KR100490832B1 - Method of preparing catalyst for removal of nox - Google Patents
Method of preparing catalyst for removal of nox Download PDFInfo
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- KR100490832B1 KR100490832B1 KR10-2002-0053429A KR20020053429A KR100490832B1 KR 100490832 B1 KR100490832 B1 KR 100490832B1 KR 20020053429 A KR20020053429 A KR 20020053429A KR 100490832 B1 KR100490832 B1 KR 100490832B1
- Authority
- KR
- South Korea
- Prior art keywords
- vanadium
- pitch
- molybdenum
- organic solvent
- catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 26
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011295 pitch Substances 0.000 claims abstract description 47
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 35
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 27
- 239000011733 molybdenum Substances 0.000 claims abstract description 27
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000011312 pitch solution Substances 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000001994 activation Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 claims description 5
- JOUSPCDMLWUHSO-UHFFFAOYSA-N oxovanadium;propan-2-ol Chemical compound [V]=O.CC(C)O.CC(C)O.CC(C)O JOUSPCDMLWUHSO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- IDIDIJSLBFQEKY-UHFFFAOYSA-N ethanol;oxovanadium Chemical compound [V]=O.CCO.CCO.CCO IDIDIJSLBFQEKY-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GOONVUGWFUNIJB-UHFFFAOYSA-N 2-amino-3,5-dibromobenzohydrazide Chemical compound NNC(=O)C1=CC(Br)=CC(Br)=C1N GOONVUGWFUNIJB-UHFFFAOYSA-N 0.000 claims description 2
- GCMDLPXRCVHIMG-UHFFFAOYSA-N dioxomolybdenum(2+) Chemical compound O=[Mo+2]=O GCMDLPXRCVHIMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 239000012298 atmosphere Substances 0.000 abstract description 6
- 150000002736 metal compounds Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000003763 carbonization Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- SJNANEOQLCKOKB-UHFFFAOYSA-N oxovanadium;propan-1-ol Chemical compound [V]=O.CCCO.CCCO.CCCO SJNANEOQLCKOKB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- FAQSSRBQWPBYQC-VGKOASNMSA-N dioxomolybdenum;(z)-4-hydroxypent-3-en-2-one Chemical compound O=[Mo]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FAQSSRBQWPBYQC-VGKOASNMSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011314 petroleum-based isotropic pitch Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003681 vanadium Chemical class 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B01J35/58—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Abstract
본 발명은 질소 산화물 제거 촉매의 제조 방법에 관한 것으로, 이 제조 방법은 바나듐 또는 몰리브덴 함유 유기 금속 화합물을 제1 유기 용매에 용해시켜 제조한 유기 금속 화합물 용액과 핏치를 제2 유기 용매에 용해시켜 제조한 핏치 용액을 상기 제1 및 제2 유기 용매의 비등점 또는 상기 핏치의 연화점 중 낮은 온도 이하에서 혼합하고; 상기 혼합 용액으로부터 유기 용매를 제거하여 바나듐 또는 몰리브덴 함유 핏치를 제조하고; 상기 바나듐 또는 몰리브덴 함유 핏치를 공기 분위기 하에 200 내지 350℃에서 열안정화하고; 상기 열안정화된 핏치와 결합제를 혼합한 후 성형하고; 얻어진 성형체를 활성화하는 공정을 포함한다.The present invention relates to a method for preparing a nitrogen oxide removal catalyst, which is prepared by dissolving an organic metal compound solution and pitch prepared by dissolving a vanadium or molybdenum-containing organometallic compound in a first organic solvent. One pitch solution is mixed below the lower temperature of the boiling point of the first and second organic solvents or the softening point of the pitch; Removing the organic solvent from the mixed solution to produce a vanadium or molybdenum containing pitch; Thermally stabilizing the vanadium or molybdenum-containing pitch at 200 to 350 ° C. under an air atmosphere; Molding after mixing the heat stabilized pitch and the binder; The process of activating the obtained molded object is included.
본 발명의 질소 산화물 제거용 촉매는 기존의 동일 조성의 활성탄소섬유계 촉매에 비하여 향상된 촉매 단위 부피당 질소 산화물 분해 성능을 가지므로 탈질 공정에서의 촉매로 활용이 가능하다.Since the catalyst for removing nitrogen oxides of the present invention has an improved performance of nitrogen oxide decomposition per unit volume of catalyst compared to existing activated carbon fiber catalysts of the same composition, it can be used as a catalyst in the denitrification process.
Description
[산업상 이용 분야][Industrial use]
본 발명은 질소 산화물 제거용 촉매의 제조 방법에 관한 것으로서, 보다 상세하게는 질소 산화물 제거율이 우수한 바나듐 또는 몰리브덴 함유 질소 산화물 제거용 촉매의 제조 방법에 관한 것이다.The present invention relates to a method for producing a catalyst for removing nitrogen oxides, and more particularly, to a method for producing a catalyst for removing vanadium or molybdenum-containing nitrogen oxides having excellent nitrogen oxide removal rates.
[종래 기술][Prior art]
NOx로 대표되는 질소 산화물은 황 산화물과 함께 산업화에 따라 각종 연소 공정 및 열분해 공정 등에서 배출되는 대표적인 대기 오염 물질로서, 환경에 미치는 위해성으로 인하여 일정한 농도 이하로 제거되어 배출되어야 한다.Nitrogen oxide, represented by NOx, is a representative air pollutant emitted from various combustion processes and pyrolysis processes along with sulfur oxide, and has to be removed and discharged below a certain concentration due to the danger to the environment.
이러한 질소 산화물을 제거하는 방법으로는 일반적으로 선택적 촉매 환원법(SCR: Selective Catalyst Reduction)이 이용되고 있으며 사용되는 대표적인 촉매로는 G. Ramis, J. Gatal., 157, 523(1995) 및 G. Centi, Appli. Catal. A, 132, 179(1995) 등과 같이 금속 산화물계 촉매를 들 수 있고, L. Pinoy, Catalyst Today, 17, 151(1993) 및 G. D대, J. Catal., 146, 334(1994) 등이 연구한 바와 같이 V2O5/TiO2 촉매가 특히 우수한 것으로 발표되고 있다. 이 방법은 금속 산화물의 촉매를 이용하여 300 내지 350℃ 정도의 고온에서 암모니아 등의 환원제를 투입하면서 반응시켜서 분해시키는 방법이다. 이 방법은 비교적 효율이 우수하나, 반응 온도가 상기와 같이 최소 300℃ 이상의 고온인 단점이 있다.Selective Catalyst Reduction (SCR) is generally used to remove such nitrogen oxides, and representative catalysts used are G. Ramis, J. Gatal., 157, 523 (1995) and G. Centi. , Appli. Catal. Metal oxide catalysts such as A, 132, 179 (1995), and the like, L. Pinoy, Catalyst Today, 17, 151 (1993) and G. D, J. Catal., 146, 334 (1994) and the like. As studied, V 2 O 5 / TiO 2 catalysts are reported to be particularly good. This method is a method of reacting and decomposing a metal oxide catalyst while introducing a reducing agent such as ammonia at a high temperature of about 300 to 350 ° C. This method is relatively excellent in efficiency, but the disadvantage is that the reaction temperature is at least 300 ℃ high temperature as described above.
이러한 단점을 해결하기 위한 방법으로 I. Mochida, 일본화학회지, No. 6, 885(1991) 및 I. Mochida, 일본 화학회지 No. 6, p. 694(1993) 등에 활성탄이나 활성 탄소 섬유를 이용하여 100℃ 정도의 낮은 온도에서도 질소 산화물을 분해할 수 있는 방법을 제시하고 있다. 그러나 이 방법은 반응 온도는 낮출 수 있으나, 반응 효율이 낮은 단점이 있다.I. Mochida, Japan Chemical Society, No. 6, 885 (1991) and I. Mochida, Japanese Chemical Society. 6, p. 694 (1993) and the like have proposed a method for decomposing nitrogen oxides using activated carbon or activated carbon fibers even at a temperature as low as 100 ° C. However, this method can lower the reaction temperature, but the disadvantage of low reaction efficiency.
본 발명은 상술한 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 탈질 성능이 우수한 바나듐 또는 몰리브덴을 포함하는 질소 산화물 제거용 촉매의 제조 방법에 관한 것이다.The present invention is to solve the above-mentioned problems, the object of the present invention relates to a method for producing a nitrogen oxide removal catalyst containing vanadium or molybdenum excellent in denitrification performance.
본 발명의 다른 목적은 반응 공간 속도가 증가하여도 동일한 반응 전환율을 나타내는 바나듐 또는 몰리브덴을 포함하는 질소 산화물 제거용 촉매의 제조 방법에 관한 것이다.Another object of the present invention relates to a method for producing a catalyst for removing nitrogen oxides, including vanadium or molybdenum, which exhibits the same reaction conversion rate even when the reaction space velocity is increased.
본 발명의 또 다른 목적은 바나듐 또는 몰리브덴이 함량의 높고 균일하게 분산된 질소 산화물 제거용 촉매의 제조 방법에 관한 것이다.Another object of the present invention relates to a method for preparing a catalyst for removing nitrogen oxides having a high and uniformly dispersed vanadium or molybdenum content.
상기 목적을 달성하기 위하여, 본 발명은 바나듐 또는 몰리브덴 함유 유기 금속 화합물을 제1 유기 용매에 용해시켜 제조한 유기 금속 화합물 용액과 핏치를 제2 유기 용매에 용해시켜 제조한 핏치 용액을 혼합하고; 상기 혼합 용액으로부터 유기 용매를 제거하여 바나듐 또는 몰리브덴 함유 핏치를 제조하고; 상기 바나듐 또는 몰리브덴 함유 핏치를 열안정화하고; 상기 열안정화된 핏치와 결합제를 혼합한 후 성형하여 성형체를 제조하고; 얻어진 성형체를 활성화하는 공정을 포함하는 질소 산화물 분해용 촉매의 제조 방법을 제공한다.In order to achieve the above object, the present invention is an organic metal compound solution prepared by dissolving a vanadium or molybdenum-containing organometallic compound in a first organic solvent and a pitch solution prepared by dissolving pitch in a second organic solvent; Removing the organic solvent from the mixed solution to produce a vanadium or molybdenum containing pitch; Thermally stabilizing the vanadium or molybdenum containing pitch; Mixing the thermally stabilized pitch and a binder and then molding to prepare a molded body; It provides a method for producing a catalyst for nitrogen oxide decomposition, including the step of activating the obtained molded article.
이하 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 바나듐 또는 몰리브덴을 포함하는 질소 산화물 제거용 촉매의 제조 방법에 관한 것이다. 이 제조 방법은 먼저, 바나듐 또는 몰리브덴 함유 유기 금속 화합물을 제1 유기 용매에 용해시켜 제조한 유기 금속 화합물 용액과 핏치를 제2 유기 용매에 용해시켜 제조한 핏치 용액을 혼합한다.The present invention relates to a method for producing a catalyst for removing nitrogen oxides including vanadium or molybdenum. In this production method, first, an organic metal compound solution prepared by dissolving a vanadium or molybdenum-containing organometallic compound in a first organic solvent and a pitch solution prepared by dissolving pitch in a second organic solvent are mixed.
상기 제1 및 제2 유기 용매로는 상기 유기 금속 화합물과 핏치를 완전히 용해할 수 있는 것이면 어떠한 것도 사용가능하나, 제거가 용이하도록 휘발성이 높고 비점이 낮은 것을 사용하는 것이 바람직하다. 이러한 제1 및 제2 유기 용매로는 테트라하이드로퓨란, 아세톤, 헥산, 알콜류, 퀴놀린 또는 피리딘을 사용할 수 있다. 이중에서 퀴놀린이나 피리딘은 높은 온도의 연화점을 갖는 핏치를 잘 용해시킬 수 있으나 상대적으로 분리 제거가 다소 곤란하며, 헥산이나 알콜류는 제거는 용이하나 고연화점 핏치의 용해가 다소 곤란하다. 가장 바람직한 용매는 테트라하이드로퓨란이나 아세톤이 비교적 높은 연화점을 갖는 핏치를 잘 용해시킬 수 있고, 휘발성이 강하고 비점이 낮아 제거가 용이하여 보다 바람직하다. As the first and second organic solvents, any one can be used as long as it can completely dissolve the organometallic compound and the pitch, but it is preferable to use one having high volatility and low boiling point for easy removal. Tetrahydrofuran, acetone, hexane, alcohols, quinoline or pyridine may be used as the first and second organic solvents. Of these, quinoline and pyridine can dissolve pitches having a softening point of high temperature, but are relatively difficult to separate and remove, and hexane or alcohols are easy to remove, but difficult to dissolve high softening pitch. The most preferred solvent is tetrahydrofuran or acetone, which can dissolve pitches having a relatively high softening point, and is more preferable because of its high volatility and low boiling point for easy removal.
상기 제1 및 제2 유기 용매로는 동일한 것을 사용할 수도 있고, 서로 상용성이 있는 다른 유기 용매를 사용할 수도 있다.As said 1st and 2nd organic solvent, the same thing may be used and another organic solvent compatible with each other may be used.
상기 유기 금속 화합물 용액은 바나듐 또는 몰리브덴 함유 유기 금속 화합물을 제1 유기 용매에 첨가하고 용해하여 제조한다. 용해 공정은 상온에서 실시할 수도 있고, 사용하는 화합물 종류에 따라 상온에서 잘 용해되지 않는 화합물을 사용할 경우에는 제1 유기 용매의 비등점 또는 사용되는 핏치의 연화점 중 낮은 온도까지 가열하면서 실시할 수도 있다. The organometallic compound solution is prepared by adding and dissolving a vanadium or molybdenum-containing organometallic compound in a first organic solvent. The dissolution step may be carried out at room temperature, or in the case of using a compound that does not dissolve well at room temperature depending on the kind of the compound to be used, it may be carried out while heating to the lower temperature of the boiling point of the first organic solvent or the softening point of the pitch used.
상기 바나듐 함유 유기 금속 화합물로는 바나듐(IV) 옥시아세틸아세테이트(Vanadium(IV) oxyacetylacetate[VO(C5H7O2) 2]), 바나듐(V) 옥시트리에톡사이드(Vanadium(V) oxytriethoxide[VO(C2H5)3], 바나듐(V) 옥시트리이소프로폭사이드(Vanadium(V) oxytriisopropoxide[(C3H7O)3VO]) 및 바나듐(V) 옥시트리프로폭사이드(Vanadium(V) oxytripropoxide[VO(OC3H7)3]로 이루어진 군에서 선택되는 것을 사용할 수 있고, 상기 몰리브덴 함유 유기 금속 화합물로는 비스(2,4-펜탄디오나토) 몰리브데늄(VI) 디옥사이드(Bis(2,4-pentanedionato) molybdenum(VI) dioxide[MoO2(C5H7O2)2]) 또는 몰리브데늄(II) 아세테이트 다이머(Molybdemum(II) acetate dimer[CH3(CO2)2Mo]2)를 사용할 수 있다. 그러나 본 발명에서 사용가능한 바나듐 또는 몰리브덴 함유 유기 금속 화합물이 이에 한정되지 않음을 당해 분야에 종사하는 사람들에게는 이해될 수 있을 것이다.The vanadium-containing organometallic compound may be vanadium (IV) oxyacetylacetate (Vanadium (IV) oxyacetylacetate [VO (C 5 H 7 O 2 ) 2 ]), vanadium (V) oxytriethoxide (Vanadium (V) oxytriethoxide [VO (C 2 H 5 ) 3 ], vanadium (V) oxytriisopropoxide (Vanadium (V) oxytriisopropoxide [(C 3 H 7 O) 3 VO]) and vanadium (V) oxytripropoxide ( Vanadium (V) oxytripropoxide [VO (OC 3 H 7 ) 3 ] can be selected from the group consisting of, as the molybdenum-containing organic metal compound bis (2,4-pentanedioato) molybdenum (VI) Dioxide (Bis (2,4-pentanedionato) molybdenum (VI) dioxide [MoO 2 (C 5 H 7 O 2 ) 2 ] or molybdenum (II) acetate dimer [CH 3 (CO 2 ) 2 Mo] 2 ) but those skilled in the art are not limited to vanadium or molybdenum-containing organometallic compounds usable in the present invention. It can be understood by them.
상기 유기 금속 화합물을 핏치 중량에 대하여 화합물 중 바나듐 또는 몰리브덴의 원자 무게를 기준으로 하여 0.01 내지 30 중량%의 양으로 첨가한다. 바나듐 또는 몰리브덴 원자 기준의 첨가량이 0.01 중량% 미만일 경우에는 공정의 복잡성에 비하여 최종 활성 탄소의 탈질 성능 향상에 크게 영향을 주지 못하므로 바람직하지 않으며, 30 중량%를 초과하여 첨가할 경우에는 구성 원료 중의 탄소의 함량이 충분히 높지 않으므로 성형이 곤란하며 또한 결합제를 추가로 첨가하여 제조하는 경우에도 비표면적이 충분히 유지되기가 곤란하여 저온에서의 탄소에 의한 촉매 분해 반응 개시가 어려워지므로 반응 온도를 더욱 높여야 되는 단점이 있다.The organometallic compound is added in an amount of 0.01 to 30% by weight, based on the atomic weight of vanadium or molybdenum in the compound, relative to the pitch weight. If the amount added based on vanadium or molybdenum atoms is less than 0.01% by weight, it is not preferable because it does not significantly affect the denitrification performance of the final activated carbon compared to the complexity of the process, and when it is added in excess of 30% by weight, It is difficult to mold because the carbon content is not high enough, and even when prepared by adding an additional binder, it is difficult to sufficiently maintain the specific surface area, making it difficult to start the catalytic decomposition reaction with carbon at low temperature, and thus the reaction temperature must be further increased. There are disadvantages.
상기 핏치 용액은 핏치를 제2 유기 용매에 첨가하고 용해하여 제조한다. 핏치로는 등방성 탄소 또는 이방성 탄소, 또는 석탄계 또는 석유계 등 모두 사용할 수 있다. The pitch solution is prepared by adding and dissolving pitch in a second organic solvent. As pitch, both isotropic carbon or anisotropic carbon, or coal-based or petroleum-based may be used.
상기 용해 공정은 상온에서 실시할 수도 있고, 상기 제2 유기 용매의 비등점 또는 핏치의 연화점 중 낮은 온도까지 가열하면서 실시할 수도 있다. 제2 용매의 사용량은 핏치를 완전히 용해시킬 수 있는 양보다 과량으로 사용하여도 무방하나, 지나치게 과량으로 사용할 경우 제거 단계에서 불필요한 에너지를 소모하게 되므로 포화량보다 약간 많은 정도를 사용하는 것이 적당하다.The said dissolution process may be performed at normal temperature, and may be performed, heating to the low temperature among the boiling point of the said 2nd organic solvent, or the softening point of a pitch. The amount of the second solvent may be used in excess of the amount that can completely dissolve the pitch, but when used in excess, it is appropriate to use slightly more than the saturation amount because it consumes unnecessary energy in the removal step.
상기 유기 금속 화합물 용액과 핏치 용액의 혼합 용액에서 제1 및 제2 유기 용매를 제거하여 바나듐 또는 몰리브덴 함유 핏치를 제조한다. 상기 제거 공정으로는 분별 증류, 감압 증류 등의 통상적인 유기 용매 제거 방법은 어떠한 방법도 사용할 수 있으며, 제거 공정에서 유기 용매를 완전하게 제거하지 못하고 잔류 유기 용매가 너무 많은 경우 안정화 단계에서 방출되어 대기 오염의 원인이 되고, 또한 유기 용매는 회수하여 재사용이 가능하므로 실질적으로 완전하게 제거하는 것이 좋다.A vanadium or molybdenum-containing pitch is prepared by removing the first and second organic solvents from the mixed solution of the organometallic compound solution and the pitch solution. Conventional organic solvent removal methods, such as fractional distillation and vacuum distillation, may be used as the removal process. Any organic solvent may not be completely removed in the removal process, and when there are too many residual organic solvents, the organic solvent may be released in a stabilization step and air. It is good to remove substantially completely because it causes contamination and the organic solvent can be recovered and reused.
얻어진 바나듐 또는 몰리브덴 함유 핏치를 이후의 공정인 탄화, 활성화 공정에서의 더욱 온도에서, 즉 이후 공정에서 용융되지 않도록 안정화 처리를 실시한다. 상기 안정화 처리 공정은 공기 분위기에서 200 내지 350℃에서 열처리하여 실시하며, 이외에도 통상적인 핏치 안정화 방법은 어떠한 방법도 사용할 수 있다.The obtained vanadium or molybdenum-containing pitch is subjected to stabilization treatment so as not to melt at a further temperature in the subsequent carbonization and activation process, that is, in the subsequent process. The stabilization treatment step is carried out by heat treatment at 200 to 350 ℃ in an air atmosphere, in addition to the conventional pitch stabilization method may be used any method.
안정화된 핏치에 결합제를 안정화 핏치 중량에 대하여 2 내지 50 중량%를 첨가하고 혼합하고, 이 혼합물을 성형하여 성형체를 제조한다. 상기 결합제의 양이 2 중량% 미만일 경우에는 원료의 성형 강도가 낮아져 성형이 가능하더라도 최종 제품의 강도가 지나치게 낮아져 촉매로서 사용이 곤란하며, 50 중량%를 초과하는 경우에는 성형 혼합물의 점도가 낮아서 성형 형태를 유지하기 곤란하며 또한 서로 달라붙기 쉽고 또한 활성화처리 후의 강도가 오히려 낮아지게 되어 바람직하지 않다. To the stabilized pitch, a binder is added and mixed with 2 to 50% by weight based on the weight of the stabilized pitch, and the mixture is molded to form a molded body. When the amount of the binder is less than 2% by weight, even if the molding strength of the raw material is lowered and molding is possible, the strength of the final product is too low to be used as a catalyst, and when it exceeds 50% by weight, the molding mixture is low in viscosity It is not preferable because it is difficult to maintain the shape, easily stick to each other, and the strength after the activation treatment is rather low.
상기 결합제로는 상기 공정으로 얻어진 바나듐 또는 몰리브덴 함유 핏치, 상기 공정을 처리하지 않은 핏치 또는 열경화성 수지를 사용할 수 있으나, 바나듐 또는 몰리브덴 함유 핏치가 금속 첨가의 효과가 우수하여 가장 바람직하다. The binder may be a vanadium or molybdenum-containing pitch obtained in the above process, a pitch which is not treated in the above process, or a thermosetting resin, but a vanadium or molybdenum-containing pitch is most preferable because of the effect of metal addition.
상기 성형체를 활성화처리 전에 탄화처리를 더욱 실시할 수도 있다. 탄화처리는 불활성 분위기에서 500 내지 1000℃의 온도에서 5분 내지 5시간 실시하는 것이 바람직하며, 탄화처리로 최종 활성 탄소의 탄소 수율을 증가시킬 수 있다. 탄화처리를 하지 않는 경우에도 활성화 과정의 초기 단계에서 탄화가 일어나므로 활성탄소의 제조는 가능하나 탄소 수율은 상대적으로 저하된다. 탄화처리 온도가 1000℃를 초과할 경우에는 핏치의 결정화가 진행되어 활성화를 저해하며 500℃ 미만에서는 탄화시간을 오래 유지시켜도 탄화가 잘 진행되지 않으므로 바람직하지 않다.The molded body may further be carbonized before the activation treatment. The carbonization treatment is preferably carried out at a temperature of 500 to 1000 ° C. for 5 minutes to 5 hours in an inert atmosphere, and the carbonization treatment may increase the carbon yield of the final activated carbon. Even when carbonization is not carried out, carbonization occurs at an early stage of the activation process, and thus the production of activated carbon is possible, but the carbon yield is relatively low. If the carbonization temperature exceeds 1000 ° C., crystallization of the pitch progresses and inhibits activation. If the carbonization temperature is lower than 500 ° C., the carbonization does not proceed well even if the carbonization time is maintained for a long time.
본 발명의 활성화 단계는 통상의 방법인 수증기, 이산화탄소 또는 공기분위기에서 열처리하는 방법이 바람직하며, 활성화 온도는 600 내지 1100℃인 것이 바람직하다. 활성화 온도가 600℃ 미만인 경우 장시간 열처리하여도 활성화 반응이 매우 늦게 진행되며, 활성화 온도가 1100℃ 초과하는 경우 반응 속도가 너무 빨라서 성형체의 분해가 급속히 일어나 수율이 저하되게 되므로 바람직하지 않다.The activation step of the present invention is preferably a method of heat treatment in a conventional method of steam, carbon dioxide or air atmosphere, the activation temperature is preferably 600 to 1100 ℃. If the activation temperature is less than 600 ℃ activating reaction proceeds very late even if the heat treatment for a long time, if the activation temperature is more than 1100 ℃ reaction rate is too fast to cause the decomposition of the molded article is rapidly reduced yield is not preferable.
이와 같이 제조된 핏치계 활성탄은 탄소 자체의 탈질 촉매 성능 및 바나듐 또는 몰리브덴에 의한 탄소의 탈질 촉매 성능을 향상시키는 작용에 의하여 탈질 반응의 전환율을 향상시키는 효과가 있으므로 활성탄을 이용한 탈질 반응 공정에서의 촉매로서 이용이 가능하다.Pitch-based activated carbon prepared as described above has the effect of improving the conversion of the denitrification reaction by the action of improving the denitrification catalyst performance of carbon itself and the denitrification catalyst performance of carbon by vanadium or molybdenum. It can be used as.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐 본 발명이 하기의 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.
(실시예 1)(Example 1)
연화점 258℃의 석유계 등방성 핏치를 테트라하이드로퓨란 유기 용매에 첨가하고, 상온에서 완전하게 용해시켜 핏치 용액을 제조하였다. 바나듐 원자만으로 환산하여 핏치 중량에 대하여 0.1 중량%만큼의 바나듐(IV) 옥시아세틸아세테이트[VO(C5H7O2)2]를 테트라하이드로퓨란 유기 용매에 첨가하고 상온에서 완전하게 용해시켜 바나듐 함유 유기 금속 화합물 용액을 제조하였다.A petroleum isotropic pitch at 258 ° C. of softening point was added to the tetrahydrofuran organic solvent and completely dissolved at room temperature to prepare a pitch solution. Vanadium (IV) oxyacetylacetate [VO (C 5 H 7 O 2 ) 2 ] is added to the tetrahydrofuran organic solvent in terms of vanadium atoms and is dissolved completely at room temperature. An organometallic compound solution was prepared.
상기 핏치 용액과 바나듐 함유 유기 금속 화합물 용액을 상온에서 1시간 동안 교반하면서 혼합하고, 이 혼합물을 감압 증류기에서 감압가열하여 테트라하이드로퓨란을 분리하여 제거하여 바나듐 함유 핏치를 제조하였다. 이 바나듐 함유 핏치를 공기를 유입시키면서 230℃에서 10시간 열안정화하였다. 안정화된 핏치에 안정화하지 않은 상기 바나듐 함유 핏치를 상기 안정화된 핏치 중량의 15 중량% 양으로 첨가하고 잘 혼합한 후 입자화장치를 이용하여 평균입경 3mm 정도의 펠렛 형태로 성형하였다. 이 성형체를 질소분위기에서 800℃에서 30분간 탄화하여 탄소화하고 계속하여 포화수증기 분위기에서 850℃로 2시간 동안 활성화하여 활성탄을 제조하였다. 이와 같이 제조된 활성탄의 비표면적은 890㎡/g을 나타내었다. 상기 활성탄을 컬럼형의 반응기에 충전하고, 100℃에서 부피 기준으로 400ppm의 NO, 10%의 산소, 400ppm의 암모니아 및 잔여 부분을 질소로 구성된 기체를 2400hr-1의 공간 속도로 통과시키면서 배출되는 기체의 NO의 농도를 연속적으로 측정하였다. 이때 촉매로 사용된 활성탄의 양은 1.2g 이었으며 그 결과 상기 바나듐 함유 활성탄 촉매에 의한 NO의 연속 분해율은 77%를 나타내었다.The pitch solution and the vanadium-containing organometallic compound solution were mixed with stirring for 1 hour at room temperature, and the mixture was heated under reduced pressure in a vacuum distillation to separate and remove tetrahydrofuran to prepare a vanadium-containing pitch. This vanadium containing pitch was heat stabilized at 230 degreeC for 10 hours, flowing in air. The unstabilized vanadium-containing pitch was added to the stabilized pitch in an amount of 15% by weight of the stabilized pitch, mixed well, and then formed into pellets having an average particle diameter of about 3 mm using a granulator. The molded body was carbonized by carbonization at 800 ° C. for 30 minutes in a nitrogen atmosphere, and then activated at 850 ° C. for 2 hours in a saturated steam atmosphere to prepare activated carbon. The specific surface area of the activated carbon thus produced was 890 m 2 / g. The activated carbon was charged into a columnar reactor, and the gas discharged while passing a gas composed of 400 ppm NO, 10% oxygen, 400 ppm ammonia, and the remaining portion of nitrogen at a space velocity of 2400 hr −1 at 100 ° C. by volume. The concentration of NO was measured continuously. At this time, the amount of activated carbon used as a catalyst was 1.2 g. As a result, the continuous decomposition rate of NO by the vanadium-containing activated carbon catalyst was 77%.
[비교예 1]Comparative Example 1
연화점 258℃의 석유계 등방성 핏치를 공기를 유입시키면서 230℃에서 10시간 동안 열안정화하였다. 안정화된 핏치에 안정화시키지 않은 상기 석유계 등방성 핏치 결합제를 상기 안정화된 핏치 중량의 15 중량% 양으로 첨가하고 잘 혼합한 후 입자화 장치를 이용하여 평균 입경 3mm 정도의 펠렛 형태로 성형하였다. 이 성형체를 질소 분위기에서 30분간 탄화하여 탄소화하고 게속하여 포화 수증기 분위기에서 850℃로 2시간 동안 활성화하여 활성탄을 제조하였다. 그 결과 제조된 활성 탄소 섬유의 BET 방법에 의해 측정한 비표면적은 920㎡/g이었다. 이와 같이 제조된 활성 탄소 섬유를 실시예 1과 같은 조건의 배연 모델 가스를 2400hr-1의 공간속도로 통과시키면서 배출된 기체의 NO 농도를 연속적으로 측정하였다. 이때 촉매로 사용된 활성탄의 양은 1.2g이었으며 그 결과 연속 분해율은 51%를 나타내었다.The petroleum-based isotropic pitch of softening point 258 ° C. was heat stabilized at 230 ° C. for 10 hours while introducing air. The petroleum isotropic pitch binder not stabilized to the stabilized pitch was added in an amount of 15% by weight of the stabilized pitch weight, mixed well, and then formed into pellets having an average particle diameter of about 3 mm using a granulation apparatus. The molded product was carbonized in a nitrogen atmosphere for 30 minutes, carbonized, and then activated at 850 ° C. for 2 hours in a saturated steam atmosphere to prepare activated carbon. As a result, the specific surface area measured by the BET method of the produced activated carbon fiber was 920 m 2 / g. The NO concentration of the exhaust gas was continuously measured while passing the activated carbon fiber thus produced through the flue gas model gas under the same conditions as in Example 1 at a space velocity of 2400 hr −1 . At this time, the amount of activated carbon used as a catalyst was 1.2 g and as a result, the continuous decomposition rate was 51%.
[실시예 2]Example 2
바나듐 원자만으로 환산하여 핏치 중량에 대하여 5 중량% 만큼의 바나듐(IV) 옥시아세틸아세테이트[VO(C5H7O2)2]를 테트라하이드로퓨란 유기 용매에 용해시켜 제조된 바나듐 함유 유기 금속 화합물 용액을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 활성탄을 제조하였다. 이와 같이 제조된 활성탄 촉매의 비표면적은 770㎡/g을 나타내었다. 상기 활성탄을 실시예 1과 동일한 조건으로 NO 기체를 통과시키면서 배출되는 기체의 NO의 농도를 연속적으로 측정하였다. 이때 촉매로 사용된 활성탄의 양은 1.2g이었으며, 그 결과 상기 바나듐 함유 활성탄 촉매에 의한 NO의 연속 분해율은 81%를 나타내었다.A vanadium-containing organometallic compound solution prepared by dissolving vanadium (IV) oxyacetylacetate [VO (C 5 H 7 O 2 ) 2 ] in a tetrahydrofuran organic solvent in terms of vanadium atoms in terms of pitch weight. Except for using the same as in Example 1 to prepare an activated carbon. The specific surface area of the activated carbon catalyst thus prepared was 770 m 2 / g. The concentration of NO of the gas discharged while the activated carbon was passed through NO gas under the same conditions as in Example 1 was continuously measured. At this time, the amount of activated carbon used as a catalyst was 1.2 g. As a result, the continuous decomposition rate of NO by the vanadium-containing activated carbon catalyst was 81%.
즉, 실시예 1 내지 2의 활성탄 촉매는 NO의 연속 분해율이 각각 77%, 81%로 비교예 1의 51%보다 매우 높게 나타났으므로 탈질 반응 공정에서 촉매로서 매우 유용하다.In other words, the activated carbon catalysts of Examples 1 and 2 were 77% and 81%, respectively, which is very high than 51% of Comparative Example 1, and thus are very useful as catalysts in the denitrification reaction process.
본 발명의 질소 산화물 제거용 촉매의 분해 성능은 동일한 무게를 기준으로 비교할 때는 다소 낮으나 동일한 반응 공간 속도에서는 최종 연속 전환율이 향상되는 결과를 나타내고 있으므로 동일한 반응기 부피에 의한 반응 효율의 향상이 가능하므로 반응기의 규모를 감소시켜 설비를 소형화할 수 있는 효과가 있다.Decomposition performance of the catalyst for removing nitrogen oxides of the present invention is somewhat lower when compared to the same weight, but at the same reaction space velocity, the final continuous conversion is improved, so that the reaction efficiency can be improved by the same reactor volume. By reducing the size, it is possible to miniaturize the equipment.
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| KR101243846B1 (en) | 2005-12-22 | 2013-03-20 | 재단법인 포항산업과학연구원 | Preparation method of superfine pitch fiber |
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| JPH08259957A (en) * | 1995-03-27 | 1996-10-08 | Osaka Gas Co Ltd | Production of metal-containing pitch for production of activated carbon fiber, production of activated carbon fiber and activated carbon fiber |
| JPH1112577A (en) * | 1990-06-04 | 1999-01-19 | Conoco Inc | Direct production of organometallic compound-containing pitch for spinning pitch carbon fiber |
| JPH1112576A (en) * | 1990-12-14 | 1999-01-19 | Conoco Inc | Meso phase pitch containing organometallic compound for spinning pitch carbon fiber |
| KR20010016595A (en) * | 2000-12-23 | 2001-03-05 | 유승곤 | Preparation method and use of Metal(Cu, Zn, Cr, v, Mo, Ti, Fe etc)-Impregnated activated carbon fiber for removal of toxicity, noxious gas |
| KR20020050986A (en) * | 2000-12-22 | 2002-06-28 | 신현준 | CATALYST FOR NOx DECOMPOSITION AND PREPARATION METHOD OF THE SAME |
| KR100407806B1 (en) * | 2001-07-20 | 2003-11-28 | 재단법인 포항산업과학연구원 | ACTIVATED CARBON FIBER CATALYST FOR REMOVAL OF SOx AND PREPARATION METHOD OF THE SAME |
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| JPH1112577A (en) * | 1990-06-04 | 1999-01-19 | Conoco Inc | Direct production of organometallic compound-containing pitch for spinning pitch carbon fiber |
| JPH1112576A (en) * | 1990-12-14 | 1999-01-19 | Conoco Inc | Meso phase pitch containing organometallic compound for spinning pitch carbon fiber |
| JPH08259957A (en) * | 1995-03-27 | 1996-10-08 | Osaka Gas Co Ltd | Production of metal-containing pitch for production of activated carbon fiber, production of activated carbon fiber and activated carbon fiber |
| KR20020050986A (en) * | 2000-12-22 | 2002-06-28 | 신현준 | CATALYST FOR NOx DECOMPOSITION AND PREPARATION METHOD OF THE SAME |
| KR20010016595A (en) * | 2000-12-23 | 2001-03-05 | 유승곤 | Preparation method and use of Metal(Cu, Zn, Cr, v, Mo, Ti, Fe etc)-Impregnated activated carbon fiber for removal of toxicity, noxious gas |
| KR100407806B1 (en) * | 2001-07-20 | 2003-11-28 | 재단법인 포항산업과학연구원 | ACTIVATED CARBON FIBER CATALYST FOR REMOVAL OF SOx AND PREPARATION METHOD OF THE SAME |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101243846B1 (en) | 2005-12-22 | 2013-03-20 | 재단법인 포항산업과학연구원 | Preparation method of superfine pitch fiber |
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