CN102836636B - Desulfurization denitration composition, preparation method and application thereof - Google Patents
Desulfurization denitration composition, preparation method and application thereof Download PDFInfo
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- CN102836636B CN102836636B CN201210332616.XA CN201210332616A CN102836636B CN 102836636 B CN102836636 B CN 102836636B CN 201210332616 A CN201210332616 A CN 201210332616A CN 102836636 B CN102836636 B CN 102836636B
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- desulfurization denitration
- flue gas
- denitration composition
- desulfurization
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 122
- 230000023556 desulfurization Effects 0.000 title claims abstract description 108
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000003546 flue gas Substances 0.000 claims abstract description 76
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 54
- 229910052760 oxygen Inorganic materials 0.000 claims description 54
- 239000001301 oxygen Substances 0.000 claims description 54
- 239000002002 slurry Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 8
- 230000001360 synchronised effect Effects 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- 238000004537 pulping Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 55
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 21
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 2
- 239000012286 potassium permanganate Substances 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 114
- 239000003463 adsorbent Substances 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910044991 metal oxide Inorganic materials 0.000 description 15
- 150000004706 metal oxides Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 230000003009 desulfurizing effect Effects 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000002250 absorbent Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 241000270666 Testudines Species 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229940075933 dithionate Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000026676 system process Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- -1 and after process Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a desulfurization denitration composition, a preparation method and application thereof. The desulfurization denitration composition comprises magnesia (MgO), silica (SiO2), calcium oxide (CaO), ferric oxide (Fe2O3), alumina (Al2O3), copper oxide (CuO), manganese dioxide (MnO2), and optional strong oxidant potassium permanganate (KMnO4). The inventive composition can synchronously remove NOx during flue gas desulfurization process, and improve desulfurization denitration efficiency.
Description
Technical field
The present invention relates to a kind of desulfurization denitration composition, preparation method and its usage, what produce after being particularly useful for industrial coal burning contains SO
2, NO
xdeng composition, the preparation method and its usage of the synchronized desulfuring and denitrifying of composition flue gas.
Background technology
Air is the most basic vital principle that the mankind depend on for existence, but produces sulfur dioxide (SO when utilizing the fossil energy such as coal, oil work by combustion
2), oxynitrides (NO
x) and particle, SO
2and NO
xbeing topmost two kinds of atmosphere pollutions, is the main cause place of causing acid rain.NO simultaneously
xalso be a kind of material causing the environmental problem such as depletion of the ozone layer and photochemical fog.These have become the key factor of restriction social and economic development, cause the extensive concern of the people of various countries.
Various countries scientist and commercial undertaking are devoted to the technical research of desulphurization denitration always.The whole world research and development sulfur method have hundreds of more than, method of denitration also has tens kinds more than, and these methods generally can be divided into dry method and wet method by technique.Absorption method can be divided into by the utilization state of product and abandon method; Physical Absorption and chemical absorbing can be divided into by absorption pattern.
Technical scheme practical, feasible, economic in existing desulfur technology has more than the ten kind technology such as spray absorbent/humidification activation sulfur removal technology in vulcanization bed combustion technology, stove, wet type lime/lime stone sulfur removal technology, seawater desulfurizing process, spray dry desulfurization technique, adsorbent reactivation sulfur removal technology, flue spray absorbent sulfur removal technology, Electron Beam Irradiation.
Existing denitration technology is mainly divided into two large classes: Combustion Process Control and burning post processing.Burning post processing comprises again: SNCR method (SNCR), selective catalytic reduction (SCR), thermal decomposition method, catalytic decomposition, gas scrubbing method, plasma Treatment process, liquid absorption method, the process of oxidative absorption method etc.
Current global desulphurization and denitration adopts associated form to carry out substantially, namely desulfurization and denitration separate and process, or the outer denitration of desulfuration in furnace and stove is combined, or wet type desulfurizing and Dry denitration are combined, although the method for this association type can reach the requirement of environment protection emission in desulphurization and denitration effect, but infrastructure investment is high, system footprint area is large, and operation is complicated, and operation and maintenance cost is very high, be exactly in developed country, general enterprises does not bear so high operation and maintenance cost yet.
Through long research and development, successfully develop several flue gas and desulfurizing and denitrifying technology.As the active carbon Absorption Desulfurization denitration synchronous process of Japanese invention, active carbon absorption technique utilizes active carbon to have larger specific area to carry out flue gas and desulfurizing and denitrifying.SO
2be the micro-porous adsorption effect by active carbon, be stored in the micropore of active carbon, then by hot recycling, generate the SO of high concentration
2gas, forms the byproducts such as high-purity sulphur, the concentrated sulfuric acid through reforming unit; NO
xenter air through the catalytic action generation water of active carbon and nitrogen under the condition of ammonification, the advantage of this method is non-secondary pollution, desulfuration efficiency can reach about 90%, shortcoming be active carbon kind very little, the high operation expense that causes of purchase cost is too high, although denitration efficiency can reach about 65% simultaneously, the curved property change of the decay denitration efficiency along with active carbon activity, stable not.
The same period Germany, the state such as Israel also invented CuO simultaneous SO_2 and NO removal technique.The method utilizes Al
2o
3or SiO
2as carrier, prepare adsorbent by impregnating method, in the temperature range of 300 ~ 450 DEG C, with the SO in flue gas
2react, the CuSO of formation
4with CuO to SCR method reductive NO
xthere is very high catalytic activity.Absorb saturated CuSO
4be conveyed to regeneration, regenerative process generally uses CH
4gas is to CuSO
4reduce, the SO of release
2can relieving haperacidity, reduce the metallic copper or Cu that obtain
2s is again with flue gas or air oxidation.The CuO generated is again for absorbing reduction process.The advantage of the method does not produce secondary pollution, can output sulphur or sulfuric acid by-products, and after process, flue gas is without the need to heating, reusable edible.This technique can reach the SO of more than 90%
2removal efficiency and 75% ~ 80% NO
xremoval efficiency.Shortcoming needs a large amount of adsorbent, and equipment is huge, and investment is large, and operation energy consumption is large.And along with the raising of various countries' environmental protection standard, the desulfuration efficiency of about 80% can not meet the new demand of current each major industrial country environmental protection standard.
China have developed wet type complex compound absorption technique with Chinese characteristics, and namely wet type FGD adds metal chelate technique.In alkalescence or neutral solution, add ferrous ion form amino light sour ferrous huge legendary turtle compound, as Fe (FDTA) and Fe (NTA).This kind of huge legendary turtle compound absorbs NO and forms nitrous phthalein industry iron huge legendary turtle compound, and the NO of coordination can with the SO dissolved
2and O
2reaction generates N
2, N
2, dithionate, sulfate, various N-S compound and ferric iron huge legendary turtle compound.This technique need by removing dithionate, sulfate and N-S compound and ferric iron huge legendary turtle compound is reduced into ferrous huge legendary turtle compound and makes regeneration of absorption solution from absorbing liquid.Wet type complex compound absorption technique can remove SO simultaneously
2and NO
x, but still under test at present.The major obstacle affecting its commercial Application is that the loss of huge legendary turtle compound in course of reaction and metal chelate regeneration difficulty, utilization rate are low, causes operating cost high.
Due at present external associating or the shortcoming such as integration desulfurization denitration technology exists flow process complexity, floor space is large, operating cost is high, single efficiency height associated efficiency is low, therefore development and operation is simple, operating cost is low, efficiency is high, the simultaneous SO_2 and NO removal technology of system stability becomes one of important directions of purifying coal-fired flue gas technical research.
Summary of the invention
In order to overcome above-mentioned defect of the prior art, present inventor conducts in-depth research.
The present invention's object is to provide a kind of desulfurization denitration composition, and this desulfurization denitration composition has good synchronized desulfuring and denitration effect.
Another object of the present invention is the application providing a kind of desulfurization denitration composition, and it is for flue gas desulfurization course simultaneous removing NO
x, the consumption of desulfurization denitration composition is little, and denitrification efficiency is high, stable.
Specifically, the application provides following technical scheme to realize above-mentioned purpose.
The invention provides a kind of desulfurization denitration composition, comprise following component: MgO, SiO
2, CaO, Fe
2o
3, Al
2o
3, CuO and MnO
2.
According to desulfurization denitration composition of the present invention, preferably, also KMnO is comprised in described desulfurization denitration composition
4.
According to desulfurization denitration composition of the present invention, preferably, described desulfurization denitration composition comprises following component:
MgO 40 ~ 50 weight portion,
CaO 0.1 ~ 1 weight portion,
SiO
210 ~ 20 weight portions,
Fe
2o
35 ~ 20 weight portions,
Al
2o
35 ~ 10 weight portions,
CuO 1 ~ 10 weight portion,
MnO
21 ~ 4 weight portion.
According to desulfurization denitration composition of the present invention, preferably, the KMnO of 1 ~ 10 weight portion is also comprised in desulfurization denitration composition
4.
According to desulfurization denitration composition of the present invention, preferably, the active oxidation content of magnesium in described MgO is more than 60wt%.
The present invention also provides the preparation method of above-mentioned desulfurization denitration composition, said components is pulverized and forms powder, then mix; The particle size range of described powder is 100 ~ 5000 orders.
The present invention also provides the purposes of above-mentioned desulfurization denitration composition, for the synchronized desulfuring and denitrifying of flue gas.
According to purposes of the present invention, preferably, comprise the steps:
<1> regulates the step of oxygen content in flue gas;
<2> pulping stage: for subsequent use after described desulfurization denitration composition is made slurry;
<3> desulphurization denitration step: will the flue gas after oxygen content and described slurry contact be have adjusted.
According to purposes of the present invention, preferably, in flue gas, oxygen content controls at 8 ~ 15vt%.
According to purposes of the present invention, preferably, regulate the step of oxygen content in flue gas to be realized by oxygen adjusting device, described oxygen adjusting device is arranged on flue gas section before flue gas enters desulphurization denitration equipment, and in the flue of described flue gas section, temperature is 125 ~ 145 DEG C.
Desulfurization denitration composition of the present invention has simultaneously to SO in flue gas
2and NO
xadsorption function, thus improve the efficiency of desulphurization denitration, under the mating reaction of both desulfurization denitration composition and oxygen adjusting device, synthesis desulfurating efficiency reach more than 90%, denitration efficiency reaches more than 50%.
Further, by inventive desulfurization denitration composition, desulphurization and denitration system operation cost is lower, and operating cost is 2/3 of conventional calcium method desulphurization system, 2/3 of common denitrating system; Stable; Removal efficiency, simple operation, operation expense etc. are all better than other process.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
In the present invention, " vt% " represents percentage by volume, and this is known in the art.
In the present invention, " order " represents the unit of fineness, is known in the art.
< desulfurization denitration composition >
The invention provides a kind of desulfurization denitration composition, described desulfurization denitration composition comprises following component: MgO, SiO
2, CaO, Fe
2o
3, Al
2o
3, CuO and MnO
2.
Metal oxide can react to form sulfate with the sulfur dioxide in flue gas; When sulfur dioxide and water react form sulfurous acid time, then metal oxide can react to form sulphite with sulfurous acid; When sulfur dioxide, sulfurous acid are oxidized to sulfur trioxide, sulfuric acid, metal oxide can also form sulfate with sulfur trioxide, sulfuric acid reaction.Meanwhile, when nitric oxide generates nitrogen dioxide because of catalytic adsorption effect, nitrogen dioxide and water generate nitric acid, when nitric acid and metal oxide generation chemical reaction, generate nitrate.
Preferably, in described desulfurization denitration composition, be 100 parts by weight with desulfurization denitration composition gross weight, comprise:
MgO is 40 ~ 50 weight portions, is preferably 45 ~ 48 weight portions;
CaO is 0.1 ~ 1 weight portion, is preferably 0.5 ~ 0.8 weight portion;
SiO
2be 10 ~ 20 weight portions, be preferably 12 ~ 15 weight portions;
Fe
2o
3be 5 ~ 20 weight portions, be preferably 6 ~ 15 weight portions;
Al
2o
3be 5 ~ 10 weight portions, be preferably 6 ~ 8 weight portions;
CuO is 1 ~ 10 weight portion, is preferably 5 ~ 8 weight portions;
MnO
2be 1 ~ 4 weight portion, be preferably 1.5 ~ 2 weight portions.
In addition, preferably, above-mentioned weight portion is 100 parts by weight with desulfurization denitration composition gross weight.
Preferably, the active oxidation content of magnesium in described MgO is more than 60wt%, preferably 60 ~ 80wt%, more preferred 65 ~ 70wt%.
Preferably, also KMnO is comprised in described desulfurization denitration composition
4.Described KMnO
4for oxidant, tetravalence sulphur can be oxidized to sexavalence sulphur by oxidant, such as, is sulfur trioxide, nitric oxide oxygen is converted into nitrogen dioxide by the oxidizing sulfur dioxide in flue gas.Can to enhance productivity like this and to the metal oxide in above-mentioned desulfurization denitration composition and SO
2, NO
xetc. providing oxygen atom (O) endlessly when reacting.
KMnO in described desulfurization denitration composition
4consumption is 1 ~ 10 weight portion, preferably 1 ~ 8 weight portion, more preferably 1 ~ 6, more preferably 1 ~ 4, more preferred 1 ~ 2 weight portion.
In addition, preferably, above-mentioned weight portion is 100 parts by weight with desulfurization denitration composition gross weight.
the preparation method > of < desulfurization denitration composition
Desulfurization denitration composition of the present invention can be Powdered, graininess, bulk etc.Desulfurization denitration composition of the present invention can be obtained by the method for this area routine.Such as, said components is pulverized and forms powder, then they are mixed.In use desulfurization denitration composition process of the present invention, usually need by adding water to form slurry.In order to improve dissolved efficiency, desulfurization denitration composition of the present invention is preferably Powdered.The particle size range of desulfurization denitration composition of the present invention is 100 ~ 5000 orders, is preferably 110 ~ 2000 orders, is more preferably 120 ~ 150 orders.
the purposes > of < desulfurization denitration composition
Present invention also offers the purposes of described desulfurization denitration composition, it is for the synchronized desulfuring and denitrifying of flue gas; Described flue gas can be any flue gas comprising the compositions such as sulfur dioxide, nitric oxide and/or nitrogen dioxide.Described desulfurization denitration composition is for removing the SO in flue gas
2and NO
x(such as NO, NO
2deng); Described desulfurization denitration composition can use any flue gas desulfurization technique, such as desulfurization by dry method, Wet Flue Gas Desulfurization Technique, and can in sweetening process simultaneous removing NO
x.
According to purposes of the present invention, preferably, for carrying out flue gas desulfurization course simultaneous removing NO in wet desulfuration tower
x.
According to purposes of the present invention, preferably, comprise the following steps:
(A) pulping stage: above-mentioned desulfurization denitration composition is made slurry.
Because described desulfurization denitration composition is Powdered, therefore, the present invention need carry out pulping stage.
Preferably, add water desulfurization denitration composition slurrying, forms metal oxide based sizing further after preferred slaking.
(B) desulphurization denitration step: by flue gas and slurry contact, to remove the SO in flue gas
2, NO
x.
The mode of contact is not particularly limited, and can be the mode sprayed by described slurry, or flue gas be passed into the mode in slurry; The more preferably mode of slurry spray.
The not special restriction of the desulphurization denitration equipment used in described desulphurization denitration step, as long as can realize the contact of desulfurization denitration composition and flue gas, is preferably the conventional calcium method of wet type or magnesium processes desulfurizing tower used.
According to purposes of the present invention, preferably, the oxygen content in described flue gas is regulated; Preferably, the oxygen content in flue gas controls, at 8 ~ 15vt%, to be more preferably 10 ~ 12vt%.Because adsorbent is to NO
2absorption be better than absorption to NO, therefore promote that NO is oxidized to NO as far as possible
2, be conducive to oxide-base adsorbent to NO
xremoval.In the present invention, the strong oxygen section of the flue gas in system process of the nitric oxide in flue gas and oxygen reaction, be converted into NO
2, transformation efficiency is about 30%, and this technical process will reduce the pressure that in tower below, chemistry and physical absorption reacts, and raising denitration efficiency is more than 20%.
According to purposes of the present invention, preferably, comprise the following steps:
<1> regulates the step of oxygen content in flue gas;
<2> pulping stage: for subsequent use after desulfurization denitration composition being made slurry;
<3> desulphurization denitration step: will the flue gas after oxygen content and described slurry contact be have adjusted.
Preferably, in flue gas, oxygen content controls at 8 ~ 15vt%.
Preferably, the step of oxygen content in flue gas is regulated to carry out before flue gas enters desulphurization denitration equipment end.
Preferably, the step of oxygen content in flue gas is regulated to be realized by oxygen adjusting device.
Preferably, described oxygen adjusting device be arranged on flue gas enter desulphurization denitration equipment (such as desulfurizing tower) end before flue in.
Preferably, be 125 ~ 145 DEG C in temperature, be preferably the flue gas section of 130 ~ 140 DEG C, regulate oxygen content in flue gas.Namely described oxygen adjusting device is arranged on temperature in flue that flue gas enters before desulphurization denitration equipment (such as desulfurizing tower) end and is 125 ~ 145 DEG C, is preferably in the flue gas section of 130 ~ 140 DEG C.
Present inventor finds in practice process, NO, NO
2and there is the phenomenon of reacting acceleration or deceleration between oxygen under certain temperature environment, in the present invention, when hastening phenomenon occurs, NO can generate NO at short notice with oxygen
2, because the inert gas that NO is namely usually alleged, difficult and other material reacts, so in denitrating system design process, how to improve NO as far as possible and generates NO
2ratio be the key whether denitration efficiency reaches setting value, when flue-gas temperature is at 125 ~ 145 DEG C, the reaction that NO and oxygen occur is the fastest, otherwise higher than 145 DEG C or lower than reaction speed when 125 DEG C start decay, so, the present invention selected suitable temperature section before flue gas enters desulfurizing tower end, installed Control for Oxygen Content and adjusting device additional, allowed the NO in flue gas be adsorbed onto enough reactions at this temperature end as far as possible and generated NO
2oxygen.
According to purposes of the present invention, preferably, comprise the following steps:
A. enter desulfurizing tower front end at flue gas and arrange described oxygen adjusting device, in control flue gas, oxygen content is between 8 ~ 15vt%;
B. above-mentioned desulfurization denitration composition is sent into medicine storing pot, add water in medicine storing pot for subsequent use after being modulated into slurry;
C. by circulating pump, slurry is blasted desulfurizing tower, in tower, complete desulphurization denitration process.
According to purposes of the present invention, preferably, described oxygen adjusting device comprises aeration system, when oxygen content in flue gas is lower than 8vt%, automatically opens aeration system and carries out oxygenation, stop when oxygen content reaches 15vt%.
Preferably, described aeration system is general industry oxygen generating plant, such as pressure swing type adsorption oxygen-preparation equipment or deep cooling oxygen generating plant.
< desulfurization denitration composition mechanism >
Denitration:
(1) NO arrives the surface of desulfurization denitration composition with flue gas, and NO changes into NO under the catalytic action of metal oxide active position simultaneously
2, accelerate it and remove.
(2) NO
2arrive adsorbent (component such as the magnesia namely in desulfurization denitration composition, lower with) surface, a part of adsorb by surface;
(3) by NO that adsorbent surface adsorbs
2mgO on gas, hydrone and surface reacts and generates nitrite, to react generation nitrate with oxygen in flue gas; Part NO
2absorbent interior is entered by adsorbent hole;
(4) NO reacts at absorbent interior and MgO, generates nitrite, and part nitrite and the oxygen entering hole react generation nitrate.
Because adsorbent is to NO
2absorption be better than absorption to NO, therefore, promote that NO is oxidized to NO as far as possible
2, be conducive to magnesium oxide-based adsorbent to NO
xremoval.In the present invention, the strong oxygen section of the flue gas of the nitric oxide in flue gas in system process and oxygen reaction, be converted into NO
2, transformation efficiency is about 15%, and this technical process will reduce the pressure that in tower below, chemistry and physical absorption reacts, and raising denitration efficiency is more than 10%.
The fundamental reaction principle (oxidation-catalysis) of denitration
NO
2+ H
2o+ desulfurization denitration composition (being called for short ESE)+catalytic oxidation → HNO
2+ catalytic oxidation →
Stable compound+O
2→ HNO
3+ ESE
Nitric oxide (NO) is insoluble in water, needs first oxidized, could be absorbed in aqueous.
Work as NO
xbe transformed into nitrous acid (HNO
2) time, desulfurization denitration composition (ESE) is combined into stable comple with it, and they are become nitric acid by continued oxidation.
HNO
2+ESE＝ESE·HNO
2
2ESE·HNO
2+O
2＝2ESE+2HNO
3
Desulfurization denitration composition of the present invention is combined with oxygen content adjusting device, can realize above-mentioned reaction.
Desulfurization:
(1) SO
2with flue gas arrive adsorbent surface, a part adsorb by surface;
(2) NO in the active sites of reactive metal oxides intermixture and flue gas
x, also promote SO in flue gas
2be combined to SO with oxygen
3conversion.
(3) by SO that adsorbent surface adsorbs
2reactive metal oxide on gas, hydrone and surface generates sulphite, to react generation sulfate with oxygen in flue gas; Part SO
2absorbent interior is entered by adsorbent hole;
(4) SO
2react at absorbent interior and metal oxide, generate sulphite, part sulphite and the oxygen entering hole react generation sulfate.
The fundamental reaction principle of desulfurization:
SO
2+ H
2o+ desulfurization denitration composition (being called for short ESE) → H
2sO
3+ ESE →
Stable compound+O
2→ H
2sO
4+ ESE
Work as SO
2be transformed into sulfurous acid (H
2sO
3) time, desulfurization denitration composition (ESE) is combined into stable comple with it, and they are become sulfuric acid by continued oxidation, and then functional group is separated with it.
H
2SO
3+ESE＝ESE·H
2SO
3
2ESE·H
2SO
3+O
2＝2ESE+2H
2SO
4
Desulfurization denitration composition of the present invention (ESE) achieves above-mentioned reaction preferably.
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1 ~ 3 basic experiment parameter sees the following form.
Table 1, basic technological parameters
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Desulfurizer inlet flue gas amount (operating mode) | Nm 3/h | 320000～720000 |
| 3 | Coal-fired sulfur | ％ | 0.8-1.2 |
| 4 | Desulfurizer inlet flue gas temperature | ℃ | 110-160 |
| 5 | Actual SO 2Content | Mg/Nm 3 | 1300～2000 |
| 6 | Actual NO XContent | Mg/Nm 3 | 300～450 |
| 7 | Design desulfurization degree | ％ | ≥90％ |
| 8 | Design denitration rate | ％ | ≥50％ |
embodiment 1
(1) modulation of desulfurization denitration composition:
According to following formula, each component is mixed, obtain desulfurization denitration composition.
(2) desulfurization denitration composition is utilized to remove SO
2, NO
xtechnique
1, slurrying:
The desulfurization denitration composition modulated is added water after slurrying, slaking and form the slurry that main component is containing metal oxide, and stay in slurry tank for subsequent use.
2, denitration:
(1) NO arrives the surface of desulfurization denitration composition with flue gas, and NO changes into NO under the catalytic action of metal oxide active position simultaneously
2, accelerate it and remove.
(2) NO
2arrive adsorbent (component such as the magnesia namely in desulfurization denitration composition, lower with) surface, a part of adsorb by surface;
(3) by NO that adsorbent surface adsorbs
2mgO on gas, hydrone and surface reacts and generates nitrite, to react generation nitrate with oxygen in flue gas; Part NO
2absorbent interior is entered by adsorbent hole;
(4) NO reacts at absorbent interior and MgO, generates nitrite, and part nitrite and the oxygen entering hole react generation nitrate.
3, desulfurization:
(1) SO
2with flue gas arrive adsorbent surface, a part adsorb by surface;
(2) NO in the active sites of reactive metal oxides intermixture and flue gas
x, also promote SO in flue gas
2be combined to SO with oxygen
3conversion.
(3) by SO that adsorbent surface adsorbs
2reactive metal oxide on gas, hydrone and surface generates sulphite, to react generation sulfate with oxygen in flue gas; Part SO
2absorbent interior is entered by adsorbent hole;
(4) SO
2react at absorbent interior and metal oxide, generate sulphite, part sulphite and the oxygen entering hole react generation sulfate.
Under these conditions, every experimental data sees table:
Table 2, sintering machine desulfuration facility toxic emission monitoring result
Desulfuration efficiency reaches 92.7%, and denitration efficiency reaches 64.3%.
Meanwhile, the consumption parameter of every consumption thing is as follows:
Every experimental data
| 1 | Power consumption | Degree | 260 |
| 2 | Water consumption | t/h | 30 |
| 3 | Desulfurization denitration composition consumption | kg/h | 860 |
Visible, the consumption of these three materials of water, electricity, desulfurizing agent is all lower than conventional desulfurization system.
embodiment 2
According to following formula, each component is mixed, obtain desulfurization denitration composition.
Embodiment 2, compared to embodiment 1, reduces content of MgO 5 weight portion, reduces MnO
22 weight portions, increase SiO
2, Fe
2o
3weight portion 5 parts, increases KMnO
42 parts, other condition is constant, and technical process is also identical with embodiment 1, obtains following parameter list:
Table 3, sintering machine desulfuration facility toxic emission monitoring result
Desulfuration efficiency 93.4%, denitration efficiency 55%.
Meanwhile, the consumption parameter of every consumption thing is as follows:
Every experimental data
| 1 | Power consumption | Degree | 260 |
| 2 | Water consumption | t/h | 30 |
| 3 | Desulfurization denitration composition consumption | kg/h | 860 |
The consumption of these three materials of water, electricity, desulfurizing agent is consistent with embodiment 1, and desulfuration efficiency has fluctuation, and denitration efficiency has decline by a relatively large margin.
embodiment 3
According to following formula, each component is mixed, obtain desulfurization denitration composition.
Embodiment 3, compared to embodiment 2, reduces content of MgO 5 weight portion, respectively reduces SiO
2, Fe
2o
3weight portion 5 parts (namely consumption is consistent with embodiment 1), increases MnO
22 weight portions, increase KMnO
48 parts, other condition is constant, and technical process is also identical with embodiment 1, obtains following parameter list:
Table 4, sintering machine desulfuration facility toxic emission monitoring result
Desulfuration efficiency reaches 93.5%, denitration efficiency 53.8%, and desulfuration efficiency reduces further than embodiment 2.
Meanwhile, the consumption parameter of every consumption thing is as follows:
Every experimental data
| 1 | Power consumption | Degree | 260 |
| 2 | Water consumption | t/h | 30 |
| 3 | Desulfurization denitration composition consumption | kg/h | 860 |
The consumption of these three materials of water, electricity, desulfurizing agent is all lower than conventional desulfurization system, but desulfuration efficiency does not have embodiment 2 good.But denitration efficiency reduces further than embodiment 2, desulfuration efficiency change is not obvious.
Can be found out by above case study on implementation, embodiment 2,3 denitration efficiency all declines to a great extent, but can meet current environmental protection standard requirement, so the desulfurization and denitrification integral method that the present invention proposes can solve the problem of the synchronous denitration of sweetening process.
In addition, present invention process process desulfurization denitration composition consumption is little, denitrification efficiency is high, operating cost lower than conventional desulfurization or denitrating system, there are larger economic advantages.
The present invention is not limited to above-mentioned embodiment, and when not deviating from flesh and blood of the present invention, any distortion that it may occur to persons skilled in the art that, improvement, replacement all fall into scope of the present invention.
Claims (9)
1. a purposes for desulfurization denitration composition, is characterized in that, described desulfurization denitration composition is used for the synchronized desulfuring and denitrifying of flue gas, comprises the steps:
<1> regulates the step of oxygen content in flue gas,
<2> pulping stage: for subsequent use after described desulfurization denitration composition is made slurry,
<3> desulphurization denitration step: will the flue gas after oxygen content and described slurry contact be have adjusted;
Wherein, in flue gas, oxygen content controls at 10 ~ 12vt%; Regulate the step of oxygen content in flue gas to be realized by oxygen adjusting device, described oxygen adjusting device is arranged on flue gas and enters flue gas section before desulphurization denitration equipment, and in the flue of described flue gas section, temperature is 125 ~ 145 DEG C;
In described desulfurization denitration composition, be 100 parts by weight with desulfurization denitration composition gross weight, comprise following component:
Active oxidation content of magnesium in described MgO is more than 60wt%;
Described desulfurization denitration composition is Powdered, and particle size range is 100 ~ 150 orders.
2. the purposes of desulfurization denitration composition according to claim 1, is characterized in that, also comprises the KMnO of 1 ~ 10 weight portion in desulfurization denitration composition
4.
3. the purposes of desulfurization denitration composition according to claim 1, is characterized in that, in described desulfurization denitration composition, is 100 parts by weight with desulfurization denitration composition gross weight, comprises following component:
4. the purposes of desulfurization denitration composition according to claim 1 and 2, is characterized in that, the active oxidation content of magnesium in described MgO is 60 ~ 80wt%.
5. the purposes of desulfurization denitration composition according to claim 4, is characterized in that, the active oxidation content of magnesium in described MgO is 65 ~ 70wt%.
6. the purposes of desulfurization denitration composition according to claim 2, is characterized in that, also comprises the KMnO of 1 ~ 8 weight portion in desulfurization denitration composition
4.
7. the purposes of desulfurization denitration composition according to claim 6, is characterized in that, also comprises the KMnO of 1 ~ 4 weight portion in desulfurization denitration composition
4.
8. the purposes of desulfurization denitration composition according to claim 1 and 2, is characterized in that, described oxygen adjusting device comprises aeration system.
9. the purposes of desulfurization denitration composition according to claim 8, is characterized in that, described aeration system is pressure swing type adsorption oxygen-preparation equipment or deep cooling oxygen generating plant.
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| CN104529205B (en) * | 2014-12-03 | 2017-09-01 | 中晶环境科技股份有限公司 | cement production device and method |
| CN104477952B (en) | 2014-12-03 | 2016-04-06 | 北京中晶佳镁环境科技股份有限公司 | Fire coal boiler fume produces the apparatus and method of magnesium sulfate |
| CN104923273B (en) * | 2015-07-07 | 2017-04-26 | 威海诺尔动力设备高新技术有限公司 | Oil catalysis function material and preparation method thereof |
| CN107500581B (en) * | 2017-09-30 | 2019-08-23 | 中晶新材料有限公司 | Cementitious material and its manufacturing method |
| CN107694535A (en) * | 2017-10-30 | 2018-02-16 | 安徽铭能保温科技有限公司 | A kind of modified magnesia fume desulfurizing agent and preparation method thereof |
| CN107899588B (en) * | 2017-11-22 | 2020-04-17 | 江苏晶晶新材料有限公司 | Denitration catalyst and preparation method thereof |
| CN110385025A (en) * | 2019-08-27 | 2019-10-29 | 邓金营 | A kind of calcium base flue gas desulfurization and denitrification agent and preparation method thereof |
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| CN1040616A (en) * | 1988-08-25 | 1990-03-21 | 化学工业部西南化工研究院 | Compound desulfurizing agent of iron-manganese-magnesium system and preparation thereof |
| CN101352645A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Flue gas catalytic oxidation denitration technique and catalyst thereof |
| CN101632897A (en) * | 2009-08-07 | 2010-01-27 | 清华大学 | Method for simultaneously removing sulfur oxides and nitric oxides in flue gas |
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| CN1040616A (en) * | 1988-08-25 | 1990-03-21 | 化学工业部西南化工研究院 | Compound desulfurizing agent of iron-manganese-magnesium system and preparation thereof |
| CN101352645A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Flue gas catalytic oxidation denitration technique and catalyst thereof |
| CN101632897A (en) * | 2009-08-07 | 2010-01-27 | 清华大学 | Method for simultaneously removing sulfur oxides and nitric oxides in flue gas |
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