CN102836636A - Desulfurization denitration composition, preparation method and application thereof - Google Patents
Desulfurization denitration composition, preparation method and application thereof Download PDFInfo
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- CN102836636A CN102836636A CN201210332616XA CN201210332616A CN102836636A CN 102836636 A CN102836636 A CN 102836636A CN 201210332616X A CN201210332616X A CN 201210332616XA CN 201210332616 A CN201210332616 A CN 201210332616A CN 102836636 A CN102836636 A CN 102836636A
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- Prior art keywords
- desulphurization denitration
- flue gas
- composition
- denitration composition
- oxygen
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- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 35
- 230000023556 desulfurization Effects 0.000 title abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003546 flue gas Substances 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 53
- 229910052760 oxygen Inorganic materials 0.000 claims description 52
- 239000001301 oxygen Substances 0.000 claims description 52
- 239000002002 slurry Substances 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000001360 synchronised effect Effects 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 30
- 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
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 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 104
- 239000003463 adsorbent Substances 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 18
- 239000000395 magnesium oxide Substances 0.000 description 15
- 229910044991 metal oxide Inorganic materials 0.000 description 15
- 150000004706 metal oxides Chemical class 0.000 description 15
- 230000003009 desulfurizing effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 241000270666 Testudines Species 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001179 sorption measurement Methods 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
- 230000003197 catalytic effect Effects 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
- 238000002474 experimental method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007921 spray 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
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000005273 aeration Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 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
- 238000012827 research and development Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 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
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 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
- 230000007423 decrease Effects 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
- 230000006872 improvement Effects 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
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000243 solution Substances 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
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000007864 aqueous solution 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
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002950 deficient 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
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 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
- 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
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 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
- 238000005987 sulfurization reaction Methods 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
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
Landscapes
- Treating Waste Gases (AREA)
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 desulphurization denitration composition, preparation method and its usage, be particularly useful for the SO that contains of industrial coal burning back generation
2, NO
XComposition, preparation method and its usage Deng the synchronized desulfuring and denitrifying of composition flue gas.
Background technology
Atmosphere is the most basic vital principle that the mankind depend on for existence, yet produces sulfur dioxide (SO when utilizing fossil energy work by combustion such as coal, oil
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.While NO
XIt also is a kind of material that causes environmental problems such as depletion of the ozone layer and photochemical fog.The key factor that these have become the restriction social and economic development has caused the people of various countries' extensive concern.
Various countries scientist and commercial undertaking are devoted to the technical research of desulphurization denitration always.More than the sulfur method of whole world research and development was existing hundreds of, method of denitration also had tens kinds more than, and these methods generally can be divided into dry method and wet method by technology.Utilizing state can be divided into absorption method and abandon method by product; Can be divided into Physical Absorption and chemical absorbing by absorption pattern.
Practical in the existing desulfur technology, feasible, economic technical scheme has surplus spray absorbent/humidification activation sulfur removal technology in a sulfuration bed combustion technology, the stove, wet type lime/lime stone sulfur removal technology, seawater desulfurizing process, spray dry desulfurization technology, adsorbent reactivation sulfur removal technology, flue spray absorbent sulfur removal technology, the electron beam irradiation method etc. ten kinds technological.
Existing denitration technology mainly is divided into two big types: Combustion Process Control and burning post processing.The burning post processing comprises again: SNCR method (SNCR), selective catalytic reduction (SCR), thermal decomposition method, catalytic decomposition method, gas scrubbing method, plasma improvement technology, liquid absorption method, the processing of oxidation absorption process etc.
Present global desulfurization, denitration adopt associated form to carry out basically, i.e. desulfurization separates processing with denitration, or desulfuration in furnace and the outer denitration associating of stove; Or wet type desulfurizing and dry method denitration are linked together etc., though the method for this association type can reach the requirement of environment protection emission on desulfurization, denitration effect, infrastructure investment is high; System's floor space is big, and operation is complicated, and operation and maintenance cost is very high; Be exactly in developed country, general enterprise can bear so high operation and maintenance cost yet.
Through long research and development, successfully develop several kinds of flue gas and desulfurizing and denitrifying technology.Active carbon like day the present invention absorbs the desulphurization denitration synchronous process, and the active carbon absorption technique is to utilize active carbon to have bigger specific area to carry out flue gas and desulfurizing and denitrifying.SO
2Be micro-porous adsorption effect, be stored in the micropore of active carbon,, generate the SO of high concentration again through heat regeneration through active carbon
2Gas forms byproducts such as high-purity sulphur, the concentrated sulfuric acid through reforming unit; NO
xBe that catalytic action generation water and the nitrogen through active carbon enters atmosphere under the condition of ammonification; The advantage of this method is a non-secondary pollution, and desulfuration efficiency can reach about 90%, shortcoming be the active carbon kind very little; The purchase cost height causes operation expense too high; Though it is denitration efficiency can reach about 65% simultaneously,, stable inadequately along with the active curved property of the decay denitration efficiency variation of active carbon.
The same period, CuO desulfurizing and denitrifying process was simultaneously also invented by state such as Germany, Israel.This method is utilized Al
2O
3Or SiO
2As carrier, prepare adsorbent with the impregnating method, in 300～450 ℃ temperature range, with the SO in the flue gas
2React the CuSO of formation
4With CuO to SCR method reductive NO
xVery high catalytic activity is arranged.Absorb saturated CuSO
4By sent for regeneration, regenerative process is generally used CH
4Gas is to CuSO
4Reduce the SO of release
2But relieving haperacidity, metallic copper or Cu that reduction obtains
2S is again with flue gas or air oxidation.The CuO that generates is used for the absorption reducing process again.The advantage of this method is not produce secondary pollution, but output sulphur or sulfuric acid byproduct are handled the back flue gas and need not heating, reusable edible.This technology can reach the SO more than 90%
2Removal efficiency and 75%～80% NO
xRemoval efficiency.Shortcoming is to need a large amount of adsorbents, and equipment is huge, and investment is big, and operation energy consumption is big.And along with the raising of various countries' environmental protection standard, about 80% desulfuration efficiency can not satisfy the new demand of current each major industrial country's environmental protection standard.
China has developed wet type complex compound absorption technique with Chinese characteristics, and promptly wet type FGD adds metal chelate technology.In alkalescence or neutral solution, add ferrous ion and form amino light sour ferrous huge legendary turtle compound, like Fe (FDTA) and Fe (NTA).This type huge legendary turtle compound absorption of N O forms nitrous phthalein industry iron huge legendary turtle compound, the NO of coordination can with the SO of dissolving
2And O
2Reaction generates N
2, N
2, dithionate, sulfate, various N-S compound and ferric iron huge legendary turtle compound.This technology needs to be reduced into ferrous huge legendary turtle compound and to make regeneration of absorption solution through from absorption liquid, removing dithionate, sulfate and N-S compound and ferric iron huge legendary turtle compound.Wet type complex compound absorption technique can remove SO simultaneously
2And NO
X, but still under test at present.The major obstacle that influences its commercial Application is that loss and metal chelate regeneration difficulty, the utilization rate of huge legendary turtle compound in the course of reaction is low, causes operating cost high.
Because there are shortcomings such as flow process is complicated, floor space is big, operating cost is high, the high associating of single efficient efficient is low at present external associating or integration desulfurization denitration technology, so development and operation is simple, operating cost is low, efficient is high, the desulphurization denitration technology becomes one of important directions of coal-fired flue-gas purification techniques research and development system stability the time.
Summary of the invention
In order to overcome above-mentioned defective of the prior art, the present inventor furthers investigate.
Purpose of the present invention is to provide a kind of desulphurization denitration composition, and this desulphurization denitration composition has synchronized desulfuring and denitration effect preferably.
Another object of the present invention is to provide a kind of application of desulphurization denitration composition, and it is used for flue gas desulfurization course simultaneous removing NO
X, the consumption of desulphurization denitration composition is little, and denitrification efficiency is high, and is stable.
Particularly, the application provides following technical scheme to realize above-mentioned purpose.
The present invention provides a kind of desulphurization denitration composition, comprises following component: MgO, SiO
2, CaO, Fe
2O
3, Al
2O
3, CuO and MnO
2
According to desulphurization denitration composition of the present invention, preferably, also comprise KMnO in the described desulphurization denitration composition
4
According to desulphurization denitration composition of the present invention, preferably, said desulphurization denitration composition comprises following component:
MgO 40～50 weight portions,
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 desulphurization denitration composition of the present invention, preferably, also comprise the KMnO of 1～10 weight portion in the desulphurization denitration composition
4
According to desulphurization denitration composition of the present invention, preferably, the active oxidation content of magnesium among the said MgO is more than the 60wt%.
The present invention also provides above-mentioned desulphurization denitration preparation of compositions method, said components is pulverized formed powder, mixes then; The particle size range of said powder is 100～5000 orders.
The present invention also provides the purposes of above-mentioned desulphurization denitration composition, is used for the synchronized desulfuring and denitrifying of flue gas.
According to purposes of the present invention, preferably, comprise the steps:
< 1>step of oxygen content in the adjusting flue gas:
< 2>slurrying step: process behind the slurry said desulphurization denitration composition subsequent use;
< 3>desulphurization denitration step: will regulate the flue gas behind the oxygen content and contact with said slurry.
According to purposes of the present invention, preferably, oxygen content is controlled at 8～15vt% in the flue gas.
According to purposes of the present invention; Preferably; The step of regulating oxygen content in the flue gas realizes that through the oxygen adjusting device said oxygen adjusting device is arranged on flue gas and gets into desulphurization denitration equipment flue gas section before, and temperature is 125～145 ℃ in the flue of said flue gas section.
Desulphurization denitration composition of the present invention has simultaneously to SO in the flue gas
2And NO
XAdsorption function, thereby improve the efficient of desulphurization denitration, under desulphurization denitration composition and the two mating reaction of oxygen adjusting device, synthesis desulfurating efficient reaches more than 90%, denitration efficiency reaches more than 50%.
Have, through desulphurization denitration composition of the present invention, desulfurization, denitrating system operating cost are lower again, and operating cost is 2/3 of a conventional calcium method desulphurization system, 2/3 of common denitrating system; Stable; Removal efficiency, simple operation property, operation expense etc. all are superior to other process.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further described, but protection scope of the present invention is not limited to this.
In the present invention, " vt% " representes percentage by volume, and this is known in the art.
In the present invention, the unit of " order " expression fineness is known in the art.
<Desulphurization denitration Zu Hewu>
The present invention provides a kind of desulphurization denitration composition, and said desulphurization 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 sulfur in smoke; When sulfur dioxide and water reaction formation sulfurous acid, then metal oxide can react to form sulphite with sulfurous acid; When sulfur dioxide, sulfurous acid were oxidized to sulfur trioxide, sulfuric acid, metal oxide can also form sulfate with sulfur trioxide, sulfuric acid reaction.Simultaneously, when nitric oxide generated nitrogen dioxide because of the catalysis suction-operated, nitrogen dioxide and water generated nitric acid, when nitric acid and metal oxide generation chemical reaction, generated nitrate.
Preferably, in the said desulphurization denitration composition, be 100 weight portions in the desulphurization denitration composition total weight, comprising:
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 weight portions in the desulphurization denitration composition total weight.
Preferably, the active oxidation content of magnesium among the said MgO is more than the 60wt%, preferred 60～80wt%, preferred again 65～70wt%.
Preferably, also comprise KMnO in the said desulphurization denitration composition
4Said KMnO
4Be oxidant, oxidant can be oxidized to sexavalence sulphur with tetravalence sulphur, for example, sulfur in smoke is oxidized to sulfur trioxide, and nitric oxide oxygen is converted into nitrogen dioxide.Can enhance productivity like this and give metal oxide and the SO in the above-mentioned desulphurization denitration composition
2, NO
XOxygen atom (O) endlessly is provided when reacting.
KMnO in said desulphurization denitration composition
4Consumption is 1～10 weight portion, and preferred 1～8 weight portion is preferred again 1～6, and is preferred again 1～4, preferred again 1～2 weight portion.
In addition, preferably, above-mentioned weight portion is 100 weight portions in the desulphurization denitration composition total weight.
<Desulphurization denitration preparation of compositions Fang Fa>
Desulphurization denitration composition of the present invention can be Powdered, graininess, bulk etc.Desulphurization denitration composition of the present invention can obtain through the conventional method in this area.For example, said components pulverize is formed powder, they are mixed get final product then.In using desulphurization denitration composition process of the present invention, usually need be through adding water to form slurry.In order to improve dissolved efficiency, desulphurization denitration composition of the present invention is preferably Powdered.The particle size range of desulphurization denitration composition of the present invention is 100～5000 orders, is preferably 110～2000 orders, more preferably 120～150 orders.
<u ><The Yong Tu > of desulphurization denitration composition;</u>
The present invention also provides the purposes of said desulphurization denitration composition, and it is used for the synchronized desulfuring and denitrifying of flue gas; Said flue gas can be any flue gas that comprises compositions such as sulfur dioxide, nitric oxide and/or nitrogen dioxide.Said desulphurization denitration composition is used for removing the SO of flue gas
2And NO
X(for example NO, NO
2Deng); Said desulphurization denitration composition can use any flue gas desulfurization technique, desulfurization by dry method, wet desulphurization technology for example, and can be in sweetening process simultaneous removing NO
X
According to purposes of the present invention, preferably, be used for carrying out in the wet desulfuration tower flue gas desulfurization course simultaneous removing NO
X
According to purposes of the present invention, preferably, may further comprise the steps:
(A) slurrying step: above-mentioned desulphurization denitration composition is processed slurry.
Because said desulphurization denitration composition is Powdered, therefore, the present invention need carry out the slurrying step.
Preferably, the desulphurization denitration composition is added water slurrying, form the metal oxide based sizing after the further preferred slaking.
(B) desulphurization denitration step: flue gas is contacted with slurry, to remove the SO in the flue gas
2, NO
X
The mode of contact is not special to be limited, and can be with the mode of said slurry spray, perhaps flue gas is fed the mode in the slurry; The mode of slurry spray more preferably.
The desulphurization denitration equipment that uses in the said desulphurization denitration step does not have special restriction, as long as can realize contacting of desulphurization denitration composition and flue gas, is preferably conventional calcium method of wet type or the used desulfurizing tower of magnesium method.
According to purposes of the present invention, preferably, regulate the oxygen content in the said flue gas; Preferably, the oxygen content in the flue gas is controlled at 8～15vt%, more preferably 10～12vt%.Because adsorbent is to NO
2Absorption be better than absorption to NO, therefore promote that as far as possible NO is oxidized to NO
2, help the oxide-base adsorbent to NO
XRemoval.Among the present invention, strong oxygen section of the flue gas in system process of the nitric oxide in the flue gas and oxygen reaction are converted into NO
2, transformation efficiency is about 30%, this technical process will reduce the chemical pressure that reacts with physical absorption in the tower of back, improve denitration efficiency more than 20%.
According to purposes of the present invention, preferably, may further comprise the steps:
< 1>step of oxygen content in the adjusting flue gas;
< 2>slurrying step: process behind the slurry desulphurization denitration composition subsequent use;
< 3>desulphurization denitration step: will regulate the flue gas behind the oxygen content and contact with said slurry.
Preferably, oxygen content is controlled at 8～15vt% in the flue gas.
The step of preferably, regulating oxygen content in the flue gas was carried out before flue gas gets into the desulphurization denitration equipment end.
The step of preferably, regulating oxygen content in the flue gas realizes through the oxygen adjusting device.
Preferably, said oxygen adjusting device is arranged in flue gas entering desulphurization denitration equipment (for example desulfurizing tower) the end flue before.
Preferably, be 125～145 ℃ in temperature, be preferably 130～140 ℃ flue gas section, regulate oxygen content in the flue gas.Be that said oxygen adjusting device is arranged on flue gas and gets into that temperature is 125～145 ℃ in the flue before desulphurization denitration equipment (for example desulfurizing tower) end, is preferably in 130～140 ℃ the flue gas section.
The present inventor finds in practice process, NO, NO
2And the phenomenon that under certain temperature environment, exists reaction to quicken or slow down between the oxygen, in the present invention, when hastening phenomenon took place, NO can generate NO at short notice with oxygen
2, because the promptly common alleged inert gas of NO, difficult and other material reacts, so in the denitrating system design process, how to improve NO as far as possible and generate NO
2Ratio be the key whether denitration efficiency reaches setting value; When flue-gas temperature during at 125～145 ℃, the reaction that NO and oxygen take place is the fastest, on the contrary be higher than 145 ℃ or when being lower than 125 ℃ reaction speed begin decay; So; The present invention selected suitable temperature section before flue gas gets into the desulfurizing tower end, install Control for Oxygen Content and adjusting device additional, let NO in the 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, may further comprise the steps:
A. get into the desulfurizing tower front end at flue gas said oxygen adjusting device is set, oxygen content is between 8～15vt% in the control flue gas;
B. above-mentioned desulphurization denitration composition is sent into medicine storing pot, in medicine storing pot, add water and be modulated into behind the slurry subsequent use;
C. through circulating pump slurry is blasted desulfurizing tower, in tower, accomplish the desulphurization denitration process.
According to purposes of the present invention, preferably, said oxygen adjusting device comprises aeration system, and oxygen content is lower than 8vt% in flue gas, opens aeration system automatically and carries out oxygenation, when oxygen content reaches 15vt%, stops.
Preferably, described aeration system is that general industry is used oxygen generating plant, for example pressure swing type adsorption oxygen-preparation equipment or deep cooling oxygen generating plant.
<Desulphurization denitration composition Ji Li>
Denitration:
(1) NO is with the surface of flue gas arrival desulphurization denitration composition, and NO changes into NO under the catalytic action of metal oxide active sites simultaneously
2, quicken it and remove.
(2) NO
2Arrive adsorbent (being the components such as magnesia in the desulphurization denitration composition, down together) surface, a part is adsorbed by the surface;
(3) be adsorbed the NO of agent surface adsorption
2Gas, hydrone and lip-deep MgO reaction generate nitrite, with the generation nitrate that reacts of oxygen in the flue gas; Part NO
2It is inner to get into adsorbent through the adsorbent hole;
(4) NO reacts with MgO in that adsorbent is inner, generates nitrite, part nitrite and the oxygen that the gets into hole generation nitrate that reacts.
Because adsorbent is to NO
2Absorption be better than absorption to NO, therefore, promote that as far as possible NO is oxidized to NO
2, help magnesium oxide-based adsorbent to NO
XRemoval.Among the present invention, strong oxygen section of the flue gas of the nitric oxide in the flue gas in system process and oxygen reaction are converted into NO
2, transformation efficiency is about 15%, this technical process will reduce the chemical pressure that reacts with physical absorption in the tower of back, improve denitration efficiency more than 10%.
The fundamental reaction principle (oxidation-catalysis) of denitration
NO
2+ H
2O+ desulphurization denitration composition (being called for short ESE)+catalytic oxidation → HNO
2+ catalytic oxidation →
Stabilized complex+O
2→ HNO
3+ ESE
Nitric oxide (NO) is insoluble in water, needs elder generation oxidized, could in the aqueous solution, be absorbed.
Work as NO
XBe transformed into nitrous acid (HNO
2) time, desulphurization denitration composition (ESE) is combined into stable comple with it, and they are continued to be oxidized to nitric acid.
HNO
2+ESE＝ESE·HNO
2
2ESE·HNO
2+O
2＝2ESE+2HNO
3
Desulphurization denitration composition of the present invention combines with the oxygen content adjusting device, can realize above-mentioned reaction.
Desulfurization:
(1) SO
2Arrive adsorbent surface with flue gas, a part is adsorbed by the surface;
(2) active sites of reactive metal oxides intermixture and the NO in the flue gas
X, also promote SO in the flue gas
2Combine to SO with oxygen
3Conversion.
(3) be adsorbed the SO of agent surface adsorption
2Gas, hydrone and lip-deep reactive metal oxide generate sulphite, with the generation sulfate that reacts of oxygen in the flue gas; Part SO
2It is inner to get into adsorbent through the adsorbent hole;
(4) SO
2React with metal oxide in that adsorbent is inner, generate sulphite, part sulphite and the oxygen that the gets into hole generation sulfate that reacts.
The fundamental reaction principle of desulfurization:
SO
2+ H
2O+ desulphurization denitration composition (being called for short ESE) → H
2SO
3+ ESE →
Stabilized complex+O
2→ H
2SO
4+ ESE
Work as SO
2Be transformed into sulfurous acid (H
2SO
3) time, desulphurization denitration composition (ESE) is combined into stable comple with it, and they are continued to be oxidized to sulfuric acid, and functional group separates with it then.
H
2SO
3+ESE＝ESE·H
2SO
3
2ESE·H
2SO
3+O
2＝2ESE+2H
2SO
4
Desulphurization denitration composition of the present invention (ESE) has been realized above-mentioned reaction preferably.
To combine specific embodiment that the present invention is further described below, 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 technology parameter
| 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 | The 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 | The design desulfurization degree | ％ | ≥90％ |
| 8 | Design denitration rate | ％ | ≥50％ |
[0116]
Embodiment 1
(1) modulation of desulphurization denitration composition:
According to following prescription each component is mixed, obtain the desulphurization denitration composition.
(2) utilize the desulphurization denitration composition to remove SO
2, NO
XTechnology
1, slurrying:
The desulphurization denitration composition that modulates added to form main component after water slurrying, the slaking be the slurry of containing metal oxide, and stay in the slurry tank subsequent use.
2, denitration:
(1) NO is with the surface of flue gas arrival desulphurization denitration composition, and NO changes into NO under the catalytic action of metal oxide active sites simultaneously
2, quicken it and remove.
(2) NO
2Arrive adsorbent (being the components such as magnesia in the desulphurization denitration composition, down together) surface, a part is adsorbed by the surface;
(3) be adsorbed the NO of agent surface adsorption
2Gas, hydrone and lip-deep MgO reaction generate nitrite, with the generation nitrate that reacts of oxygen in the flue gas; Part NO
2It is inner to get into adsorbent through the adsorbent hole;
(4) NO reacts with MgO in that adsorbent is inner, generates nitrite, part nitrite and the oxygen that the gets into hole generation nitrate that reacts.
3, desulfurization:
(1) SO
2Arrive adsorbent surface with flue gas, a part is adsorbed by the surface;
(2) active sites of reactive metal oxides intermixture and the NO in the flue gas
X, also promote SO in the flue gas
2Combine to SO with oxygen
3Conversion.
(3) be adsorbed the SO of agent surface adsorption
2Gas, hydrone and lip-deep reactive metal oxide generate sulphite, with the generation sulfate that reacts of oxygen in the flue gas; Part SO
2It is inner to get into adsorbent through the adsorbent hole;
(4) SO
2React with metal oxide in that adsorbent is inner, generate sulphite, part sulphite and the oxygen that the gets into hole generation sulfate that reacts.
Under these conditions, the experiments data see table:
Table 2, sintering machine desulfuration facility toxic emission monitoring result
Desulfuration efficiency reaches 92.7%, and denitration efficiency reaches 64.3%.
Simultaneously, the consumption parameter of each item consumption thing is following:
The experiments data
| 1 | Power consumption | Degree | 260 |
| 2 | Water consumption | t/h | 30 |
| 3 | Desulphurization denitration composition consumption | kg/h | 860 |
[0140]It is thus clear that the consumption of water, electricity, these three materials of desulfurizing agent is all low than conventional desulphurization system.
Embodiment 2
According to following prescription each component is mixed, obtain the desulphurization denitration composition.
Embodiment 2 reduces MgO content 5 weight portions, reduces MnO than embodiment 1
22 weight portions increase SiO
2, Fe
2O
35 parts of weight portions increase 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%.
Simultaneously, the consumption parameter of each item consumption thing is following:
The experiments data
| 1 | Power consumption | Degree | 260 |
| 2 | Water consumption | t/h | 30 |
| 3 | Desulphurization denitration composition consumption | kg/h | 860 |
The consumption of water, electricity, these three materials of desulfurizing agent is with embodiment 1 unanimity, and desulfuration efficiency has fluctuation, and denitration efficiency has decline by a relatively large margin.
Embodiment 3
According to following prescription each component is mixed, obtain the desulphurization denitration composition.
Embodiment 3 is than embodiment 2, reduces MgO content 5 weight portions, respectively reduces SiO
2, Fe
2O
35 parts of weight portions (being that consumption is consistent with embodiment 1) increase 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 further reduces than embodiment 2.
Simultaneously, the consumption parameter of each item consumption thing is following:
The experiments data
| 1 | Power consumption | Degree | 260 |
| 2 | Water consumption | t/h | 30 |
| 3 | Desulphurization denitration composition consumption | kg/h | 860 |
The consumption of water, electricity, these three materials of desulfurizing agent all is lower than conventional desulphurization system, but desulfuration efficiency does not have embodiment 2 good.But denitration efficiency further reduces than embodiment 2, and desulfuration efficiency changes not obvious.
Can find out that through above case study on implementation embodiment 2,3 denitration efficiencies all decline to a great extent, but can satisfy 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, technical process desulphurization denitration composition consumption of the present invention is little, denitrification efficiency is high, operating cost is lower than conventional desulfurization or denitrating system, has than the large economy advantage.
The present invention is not limited to above-mentioned embodiment, and under the situation that does not deviate 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 (10)
1. a desulphurization denitration composition is characterized in that, comprises following component: MgO, SiO
2, CaO, Fe
2O
3, Al
2O
3, CuO and MnO
2
2. desulphurization denitration composition according to claim 1 is characterized in that, described desulphurization denitration composition also comprises KMnO
4
3. desulphurization denitration composition according to claim 1 is characterized in that, comprises following component:
MgO 40～50 weight portions,
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.
4. desulphurization denitration composition according to claim 3 is characterized in that, also comprises the KMnO of 1～10 weight portion in the desulphurization denitration composition
4
5. according to each described desulphurization denitration composition of claim 1～4, it is characterized in that the active oxidation content of magnesium among the said MgO is more than the 60wt%.
6. according to each described desulphurization denitration preparation of compositions method of claim 1～5, it is characterized in that, said components is pulverized formed powder, mix then; The particle size range of said powder is 100～5000 orders.
7. according to the purposes of each described desulphurization denitration composition of claim 1～5, it is characterized in that, be used for the synchronized desulfuring and denitrifying of flue gas.
8. purposes according to claim 7 is characterized in that, comprises the steps:
< 1>step of oxygen content in the adjusting flue gas;
< 2>slurrying step: process behind the slurry said desulphurization denitration composition subsequent use;
< 3>desulphurization denitration step: will regulate the flue gas behind the oxygen content and contact with said slurry.
9. purposes according to claim 8 is characterized in that oxygen content is controlled at 8～15vt% in the flue gas.
10. purposes according to claim 9; It is characterized in that; The step of regulating oxygen content in the flue gas realizes that through the oxygen adjusting device said oxygen adjusting device is arranged on flue gas and gets into desulphurization denitration equipment flue gas section before, and temperature is 125～145 ℃ in the flue of said flue gas section.
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Cited By (8)
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| CN104446064A (en) * | 2014-12-03 | 2015-03-25 | 北京中晶佳镁环境科技股份有限公司 | Device and method for producing cement by virtue of flue gas desulfurization |
| CN104529205A (en) * | 2014-12-03 | 2015-04-22 | 北京中晶佳镁环境科技股份有限公司 | Cement production apparatus and method |
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| CN107899588A (en) * | 2017-11-22 | 2018-04-13 | 江苏晶晶新材料有限公司 | A kind of denitrating catalyst and preparation method thereof |
| US10131546B2 (en) | 2014-12-03 | 2018-11-20 | Shanghui TONG | Apparatus and method for producing magnesium sulfate from coal-fired boiler flue gas |
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| US10131546B2 (en) | 2014-12-03 | 2018-11-20 | Shanghui TONG | Apparatus and method for producing magnesium sulfate from coal-fired boiler flue gas |
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| US11339091B2 (en) * | 2017-09-30 | 2022-05-24 | Environment Sustainable System Engineering Technology Co., Ltd. | Cementitious material and production method thereof |
| 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 |
| CN107899588A (en) * | 2017-11-22 | 2018-04-13 | 江苏晶晶新材料有限公司 | A kind of denitrating catalyst 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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Address after: 100176 Beijing economic and Technological Development Zone, Ronghua Road, No. 10 ronghua international building, room 20, floor 2008, room 3 Patentee after: BEIJING ZHONGJING JIAMEI ENVIRONMENT SCIENCE & TECHNOLOGY CO., LTD. Address before: 100176, No. 2, building 30, floor 1, 102 North Street, Beijing economic and Technological Development Zone, Beijing, China Patentee before: BEIJING ZHONGJING JIAMEI ENVIRONMENTAL TECHNOLOGY CO., LTD. |
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| CP01 | Change in the name or title of a patent holder |
Address after: 100176 Beijing economic and Technological Development Zone, Ronghua Road, No. 10 ronghua international building, room 20, floor 2008, room 3 Patentee after: MICROTEK environmental Polytron Technologies Inc Address before: 100176 Beijing economic and Technological Development Zone, Ronghua Road, No. 10 ronghua international building, room 20, floor 2008, room 3 Patentee before: BEIJING ZHONGJING JIAMEI ENVIRONMENT SCIENCE & TECHNOLOGY CO., LTD. |
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