CN107469831A - Dry-desulphurizer and its production method and application - Google Patents
Dry-desulphurizer and its production method and application Download PDFInfo
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- CN107469831A CN107469831A CN201710919186.4A CN201710919186A CN107469831A CN 107469831 A CN107469831 A CN 107469831A CN 201710919186 A CN201710919186 A CN 201710919186A CN 107469831 A CN107469831 A CN 107469831A
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- desulfurizing agent
- weight
- flue gas
- desulfurizing
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 66
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003546 flue gas Substances 0.000 claims abstract description 48
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 28
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 26
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 35
- 230000023556 desulfurization Effects 0.000 claims description 23
- 239000000395 magnesium oxide Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000002250 absorbent Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 229910018871 CoO 2 Inorganic materials 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 16
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241001466460 Alveolata Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- -1 V2O5 Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a kind of dry-desulphurizer and its production method and application.Based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components：TiO230~60 parts by weight, ZrO210~30 parts by weight, V2O52~10 parts by weight, the parts by weight of CoO 2~10, Co2O31~5 parts by weight, MnO25~15 parts by weight.The dry-desulphurizer of the present invention is good to the catalytic oxidation effect of the sulfur dioxide in flue gas, thus desulfuration efficiency is high.
Description
Technical field
The present invention relates to a kind of dry-desulphurizer and its production method and application, especially a kind of dry-desulphurizer and its life
Production method and flue gas dry desulfurizing method.
Background technology
China is the country using coal as main energy sources, in primary energy production and consumption structure, coal proportion difference
Up to 75% and 68.9%.84% coal is utilized by combustion system.It is big caused by coal-fired as consumption of coal constantly increases
Gas pollution (such as dust, SO2、NOxAnd CO2Deng) be continuously increased.SO2Discharge occupies world head for years more than 20,000,000 tons
Position.This causes China's acid rain and SO2Pollution is on the rise.The discharge capacity of coal-burning power plant's pollutant accounts for whole industrial discharge total amounts
50% or so, indivedual areas are likely to be breached more than 90%.Therefore, SO caused by power plant soot2Control turns into China's air
One of main task of contamination control.
Flue gas desulfurization is control thermal power plant SO2One of main path of discharge, and unique extensive business in the world
The desulfurization method of industryization application, technology maturation are reliable.The technique in the world for flue gas desulfurization mainly includes at present：Stone
Lime stone-gypsum wet, Method of Soda, Dual alkali, magnesium oxide method, semidry method, flue gas CFB dry method, seawater method, electronic beam method, ammoniacal liquor
Washing method etc..At home in 300MW and above capacity fired power generating unit, more than 90%, which employs Gypsum Wet flue gas, takes off
Sulphur technique.And flue gas CFB dry desulfurizations also there are certain applications at home, but all it is used in 300MW and following fired power generating unit.
Conventional dry method flue gas technology has in-furnace calcium spraying circulating fluid bed reactor desulfurization technology, dry reactive charcoal or activity
Jiao Fa.In-furnace calcium spraying circulating fluid bed reactor desulfurization technology is to spray into lime stone CaCO in boiler furnace suitable position3, play
Part sulfur fixation, circulating fluid bed reactor is installed before back-end ductwork electric cleaner, unreacted CaO is with flying dust in stove
It is transported in circulating fluid bed reactor, bulky grain CaO is crushed by wherein turbulent flow in circulating fluid bed reactor, is SO2Instead
Bigger surface area should be provided, so as to improve the desulfurization degree of whole system.But dry desulfurization process, Ca/S ratios are relative to wet method
The height of desulfurization；Vulcanization pressure drop of column fluctuation of service can cause to export SO2Fluctuation of concentration is big；And due to dry desulfurization be gas-
Gu reaction, reaction rate are relatively slow.
Catalyst is the key of desulfurization by dry method, develops a kind of efficiently dry desulfurization catalyst for improving desulfuration efficiency
With vital meaning.CN1597094A discloses a kind of preparation side of the Alveolate activated carbon base catalyst for desulfurization
Method.The catalyst is by addition phenolic resin or furane resins bonding agent in active powdered carbon, then is carbonized after extrusion forming,
And proofing is prepared in the solution that ammonium metavanadate and oxalic acid mix through drying, roasting, oxidation.
The content of the invention
It is an object of the present invention to provide a kind of other kinds of dry-desulphurizer, its desulfuration efficiency are very high.
It is another object of the present invention to provide a kind of production method of desulfurizing agent, its technique is simple, and cost is cheap.
It is yet a further object of the present invention to provide a kind of method of flue gas dry desulfurizing, and it can improve making for desulfurizing agent
Use effect.
The present invention, which adopts the following technical scheme that, realizes above-mentioned purpose.
The present invention provides a kind of dry-desulphurizer, and based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components：
According to the desulfurizing agent of the present invention, it is preferable that based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components：
According to the desulfurizing agent of the present invention, it is preferable that based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components：
According to the desulfurizing agent of the present invention, it is preferable that the average grain diameter of the desulfurizing agent is 0.5~10 micron.
According to the desulfurizing agent of the present invention, it is preferable that described TiO2、ZrO2、V2O5、CoO、Co2O3And MnO2Raw material it is equal
For nano-scale oxide.
The present invention also provides the production method of above-mentioned desulfurizing agent, comprises the following steps：
(1) by V2O5、CoO、Co2O3And MnO2Addition contains TiO2And ZrO2Slurries in, be 100~300rpm in rotating speed
Lower stirring 5~50 hours, forms mixed liquor；
(2) earthquake frequency is under 20~200kHz ul-trasonic irradiation, is described in 2~20wt% ammoniacal liquor adds by concentration
Mixed liquor, until the pH value of reaction system is 7~10；After continuing stirring 1~5 hour, liquor potassic permanganate is added dropwise, until reaction
The pH value of system is 4~6, continues stirring 1~5 hour, is filtered by vacuum, adds water washing, obtain paste；
(3) paste is dried at 100~130 DEG C, is ground into molecule；By the molecule 300~
Calcined 1~5 hour at 1000 DEG C, obtain the desulfurizing agent.
In accordance with the present production process, it is preferable that in step (2), the addition speed of ammoniacal liquor is 0.1~20mL/min,
And the rate of addition of liquor potassic permanganate is 0.1~20mL/min.
The present invention also provides a kind of method of flue gas dry desulfurizing, flue gas is fully contacted with above-mentioned desulfurizing agent, Ran Houyu
Main component contacts for the absorbent dry powder of magnesia, so as to remove the sulfur dioxide in flue gas.
Method in accordance with the invention it is preferred that with before desulfurization agent, the content of sulfur dioxide of flue gas for 1000~
3000mg/Nm3, flow velocity is 2~5m/s and temperature is 105~160 DEG C.
Method in accordance with the invention it is preferred that the magnesia includes 70~85wt% activated magnesia, and nanoscale
Content of the magnesia in the magnesia is 10~20wt%.
Oxidizing sulfur dioxide can be sulfur trioxide by the dry-desulphurizer of the present invention, then be inhaled with absorbents such as magnesia
Sulfur trioxide is received, so as to reach desulfurized effect.The desulfurized effect of the desulfurizing agent of the present invention is good, and consumption is few, and energy consumption is low, and cost is few,
Which solve using activated carbon method removing SO2During removal efficiency it is relatively low the defects of.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
In the present invention, nanoscale represents 1~100nm, preferably 10~60nm.
<Dry-desulphurizer>
The dry-desulphurizer of the present invention is a kind of desulphurization catalyst.The desulfurizing agent can include carrier and active component, living
Property composition is supported on carrier, for being sulfur trioxide by the oxidizing sulfur dioxide in flue gas.Carrier can be nanoscale both sexes
Oxide.Carrier is TiO2And ZrO2Combination.Active component includes nanosize metal oxide；The nanosize metal oxide
Including V2O5、CoO、Co2O3And MnO2.These active components coordinate SO2Catalysis oxidation is SO3.Such combination can be abundant
It is sulfur trioxide by the oxidizing sulfur dioxide in flue gas.
The present invention uses the active component of vanadium, cobalt, manganese as desulfurizing agent, and it is V that it, which is primarily present form,2O5、CoO、Co2O3、
MnO2.These active components can provide the active sites of catalytic reaction, to reactant SO2Adsorbed, and promote reaction to carry out.
Ti makees the main carriers of desulfurizer activity composition, mainly with TiO2Form is present.Ti presence is similarly SO2Certain absorption is provided
Property, add possibility of the reactant in desulfurizing agent adsorption.ZrO2And TiO2Carrier is combined together as, Zr can substitute original
There is the position of Ti in lattice, form ZrTiO4.Now new acidity and basicity, SO will be formed on carrier2When occupying desulfurizing agent,
These alkalescence point positions can attract SO2, target position is occupied in formation, so as to the active sites of effective protection activity composition.
According to an embodiment of the invention, based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes 30~60 parts by weight
TiO2, 10~30 parts by weight ZrO2, 2~10 parts by weight V2O5, 2~10 parts by weight CoO, 1~5 parts by weight Co2O3With 5~15 weight
Part MnO2.Preferably, the desulfurizing agent includes 35~60 parts by weight TiO2, 15~25 parts by weight ZrO2, 3~8 parts by weight V2O5, 2.5
~7 parts by weight CoO, 1.5~4 parts by weight Co2O3With 6~12 parts by weight MnO2.It is highly preferred that the desulfurizing agent includes 50~53 weights
Measure part TiO2, 20~25 parts by weight ZrO2, 6~8 parts by weight V2O5, 6~8 parts by weight CoO, 3~5 parts by weight Co2O3With 8~10 weights
Measure part MnO2.Above-mentioned active component is controlled in above range, its oxidation to the sulfur dioxide in flue gas can be significantly improved
Effect, so as to improve desulfurized effect.In the present invention, desulfurizing agent can be by including above-mentioned TiO2、ZrO2、V2O5、CoO、Co2O3With
MnO2Raw material be made.According to the preferred embodiment of the present invention, desulfurizing agent is only by above-mentioned TiO2、ZrO2、V2O5、CoO、Co2O3
And MnO2It is made.
The average grain diameter of the desulfurizing agent of the present invention is 0.5~10 micron, preferably 1~5 micron.Average grain diameter can use
Sieve method obtains.In the present invention, described TiO2、ZrO2、V2O5、CoO、Co2O3And MnO2Raw material be nanoscale
Thing.In the desulfurizing agent of shaping, V2O5、CoO、Co2O3And MnO2Size can be 2~100nm, specific surface area can reach
100~300m2/g。
<Production method>
The desulfurizing agent of the present invention can be produced using nano-metal-oxide.V is prepared first2O5、CoO、Co2O3、
MnO2Nanosize metal oxide.Common methods have sol-gel process, Hydrolyze method, hydrothermal synthesis method etc., it is preferred to use molten
Glue-gel method.For example, using vanadium, cobalt, manganese nitrate solution as predecessor, hydrolyzed, contracted in the solution with these nitrate respectively
Sol solutionses are synthesized, then heating removes solvent and changes into gel, crystal formation is finally made, granularity is controllable and uniform particle degree is high
Inorganic nano metal oxide.These methods are all well known in the art, are repeated no more here.
The production method of the present invention includes (1) blend step；(2) reactions steps：(3) calcination stepses etc. are dried.
The present invention blend step be：By nano-scale oxide V2O5、CoO、Co2O3And MnO2Addition contains TiO2And ZrO2
Slurries in, rotating speed be 100~300rpm under stir 5~50 hours, formation mixed liquor.Rotating speed is preferably 200~250rpm；
Mixing time is preferably 10~48 hours.
The present invention reactions steps be：Earthquake frequency is 20~200kHz, is preferably 50~100kHz ultrasonic wave work
It is 2~20wt%, preferably 5~10wt% ammoniacal liquor addition mixed liquor by concentration, until the pH value of reaction system is under
7~10, such as 7~8；Continue stirring 1~5 hour, be preferably after 2~3 hours, liquor potassic permanganate is added dropwise, until reactant
The pH value of system is 4~6, such as 5~5.5, continues stirring 1~5 hour, is preferably 2~3 hours, vacuum filtration, adds water washing,
Obtain paste.The addition speed of ammoniacal liquor can be 0.1~20mL/min, preferably 3~10mL/min.Liquor potassic permanganate
Rate of addition is 0.1~20mL/min, preferably 1~5mL/min.So be advantageous to obtain the nano metal oxide of size uniform
Thing.In the present invention, the liquor potassic permanganate can be acid permanganate soln.
The present invention drying calcination stepses be：By the paste at 100~130 DEG C, for example, being dried at 105~110 DEG C
It is dry, obtain drying object；Then drying object is ground into molecule；By the molecule 300~1000 DEG C, be preferably 500
It is calcined at~800 DEG C 1~5 hour, such as 2~3 hours, obtains desulfurizing agent.
<Flue gas dry desulfurizing method>
The method of the flue gas dry desulfurizing of the present invention includes flue gas desulfurization step：Flue gas and above-mentioned desulfurizing agent are fully connect
Touch, then contacted with main component for the absorbent dry powder of magnesia, so as to remove the sulfur dioxide in flue gas.
In the method for the invention, the content of sulfur dioxide of flue gas can be 1000~3000mg/Nm3, be preferably 1500
~2500mg/Nm3, more preferably 1600~2000mg/Nm3.Oxygen content can be 10~25vol%, be preferably 15~
20vol%.Temperature can be 105~160 DEG C；Preferably 120~135 DEG C.In addition, the flow velocity of flue gas can be 2~5m/s, it is excellent
Elect 2.5~3.5m/s as.Above-mentioned Gas Parameters represent the parameter at smoke inlet；The parameter of smoke outlet is according to actual de-
Depending on sulphur situation.Using above-mentioned technological parameter, be advantageous to improve desulfuration efficiency.Flue gas fully contacts with desulfurizing agent, by flue gas
Sulphur Dioxide be sulfur trioxide, formed pretreated fumes.
The magnesia of the present invention can include light calcined magnesia, micron order magnesia and/or nanoscale magnesium.According to this
One embodiment of invention, the magnesia include 70~85wt% activated magnesia, preferably 80~85% activity
Magnesia；And content of the nanoscale magnesium in the magnesia is 10~20wt%, preferably 15~20wt%.Pass through profit
With the exclusive property of some nanoparticles of nanoscale magnesium, desulfuration efficiency can be improved.So it is more beneficial for magnesium sulfate
Formed, so as to improve flue gas desulfurization effect.In the present invention, the absorbent can also change including calcium oxide and silica etc.
Property agent.Modifying agent is micron order, nano level metal oxide.In order to improve removal efficiency, absorbent of the invention is powder
Shape.Its particle diameter can be 0.5~10 micron, preferably 1~5 micron.So directly absorbent can be mixed with flue gas, and then
The removing of sulfur dioxide is carried out to flue gas, so as to complete the desulfurization of flue gas in the case where not needing a large amount of water, and is not produced
A large amount of industrial wastes.For example, absorbent dry powder is sufficiently mixed with pretreated fumes in flue, enter subsequently into absorption tower
Row desulfurization process, the flue gas after desulfurization are discharged by chimney.
Embodiment 1
Desulfurizing agent is produced according to the formula of table 1.By nano-scale oxide V2O5、CoO、Co2O3And MnO2Addition contains TiO2
And ZrO2Slurries in, rotating speed be 200pm under stir 48 hours, formation mixed liquor.Earthquake frequency is 100kHz ultrasound
It is that 10wt% ammoniacal liquor adds the mixed liquor by concentration, until the pH value of reaction system is 7 under ripple effect；Continue stirring 3 hours
Afterwards, liquor potassic permanganate is added dropwise, until the pH value of reaction system is 5, continues stirring 2 hours, vacuum filtration, adds water washing, obtain
To paste.The addition speed of ammoniacal liquor is 5mL/min；The rate of addition of liquor potassic permanganate is 2mL/min.By the paste
Dried at 105 DEG C, be ground into molecule；The molecule is calcined 3 hours at 500 DEG C, obtains desulfurizing agent F1.
The formula of table 1, desulfurizing agent F1
Catalysis oxidation is carried out to flue gas using the desulfurizing agent, and absorbed using magnesia dry powder.The flow velocity of flue gas is
2.5m/s；The other specification of smoke inlet, the parameter of exhanst gas outlet are as shown in tables 2 and 3.The sulfur dioxide of flue gas is dense after purification
Spend 25mg/Nm3, desulfuration efficiency 95.01%.
Table 2, smoke inlet parameter
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Inlet flue gas amount (operating mode) | m3/h | 240000 |
| 2 | Inlet flue gas amount (mark condition) | Nm3/h | 166718 |
| 3 | Desulfurizing tower inlet flue gas temperature | ℃ | 120 |
| 4 | SO2Entrance concentration | mg/Nm3 | 2000 |
| 5 | Humidity of flue gas | % | 5.6 |
Table 3, exhanst gas outlet parameter
| Sequence number | Project | Quantity | Unit |
| 1 | Exiting flue gas amount (operating mode) | 824493 | m3/h |
| 2 | Exhaust gas temperature | 65 | ℃ |
| 3 | Sulfur dioxide emissioning concentration | 25 | mg/Nm3 |
| 4 | Desulfuration efficiency | 95.01 | % |
| 5 | The quantum of output of accessory substance | 38.45 | t/h |
Embodiment 2
Formula according to table 4 obtains desulfurizing agent F2, and remaining condition is same as Example 1.Flue gas is entered using the desulfurizing agent
Row catalysis oxidation, and absorbed using magnesia dry powder.The concentration of the sulfur dioxide of flue gas is 17mg/Nm after purification3, desulfurization
Efficiency is 96.63%.The parameter of smoke inlet is as shown in table 5 with embodiment 1, the parameter of exhanst gas outlet.
The formula of table 4, desulfurizing agent F2
| TiO2 | 53.0 parts by weight |
| ZrO2 | 23.0 parts by weight |
| V2O5 | 6.0 parts by weight |
| CoO | 6.0 parts by weight |
| Co2O3 | 4.0 parts by weight |
| MnO2 | 8.0 parts by weight |
Table 5, exhanst gas outlet parameter
| Sequence number | Project | Quantity | Unit |
| 1 | Exiting flue gas amount (operating mode) | 818347 | m3/h |
| 2 | Exhaust gas temperature | 65 | ℃ |
| 3 | Sulfur dioxide emissioning concentration | 17 | mg/Nm3 |
| 4 | Desulfuration efficiency | 96.63 | % |
| 5 | The quantum of output of accessory substance | 39.27 | t/h |
Embodiment 3
Formula according to table 6 obtains desulfurizing agent F3, and remaining condition is same as Example 1.Flue gas is entered using the desulfurizing agent
Row catalysis oxidation, and absorbed using magnesia dry powder.The concentration of the sulfur dioxide of flue gas is 9mg/Nm after purification3, desulfurization
Efficiency is 98.25%.The parameter of smoke inlet is as shown in table 7 with embodiment 1, the parameter of exhanst gas outlet.
The formula of table 6, desulfurizing agent F3
| TiO2 | 51.0 parts by weight |
| ZrO2 | 23.0 parts by weight |
| V2O5 | 8.0 parts by weight |
| CoO | 6.0 parts by weight |
| Co2O3 | 4.0 parts by weight |
| MnO2 | 8.0 parts by weight |
Table 7, exhanst gas outlet parameter
| Sequence number | Project | Quantity | Unit |
| 1 | Desulfurizing tower exiting flue gas amount (operating mode) | 802375 | m3/h |
| 2 | Exhaust gas temperature | 65 | ℃ |
| 3 | Sulfur dioxide emissioning concentration | 9 | mg/Nm3 |
| 4 | Desulfuration efficiency | 98.25 | % |
| 5 | The quantum of output of accessory substance | 40.27 | t/h |
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the substantive content of the present invention, this area skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of dry-desulphurizer, it is characterised in that based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components：
2. desulfurizing agent according to claim 1, it is characterised in that based on 100 parts by weight desulfurizing agents, the desulfurizing agent include with
Lower component：
3. desulfurizing agent according to claim 1, it is characterised in that based on 100 parts by weight desulfurizing agents, the desulfurizing agent include with
Lower component：
4. desulfurizing agent according to claim 1, it is characterised in that the average grain diameter of the desulfurizing agent is 0.5~10 micron.
5. according to the desulfurizing agent described in any one of Claims 1 to 4, it is characterised in that described TiO2、ZrO2、V2O5、CoO、
Co2O3And MnO2Raw material be nano-scale oxide.
6. the production method of desulfurizing agent according to claim 5, it is characterised in that comprise the following steps：
(1) by V2O5、CoO、Co2O3And MnO2Addition contains TiO2And ZrO2Slurries in, rotating speed be 100~300rpm under stir
Mix 5~50 hours, form mixed liquor；
(2) earthquake frequency is under 20~200kHz ul-trasonic irradiation, is that 2~20wt% ammoniacal liquor adds the mixing by concentration
Liquid, until the pH value of reaction system is 7~10；After continuing stirring 1~5 hour, liquor potassic permanganate is added dropwise, until reaction system
PH value be 4~6, continue stirring 1~5 hour, be filtered by vacuum, add water washing, obtain paste；
(3) paste is dried at 100~130 DEG C, is ground into molecule；By the molecule 300~1000
Calcined 1~5 hour at DEG C, obtain the desulfurizing agent.
7. production method according to claim 6, it is characterised in that in step (2), the addition speed of ammoniacal liquor for 0.1~
20mL/min, and the rate of addition of liquor potassic permanganate is 0.1~20mL/min.
A kind of 8. method of flue gas dry desulfurizing, it is characterised in that by the desulfurization described in flue gas and any one of Claims 1 to 5
Agent fully contacts, and is then contacted with main component for the absorbent dry powder of magnesia, so as to remove the sulfur dioxide in flue gas.
9. according to the method for claim 8, it is characterised in that before desulfurization agent, the content of sulfur dioxide of flue gas
For 1000~3000mg/Nm3, flow velocity is 2~5m/s and temperature is 105~160 DEG C.
10. according to the method for claim 8, it is characterised in that the magnesia includes 70~85wt% active oxidation
Magnesium, and content of the nanoscale magnesium in the magnesia is 10~20wt%.
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| CN112774705A (en) * | 2020-12-17 | 2021-05-11 | 南京永能新材料有限公司 | Desulfurization catalyst for cement kiln flue gas and preparation method and application thereof |
| CN115445411A (en) * | 2022-07-07 | 2022-12-09 | 南京永能新材料有限公司 | Solid waste powder desulfurizer for cement kiln and preparation method thereof |
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