WO2001087466A1 - Procede et appareil pour la decomposition des composants organiques halogenes dans des gaz d'echappement - Google Patents
Procede et appareil pour la decomposition des composants organiques halogenes dans des gaz d'echappement Download PDFInfo
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- WO2001087466A1 WO2001087466A1 PCT/JP2001/004160 JP0104160W WO0187466A1 WO 2001087466 A1 WO2001087466 A1 WO 2001087466A1 JP 0104160 W JP0104160 W JP 0104160W WO 0187466 A1 WO0187466 A1 WO 0187466A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- exhaust gas
- manganese oxide
- manganese
- halogenated organic
- packed bed
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 68
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 50
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 271
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000007664 blowing Methods 0.000 claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims description 28
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 230000008929 regeneration Effects 0.000 claims description 16
- 238000011069 regeneration method Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 11
- 230000001172 regenerating effect Effects 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 235000019512 sardine Nutrition 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 241001125048 Sardina Species 0.000 claims 2
- 241000245665 Taraxacum Species 0.000 claims 2
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 claims 2
- 230000007423 decrease Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 100
- 239000000428 dust Substances 0.000 description 28
- 150000002013 dioxins Chemical class 0.000 description 23
- 239000010410 layer Substances 0.000 description 18
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000010881 fly ash Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000002144 chemical decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000010813 municipal solid waste Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- -1 dioxins Chemical class 0.000 description 2
- 230000005264 electron capture Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- HPARLNRMYDSBNO-UHFFFAOYSA-N 1,4-benzodioxine Chemical compound C1=CC=C2OC=COC2=C1 HPARLNRMYDSBNO-UHFFFAOYSA-N 0.000 description 1
- WRSMJZYBNIAAEE-UHFFFAOYSA-N 1-chlorodibenzofuran Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2Cl WRSMJZYBNIAAEE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000555825 Clupeidae Species 0.000 description 1
- WJWZQFKHOYDCIJ-UHFFFAOYSA-N O.[O--].[O--].[Mn++].[Mn++] Chemical compound O.[O--].[O--].[Mn++].[Mn++] WJWZQFKHOYDCIJ-UHFFFAOYSA-N 0.000 description 1
- 102000003743 Relaxin Human genes 0.000 description 1
- 108090000103 Relaxin Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- NFBOHOGPQUYFRF-UHFFFAOYSA-N oxanthrene Chemical compound C1=CC=C2OC3=CC=CC=C3OC2=C1 NFBOHOGPQUYFRF-UHFFFAOYSA-N 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/003—Arrangements of devices for treating smoke or fumes for supplying chemicals to fumes, e.g. using injection devices
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/70—Organic halogen compounds
-
- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/30—Halogen; Compounds thereof
- F23J2215/301—Dioxins; Furans
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2217/00—Intercepting solids
- F23J2217/10—Intercepting solids by filters
- F23J2217/105—Granular bed
Definitions
- the present invention relates to dioxin contained in exhaust gas generated when burning municipal solid waste, industrial waste, medical waste, raw material for sintering steel and the like.
- the present invention relates to a method and an apparatus for decomposing a halogenated organic compound such as a class.
- a halogenated organic compound such as a class.
- the halogenated organic I ⁇ was specifically, black hole benzenes, chlorodibenzo di O relaxin, chloro dibenzofuran, port 1 J chlorinated organic compounds such as chloride Bifue sulfonyl, other bromo benzenes, Puromoji Examples include benzodioxin, promodibenzofuran, polybrominated dibenzobifluorene benzenes, fluo dibenzodioxin, fluorodibenzofuran, and polyfluorinated biphenyl.
- the chemical decomposition method has the characteristic that the reaction can be performed in a low temperature range and that dioxins can be efficiently produced in a short time.
- An object of the present invention is to provide a method and an apparatus capable of decomposing a halogenated organic compound in exhaust gas easily and inexpensively without significantly reducing the processing capacity.
- This object is achieved by a method for decomposing a halogenated organic compound in exhaust gas, which comprises a step of blowing a composition containing at least one of trivalent and tetravalent manganese oxides into the exhaust gas.
- the present invention also provides a method for decomposing a halogenated organic compound in exhaust gas, the method including a step of passing the exhaust gas through a moving packed bed in which a composition containing at least one of trivalent and tetravalent manganese oxides moves. The goal is achieved.
- FIG. 1 is a diagram showing a refuse incineration plant provided with a device for decomposing halogenated organic compounds in exhaust gas, which is an example of the present invention.
- FIG. 2 is a diagram showing the time-dependent change in dioxin concentration.
- FIG. 3 shows another apparatus for decomposing a halogenated organic compound in an exhaust gas according to the present invention. It is a figure showing refuse incineration equipment.
- FIG. 4 is a diagram showing an apparatus for decomposing a halogenated organic compound in exhaust gas, which is an example of the present invention.
- FIG. 5 is a diagram showing an X-ray diffraction analysis result of the manganese oxide after the regeneration treatment.
- FIG. 6 is a diagram showing a refuse incineration plant provided with another apparatus for decomposing a halogenated organic compound in exhaust gas according to the present invention.
- FIG. 7 is a diagram showing a device for decomposing a halogenated organic compound in exhaust gas, which is another example of the present invention.
- MODES FOR CARRYING OUT THE INVENTION We studied a method for chemically decomposing halogenated organic compounds such as dioxins in exhaust gas. It has been found that if a composition containing at least one kind is blown, the catalyst layer will not be clogged or the like, and the halogenated organic compound can be decomposed without reducing the processing capacity. Further, in this method, a composition containing at least one of trivalent and tetravalent manganese oxides is always blown, so that the decomposition performance of the halogenated organic compound is degraded. Furthermore, this method is an inexpensive and simple method, since only a composition containing at least one of trivalent and tetravalent manganese oxides is blown.
- the composition containing at least one of trivalent and tetravalent manganese oxides includes manganese trioxide, manganese dioxide, a mixture thereof, or a manganese ore containing them (BHP ore, indian manganese ore, Manganese oxides such as Mt. Newman ore and Hamasley ore can be used. In place of such manganese Sani ⁇ , CeO 2 or Fe 2 0 3, similar effects by blowing composition comprising a can be obtained.
- the decomposition reaction of the halogenated organic compound by the manganese oxide proceeds when the exhaust gas temperature is about 50 ° C, and is accelerated as the temperature rises. However, practically, it is preferably 100 ° C or more. However, for example, when the temperature exceeds 530 ° C, the tetravalent manganese oxide, diacid manganese oxide, decomposes by itself, and when it exceeds 950, the trivalent manganese oxide Manganese dioxide is self-generated. Therefore, it is desirable to carry out the reaction in a temperature range that does not achieve these temperatures.However, even at about 1000 ° C, the decomposition reaction of the halogenated organic compound does not occur because undecomposed manganese tridioxide is present. proceed.
- the reaction is performed in a temperature range in which dioxins are in the gas phase or in a temperature range in which dioxins do not adsorb to dust, at 400 ° C or higher, more preferably 450 ° C or higher.
- the decomposition of the halogenated organic compound by the manganese oxide in the present invention is an oxidation reaction, and the final products are carbon dioxide, water, HC1, and the like.
- the amount of halogenated organic compounds in the exhaust gas was measured using a gas chromatograph mass spectrometer or a measuring device such as a gas chromatograph electron capture detector, and the manganese oxide was blown based on the amount. By controlling the flow rate, it is possible to decompose the organic compound with an appropriate amount of blow without excess or shortage.
- a method of injecting manganese oxide into exhaust gas for example, there is a method of injecting manganese oxide powder directly into exhaust gas from a blowing nozzle of slaked lime or activated carbon provided in a flue of a refuse incineration plant.
- the manganese oxide powder may be mixed with a liquid such as water, and may be blown into a slurry.
- a refuse incinerator where water spray is performed to lower the gas temperature, halogenated organic compounds in the exhaust gas can be decomposed even if a manganese oxide slurry is sprayed instead of this water.
- the particle size of the manganese oxide powder be 10 or less to ensure that the halogenated organic compounds in the exhaust gas are decomposed in the flue of refuse incineration equipment. Since the manganese oxide present in the surface layer of the powder particles is considered to be involved in the decomposition of the halogenated organic compound, it is desirable that the particle size be as fine as possible. Considering the above, it is more desirable to set it to 5-100 m.
- the blown manganese oxide is collected together with dust, slaked lime, activated carbon, and fly ash by a collecting device such as a dust collector, and the collected matter is blown off by sending pulsed air, collected, and then blown back into the exhaust gas, which is halogen. Can be reused for the decomposition of organic compounds.
- the recovered material containing manganese oxide can also be effectively used as a raw material for blast furnaces, converters, electric furnaces, and as a raw material for sintering machines. Therefore, emission of manganese oxide as waste The amount can be greatly reduced.
- a collection means a method of passing through water or collecting dust by ultrasonic waves can be applied.
- the recovered material containing manganese oxide deficient in oxygen due to the decomposition of the halogenated organic compound may be heated in the air or in a high-concentration oxygen atmosphere, or may be easily released from oxygen, such as ozone, hydrogen peroxide or hydrogen peroxide.
- a more efficient treatment is achieved by regenerating the manganese oxide, which is depleted of oxygen, by contacting it with a manganese acid-powered rim at a certain temperature to oxidize the oxygen-deficient manganese oxide.
- the decomposition of halogenated organic compounds can be performed well, and the amount of manganese oxide used and the amount of waste discharged can be significantly reduced.
- manganese oxide is collected separately and subjected to regeneration treatment, the use of manganese oxide is smaller than the conventional technology in which an oxidizing agent is added to exhaust gas to regenerate oxygen-deficient manganese oxide.
- the amount can be more appropriately controlled, and the amount of the halogenated organic compound can be reduced more efficiently.
- halogenated organic compounds can be more efficiently removed using manganese oxide from which impurities have been removed. Can be disassembled.
- the separated manganese oxide is regenerated and blown into the exhaust gas, as described above.
- the exhaust gas and the manganese oxide contact Is effectively performed, and the halogenated organic compounds in the exhaust gas can be almost completely decomposed.
- the moving packed layer means that the layer filled with manganese oxide is moved in one direction, and the manganese oxide reacting with the halogenated organic compound in the exhaust gas is sequentially moved and discharged from one end, A layer that can be supplied with a composition containing at least one of trivalent and tetravalent manganese oxides from the other end to react with the halogenated organic compound. Therefore, even if clogging occurs due to dust and fly ash in the exhaust gas, the clogged portion moves and is discharged sequentially, so that the processing capacity does not significantly decrease.
- a composition containing at least one of trivalent and tetravalent manganese oxides is fixedly filled, and one or more forcefully detachable Even if a fixed packing layer divided into a plurality of parts is used, it can be easily replaced even if clogging occurs because it is removable, and the processing capacity does not decrease significantly. Further, if the packed bed is divided into a plurality of pieces and the force cartridge method is used, replacement can be performed for each individual cartridge, so that replacement can be performed more easily and quickly.
- the amount of the halogenated organic compound in the exhaust gas is measured, and if the amount of the manganese oxide is controlled based on the amount, the appropriate amount can be obtained.
- the moving amount can decompose the halogenated organic compound. Also, in this case, there is also an effect of removing a part of dust and fly ash in the exhaust gas, and the burden on a downstream dust collector can be reduced, so that the size of the dust collector can be reduced.
- manganese oxide reacts with HC1 gas and chlorine gas in exhaust gas, so that resynthesis of dioxins can be prevented.
- Collecting the mobile and fixed packed beds containing used manganese oxide and re-supplying it to the mobile and fixed packed beds or reusing it as a raw material for steelmaking can reduce the waste as manganese oxide.
- the emission amount can be reduced, and the amount of manganese oxide used in the present invention can be greatly reduced. It is also possible to separate only manganese oxide from the recovered material and supply it to the mobile packed bed or fixed packed bed again. Furthermore, the manganese oxide can be separately regenerated by the method described above and supplied again to the moving packed bed or the fixed packed bed.
- the composition containing at least one of the trivalent and tetravalent manganese oxides to be filled in the mobile packed bed or the fixed packed bed is manganese dioxide, manganese dioxide, a mixture thereof, or a mixture thereof.
- Manganese oxides such as manganese ore (BHP ore, Indian manganese ore, Mt. Eumanite, Hamazley ore, etc.) can be used. Also, in place of such manganese oxide, the same effect can be obtained by filling a composition comprising CeO 2 or FeA.
- the manganese oxide used in the mobile packed bed and fixed packed bed should be 0.5 to 15 mm, more preferably 0.5 to 10 mm, so that clogging due to dust and fly ash in the exhaust gas does not occur. It is preferred to have a particle size of mm.
- the decomposition reaction of halogenated organic compounds can be performed more efficiently if the exhaust gas is introduced horizontally or from below and passed vertically. it can. In this case, it is desirable to remove the exhaust gas in advance in order to eliminate the influence of dust.
- a moving packed bed or a fixed packed bed can be installed in the flue of the exhaust gas to allow the exhaust gas to pass.
- the method of decomposing organic compounds in exhaust gas which is the method of the present invention described above, includes a blowing device for blowing manganese oxide, a moving packed bed in which manganese oxide moves, or a manganese oxide filled material. It can be realized by a device for decomposing halogenated organic compounds in exhaust gas, which has a detachable fixed packing layer divided into one or more parts.
- a measuring device for measuring the amount of the halogenated organic compound in the exhaust gas, and the amount of the manganese oxide, based on the measured amount of the organic compound, and A control device for controlling the amount of movement can be provided.
- collection devices such as S3 ⁇ 4 machines that collect manganese oxides together with dust, etc., collection devices that collect collected materials, centrifugal separators that separate manganese oxides from collected materials, Provide a reprocessing equipment to oxidize manganese oxides or separated manganese oxides by heating them in air or under a high-concentration oxygen atmosphere, or by contacting them with ozone, hydrogen peroxide, potassium permanganate, etc. Can be.
- Example 1 Example 1
- Manganese oxide blowing equipment for garbage incinerator, manganese oxide with dust Using a test refuse incinerator equipped with a collection device that collects collected garbage and a collection device that collects collected material, manganese ore from Australia, which has been ground to a particle size of 20 to 30 by a blowing device, is transported to the flue by a blower. Then, it was blown from the blow nozzle. At this time, the contents of injectors 1. a 5 m 3. The cutout can be cut out by a fixed amount using a table feeder, and the cutout amount is adjusted so that the blow rate is 1 kg / h. The flue gas temperature in the stack was about 450C. The injected manganese oxide was collected at 200 ° C by an electric precipitator, which was a collecting device, and collected together with dust by a collecting device.
- FIG. 1 shows a refuse incineration plant provided with an apparatus for decomposing a halogenated organic compound in exhaust gas, which is an example of the present invention.
- the refuse supplied from the refuse input hopper 12 provided at the entrance side of the combustion chamber 11 is blown into the combustion air from the combustion air supply unit 15 through the control valve 16 and the wind box 14, and Burned.
- the waste incinerator can process 48 tons of waste a day.
- Exhaust gas generated by combustion is decomposed into halogenated organic compounds such as dioxins by manganese oxide which is blown into the flue 1 on the outlet side of the combustion chamber 11 by a blowing device 2 consisting of a storage hopper, table feeder and blower. After that, it is released from the chimney 19 through the main blower 18.
- manganese oxide is a trapping device Collected by the dust collector 10.
- a gas chromatograph 20 equipped with a sample concentrator and an electron capture detector is provided downstream of the consolidator 10, and the benzene (monochrome benzene) is measured.
- the dioxin concentration is calculated by the controller 21 to which the correlation of the dioxin concentration is input. In this case, benzene was measured, but dioxin concentration can be calculated by measuring phenols.
- Figure 2 shows the time course of dioxin concentration.
- Table 2 shows the usage of manganese ore.
- FIG. 3 shows another apparatus for decomposing halogenated organic compounds in exhaust gas according to the present invention. Indicates waste incineration equipment.
- a dust collector 10 that collects manganese oxides together with dust
- a collection device 4 that collects collected matter downstream of it
- a manganese oxide A separation device 5 for separating the material and a regeneration treatment device 6 for oxidizing the separated manganese oxide are provided. Then, the regenerated manganese oxide is blown into the flue 1 on the outlet side of the combustion chamber 11 by the blowing device I, and is reused for decomposing the halogenated organic compound.
- the collection device 4 is a receiving tank for the particles that have been removed by the dust collector 10. It is desirable that the manganese oxide collected by the dust collector 10 be collected before the amount of collected particles increases and the filter speed decreases.
- the separation device 5 is, for example, a cycle opening.
- the regenerating apparatus 6 is, for example, a heating furnace capable of heating at 500 at 2% for 2 hours in an atmosphere with an oxygen concentration of 32%.
- Example 4
- FIG. 4 shows an apparatus for decomposing a halogenated organic compound in exhaust gas, which is an example of the present invention.
- Exhaust gas generated from the exhaust gas generator 30 is removed by the dust collector 10 provided in the flue 1 and then sent to the mobile packed bed 7 of manganese oxide, which is set in the electric furnace 33 and set at a predetermined temperature, and is filled.
- the manganese oxide passes from the bottom to the top of the layer 7 in the opposite direction to the direction of movement.
- halogenated organic compounds in the exhaust gas are emitted.
- the exhaust gas is sucked by the pump 31 and returns to the flue 1 to be discharged.
- the manganese oxide that has moved through the moving packed bed 7 is quantitatively discharged by a quantitative feeder and collected by the recovery device 4.
- the same amount of manganese oxide as the amount discharged is supplied from 32 manganese oxide supply machines, and the manganese oxide is adjusted so that a fixed amount of manganese oxide always moves in the mobile packed bed 7.
- the exhaust gas before the decomposition reaction is sampled from the sampling nozzle 34a, and the exhaust gas after the decomposition reaction is sampled from the sampling nozzle 34b.
- a moving packed bed 7 having an inner diameter of 100 and a height of 500 m was filled with manganese oxide ground to a particle size of 1 mm at a porosity of about 50%, and moved at a moving speed of 50 bands / h.
- the temperature of the moving packed bed 7 was set to 450 ° C. by the electric furnace 33.
- the exhaust gas was sucked by the pump 31 so that the gas flow rate became 1 HI 3 I min, and the exhaust gas was sampled from the sampling nozzles 34a and 34b to measure the concentration of dioxins. Table 3 shows the results.
- dioxins are almost 100 ⁇ .
- TEQ Toxicity conversion temperature
- Degree of manganese oxide discharged from the moving packed bed 7 is recovered by the recovery device 4, and is subjected to a regeneration treatment at 800 ° C for 1 hour in an electric furnace while flowing air. Line diffraction analysis was performed.
- Figure 5 shows the results.
- a (a) the analysis result after regeneration treatment, (b) the analysis of the standard sample Mn 2 0 3.
- FIG. 6 shows a refuse incineration plant provided with another apparatus for decomposing halogenated organic compounds in exhaust gas according to the present invention.
- the exhaust gas discharged from the combustion chamber 11 passes horizontally through the moving packed bed 7 of manganese oxide provided in the flue 1 on the outlet side of the combustion chamber 11. At this time, the exhaust gas comes into contact with the manganese oxide moving from the top to the bottom in the moving packed bed 7, and the halogenated organic compound in the exhaust gas is decomposed. After that, the exhaust gas is cleaned of dust and fly ash by the dust collector 10 and discharged from the chimney 19 through the main blower 18.
- the temperature of the exhaust gas passing through the moving packed bed 7 is desirably, for example, 450 ° C. or more.
- the moving packed bed 7 removes a part of dust and fly ash in the exhaust gas, the burden on the subsequent dust collector 10 can be reduced and the dust collector 10 can be reduced in size.
- a recovery device 4 Downstream of the moving packed bed 7, a recovery device 4 that collects manganese oxides together with dust, etc.4, a separation device 5 that separates manganese oxides from collected materials, and a regeneration treatment device that oxidizes the separated manganese oxides 6 are provided sequentially. Then, the regenerated manganese oxide is supplied from the supply device 8 to the moving packed bed 7 and reused.
- the regeneration treatment for example, treatment may be performed at 500 ° C. for 2 hours in an atmosphere having an oxygen concentration of 32%.
- FIG. 7 shows an apparatus for decomposing a halogenated organic compound in exhaust gas, which is another example of the present invention.
- Exhaust gas generated from the exhaust gas generator 30 is removed by a dust collector 10 provided in a flue 1 with an inner diameter of 50, and then sent to a cartridge-type fixed packed bed 36 filled with manganese oxide, and then discharged. You. At this time, the exhaust gas is sent to one of the cartridge-type packed beds 36 by the switching valve 35 so that the other cartridge-type packed bed 36 to which no exhaust gas is sent can be replaced.
- the size of one cartridge-type packed bed 36 is 50 thigh inside diameter and 200 mm in height.
- the cartridge-type packed bed 36 was filled with manganese oxide crushed to a particle size of 10 particles, and the exhaust gas of 450 was passed at a flow rate of 1 m 3 / min. Exhaust gas before and after the reaction was sampled, and the concentration of dioxins was measured. The switching of the force-bridge type packed bed by the switching valve 35 was performed every 24 hours. Table 4 shows the results Show.
- dioxins are reduced to almost 100.
- Example filled with Mn 2 0 3 to force one Toritsuji type fixed packed bed 36 of 6 was passed through at 600 ° C exhaust gas flow rate 1 m 3 / min.
- the exhaust gas before and after the reaction was sampled, and the concentration of dioxins was measured. Table 5 shows the results.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Treating Waste Gases (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01932135A EP1291070A1 (en) | 2000-05-19 | 2001-05-18 | Method and apparatus for decomposing halogenated organic compound in exhaust gas |
US10/287,093 US20030095918A1 (en) | 2000-05-19 | 2002-11-04 | Method for decomposing halogenated organic compound in flue gas and apparatus therefor |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000147842 | 2000-05-19 | ||
JP2000-147842 | 2000-05-19 | ||
JP2000214812 | 2000-07-14 | ||
JP2000-214812 | 2000-07-14 | ||
JP2001-106897 | 2001-04-05 | ||
JP2001106897 | 2001-04-05 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/287,093 Continuation US20030095918A1 (en) | 2000-05-19 | 2002-11-04 | Method for decomposing halogenated organic compound in flue gas and apparatus therefor |
Publications (1)
Publication Number | Publication Date |
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WO2001087466A1 true WO2001087466A1 (fr) | 2001-11-22 |
Family
ID=27343424
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2001/004160 WO2001087466A1 (fr) | 2000-05-19 | 2001-05-18 | Procede et appareil pour la decomposition des composants organiques halogenes dans des gaz d'echappement |
Country Status (4)
Country | Link |
---|---|
US (1) | US20030095918A1 (ja) |
EP (1) | EP1291070A1 (ja) |
KR (1) | KR20030001461A (ja) |
WO (1) | WO2001087466A1 (ja) |
Families Citing this family (6)
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MX2010008091A (es) * | 2008-02-11 | 2010-08-23 | Ecolab Inc | Uso de complejos activadores para aumentar la limpieza a baja temperatura en sistemas de limpieza con peroxido alcalino. |
US20090325841A1 (en) | 2008-02-11 | 2009-12-31 | Ecolab Inc. | Use of activator complexes to enhance lower temperature cleaning in alkaline peroxide cleaning systems |
CN105579129B (zh) * | 2013-10-16 | 2018-12-21 | 沙特基础工业公司 | 二氧化碳流股的纯化 |
EP3057684B1 (en) | 2013-10-16 | 2018-03-21 | Saudi Basic Industries Corporation | Process for the removal of chlorinated hydrocarbons from co2 |
DE102015203244A1 (de) * | 2015-02-24 | 2016-08-25 | Steinmüller Babcock Environment Gmbh | Mehrzugkessel |
CN116651200B (zh) * | 2023-07-20 | 2025-03-14 | 内蒙古科技大学 | 一种利用电解锰渣脱除金属冶炼尾气中二噁英的方法与装置 |
Citations (7)
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JPH0760123A (ja) * | 1993-08-20 | 1995-03-07 | Nippon Steel Corp | 排煙浄化処理用触媒の再生方法 |
JPH0760122A (ja) * | 1993-08-20 | 1995-03-07 | Nippon Steel Corp | 排煙浄化処理用触媒の再生方法 |
JPH07124441A (ja) * | 1993-11-05 | 1995-05-16 | Nippon Steel Corp | 含塵排ガス中の微量有機塩素化合物除去方法 |
JPH07243636A (ja) * | 1994-03-09 | 1995-09-19 | Mitsui Toatsu Chem Inc | 廃棄物の燃焼処理方法及び装置 |
JPH11226397A (ja) * | 1998-02-20 | 1999-08-24 | Chiyoda Corp | 難分解性有機塩素化合物の分解触媒 |
JP2000135432A (ja) * | 1998-10-30 | 2000-05-16 | Kobe Steel Ltd | ダイオキシン類除去剤 |
JP2000202240A (ja) * | 1999-01-19 | 2000-07-25 | Nkk Corp | 塩素化有機化合物の分解方法 |
Family Cites Families (3)
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US4059675A (en) * | 1976-05-24 | 1977-11-22 | Continental Oil Company | Decomposition of halogenated organic compounds |
US5344630A (en) * | 1991-06-28 | 1994-09-06 | Rohm And Haas Company | Deep oxidation of halogenated organics with porous carbonaceous materials |
US5283041A (en) * | 1992-08-13 | 1994-02-01 | Engelhard Corporation | Catalytic incineration of organic compounds |
-
2001
- 2001-05-18 KR KR1020027014557A patent/KR20030001461A/ko not_active Ceased
- 2001-05-18 WO PCT/JP2001/004160 patent/WO2001087466A1/ja not_active Application Discontinuation
- 2001-05-18 EP EP01932135A patent/EP1291070A1/en not_active Withdrawn
-
2002
- 2002-11-04 US US10/287,093 patent/US20030095918A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0760123A (ja) * | 1993-08-20 | 1995-03-07 | Nippon Steel Corp | 排煙浄化処理用触媒の再生方法 |
JPH0760122A (ja) * | 1993-08-20 | 1995-03-07 | Nippon Steel Corp | 排煙浄化処理用触媒の再生方法 |
JPH07124441A (ja) * | 1993-11-05 | 1995-05-16 | Nippon Steel Corp | 含塵排ガス中の微量有機塩素化合物除去方法 |
JPH07243636A (ja) * | 1994-03-09 | 1995-09-19 | Mitsui Toatsu Chem Inc | 廃棄物の燃焼処理方法及び装置 |
JPH11226397A (ja) * | 1998-02-20 | 1999-08-24 | Chiyoda Corp | 難分解性有機塩素化合物の分解触媒 |
JP2000135432A (ja) * | 1998-10-30 | 2000-05-16 | Kobe Steel Ltd | ダイオキシン類除去剤 |
JP2000202240A (ja) * | 1999-01-19 | 2000-07-25 | Nkk Corp | 塩素化有機化合物の分解方法 |
Also Published As
Publication number | Publication date |
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KR20030001461A (ko) | 2003-01-06 |
EP1291070A1 (en) | 2003-03-12 |
US20030095918A1 (en) | 2003-05-22 |
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