TWI224524B - A method for preparing catalyst for selective catalytic reduction of nitrogen oxides - Google Patents
A method for preparing catalyst for selective catalytic reduction of nitrogen oxides Download PDFInfo
- Publication number
- TWI224524B TWI224524B TW090108428A TW90108428A TWI224524B TW I224524 B TWI224524 B TW I224524B TW 090108428 A TW090108428 A TW 090108428A TW 90108428 A TW90108428 A TW 90108428A TW I224524 B TWI224524 B TW I224524B
- Authority
- TW
- Taiwan
- Prior art keywords
- catalyst
- weight
- nitrogen oxides
- catalytic reduction
- selective catalytic
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000000463 material Substances 0.000 claims description 59
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000002079 cooperative effect Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 235000003642 hunger Nutrition 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- -1 vanadium Chemical class 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 241000287463 Phalacrocorax Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NZPGFUCQQUDSQG-UHFFFAOYSA-N [Mo].[Re] Chemical compound [Mo].[Re] NZPGFUCQQUDSQG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/30—Regeneration or reactivation of catalysts comprising compounds of sulfur, selenium or tellurium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
經濟部智慧財產局員工消費合作社印製 1224524 A7 —— ________B7 五、發明説明（1 ) 用於氮氧化物之選擇性催化還原作用的催化劑及其製備方 法 發明領域 本發明大致上係關於用於氮氧化物之選擇性催化還原 作用之催化劑及其製備方法。更特別地，本發明係關於藉 由使用不適用於氮氧化物之選擇性催化還原作用的一般催 化劑的原料製備之催化劑，此原料例如在油精製廠之加氫 脫硫作用線上主要以釩、鎳及硫吸附的廢催化劑，其中用 於加氫脫硫作用之催化劑含有鉬、鐵、鈷、矽及其類似物， 及其製備方法。 習知技術 般而口，在例如經氣體、石油及柴油燃料等烴燃料 之燃燒過程中釋出的廢氣可造成環境之嚴重污染。出現在 此廢氣中的各種不同的污染物為含有烴及氧之化合物，尤 其是氮氧化物（N0X)及一氧化碳（c〇)。因此，廣泛及 徹底地研究已進行多年，以供降低由媒·蒸汽發電廠、焚化 爐及汽車工業之燃燒系統排放之有害氣體的量。 用於有效地消除氮氧化物⑽χ)的技術一般係區分 成同時使用催化劑及還原劑之選擇性催化還原作用 (SCR)，僅使用還原劑但未使用催化劑之選擇性非_催化 還原仙（SNQR)，在㈣職器之燃燒狀態的低Ν〇χ 燃燒器及其類似技術。 在上述之技術中，考慮二次污染之產生、去除效率、 操作成本等’選擇性催化還原作用係評價為用於 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） C請先閱讀背面之注意事項存填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1224524 A7 —— ________B7 V. Description of the invention (1) Catalyst for selective catalytic reduction of nitrogen oxides and preparation method thereof FIELD OF THE INVENTION The present invention relates generally to the use of nitrogen Catalyst for selective catalytic reduction of oxides and preparation method thereof. More specifically, the present invention relates to a catalyst prepared by using a raw material that is not suitable for a general catalyst for selective catalytic reduction of nitrogen oxides, such as vanadium, Spent catalyst for nickel and sulfur adsorption, wherein the catalyst for hydrodesulfurization contains molybdenum, iron, cobalt, silicon, and the like, and a preparation method thereof. Conventional technology, in general, the exhaust gas released during the combustion of hydrocarbon fuels such as gas, petroleum and diesel fuel can cause serious pollution to the environment. The various pollutants present in this exhaust gas are compounds containing hydrocarbons and oxygen, especially nitrogen oxides (NOx) and carbon monoxide (c0). Therefore, extensive and thorough research has been carried out for many years to reduce the amount of harmful gases emitted by combustion systems in media steam plants, incinerators, and the automotive industry. The technology for effectively eliminating nitrogen oxides (⑽χ) is generally divided into selective catalytic reduction (SCR) using a catalyst and a reducing agent simultaneously, and selective non-catalytic reduction (SNQR) using only a reducing agent but no catalyst. ), Low NOx burner and similar technology in the burning state of the burner. In the above-mentioned technology, considering the generation, removal efficiency, and operating cost of secondary pollution, the 'selective catalytic reduction' is evaluated as being used for this paper standard. Applicable to China National Standard (CNS) A4 specification (210X297 mm) C Please first (Read the notes on the back and fill in this page)
1224524 I五 經濟部智慧財產局員工消費合作社印製 A71224524 I5 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7
化物最有效的技術。在利用選擇性催化還原作用技術的例 子中’氮氧化物之去除效率可達9〇%或更高及催化劑的耐 用期係約2至5年。再者，SCR技術在技術層面上係有利的， 因為在焚化爐中可伴隨氮氧化物去除有毒的戴奥辛。 可用於選擇性催化還原作用之催化劑依其外部形態， 可區分成擠壓式催化劑、金屬板催化劑及丸狀催化劑。目 月’J ’擠壓式催化劑及金屬板催化劑為廣泛使用於蒸汽廠及 焚化爐’及丸狀催化劑係適用於硝酸及己内酯等之製備過 転。催化劑組成物主要包含例如釩、鉬、鎢及其類似物活 性金屬之氧化物，且進一步包含其他用於移轉活化溫度範 圍及增強催化劑之耐用性的過渡金屬成分。 在選擇性催化還原作用技術可用於作為載體者為二氧 化鈦（Ti〇2)、三氧化二鋁（Al2〇3)、二氧化矽及其類 似物’其中較佳為使用二氧化鈦，以其防中毒性之角度來 看。 在選擇性催化還原作用技術中，藉由以催化成分浸潰 該載體製造之催化劑可塗覆在例如金屬板或陶瓷蜂巢體之 結構體上，以供製備催化體，廢氣可通過此催化體，藉此 吸附例如氮氧化物之有害氣體並接著還原成無害物質。 在此方面，美國專利第5,827,489號揭露一種供製備用 於選擇性催化還原作用之催化劑的方法，此催化劑含有結 晶相氧化物，其係藉由利用例如飢、$目、錄及鶴等催化成 分浸潰例如氧化鈦、氧化鋁、氧化矽及氧化鍅等無機氧化 物載體，接著加熱處理。此專利應用一載體及相對於用於 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇><297公菱） (請先閱讀背面之注意事項再填寫本頁) Γ 1224524 A7 B7 五、發明説明（3 ) (請先閱讀背面之注意事項再填寫本頁) 選擇性還原作用之硫氧化物，具有超抗中毒性之催化劑成 分，及具有自由控制活性金屬量、催化劑之比表面積及孔 洞尺寸的優點，以供製備具有最適性能之催化劑，其中添 加適量的硫酸鹽。另一方面，其遭遇高製備成本的問題， 因為用於作為載體之各個單一材料（或前驅物）及催化劑 需藉由催化劑生產及混合的方法來製備。 另一方面，韓國專利公開案第95-72277號關於由油精 製廠之加氫脫硫製程中釋出之廢催化劑的再循環。根據該 發明，在作為還原劑之氨存在下，藉由再循環此種廢催化 劑製備之用於選擇性催化還原作用的催化劑，與藉由單一 材料之組合方法製備的催化劑相較，由於低的製備成本、 相對於硫氧化物之固有抗中毒性，及含有高含量之具有絕 佳之對氮氧化物的活性的金屬成分而較有利。 然而，由於上述發明遭遇之於去硫化方法後，由不同 卸出線釋出之廢催化劑具有不同性能的問題，因此降低催 化性能。在將廢催化劑使用於選擇性催化還原作用之例 子，以廢催化劑之總釋出量為基準，僅可以30%回收率再 循環，以及因此已完成徹底的研究來解決此問題。 經濟部智慧財產局員工消費合作社印製 發明揭露 導引至本發明，藉由本案發明人針對避免習知技術遭 遇的問題，對由油精製廠之加氫脫硫製程的全面及徹底的 研究，結果發現不適用於作為氮氧化物之選擇性催化還原 作用的原料可再循環以供製備用於氮氧化物之選擇性催化 還原作用的催化劑，其具有絕佳之氮氧化物的去除效率。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1224524 經濟部智慧財產局員工消費合作社印製 A7 B7 發明説明（4) 因此，本發明之一目的為藉由使用廢催化劑提供一種 用於氮氧化物之選擇性催化還原作用的催化劑，其可增加 廢催化劑回收的效率及具有絕佳之氮氧化物去除效率。 本發明之另一目的為提供一種利用廢催化劑製備用於 氮氧化物之選擇性催化還原作用的催化劑之方法。 為了達到本發明之該等目的，本發明提供一種由廢催 化劑製備用於氮氧化物之選擇性催化還原作用的催化劑之 方法，該廢催化劑已於油精製廠之加氫脫硫作用線上吸附 有釩、鎳及硫，其中用於加氫脫硫作用之催化劑在氧化銘 載體上含有鉬、鐵、始及矽，該方法包含下述步驟： 提供來自該廢催化劑之第一材料，包含1〇重量％或更 尚的飢’ 5重量％或更高的鎳，5重量％或更高的硫及3重量 %或更低的鉬，以及比表面積為60 m2/g或更低，以及孔洞 尺寸為250 A或更大； 提供來自該廢催化劑之第二材料，包含3重量％或更低 的釩，4重量％或更低的鎳，2重量％或更低的硫及5重量％ 或更鬲的鉬，以及比表面積為130 m2/g或更大，以及孔洞 尺寸為150 A或更小； 在300至400°C下分別預處理該第一及第二材料，將各 個預處理之材料磨成粉狀至平均顆粒尺寸為1〇〇至2〇〇篩 目； 將第一材料與酸及水混合，接著與第二材料混合，以 及 在100至120C；下乾燥混合物，且接著在“ο至55〇°C下 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） (請先閱讀背面之注意事項再填寫本頁)The most effective technology. In the case of using the selective catalytic reduction technology, the removal efficiency of 'nitrogen oxides can reach 90% or more and the durability of the catalyst is about 2 to 5 years. Furthermore, SCR technology is technically advantageous because in the incinerator it can be accompanied by the removal of toxic dioxin by nitrogen oxides. The catalysts that can be used for selective catalytic reduction can be divided into extrusion catalysts, metal plate catalysts and pellet catalysts according to their external forms. "J" extrusion catalysts and metal plate catalysts are widely used in steam plants and incinerators, and pellet catalysts are suitable for the preparation of nitric acid and caprolactone. The catalyst composition mainly includes oxides of active metals such as vanadium, molybdenum, tungsten, and the like, and further contains other transition metal components for shifting the activation temperature range and enhancing the durability of the catalyst. Among the selective catalytic reduction technologies that can be used as carriers are titanium dioxide (Ti02), aluminum oxide (Al203), silicon dioxide and the like. Among them, titanium dioxide is preferably used to prevent toxicity Perspective. In the selective catalytic reduction technology, a catalyst manufactured by impregnating the carrier with a catalytic component can be coated on a structure such as a metal plate or a ceramic honeycomb body to prepare a catalyst body, and the exhaust gas can pass through the catalyst body, Thereby, harmful gases such as nitrogen oxides are adsorbed and then reduced to harmless substances. In this regard, U.S. Patent No. 5,827,489 discloses a method for preparing a catalyst for selective catalytic reduction, which catalyst contains crystalline phase oxides by utilizing catalytic components such as Hungry, $, $ ,, and Crane Impregnation of inorganic oxide supports such as titanium oxide, aluminum oxide, silicon oxide and hafnium oxide, followed by heat treatment. This patent applies a carrier and applies Chinese National Standard (CNS) A4 specifications (2 丨 〇 > < 297 Gongling) relative to the paper size (Please read the precautions on the back before filling this page) Γ 1224524 A7 B7 V. Description of the invention (3) (Please read the precautions on the back before filling this page) Selective reduction of sulfur oxides, super-toxic catalyst components, and free control of active metal content and catalyst ratio Advantages of surface area and pore size for the preparation of catalysts with optimal performance, in which an appropriate amount of sulfate is added. On the other hand, it suffers from a problem of high production cost, because each single material (or precursor) and catalyst used as a carrier needs to be prepared by a method of catalyst production and mixing. On the other hand, Korean Patent Laid-Open No. 95-72277 relates to the recycling of waste catalyst released in the hydrodesulfurization process of an oil refinery. According to the invention, a catalyst for selective catalytic reduction prepared by recycling such a spent catalyst in the presence of ammonia as a reducing agent is compared with a catalyst prepared by a single material combination method because of a low The cost of preparation, the inherent resistance to sulfur oxides relative to sulfur oxides, and the high content of metal components with excellent activity against nitrogen oxides are advantageous. However, since the above-mentioned invention suffers from the problem that after the desulfurization method, spent catalysts released from different discharge lines have different properties, the catalytic performance is reduced. In the case of using the spent catalyst for selective catalytic reduction, based on the total amount of spent catalyst released, it can be recycled only at a recovery rate of 30%, and therefore thorough research has been done to solve this problem. The disclosure of the invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs led to the present invention. With the inventor of this case, in order to avoid the problems encountered by the conventional technology, a comprehensive and thorough study of the hydrodesulfurization process by the oil refinery, As a result, it was found that the raw materials that are not suitable for the selective catalytic reduction of nitrogen oxides can be recycled for preparing a catalyst for the selective catalytic reduction of nitrogen oxides, which has excellent nitrogen oxide removal efficiency. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1224524 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 Invention description (4) Therefore, one object of the present invention is to provide by using waste catalyst A catalyst for selective catalytic reduction of nitrogen oxides, which can increase the recovery efficiency of waste catalysts and has excellent nitrogen oxide removal efficiency. Another object of the present invention is to provide a method for preparing a catalyst for selective catalytic reduction of nitrogen oxides by using a waste catalyst. In order to achieve the objects of the present invention, the present invention provides a method for preparing a catalyst for selective catalytic reduction of nitrogen oxides from a waste catalyst which has been adsorbed on a hydrodesulfurization line of an oil refinery Vanadium, nickel, and sulfur, in which the catalyst used for hydrodesulfurization contains molybdenum, iron, starting, and silicon on an oxide carrier, the method includes the following steps: providing a first material from the spent catalyst, including 10 Weight percent or higher hunger '5 weight percent or higher nickel, 5 weight percent or higher sulfur and 3 weight percent or lower molybdenum, and a specific surface area of 60 m2 / g or lower, and pore size 250 A or more; a second material from the spent catalyst is provided, containing 3% by weight or less of vanadium, 4% by weight or less of nickel, 2% by weight or less of sulfur, and 5% by weight or more Rhenium molybdenum, and a specific surface area of 130 m2 / g or more, and a pore size of 150 A or less; pre-treat the first and second materials at 300 to 400 ° C, respectively, and each pre-treated material Milled to a powder size to an average particle size of 100 to 2 Sieve mesh; mix the first material with acid and water, then mix with the second material, and dry the mixture at 100 to 120C; and then at "ο to 55 ° C, this paper size applies Chinese national standards (CNS ) A4 specification (21〇 > < 297mm) (Please read the precautions on the back before filling this page)
經濟部智慧財產局員工消費合作社印製 1224524 A7 ——一 _ B7 五、發明説明（5 ) 煅燒。 圊式之簡要說明 本發明之上述及其他目的、特徵及其他優點將可由下 述之詳細說明並配合後附圖式而更清楚地瞭解，其中： 第1圖顯示根據本發明之製備用於氮氧化物之選擇性 催化還原作用的催化劑的方法流程圖，該方法係藉由提供 第一材料，其包含高含量之釩、鎳及硫及低含量之鉬及具 有較大的孔洞尺寸及較小的比表面積，以及第二材料，其 包含低含量之釩、鎳及硫及具有較小的孔洞尺寸及較大的 比表面積。 完成本發明之最佳實施態樣 根據本發明之用於氮氧化物之選擇性催化還原作用的 催化劑應具有所欲含量的活性金屬内容物，一定的比表面 積及其載體的孔洞尺寸，且在符合商業化之標準要求的嚴 刻的實驗條件下亦呈現90%或更高的氮氧化物去除效率。 一般而言，當選擇性催化還原作用之催化劑係利用廢 催化劑製備時，即使具有相同之載體及催化成分作為廢催 化劑，依比表面積及根據載體之孔洞性質之孔洞尺寸，及 活性金屬之適當量而定，用於氮氧化物之選擇性催化還原 作用的催化劑具有不同性能。尤其’具有高量活性金屬及 小比表面積的催化劑，具有絕佳的氮氧化物去除效率但狹 窄的活性溫度範®。另一方面，在具有小量活性金屬及大 比表面積的催化劑例子中，氮氧化物之去除效率變得低且 其活性溫度範圍係遷移至高溫。 本紙張尺度適财關家襟準（CNS ) Α4規格（210X^97公酱）Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1224524 A7 —— I _ B7 V. Description of Invention (5) Calcination. Brief Description of Formulas The above and other objects, features, and other advantages of the present invention will be more clearly understood from the following detailed description and the accompanying drawings, in which: Figure 1 shows the preparation of nitrogen for nitrogen according to the present invention. Method flow chart for a catalyst for selective catalytic reduction of oxides, the method is to provide a first material comprising a high content of vanadium, nickel and sulfur and a low content of molybdenum and having a larger pore size and smaller Specific surface area, and a second material, which contains low levels of vanadium, nickel, and sulfur and has a smaller pore size and a larger specific surface area. Completing the best mode of the present invention The catalyst for selective catalytic reduction of nitrogen oxides according to the present invention should have a desired content of active metal content, a certain specific surface area and the pore size of its support, and Nitrogen oxide removal efficiency of 90% or higher is also shown under stringent experimental conditions that meet commercial standards. Generally speaking, when the catalyst for selective catalytic reduction is prepared by using waste catalyst, even if it has the same support and catalytic components as the waste catalyst, it depends on the specific surface area and the pore size according to the pore properties of the support, and the appropriate amount of active metal Depending on the catalyst used for the selective catalytic reduction of nitrogen oxides, they have different properties. In particular, ‘catalysts with high amounts of active metals and small specific surface area have excellent nitrogen oxide removal efficiency but a narrow active temperature range®. On the other hand, in the case of a catalyst having a small amount of active metal and a large specific surface area, nitrogen oxide removal efficiency becomes low and its active temperature range migrates to a high temperature. The paper size is suitable for financial and family care (CNS) Α4 size (210X ^ 97 male sauce)
li-一:---F! (請先閱讀背面之注意事項再填寫本頁) 、1T • I I- 1 I I . 1224524 A7 B7 五、發明説明（6 ) 一般而言，加氫脫硫方法係區分成四步驟，其中第一 及第二步驟為去除金屬及第三及第四步驟為去除硫。因 此，根據金屬的吸附作用，用於去除金屬之催化劑具有過 量的活性金屬且因此具有較小的比表面積。然而，第三及 第四步驟之加氫脫硫作用，其為一化學反應，將原料中的 硫改變成Hj，且因此用於去除硫的催化劑，因為大量的 金屬係吸附在第一及第二步驟中而具有相對低的金屬含 量。 當具有該二性質之廢催化劑使用於製備用於選擇性催 化還原作用之催化劑時，其中氨係用於作為還原劑，用於 去除金屬之催化劑具有過量的活性金屬及較小的比表面 積’因此具有高氮氧化物去除效率但狹窄的活性溫度範 圍。另一用於去除硫的具有小量活性金屬及較大比表面積 的催化劑，具有低氮氧化物去除效率及遷移至高溫的活性 溫度範圍’因此不符合本發明之用於選擇性催化還原催化 劑的標準要求。由油精製廠之加氫脫硫作用線釋出的廢催 化劑之總量的約70%或更高具有上述二性質中之一者。 參考第1圖，其顯示根據本發明之用於氮氧化物之選 擇性催化還原作用的催化劑之製備方法。在本發明中，用 於去除氮氧化物之催化劑係由油精製廠之加氫脫硫作用線 釋出的廢催化劑。原料係分類成第一材料，其包含過量的 飢、鎳及硫及少量的鉬，且具有較小比表面積及較大孔洞 尺寸；以及第二材料，其包含小量之飢、鎳及硫及過量的 錮，及具有較大比表面積及較小孔洞尺木。此等材料各自 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 、言li- 一: --- F! (Please read the precautions on the back before filling this page), 1T • I I- 1 II. 1224524 A7 B7 5. Description of the invention (6) Generally speaking, hydrodesulfurization method The system is divided into four steps, wherein the first and second steps are for removing metal and the third and fourth steps are for removing sulfur. Therefore, the catalyst for removing metal has an excessive amount of active metal and therefore has a small specific surface area according to the adsorption effect of the metal. However, the hydrodesulfurization in the third and fourth steps is a chemical reaction that changes sulfur in the raw material to Hj, and is therefore a catalyst for removing sulfur because a large amount of metal is adsorbed on the first and the third It has a relatively low metal content in two steps. When a waste catalyst having these two properties is used to prepare a catalyst for selective catalytic reduction, ammonia is used as a reducing agent, and the catalyst for removing metal has an excess of active metal and a small specific surface area. It has a high nitrogen oxide removal efficiency but a narrow active temperature range. Another catalyst for removing sulfur with a small amount of active metal and a large specific surface area has a low nitrogen oxide removal efficiency and an active temperature range that migrates to a high temperature, and therefore does not comply with the present invention for a selective catalytic reduction catalyst. standard requirement. About 70% or more of the total amount of waste catalyst released from the hydrodesulfurization line of the oil refining plant has one of the above two properties. Referring to Fig. 1, there is shown a method for preparing a catalyst for selective catalytic reduction of nitrogen oxides according to the present invention. In the present invention, the catalyst for removing nitrogen oxides is a waste catalyst released from a hydrodesulfurization line of an oil refining plant. The raw material is classified into a first material, which contains an excessive amount of hunger, nickel and sulfur, and a small amount of molybdenum, and has a small specific surface area and a large pore size; and a second material, which contains a small amount of hunger, nickel and sulfur, and Excessive cormorants, and larger specific surface area and smaller holes. Each of these materials is in accordance with the Chinese National Standard (CNS) A4 size (210X297 mm). (Please read the precautions on the back before filling out this page.) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs.
1224524 A7 B7 五、發明説明（7 ) 經過預處理及磨成粉狀。 (請先閱讀背面之注意事項再填寫本頁) 第一材料包含10重量％或更高的釩，5重量％或更高的 鎳，5重量％或更高的硫及3重量％或更低的鉬，以及具有 例如比表面積為60 m2/g或更低，以及孔洞尺寸為250人或 更大等性質，而第二材料包含3重量％或更低的釩，4重量 %或更低的鎳，2重量％或更低的硫及5重量％或更高的鉬， 以及具有例如比表面積為130 m2/g或更大，以及孔洞尺寸 為150人或更小等性質。 於第1圖中，該第一及第二材料係藉由在300至400°C 下加熱3至5小時來進行預處理，以供去除油、碳及硫、廢 催化劑之不純物。在此熱處理的溫度下，其為標準處理條 件，可有效地去除碳及硫。 接著，將各自經過熱處理之第一及第二材料磨成粉末 至平均顆粒尺寸為100至200篩目。進行此磨成粉末之步驟 以使當混合第一材料及第二材料時，第一材料中之活性成 分之化學溶解作用變得容易，以及移動第二材料與自第一 材料中溶出之活性成分。因此，要求平均顆粒尺寸在上述 範圍内。 經濟部智慧財產局員工消費合作社印製 經磨成粉末之第一材料係與酸混合且接著添加第二材 料，其中第一材料及第二材料係以重量比4 : 6至2 : 8來混 合。若第一材料之混合量低於整個混合物材料之20重量 %，沽化金屬在混合物材料中不足，且比表面積變得過大。 另一方面，若其量超過40重量％，活性金屬在混合物材料 中為過量，且比表面積變得太低。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- 1224524 經濟部智慧財產局員工消費合作社印製 五 發明説明（8) 藉由添加酸及水至製備材過量活性成分係溶解錢中，材料中含有之 分布於第二材料中。 且因此洛解之活性成分係再 田/舌性成分藉由酸處理 一 積增加且因此過量之活性 /，虱化鋁载體之比表面第二材料的孔财。、.Μ狀具有大比表面積之(V:: 一二次，致於與第-材料中之氧化飢 飢是氮氧化物 酸庫溶鲑如， 疋原作用甲的較佳活性金屬。於本發明之酸的你|孚糸苗故 頁機成刀。可使用同時，g”/ 、 ο、 檸檬酸、稀硝酸及其類似物。金屬外，會溶解氧化銘栽體。 “加除了-解 日士，製備之混合物係在議至12代下乾燥23至25小 守且接者在450至550°C下加埶3至5小_ 於去除氮氧化物之催化劑。”、、]時，以致能製備用留下乾燥步驟，經由該乾燥步驟去除水分且因此僅 料之活2屬，以使第二材料初步浸潰於經溶解之第一材 ”'，屬中。完成煅燒步驟以使該經浸潰之、、舌性金屬 ΠΓ之溫度下結晶化成其氧化“=可極佳:=?結晶化及氧化紹載體之比表面積的最適化 如上述，用於氮氧化物之選擇性催化還原作用的催化 劑包含3至10重量％之飢，3至10重量％之錄，2至5重量％ ------：---衣-- (請先閱讀背面之注意事項再填寫本頁) 、11 本紙張尺度適用中國國家標準（CNS )八4規格（2 1 〇 χ 297公釐） .m 11-1224524 A7 B7 V. Description of the invention (7) Pretreated and ground into powder. (Please read the notes on the back before filling this page) The first material contains 10% by weight or more of vanadium, 5% by weight or more of nickel, 5% by weight or more of sulfur and 3% by weight or less Molybdenum, and has properties such as a specific surface area of 60 m2 / g or less, and a pore size of 250 people or more, while the second material contains 3% by weight or less of vanadium, 4% by weight or less Nickel, 2% by weight or less of sulfur and 5% by weight or more of molybdenum, and have properties such as a specific surface area of 130 m2 / g or more, and a pore size of 150 people or less. In Figure 1, the first and second materials are pretreated by heating at 300 to 400 ° C for 3 to 5 hours to remove impurities such as oil, carbon, sulfur, and spent catalyst. At this heat treatment temperature, it is a standard processing condition and can effectively remove carbon and sulfur. Next, the respective heat-treated first and second materials are ground to a powder to an average particle size of 100 to 200 mesh. This step of pulverizing is performed so that when the first material and the second material are mixed, the chemical dissolution of the active ingredient in the first material becomes easy, and the second material and the active ingredient eluted from the first material are moved . Therefore, it is required that the average particle size is within the above range. The first material printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which is ground into a powder, is mixed with an acid and then a second material is added, wherein the first material and the second material are mixed in a weight ratio of 4: 6 to 2: 8 . If the mixing amount of the first material is less than 20% by weight of the entire mixture material, the sold metal is insufficient in the mixture material, and the specific surface area becomes excessively large. On the other hand, if the amount exceeds 40% by weight, the active metal is excessive in the mixture material and the specific surface area becomes too low. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 1224524 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Five invention notes (8) By adding acid and water to the active material system of excess material In dissolved money, the content contained in the material is distributed in the second material. And therefore, the active ingredient of Luojie is a second field of pores of the second surface of the aluminum surface of the aluminum carrier, which is increased by the acid treatment and the active ingredient is increased by acid treatment. , .M shape has a large specific surface area (V :: once or twice, and the oxidizing hunger in the-material is the preferred active metal of nitric acid-soluble salmon such as, lutetium, etc. in the present You invented the acid | Fu Miao Miao Gu page machine into a knife. Can be used at the same time, g "/, ο, citric acid, dilute nitric acid and the like. Besides metal, it will dissolve the oxidized Ming plant." Addition-solution In Japan, the prepared mixture is dried at 23 to 25 hours under the 12th generation and then added at 3 to 5 hours at 450 to 550 ° C for the catalyst for removing nitrogen oxides. ",,], So that the preparation can be left with a drying step, through which the moisture is removed and therefore only 2 genera are expected, so that the second material is initially immersed in the dissolved first material "', genera. The calcination step is completed so that The impregnated, lingual metal ΠΓ crystallizes to its oxidation "= can be excellent: =? Crystallization and the optimization of the specific surface area of the oxide carrier as described above, for selective catalysis of nitrogen oxides The reduction catalyst contains 3 to 10% by weight of hunger, 3 to 10% by weight, 2 to 5% by weight ------: --- - (Please read the back of the precautions to fill out this page), 11 paper scale applicable Chinese National Standard (CNS) eight 4 Specifications (21 square χ 297 mm) .m 11-
經濟部智慧財產局員工消費合作社印製 之硫及3至10重量％之名目 日p目女 /〇之鉬，且因此具有例如比表面積為60 至140m/g及孔洞尺寸為15〇至25〇人等性質。 藉由塗覆催化劑至陶糾巢體或金屬板之催化體可去 除氮氧化物達90%或更高之喊，且亦增加廢催 的效率。 本發明之更佳瞭解可基於下述實施例而獲得，此等實 施例係撰述以供解釋朗，但不可解釋成限制本發明。實施例1及2 各自具有藉由XRF或ICP法測量之如下述表丄所示之 組成的第-及第二材料’係在3G(rc下加熱4小時，並接著 磨成粉末至平均顆粒尺寸為2〇〇篩目。經磨成粉末之第一材 料係與第對應於第一材料中之釩量為2倍的草酸混合，且接 著與第二材料，以第一材料相對於第二材料之重量比為 3 : 7來混合。接著，在10(rc下乾燥此混合物24小時，並接 著在500°C下煅燒5小時，以產生催化劑，其接著模塑成如 至40篩目，並測量其催化性能。結果如下述表2所示。 催化劑之性能試驗之進行係在5〇〇 ppm NO及5〇〇 n Jr NH3之存在下，在i〇0,000/hr2氣體時空間速率之嚴袼條件 下，以及反應溫度係在30°C至500°C之範圍内以5。(：/分鐘之 速率升高。 如下述表1及2所示，具有小比表面積及大孔洞尺寸 之第一材料具有低於80%之氮氧化物還原催化活性以及狹 窄的活性溫度範圍，然而具有大比表面積及小孔洞尺寸之 第二材料具有低於80%之活性且活性溫度遷移至高溫。發 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ------.----- (請先閲讀背面之注意事項再填寫本頁) 訂Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs consume sulfur printed by the cooperative and 3 to 10% by weight of the nominal day p / n / molybdenum, and therefore have, for example, a specific surface area of 60 to 140 m / g and a hole size of 150 to 25 People and other properties. By coating the catalyst on the ceramic entangled body or the metal plate, the catalyst can remove 90% or more of nitrogen oxides, and also increase the efficiency of waste catalyst. A better understanding of the present invention can be obtained based on the following examples, which are written for explanation, but should not be construed as limiting the present invention. Examples 1 and 2 The first and second materials each having a composition as shown in Table 下述 below measured by XRF or ICP method were heated at 3G (rc for 4 hours, and then ground to a powder to an average particle size The sieve is 200. The first material that is ground into powder is mixed with oxalic acid corresponding to twice the amount of vanadium in the first material, and then mixed with the second material, with the first material relative to the second material. The weight ratio is 3: 7 for mixing. Then, the mixture is dried at 10 ° C. for 24 hours, and then calcined at 500 ° C. for 5 hours to produce a catalyst, which is then molded into a mesh size of up to 40 mesh, and The catalytic performance was measured. The results are shown in Table 2 below. The performance test of the catalyst was performed in the presence of 5000 ppm NO and 5000 n Jr NH3, and the severe space velocity at the time of 100,000 / hr2 gas Under the conditions, and the reaction temperature is in the range of 30 ° C to 500 ° C, it is increased at a rate of 5. (: / min. As shown in Tables 1 and 2 below, it has the first small surface area and large pore size. The material has a nitrogen oxide reduction catalytic activity of less than 80% and a narrow active temperature range. The second material with large specific surface area and small pore size has an activity of less than 80% and the active temperature migrates to high temperature. The paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) ---- --.----- (Please read the notes on the back before filling this page) Order
Hi -I _Hi -I _
• J II -12- 1224524 A7 B7 一一·^ _ 五、發明説明（^) (請先閱讀背面之注意事項再填寫本頁) 現到包含例如下述表2所示之催化成分的催化劑符合適於 去除氮氧化物之選擇性催化還原作用的條件，對應3至1〇 重量％之釩，3至10重量％之鎳，及3至10重量％之鉬及比 表面積為60至140 m2/g及孔洞尺寸為150至250人，藉此具有 90%或更高之氮還原催化活性。 表1 實施例 成分（重量度） 催化劑性質 催化劑性能 V Ni Mo S 比表 面積 (m2/g) 孔洞 尺寸 (A) 最大 活性 (%) 活性範 圍（。C) 1 第一 材料 17.2 5.4 0.5 6.7 38.1 382.4 78.3 320-380 2 第二 材料 3.3 3.6 10.3 1.6 168.7 147.9 76.6 360-420 3 第一 材料 17.4 5.6 1.7 5.4 53.9 192.4 76.1 320-380— 4 第二 材料 3.5 3.6 6.8 2.0 157.8 135.3 75.6 360-420 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -13- 1224524 A7 B7 五、發明説明（n) 表2 實施例 成分（重量度） 催化劑性質 催化劑性能 V Ni Mo S 比表 孔洞 最大 活性範 面積 尺寸 活性 圍ΓΟ (m2/g) (A) (%) 1 8.7 3.1 4.1 1.5 134.7 183.3 94.1 280-400 2 8.0 3.0 5.3 2.7 130.4 161.3 93.7 280-400 (請先閱讀背面之注意事項再填寫本頁) 工業應用性 因此，可用於去除氮氧化物者為根據本發明之利用自 加氫硫化製程中釋出之廢催化劑製備的催化劑。此催化劑 之比表面積為60至140 m2/g及孔洞尺寸為150至250A，以3 至10重量％之釩，3至10重量％之鎳，及3至10重量％之鉬 為主，其係適用於氮氧化物之選擇性催化還原作用。本發 明之催化劑可去除氮氧化物達90%或更高之程度，在催化 劑性能之效率上呈現增加10%或更高。再者，此催化劑可 增加廢催化劑回收的效率。 經濟部智慧財產局員工消費合作社印製 本發明已以解釋說明之方式描述，且應瞭解到所使用 之用語的本質為描述性而非限制性。基於上述教示，本發 明可有許多改良及變化。因此，應可瞭解到在後附之申請 專利範圍的範疇内，本發明可以除了特定描述者之外的方 式實施。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） •14-• J II -12- 1224524 A7 B7 One by one ^ _ V. Description of the invention (^) (Please read the precautions on the back before filling out this page) Now the catalysts including the catalytic components shown in Table 2 below conform to Conditions suitable for selective catalytic reduction of nitrogen oxides, corresponding to 3 to 10% by weight of vanadium, 3 to 10% by weight of nickel, 3 to 10% by weight of molybdenum and a specific surface area of 60 to 140 m2 / The g and pore size are 150 to 250 people, thereby having a nitrogen reduction catalytic activity of 90% or more. Table 1 Example composition (weight) Catalyst properties Catalyst performance V Ni Mo S Specific surface area (m2 / g) Hole size (A) Maximum activity (%) Active range (.C) 1 First material 17.2 5.4 0.5 6.7 38.1 382.4 78.3 320-380 2 Second material 3.3 3.6 10.3 1.6 168.7 147.9 76.6 360-420 3 First material 17.4 5.6 1.7 5.4 53.9 192.4 76.1 320-380— 4 Second material 3.5 3.6 6.8 2.0 157.8 135.3 75.6 360-420 Wisdom of the Ministry of Economic Affairs Printed by the staff of the Property Bureau, Consumer Cooperatives. The paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) -13- 1224524 A7 B7 V. Description of the invention (n) Table 2 Example composition (weight) Catalyst properties Catalyst Performance V Ni Mo S Specific surface area Maximum active range area Size Active range ΓΟ (m2 / g) (A) (%) 1 8.7 3.1 4.1 1.5 134.7 183.3 94.1 280-400 2 8.0 3.0 5.3 2.7 130.4 161.3 93.7 280-400 ( (Please read the notes on the back before filling in this page) Industrial Applicability Therefore, those that can be used to remove nitrogen oxides are waste catalysts released from the hydrosulfurization process according to the present invention. Catalyst for catalyst preparation. The catalyst has a specific surface area of 60 to 140 m2 / g and a pore size of 150 to 250 A. It is mainly composed of 3 to 10% by weight of vanadium, 3 to 10% by weight of nickel, and 3 to 10% by weight of molybdenum. Suitable for selective catalytic reduction of nitrogen oxides. The catalyst of the present invention can remove nitrogen oxides to the extent of 90% or more, and shows an increase of 10% or more in the efficiency of the catalyst performance. Furthermore, this catalyst can increase the efficiency of recovering spent catalyst. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics The present invention has been described by way of illustration and it should be understood that the terms used are descriptive rather than restrictive in nature. Based on the above teachings, the present invention can have many improvements and changes. Therefore, it should be understood that, within the scope of the appended patent application, the present invention can be implemented in a manner other than a specific description. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) • 14-
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