CN103480270B - A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent - Google Patents
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent Download PDFInfo
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- CN103480270B CN103480270B CN201310418638.2A CN201310418638A CN103480270B CN 103480270 B CN103480270 B CN 103480270B CN 201310418638 A CN201310418638 A CN 201310418638A CN 103480270 B CN103480270 B CN 103480270B
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- flue gas
- living beings
- desulfurization denitrification
- temperature flue
- denitrification agent
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- 239000003546 flue gas Substances 0.000 title claims abstract description 86
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 69
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 68
- 230000023556 desulfurization Effects 0.000 title claims abstract description 68
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000011084 recovery Methods 0.000 claims abstract description 39
- 239000002699 waste material Substances 0.000 claims abstract description 36
- 239000002918 waste heat Substances 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- 239000002028 Biomass Substances 0.000 claims abstract description 19
- 239000005864 Sulphur Substances 0.000 claims abstract description 16
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 239000010791 domestic waste Substances 0.000 claims abstract description 7
- 239000010902 straw Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 239000002808 molecular sieve Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 229910000765 intermetallic Inorganic materials 0.000 claims description 12
- 239000000428 dust Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- -1 molecular sieve metal oxide Chemical class 0.000 claims description 8
- 230000003009 desulfurizing effect Effects 0.000 claims description 7
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000011345 viscous material Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 244000144985 peep Species 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 abstract description 8
- 239000000779 smoke Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 3
- 238000011953 bioanalysis Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Treating Waste Gases (AREA)
Abstract
The invention discloses a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent, belong to flue gas desulfurization and denitrification technology basin.This system comprises reative cell, waste heat recovery room and sulfur recovery room three parts.Described reative cell is connected with smoke inlet, and its top is the hopper loading living beings desulfurization denitrification agent, and bottom is the feed bin loading inefficacy living beings desulfurization denitrification agent, and reative cell is also equipped with the load coil for maintaining its temperature; Described waste heat recovery room is equipped with the waste-heat recoverer for heat in recovered flue gas; Be equipped with U-shaped condenser pipe in sulfur recovery room and be used for maintaining sulfur recovery room temperature and make sulphur have the resistance heating tube of good fluidity.The present invention can direct purification high-temperature flue gas, effectively use the biomass waste material comprising agricultural crop straw, crops processing waste, forestry processing waste or domestic waste etc. to administer smoke pollution, but also can recovery waste heat, and the sulphur in flue gas can be reclaimed with the form of simple substance product.
Description
Technical field
The present invention relates to a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent, can direct purification high-temperature flue gas, particularly containing low concentration SO
2with NO
xhigh-temperature flue gas; Belong to flue gas desulfurization and denitrification technology basin.
Background technology
What the fields such as metallurgy, thermal power generation and chemical industry produced contains low concentration SO
2with NO
xflue gas serious pollution is caused to environment, to flue gas implement desulphurization denitration imperative.At present, more ripe method generally adopts the independent removing sulfuldioxide of multisystem (what is called removes separately and refers to that denitration and desulfurization substep carry out), various pollutants in flue gas can be reached higher clearance by this technology, but flue gas purification system is numerous and jumbled, occupation of land is many, investment and the operating cost of equipment are high, and the high-temperature flue gas of difficult direct purification more than 600 DEG C.For this reason, people have studied the synchronized desulfuring and denitrifying technology of flue gas.
The flue gas synchronized desulfuring and denitrifying technology studied at present mainly contains dry method, wet method and bioanalysis.Impulse electric corona method, Electron Beam Irradiation and dry type catalysis method are the Typical Representatives in dry desulfurization denitration, although dry method has the advantage of the aspects such as non-secondary pollution, also there is the problem that processing cost is high, invest the aspects such as large and NH_3 leakage.What study more ripe in Wet technique is calcium-base absorbing agent catalytic oxidation, this method is a kind of technology grown up on the basis adding calcium wet desulfurizing process, although have the advantages such as technique is simple, the secondary pollutions such as by-product calcium sulfate and flue gas need the defect of cooling process to avoid.Bioanalysis utilizes microorganism to carry out SO in smoke treatment
2with NO
xmethod, although research shows that this method has investment and the advantage such as operating cost is low, this method requires to lower the temperature to smoke treatment equally, and in addition, this method is also in conceptual phase.
On the other hand, China is the country that a biomass resource enriches very much, also create the biomass waste material comprising agricultural crop straw, crops processing waste, forestry processing waste or domestic waste etc. in a large number thus, these waste material major parts are not all used effectively.
Summary of the invention
The object of the invention is to overcome prior art deficiency and provide a kind of structure simple, easy to operate, can directly to high-temperature flue gas, high-temperature flue gas, particularly containing low concentration SO
2with NO
xhigh-temperature flue gas implement the high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of desulphurization denitration simultaneously.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, comprise retort, retort top is the hopper (101) loading living beings desulfurization denitrification agent, bottom is the feed bin (105) loading inefficacy living beings denitration desulfurizing agent, and middle part is reative cell (1); High-temperature flue gas entry (K001) is provided with on the top of reative cell, bottom is provided with exhanst gas outlet, reative cell sidewall is provided with the load coil (104) for maintaining reative cell (1) temperature, and reative cell is mid-is placed with living beings desulfurization denitrification agent (102); Described exhanst gas outlet is by being communicated with waste heat recovery room (2) communicating pipe (1122), and waste heat recovery room (2) were communicated with sulfur recovery room (3) by communicating pipe (2233).
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, be equipped with the waste-heat recoverer (201) for waste heat in recovered flue gas in described waste heat recovery room (2), bottom is provided with the feed bin (202) for receiving waste heat recovery room dust.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, be equipped with in described sulfur recovery room (3) for the U-shaped condenser pipe (301) to sulphur steam-condensation, being provided with for maintaining sulfur recovery room temperature and ensureing that sulphur has the resistance heating tube (302) of good fluidity, being placed with the container (303) for receiving liquid sulfur in sulfur recovery room (3) bottom.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, in described high-temperature flue gas entry (K001) place and communicating pipe (1122), be placed with Web materials (103), (106) respectively, the material of described Web materials (103), (106) is any one in pottery, FeCrAl, Fe-Al intermetallic compound, Ni-Al intermetallic compound, and the mesh size of Web materials is less than the size of living beings desulfurization denitrification agent; Described Web materials (103) ability high-temperature flue gas burn into and good air permeability, can be used to stop desulfurization denitrification agent (102) to be escaped from reative cell; Described Web materials (106) ability high-temperature flue gas burn into and good air permeability, can implement to filter, can be used to stop desulfurization denitrification agent (102) to enter waste heat recovery room (2) to dust.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, described waste-heat recoverer (201) refers to and adopts manufactured by known technology, to can be used to waste heat in recovered flue gas device.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, Web materials (203) is placed with in described communicating pipe (2233), the material of described Web materials (203) is any one in pottery, FeCrAl, Fe-Al intermetallic compound, Ni-Al intermetallic compound, and the mesh size of Web materials is less than 5um; Described Web materials (203) ability high-temperature flue gas burn into and good air permeability, can implement to filter to dust.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, is equipped with in sulfur recovery room (3) bottom for observing the peep hole (304) receiving sulphur storage capacity in liquid Sulfur capacity device (303).
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, described living beings desulfurization denitrification agent, comprises following component and forms by mass percentage:
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, described biomass waste material is selected from one or more mixtures formed by arbitrary ratio mixing in agricultural crop straw, crops processing waste, forestry processing waste, domestic waste, mass percentage≤10% of water in biomass waste material, granularity≤3mm.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, in modified zeolite class catalyst, zeolitic catalyst is selected from HZSM-5 molecular sieve; Modification refers on HZSM-5 molecular sieve metal oxide-loaded; Described metal oxide is selected from the oxide of any one metallic element in Fe, Cu, Ce, Co, and in the metal oxide of load, the quality of metallic element accounts for 8 ~ 12% of HZSM-5 molecular sieve quality.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, the preparation method of described modified zeolite class catalyst is: first, get Fe, Cu, the nitrate of Ce or Co, be mixed with the Fe that mass percentage concentration is 10 ~ 30%, Cu, the nitrate solution of Ce or Co, then, be that 20 ~ 40 object HZSM-5 molecular sieves at least flood once in described nitrate solution by granularity, filter, gained filter residue is after 100 ~ 120 DEG C of dry 1.5-2h, again in 500 ~ 550 DEG C of roasting 2-4h, repeat above-mentioned dipping, drying and roasting process, finally weigh, until the quality of metallic element accounts for 8 ~ 12% of HZSM-5 molecular sieve quality in the metal oxide of load.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, described modified activated carbon is that active carbon is crushed to 20 ~ 40 orders, be after soaking 0.5 ~ 4h in the salpeter solution of 10 ~ 65% in mass percentage concentration, in 100 ~ 120 DEG C of dry 1.5-2h, the product obtained.
A kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of the present invention, described living beings binding agent production technology is: after the stalk being averaged size≤3mm soaks 1 ~ 3 day in water, the white lime accounting for stalk quality 30 ~ 35% is added in water, stir, obtain mixture, then, mixture is heated to 95 ~ 100 DEG C, insulation 3 ~ 4h, the yellow, viscous material obtained is living beings binding agent; The quality of water is 8 ~ 10 times of stalk weight.
Why denitration desulphurization system based on biomass waste material of the present invention directly can carry out simultaneous SO_2 and NO removal to more than 600 DEG C high-temperature flue gas, be because, put living beings desulfurization denitrification agent in the reaction chamber, when high-temperature flue gas is by denitration desulfurizing agent of the present invention, will there is cracking in the components of biomass in denitration desulfurizing agent, produce and comprise CO, CH
4, H
2with NH
3etc. the pyrolysis gas of main component; Under the zeolitic catalyst of these gases metal oxide in load and active carbon effect, following serial reaction occurs, these reactions can ensure that most of sulphur in high-temperature flue gas is transformed into simple substance sulphur and nitre in flue gas realizes innoxious.
CH
4+4NO→2N
2+CO
2+2H
2O;
CH
4+2SO
2→S
2+CO
2+2H
2O;
CH
4+SO
2→H
2S+CO+H
2O;
2H
2+SO
2→S+2H
2O;
3H
2+SO
2→H
2S+2H
2O;
2H
2S+SO
2→2H
2O+3S;
4NO+4NH
3+O
2→4N
2+6H
2O;
2CO+SO
2→S+2CO
2；
The present invention, owing to adopting technique scheme, maintains reaction chamber temperature by the load coil being located at reative cell side, utilizes the living beings desulfurization denitrification agent put in the reaction chamber at high temperature cracking to occur, produces and comprise CO, CH
4, H
2with NH
3etc. the pyrolysis gas of main component; With low concentration SO in high-temperature flue gas under the zeolitic catalyst of these gases metal oxide in load and active carbon effect
2with NO
xreact, realize low concentration SO in high-temperature flue gas
2with NO
xpurification; Subsequently, U-shaped condenser pipe that flue gas is arranged in the feed bin of the dust of follow-up waste heat recovery room (2), sulfur recovery room (3) collects dust in flue gas and elemental sulfur respectively.
System provided by the present invention, not only carry out direct purification flue gas using biological material as desulfurization denitrification agent, but also waste heat in recyclable flue gas the sulphur in flue gas is reclaimed with the form of elemental sulfur, also effectively accomplish " treatment of wastes with processes of wastes against one another " in addition, namely accomplished that the biomass waste material with comprising agricultural crop straw, crops processing waste, forestry processing waste or domestic waste etc. administers smoke pollution, for the biomass waste material that China's storage is huge have found a Processes For Effective Conversion, effectively reduce biomass waste material to the pollution of environment.
Adopt the high-temperature flue gas treatment system based on living beings desulfurization denitrification agent of technique scheme, its advantage and good effect as follows:
(1) compared with known technology, high-efficiency desulfurization and denitration while the present invention directly can realize high-temperature flue gas, particularly low concentration high-temperature flue gas, the sulfur dioxide simultaneously in effective reduction flue gas and the discharge of oxynitrides.
(2) achieve sulfur dioxide in flue gas resource and be transformed into elemental sulfur product;
(3) waste heat in flue gas has effectively been reclaimed;
(4) object of " treatment of wastes with processes of wastes against one another " is reached, namely the object of administering smoke pollution with the biomass waste material comprising agricultural crop straw, crops processing waste, forestry processing waste or domestic waste etc. has been accomplished, this not only opens a new direction for the efficiency utilization of biomass waste material, and also reduces the pollution of biomass waste material to environment.
Accompanying drawing explanation
Fig. 1 is based on the high-temperature flue gas purification system of living beings desulfurization denitrification agent.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment
See Fig. 1, high-temperature flue gas treatment system based on living beings desulfurization denitrification agent disclosed in this invention, comprise retort, retort top is the hopper (101) loading living beings desulfurization denitrification agent, bottom is the feed bin (105) loading inefficacy living beings denitration desulfurizing agent, and middle part is reative cell (1); High-temperature flue gas entry (K001) is provided with on the top of reative cell (1), bottom is provided with exhanst gas outlet, reative cell (1) sidewall is provided with the load coil (104) for maintaining reative cell (1) temperature, and reative cell is mid-is placed with living beings desulfurization denitrification agent; Described exhanst gas outlet is by being communicated with waste heat recovery room (2) communicating pipe (1122), and waste heat recovery room (2) were communicated with sulfur recovery room (3) by communicating pipe (2233); Be equipped with the waste-heat recoverer (201) for waste heat in recovered flue gas in described waste heat recovery room (2), bottom is provided with the feed bin (202) for receiving waste heat recovery room dust; Be equipped with in described sulfur recovery room (3) for the U-shaped condenser pipe (301) to sulphur steam-condensation, being provided with for maintaining sulfur recovery room temperature and ensureing that sulphur has the resistance heating tube (302) of good fluidity, being placed with the container (303) for receiving liquid sulfur in sulfur recovery room (3) bottom; In described high-temperature flue gas entry (K001) place and communicating pipe (1122), be placed with Web materials (103), (106) respectively, the material of described Web materials (103), (106) is any one in pottery, FeCrAl, Fe-Al intermetallic compound, Ni-Al intermetallic compound, and the mesh size of Web materials is less than the size of living beings desulfurization denitrification agent; Described Web materials (103) ability high-temperature flue gas burn into and good air permeability, can be used to stop desulfurization denitrification agent (102) to be escaped from reative cell; Described Web materials (106) ability high-temperature flue gas burn into and good air permeability, can implement to filter, can be used to stop desulfurization denitrification agent (102) to enter waste heat recovery room (2) to dust; Described waste-heat recoverer (201) refers to and adopts manufactured by known technology, to can be used to waste heat in recovered flue gas device; Web materials (203) is placed with in described communicating pipe (2233), the material of described Web materials (203) is any one in pottery, FeCrAl, Fe-Al intermetallic compound, Ni-Al intermetallic compound, and the mesh size of Web materials is less than 5um; Described Web materials (203) ability high-temperature flue gas burn into and good air permeability, can implement to filter to dust; Be equipped with in sulfur recovery room (3) bottom for observing the peep hole (304) receiving sulphur storage capacity in liquid Sulfur capacity device (303).
In the present embodiment, described living beings desulfurization denitrification agent, comprises following component and forms by mass percentage:
In the present embodiment, described biomass waste material is selected from one or more mixtures formed by arbitrary ratio mixing in agricultural crop straw, crops processing waste, forestry processing waste, domestic waste, mass percentage≤10% of water in biomass waste material, granularity≤3mm.
In the present embodiment modified zeolite class used catalyst, zeolitic catalyst is selected from HZSM-5 molecular sieve; Modification refers on HZSM-5 molecular sieve metal oxide-loaded; Described metal oxide is selected from the oxide of any one metallic element in Fe, Cu, Ce, Co, and in the metal oxide of load, the quality of metallic element accounts for 8 ~ 12% of HZSM-5 molecular sieve quality.
In the present embodiment, the preparation method of described modified zeolite class catalyst is: first, get Fe, Cu, the nitrate of Ce or Co, be mixed with the Fe that mass percentage concentration is 10 ~ 30%, Cu, the nitrate solution of Ce or Co, then, be that 20 ~ 40 object HZSM-5 molecular sieves at least flood once in described nitrate solution by granularity, filter, gained filter residue is after 100 ~ 120 DEG C of dry 1.5-2h, again in 500 ~ 550 DEG C of roasting 2-4h, repeat above-mentioned dipping, drying and roasting process, finally weigh, until the quality of metallic element accounts for 8 ~ 12% of HZSM-5 molecular sieve quality in the metal oxide of load.
In the present embodiment, described modified activated carbon is that active carbon is crushed to 20 ~ 40 orders, is after soaking 0.5 ~ 4h in the salpeter solution of 10 ~ 65% in mass percentage concentration, in 100 ~ 120 DEG C of dry 1.5-2h, and the product obtained.
In the present embodiment, described living beings binding agent production technology is: after the stalk being averaged size≤3mm soaks 1 ~ 3 day in water, the white lime accounting for stalk quality 30 ~ 35% is added in water, stir, obtain mixture, then, mixture is heated to 95 ~ 100 DEG C, insulation 3 ~ 4h, the yellow, viscous material obtained is living beings binding agent; The quality of water is 8 ~ 10 times of stalk weight.
See Fig. 1, the high-temperature flue gas treatment system that the present invention is based on living beings desulfurization denitrification agent implements the process of purification to high-temperature flue gas, describe in detail below in conjunction with accompanying drawing.
First, living beings desulfurization denitrification agent is prepared.
The preparation of living beings desulfurization denitrification agent comprises the steps:
Prepare with the desulfurization denitrification agent that the modified zeolite class catalyst of loaded Cu molecular sieve, modified activated carbon, stalk and living beings binding agent are raw material.
The preparation process of the present embodiment desulfurization denitrification agent:
The first step, the preparation of raw material.
(1) living beings binding agent is prepared, after the stalk being averaged size≤3mm soaks 2 days in water, the white lime accounting for stalk quality 33% is added in water, stir, obtain mixture, then, mixture is heated to 95 ~ 100 DEG C, insulation 4h, the yellow, viscous material obtained is living beings binding agent; The quality of water is 8 ~ 10 times of stalk weight.
In addition, below 3mm is crushed to drying the stalk being less than 10% to moisture with plant pulverizer.
(2) zeolitic catalyst of powdery load metallic copper thing is prepared.First Cu (the NO that concentration is 10% is prepared
3)
2be immersed in this solution with being about to be crushed to 20 ~ 40 object HZSM-5 molecular sieves, filter gained powder after 100 DEG C of dry 1.5h, again at 550 DEG C of roasting 2h, finally weigh and calculate powder gain in weight, when metallic element Cu content in molecular sieve lower than 10% time, repeat above-mentioned dipping, drying and roasting process, until the content of metallic element Cu reaches 10wt% in molecular sieve.
(3) prepare modified activated carbon, be about to be crushed to 20 ~ 40 object active carbons and soak 0.5h at concentration 65% salpeter solution, then at 120 DEG C of dry 1.5h, obtain modified active carbon powder.
Second step, batch mixing.
(1) the powdered zeolite class catalyst of same quality and powdered modified active carbon is taken, by they Homogeneous phase mixing in three-dimensional material mixer;
(2) catalyst and modified activated carbon mixed-powder are joined in living beings binding agent under the effect of stirring, the quality of the living beings binding agent got and the mass ratio of mixed-powder are 1:1; Then, take prepared by the first step, to add in living beings binding agent with the powdery stalk of catalyst and modified activated carbon mixed-powder equal quality and fully to mix thoroughly.
3rd step, dry and shaping.By second step gained mixture, reach 15% by natural air drying to mixture moisture.Adopt former air-dry rear mixture to be molded into the product of 10mm particle diameter, briquetting pressure is 20MPa.。
4th step, removes free water.The hot blast that shaped article by the 3rd step is placed in 120 DEG C processes 2h, obtains the denitration desulfurizing agent based on biomass waste material of the present invention.
Second largest part: based on the gas cleaning implementation process of living beings desulfurization denitrification agent, this process mainly comprises following key step:
The first step, by all parts assembling present system shown in schematic diagram, and valve-off F2, F5 and F7, open valve F0, F4 and F8;
Second step, prepared desulfurization denitrification agent (102) is added in reative cell (1) from hopper (101), and make to be full of desulfurization denitrification agent in reative cell, then valve-off F0, open valve F1, make high-temperature flue gas enter reative cell (1) from air inlet K001, open induction power supply to induction coil (104) energising, to ensure that the temperature of reative cell (1) is more than 600 DEG C simultaneously;
3rd step, starts waste-heat recoverer 201; And give U-shaped condenser pipe 301 logical upper cooling water, the power supply of starting resistance heater (302), makes the temperature of sulfur recovery room control at 130 ~ 160 DEG C simultaneously;
4th step, detects outlet K002 institute and is vented the composition of body, once find sulfureous in flue gas and the content overproof of nitre, namely opens valve F2, releases the desulfurization denitrification agent of a part of inefficacy, open valve F0 simultaneously, is supplemented by new desulfurization denitrification agent into such as reative cell 1;
After system running a period of time, after the desulfurization denitrification agent that lost efficacy in feed bin 105 is filled, namely open valve F3, discharged;
After system running a period of time, open valve F5, make because the gravity dust fallen in waste heat recovery room 2 enters feed bin 202; After dust is filled in feed bin 202, namely open valve F6 and discharged;
After system running a period of time, after in container 303, sulphur fills with, valve-off F7, and dismantle bolt 305, the container containing sulphur is taken out; Then, load a new container, open valve F7 simultaneously.
Claims (10)
1. the high-temperature flue gas treatment system based on living beings desulfurization denitrification agent, comprise retort, it is characterized in that: retort top is the hopper (101) loading living beings desulfurization denitrification agent, bottom is the feed bin (105) loading inefficacy living beings denitration desulfurizing agent, and middle part is reative cell (1); High-temperature flue gas entry (K001) is provided with on the top of reative cell, bottom is provided with exhanst gas outlet, reative cell sidewall is provided with the load coil (104) for maintaining reative cell (1) temperature, and reative cell is mid-is placed with living beings desulfurization denitrification agent (102); Described exhanst gas outlet is by being communicated with waste heat recovery room (2) the first communicating pipe (1122), and waste heat recovery room (2) were communicated with sulfur recovery room (3) by the second communicating pipe (2233);
In described high-temperature flue gas entry (K001) place and the first communicating pipe (1122), be placed with the first Web materials (103,106) respectively, the material of described first Web materials (103,106) is any one in pottery, FeCrAl, Fe-Al intermetallic compound, Ni-Al intermetallic compound, and the mesh size of Web materials is less than the size of living beings desulfurization denitrification agent.
2. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 1, it is characterized in that: be equipped with the waste-heat recoverer (201) for waste heat in recovered flue gas in described waste heat recovery room (2), bottom is provided with the feed bin (202) for receiving waste heat recovery room dust.
3. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 1, it is characterized in that: be equipped with for the U-shaped condenser pipe (301) to sulphur steam-condensation in described sulfur recovery room (3), being provided with for maintaining sulfur recovery room temperature and ensureing that sulphur has the resistance heating tube (302) of good fluidity, being placed with the container (303) for receiving liquid sulfur in sulfur recovery room (3) bottom.
4. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 1, it is characterized in that: in described second communicating pipe (2233), be placed with the second Web materials (203), the material of described second Web materials (203) is any one in pottery, FeCrAl, Fe-Al intermetallic compound, Ni-Al intermetallic compound, and the mesh size of the second Web materials is less than 5 μm.
5. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 1 or 3, is characterized in that: be equipped with in sulfur recovery room (3) bottom for observing the peep hole (304) receiving sulphur storage capacity in liquid Sulfur capacity device (303).
6. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 1, is characterized in that: described living beings desulfurization denitrification agent, comprises following component and form by mass percentage:
Biomass waste material 30-40%
Modified zeolite class catalyst 10-20%
Modified activated carbon 10-20%
Living beings binding agent 30-40%;
In modified zeolite class catalyst, zeolitic catalyst is selected from HZSM-5 molecular sieve; Modification refers on HZSM-5 molecular sieve metal oxide-loaded; Described metal oxide is selected from the oxide of any one metallic element in Fe, Cu, Ce, Co, and in the metal oxide of load, the quality of metallic element accounts for 8 ~ 12% of HZSM-5 molecular sieve quality.
7. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 6, it is characterized in that: described biomass waste material is selected from one or more mixtures formed by arbitrary ratio mixing in agricultural crop straw, crops processing waste, forestry processing waste, domestic waste, mass percentage≤10% of water in biomass waste material, granularity≤3mm.
8. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 6, it is characterized in that: the preparation method of described modified zeolite class catalyst is: first, get Fe, Cu, the nitrate of Ce or Co, be mixed with the Fe that mass percentage concentration is 10 ~ 30%, Cu, the nitrate solution of Ce or Co, then, be that 20 ~ 40 object HZSM-5 molecular sieves at least flood once in described nitrate solution by granularity, filter, gained filter residue is after 100 ~ 120 DEG C of dry 1.5-2h, again in 500 ~ 550 DEG C of roasting 2-4h, repeat above-mentioned dipping, drying and roasting process, finally weigh, until the quality of metallic element accounts for 8 ~ 12% of HZSM-5 molecular sieve quality in the metal oxide of load.
9. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 6, it is characterized in that: described modified activated carbon is that active carbon is crushed to 20 ~ 40 orders, be after soaking 0.5 ~ 4h in the salpeter solution of 10 ~ 65% in mass percentage concentration, in 100 ~ 120 DEG C of dry 1.5-2h, the product obtained.
10. a kind of high-temperature flue gas treatment system based on living beings desulfurization denitrification agent according to claim 6, it is characterized in that: described living beings binding agent production technology is: after the stalk being averaged size≤3mm soaks 1 ~ 3 day in water, the white lime accounting for stalk quality 30 ~ 35% is added in water, stir, obtain mixture, then, mixture is heated to 95 ~ 100 DEG C, insulation 3 ~ 4h, the yellow, viscous material obtained is living beings binding agent; The quality of water is 8 ~ 10 times of stalk weight.
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