CN1321721C - Method of dealing with gases containing boric acid - Google Patents
Method of dealing with gases containing boric acid Download PDFInfo
- Publication number
- CN1321721C CN1321721C CNB02142621XA CN02142621A CN1321721C CN 1321721 C CN1321721 C CN 1321721C CN B02142621X A CNB02142621X A CN B02142621XA CN 02142621 A CN02142621 A CN 02142621A CN 1321721 C CN1321721 C CN 1321721C
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- China
- Prior art keywords
- gas
- boric acid
- alkali metal
- aforementioned
- metal carbonate
- Prior art date
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Links
- 239000004327 boric acid Substances 0.000 title claims abstract description 69
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000007789 gas Substances 0.000 title claims description 68
- 238000000034 method Methods 0.000 title abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 56
- 239000003513 alkali Substances 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 55
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 55
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000003672 processing method Methods 0.000 claims description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- -1 alkali metal hydrogencarbonate Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000779 smoke Substances 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 239000000428 dust Substances 0.000 abstract description 5
- 235000013339 cereals Nutrition 0.000 description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
- 239000000843 powder Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 16
- 239000003595 mist Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 206010022000 influenza Diseases 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 229940072033 potash Drugs 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
The present invention relates to a treatment method for safely and effectively removing gas containing boric acid components from gas containing boric acid components by an existing bag filter or an electric dust remover. The treatment method is a gas treatment method which removes boric acid components from gas by adding solid alkali metallic carbonate in gas containing boric acid components with the concentration of more than 15 mg/m converted into B2O3 under a standard state.
Description
Technical field
The present invention relates to from the gas that contains boric acid component, effectively remove the method for boric acid component.
Background technology
In the past, when making silicic-boric acid glass, glaze or enamel ironware etc., use borax or boric acid as raw material, and therefore, contained boric acid component in industrial smelting furnace exhaust or heating furnace exhaust, this has become a reason of atmosphere pollution.In addition, in the coal power station etc., contain boric acid component in the feed coal, therefore, contain boric acid component in the exhaust after the burning, this has also become a reason of atmosphere pollution.As everyone knows, drain into the reason that boric acid component in the surrounding environment has become water quality or soil pollution again.
For example, in the high-temperature fusion process of using borax, sneaked into boric acid in its exhaust, this boric acid has the H of using according to its temperature and steam partial pressure
3BO
3, HBO
2, B
2O
3The molecular structure that the five equilibrium minor is represented.
In the past, also there was not effective method can remove these boric acid components, though adopted the wet washing that uses alkaline matters such as NaOH; The potassium hydroxide powder is dispersed in the flue, then the method for the potassium hydroxide powder being removed together with acid ingredient with bag hose or electric cleaner; And handle contains the method for the gas process filter secondary filter that has produced boric acid particles etc.But, the boric acid component concentration after removing processing is fully reduced, not the highly effective method of removing therefore.
For example, when using wet washing etc.,, cause that then delivery temperature descends if for the removal efficient that improves boric acid component increases the aqueous slkali internal circulating load, when delivery temperature is lower than the dew point of acid, the SO in the gas
3Gas or sulfuric acid gas are (hereinafter referred to as SO
3Composition) becomes sulfuric acid mist, have the danger that causes corrosion.In addition,, the concentration of sodium carbonate in the reaction product, sodium sulphate, Boratex is risen, cause crystallization to separate out, stop up pipeloop if improve the alkali concn of circulation fluid.On the other hand, in to processed gas, inject the method for potassium hydroxide micro mist, because the reactivity of potassium hydroxide and boric acid component is poor, so must use the potassium hydroxide micro mist in a large number, also must use maximization equipment, and the processing of reactant that must reclaim and unreacted solid waste, thereby cause the problem that cost increases.In addition, in method,, be necessary after gasification, to make the boric acid component cooling to separate out,, therefore the very expensive bag hose of special price must be set because temperature will reach below the dew point of sulfuric acid and hydrochloric acid in order fully to remove boric acid component to the gas secondary filter.
Summary of the invention
The invention provides the gas processing method of removing contained boric acid component in the gas.In the method, make to contain under the standard state to be converted into B
2O
3Concentration at 15mg/m
3The gas of above boric acid component contacts with the solid alkali metal carbonate class more than a kind that is selected from alkali carbonate and alkali metal hydrogencarbonate, removes the boric acid component in the aforementioned gas.
The present invention can effectively remove boric acid component from gas, this is difficult to accomplish with processing method in the past.In addition, dry type exhaust gas treatment device such as used powder dispersal device, bag hose is equally applicable to the present invention in the processing method in the past.
The method that the present invention also provides the operation to denitrification apparatus to be further improved, and the method that the boron component in the exhaust that in the past went out of use is effectively utilized in addition.
Description of drawings
Fig. 1 is to the flow chart by the processing method of the gas of the boronic acid containing composition of discharging in the glass-melting furnace.
The explanation of symbol:
1: the glass-melting furnace of boronic acid containing composition, 2: stabilizer, 3: bag hose, 4: exhaust fan, 5: exhaust gas denitration device, 6: chimney, 7: alkaline water, 8: being sodium bicarbonate powder in the example 1, is potassium hydroxide powder, 9 in the example 2: the dust of capture, 10: the 1 flues, 11: the 2 flues, 12: the 3 flues, 13: the 4 flues, 14: the 5 flues.
The specific embodiment
The gas (to call processed gas in the following text) that contains boric acid component of the present invention comprises gas of discharging etc. from the heating process of the glass that contains boric acid component or other inorganic material or fusion operation.Gas that produces in the exhaust that produces when specifically comprising vycol, glass curtain wall heat-insulating material, glass fibre, liquid crystal display with the manufacturing of glass, glass material glaze, ferro-boron, porcelain etc. or other operations etc. contains the gas of boric acid component.The described boric acid component of this specification refers to H
3BO
3Or its dehydrate, mainly with H
3BO
3, HBO
2, B
2O
3Expression.The concentration of boric acid component is to be converted into B
2O
3Meter.Method of the present invention has the effect that sour gas is all removed, and has also comprised boron trifluoride (BF in the processed gas that contains boric acid component
3) or boron chloride (BCl
3) they can be removed simultaneously when waiting sour gas.Removable other sour gas comprise HCl, SO
2, SO
3, H
2SO
4, HF, HBr, HI etc.
The contained boric acid component amount of processed gas of the present invention is converted into B under standard state
2O
3At 15mg/m
3More than.But, even contained boric acid component amount is converted into B in the processed gas
2O
3At 15mg/m
3Below, the present invention is still effective.
In the present invention, be dispersed in the solid alkali metal carbonate class in the processed gas and evenly dispersion, contact, remove after the neutralization with the boric acid component that is gaseous state.When also comprising other acid (as sulfuric acid) except that boric acid in processed gas, processed gas is in the above temperature of its dew point and is advisable.As other examples, also can make the solid alkali metal carbonate class granularly, spherical or block, use after forming packed layer with this shaping thing again.When handling a large amount of high-temperature exhaust air, adopt the method that the powder of solid alkali metal carbonate class is dispersed in the exhaust uptake to be advisable.
In the present invention, as long as the solid alkali metal carbonate class can be removed boric acid component after neutralization reaction, it is not particularly limited.Using the solid alkali metal carbonate time-like, considering that from big this point of gas treatment amount of unit mass be advisable to use anhydrous salt, certainly, moisture salt also is spendable equally.
As alkali metal hydrogencarbonate since its can be in a large number and cheapness buy, no hygroscopicity, granulation is easy, it is convenient to preserve, and also further pulverizes back acquisition fine particle size easily, so, can form porous matter (1m behind the sintering
2More than/the g) sodium carbonate, wherein good especially is sodium acid carbonate.In the process of carrying out gas purification etc.,, then can use saleratus if should not use sodium.
In addition,, can use sodium carbonate, potash etc. as the alkali carbonate class, from can be in a large number and cheapness buy consideration, should use sodium carbonate.It is good then using potash in the occasion that should not use sodium.As sodium carbonate, be particularly suitable for using the porous matter sodium carbonate that is called light ash, because its specific area is big, and micronizing easily.
When using porous matter sodium carbonate, preferably its specific area is 1m
2The light ash that/g is above.Beyond porous matter, the little then specific area of average grain diameter increases, even be called the non-porous matter sodium carbonate of heavy ash, also can make its specific area reach 1m after micronizing
2More than/the g, thereby make its reactive raising.Consider that from easy pulverizing and porous matter light ash has that specific area is bigger, the better advantage of performance.On the other hand, heavy ash has advantages such as buy, volume is little, freight charges are low general easily.Described specific area is the value that obtains by the BET method.
These solid alkali metal carbonate classes can be used separately also can mix use, without any difference.In addition, as described below, in order to improve the flowability of solid alkali metal carbonate class and powder thereof, the anticaking agent that adds in order to prevent to lump can use natural prodcuts or sintetics again.Using sodium carbonate or potash as the solid alkali metal carbonate time-like, because its hygroscopicity is strong, need be under the long-term packed state and takes care of, therefore adopt the packaging material after anti-wet process to be packaged as suitable.Poisture-penetrability when concrete packaging material press 40 ℃ that JIS-Z0208 stipulates to adopt is at 5g/m
2Material below day is advisable.Described moisture permeability is meant that a packaging material is as the interface, interface one side is the air of relative humidity 90%, the interface opposite side is the calcium chloride that keeps dry state, then through be converted into the numerical value of per unit area packaging material after 24 hours by the steam quality at interface.Moisture permeability when it is desirable to 40 ℃ especially is at 1g/m
2Below day.
The volume average particle size of used solid alkali metal carbonate class is preferably 1～100 μ m.Like this, the specific area of solid alkali metal carbonate class particle is bigger, and reactive higher with boric acid component can effectively be removed boric acid component.In addition,,, the distance of the particle diffusion of boric acid component in flue can be shortened, reactivity can be improved so the individual number density in the processed gas improves because the particle number of unit mass is more.From the effect of removing of boric acid component, to the lower limit not specially provided for of average grain diameter, if but average grain diameter less than 1 μ m, then crushing operation can improve the cost that industry is made.If average grain diameter surpasses 0.1mm, when then being dispersed in the flue, can not fully reacting and directly sink to bottom the flue, so also undesirable.Therefore, average grain diameter better is below 50 μ m, is more preferably below 30 μ m, and good especially is below 20 μ m.
In the present invention, average grain diameter is meant with laser diffraction and scattering formula particle size distribution device and measures, and full volumetric as 100%, is asked for accumulation curve, and the particle diameter when its cumulative volume arrives 50% just is called average grain diameter (μ m).
The solid alkali metal carbonate class is corresponding to being converted into B to the dispersion volume of processed gas
2O
3Be the boric acid component in 1 mole the gas, with 0.5～50 times of mole (for example, sodium acid carbonate NaHCO
3The molal quantity that converts and represent, sodium carbonate Na
2CO
3The molal quantity that converts and represent) is advisable.If 0.5 times of mole of dispersion volume less than, equivalent is not enough when then reacting with boric acid component, makes the reduction amount of boric acid component insufficient, and effect is undesirable; If addition surpasses 50 times of moles, then cost is too high, and is also undesirable.In addition, contain sour gas such as sulfur oxide, hydrogen chloride, hydrogen fluoride under many situations in the exhaust, solid alkali metal carbonate class of the present invention and these sour gas have very high reactivity, thereby have been consumed by reaction.So, for removing other various sour gas, be used in combination with the Wet-type spray of the distribution of calcium hydroxide powder or NaOH and be advisable, the dispersion volume of above-mentioned solid alkali metal carbonate class is reduced.
The method that the solid alkali metal carbonate class is scattered in processed gas comprises method that carry to inject flue etc. by air, use jet pump to attract marginal not to go into the method for powder by the Compressed Gas limit, and described laterly pulverize the i.e. method of directly injecting from the outlet of pulverizer etc. before use at once.
For removing the solid alkali metal carbonate class that is dispersed in the processed gas, can use equipment such as electric cleaner, bag hose, venturi scrubber, packed column.
Utilize method of the present invention, make under the standard state and be converted into B
2O
3Processed gas in the concentration of boric acid component can drop to below the 60 quality % before handling, be more preferably below the 50 quality % that drop to before handling.
Under the situation about re-using after the solid alkali metal carbonate class of macroparticle need be pulverized, the method of adjustment of its average grain diameter is included in the method for pulverizing at once (hereinafter referred to as on-the-spot comminuting method) before flue etc. scatters, broken and be kept at and be provided with the method (hereinafter referred to as the precomminution method) that use the back in the storage tank the macroparticle micro mist in advance.
For on-the-spot comminuting method, at ordinary times macroparticle is kept in the storage tank, the weight feed pulverizer is pulverized at once before use, directly intersperses among then in flue etc.Used pulverizer comprises jet mills such as impact grinders such as pin grinder, flour mill or jet grater etc.For reaching the efficient pulverizing below the average grain diameter 20 μ m, should use pulverizer with grading plant.In addition, be to improve the reactivity with boric acid component, make solid alkali metal carbonate class particle through pulverize, after the classification, its sieve down cumulative particle size distribution reach 90% particle particle diameter below 60 μ m, and then be advisable in the injecting gas.If the particle diameter of 90% particle at 30 μ m with next better.Described grader can use wind-force formula grader.The ACM flour mill) etc. described pulverizer can use the dry type impact type atomizer that ホ ソ カ ヮ ミ Network ロ Application Co., Ltd. makes, and (trade name: inside is provided with the machine of dry type wind classification device.
For the precomminution method, in advance macroparticle is ground into required average grain diameter and is kept in the storage tank, again it is interspersed among in use in flue etc.Used pulverizer except the above, also can use medium-type pulverizers such as ball mill, oscillating mill, media agitator mill.In addition, also can adopt method dry again after the wet crushing mill micro mist is broken.
Generally speaking, on-the-spot comminuting method is applicable to the big occasion of use amount that special-purpose disintegrating apparatus can be set; The precomminution method is applicable to concentrates the back after pulverize in other places, little or reach the fine occasion of removing boric acid component in the 10 μ m left and right sides to use amount.
The average grain diameter of pulverized raw material is advisable with 50～500 μ m, if the discontented 50 μ m of average grain diameter then have any problem to the pulverizer stable supplying, so undesirable; If average grain diameter surpasses 500 μ m, be crushed to below the 20 μ m, then pulverizer equipment is huge, so also undesirable.
In the precomminution method, aggegation during preservation takes place in crushed material, just is difficult to so in use crushed material is supplied with flue etc. quantitatively.Therefore, can will be pulverized with anticaking agent, or pulverize back adding anticaking agent by comminuted material.
Described anticaking agent prevents the mutual contact of solid alkali metal carbonate class particle between solid alkali metal carbonate class particle, thereby has prevented the caking of solid alkali metal carbonate class particle.Because the interpolation of anticaking agent can stop the solid alkali metal carbonate class when pulverizing or the aggegation of solid alkali metal carbonate class micro mist when scattering, and therefore also is applicable to on-the-spot comminuting method.
The average grain diameter of anticaking agent is advisable with 0.005～5 μ m.If it is the average grain diameter of anticaking agent below 0.005 μ m, then prevents the poor effect of luming, and can't buy from market as inexpensive industrial product, therefore undesirable.If average grain diameter surpasses 5 μ m, when then raw material was particulate, even add the anticaking agent of equal in quality ratio, because the number of anticaking agent is few, it prevents that the effect of luming is just poor, and was therefore also undesirable.The average grain diameter of anticaking agent for better, and is the best with 0.005～0.1 μ m with 0.005～2 μ m.
Described anticaking agent can use well-known to stop powder agglomeration or to improve the additive of rollability as purpose, comprise magnesium carbonate, silica, aluminium oxide, aluminosilicate, zeolite, talcum powder, stearate etc., also can mix and use above-mentioned several materials.Wherein preferred silica, and in silica preferred especially average grain diameter little, stop the effect of caking and improve mobile effect all good, and the wet silica of buying easily.
When using wet silica, should use according to the solid alkali metal carbonate class in device the distribution position and in water the hydrophily of the favorable dispersibility silica that wets.Its reason is, if use hydrophobic wet silica, though to the flowability of solid alkali metal carbonate class improve respond well, but, with the situation of scattering solid alkali metal carbonate class and anticaking agent thereof at the upper reaches of wet type flue gas desulfurization equipment is example, in the absorption tower of flue gas desulfurization equipment aggegation the wet silica of hydrophobicity, and form film at gas-liquid interface, like this might be owing to stir and mixing enters in the film air, and the foamed phenomenon that bubble can't disappear appears.In addition, discarded situation is to be advisable with hydrophilic wet silica too after reacted solid alkali metal carbonate class is dissolved in water.
Wet silica just has hydrophily as not doing the hydrophobicity processing, is suitable for use as anticaking agent.Hydrophilic wet silica does not float on the surface but is dispersed in the water, therefore, does not take place because the fault that above-mentioned foaming causes.On the other hand, between place of scattering solid alkali metal carbonate class and anticaking agent thereof and flue gas desulfurization equipment, be provided with in the method for electric cleaner, because fault such as aforementioned foaming does not take place,, be hydrophobic or hydrophilicly all can use as anticaking agent.
Also can use zeolite as anticaking agent.Zeolite is poor as the effect specific humidity silica of anticaking agent, but since zeolite can with the acid ingredient generation neutralization reaction in the processed gas, therefore can use.Particularly preferably be the synthetic zeolite that is called 4A type zeolite, its average grain diameter is little, is about 1～5 μ m, and contains sodium, therefore also has the neutralization with acid ingredient.And described zeolite powder after drying also can be made drier and use caking or aggegation that the solid alkali metal carbonate class micro mist after it can suppress to pulverize causes because of suction.Therefore, if be used in combination zeolite and wet silica, then effect is better, and this is specially adapted to select for use the occasion of sodium carbonate as the solid alkali metal carbonate class, can prevent the sodium carbonate moisture absorption and generates a hydrated salt, can prevent caking again.
The consumption of anticaking agent of the present invention is 0.1～5 weight % of solid alkali metal carbonate class.If it is addition less than 0.1 weight % then improves weak effect to the flowability of solid alkali metal carbonate class, therefore undesirable.On the other hand, if addition surpasses 5 weight %, then the flowability of solid alkali metal carbonate class is improved effect and is not improved with the increase of its addition, and cost just rises like this, so also undesirable.Particularly preferred addition is 0.3～2 weight %.
Caking as the solid alkali metal carbonate class prevents and the mobile method of improving, and can add average particle and surpass the solid alkali metal carbonate class coarse grain of 20 μ m, particularly particle diameters more than 50 μ m in the solid alkali metal carbonate class micro mist of average grain diameter below 20 μ m.With the precomminution method solid alkali metal carbonate class micro mist is being kept under the situation that is used further to gas treatment in the storage tank behind the certain hour like this, can improving the discharge of the micro mist from storage tank described later.Under the weight and volume effect of bigger corase particles, make the loose caking that forms by particulate scatter.
Again carry out gas treatment after also can adding in the solid alkali metal carbonate class micro mist below the average grain diameter 20 μ m together to anticaking agent and above-mentioned coarse grain.The combined amount of coarse grain is generally 10～30 weight % of the total amount of the following solid alkali metal carbonate class of average grain diameter 20 μ m and this coarse grain.For example, under the situation of solid alkali metal carbonate class with sodium acid carbonate or sodium carbonate, can correspondingly use coarse-grained sodium acid carbonate or sodium carbonate respectively.
Sneak into coarse grain according to above-mentioned usage ratio, can prevent powder and only discharge at the middle body of storage tank, and " shrinkage pool " phenomenon that near the powder cell wall still left behind, this effect can obtain by utilizing physical method to sneak into macroparticle.Consider that from the effect of removing of boric acid component when using the similar coarse grain of solid alkali metal carbonate class, this coarse grain itself also has the function of removing boric acid component to a certain degree.
Gas processing method of the present invention is after removing boric acid component, preferably uses flue gas desulfurization equipment.By the use of flue gas desulfurization equipment, can effectively remove SO in the gas
2, SO
3And sulfuric acid composition.
The present invention is a dry process, and solid alkali metal carbonate class powder is dispersed in the processed gas, and therefore, equipment therefor is different with wet type, and its device and operational management are convenient, stable operation.In addition, situations such as calcium hydroxide, calcium carbonate or magnesium hydroxide are different with using, and residue after the neutralization and unreacted reactant are water miscible.Therefore, remove boric acid with known drainage processing method, just can reduce solid waste if be dissolved in water.
Among the present invention, processed gas can be handled with flue gas desulfurization equipment or smoke evacuation denitrification apparatus after the solid alkali metal carbonate class is handled again.
In the present invention, when handling processed gas, particularly adopt under the situation of sodium acid carbonate, saleratus, light ash or potash, can make with V with the smoke evacuation denitrification apparatus
2O
5Deng the SO of porch that is the denitrating catalyst layer of active component
xConcentration is reduced to below the 10ppm, is more preferably and reduces to below the 5ppm.So just can prolong the service life of catalyst.The NH that is used in combination because of denitration
3And SO
3Reaction can prevent to generate NH
4HSO
4
In the present invention, handling with the boric acid component with the solid alkali metal carbonate class is the exhaust from the glass melting operation of raw material, the potassium borate slaine of Chan Shenging captures with bag hose after treatment, and the potassium borate slaine of capture can be used as part of raw materials recirculation and is used in the fusion operation.In reactant, also comprised under the situation of the reaction product that forms with sour gas except that boric acid with the solid alkali metal carbonate class of captures such as bag hose, consider its composition, and adjust other proportion of raw materials, be used in the fusion operation as the food ingredient of glass.
In order to confirm to add behind the sodium acid carbonate, contain the test of scattering sodium bicarbonate powder in the exhaust of glass-melting furnace of boric acid actually to removing the effect of gas mesoboric acid composition.
Below according to Fig. 1 embodiments of the invention are described.
The about 500 ℃ of exhausts that produce in the smelting furnace 1 are sent into stabilizer 2 by the 1st flue 10.In stabilizer 2, add alkaline water 7 and remove SO
2Deng, and make gas temperature reduce to about 200 ℃.Then, to injecting sodium bicarbonate powder 8 in the exhaust that enters the 2nd flue 11 between stabilizer 2 and the bag hose 3, boric acid component is removed in neutralization, is sent to bag hose 3 again, then dust and the remaining SO that is not removed in stabilizer 2
2With the boric acid component reaction, remove the dust of generation etc.Outside the dust 9 that traps with bag hose 3 is exhausted from system.On the other hand, the exhaust by bag hose utilizes exhaust fan 4 effects to be admitted to the 4th flue 13 behind the 3rd flue 12, is admitted to chimney 6 by the 5th flue 14 again, discharges from chimney 6 at last.
The glass-melting furnace that contains boric acid component is the open hearth of heat exchange type, and its heavy oil consumption amount is 450L/h, extraction flow 8000m
3/ h is converted into B from the boric acid component in the exhaust in the stove
2O
3Be 600mg/m
3L represents the unit " liter " of capacity, and the volume of gas is meant the volume under the standard state.
As shown in Figure 1, sampling to exhaust is the 3rd flue 12 places that export at bag hose, absorb and fixedly contain the boric acid component of exhaust with cylindrical filter paper and water,, be converted into B again by ICP luminescence analysis (inductively coupled plasma atom spectrum analysis) analysis boric acid component
2O
3
In the present embodiment, the マ ィ Network ロ ト ラ that uses Nikkiso Company Limited to make
ッNetwork FRA 9220 measures average grain diameter.That in addition, the ICP apparatus for analyzing luminosity uses is the SPS4000 that セ ィ コ one Electronics Co., Ltd makes.
[example 1 (embodiment)]
(Dry-crusher that ホ ソ カ ヮ ミ Network ロ Application company makes, trade name: the ACM flour mill) being ground into average grain diameter is that 9 μ m and the particle diameter of accumulating 90% particle of undersize degree distribution are the sodium bicarbonate powder of 19 μ m with pulverizer the sodium acid carbonate of average grain diameter 102 μ m (Asahi Glass Co., Ltd's manufacturing).When micro mist was broken, (Japanese ァ ェ ロ ジ Le Co., Ltd. made trade name: AEROSIL-R90G) add, be blended in the sodium bicarbonate powder by 1.0 weight % (is benchmark with the sodium bicarbonate powder) the wet silica of the hydrophily of average grain diameter 0.01 μ m.
The results are shown in table 1 when injecting sodium bicarbonate powder.The B of the dispersion volume of sodium acid carbonate corresponding to 1 mole
2O
3Multiple represent.
In addition, under situation about not scattering as the sodium acid carbonate micro mist of solid alkali metal carbonate class, forming from the exhaust of chimney is the O that contains 10 volume %
2, 15 volume ppm SO
2
Table 1
| Numbering | Sodium acid carbonate dispersion volume [times mol] | Be converted into B 2O 3Concentration (mg/m 3) | B 2O 3Residual rate (quality %) | |
| Blank | Injection | |||
| 1-1 | 15 | 82 | 39 | 48 |
| 1-2 | 25 | 75 | 14 | 18 |
At the 4th flue 13 places of exhaust fan 4 outlets, with automatic continuous analysis instrument record SO
2Change in concentration, SO shown in the record
2Concentration is reduced to 3 volume ppm from 15 volume ppm, shows SO
2Remove effect.Like this, just can realize denitrification apparatus with V
2O
5Deng the prolongation in service life that is the denitrating catalyst layer of active component.In addition, the injection of sodium bicarbonate powder is to bag hose 3 did not influence such as existing equipment such as grade.
[example 2]
Be that the calcium hydroxide of 33 μ m replaces the sodium acid carbonate in the example 1 except that using average grain diameter 4 μ m, 90% particle diameter in the test, other conditions are all identical with example 1, and it the results are shown in table 2.
Under the occasion of not scattering calcium hydroxide, forming from the exhaust of chimney during test is the O that contains 10 volume %
2, 15 volume ppm SO
2
Table 2
| Numbering | Calcium hydroxide dispersion volume [times mol] | Be converted into B 2O 3Concentration (mg/m 3) | B 2O 3Residual rate (quality %) | |
| Blank | Injection | |||
| 2-1 | 20 | 71 | 58 | 82 |
| 2-2 | 25 | 75 | 46 | 61 |
Identical with example 1, record SO
2Change in concentration, SO
2Concentration becomes 12 volume ppm from 15 volume ppm, does not obviously reduce as can be known.In addition, the distribution of calcium hydroxide is to existing equipment did not influence such as bag hoses.
Claims (10)
1. the processing method of the gas of boronic acid containing composition is characterized in that, makes to contain under the standard state to be converted into B
2O
3Concentration at 15mg/m
3The gas of above boric acid component contacts with the solid alkali metal carbonate class more than a kind that is selected from alkali carbonate and alkali metal hydrogencarbonate, remove the boric acid component in the aforementioned gas, wherein, the volume average particle size of aforementioned solid alkali metal carbonate class is 1～20 μ m, and aforementioned solid alkali metal carbonate class contains anticaking agent.
2. gas processing method as claimed in claim 1, its feature also are, contact with aforementioned solid alkali metal carbonate class by the aforementioned gas that contains boric acid component, make under the standard state in the gas and are converted into B
2O
3The concentration of boric acid component reduce to below the 60 quality % before handling.
3. gas processing method as claimed in claim 1 or 2, its feature are that also aforementioned anticaking agent comprises wet silica.
4. gas processing method as claimed in claim 1, its feature are that also aforementioned solid alkali metal carbonate class is a sodium carbonate.
5. gas processing method as claimed in claim 4, its feature are that also aforementioned sodium carbonate is that specific area is at 1m
2The light ash that/g is above.
6. gas processing method as claimed in claim 1, its feature are that also aforementioned solid alkali metal carbonate class is a sodium acid carbonate.
7. gas processing method as claimed in claim 1, its feature are that also the aforementioned gas that contains boric acid component is the gas from the heating process of glass or the discharge of fusion operation.
8. gas processing method as claimed in claim 1, its feature are that also the aforementioned gas that contains boric acid component is handled with flue gas desulfurization equipment again after aforementioned solid alkali metal carbonate class is handled.
9. gas processing method as claimed in claim 1, its feature are that also the aforementioned gas that contains boric acid component is handled with the smoke evacuation denitrification apparatus again after aforementioned solid alkali metal carbonate class is handled.
10. gas processing method as claimed in claim 1, its feature also is, the aforementioned gas that contains boric acid component is after aforementioned solid alkali metal carbonate class is handled, and the boric acid base slaine of treated generation enters the glass melting operation as the feedstock recycle of boronic acid containing composition.
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|---|---|---|---|
| CNB02142621XA CN1321721C (en) | 2002-09-09 | 2002-09-09 | Method of dealing with gases containing boric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02142621XA CN1321721C (en) | 2002-09-09 | 2002-09-09 | Method of dealing with gases containing boric acid |
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| CN1321721C true CN1321721C (en) | 2007-06-20 |
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| CNB02142621XA Expired - Fee Related CN1321721C (en) | 2002-09-09 | 2002-09-09 | Method of dealing with gases containing boric acid |
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| JP5644109B2 (en) * | 2007-12-05 | 2014-12-24 | 旭硝子株式会社 | Method for producing boron-containing glass product and method for purifying exhaust gas generated during production of boron-containing glass product |
| CN102093592B (en) * | 2010-12-31 | 2012-11-21 | 常州市英特玛柯橡塑科技有限公司 | Auxiliary foaming agent and preparation method thereof |
| KR102086435B1 (en) * | 2012-11-15 | 2020-03-09 | 에이지씨 가부시키가이샤 | Method for producing alkali-free glass |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4631178A (en) * | 1983-04-18 | 1986-12-23 | Owens-Corning Fiberglas Corporation | Method of removing boric oxide from flue gases |
| CN1045928A (en) * | 1989-03-28 | 1990-10-10 | 索格股份公司 | Method for purifying waste gas discharged from glass melting furnace |
-
2002
- 2002-09-09 CN CNB02142621XA patent/CN1321721C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4631178A (en) * | 1983-04-18 | 1986-12-23 | Owens-Corning Fiberglas Corporation | Method of removing boric oxide from flue gases |
| CN1045928A (en) * | 1989-03-28 | 1990-10-10 | 索格股份公司 | Method for purifying waste gas discharged from glass melting furnace |
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