JPS5837008B2 - Removal of nitrogen oxides and sulfur oxides from gases - Google Patents
Removal of nitrogen oxides and sulfur oxides from gasesInfo
- Publication number
- JPS5837008B2 JPS5837008B2 JP48097408A JP9740873A JPS5837008B2 JP S5837008 B2 JPS5837008 B2 JP S5837008B2 JP 48097408 A JP48097408 A JP 48097408A JP 9740873 A JP9740873 A JP 9740873A JP S5837008 B2 JPS5837008 B2 JP S5837008B2
- Authority
- JP
- Japan
- Prior art keywords
- oxides
- nox
- sulfur
- removal
- ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 145
- 229910052815 sulfur oxide Inorganic materials 0.000 title claims description 26
- 239000007789 gas Substances 0.000 title claims description 24
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 title claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 70
- 229910021529 ammonia Inorganic materials 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 11
- 239000002594 sorbent Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 46
- 239000003546 flue gas Substances 0.000 description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 26
- 238000001179 sorption measurement Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 11
- 239000005751 Copper oxide Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910000431 copper oxide Inorganic materials 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- -1 NO and NO2 Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
Classifications
-
- 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
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Treating Waste Gases (AREA)
- Chimneys And Flues (AREA)
Description
【発明の詳細な説明】
本発明は、煙道ガスの如き廃ガスから窒素酸化物及び硫
黄酸化物を除去することに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the removal of nitrogen oxides and sulfur oxides from waste gases such as flue gases.
窒素酸化物及び硫黄酸化物の両方とも大気汚染物である
。Both nitrogen oxides and sulfur oxides are air pollutants.
ＮＯ及びＮＯ２を含めて窒素酸化物は一般にＮＯｘで表
わされ、そしてこれらは炭化水素との光化学反応に関与
してスモッグの形戒をもたらす。Nitrogen oxides, including NO and NO2, are commonly referred to as NOx, and they participate in photochemical reactions with hydrocarbons resulting in the formation of smog.
硫黄酸化物（ＳＯ２及びＳ０３、一般にはＳＯｘで表わ
される）は呼吸器系に対する刺激物であり、植物及び動
物の生命にも有害であり、そして種々の金属及び建築材
料に対して腐食性で且つ有害である。Sulfur oxides (SO2 and SO3, commonly denoted SOx) are irritants to the respiratory system, are also harmful to plant and animal life, and are corrosive and corrosive to various metals and building materials. Harmful.
本発明は、硫黄酸化物、窒素酸化物及び酸素を含有する
煙道ガスの如き廃ガス流れから硫黄酸化物及び窒素酸化
物の両方を除去する方法を提供する。The present invention provides a method for removing both sulfur oxides and nitrogen oxides from waste gas streams, such as flue gases, containing sulfur oxides, nitrogen oxides, and oxygen.
本発明に従えば、硫黄酸化物及び窒素酸化物は、硫黄酸
化物、窒素酸化物及び酸素を含有するガス流れにアンモ
ニアを加えそして前記ガス流れをＳＯｘの選択的除去用
の収着剤及びＮＯｘの選択的還元用の触媒の両方である
固体接触物質と酸化条件下に接触させることによって該
ガス流れから同時に除去される。According to the present invention, sulfur oxides and nitrogen oxides are added to a gas stream containing sulfur oxides, nitrogen oxides and oxygen with ammonia and treated as a sorbent for selective removal of SOx and NOx. is simultaneously removed from the gas stream by contacting it under oxidizing conditions with a solid contact material that is both a catalyst for the selective reduction of .
酸化銅を担持するアルミナが両方の機能を果す好ましい
接触物質である。Alumina carrying copper oxide is a preferred contact material that performs both functions.
本発明の好ましい具体例に従えば、硫黄酸化物及び窒素
酸化物は、循環再生法で煙道ガスから同時に除去される
。According to a preferred embodiment of the invention, sulfur oxides and nitrogen oxides are simultaneously removed from the flue gas in a cyclic regeneration process.
本発明のこの具体例に従って処理される煙道ガスは、石
炭の如き硫黄含有固体燃料又は燃料油の如き硫黄含有液
体燃料（残油又は他の重質油を含めて）をバーナーにお
いて空気と共に燃焼させることによって形成される。The flue gas treated in accordance with this embodiment of the invention comprises burning a sulfur-containing solid fuel such as coal or a sulfur-containing liquid fuel such as fuel oil (including residual oil or other heavy oil) with air in a burner. It is formed by letting
かくして発生された煙道ガスは、過剰空気の使用による
少量の酸素例えば約０．５〜約８容量饅の酸素、微量の
ＳＯ３ と共に約ｏ．ｉ〜０，５容量φ更に普通には約
０．２〜０．３容量俤のＳ０２ （これらの硫黄酸化物
の量は燃料中の硫黄の量に左右される）、及び約１５０
〜約１５００ｐｐｍの窒素酸化物（ＮＯ及びＮＯ２の両
方、主として前者）（これらの量は燃料の窒素含量並び
に燃焼温度及び条件に左右される）を通常含有する。The flue gas thus generated is about o. i ~ 0,5 volume φ, more commonly about 0.2-0.3 volume S02 (the amount of these sulfur oxides depends on the amount of sulfur in the fuel), and about 150
It typically contains up to about 1500 ppm of nitrogen oxides (both NO and NO2, primarily the former) (these amounts depend on the nitrogen content of the fuel and the combustion temperature and conditions).
電力発生装置で発生する煙道ガスは、本発明に従って処
理することのできる煙道ガスの普通の源である。Flue gas generated by power generators is a common source of flue gas that can be treated in accordance with the present invention.
本発明の方法によって、約９０％の流入硫黄酸化物（Ｓ
Ｏｘ）及び約９０％の流入窒素酸化物（ＮＯｘ）を除去
することができる。By the method of the present invention, approximately 90% of the influent sulfur oxides (S
Oxygen oxides (Ox) and approximately 90% of incoming nitrogen oxides (NOx) can be removed.
アンモニアは、煙道ガス流れの温度が約６００〜約９０
０”Ｆ（３１６〜４８２°Ｃ）であるときに例えば該ガ
スが普通の電力発生装置のエコノマイザーを通ってその
温度が通常約６００〜約７０００Ｆ（３１６〜３７１℃
）になった後に該ガス流れに加えられる。Ammonia has a flue gas stream temperature of about 600 to about 90
For example, when the gas is passed through an economizer in a common power generator, its temperature is typically about 600 to about 7000 F (316 to 371 C).
) is added to the gas stream.
アンモニアの量は、存在する窒素酸化物（ＮＯｘで表わ
される）１モル当り少なくとも約０．５モルである。The amount of ammonia is at least about 0.5 mole per mole of nitrogen oxide (expressed as NOx) present.
これは、窒素酸化物（ＮＯｘは９０φがＮＯで１０咎が
ＮＯ２であると仮定して）の還元に必要とされる化学量
論的量の少なくとも約０．７倍である。This is at least about 0.7 times the stoichiometric amount required for the reduction of nitrogen oxides (assuming 90 mm of NOx and 10 mm of NO2).
ＮＯｘの還元は、次の式に従って表わすことができる。The reduction of NOx can be expressed according to the following equation.
６ＮＯ＋４ＮＨ３−−→５Ｎ２＋６Ｈ２０３ＮＯ２＋４
ＮＨ３−一→７／２Ｎ２＋６Ｈ２０好ましいアンモニア
量はＮＯｘ １モル当り少なくとも０．６モルであり、
そして最も好ましい量はＮＯｘ １モル当りＮＨ３化学
量論的量から約４モルの範囲内である。6NO+4NH3--→5N2+6H203NO2+4
NH3−1→7/2N2+6H20 The preferred amount of ammonia is at least 0.6 mole per mole of NOx;
And the most preferred amount is within the range of about 4 moles of NH3 per mole of NOx.
アンモニアが化学量論酌量を一旦越えると、ＮＯｘのほ
ゾ定量的な還元が達成され、そしてアンモニアの量の増
加は意義ある程に低いレベルのＮＯｘ流出をもたらさな
い。Once the stoichiometric amount of ammonia is exceeded, a fairly quantitative reduction of NOx is achieved and increasing the amount of ammonia does not result in significantly lower levels of NOx efflux.
実質的過剰のアンモニアが供給されるときでさえも、流
出する煙道ガス中にはアンモニアは通常検出されない。Even when a substantial excess of ammonia is supplied, no ammonia is usually detected in the exiting flue gas.
また、流出するＮＯｘ及びＳＯｘの両方とも、実質的過
剰のアンモニアを供給したときでさえも全く低い。Also, both NOx and SOx effluent are quite low even when feeding a substantial excess of ammonia.
これは、酸素による酸化窒素へのアンモニアの意義ある
酸化が全く起らないことを示唆する。This suggests that no significant oxidation of ammonia to nitrogen oxide by oxygen occurs.
加えられたアンモニアを含有する煙道ガス流れは、二酸
化硫黄及び窒素酸化物の両方の量を減少させるために約
６００〜約９００’Ｆ（３１６〜４８２℃）好ましくは
約６５０〜約８０００Ｆ（３４３〜４２７℃）のガス流
入温度で接触物質と接触される。The flue gas stream containing added ammonia is heated to a temperature of about 600 to about 900'F (316-482C), preferably about 650 to about 8000'F (343C) to reduce the amount of both sulfur dioxide and nitrogen oxides. The contact material is contacted at a gas inlet temperature of ˜427° C.).
前記接触物質は、アルミナの如き本質上不活性の多孔質
担体に酸化銅の如き活性物質を担持させてなる。The contact material comprises an essentially inert porous support such as alumina carrying an active material such as copper oxide.
酸化銅担持アルミナが好ましい接触物質である。Copper oxide supported alumina is the preferred contact material.
活性物質は、ＳＯｘの選択的除去剤及びＮＯｘの選択的
還元触媒の両方として作用する酸化鋼を含むことができ
る。The active material can include oxidized steel that acts as both a selective SOx scavenger and a NOx selective reduction catalyst.
ＮＯｘ還元触媒は、サルフエート化（例えば、触媒金属
酸化物とＳＯ２及び酸素との反応によって）されたとき
でさえも通常の煙道ガス脱硫温度の全範囲にわたってそ
の触媒活性を保持しなければならず、そして硫黄酸化物
によって毒されてはならない。The NOx reduction catalyst must retain its catalytic activity over the full range of normal flue gas desulfurization temperatures even when sulfated (e.g., by reaction of the catalytic metal oxide with SO2 and oxygen). , and must not be poisoned by sulfur oxides.
ＳＯｘ除去物質は、硫黄酸化物を選択的に除去でき且つ
再生され得なければならない。The SOx removal material must be capable of selectively removing sulfur oxides and capable of being regenerated.
操作サイクルの過程の間、活性物質中の金属は、幾つか
の形態例えば酸化物、サルフエート及び遊離金属を経る
可能性がある。During the course of the operating cycle, the metal in the active material can pass through several forms, such as oxide, sulfate and free metal.
活性物質は、少なくとも約８０そして好ましくは少なく
とも約１ ０ ０ ｍ”／ ．！ｉ’の表面積（窒素吸
着によって）を有する高表面担体に付着又は担持される
。The active substance is attached or supported on a high surface support having a surface area (by nitrogen adsorption) of at least about 80 and preferably at least about 100 m''/.!i'.
この目的に対して、アルミナ、アルミナーシリカ、シリ
カ等の如き慣用の本質的に不活性の耐火性担体物質を用
いることができる。For this purpose, conventional essentially inert refractory support materials such as alumina, alumina-silica, silica, etc. can be used.
担体物質の選択は、活性物質の選択によってある程度指
図される。The choice of carrier material is dictated in part by the choice of active substance.
かくして、酸化銅担体アルミナが本発明に対して特に良
好な接触物質であり、そして酸化銅枳体シリカはその次
に望ましい。Thus, copper oxide supported alumina is a particularly good contact material for the present invention, and copper oxide framework silica is a second preferred contact material.
燃焼ガスと接触物質との接触は、該ガスを接触物質の固
定床に通すことによって達成されるのが好ましい。Contacting the combustion gases with the contacting material is preferably accomplished by passing the gases through a fixed bed of contacting material.
空間速度は約１，０００〜約１０，０００Ｖ／Ｖ／ｈｒ
の範囲内であってよいが、好ましい空間速度は約２，０
００〜約５，０ ０ ０ Ｖ／Ｖ／ｈｒの範囲内である
。Space velocity is approximately 1,000 to approximately 10,000V/V/hr
, but the preferred space velocity is about 2.0
00 to about 5,000 V/V/hr.
空間速度は、二酸化硫黄除去のための要件によって通常
制限される。Space velocity is usually limited by the requirements for sulfur dioxide removal.
一般的に言えば、窒素酸化物除去は、二酸化硫黄除去よ
りもずっと高い空間速度で効率的に達或できる。Generally speaking, nitrogen oxide removal can be efficiently accomplished at much higher space velocities than sulfur dioxide removal.
通常、本発明の方法は実質上大気圧で特に電力設備にお
いて実施される。Typically, the method of the invention is carried out at substantially atmospheric pressure, particularly in power installations.
酸化銅担持アルミナは、最適なＳＯ２除去の条件下で例
えば上記の如く約６００〜９００’Ｆ（３１６〜４８２
°Ｃ）の温度及び約１，０００〜５， ０ ０ ０ Ｖ
／Ｖ／ ｈｒの空間速度で二酸化硫黄及び窒素酸化物の
両方の効果的な除去を驚くほど提供する。Copper oxide-supported alumina has a temperature of about 600-900'F (316-482'F) under optimal SO2 removal conditions, e.g.
°C) and approximately 1,000 to 5,000 V
It surprisingly provides effective removal of both sulfur dioxide and nitrogen oxides at space velocities of /V/hr.
ＮＯｘの除去において酸化銅よりも有効である他の物質
が知られているけれども、か＼る他の物質は、本発明の
接触物質の他の望ましい条件、即ち、それらが通常の煙
道ガス脱硫温度の全範囲（この通常の範囲はＮＯｘ接触
除去のために通常使用される温度に及ぶ）にわたって有
効であること、それらが、これらの温度においてＮＯｘ
へのアンモニアの望まれない酸化を引起さないこと、そ
れらが硫黄酸化物によって毒されないこと及び？れらが
硫黄酸化物を除去でき且つ再生され得ることという条件
を満たさない。Although other materials are known to be more effective than copper oxide in removing NOx, such other materials may meet other desirable conditions of the contact materials of the present invention, i.e., if they are compatible with conventional flue gas desulfurization. be effective over a full range of temperatures (this normal range spans the temperatures typically used for NOx catalytic removal);
do not cause unwanted oxidation of ammonia to ?, that they are not poisoned by sulfur oxides and? They do not meet the conditions that they can remove sulfur oxides and be regenerated.
接触物質は、水素一酸化炭素、これらの混合物の如き還
元ガス又はメタン、エタン、プロパン若しくはブタンの
如き炭化水素で再生し得る。The contact material may be regenerated with a reducing gas such as hydrogen, carbon monoxide, mixtures thereof, or a hydrocarbon such as methane, ethane, propane or butane.
還元ガスは、スチームと混合させてよい。The reducing gas may be mixed with steam.
好ましい再生ガスは、約１０〜５０モルφの水素と約５
０〜９０モル饅のスチームとの混合物である。The preferred regeneration gas is about 10-50 moles φ of hydrogen and about 5
It is a mixture with 0 to 90 moles of steam.
約４０容量φの水素と６０容量悌のスチームとの混合物
が特に好ましい。Particularly preferred is a mixture of approximately 40 volumes of hydrogen and 60 volumes of steam.
再生ガス流入温度は、通常、煙道ガス流入温度例えば約
６００〜９００″Ｆ（３１６〜４８２℃）とほゾ同じで
ある。The regeneration gas inlet temperature is typically about the same as the flue gas inlet temperature, for example about 600-900"F (316-482C).
また、こ＼における再生ガスはＮＯｘ除去が目的でない
ところの処理における煙道ガス脱流吸着剤用の慣用の再
生ガスでもあることが認められよう。It will also be appreciated that the regeneration gas here is also a conventional regeneration gas for flue gas deflow adsorbents in processes where NOx removal is not the objective.
本発明のこの具体例の循環プロセスは、酸素、二酸化硫
黄（少量のＳＯを含む又は含まないのどちらか）及び窒
素酸化物を含有する廃ガスが接触物質と接触状態に通さ
れる吸着（又は脱硫）工程又は期間及びそれに続いての
再生期間を包含する。The cyclic process of this embodiment of the invention involves adsorption (or desulfurization) step or period followed by a regeneration period.
反応器は、所望ならば吸着及び再生期間の両方の後にス
チーム又は窒素の如き不活性ガスでバージングすること
ができる。The reactor can be purged with steam or an inert gas such as nitrogen after both the adsorption and regeneration periods if desired.
煙道ガス又は他の廃ガスの流れは、二酸化硫黄が流出煙
道ガス中にブレークスルーするまで接触物質と接触され
る。The flue gas or other waste gas stream is contacted with the contact material until sulfur dioxide breaks through into the effluent flue gas.
ブレークスルーは、全収着サイクルにわたっての流出ガ
ス中のＳ０２の濃度が指定の百分率例えば全吸着期間に
わたって流入ガス中に送られるＳＯ２の量の１０俤に達
したときに起ると定義することができる。Breakthrough can be defined as occurring when the concentration of SO2 in the effluent gas over the entire sorption cycle reaches a specified percentage, e.g. can.
ブレークスルーが起ると、収着期間は停止されそして触
媒物質は再生される。When breakthrough occurs, the sorption period is stopped and the catalytic material is regenerated.
接触物質は、触媒及び収着剤製造の業界において知られ
ている技術によって調製することができる。The contact material can be prepared by techniques known in the catalyst and sorbent manufacturing industry.
担体は、任意の所望形状例えば球体、押出物（本質的に
は円柱状）又はリングの形状であってよく、そして所望
の寸法であってよい。The carrier may be of any desired shape, such as a sphere, an extrudate (essentially cylindrical) or a ring, and of any desired dimensions.
予めか焼した担体は、公知の含浸溶液例えば酸化銅表面
層が望まれるときには硝酸鋼水溶液を用いて公知手段に
よって含浸され、次いでか焼によって含浸塩をその相当
する酸化物に転化することができる。The precalcined support can be impregnated by known means with known impregnating solutions, for example an aqueous steel nitrate solution when a copper oxide surface layer is desired, and then the impregnating salt can be converted to its corresponding oxide by calcination. .
酸化物は、所望ならば、水素又は他の還元ガスで遊離金
属に還元させ得る。The oxide may be reduced to free metal with hydrogen or other reducing gas if desired.
慣用の含浸技術によって、活性物質が担体物質の全体に
わたって担体の細孔に分配された接触物質がもたらされ
る。Conventional impregnation techniques provide a contact material in which the active substance is distributed throughout the carrier material and into the pores of the carrier.
活性？質が担体粒子の外面近くの比較的狭い帯域に制限
されるときに、より効果的な結果が本発明に従って達成
される。Active? More effective results are achieved according to the invention when the quality is restricted to a relatively narrow band near the outer surface of the carrier particle.
この帯域は、通常、０．０３５ｉｎ（０．８９ｏａ）を
越えない深さを有しモして担体容積のせいぜい７０饅好
ましくは約２０〜４０％を占める外面層である。This zone is usually an outer surface layer having a depth not exceeding 0.035 inches (0.89 oa) and occupying no more than 70%, preferably about 20-40%, of the carrier volume.
帯域含浸又は”表面含浸”は、担体粒子に含浸水溶液を
タンブリングさせなから吹付被覆することによって、又
は米国特許第２，７ ４ ６，９ ３ ６号に記載され
る技術によって、或いは他の望ましい手段によって達或
できる。Zone impregnation or "surface impregnation" may be performed by spray coating the carrier particles with an aqueous impregnating solution by tumbling or by the technique described in U.S. Pat. No. 2,746,936, or as otherwise desired. It can be achieved by means.
好ましい表面含浸技術は、か焼した担体粒子を極性水不
混和性揮発性液体好ましくはｎ−ペンタノール又はＣ，
″オキソ”アルコール（Ｃ６第一アルコール異性体の混
合物）の如きＣ，〜Ｃ ｔＯ第一アルコール中に浸漬さ
せ、その水不混和性液体から担体粒子を硝酸鋼の如き含
浸水溶液に移し、所望の含浸深さに依存する制御した時
間の間前記水溶液中に浸漬させ、次いで粒子を乾燥しモ
してか焼することである。A preferred surface impregnation technique involves injecting the calcined support particles with a polar water-immiscible volatile liquid, preferably n-pentanol or C,
The carrier particles are transferred from the water-immiscible liquid to an impregnating aqueous solution such as steel nitrate by soaking in a C,~CtO primary alcohol such as "oxo" alcohol (a mixture of C6 primary alcohol isomers) and forming the desired After being immersed in the aqueous solution for a controlled period of time depending on the impregnation depth, the particles are then dried and calcined.
活性物質が担体の細孔内に分配されているような接触物
質に優る表面含浸接触物質の利点は、ＳＯ２ブレークス
ルーが起るときにサルフエート化される活性物質の百分
率によって測定したときの高ＳＯ除去能が慣用の完全含
浸接触物質の場合におけるよりも表面含浸接触物質の場
合に高いということである。The advantage of surface-impregnated contact materials over contact materials in which the active material is distributed within the pores of the support is the high SO2 as measured by the percentage of active material that is sulfated when SO2 breakthrough occurs. The removal capacity is higher in the case of surface impregnated contact materials than in the case of conventional fully impregnated contact materials.
ＳＯｘ及びＮＯｘの両方の同時的減少は、どちらかの汚
染物の除去に対する接触物質の効率に悪影響を及ぼさな
い。Simultaneous reduction of both SOx and NOx does not adversely affect the efficiency of the contact material for removal of either contaminant.
これに反して、硫黄酸化物除去は、本法に従ってアンモ
ニアが加えられそしてＮＯｘが同時に除去されるときに
僅かに実際的に高められるようである。In contrast, sulfur oxide removal appears to be slightly practically enhanced when ammonia is added and NOx is simultaneously removed according to the present method.
更に、ＮＯｘの減少量は、こ＼で特定した非貴金属接触
物質を用いるという条件がつけば、ガス流れ中にＳＯ２
が存在する場合とＳＯ２が不在の場合とで全く同じであ
るようである。Furthermore, the reduction in NOx is significantly reduced by reducing SO2 in the gas stream, provided that the non-precious metal contact material specified here is used.
appears to be exactly the same in the presence of SO2 as in the absence of SO2.
これは、ＮＯｘの除去のために有効な多くの触媒取り分
け貴金属触媒が硫黄化合物によって毒されるので本発明
法では使用できないという事実にかんがみ全く驚くべき
ことである。This is quite surprising in view of the fact that many catalysts, especially noble metal catalysts, which are effective for the removal of NOx, are poisoned by sulfur compounds and cannot be used in the process of the invention.
こ＼で、本発明を次の実施例を参照しながら更に説明す
る。The invention will now be further described with reference to the following examples.
例１
本例は、酸化銅担持アルミナの固定床を触媒として用い
て煙道ガスから窒素酸化物及び硫黄酸化物を同時に除去
することを例示する。Example 1 This example illustrates the simultaneous removal of nitrogen oxides and sulfur oxides from flue gas using a fixed bed of copper oxide supported alumina as a catalyst.
本実験における反応器は、熱損失を防止するために反応
器管を包囲する電熱式ジャケットを有する長さ５２ｉｎ
（ １ ３．２ １ｃｒｆＬ）で内径３ ｉ ｎ （
７．６ ２ｃＩｒＬ）の管状反応器であった。The reactor in this experiment was 52 inches long with an electrically heated jacket surrounding the reactor tube to prevent heat loss.
(1 3.2 1crfL) and inner diameter 3 in (
7.6 2cIrL) tubular reactor.
反応器は深さ４８ ｉｎ（ １ ２．１ ９ｃＩｒＬ）
の酸化銅担持アルミナリングの固定触媒床を収容してお
り、そして反応器の底部には含浸されていないリングが
４ ｉｎ （ １ ０．１ ６６ｒＩＬ）あった。Reactor is 48 inches deep (12.19 cIrL)
contained a fixed catalyst bed of copper oxide-supported alumina rings, and there were 4 in (10.166 rIL) of unimpregnated rings at the bottom of the reactor.
触媒床容積は０．１ ９６ ｆｔ３（ ０．０ ０ ５
５ｍ３）であり、触媒床重量は２６８４．４ｇであり
、そして触媒床の銅含量は０．６０５！９モル（３９．
１ｇ）であって、これは１．４５重量係の全銅含量を表
わしている。The catalyst bed volume is 0.196 ft3 (0.005
5 m3), the catalyst bed weight is 2684.4 g, and the copper content of the catalyst bed is 0.605!9 mol (39.
1 g), representing a total copper content of 1.45 parts by weight.
触媒床は頂部から底部までにわたって３つの帯域（Ａ，
Ｂ及びＣと称する）よりなっており、そしてその各々は
僅かに異なる粒子寸法、多孔率特性及び銅含量を有して
いる。The catalyst bed consists of three zones (A,
B and C), each having slightly different particle size, porosity characteristics and copper content.
触媒Ａは１ ７ ６ ｍ”／ ｇの表面積（ＢＥＴ法）
、０．３８ｃｃ／９の小孔の孔容積（ＢＥＴ法）及び０
．２４ｃｃ ／ ｇの大孔の孔容積（水銀多孔度計法）
を有していた。Catalyst A has a surface area of 176 m”/g (BET method)
, 0.38cc/9 small hole pore volume (BET method) and 0.
．． Pore volume of large pores of 24cc/g (mercury porosimeter method)
It had
触媒Ｂ及びＣは触媒Ａとほマ同じ表面積及び全孔容積を
有していたが、しかし大孔の孔容積の百分率が大きかっ
た。Catalysts B and C had nearly the same surface area and total pore volume as Catalyst A, but had a larger percentage of large pore volume.
他の物理的特性を以下の第１表に記載する。Other physical properties are listed in Table 1 below.
各粒子の両端は非平行面によって形或されたので、各粒
子は最大長さを有し、その両方とも軸に対して平行の線
に現われそして粒子の外面に位置する。Since the ends of each particle were shaped by non-parallel faces, each particle has a maximum length, both of which appear in a line parallel to the axis and located on the outer surface of the particle.
軸長さは、最大長さと最小長さとの平均である。The axial length is the average of the maximum and minimum lengths.
３つの床帯域のすべてにある触媒は表面含浸触媒であっ
て、この場合に銅の全部は、外面から特定の深さを内部
にそして内面から同じ特定の深さを内部へと伸びる環状
帯域において付着されている。The catalyst in all three bed zones is a surface-impregnated catalyst in which all of the copper is deposited in an annular zone extending from the outer surface to a specified depth inward and from the inner surface to the same specified depth. It is attached.
特性を以下の第１表に記載する。The properties are listed in Table 1 below.
（１，０００下即ち５３８゜Ｃ）したアルミナから調製
された。(below 1,000 or 538°C) alumina.
これらの３つの触媒は、別個のバッチで調製された。These three catalysts were prepared in separate batches.
各場合において、担体粒子はヘキシルアルコール（オキ
ソ法によって製造）中に室温で浸漬さ札次いでペーパー
タオルで乾燥状態に吸い取らせ、そして直ちに硝酸銅水
溶液を含浸させた。In each case, the carrier particles were soaked in hexyl alcohol (prepared by the oxo method) at room temperature, then blotted dry with a paper towel, and immediately impregnated with an aqueous solution of copper nitrate.
これは、粒子を該溶液中に制御した時間の間浸漬させる
ことによって行われた。This was done by soaking the particles in the solution for a controlled period of time.
硝酸銅溶液濃度及び含浸時間を以下の第２表に記載する
。The copper nitrate solution concentrations and impregnation times are listed in Table 2 below.
含浸時間、分 １．７５ １．７０ １．００こ
の含浸技術は、表面含浸粒子、即ち、粒子の内面及び外
面から特定の深さ（第１表に記載した如き）だけ含浸さ
れた粒子を与えた。Impregnation time, min 1.75 1.70 1.00 This impregnation technique provides surface impregnated particles, i.e. particles impregnated to a specified depth (as listed in Table 1) from the inner and outer surfaces of the particle. Ta.
粒子を１９０°Ｆ（８８°Ｇ）で１５時間風乾させ、次
いで３０００Ｆ（１４９℃）で１時間、５０００Ｆ（２
６０°Ｃ）で１時間そして８００°Ｆ（４２７°０で３
時間か焼した。The particles were air dried at 190°F (88°G) for 15 hours, then 3000F (149°C) for 1 hour, and 5000F (2
60°C) for 1 hour and 800°F (427°0 for 3 hours).
Calcined for an hour.
か焼によって、硝酸銅は酸化銅Ｉこ転化された。Upon calcination, copper nitrate was converted to copper oxide.
ＢＪＩガスシリンダからのアンモニアをロタメータ（フ
ィッシャー・ポーター、型ＡＯ８Ｆ一１／１６ｉｎ
２０８）によって計量し、そしテソれを約６８０’Ｆ（
３６０’Ｃ）の温度にある影道ガスの流れに加えた。Ammonia from a BJI gas cylinder was measured using a rotameter (Fisher-Porter, model AO8F-1/16 in.
208) and set the temperature at approximately 680'F (
Added to the stream of gas at a temperature of 360'C).
煙道ガスは、ボイラーでの石炭の燃焼によって得られた
もので、約６．８容量饅の酸素及び約４００〜６００ｐ
ｐｍ（容量）の窒素酸化物を含有していた。The flue gas was obtained by burning coal in a boiler and contained about 6.8 volumes of oxygen and about 400-600 p.
pm (by volume) of nitrogen oxides.
また、煙道ガスは、約０．２５〜０．３容量φの二酸化
硫黄、微量の三酸化硫黄及び少量のフライアツシュも含
有していた。The flue gas also contained approximately 0.25-0.3 volumes φ of sulfur dioxide, trace amounts of sulfur trioxide, and small amounts of fly ash.
アンモニアを加えた熱煙道ガス混合物を、２，０ ０
０Ｖ／Ｖ／ｈｒ（７）空間速度（ＳＴＰ）に相当する６
．５３ＳＣＦＭ （参考温度６０’Ｆ即ち１６℃）の
一定流量で管状反応器を下方へと通した。The hot flue gas mixture with ammonia added to 2,00
0V/V/hr (7) 6 corresponding to space velocity (STP)
．． A constant flow rate of 53 SCFM (reference temperature 60'F or 16°C) was passed downward through the tubular reactor.
以下の第３表に示されるように、収着期間の間アンモニ
ア供給速度を変えた。The ammonia feed rate was varied during the sorption period as shown in Table 3 below.
流出煙道ガスの試料は、約１分（第３表に示されるよう
に各吸着期間の開始から測定したときの正確な時間）の
間隙で得られた。Samples of the effluent flue gas were obtained at intervals of approximately 1 minute (exact time as measured from the start of each adsorption period as shown in Table 3).
これらの試料を、３５０ｐのＫＨＣＯ３、２．２２０，
！ｉ’のＫ２ＣＯ３、３３０ｇのＫＮＯ２及び２５０ｇ
のＫＮＯ３ を含有する塩混合物の５ｌ水溶液に通した
。These samples were treated with 350 p of KHCO3, 2.220,
! i' K2CO3, 330g KNO2 and 250g
of KNO3 in water.
これは、ＳＯ２を定量的に除去した。This removed SO2 quantitatively.
脱硫試料流れの窒素酸化物含量は、５５０ｐｐｍ、１，
５ ０ ０ ｐｐｍ及び５，０ ０ ０ ｐｐｍ目盛を
有するダイナサイエンセズ社のＮＸ−１３０″全窒素酸
化物”監視器を備えたダイナサイエンセズ社の空気汚染
監視装置で測定された。The nitrogen oxide content of the desulfurization sample stream was 550 ppm, 1,
Measurements were made with a Dyna Sciences air pollution monitor equipped with a Dyna Sciences NX-130"Total Nitrogen Oxide" monitor with 500 ppm and 5,000 ppm scales.
この装置は、米国カリフォルニア州ロスアンゼルス所在
のザ・ホイツタカー・コーポレーションの子会社である
グイナサイエンセズ・コーポレーションによって製作販
売されている。This device is manufactured and sold by Guina Sciences Corporation, a subsidiary of The Whittaker Corporation, located in Los Angeles, California, USA.
別の方法として、窒素酸化物は、１９７１年８月１７日
（火曜日）にザ・フエデラル・レジスター（ ｔｈｅ
Ｆｅｄｅｒａ１Ｒｅｇｉｓ ｔｅｒ ）の第３６巻第１
５９号第■編第１５，７１８〜１５，７２０に発表され
た環境保護庁認可法（方法７・・・・・・定置源からの
窒素酸化物放出物の測定）（これは、フエニルジスルホ
ン酸を試剤として用いる湿式法である）によって測定さ
れた。Alternatively, nitrogen oxides were published on Tuesday, August 17, 1971 in The Federal Register (the
Federa1Register) Volume 36, No.1
Environmental Protection Agency Approved Method (Method 7: Measurement of Nitrogen Oxide Emissions from Stationary Sources) published in No. (a wet method using acid as a reagent).
この湿式法は、以後ＰＤＳ法と称する。This wet method is hereinafter referred to as the PDS method.
計量は工業的に調製された標準ガス試料に対して目盛を
定め、そしてこの試料はＰＤＳ法によって分析された。The measurements were calibrated against an industrially prepared standard gas sample, and this sample was analyzed by the PDS method.
収着期間は、９分間続けられた。The sorption period lasted 9 minutes.
次いで、反応器をスチームの下向き流れで約１．２５Ｓ
ＣＦＭ において約０．５分間バージングした。The reactor was then heated with a downward flow of steam for about 1.25S.
Barged in CFM for approximately 0.5 minutes.
次いで、触媒−収着剤を、１分間の期間にわたって約０
．４ｇモルの水素を提供する流量で反応器を下向きに流
れる水素４０容量饅とスチーム６０容量φとの混合物で
再生した。The catalyst-sorbent is then heated to about 0 for a period of 1 minute.
．． The reactor was regenerated with a mixture of 40 volumes of hydrogen and 60 volumes of steam φ flowing downward through the reactor at a flow rate to provide 4 g moles of hydrogen.
これは、ＳＯ２として触媒一収着剤に化学的に結合した
硫黄の脱着を引起こし、且つ触媒一収着剤物質を主とし
て金属銅に転化させた。This caused the desorption of the sulfur chemically bound to the catalyst-sorbent as SO2 and converted the catalyst-sorbent material primarily to metallic copper.
次いで、反応器を窒素の下向き流れで約０．２５ＳＣＦ
Ｍ の速度において約０．５分間バージングし、次いで
新しい収着期間を開始した。The reactor was then flushed with a downward flow of nitrogen to approximately 0.25 SCF
Barged for approximately 0.5 min at a speed of M and then started a new sorption period.
この態様で、多数の完全操作サイクルを実施した。A number of complete operating cycles were performed in this manner.
アンモユアの添加量、及び幾つかの代表的なサイクルの
収着期間における流出煙道ガスのＮＯｘ測定値を以下の
第３表及び第４表に記載する。The ammoure loading and effluent flue gas NOx measurements during the sorption period for several representative cycles are listed in Tables 3 and 4 below.
第３表に記載したサイクルでは、流出ＮＯｘの測定は、
ダイナサイエンセズ社の空気汚染監視装置によって行わ
れた。For the cycles listed in Table 3, the measurement of effluent NOx is:
The tests were conducted using Dynasciences' air pollution monitoring equipment.
なお、サイクルのいくらかにおける初期の読みのいくら
かは、先のサイクルの最終読みによって影響を受けた。Note that some of the early readings in some of the cycles were influenced by the final readings of previous cycles.
というのは、２分間の再生及びパージ期間中に装置の試
料系が全く流れなかったからである。This is because the sample system of the device did not flow at all during the 2 minute regeneration and purge period.
第４表に記載したサイクルでは、ＮＯｘ測定のＰＤＳ法
を用いた。In the cycles listed in Table 4, the PDS method of NOx measurement was used.
上記サイクルでは、アンモニアは、９８〜１０１°Ｆ（
３７〜３８°Ｃ）の温度及び５ｐｓｉｇ（ ０． ３’
５ ｋｇ／ｄゲージ）の圧力でロタメータを経て供給
された。In the above cycle, the ammonia is 98-101°F (
37-38°C) and 5 psig (0.3'
It was fed through a rotameter at a pressure of 5 kg/d gauge).
多数の操作サイクルを実施したが、その間に窒素酸化物
流出物測定は行れなかった。A number of operating cycles were performed during which no nitrogen oxide effluent measurements were made.
これは、上記サイクルが連続サイクルでない理由を説明
する。This explains why the above cycle is not a continuous cycle.
ダイナサイエンセズ社の空気汚染監視装置によって分析
した試験の外に、一連の試料を捕集することによってＳ
Ｏｘ及びＮＯｘ除去操作を組合せた幾つかのサイクルを
分析した（先に提供したザ・フエデラル・レジスター参
考文献に略述されるフ本＊エニルジスルホン酸（ＰＤＳ
）法について記載した如き排気済みの試料フラスコを用
いて各試料について１５〜２０秒の期間にわたって）。In addition to testing analyzed by DynaSciences' air pollution monitoring equipment, S.
Several cycles of combined Ox and NOx removal operations were analyzed (e.g., polyvinyldisulfonic acid (PDS) as outlined in The Federal Register reference provided above).
) over a period of 15-20 seconds for each sample using an evacuated sample flask as described for the method).
これらの結果を以下の第４表に示すが、これらは、処理
しようとする煙道ガスにおいて所定のＮＨ３／ＮＯＸ比
に関して除去されたＮＯｘの比率に係る第３表の結果と
実質上一致することを示す。These results are shown in Table 4 below and are in substantial agreement with the results in Table 3 regarding the proportion of NOx removed for a given NH3/NOX ratio in the flue gas to be treated. shows.
第３表及び第４表に記載した試験の間に、煙道ガスから
約９０饅〜９５φのＳＯｘが除去された。During the tests described in Tables 3 and 4, approximately 90 to 95 φ of SOx was removed from the flue gas.
収着剤中の銅がアンモニアの不在下に実質的な量のＮＯ
ｘを還元できるかどうかを決定するために２つの追加的
なサイクルを実施した。Copper in the sorbent absorbs substantial amounts of NO in the absence of ammonia.
Two additional cycles were performed to determine whether x could be reduced.
以下の第５表は、アンモニアを全く使用しなかったこと
を除いて、本例における他のサイクルと同じ態様で実施
された２つのサイクルを示す。Table 5 below shows two cycles that were performed in the same manner as the other cycles in this example, except that no ammonia was used.
各々において、アンモニアを加えての最後の前述のサイ
クルは数サイクル繰返して実施されたので、反応器から
アンモニアがバージングされた。In each case, the last aforementioned cycle of adding ammonia was repeated several times so that the reactor was barged with ammonia.
窒素酸化物含量はＰＤＳ法によって測定された。Nitrogen oxide content was measured by PDS method.
以下のデータから、新たに還元された銅は収着期間の開
始時にいくらかのＮＯｘを還することかできると結論さ
れる。From the data below, it is concluded that the newly reduced copper can return some NOx at the beginning of the sorption period.
しかしながら、収着の数分後に存在する酸化又はサルフ
エート化された銅はＮＯｘを還元しないことも明らかで
ある。However, it is also clear that the oxidized or sulfated copper present after several minutes of sorption does not reduce NOx.
それ故に、ＮＨ３添加期間中における連続的ＮＯｘ除去
は、ＮＨ３によるＮＯｘの選択的還元によるものである
。Therefore, continuous NOx removal during the NH3 addition period is due to selective reduction of NOx by NH3.
例２
本例は、市販の酸化銅担持アルミナ固定床触媒−収着剤
を収容する実験室的反応器で合成煙道ガスから酸化窒素
又は二酸化硫黄を同時に除去することを例示する。Example 2 This example illustrates the simultaneous removal of nitrogen oxide or sulfur dioxide from a synthetic flue gas in a laboratory reactor containing a commercially available copper oxide supported alumina fixed bed catalyst-sorbent.
反応器は直径１ ｉｎ （ ２．５４ｃＩｆＬ）のガラ
ス製反応器であって、これは、触媒一収着剤として、初
期において酸化銅の形態にあるＣｕを８重量φ含浸サせ
た１０〜１４メッシュのアルミナ球体２ ４．９ Ｅｌ
（ ３ ０ｃｃ）を収容していた。The reactor is a 1 in (2.54 cIfL) glass reactor that is initially impregnated with 8 wt φ of Cu in the form of copper oxide as a catalyst and sorbent. Mesh alumina sphere 2 4.9 El
(30cc).
合或煙道ガスは、０．２７容量φのＳＯ２、０．１２容
量係のＮＯ５．０容量係の酸素、０．６〜２．０容量幅
の水蒸気及び残部の窒素を含有していた。The flue gas contained 0.27 volume φ of SO2, 0.12 volume of NO5.0 volume of oxygen, water vapor ranging from 0.6 to 2.0 volume, and the balance nitrogen.
３０分の収着期間、１分のパージ期間、２分の再生期間
及び第二の１分のパージ期間よりなる多数のサイクルを
実施した。A number of cycles were performed consisting of a 30 minute sorption period, a 1 minute purge period, a 2 minute regeneration period and a second 1 minute purge period.
各収着期間の間、予め定めた量のアンモニアを予め定め
た量の水中に溶解させた。During each sorption period, a predetermined amount of ammonia was dissolved in a predetermined amount of water.
得られた溶液を蒸発させ、そしてアンモニアースチーム
混合物を合戒煙道ガスの残りの成分に加えた。The resulting solution was evaporated and the ammonia steam mixture was added to the remaining components of the hexane flue gas.
得られた混合物を、６５０’Ｆ（３４３℃）の流入温度
及び５， Ｏ Ｏ Ｏ Ｖ／Ｖ／ ｈ ｒの空間速度で
反応器に通した。The resulting mixture was passed through the reactor at an inlet temperature of 650'F (343°C) and a space velocity of 5,000 V/V/hr.
流出ＮＯ濃度は、例１に記載したダイナサイエンセズ社
の測定装置を用いて測定された。Effluent NO concentration was measured using the Dyna Sciences measurement device described in Example 1.
各収着期間の後、反応器を窒素で１分間バージングした
。After each sorption period, the reactor was purged with nitrogen for 1 minute.
次いで、触媒一収着剤を、８６容量φの水素と申＊１４
容量φの水蒸気とのガス混合物で２分間再生した。Next, the catalyst and sorbent were replaced with 86 volumes of hydrogen *14
It was regenerated for 2 minutes with a gas mixture with a volume φ of water vapor.
次いで、反応器を窒素で１分間バージングした。The reactor was then purged with nitrogen for 1 minute.
次いで、操作サイクルを反復した。比較目的のためにあ
るサイクルの間にはアンモニアを省いたが、他の点にお
いてはこれらのサイクルはアンモニアを加えた他のサイ
クルと同じ態様で実施された。The operating cycle was then repeated. Although ammonia was omitted during some cycles for comparison purposes, these cycles were otherwise run in the same manner as the other cycles with the addition of ammonia.
以下の第６表は、種々の添加量のアンモニアを用いた種
々のサイクルの収着期間においての流出ガス中のＮＯ及
びＳＯ２の量を示す。Table 6 below shows the amounts of NO and SO2 in the effluent gas during the sorption period of various cycles with various loadings of ammonia.
流出ＮＯの量は、（ａ）１つ又はそれ以上の全収着期間
及び（ｂ）１つ又はそれ以上の収着期間の最後の２３分
についての平均値である。The amount of effluent NO is the average value over (a) the entire sorption period(s) and (b) the last 23 minutes of the sorption period(s).
流出Ｓ０２値は、１つ又はそれ以上の全収着期間につい
ての平均値である。The effluent S02 value is the average value over one or more entire sorption periods.
第６表における１つの実験において１つよりも多くのサ
イクルが含まれる場合には、流出ＮＯ及びＳＯ２濃度は
平均値を表わす。If more than one cycle is included in one experiment in Table 6, the effluent NO and SO2 concentrations represent average values.
すべての供給材料及び流出物の濃度は、容量比によるｐ
ｐｍ単位である。All feed and effluent concentrations are determined by volume ratio p
The unit is pm.
第６表から、次のこと、即ち、
（１）アンモニア添加は、ＳＯ２除去に影響を及ぼさな
いこと（実験１を実験２と、実験４、５及び６を実験３
と比較）、
（２）アンモニアはＳＯ２の存在下でＮＯを除去するこ
とを（実験４、５及び６を実験３と比較）、（３）ＮＯ
除去の効率はＮＨ３／ＮＯモル比の函数であること（実
験３〜６）、及び
（４）触媒一収着剤床はＮＨ３ の不在下にＮＯを除去
しないこと、
が分る。From Table 6, it can be concluded that: (1) Ammonia addition has no effect on SO2 removal (Experiment 1 is referred to as Experiment 2, and Experiments 4, 5 and 6 are referred to as Experiment 3).
(2) ammonia removes NO in the presence of SO (compare experiments 4, 5 and 6 with experiment 3), (3) NO
We find that the efficiency of removal is a function of the NH3/NO molar ratio (Experiments 3-6) and (4) that the catalyst-sorbent bed does not remove NO in the absence of NH3.
上記サイクルが取られるところの実験は、本発明に対し
て密接な関係がない多数のサイクルを含んでいた。The experiments in which the above cycles were taken included a number of cycles that were not germane to the present invention.
それ故に、サイクル番号は連続的でな０）。Therefore, the cycle numbers are not consecutive (0).
Claims (1)
れにアンモニアを加え、そして前記ガス流れを、ＳＯｘ
の除去のための選択的収着剤及びＮＯｘの選択的還元の
ための触媒の両方である酸化銅担持担体物質からなる固
体接触物質と酸化条件下に接触させることからなる、窒
素酸化物、硫黄酸化物及び酸素を含有するガス流れから
窒素酸化物及び硫黄酸化物を同時に除去する方法。1 Adding ammonia to a gas stream containing nitrogen oxides, sulfur oxides and oxygen and converting the gas stream into SOx
nitrogen oxides, sulfur, by contacting them under oxidizing conditions with a solid contact material consisting of a copper oxide-supported support material that is both a selective sorbent for the removal of NOx and a catalyst for the selective reduction of NOx. A method for simultaneously removing nitrogen oxides and sulfur oxides from a gas stream containing oxides and oxygen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28581872A | 1972-09-01 | 1972-09-01 | |
| US285818 | 1972-09-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS4975463A JPS4975463A (en) | 1974-07-22 |
| JPS5837008B2 true JPS5837008B2 (en) | 1983-08-13 |
Family
ID=23095826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP48097408A Expired JPS5837008B2 (en) | 1972-09-01 | 1973-08-31 | Removal of nitrogen oxides and sulfur oxides from gases |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5837008B2 (en) |
| BE (1) | BE804316A (en) |
| CA (1) | CA1007829A (en) |
| DE (1) | DE2341241C2 (en) |
| ES (1) | ES418370A1 (en) |
| FR (1) | FR2197629B1 (en) |
| GB (1) | GB1438119A (en) |
| IT (1) | IT993100B (en) |
| NL (1) | NL157219B (en) |
| SE (1) | SE408758B (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1474184A (en) * | 1973-05-08 | 1977-05-18 | Shell Int Research | Process for removing sulphur oxides and particulate matter from waste gases and apparatus therefor |
| JPS5343916B2 (en) * | 1973-05-21 | 1978-11-24 | ||
| US4107272A (en) * | 1973-05-21 | 1978-08-15 | Hitachi, Ltd. | Process for removing nitrogen oxides using ammonia as a reductant and sulfated metallic catalysts |
| JPS5437591B2 (en) * | 1975-03-08 | 1979-11-15 | ||
| JPS50157257A (en) * | 1974-06-10 | 1975-12-19 | ||
| US4119703A (en) * | 1974-06-11 | 1978-10-10 | Japan Gasoline Company, Ltd. | Process for removal of nitrogen oxides from waste gas |
| JPS5515247B2 (en) * | 1974-06-11 | 1980-04-22 | ||
| JPS5230285A (en) * | 1975-09-03 | 1977-03-07 | Seitetsu Kagaku Co Ltd | Regeneration method of catalyst |
| JPS609201B2 (en) * | 1975-09-29 | 1985-03-08 | 株式会社日立製作所 | Exhaust heat recovery boiler equipment |
| US4011299A (en) * | 1975-10-01 | 1977-03-08 | Monsanto Company | Process for removing sulfur dioxide and nitrogen oxides from gases |
| US4473535A (en) * | 1976-01-26 | 1984-09-25 | Northeast Utilities Service Company | Process for reducing nitric oxides |
| NL7601371A (en) * | 1976-02-11 | 1977-08-15 | Shell Int Research | PROCEDURE FOR THE SIMULTANEOUS REMOVAL OF NITROGEN OXIDES AND SULFUR OXIDES FROM A GAS FLOW. |
| JPS5296966A (en) * | 1976-02-12 | 1977-08-15 | Hitachi Ltd | Treatment of exhaust gas containing nitrogen oxides and sulfur oxides |
| JPS5477278A (en) * | 1977-12-02 | 1979-06-20 | Agency Of Ind Science & Technol | Concurrent removal of nitrogen oxides and sulfur oxides in combuster exhaust gas |
| US4192855A (en) * | 1978-04-10 | 1980-03-11 | Uop Inc. | Process for the simultaneous separation of sulfur and nitrogen oxides from a gaseous mixture |
| US4170627A (en) * | 1978-04-10 | 1979-10-09 | Uop Inc. | Process for the simultaneous separation of sulfur and nitrogen oxides from a gaseous mixture |
| DE2852336C2 (en) * | 1978-12-04 | 1986-10-16 | Walther & Cie AG, 5000 Köln | Process for the separation of NO? X? and SO? x? from combustion exhaust gases |
| DE2911712C2 (en) * | 1979-03-24 | 1991-10-31 | Bergwerksverband Gmbh, 4300 Essen | Process for removing sulfur oxides and nitrogen oxides from exhaust gases |
| CA1130540A (en) * | 1979-07-31 | 1982-08-31 | Francis X. Mayer | Magnetically stabilized fluid cross-flow contactor and process for using the same |
| NL7906181A (en) * | 1979-08-14 | 1981-02-17 | Shell Int Research | PROCESS FOR THE SIMULTANEOUS REMOVAL OF NITROGEN OXIDES AND SULFUR OXIDES FROM A GAS FLOW. |
| FR2466434A1 (en) * | 1979-10-01 | 1981-04-10 | Uop Inc | Sepn. of sulphur and nitrogen oxide(s) from gas mixt. - by contacting mixt. and ammonia with sulphur oxide(s) acceptor of copper (oxide) dispersed on ruthenium and rhenium oxide(s) compsn. |
| JPS57107230A (en) * | 1980-12-24 | 1982-07-03 | Mitsubishi Heavy Ind Ltd | Dry type simultaneous desulfurization and denitration process |
| DE3567382D1 (en) * | 1984-06-28 | 1989-02-16 | Bergwerksverband Gmbh | Process for separating so 2? and no x? |
| DE3423761A1 (en) * | 1984-06-28 | 1986-01-09 | Bergwerksverband Gmbh, 4300 Essen | Process for separating out SO2 and NOx |
| DE3426796C2 (en) * | 1984-07-20 | 1987-04-23 | Hölter, Heinz, Dipl.-Ing., 4390 Gladbeck | Process for the separation of SO↓2↓,SO↓3↓,NO↓x↓ and dust from exhaust gases |
| DE3429332A1 (en) * | 1984-08-09 | 1986-02-20 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR SEPARATING NO (DOWN ARROW) X (DOWN ARROW) AND SO (DOWN ARROW) 2 (DOWN ARROW) FROM SMOKE GASES |
| US5202101A (en) * | 1991-03-21 | 1993-04-13 | General Electric Environmental Services | Regenerative process and system for the simultaneous removal of particulates and the oxides of sulfur and nitrogen from a gas stream |
| CN111841271A (en) * | 2019-04-28 | 2020-10-30 | 中冶长天国际工程有限责任公司 | Flue gas desulfurization and denitrification method and system by utilizing co-treatment of carbon monoxide |
| CN113083005B (en) * | 2021-03-24 | 2022-07-19 | 武汉科技大学 | Application of coal-fired process pollutant control based on directional blending of coal ash mineral components |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL149463B (en) * | 1964-09-14 | 1976-05-17 | Shell Int Research | PROCESS FOR THE REMOVAL OF SULFUR DIOXIDE FROM OXYGEN CONTAINING GAS MIXTURES. |
| US3449063A (en) * | 1966-05-13 | 1969-06-10 | Ethyl Corp | Method of controlling exhaust emission |
| US3630943A (en) * | 1969-08-14 | 1971-12-28 | Us Interior | Preparation of absorbents for sulfur oxide removal |
-
1973
- 1973-08-01 GB GB3652973A patent/GB1438119A/en not_active Expired
- 1973-08-01 CA CA177,912A patent/CA1007829A/en not_active Expired
- 1973-08-16 DE DE2341241A patent/DE2341241C2/en not_active Expired
- 1973-08-30 IT IT28398/73A patent/IT993100B/en active
- 1973-08-31 ES ES418370A patent/ES418370A1/en not_active Expired
- 1973-08-31 NL NL7312059.A patent/NL157219B/en not_active Application Discontinuation
- 1973-08-31 SE SE7311914A patent/SE408758B/en unknown
- 1973-08-31 BE BE135199A patent/BE804316A/en not_active IP Right Cessation
- 1973-08-31 FR FR7331626A patent/FR2197629B1/fr not_active Expired
- 1973-08-31 JP JP48097408A patent/JPS5837008B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2341241C2 (en) | 1987-03-26 |
| BE804316A (en) | 1974-02-28 |
| NL157219B (en) | 1978-07-17 |
| JPS4975463A (en) | 1974-07-22 |
| DE2341241A1 (en) | 1974-03-14 |
| FR2197629A1 (en) | 1974-03-29 |
| SE408758B (en) | 1979-07-09 |
| GB1438119A (en) | 1976-06-03 |
| CA1007829A (en) | 1977-04-05 |
| FR2197629B1 (en) | 1984-02-10 |
| NL7312059A (en) | 1974-03-05 |
| IT993100B (en) | 1975-09-30 |
| ES418370A1 (en) | 1976-04-01 |
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