239000013535 sea water Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 12
- 239000000347 magnesium hydroxide Substances 0.000 description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 9
- 229910019440 Mg(OH) Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 235000014380 magnesium carbonate Nutrition 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
- B01D47/02—Separating dispersed particles from gases, air or vapours by liquid as separating agent by passing the gas or air or vapour over or through a liquid bath
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/346—Controlling the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention has one implementation proposal that light burned magnesia is utilized as a desulfurizer, the method for processing by using MgO directly without any hydration is adopted, the desulfurizer is supplied to an absorbent groove arranged at the bottom of a thionizer. The invention has another implementation proposal that: magnesia powder is used for spraying waste gas containing SOx in a flue, the magnesia absorbs the SO3 in stack gas and enters into an absorption tower at the same time, the magnesia is collected by cycle liquid, the cycle liquid is recycled from the bottom of the absorption tower and is tested, and then the cycle liquid passes through a retarded oxidation device to keep the consistency of sulfite ion in the cycle liquid, thereby enhancing the activity of the magnesia, and controlling the feeding rate of the magnesia automatically.
Description
The present invention relates to wet flue-gas sulfur method and system, in order to remove the SO in flue gas and the similar waste gas
x
As the example of this class desulfurization process for flue gases, a kind of method of utilizing magnesium desulfurization from flue gas of normal traditionally employing.
This desulfurization process for flue gases of magnesium that utilizes will be narrated hereinafter.At first, with clear being described as follows of technical terms more used herein.
Magnesite: mainly by MgCO
3A kind of ore of forming.
Light burned magnesia: by at about 800-1, calcined magnesite (MgCO under 100 ℃ of lower temperatures
3→ MgO+CO
2) and the MgO that makes.
Sea water magnesia: by the synthetic Mg(OH of the bittern composition in the seawater)
2
Hydrous magnesium (hydromagnesium): the Mg(OH that makes by the hydration light burned magnesia)
2
Now absorb SO by traditional desulfurization process for flue gases that utilizes magnesium
2Process be discussed below.Traditional desulfurization process for flue gases that utilizes magnesium is to utilize Mg(OH)
2Make the wet type desulfurizing method of absorbent, SO
2The fundamental reaction that absorbs is as follows:
The desulfurization waste liquor that is generated discharges with the abundant oxidation of air, filtration then by formula (4).
The desulfurization process for flue gases that utilizes magnesium is without any need for additional equipment for after-treatment, because desulfurization waste liquor can be discharged into river or in the sea through air oxidation with after filtering.Like this, compare with the desulfurization process for flue gases that utilizes calcium, this method has the few advantage of required capital cost.In addition, owing in system or pipe-line system, there is not CaCO basically
3, Ca-SO
4Or the similar substance deposition, upkeep operation is easy to carry out, and can reach high desulfuration efficiency.Therefore, this desulphurization system is widely used in independently medium-sized and flue gas treatment small power station's boiler.Yet utilizing sea water magnesia is expensive as the desulfurization profit.Therefore, present situation is, makes hydrous magnesium after light burned magnesia grinding, classification and the hydration that calcined magnesite is obtained, in order to the expense (thereby reducing running cost) that reduces desulfurizing agent.
Referring now to schematic flow sheet Fig. 3 and Fig. 4, some examples of the concrete flue gas desulfurization method of implementing of utilizing magnesium traditionally are described as follows.Fig. 3 is the system that waste gas and liquid-absorbant is carried out counter current contacting, and Fig. 4 carries out waste gas and flows the system that contacts with liquid-absorbant.The basic structure of these systems is as follows:
(1) cooling of waste gas
(2) supply of liquid-absorbant
The mixture 26 of desulfurizing agent and water infeeds in the absorbent groove 23 that is installed in the desulfurizing tower bottom under control PH.
(3) SO
2The absorption of gas
Liquid-absorbant in the absorbent groove 23 24 sprays are entered the boiler waste gas 25 of desulfurizing tower.This spray liquid-absorbant absorbs the SO in the waste gas
2After, drop in the absorbent groove 23.
(4) discharging of desulfurize discharge gas
When boiler waste gas 25 flows through desulfurizing tower 21, contact with liquid-absorbant.So, be cooled, desulfurization, then by outlet 27 dischargings.Numbering 28 expression packed beds.
(5) air blasts the bottom of desulfurizing tower
For preventing smokeshade sedimentation and the alluvial in the boiler waste gas, and be arranged in the sulfite ion (SO of the liquid-absorbant 24 of desulfurizing tower bottom for control
2-
3) concentration, blast air with air blast 29.
(6) discharging of desulfurization waste liquor
Before the liquid-absorbant of new preparation infeeds the absorbent groove 23 that is installed in the desulfurizing tower bottom, earlier the waste liq absorbent in the absorbent groove 23 is discharged.The liquid-absorbant of discharging carries out air oxidation in oxidizing tower 30, with its COD of abundant reduction (COD), after filtering, as waste liquid 31 dischargings.
Below, with reference to the traditional system of schematic flow sheet 2 explanations to desulfurizing tower feed fluid absorbent.
(1) dispersion of light burned magnesia in water
The water of light burned magnesia in the MgO storage tank 1 and water supply line 2 supplies is introduced MgO dissolving tanks 3 by pipeline 10 and 11 respectively, and stir with agitator 4.
(2) the light burned magnesia particle is levigate
Light burned magnesia dispersion in the MgO dissolving tank 3 is transported to subsider 6 by pipeline 14.In subsider 6, the light burned magnesia of coarsegrain separates through sedimentation, is transported to wet lapping machine 7 by pipeline 15, and it is levigate.
(3) generate hydrous magnesium by hydration
Contain the particulate light burned magnesia and in subsider unsegregated liquid with contain the liquid of levigate light burned magnesia in wet lapping machine 7, send into MgO hydration groove 8 by pipeline 16 and 17 respectively.To send into MgO hydration groove 8, contain the liquid heating of thin light burned magnesia, and with agitator 9 stirrings several hours, to obtain hydrous magnesium.
(4) liquid that contains hydrous magnesium infeeds desulfurizing tower
Desulfurizing agent is dehydration fully in MgO hydration groove 8, and the hydrous magnesium of Sheng Chenging is sent in the absorbent groove 23 that is installed in the desulfurizing tower bottom by pipeline 12 like this.
As mentioned above, transferring to use inexpensive light burned magnesia from the sea water magnesia of tradition use is in order to reduce the expense of the desulfurizing agent that constitutes most of running cost.Yet, when using light burned magnesia, infeed before the absorbent groove that is installed in the desulfurizing tower bottom at this desulfurizing agent as desulfurizing agent, must satisfy following two prerequisites.
(ⅰ) granularity of light burned magnesia must reduce.
(ⅱ) light burned magnesia must be converted into hydrous magnesium [Mg(OH)
2].
With adopt sea water magnesia as desulfurizing agent different be, in order to satisfy above-mentioned prerequisite, subsider 6, wet lapping machine 7, MgO hydration groove 8(comprise big capacity storage tank, heating and heat accumulation equipment and agitator) and the pipeline and the pump that are installed between these equipment all be needs.This just causes capital cost and floor space to increase unfriendly.For the purpose of reference, incite somebody to action) mainly by Mg(OH
2The particle size distribution of the sea water magnesia of forming the results are shown in Figure 10, and the particle size distribution of the commodity light burned magnesia of will be mainly being made up of MgO the results are shown in Figure 11.
In traditional FGD system that utilizes magnesium, utilizing magnesium hydroxide is well-known as the system of absorbent.The structure of this system is shown in Figure 13.In this system, flue gas till the dew point that reaches water nearly, then, is sent it into absorption tower 49 by cooling pipe 40 damping and cooling, sprays by pipeloop 47 and packed bed 48 feed fluid absorbents in this tower, thereby makes SO
xBe absorbed effectively by gas-liquid reaction.
Contain SO at waste gas
3Situation under, traditional wet type desulfurizing system in cooling procedure with SO
3Be converted into mist.Therefore, contact unless make between liquid and the mist, otherwise SO
3Can not be removed, the result causes SO
3Removal efficient low.For these reasons, the SO that in FGD system, produces
3Mist can discharge and not remove.Therefore, in some cases, wet type electric precipitator 43 has been installed in order to remove SO in the exit of FGD system
3
Numbering 41 expression magnesium hydroxide supply grooves among Figure 13.By magnesium hydroxide replenishment pump 42 magnesium hydroxide is infeeded absorption tower 49 from groove 41.The pump of circulating fluid spray piping 47 and cooling pipe 40 is supplied with circulating fluid in numbering 50 expressions.Numbering 51,44 and 53 is represented wastewater treatment equipment, chimney and oxidation air blast respectively.
Some are arranged with the example of magnesia, in this case, still magnesia will be converted into magnesium hydroxide, utilize the latter to make absorbent as absorbent.
Therefore, doing with magnesia under the situation of absorbent, traditional system need become the magnesia hydration device of hydrous magnesium.Like this, make absorbent relatively with utilizing magnesium hydroxide, though can reduce running cost,, the hydrating apparatus expense is absolutely necessary.
The present invention is intended to solve the problem of above-mentioned existence, and one of its purpose provides a kind of method of utilizing light burned magnesia (MgO) as the flue gas desulfurization of desulfurizing agent more easily, wherein, for example subsider, wet lapping machine and MgO hydration groove all can save some equipment.
To achieve these goals, the invention provides a kind of method of flue gas desulfurization, this method comprises utilizes light burned magnesia as desulfurizing agent, and take the direct mode of introducing desulfurizing agent with MgO without any hydration-treated, supply with desulfurizing agent to the absorbent groove that is installed in the desulfurizing tower bottom.
As mentioned above, in traditional method, use light burned magnesia must satisfy following two prerequisites:
(ⅰ) granularity of light burned magnesia must reduce.
(ⅱ) light burned magnesia must be converted into hydrous magnesium [Mg(OH)
2].
Intention from the condition identical with sea water magnesia (extensively adopting so far) to the absorbent groove that is installed in the desulfurizing tower bottom that supply with desulfurizing agent under is depended on the basis of above-mentioned prerequisite.
As shown in figure 11, the particle mean size that the commodity light burned magnesia has is about 20 μ m, and it is much larger than the granularity (being several microns) of sea water magnesia.In addition, its particle size distribution broad.(have less and be expensive, and do not have advantage as the substitute of sea water magnesia than the commodity light burned magnesia of uniform particle size.) therefore, the high equipment of price for example wet lapping machine is still and needs.
Use so that the granularity of light burned magnesia reduces in order to seek method a kind of chemistry rather than machinery, and confirm that transforming light burned magnesia is that hydrous magnesium is not absolutely necessary, the present invention has carried out various tests.
(1) sulfite ion (SO
2-
3) be effective for the granularity that reduces light burned magnesia.
(ⅰ) test 1: confirmed the granularity of light burned magnesia and the relation between its rate of dissolution.
The method of the rate of dissolution of mensuration light burned magnesia is as follows: it is 50 ℃ that 200 ml pure waters remain on temperature, with agitator continuous stirring under the rotating speed of 180rpm.Then, take by weighing 18 mMs (in Mg) and have the known granularity and the light burned magnesia of principal component, it is added in the entry.Then, add 2N H
2SO
4With the PH that keeps this liquid is 6.0.(can produce alkaline solution because light burned magnesia dissolves in water, its required sour consumption that neutralizes is the indication of light burned magnesia meltage).From adding the start time of light burned magnesia, record dissolving 80% constitutes the required time of MgO of light burned magnesia main component (〉=90%).As a result, obtain the granularity of light burned magnesia and the relation between its rate of dissolution, as shown in Figure 5.As can be seen from Figure 5, along with the granularity of light burned magnesia reduces, its rate of dissolution increases.
(ⅱ) test 2: confirmed interpolation sulfite ion (SO
2-
3) can promote the light burned magnesia dissolving.
Except before adding light burned magnesia, with the Ma of known quantity
2SO
3(that is SO,
2-
3) add in the pure water outside, adopt the same quadrat method of narration in the test 1 to measure the rate of dissolution of light burned magnesia.Then, add the light burned magnesia that particle mean size is 17 μ m and known composition that has of scheduled volume, the time that the record dissolving is required.As a result, obtain SO in the liquid
2-
3The relation of concentration and light burned magnesia rate of dissolution, as shown in Figure 6.As can be seen from Figure 6, along with SO in the liquid
2-
3Concentration raises, and the rate of dissolution of light burned magnesia increases.There is not SO
2-
3Situation under, dissolving the required time is 34 minutes.
The condition of the dissolving MgO that adopts among Fig. 6 is as follows:
1) temperature of liquid: 50 ℃.
2) PH:6.0 of liquid.
3) MgO of dissolving amount: 90mmol/L.
4) mixing speed: 180rpm.
(MgO) is as follows for used light burned magnesia:
1) trade mark: Sobuekure KDB.
2) particle mean size: 17 μ m.
Sum up The above results, confirm that by testing 1 the rate of dissolution of light burned magnesia in water depends on its granularity, along with reducing of granularity, its rate of dissolution increases.In addition, confirm in the liquid sulfite ion (SO is arranged by testing 2
2-
3) exist, can promote the light burned magnesia dissolving effectively.When the result with test 1 considered, this effect can be thought the promotion to the reduction of light burned magnesia granularity.Thus, be the sea water magnesia of 3.5 μ m when being undertaken when having particle mean size by test 1 condition, dissolving constitutes the Mg(OH of its main component (〉=90%))
2The required time is 1.5-2.0 minute.For the dissolving that obtains equating has the time that particle mean size is the light burned magnesia of 17 μ m, as can be seen from Figure 6, SO in the liquid
2-
3Concentration must be not less than 10mmol/L.
Usually, can think that light burned magnesia has the crystal structure of rhombus, the reduction of its granularity is by the method and hydration (needing a large amount of heat energy and the long reaction time) combination of machinery are carried out traditionally.Yet, confirm by testing 1 and 2, if in liquid, sulfite ion (SO is arranged in order to the dissolving light burned magnesia
2-
3) exist, the granularity of light burned magnesia can reduce in the short time effectively.
As above relevant SO
2Absorption process described in, in utilizing the true FGD system of magnesium, generate the MgSO of q.s
3(that is SO,
2-
3), and be present in the absorbent groove that is installed in the desulfurizing tower bottom, in order to reduce the light burned magnesia granularity.In order to reach high desulfuration efficiency (referring to Fig. 7), MgSO
3It also is requisite material in a kind of liquid-absorbant.In real system, the MgSO in the control liquid-absorbant
3Concentration makes it be not less than 10mmol/L.In addition, the control of the temperature of the liquid-absorbant bottom desulfurizing tower is about 60 ℃, to be suitable for dissolving, because its can contact with the hot waste gas that comes from boiler.
Operating condition (and analog computation) used among Fig. 7 is as follows:
1) SO in the waste gas
2Concentration: 1,200ppm.
2) flow velocity of waste gas: 2 * 10
5Nm
3/ h.
3) flow velocity of circulating fluid absorbent: 2,000m
3/ h.
4) PH:6.5 of liquid-absorbant.
5) internal temperature on absorption tower: 60 ℃.
6) filler: HEILEX-500.
7) diameter of packed bed: 7.4mu.
8) height of packed bed: 2.4mH.
(2) absorb SO
2, not necessarily need light burned magnesia is converted into hydrous magnesium
Test 3: compared light burned magnesia and sea water magnesia to SO
2The absorbability of gas.
Test method is as follows: prepared to be equipped with the glass absorption bottle of 100 ml pure waters (at room temperature), and with agitator continuous stirring water under the rotating speed of 180rpm.Take by weighing 41.15 mMs (in Mg) sea water magnesia or light burned magnesia, add wherein.The 1.48N liter/minute speed under in absorption bottle with standard contain 4,800ppm is at N
2In SO
2Gas blasts and by liquid, and behind the bubbling, record is along with the time changes SO in the PH of liquid and the liquid
2Concentration.
The result of the test of light burned magnesia is shown in Fig. 8, and the result of the test of sea water magnesia is shown in Fig. 9.By relatively finding out, the both shows substantially the same absorption SO
2The ability of gas.That is, 1 mole of Mg absorbs about 2 moles SO in every kind of absorbent
2Find thus, absorb SO
2, not necessarily need light burned magnesia is converted into hydrous magnesium.
Another object of the present invention provides a kind of wet FGD system, and this system utilizes magnesia as absorbent, can remove the SO in the waste gas effectively
3, and without any need for the equipment of hydrated magnesium.
A further object of the present invention provides a kind of wet FGD system, and this system has the absorption tower, can improve magnesian activity.
The present invention also has another purpose, and the method for the wet flue-gas desulfurization of adopting above-mentioned arbitrary system promptly is provided, and wherein, can keep stable SO
xRemoval efficiency, and can not produce fouling or similar problem.
To achieve these goals, the invention provides a kind of wet FGD system, wherein, (contain SO at processing combusting heavy oil boiler or similar waste gas
2And SO
3) time, magnesia (MgO) powder is directly sprayed flue gas, with this as removing SO
3The means of gas thereafter, are collected this powder by the circulating fluid in the wet-type absorption tower, and are used as absorption SO with the slurry form
xThe absorbent of gas.
In addition, in order to effectively utilize wet absorption SO
xThe MgO powder, directly collect MgO by the circulating fluid that contains sulfite ion, with replace with its hydration be magnesium hydroxide [Mg(OH)
2].
As a result, improved the solubility of MgO, and its activity as absorbent strengthens also.
Wet FGD system according to another embodiment of the invention comprises, except that the following formula device, is connected the oxidation restraining device on absorption tower, in order to the sulfite ion in the circulating fluid that guarantees scheduled volume.This oxidation restraining device comprises an equipment: when the ion concentration of inferior sulfate radical in the circulating fluid reduces, infeed the feed rate of the oxidation air of bottom, absorption tower in order to reduction.
In addition, according to above-mentioned wet FGD system of the present invention, adopt a kind of method of wet flue-gas desulfurization, wherein, magnesian injection rate is according to SO in the waste gas
2The flow velocity of concentration, waste gas and the absorption tower in the PH of liquid control.
Can lower price buy on market by the magnesia that calcining magnesium carbonate generates.In addition, can buy on market that to have granularity be ten to tens microns fine-powdered magnesia.By being sprayed at, this powder contains SO
xBoiler waste gas in, magnesia can with the SO in the waste gas
3Reaction.
Be applied under the situation of boiler, the position of spraying powder is the exhaust pass place at air heater.It is 150-200 ℃ that the position that meets the requirements should have temperature, and this temperature is higher than the dew point of acid.In order to guarantee enough solid-solid/liquid/gas reactions time, the position of sprinkling is preferably in the upstream of wet-type absorption tower, and as far as possible a little further.
Usually, the waste gas flow velocity in the flue is not less than 15m/s.Therefore, buy on the market magnesia can introduce the wet-type absorption tower that is arranged in the downstream, and unlikely sedimentation in gas.
On the other hand, magnesian addition can be selected, so that it is almost equal in SO
2Amount, like this, can guarantee itself and SO
3Sufficiently high equivalent proportion.If (MgO and SO
2Mol ratio be adjusted to 1, MgO and SO
3Mol ratio will be near 50, because SO
3Amount equal the SO of about 1-2%
2Amount).
Therefore, though MgO and SO
2Reaction be solid-solid/liquid/gas reactions, still, by increasing MgO and SO
2Ratio can obtain quite high SO
xRemoval efficiency.
SO
3Generate magnesium sulfate (MgSO with the MgO reaction
4).
After this, the powder that unreacted MgO powder and part is converted into magnesium sulfate is introduced in the wet-type absorption tower, contact with wherein circulating fluid, with its merging formation thin pulp body.Be appreciated that because MgSO
4Have high solubility, it can dissolve in circulating fluid, and can not produce the problem of fouling.
After wet-type absorption tower, this system is substantially the same with traditional system that utilizes magnesium hydroxide.Yet, stop up in order to prevent magnesium hydroxide powder, preferably use the absorption tower of downflow system, and make vapor/liquid ratio sufficiently high.
Yet, in absorption cell, being provided with the occasion that suppresses oxidation unit according to the present invention, system can operate in such a way, promptly guarantees to have in circulating fluid the sulfite ion of scheduled volume, to increase magnesian activity.As a result, promote magnesian dissolving, thereby can stably absorb SO
2
In addition, when adopting the sulfur method of system of the present invention, wherein, magnesian addition is equivalent to SO in the gas
xConcentration, and, make it to be controlled within the preset range along with the flow velocity of the PH of liquid in absorption tower control gas, like this, although SO
2And SO
3Change in concentration, still can keep stable removal efficiency, and unlikely generation fouling or similar problem.
Fig. 1 is the schematic flow sheet of explanation method of first kind of embodiment supply absorbent according to the present invention;
Fig. 2 is an embodiment of explanation conventional method is supplied with a schematic flow sheet from absorbent to desulfurizing tower;
Fig. 3 is the schematic flow sheet of an embodiment in the traditional FGD system that utilizes magnesium of explanation;
Fig. 4 is the schematic flow sheet of another embodiment in the traditional FGD system that utilizes magnesium of explanation;
Fig. 5 is the particle mean size of explanation MgO and the graph of a relation between the dissolving required time;
Fig. 6 is explanation SO
2-
3Amount and the graph of a relation between the MgO reaction required time;
Fig. 7 is SO in the explanation liquid-absorbant
2-
3Graph of a relation between concentration and the desulfuration efficiency;
Fig. 8 is that explanation contains the liquid of MgO to SO
2The absorption characteristic figure of gas;
Fig. 9 is that explanation contains Mg(OH)
2Liquid to SO
2The absorption characteristic figure of gas;
Figure 10 is particle size distribution figure as a result in the example of explanation sea water magnesia;
Figure 11 is particle size distribution figure as a result in the example of explanation light burned magnesia;
Figure 12 is the structural representation that the wet FGD system of explanation second embodiment according to the present invention partly cuts; With
Figure 13 is the structural representation that explanation utilizes traditional flue gas desulfurization components of system as directed of magnesium hydroxide to cut.
First embodiment of the present invention describes with reference to Fig. 1.
(1) dispersion of light burned magnesia in water
The water of light burned magnesia in the MgO storage tank 1 and water supply line 2 supplies is introduced MgO dissolving tanks 3 by pipeline 10 and 11 respectively, and stir with agitator 4.
(2) supply with the dispersion of light burned magnesia to desulfurizing tower
By pipeline 12 liquid in the MgO dissolving tank 3 is introduced in the absorbent groove 5 that is installed in the desulfurizing tower bottom.Sulfite ion (the SO that every liter tens mM is arranged in absorbent groove 5 usually,
2-
3) exist, because granularity is reduced to the granularity that is used as the sea water magnesia of desulfurizing agent no better than traditionally, make the light burned magnesia dissolving.Like this Rong Xie light burned magnesia show to SO
2The absorbability of gas can match in excellence or beauty with the absorbability of sea water magnesia.
(3) SO in absorbent groove 5
2-
3When concentration was hanged down, it is also low that the granularity of introducing the light burned magnesia particle of absorbent groove 5 from MgO dissolving tank 3 by pipeline 12 reduces (or dissolving) rate, so that the time of staying in absorbent groove 5 must prolong.In this case, must the liquid in the absorbent groove 5 be recycled to MgO dissolving tank 3 by pipeline 13.
When light burned magnesia used according to the invention during,, just can save some equipment for example subsider, wet lapping machine and MgO hydration groove by light burned magnesia being supplied to the absorbent groove that is installed in the desulfurizing tower bottom as desulfurizing agent.Like this, this system just is simplified to and uses the same degree of sea water magnesia as desulfurizing agent greatly.This just can realize reducing the floor space of desulphurization plant and capital cost and owing to having cancelled heater and pump has been saved electric power.The maintenance of operation in addition,, maintenance and system is all very convenient.
Be that another kind that second embodiment according to the present invention constitutes utilizes magnesian FGD system below, specify as follows with reference to Figure 12.
Among Figure 12, similarly partly be marked with identical numbering, no longer repeat specification with Figure 13.
Among Figure 12, contain SO
x(be SO
2And SO
3) the gas flue 65 of flowing through, wherein infeeding granularity by nozzle 66 is ten to tens microns magnesium oxide powder.More specifically, the magnesium oxide powder in the bunker bucket 61 is sent a part by batcher 62, adopts proper device for example to spray conveyer 63 superchargings, infeeds the flue gas in the flue 65 then.Numbering 64 is represented air blast.
What meet the requirements is that magnesia is sprayed flue gas equably.The magnesia that sprays directly can be sent in the wet-type absorption tower 49, when it floats, absorbed SO in flue gas
3The magnesia of introducing in the absorption tower 49 contacts and is collected with a large amount of circulating fluid that spray through injection pipe 47.Because magnesia has 10 μ m or bigger granularity, collects by Wet-type spray easily.
Circulating fluid falls by absorption tower 49, while and SO
2The contact of generation solution-air.In order to improve the efficient of solution-air contact, it is effective equipping a packed bed 48.The structure of this packed bed 48 must unlikelyly cause the precipitation accumulation, for example can take the form of grid.Circulating fluid adopts circulating pump 50 to circulate repeatedly from the bottom on absorption tower.Similar with traditional FGD system that utilizes magnesium hydroxide, water is supplied with from the outside, simultaneously, a part of liquid is effluxed, and is transported to wastewater treatment equipment 51, and like this, the salinity in the liquid can excessively not increase.
In order to guarantee that sulfite ion can adopt the ion concentration of inferior sulfate radical in the ion concentration of inferior sulfate radical detector 78 detection circulating fluids more than scheduled volume in the circulating fluid.If the ion concentration of inferior sulfate radical step-down adopts control valve 79, control the feed rate that infeeds the oxidation air of bottom, absorption tower by oxidation nozzle 72, so that the oxidation that inhibition is produced by oxidation air blast 73.The existence of sulfite ion in liquid, can make the activity of MgO bring up to traditional magnesium hydroxide [Mg(OH)
2] level that slurry is identical.
In Figure 12, though the delivery rate of oxidation air can control automatically,, under the situation of system, also can use manual adjustment by the operation of the feed conditions of previously-known.
The delivery rate of MgO powder is measured SO in the gas by control device 74 according to detector 76
xConcentration and detector 77 signal that flow velocity transmitted of measuring gases control, in such a manner, the MgO powder can with SO
xFeed under the corresponding speed of load.In addition, in order to prevent to produce fouling or similar problem in the absorption tower 49, transmit signal from PH meter 75 and give control device 74, and be used for controlling the feed rate of MgO powder, so that it is controlled in the predetermined scope.
Utilizing in the magnesian wet FGD system (specifically narration hereinbefore) of building up according to the present invention, can be according to SO in the waste gas
xConcentration directly magnesium oxide powder is blasted flue, remove SO
xGas.In addition, can take with the traditional wet absorption tower in identical mode, the spray circulating fluid is collected the magnesium oxide powder that is dispersed in the flue, thereby realizes the recovery with powder of resupplying of absorbent.
Particularly taked a kind of configuration, wherein, the device that suppresses oxidation has been installed, guaranteed the scheduled volume of sulfite ion, this does not just need special hydration MgO is Mg(OH)
2Equipment is because improved the activity of MgO.This configuration and above-mentioned SO
3Under the removal effect acting in conjunction, make the FGD system that utilizes magnesium produce functional improvement and the obvious effect that reduces construction cost.In addition, use inexpensive magnesia absorbent also to make the reduction running cost become possibility.
In addition, by adopting the method for operating that the present invention told about, FGD system of the present invention can be at corresponding SO
xOperation stably under the load, and can not produce fouling or similar problem.
Claims (4)
1, a kind of method of flue gas desulfurization, this method comprise utilizes light burned magnesia as desulfurizing agent, directly introduces the mode of desulfurizing agent without any hydration-treated with MgO, supplies with desulfurizing agent to the absorbent groove that is installed in the desulfurizing tower bottom.
2, a kind of wet FGD system that utilizes magnesia as absorbent, this system comprises the magnesia spray equipment, in order to magnesium oxide powder is directly sprayed flue gas, thus the SO in a part of magnesia and flue gas
3Produce solid-solid/liquid/gas reactions and wet-type absorption tower that is installed in magnesia spray equipment downstream between the gas, in order to collect magnesium oxide powder and magnesia and SO by circulating fluid
3Product, simultaneously, by gas-liquid reaction with SO
2GAS ABSORPTION is in circulating fluid.
3,, thereby comprise in addition that also the oxidation restraining device guarantees that in order to the oxidation that suppresses in the absorption tower sulfite ion is more than scheduled volume in the circulating fluid according to the wet FGD system of claim 2.
4, the wet flue-gas sulfur method that uses in claim 2 or 3 systems, wherein magnesian injection rate is according to SO in the flue gas
2The flow velocity of concentration, flue gas and the absorption tower in the PH of liquid control.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5171457A JP2994913B2 (en) | 1993-07-12 | 1993-07-12 | Wet flue gas desulfurization apparatus using magnesium oxide and desulfurization method thereof |
| JP171457/93 | 1993-07-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1102357A true CN1102357A (en) | 1995-05-10 |
| CN1048188C CN1048188C (en) | 2000-01-12 |
Family
ID=15923465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94108254A Expired - Fee Related CN1048188C (en) | 1993-07-12 | 1994-07-12 | Flue gas desulfurization method and system |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2994913B2 (en) |
| KR (1) | KR0125122B1 (en) |
| CN (1) | CN1048188C (en) |
| IT (1) | IT1272321B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446871A (en) * | 2013-09-09 | 2013-12-18 | 新疆蓝天镁业股份有限公司 | Light-calcined magnesia calcining furnace desulfurization technique and system |
| CN103698466A (en) * | 2013-12-20 | 2014-04-02 | 广东韶钢松山股份有限公司 | Rapid test method for activity of magnesium oxide |
| CN109069982A (en) * | 2016-05-11 | 2018-12-21 | 雅苒海洋技术有限公司 | The desulfurization of ship stack gases |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100336938B1 (en) * | 1999-09-16 | 2002-05-16 | 손재익 | Control method for SO3 ion concentrations in wet flue-gas desufurization systems using Mg(OH)2 as reagent |
| KR100905746B1 (en) * | 2007-07-10 | 2009-07-01 | 에이취아이엠테크(주) | Composition comprising micro particle of magnesium oxide for desulfurizating flue gas |
| KR102059188B1 (en) * | 2018-02-27 | 2019-12-24 | 두산중공업 주식회사 | Wet flue gas desulfurization apparatus and wet flue gas desulfurization method |
| CN110508101A (en) * | 2019-09-02 | 2019-11-29 | 南京圣创科技有限公司 | A kind of high-efficiency flue gas desulfurization method and device that multi-region alternating temperature absorbs |
| CN117180967A (en) * | 2023-10-23 | 2023-12-08 | 上海市政工程设计研究总院（集团）有限公司 | Exhaust gas treatment system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636415A (en) * | 1985-02-08 | 1987-01-13 | General Electric Company | Precipitated silica insulation |
| JPH03143527A (en) * | 1989-01-10 | 1991-06-19 | Kenichi Nakagawa | Method for desulfurizing waste gas |
-
1993
- 1993-07-12 JP JP5171457A patent/JP2994913B2/en not_active Expired - Fee Related
-
1994
- 1994-07-08 IT ITRM940444A patent/IT1272321B/en active IP Right Grant
- 1994-07-12 CN CN94108254A patent/CN1048188C/en not_active Expired - Fee Related
- 1994-07-12 KR KR1019940016701A patent/KR0125122B1/en not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446871A (en) * | 2013-09-09 | 2013-12-18 | 新疆蓝天镁业股份有限公司 | Light-calcined magnesia calcining furnace desulfurization technique and system |
| CN103698466A (en) * | 2013-12-20 | 2014-04-02 | 广东韶钢松山股份有限公司 | Rapid test method for activity of magnesium oxide |
| CN103698466B (en) * | 2013-12-20 | 2015-07-29 | 广东韶钢松山股份有限公司 | A kind of rapid test method for activity of magnesium oxide |
| CN109069982A (en) * | 2016-05-11 | 2018-12-21 | 雅苒海洋技术有限公司 | The desulfurization of ship stack gases |
| CN109069982B (en) * | 2016-05-11 | 2021-09-17 | 雅苒海洋技术有限公司 | Desulfurization of marine flue gas |
Also Published As
| Publication number | Publication date |
|---|---|
| KR950002840A (en) | 1995-02-16 |
| KR0125122B1 (en) | 1997-11-27 |
| ITRM940444A0 (en) | 1994-07-08 |
| IT1272321B (en) | 1997-06-16 |
| JP2994913B2 (en) | 1999-12-27 |
| CN1048188C (en) | 2000-01-12 |
| JPH0724252A (en) | 1995-01-27 |
| ITRM940444A1 (en) | 1996-01-08 |
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