CN100427180C - Method for deacidizing low sulfur dioxide concentration by using gas produced by biomass pyrolysis - Google Patents
Method for deacidizing low sulfur dioxide concentration by using gas produced by biomass pyrolysis Download PDFInfo
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- CN100427180C CN100427180C CNB2007100656379A CN200710065637A CN100427180C CN 100427180 C CN100427180 C CN 100427180C CN B2007100656379 A CNB2007100656379 A CN B2007100656379A CN 200710065637 A CN200710065637 A CN 200710065637A CN 100427180 C CN100427180 C CN 100427180C
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 26
- 239000002028 Biomass Substances 0.000 title claims abstract description 16
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims description 28
- 239000007789 gas Substances 0.000 claims abstract description 39
- 239000003546 flue gas Substances 0.000 claims abstract description 26
- 238000006722 reduction reaction Methods 0.000 claims abstract description 26
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 230000003009 desulfurizing effect Effects 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- 239000010902 straw Substances 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 210000000952 spleen Anatomy 0.000 claims description 6
- -1 cornstalk Substances 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 239000010903 husk Substances 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241000345998 Calamus manan Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 235000012950 rattan cane Nutrition 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 240000000111 Saccharum officinarum Species 0.000 claims 1
- 235000007201 Saccharum officinarum Nutrition 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 19
- 239000002699 waste material Substances 0.000 abstract description 15
- 238000006477 desulfuration reaction Methods 0.000 abstract description 13
- 230000023556 desulfurization Effects 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 239000005864 Sulphur Substances 0.000 description 9
- 235000010269 sulphur dioxide Nutrition 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-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
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
Abstract
The invention relates to a process for reducing SO2 to elemental sulfur in flue gas by using biomass pyrolysis gas, which belongs to the desulfurization technic field. The pyrolysis reaction for the biomass is carried out in a pyrolysis oven to generate a mixed pyrolysis gas used as desulfurizer which mainly comprises CO, CH4, and H2, the prepared catalyst is filled in a reductive decomposition oven, the mixed pyrolysis gas and the flue gas containing low-concentration SO2 are introduced into the reductive decomposition oven to have a reduction reaction at temperature of between 600DEG C and1000DEG C for 1h to 3h, the volume percentage of the SO2 gas from reductive decomposition oven can be up to 0.006% to 0.65%, and the desulfurization percent can be up to 80% to 98%, thereby realizing waste reutilization.
Description
(1) technical field
The present invention relates to a kind of pyrolysis gas of biomass that utilizes with the method for sulfur in smoke gas reduction, belong to the flue gas desulfurization technique field for elemental sulfur.
(2) background technology
High concentration SO
2Flue gas can adopt the method for contact catalysis relieving haperacidity to reclaim the sulphur resource, and China's smelting industry all adopts this method basically at present, however low concentration SO
2Flue gas desulfurization technique still is in the starting stage.The Industrial Boiler of departments such as power plants boiler smoke and iron and steel, coloured, building materials, Industrial Stoves discharging mainly be this class flue gas.SO in this class flue gas
2Concentration lower (＜3%), if adopt known desulfurization relieving haperacidity method, technology and difficulty is very big economically all exists in the waste residue that traditional in addition flue gas desulfurization technique produces in sweetening process, the processing of waste liquid to increase the weight of economic pressures, generation secondary pollution problem.Simultaneously, China is the country that a sulphur resource lacks relatively, and the import volume of China's sulphur in 2000 just reaches 4Mt, adds upper inlet phosphate fertilizer (by its consumption acid conversion) and has been equivalent to imported sulphur 5Mt.The external interdependency of China's sulphur resource had surpassed 50% in 2005, and present worldwide sulphur resource provisioning anxiety, the sulphur rise in price.Therefore, from the angle of the environmental protection and the utilization of resources, utilize reducing process to reclaim elemental sulfur, walk the road of sustainable development, reaching the purpose that turns waste into wealth is trend of the times.
At present, known flue gas desulfurization technique is mainly based on wet method, comprises that alkali compounds based on alkali metal and alkaline-earth metal is as the absorption process of absorbent and the absorption method of absorption regeneration.For these technology, all exist waste residue, waste liquid and desorption product are carried out the subsequent treatment problem, deal with improperly and certainly will cause secondary pollution, make troubles for the operation transportation, and the fund consumption is big.
The wet method fume gas desulfurizing method that utilizes zinc oxide material to absorb low concentration sulphur dioxide flue gas is disclosed in the patent documentation of publication number CN1449861A, the handled sulfur dioxide concentration of this method is 0.03%～3%, to be granularity less than 100 orders account for used absorbent contains zinc oxide more than 90% greater than 40% material, control absorbs terminal point pH value 4.5～5.0, add in the circulation fluid less than 0.1% hydroquinones oxygen-inhibiting agent, absorb slag and use the method for acid decomposition to handle.This method is operated under the middle strong acidity condition, has the hidden danger of certain environment, and subsequent process inevitably will separate and handle absorbing slag, also will consider the SO that desorption gets off simultaneously
2, increased the expense and the complexity of desulfurization.
A kind of flue gas dry desulfurizing pollution-controlling technique is disclosed in the patent documentation of publication number CN1448209A.The employed desulfurizing agent of this method is made up of reactant and activating agent, pore creating material, it is characterized in that described desulfurizing agent is the reactant (alkaline matter) of 80%-97%, and the activating agent of 3%-20% and pore creating material (sulfate of aluminium) are formed.Activating agent can also be alum, aluminum sulfate, ferric sulfate, ferrous sulfate, zinc sulfate, manganese sulfate, magnesium sulfate, iron chloride, frerrous chloride.Pore creating material can also be silicic acid, potassium silicate, aluminum sulfate, aluminium polychloride, polyaluminium sulfate etc.This method adds too much chemical substance in making the desulfurizing agent process, in increase expense and complexity, the security of its waste residue utilization remains to be investigated.
Regenerative resource is the alternative energy technical theme that country is provided with in " 15 " 863 Program, China is the abundant country of a biomass energy, have an appointment every year 700000000 tons agricultural crop straw, rice husk, forestry waste material, wherein about 80% agricultural crop straw is burned in the direct combustion mode, has caused the huge waste of the energy and has polluted our environment.If we utilize living beings to obtain containing CO, CH by pyrolytic technique
4, H
2Gaseous mixture, utilize its pyrolysis gas to reduce sulfur dioxide as desulfurizing agent, not only can make full use of abundant living beings renewable resource, also the acquisition for desulfurizing agent provides a kind of new approach, and reclaimed potential sulphur resource, and reduced the sulfur dioxide that in atmosphere, discharges, produced good economic benefit, form a recycling economy industrial chain in desulfur technology field, realized the comprehensive utilization of living beings and waste gas sulfur dioxide.
(3) summary of the invention
The object of the present invention is to provide and a kind ofly reduce low concentration SO as desulfurizing agent with pyrolysis gas of biomass
2The method of flue gas is carried out pyrolytic reaction with living beings in pyrolysis oven, generate mainly to contain CO, CH
4, H
2The mixing furnace gas as desulfurizing agent, itself and low concentration SO
2Enter together in the reduction decomposition stove, carry out reduction decomposition reaction, the SO that comes out from the reduction decomposition stove
2The gas volume percentage composition reaches 0.006%～0.6%, and desulfurization degree reaches 80%～98%.And realize the treatment of wastes with processes of wastes against one another, the purpose that turns waste into wealth.
The present invention finishes according to the following steps:
1, pyrolysis gas of biomass reduction sulfur dioxide reacts employed catalyst for being carried on γ-Al
2O
3Or TiO
2And transition metal oxide or rare earth oxides such as praseodymium, neodymium, lanthanum or samarium such as the iron on the mixture of the two, cobalt, nickel, molybdenum or zinc.The preparation method is as follows: with the nitrate solution impregnated carrier 4h～6h of 5%～15% respective metal, under 110 ℃～120 ℃, be dried to moisture and be lower than 2wt%, be decomposed to form corresponding oxide at 500 ℃～600 ℃ following roasting 4～6h to nitrate then, use SO at last
2: N
2Make behind gaseous mixture presulfurization 1.5～3h of=1: 9.This catalyst is loaded on makes the catalytic reduction fixed bed in the reduction decomposition stove.
2, the desulfurizing agent raw material is living beings, comprises one or more mixtures in the plain material of fibre-bearings such as straw, rice husk, straw, cornstalk, straw, rattan, bamboo, wood chip, coconut husk, bagasse.To dry living beings that the back moisture is not more than 20wt%, to be crushed to particle diameter be below the 20mm.Living beings after crushed enter carries out pyrolytic reaction in the pyrolysis oven, 400～600 ℃ of control pyrolysis oven temperature, and reaction time 0.5～1.5h detects CO, CH in the furnace gas with the flue gas analyzer on-line continuous in the course of reaction
4, H
2Concentration.When volumn concentration is 10～40%CO, 10～40%CH
4, 10～30%H
2The time be that the qualified heat of mixing is vented one's spleen.
3, the heat of mixing is vented one's spleen and low concentration SO
2Flue gas is respectively with 15m
3/ h～50m
3/ h and 18m
3/ h～40m
3The flow velocity of/h enters in the reduction decomposition stove catalytic reduction fixed bed and carries out reduction reaction, and handled low-concentration flue gas contains SO
2Volumn concentration is 0.03%～3%, and the control furnace temperature is 600 ℃～1000 ℃, reaction time 1～3h.Detect CO, CH in the furnace gas with the flue gas analyzer on-line continuous in the course of reaction
4, H
2, SO
2Concentration.The key reaction equation that takes place in reduction process is:
2CO+SO
2→2CO
2+S (1)
2H
2+SO
2→2H
2O+S (2)
3H
2+SO
2→H
2S+2H
2O (3)
CH
4+2SO
2→2S+CO
2+2H
2O (4)
CH
4+SO
2→H
2S+CO+H
2O (5)
2H
2S+SO
2→2H
2O+3S (6)
The gas volume percentage composition that comes out when the reduction decomposition stove is 0.1～0.5%CO, 0.1～0.5%CH
4, 0.1～0.5%H
2, 0.006～0.6%SO
2The time, reaction is finished.Desulfurization degree reaches 80%～98%.Furnace gas reclaims elemental sulfur by condensing unit, and the elemental sulfur productive rate reaches more than 75%.
Compare with prior art, the present invention has following advantage:
(1) made full use of existing abundant biomass resource, for the utilization of regenerative resource and the acquisition of desulfurizing agent provide a kind of new way.Effectively reduce the discharging of sulfur dioxide.
(2) the desulfurizing agent raw material has used the living beings that are easy to get, and raw material sources are not limited by regions resources.
(3) technical process has been utilized each component of pyrolysis gas of biomass to greatest extent, has realized the purpose of the treatment of wastes with processes of wastes against one another.
(4) use dry desulfurization to reclaim the sulphur of economically valuable, realized the purpose that turns waste into wealth.
The present invention is applicable to the improvement of industry low concentration sulphur dioxide flue gas such as thermal power plant, smelting, chemical industry, gas washing in SA production, has broad application prospects.
(4) description of drawings
Fig. 1 is a process chart of the present invention.
(5) specific embodiment
Embodiment 1: with TiO
2Carrier places 15% iron nitrate solution to flood 4h, is being dried under 110～120 ℃ below the moisture 2wt%, is decomposed to form iron oxide at 500～600 ℃ of following roasting 4.5～5h to ferric nitrate then, uses gaseous mixture (SO at last
2: N
2=1: 9) make behind the presulfurization 2h.The catalyst for preparing is loaded into and makes the catalytic reduction fixed bed in the reduction decomposition stove; The desulfurizing agent raw material is a straw, to dry back moisture and be 10% straw, to be crushed to particle diameter be below the 20mm, and straw after crushed enters and carries out pyrolytic reaction in the pyrolysis oven, and temperature is controlled at 450 ℃～550 ℃, reaction 1h detects CO, CH in the furnace gas with the flue gas analyzer on-line continuous in the course of reaction
4, H
2Concentration, generate and mainly to contain 30%CO, 30%CH
4, 20%H
2The heat of mixing vent one's spleen; The heat of mixing is vented one's spleen with flow velocity 15m
3/ h enters in the reduction decomposition stove, contains 3%SO
2Flue gas with flow velocity 20m
3/ h enters in the reduction decomposition stove, and the control furnace temperature is 650 ℃～800 ℃, pyrolysis gas of biomass and SO
2In the reduction decomposition stove, carry out reduction reaction 1.5～2.5h.Detect CO, CH in the furnace gas with the flue gas analyzer on-line continuous in the course of reaction
4, H
2, SO
2Concentration, the gas volume percentage composition that comes out from the reduction decomposition stove is 0.1%CO, 0.2%CH
4, 0.1%H
2, 0.15%SO
2The mixing furnace gas, desulfurization degree reaches 95%.Furnace gas reclaims elemental sulfur by condensing unit, and the elemental sulfur rate of recovery reaches 85%.
Embodiment 2: with γ-Al
2O
3Carrier places 5% lanthanum nitrate hexahydrate to flood 6h, is dried to moisture 0.5wt% under 110～120 ℃, is decomposed to form lanthana at 600 ℃ of following roasting 4h to lanthanum nitrate then, uses gaseous mixture (SO at last
2: N
2=1: 9) make behind the presulfurization 1.5h.The catalyst for preparing is loaded in the reduction decomposition stove; The desulfurizing agent raw material is a wood chip, to dry back moisture and be 15% wood dust, to be broken to particle diameter be below the 3mm, wood chip after crushed enters in the pyrolysis oven, temperature is controlled at 500 ℃～600 ℃, living beings are carried out pyrolytic reaction 1h in pyrolysis oven, detect CO, CH in the furnace gas with the flue gas analyzer on-line continuous in the course of reaction
4, H
2Concentration.Generate and mainly contain 20%CO, 40%CH
4, 10%H
2The mixing furnace gas; Pyrolytic reaction obtains contains 20%CO, 40%CH
4, 10%H
2The mixing furnace gas with flow velocity 28m
3/ h enters in the reduction decomposition stove, contains 1%SO
2Flue gas with flow velocity 36m
3/ h enters in the reduction decomposition stove, and the control furnace temperature is 750 ℃～950 ℃, pyrolysis gas of biomass and SO
2In the reduction decomposition stove, carry out reduction reaction 1.5h～2h.Detect CO, CH in the furnace gas with the flue gas analyzer on-line continuous in the course of reaction
4, H
2, SO
2Concentration, the gas volume percentage composition that comes out from the reduction decomposition stove is 0.2%CO, 0.1%CH
4, 0.1%H
2, 0.01%SO
2The mixing furnace gas, desulfurization degree reaches 90%.Furnace gas reclaims elemental sulfur by condensing unit, and the elemental sulfur rate of recovery reaches 80%.
Claims (4)
1, a kind of method with the pyrolysis gas of biomass deacidizing low sulfur dioxide concentration is characterized in that, finishes according to the following steps:
1). the desulfurizing agent raw material is living beings, to dry living beings that the back moisture is not more than 20wt%, to be crushed to particle diameter be below the 20mm, enters and carry out pyrolytic reaction in the pyrolysis oven, 400～600 ℃ of control pyrolysis oven temperature, reaction time 0.5～1.5h, CO, CH in the furnace gas that generates
4, H
2The concentration volumn concentration reach 10～40%CO, 10～40%CH
4, 10～30%H
2The time be that the qualified heat of mixing is vented one's spleen;
2). the heat of mixing is vented one's spleen and low concentration SO
2Flue gas enters in the catalytic reduction fixed bed of reduction decomposition stove and carries out reduction reaction, and the control furnace temperature is 600 ℃～1000 ℃, reaction time 1～3h, CO, CH in the furnace gas that the reduction decomposition fire grate comes out
4, H
2, SO
2The concentration volumn concentration be 0.1～0.5%CO, 0.1～0.5%CH
4, 0.1～0.5%H
2, 0.006～0.6%SO
2The time, reaction is finished, and contains SO
2Flue gas desulphuization rate reaches 80%～98%.
2, the method with the pyrolysis gas of biomass deacidizing low sulfur dioxide concentration according to claim 1 is characterized in that described catalytic reduction fixed bed catalyst system therefor is for being carried on γ-Al
2O
3Or TiO
2Or the oxide of the iron on the mixture of the two, cobalt, nickel, molybdenum, praseodymium, neodymium, zinc, lanthanum or samarium, the preparation method is as follows: with the nitrate solution impregnated carrier 4h～6h of 5%～15% respective metal, under 110～120 ℃, be dried to moisture and be lower than 2wt%, be decomposed to form corresponding oxide at 500 ℃～600 ℃ following roasting 4～6h to nitrate then, use SO at last
2: N
2Make behind gaseous mixture presulfurization 1.5～3h of=1: 9, this catalyst is loaded on makes the catalytic reduction fixed bed in the reduction decomposition stove.
3, the method with the pyrolysis gas of biomass deacidizing low sulfur dioxide concentration according to claim 1, it is characterized in that described desulfurizing agent raw material comprises one or more mixtures in straw, rice husk, straw, cornstalk, straw, rattan, bamboo, wood chip, coconut husk, the sugarcane slag charge.
4, according to each described method among the claim 1-3, it is characterized in that handled flue gas contains SO with the pyrolysis gas of biomass deacidizing low sulfur dioxide concentration
2Volumn concentration be 0.03%～3%.
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| US9266062B2 (en) | 2011-07-28 | 2016-02-23 | China Petroleum & Chemical Corporation | Method of removing sulfur oxides and nitrogen oxides in the flue gas |
| CN103480270B (en) * | 2013-09-13 | 2015-12-02 | 北京矿迪科技有限公司 | A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent |
| CN109354149A (en) * | 2018-11-12 | 2019-02-19 | 昆明理工大学 | A kind of processing method of the waste water containing heavy metal-polluted acid |
| CN113023684B (en) * | 2021-03-09 | 2022-09-13 | 山东大学 | System and method for preparing sulfur by catalytic reduction of high-sulfur flue gas by using carbon/iron sulfide |
| CN114853611B (en) * | 2022-05-16 | 2023-03-24 | 华中科技大学 | Method for treating biomass pyrolysis gas |
| CN115253632A (en) * | 2022-07-20 | 2022-11-01 | 山东大学 | Method for reducing sulfur nitrate and solidifying heavy metal in sulfur-containing flue gas gasified sludge adjusting atmosphere |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165051A (en) * | 1997-02-25 | 1997-11-19 | 沈阳环境科学研究所 | High efficiency flue gas desulfurization technology |
| WO2004076035A1 (en) * | 2003-02-28 | 2004-09-10 | Japan Science And Technology Agency | Method for carrying out desulfurization and denitration |
| CN1899668A (en) * | 2006-06-30 | 2007-01-24 | 昆明理工大学 | Phosphate rock slurry catalytically oxidaizing process for removing low concentration SO2 |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165051A (en) * | 1997-02-25 | 1997-11-19 | 沈阳环境科学研究所 | High efficiency flue gas desulfurization technology |
| WO2004076035A1 (en) * | 2003-02-28 | 2004-09-10 | Japan Science And Technology Agency | Method for carrying out desulfurization and denitration |
| CN1899668A (en) * | 2006-06-30 | 2007-01-24 | 昆明理工大学 | Phosphate rock slurry catalytically oxidaizing process for removing low concentration SO2 |
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