CN1058353A - Be used for removing the composite clay materials of sulfur oxide from air-flow - Google Patents
Be used for removing the composite clay materials of sulfur oxide from air-flow Download PDFInfo
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- CN1058353A CN1058353A CN 91104912 CN91104912A CN1058353A CN 1058353 A CN1058353 A CN 1058353A CN 91104912 CN91104912 CN 91104912 CN 91104912 A CN91104912 A CN 91104912A CN 1058353 A CN1058353 A CN 1058353A
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- clay
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- air
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- 239000004927 clay Substances 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims description 8
- 239000002131 composite material Substances 0.000 title claims description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 title description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 34
- 239000011575 calcium Substances 0.000 claims description 33
- 239000000725 suspension Substances 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 8
- 235000011092 calcium acetate Nutrition 0.000 claims description 8
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 8
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 7
- 239000001639 calcium acetate Substances 0.000 claims description 7
- 229960005147 calcium acetate Drugs 0.000 claims description 7
- 235000019255 calcium formate Nutrition 0.000 claims description 7
- 229910000271 hectorite Inorganic materials 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 150000001447 alkali salts Chemical class 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229940044172 calcium formate Drugs 0.000 claims description 6
- 239000004281 calcium formate Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims 1
- 239000000440 bentonite Substances 0.000 claims 1
- 229910000278 bentonite Inorganic materials 0.000 claims 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 229910001919 chlorite Inorganic materials 0.000 claims 1
- 229910052619 chlorite group Inorganic materials 0.000 claims 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910000275 saponite Inorganic materials 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003546 flue gas Substances 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 235000001465 calcium Nutrition 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 7
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000002594 sorbent Substances 0.000 description 7
- 241000370738 Chlorion Species 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- 235000019738 Limestone Nutrition 0.000 description 6
- 240000006909 Tilia x europaea Species 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- 239000006028 limestone Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910021647 smectite Inorganic materials 0.000 description 5
- 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 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000012717 electrostatic precipitator Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000273 nontronite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101150040772 CALY gene Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Disclose a kind of preparation and use method for compositions of being used for, said composition comprises the precursor of a kind of montmorillonitic clay and a kind of alkaline matter or alkaline matter, the SO in the flue gas stream of these alkaline matters or its first mass-energy and heat
XReaction.These alkaline matters or its precursor preferably are scattered in a kind of decentralized photo of clay bodies in mutually.With said composition heating with form a kind of can with the SO in the flue gas
XThe alkaline matter of reaction.
Description
The present invention relates to alkali metal oxide and alkaline earth oxide or the carbonate of a kind of carrier band on clay, wherein the clay as the host belongs to smectites, the invention still further relates to the preparation method of these combination clay materials.More particularly, the present invention relates to exploitation is used for removing SO from flue gas
x(SO
2And SO
3) improved method for compositions.
Adopted first in the London in 1933 by washing flue gas control SO
2The method of content.Yet,, just begin this technology is applied in the coal fired boiler device until the seventies in the U.S..1964, for the first time use lime on a large scale or lime stone washs flue gas in the Soviet Union.Be right after thereafter be this device in the large-scale sulfuric acid plant that was built in Japan in 1966.The law amendment of having passed through to purify air in 1970 (Clean Air Act Amendments).This law is by Bureau for Environmental Protection of the United States Federal (United States Environmental Protection Agency(EPA)) put teeth in; the clause regulation of this law, power plant that build later on August 17th, 1971 or reconstruction all must restriction SO
xDischarge capacity.This law has promoted the research of relevant flue gas desulfurization (FGD) widely.Amount to the wet method exhaust treatment system (comprising lime, lime stone and sode ash system) of in January, 1984 calcium base and to account for 84% of existing and FGD capacity of equipment that plan is built altogether.The law that purifies air was revised in 1977, its objective is and will further control SO
xDischarge capacity.More and more the great number capital cost of Duo federal legal provision and present wet method FGD device and operating cost encourage people to continue to study some new or improved stack gas cleaning technologies.
Because SO
xRelevant with the formation of " acid rain ", so the SO in control power plant
xDischarge capacity be a worldwide problem.Therefore, research is to SO
xControl need the effort in the whole world.Relevant application calcium based system reduces SO
xThe up-to-date patent document of discharge capacity is the U.S. Pat 4,731,233 of Thompson and Nuzio.In most of the cases why adopt lime stone or lime to be because they are cheap and enough supplys are arranged as the raw material of industry.
A lot of control SO is arranged
xThe method of discharge capacity can be used for existing power plant or the new power set built in.These methods can be classified residing position in realizing the combustion system that control is polluted according to equipment therefor.The control method is to remove the compound of desulfuration, nitrogen and ash content before burning from fuel before the burning.In most of the cases, this control method comprises the purification techniques of using coal.The Combustion Process Control method comprises employing combustion process stage by stage, promptly sprays into the fluidized bed combustion of lime stone and adding lime stone in boiler furnace.Burning back control method is after pollutant forms and be not removed before being discharged into atmosphere as yet.This method should comprise spraying in the conveyance conduit and sprays into sorbent (Jozewicz dry and that be mixed with electrostatic precipitator (ESP)/fabric filter in dry sorbent, the conveyance conduit, W., Chang, J.C.S., Sedman, C.B.and Brna, T.G., React.Solids, 6,243(1988)).
Flue gas treating system can be divided into two kinds of wet method and dry method, and this will depend on the moisture in processed flue gas and the useless sorbent.Wet method system is with water vapour that flue gas is saturated fully.Flue gas is contacted with a kind of liquid or slurry stream.The dry method system makes flue gas contact with a kind of dried or wet sorbent, but its water consumption must not make flue gas saturated fully.What the dry method system finally generated is a kind of dried product or useless sorbent material, and the final generation of wet method system is slurries or mud.
Though the calcium based system is control SO
xMain means, but these systems are not no problem.The coalescent serious problems that may exist of particle are to be converted into CaSO
x(CaSO
3And CaSO
4) conversion ratio be lower than optimum value.The activity of calcium component reduces along with the increase of its granularity.Be CaSO in addition
4Occupied volume is greater than usually the volume as the CaO of active component.Therefore, along with the progress of course of reaction, volume also constantly increases, the porous feature that will make CaO lose it so originally to have.Its result causes SO
XAnd O
2Obstruction, make them can not enter active CaO center ((Gullett, B.K.and Blom, J.A., React.Solids, 3 337(1978); Gullett, B.K., Blom, J.A.and Cunningham, R.T., React.Solids, 6 263(1988); Chang, E.Y.and Thodes, G., AIChE J., 30 450(1984); Thibault, J.D., Steward, F.R.and Ruthven, D.M., Can.J.Chem.Eng., 60 796(1982)).
The prior art in this field use lime stone, lime or calcium hydroxide as the precursor that forms the active CaO composition or utilize Ca(OH)
2As active component.Usually, active component is used as the main body phase rather than is used as decentralized photo ((Chang, J.C.S.and Kaplan, N., Envir.Prog., 3 267(1984); Gullett, B.K., Blom, J.A.and Cunningem, R.T., React.Solids, 6 263(1988); Chang, E.Y.and Thodes, G., AIChE J., 30 450(1984); Fuller, E.L.and YOOS, T.R., Langmuir, 3 753(1987)).) nearest research work concentrates at Ca(OH)
2A kind of flying dust of middle interpolation is to improve it at control SO
xThe activity of aspect ((Jozewicz, W.and Rochelle, G.T., Envir.Prog.5 219(1986); Jozewicz, W., Chang, J.C.S., Sedman, C.B.and Brna, T.G., JAPCA, 38 1027(1988); Jozewicz, W., Jorgensen, C., Chang, J.C.S., Sedman, C.B.and Brna, T.G., JAPCA, 38796(1988); Jozewicz, W., Chang, J.C.S., Sedman, C.B.and Brna, T.G., React.Solids, 6 243(1988); Jozewicz, W., Chang, J.C.S., Sedman, C.B.and Brna, T.G., EPA/600/D-87/095, (NTIS PB87-175857/AS); Jozewicz, W., Chang, J.C.S., Sedman, C.B.and Brna, T.G., EPA/600/D-87/135, (NTIS PB87-182663)).) said flying dust is a kind of siliceous material, it can form various calcium silicates with calcium.Some diatomite, montmorillonitic clay and kaolin also are considered to a kind of active SiO that contains
2Material ((Jozewicz, W., Chang, J.C.S., Sedman, C.B.and Brna, T.G.React, Solids, 6 243(1988)).
Therefore, an object of the present invention is to provide a kind of method that is used to prepare improved sorbent combinations thing, said sorbent combinations thing comprises as the montmorillonitic clay of main body phase and relative more a spot of alkali compounds as active component.In addition, a further object of the invention provides a kind of improved composition, and this composition should all have bigger activity in whole service time, therefore can remove SO more effectively
xHave, a further object of the invention provides a kind of its preparation and uses all comparatively economic composition again.Can make each purpose of the present invention become more and more clearer by following explanation and accompanying drawing.
Fig. 1 is a curve map, and its expression is called as the Cu K α X-ray diffraction figure (XRPD) that composition had of sample 1, and said composition is CaCO
3: the Na-montmorillonite, when with A: when Z represents, A=1 and Z=1.
Fig. 2 is a curve map, and it shows thermogravimetric analysis (TGA) curve of sample 1.
Fig. 3 is a curve map, and it shows the CaCO of sample 1,3 and precipitation
3To SO
2The initial absorption situation.
Fig. 4 is a curve map; It shows sample 17(Ca(CH
3CO
2)
2: the Cu K α XRPD figure that Na-montmorillonite=1.5: 1) is had.
Fig. 5 is a curve map, and it shows temperature to sample 1,22,23 and 24(CaCO
3: the Na-montmorillonite all equals 1: 1) absorption SO
2Influence.
The present invention relates to a kind of SO that can be used to from air-flow, removexThe preparation method of composition, the method comprises: prepare the suspension of a kind of montmorillonitic clay in water; A kind of alkali metal, alkali salt and alkali of being selected from is added in the above-mentioned slurry; This suspension drying to prepare required composition, when being heated, said composition (preferably is at least about 500 ℃), SOxCan from gas, be removed by alkali compounds.
In addition, the present invention also relates to a kind ofly can from air-flow, remove SO
xThe preparation of compositions method, this method comprises the following steps: to prepare the suspension of a kind of montmorillonitic clay in water; With a certain amount of, the alkali compounds that is selected from the precursor of alkaline matter and alkaline matter adds in the slurry; This suspension at air drying, wherein, when being heated, obtaining composition (preferably is at least about 500 ℃), SO
2From gas, removed.
Have again, the invention still further relates to and a kind ofly can from air-flow, remove SO
xThe preparation of compositions method, this method comprises the following steps: to provide a kind of montmorillonitic clay waterborne suspension that contains; A certain amount of sodium carbonate is dissolved in this slurry; The soluble alkaline earth salt that adds stoichiometric amount is so that it and sodium carbonate reaction, make in the suspension of clay the carbonate deposition that generates alkaline-earth metal, the washing said composition, and with this suspension drying, obtain composition, wherein, when the composition that is obtained is heated (preferably at least about 500 ℃), SO
XFrom gas, removed.
At last, the invention still further relates to a kind of SO that can be used for from air-flow, removing
XComposition, when said composition is heated (preferably at least about 500 ℃), SO
XFrom air-flow, removed, in said composition mixture, contained: a kind of from alkali metal, alkaline-earth metal salt and alkaline matter the alkali compounds selected; And a kind of montmorillonitic clay, alkali compounds wherein is added in the clay water suspension, then with this suspension drying to form required composition.
The invention provides a kind of production method for compositions that is used for, said composition is made up of alkali metal or alkaline-earth metal/montmorillonitic clay, wherein the ratio of alkali metal or alkaline-earth metal/montmorillonitic clay is different from prior art, specifically, method provided by the present invention comprises two kinds of possible measures, a kind of measure is to be under the condition of suspended state when clay, makes the CaCO that generates from calcium salt
3Or Ca(OH)
2Be deposited in clay particle surface or sneak into wherein, another kind of measure is to add the aqueous solution of alkali metal containing or alkaline-earth metal sodium or calcium are immersed in the clay particle in the suspension of clay, obtains required ratio whereby.The material that obtains like this is used for removing SO in the flue gas
x
According to a method of the present invention, at first prepare a kind of 0.5-1.5%(weight) clay water suspension.Under agitation toward wherein dripping Na
2CO
3The aqueous solution.And then by similar methods adding CaCl
22H
2O.The adding of calcium compound causes generating CaCO
3Precipitation.Can change Na
2CO
3And CaCl
22H
2The addition of O is to obtain required CaCO
3Weight ratio to clay.With the deionized-distilled water washing product that obtains, and remove superfluous chlorion and sodium ion with centrifugal/decantation or dialysis, then at room temperature or in baking oven 100 ℃ descend drying.In washing process, utilize liquor argenti nitratis ophthalmicus can generate this character of silver nitride precipitation and check whether washing is abundant.Test is negative reaction as silver chlorate, and it is clean to represent that then chloride has removed.Preferably wash this prepared product, because if do not remove chloride, then product and SO
xReactivity will reduce.Chloride is to removing SO
xAdverse effect arranged, this point is also confirmed by other research work, this research paper has been estimated under the operating condition of closed circuit-circulation, magnesium and chlorion are to influence (Chang, J.C.S., the Kaplan of lime absorption-regeneration two-part alkali process, N, and Brna, T.G.in " Fossil Fuels Utilization:EnvironmentalConcerns " (Eds.R.Markuszewski, B.Blaustain) Chap.15).Reactivity of lime reduces with the rising of chlorine ion concentration.When chlorine ion concentration reaches 80, after the 000ppm, this influence is obvious especially.
X-ray powder diffraction pattern shape (XRPD) shows that clay still keeps its original layer structure, and has an appointment 10
The bottom surface distance.The CaCO of crystallization
3Also appear at simultaneously in the XRPD figure.
Carry out Ca(OH with similar methods)
2Precipitation operation.Containing required OH
-The 50%(weight of amount) NaOH solution adds in the entry.Under agitation this drips of solution is added in the slurry.After dripping NaOH solution, add CaCl with similar methods
22H
2The aqueous solution of O.
Precipitate the CaCO that generates on the spot
3, its granularity is less than by with CaCO
3Carry out the granularity that physical mixed can reach with clay.
In some preparation of compositions thing, also add a kind of oxidation catalyst.Iron is with FeCl
36H
2O or Fe(NO
3)
39H
2The form of O adds.With this salt thermal decomposition the time, just formed Fe
2O
3; This Fe
2O
3Can catalysis SO
2Become SO
3Oxidizing process.CaO and SO
3Reaction temperature than it and SO
2Reaction temperature low, therefore, for will from air-flow, removing SO
x, just need to adopt bigger temperature range.There are various transition metal to can be used as oxidation catalyst.
Product is being exposed to SO
xIn before, need earlier it to be heated to 900 ℃ in air.Measuring thermogravimetric analysis (TGA) by example weight has shown and has lost H
3O and CO
2Heat treatment makes CaCO
3Resolve into CaO.In addition, also cause the diffracted intensity of the expression clay in diffraction pattern sharply to descend CaCO
3/ Na-smectite composition is 9.4
The place has only kept lower diffracted intensity.
The second method of preparation high dispersive alkali metal or alkaline-earth metal material is that the compound of water miscible sodium or calcium is flooded in the clay.As mentioned above, at the following aequum of stirred suspension, lysed alkali metal or alkaline earth metal compound are added in the slurry.Example is spendable calcium formate, calcium acetate and sodium acid carbonate as preparing in preparation process, but other soluble alkali metal salts and alkali salt also can use.Not having in the muriatic preparation process of back, do not need to wash.Can directly place suspension and at room temperature carry out drying on the glass plate.
The XRPD figure of the sample that calcium formate and Na-montmorillonite combine by 1: 1 part by weight contains the diffraction maximum of crystallization calcium formate and belongs to the d(001 of typical clay) distance (10
).Equal 22.7 in the d-distance
A small peak has also appearred in the place, and this shows has some formates to insert.In contrast test, for the calcium acetate that makes with infusion method/Na-smectite composition, its XRPD figure does not demonstrate the diffraction maximum of crystallization calcium acetate.The substitute is, main diffraction maximum appears at the d-distance and equals 24.0
The place, this shows, the small material that most calcium acetate and clay form has inserted combining form (the T.J.Pinnavaia in " Chemical Physics of Intercalation " that has become a kind of novel substance between each layer of clay host, Ed.by A.P.Legrand and S.Fla Fandrois, NATO ASI Series, Series B: Physics Vol.172, pp 233-252(1987).
According to the present invention, from above-mentioned salting liquid, be settled out CaCO
3The time, perhaps using Ca(CHOO)
3, Ca(CH
3CO
2)
2Or NaHCO
3During immersion, the product that is obtained has a kind of structure of calcium/clay composition.Using NaHCO
3Under the situation of soaking, formed a kind of sodium/clay composition.When handling with infusion method, between clay and calcium acetate, a kind of comparatively moderate insertion effect has taken place, this point has been taken place to change and be confirmed by the XRPD figure of clay, and the result is a kind of non-composition that inserts regularly in the clay of acquisition.
Though CaCO
3, NaHCO
3, Ca(CHO
2)
2With Ca(CH
3CO
2)
2All be to be fit to be used for removing SO
xAlkaline matter or the precursor of alkaline matter, they can be by forming composition with montmorillonitic clay in 100-900 ℃ temperature range with SO
xRemove, but some calcium salt, for example calcium hydroxide Ca(OH)
2Reagent such as (or quick limes) just is not suitable for this purpose, and is too unstable on carrier because these salt at high temperature, and this may be because SO is removed thereby their are lost in they and clay carrier generation chemical reaction from air-flow
xAbility.
The granularity of montmorillonitic clay is preferably less than 2 microns.And preferably granularity between 0.1 to 2 micron.
The weight ratio of salt pair clay can be between about 1 to 3 and 5 to 1.Remove SO as long as reach
xEffect, any part by weight can use, but preferably makes the main body phase with clay.
Available spray drying process, feed tray drying method or the like the various means that comprise make the composition material drying.In the water-washing step on stream, available centrifugal process is separated solid and solution.
Embodiment 1
Select a kind of originate from U.S. Russia bosom Mingzhou Crook County, the Na-montmorillonite as the representative member in the silicate montmorillonite family with 2: 1 layer windings.In deionized distilled water, make clay content be equivalent to 1.4%(weight this clay dispersion).Application comes by grading by the settlement action in water about the Stokes' law of sedimentation under the gravity effect, is limited to 2 μ m on the granularity.This step is repeated 2 times.Also can remove the quartz impurity insoluble that may be present in the clay by settlement action with other.To place through the clay that purifies on the glass plate at air drying, perhaps with its form storage with water slurry.
CaCO
3: the required part by weight A of Na-montmorillonite: Z can reach as follows: at first preparing a kind of concentration is 1.4%(weight) the solution of Na-montmorillonite in deionized-distilled water.Get the solution that gross weight is 20g.A=Z=1 wishes to obtain 0.28g in the present embodiment, or 2.8 * 10
-3The CaCO of mol
3For this reason, with 0.28 * 10
-3The Na of mol
2CO
3Being dissolved in the deionized-distilled water and making the gross weight of solution is 20g.Under agitation this Na
2CO
3Solution adds in the Na-montmorillonite suspension at leisure.At Na
2CO
3After solution dropwises, in this solution, add CaCl by similar methods
2H
2O solution.The purpose that at first adds sodium salt is in order to prevent that the sodium in calcium and the montmorillonite from carrying out cation exchange.
Preparation process is washed and centrifugal product repeatedly with deionized-distilled water after finishing, to remove superfluous chlorion and sodium ion.Detect cleaning solution with liquor argenti nitratis ophthalmicus, so that determine in the cleaning solution whether Ex-all of chlorion.Place product on the glass plate at room temperature dry.The XRPD figure of product is shown in Fig. 1.At 5.8 ° (15.1
) what occur is the main peak of Na-montmorillonite, and at 29.5 ° (3.0
) that locate to occur is CaCO
3Main peak.
Estimate the sample that makes as stated above, the result shows that it can remove SO effectively from admixture of gas
2This sample is heated to 900 ℃ and kept 30 minutes by the programming rate of 5 ℃/min under 900 ℃, and then feeds 5000ppm SO
2Aerial air-flow, totally 1 hour feeding time.SO shown in Fig. 2
2Absorbing state.This sample demonstrates 88% CaCO
3Transform, and in incipient 1 minute, reached 19% conversion ratio.Conversion ratio calculates by following reaction: CaO+SO
2+ O
2(900 ℃)/() CaSO
4
Embodiment 2 and 3
The product that embodiment 2 and 3 makes is called sample 2 and 3, and these samples are pressed the method preparation of embodiment 1, have just changed Na
2CO
3And CaCl
22H
2The consumption of O is so that these two samples accord with A=3, Z=1 respectively; A=0.33, Z=1.Come test specimen 2 and 3 couples of SO according to the method that embodiment 1 is put down in writing
2Absorbing state.Sample 2 demonstrates CaCO
3Total conversion reach 100%, and in the 1st minute of reaction beginning, reached 14% conversion ratio.Sample 3 provides CaCO
3Total conversion be 100%, and in the 1st minute of reaction beginning, reach 36%.Fig. 3 illustrates owing to change CaCO
3: the weight ratio of Na-montmorillonite and the sample 1,3 and the CaCO that obtain
3To initial SO
2The influence of absorbing state.
Embodiment 4 to 6
According to the method for embodiment 1, use other members in the montmorillonite family to replace preparing a series of 1: 1 CaCO through pure montmorillonite
3: the montmorillonitic clay composition, said other members comprise: Bentone EW P ﹠amp; G GST-865(sample 4); Nontronite (sample 5); Fluorine hectorite (fluorohectorite) (sample 6).Test these composition sample to SO according to embodiment 1 described method
2Reactivity.After reaction 1 hour, the total conversion that the Bentone goods provide is 98%, and the total conversion that the nontronite sample provides is 78%, and the total conversion that fluorine hectorite sample provides is 90%.
Embodiment 7 to 9
According to the present invention, utilize the method for embodiment 1, make a series of A: Z Na-montmorillonite sample, different is to have saved washing step, and changed baking temperature.Sample 7 and 8 has A=1, Z=1 and A=0.33, Z=1 respectively.They are all at room temperature dry.Sample 9 has A=1, Z=1, and drying is to carry out in 100 ℃ air.Experimental condition by embodiment 1 is measured, and the result shows that sample 7,8,9 total conversions that had are respectively 52%, 59% and 42%.Chlorion hinders conversion ratio.
Embodiment 10
With the method for co-precipitation, utilize FeCl
36H
2O prepares a kind of CaCO of iron content as source of iron
3: the Na-smectite composition, said composition has A=Z=1, is called sample 10.Add Na according to embodiment 1 described method
2CO
3, difference is toward CaCl
22H
2Add FeCl in the O solution
36H
2O makes a kind of Fe of containing amount whereby and is 1.5%(weight) composition.When this sample under embodiment 1 described condition with SO
2React after 1 hour, it demonstrates CaCO
3Total conversion be 42.5%.
Embodiment 11
Use Fe(NO
3)
39H
2O has prepared a kind of CaCO of iron content as the source of Fe
3: Na-montmorillonite sample, it has A=Z=1, is called sample 11.The CaCO that has prepared a kind of A=1, Z=1 according to embodiment 1 described method
3-smectite composition.Press 0.5%(weight) content ratio Fe(NO
3)
39H
2O is dissolved in the deionized-distilled water earlier, and then this solution is added CaCO
3In/Na-montmorillonite the suspension.Place on the glass plate product at room temperature dry.This sample under embodiment 1 described condition with SO
2React after 1 hour, it demonstrates CaCO
3Total conversion be 88%.
Embodiment 12 and 13
With NaOH, CaCl
22H
2O and Na-montmorillonite have prepared a kind of Ca(OH as raw material)
2With the weight ratio of Na-montmorillonite be 1: 1 composition, it is called sample 12.Is a concentration 50%(weight) NaOH solution by it and CaCl
22H
2The stoichiometric amount of O reaction adds and is aly stirring, and weight is 50 grams, and concentration is 0.5%(weight) the suspension of Na-montmorillonite in.After in slurry, adding NaOH, the CaCl of adding equivalent in this suspension again
22H
2O solution is to prepare a kind of 1: 1 Ca(OH)
2: the Na-smectite composition.Press the method for embodiment 1, with the deionized-distilled water washing product that obtains.The 2nd sample of present embodiment is called sample 13, and it is by 3: 1 Ca(OH)
3: the Na-montmorillonite is prepared from.When making it at 900 ℃ of following and SO with embodiment 1 described experimental condition in these two samples
2React after 1 hour, sample 12 and 13 shown total conversions are respectively 5% and 1%.For these two samples, when with its carrier band on montmorillonitic clay the time, Ca(OH)
2It and SO under said reaction condition, have been lost
xRespond.By inference, Ca(OH)
2May react with clay, generate a kind of SO
xThe calcium silicates that is inertia.
Embodiment 14 and 15
A certain amount of calcium formate Ca(HCOO)
2Be dissolved in a small amount of as far as possible deionized-distilled water.Obtaining solution is being added a 1.4%(weight at leisure under constantly stirring) Na-montmorillonite slurries in.Change the Ca(HCOO that adds in the clay slurry)
2Quantity, to prepare a kind of Ca(HCOO)
2: Na-montmorillonite ratio is the sample 15 that 1: 1 sample 14 and ratio are 3: 1.Place on the glass plate obtaining product at room temperature dry.Under embodiment 1 described condition, with SO
2React after 1 hour the total conversion that sample 14 provides (pressing Ca(HCOO)
2Meter) is 60%, and is 24% at initial 1 minute conversion ratio.Correspondingly, the conversion ratio that obtained after the reaction time of 1 hour and 1 minute of sample 15 is respectively 94% and 14%.
Embodiment 16 to 19
According to the present invention, utilize the step that is used to prepare clay calcium formate composition in embodiment 14 and 15 to prepare a series of calcium acetate: the composition sample of Na-montmorillonite.Change Ca(H
3CCOO)
2XH
2The consumption of O is to obtain Ca(CH
3CO
2)
2: the part by weight of Na-montmorillonite is 1: 1 a sample 16; Ratio is 1.5: 1 a sample 17; Ratio is 0.33: 1 a sample 18; And ratio is 5.0: 1 a sample 19.
The diffraction pattern of the XRPD of the product that is got by sample 17 is shown among Fig. 4.This diffraction pattern does not demonstrate the Ca(H of any crystallization
3CCOO)
2But it demonstrates the increase corresponding to the d-distance of caly structure.Under embodiment 1 described condition, each sample and SO
2React after 1 hour, concerning sample 16 to 19, their conversion ratio is respectively 52,36,15 and 78%.
A kind of by NaHCO
3The sample of carrier band on the Na-montmorillonite, its preparation method is as follows: the sodium acid carbonate of aequum is dissolved in a small amount of as far as possible deionized-distilled water, and obtaining solution added in the suspension of a clay under constantly stirring at leisure, then obtaining mixture is placed on the glass plate at air drying.NaHCO
3: the ratio of clay is 1: 2.The sample that obtains is called sample 20, and this sample is under embodiment 1 described condition, with SO
2React the total conversion that is obtained after 1 hour and (press NaHCO
3Meter) be 31%.
Embodiment 21
From the sample 20 of embodiment 20, take out the sample of some, test it down to SO at 500 ℃
2Reactivity.Said sample is heated to 500 ℃ by the programming rate of 5 ℃/min.This sample was continued to keep 30 minutes under 500 ℃.Make one contain 5000ppm SO then
2Circulation of air crossed this sample totally 1 hour, total gas flow rate is 200CC/min, simultaneously sample is maintained 500 ℃.Sample was kept under 500 ℃ 30 minutes again and the loss in weight is not taken place.With SO
2React and press NaHCO after 1 hour
3The total conversion of content meter is 46%.
Embodiment 22
Get quantity of sample 1,, test this sample down to SO at 500 ℃ according to embodiment 21 described conditions
2Absorbing state.At this moment the conversion ratio of this sample is 0%.This illustrates that this temperature crosses low so that can not transform CaCO effectively
3
Embodiment 23
Get quantity of sample 1 test it under 700 ℃ to SO
2Absorbing state, be heated to 700 ℃ according to the programming rate of 5 ℃/min.Under 700 ℃, kept 30 minutes, and then feeding contains 5000ppm SO
2Air stream.Sample was kept under 700 ℃ 30 minutes again and do not had the loss in weight.At this moment press CaCO
3The conversion ratio of meter is 11%, and this shows that temperature is high more, and the result is good more.
Embodiment 24
Get quantity of sample 1 test it under 800 ℃ to SO
2Absorbing state, according to the heating of the programming rate of 5 ℃/min, until reaching till 800 ℃.Under 800 ℃, kept again 30 minutes, and then feeding contains 5000ppm SO
2Air stream.Stopping to feed SO
2Afterwards sample was kept under 800 ℃ 30 minutes again and do not had the loss in weight.At this moment press CaCO
3The conversion ratio of meter is 75%.The sample of embodiment 1,22,23 and 24 is tested, and temperature is to 1: CaCO 1%(weight)
3/ Na-montmorillonite absorption of sample SO
2Influence be shown among Fig. 5.
Press embodiment 1 described condition test two samples to SO
2Reactivity, in air-flow, added water vapour during test.Get quantity of sample 1 and test, 0.22 H is arranged in air-flow during test
2O dividing potential drop, the total conversion that the result obtained are 111%, partly cause wherein may be since steam by the cause of absorption of sample.The 2nd sample be from sample 18, with this sample at 0.064H
2Test in the air-flow of O dividing potential drop, the total conversion that the result obtained is 64%.
Test specimen 1,10 and 11 under 700 ℃ to SO
2Reactivity.As embodiment 1, earlier sample is heated to 900 ℃ by the programming rate of 5 ℃/min, and then is cooled to 700 ℃ by the cooling rate of 5 ℃/min.Sample was kept under 700 ℃ 30 minutes, fed the SO of 5000ppm then in the air-flow
2Totally 1 hour.Under these conditions, sample 1,10 and 11 conversion ratio are respectively 61%, 38% and 54%.
Utilize the method for embodiment 1, a kind of hectorite from California, USA San Bernardino County is carried out purifying.Method according to embodiment 1 prepares a kind of 1: 1 CaCO
3: the HECTABRITE DP composition.With dialysis the chlorion of surplus is removed.Test the composition that obtained to SO according to embodiment 1 described method
2Reactivity.After reaction 1 hour, the total conversion that this sample obtained is 85%, and reaches 24% in the 1st minute that reacts after beginning.
The result of each time embodiment
The sample that table 1 has been listed embodiment 1 to 29 all each time embodiment reaction after 1 minute and after 1 hour to SO
2The data that absorb.If all being the programming rates by 5 ℃/min, not special statement, all samples be heated to 900 ℃.With temperature maintenance 900 ℃ following 30 minutes, and then feed the SO of 5000ppm in the air-flow
2Totally 1 hour.Stopping to feed SO
2After sample was kept under 900 ℃ 30 minutes again, to test the heat endurance of these products.
Table 1
Use alkaline matter/clay composition to test them and remove SO
2Activity
Implement alkaline matter/reaction temperature conversion ratio
a
Example clay proportional band ℃ 1min 60min indicates
1 CaCO
3/Na- 1∶1 900 19 88
Montmorillonite
2??3∶1??900??14??100
3??0.33∶1??900??36??100
7??1∶1??900??13??52
Do not wash at 8 0.33: 1 900 15 59
9b did not wash in 1: 1 900 6 42
10 1: 1 900 5 43 mix FeCl
3
11 1: 1 900 13 88 mix Fe(NO
3)
3
12 Ca（OH）
2/ 1∶1 900 C 5
The Na-montmorillonite
13??3∶1??900??C??1
14 calcium formates/Na-1: 1 900 24 60
Montmorillonite
15??3∶1??900??14??94
16 calcium acetates/Na-1: 1 900 25 52
Montmorillonite
17??1.5∶1??900??4??36
18??0.33∶1??900??8??15
19??5∶1??900??26??78
20 NaHCO
3/Na- 1∶2 900 11 33
Montmorillonite
21??1∶2??500??16??46
1: 2 100 active
22 CaCO
3/Na- 1∶1 500 C C
Montmorillonite 11
23??1∶1??700??4??11
24??1∶1??800??12??75
25 1∶1 800 34 111 PH
2O 0.22
26 1∶1 800 17 64 PH
2O 0.064
900 ℃ of 27 1: 1 700 7 61 preheatings
900 ℃ of 28 1: 1 700 12 38 preheatings
900 ℃ of 29 1: 1 700 9 54 preheatings
30 CaCO
3/N
+ a- 1∶1 900 24 85
Hectorite
4 CaCO
3/ 1∶1 900 14 98
Bentone
5 CaCO
3/ 1∶1 900 26 78
Nontron
6 CaCO
3/ 1∶1 900 11 90
The fluorine hectorite
CaCO
3Precipitate 900 9 82
B.100 ℃ dry down.
C. do not have significantly and absorb.
The present invention at length lists relevant embodiment, obviously, according to these disclosed contents, for the person of ordinary skill of the art, can on basis of the present invention, make a lot of variations now, but these variations still are included within the scope disclosed in this invention, and therefore, the present invention only is subjected to the qualification of following appended claims.
Claims (18)
1, a kind ofly can be used for from air-flow, removing SO
XThe preparation of compositions method, this method comprises:
(a) provide the suspension of a kind of montmorillonitic clay in water;
(b) a kind of a kind of alkali domestic animal compound that is selected from alkaline metal salt, alkali salt and alkali is added in the above-mentioned slurry;
(c) with this suspension drying to obtain a kind of composition, wherein, when said composition was heated, the alkali compounds that the sulfur dioxide in the gas is combined in the thing was removed.
2, method as claimed in claim 1, wherein the weight ratio of salt pair clay is between about 1: 3 to 5: 1.
3, a kind ofly can from air-flow, remove SO
xThe preparation of compositions method, this method comprises the following steps:
(a) provide the suspension of a kind of montmorillonitic clay in water;
(b) a certain amount of sodium carbonate is dissolved in the above-mentioned slurry;
(c) add a kind of alkali salt of solubility, its addition equals it and the stoichiometric amount of sodium carbonate reaction, precipitates so that form a kind of alkaline earth metal carbonate in the suspension of clay; And
(d) with this suspension drying to obtain a kind of composition, when said composition was heated, it can be SO
xFrom air-flow, remove.
4, method as claimed in claim 3 wherein reclaims alkaline earth metal carbonate and clay by the centrifugal drying dehydration.
5, method as claimed in claim 4, wherein said by the isolated alkaline earth metal carbonate of centrifugal process with clay is washed and used the air drying.
6, method as claimed in claim 4 wherein under temperature reaches about 100 ℃ condition, is carried out the air drying with said alkaline earth metal carbonate and the clay that goes out by centrifugation.
7, method as claimed in claim 3, alkaline earth metal carbonate wherein and clay and be selected from iron chloride and ferric nitrate in a kind of molysite mix.
8, method as claimed in claim 3, montmorillonitic clay wherein are to be selected from montmorillonite, fluorine hectorite, bentonite, chlorite, hectorite, saponite and beidellite.
9, method as claimed in claim 3, alkaline-earth metal wherein are to be selected from magnesium and calcium.
10, a kind ofly can from air-flow, remove SO
xThe preparation of compositions method, this method comprises the steps:
(a) provide the suspension of a kind of montmorillonitic clay in water;
(b) a kind of alkali compounds in the precursor that is selected from alkaline matter, alkaline matter is added in the slurry; And
(c) with this suspension at air drying, wherein, when said composition is heated, SO
xFrom air-flow, removed.
11, as the method for claim 10, wherein the precursor of said alkaline matter is selected from NaHCO
3, Na
2CO
3, calcium acetate and calcium formate.
12, as the method for claim 10, alkali metal compound wherein to the ratio of clay between about 1: 3 to 5: 1.
13, from admixture of gas, remove SO
xA kind of method, this method comprises:
(a) provide a kind of drying composite that is scattered in the alkali compounds in the montmorillonitic clay, said alkali compounds is selected from alkali metal salt, alkali salt and alkaline matter, and
(b) containing SO
xThe condition that exists of gas under this mixture of heating to remove SO
x
14, as the method for claim 13, wherein said mixture contains a kind ofly can make SO
2Be oxidized to SO
3Molysite.
15, a kind of composition when said composition is heated, can be used to remove SO from air-flow
x; Said composition contains the following material with the admixture form:
(a) be selected from a kind of alkali compounds in alkali metal salt, alkali salt and the alkaline matter; And
(b) a kind of montmorillonitic clay wherein is added to alkali compounds in a kind of water slurry of clay, is dried then to form described composition.
16, as the composition of claim 15, admixture wherein comprises a kind of molysite, and when said composition was heated, said molysite can be SO
2Be oxidized to SO
3
17, as the composition of claim 15, the granularity of its medium clay soil is less than about 2 μ m.
18, as the composition of claim 15, clay wherein is by carrying out sedimentation to obtain the clay that a kind of granularity is 2 μ m in water.
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|---|---|---|---|
| CN 91104912 CN1031106C (en) | 1991-07-16 | 1991-07-16 | Composite clay materials for removal of SOx from gas streams |
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|---|---|---|---|
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| CN115400577A (en) * | 2022-09-01 | 2022-11-29 | 宁波大学 | Desulfurization method for mixed pulping of steel slag, clay and limestone and mixed desulfurizer |
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| CN115400577A (en) * | 2022-09-01 | 2022-11-29 | 宁波大学 | Desulfurization method for mixed pulping of steel slag, clay and limestone and mixed desulfurizer |
| CN115400577B (en) * | 2022-09-01 | 2024-04-12 | 宁波大学 | Method for pulping and desulfurizing steel slag, clay and limestone by mixing and mixed desulfurizing agent |
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