KR100671493B1 - Vanadia-Titania Xerogel Catalysts for Ammoxidation and Preparing Method of the same - Google Patents
Vanadia-Titania Xerogel Catalysts for Ammoxidation and Preparing Method of the same Download PDFInfo
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- KR100671493B1 KR100671493B1 KR1020040106004A KR20040106004A KR100671493B1 KR 100671493 B1 KR100671493 B1 KR 100671493B1 KR 1020040106004 A KR1020040106004 A KR 1020040106004A KR 20040106004 A KR20040106004 A KR 20040106004A KR 100671493 B1 KR100671493 B1 KR 100671493B1
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- catalyst
- vanadia
- titania
- girogel
- gel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- -1 nitrile compound Chemical class 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 150000002924 oxiranes Chemical class 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000000499 gel Substances 0.000 description 25
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 17
- 238000003980 solgel method Methods 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- IYSVGEBODXGIBU-UHFFFAOYSA-N benzene-1,3-dicarbonitrile 1,3-xylene Chemical compound CC1=CC=CC(C)=C1.N#CC1=CC=CC(C#N)=C1 IYSVGEBODXGIBU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- HPLXJFZCZSBAAH-UHFFFAOYSA-N [V+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [V+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HPLXJFZCZSBAAH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- UARDWXPTHFQYJK-UHFFFAOYSA-K trichlorotitanium(1+) Chemical compound Cl[Ti+](Cl)Cl UARDWXPTHFQYJK-UHFFFAOYSA-K 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
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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
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/23—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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 탄화수소화합물을 암모니아, 산소와 반응시키는 암옥시화 반응으로 니트릴화합물을 제조하는데 사용되는 바나디아-티타니아 지로젤 촉매, 그 제조 방법 및 반응성에 관한 것이다. 본 발명의 바나디아-티타니아 지로젤 촉매는, 나노입자 크기의 기공이 네트워크화된 구조를 가지는 지로젤이고, 바나디아 및 티타니아로 구성되며, 상기 바나디아의 함량이 전체 촉매 중량의 1∼10중량%, 바람직하게는 3∼5중량%인 것을 내용으로 한다. 또한, 본 발명의 바나디아-티타니아 지로젤 촉매는 크롬, 안티몬, 주석, 철, 비스무스, 및 몰리브덴으로 구성되는 군으로부터 1이상 선택된 금속산화물, 인 또는 칼륨을 더 함유할 수 있다. 본 발명에 의한 바나디아-티타니아 지로젤 촉매는, 탄화수소화합물의 암옥시화 반응에 사용하였을 때, 낮은 바나디아 함량에서도 넓은 반응온도 범위에서 탄화수소화합물의 전환율과 니트릴화합물의 수율 및 선택성을 크게 향상시킬 수 있는 저비용 고효율의 촉매이다. The present invention relates to a vanadia-titania girogel catalyst used to prepare a nitrile compound by a dark oxidation reaction in which a hydrocarbon compound is reacted with ammonia and oxygen, a preparation method thereof, and a reactivity thereof. The vanadia-titania geogel catalyst of the present invention is a geogel having a network structure of nanoparticle-sized pores, and is composed of vanadia and titania, wherein the amount of vanadia is 1 to 10% by weight of the total catalyst weight. Preferably, it is 3 to 5 weight%. In addition, the vanadia-titania geogel catalyst of the present invention may further contain at least one metal oxide, phosphorus or potassium selected from the group consisting of chromium, antimony, tin, iron, bismuth, and molybdenum. The vanadia-titania girogel catalyst according to the present invention can greatly improve the conversion of hydrocarbon compounds and the yield and selectivity of nitrile compounds at a wide reaction temperature range even at low vanadia content when used in the dark oxidation of hydrocarbon compounds. It is a low cost and high efficiency catalyst.
암옥시화 반응, 촉매, m-크실렌, 지로젤, 바나디아, 티타니아Dark oxidation reaction, catalyst, m-xylene, girogel, vanadia, titania
Description
도 1은 본 발명의 일실시예에 의한 5중량%바나디아-티타니아 지로젤 촉매의 전자현미경(TEM) 사진이다. 1 is an electron microscope (TEM) photograph of a 5 wt% vanadia-titania girogel catalyst according to an embodiment of the present invention.
본 발명은 탄화수소화합물을 암모니아, 산소와 반응시키는 암옥시화 반응(ammoxidaiton)으로 니트릴화합물을 제조하는데 사용되는 바나디아-티타니아 지로젤(xerogel) 촉매, 그 제조 방법 및 반응성에 관한 것이다. 더욱 상세하게는 솔-젤 법을 이용하여 만든 바나디아-티타니아 습윤젤을 오븐건조 후, 산소를 흘리면서 소성하여 바나디아-티타니아 지로젤 촉매를 제조하고, 이를 m-크실렌의 암옥시화 반응의 촉매로 사용하는 기술에 관한 것이다. The present invention relates to a vanadia-titania xerogel catalyst used to prepare a nitrile compound by an ammoxidaiton in which a hydrocarbon compound is reacted with ammonia and oxygen, a preparation method thereof, and a reactivity thereof. More specifically, the vanadium-titania wetting gel made using the sol-gel method is oven dried, and then calcined with oxygen, thereby preparing a vanadia-titania girogel catalyst, which is a catalyst for the dark oxidation of m -xylene. It relates to the technology to use.
m-크실렌의 암옥시화 반응은 이소프탈로니트릴을 생산하기 위한 것으로서, 상업적으로 매우 중요한 반응이다. 이소프탈로니트릴 생성물은 매우 다양한 화학제 품, 살균제와 제초제, 폴리아미드와 폴리우레탄과 같은 화학제품의 중간 원료로 사용된다[Rizayev R. G., Mamedov E. A., Vislovskii V. P. and Sheinin V. E., Appl. Catal. A: Gen, 83 (1992) 103]. 또한, 이소프탈로니트릴의 수소화 반응에 의하여 생성되는 m-크실렌디아민은 가스보존능력이 기존의 용기용 필름인 PET 보다 뛰어나 고부가가치의 물질로 각광을 받고 있다. The dark oxidization reaction of m -xylene is for producing isophthalonitrile and is a very important reaction commercially. Isophthalonitrile products are used as intermediates for a wide variety of chemicals, fungicides and herbicides, and chemicals such as polyamides and polyurethanes [Rizayev RG, Mamedov EA, Vislovskii VP and Sheinin VE, Appl. Catal. A: Gen, 83 (1992) 103]. In addition, m -xylenediamine produced by the hydrogenation reaction of isophthalonitrile is in the spotlight as a high value-added material excellent gas storage capacity than PET, a conventional container film.
m-크실렌의 암옥시화 반응에 사용되는 촉매는 활성물질인 바나디아를 주성분으로 한 단일성분 산화물, 또는 여기에 크롬, 안티몬, 주석, 비스무스, 몰리브덴, 인과 같은 조촉매를 첨가하여 만든 복합 산화물이다. 기존의 촉매 제조법으로는, 전구체 혼합용액의 가수분해에 의한 방법[Gasior M, Grzybowska-Swierkoaz B and Haber J., Vanadia catalysts for process of oxidation of aromatic hydrocarbons, Polish scientific publishers, Warsaw-Cracow, 133 (1984)]과 이온 교환을 수반하는 무기염으로부터의 흡착[Rozeboom F., Medema J. and Gellings. P. J., J. Phys. Chem., 111 (1978) 215]을 이용한 방법이 소개되고 있으며, 이미 성형된 티타니아, 실리카의 실린더 펠렛이나 분말에 바나디움염 수용액을 함침하고 건조 소성하는 방법이 가장 일반적으로 사용되는 방법이다. 그러나, 이러한 방법은 낮은 비표면적과 높은 온도에서 티타니아의 아나타제 상이 낮은 열적안정성으로 인하여 부분적으로 루타일 상으로 변형되어 결과적으로 촉매 성능이 낮아지는 단점을 가지고 있다. 미츠비시(Mitsubishi)에서 상업화한 m-크실렌의 암옥시화 반응용 촉매 [미합중국특허 6,392,048호] [미합중국특허 6,646,163호]는 실리카 솔에 함침하고 가열 농축하여 분무건조에 의해 제조된다. 그러나, 활성이 좋은 이 촉매는 바나 디아를 포함한 활성물질의 함량이 50%가 넘고, 스탠다드 오일 컴패니(Standard oil company)에서 제조한 담지체인 티타니아에 함침한 촉매 [미합중국 특허 5,183,793호] 역시 바나디아를 포함한 활성물질의 함량이 18%이다. 따라서, 고가의 암옥시화 촉매의 비용과 효능 면에서 촉매의 함량을 줄이면서 효율을 높이는 개선이 필요하다. The catalyst used for the dark oxidization reaction of m -xylene is a single component oxide mainly composed of vanadia, an active substance, or a complex oxide made by adding a promoter such as chromium, antimony, tin, bismuth, molybdenum, and phosphorus to it. . Conventional catalyst preparation methods include hydrolysis of precursor mixtures [Gasior M, Grzybowska-Swierkoaz B and Haber J., Vanadia catalysts for process of oxidation of aromatic hydrocarbons, Polish scientific publishers, Warsaw-Cracow, 133 (1984 ) And adsorption from inorganic salts with ion exchange [Rozeboom F., Medema J. and Gellings. PJ, J. Phys. Chem., 111 (1978) 215] is introduced, and the method of impregnating an aqueous solution of vanadium salt in a cylinder pellet or powder of titania and silica that has already been formed is the most commonly used method. However, this method has the disadvantage that at low specific surface area and high temperature, the anatase phase of titania is partially transformed into rutile phase due to low thermal stability, resulting in lower catalytic performance. Catalysts for the dark oxidization reaction of m -xylene commercialized by Mitsubishi (US Pat. No. 6,392,048) [US Pat. No. 6,646,163] are prepared by spray drying by impregnation in silica sol and heat concentration. However, this active catalyst contains more than 50% of active substance including vanadium and impregnated in titania, a carrier manufactured by Standard oil company [US Pat. No. 5,183,793]. The active substance content is 18%. Accordingly, there is a need for an improvement in increasing the efficiency while reducing the content of the catalyst in terms of cost and efficacy of the expensive dark oxidizing catalyst.
이런 단점을 보완하기 위한 방법으로 솔-젤 법을 촉매 제조 방법으로 활용할 수 있다. 금속 알콕사이드 전구체를 사용하여 처음 시도되었던 솔-젤 법은 가수분해와 중합반응을 통해 나노 크기의 금속 산화물 입자의 솔을 형성한다. 솔-젤 법은 많은 다른 재료의 합성 방법에서도 물성을 제어하기 용이하고 제조 방법이 쉽고 효과적이라고 많은 문헌에서 제시하였으며 높은 비표면적과 티타니아의 활성면의 안정화로 산화반응에서 높은 촉매 활성을 보인다고 발표되었다. [Rodella C. B., Franco R. W. A., Magon C. J., Donoso J. P. and Nunes L. A. O, J. Sol-Gel. Tech., 25 (2002) 83] In order to compensate for this disadvantage, the sol-gel method may be used as a catalyst preparation method. The sol-gel method, which was first attempted using metal alkoxide precursors, forms a sol of nano-sized metal oxide particles through hydrolysis and polymerization. The sol-gel method has been suggested in many literatures that it is easy to control the physical properties and the preparation method is easy and effective even in the synthesis of many other materials, and it has been reported that the high specific surface area and the stabilization of the active surface of titania show high catalytic activity in oxidation reaction. . Rodella C. B., Franco R. W. A., Magon C. J., Donoso J. P. and Nunes L. A. O, J. Sol-Gel. Tech., 25 (2002) 83]
본 발명은 상술한 바와 같이, 솔-젤 법으로 제조된 바나디아-티타니아 습윤젤을 건조한 후 소성하여 제조함으로써, 나노입자 크기의 기공이 네트워크화된 구조를 가지고, 활성물질인 바나디아의 함량이 낮아 저비용이면서 고효율을 가지는, 바나디아-티타니아 지로젤 촉매 및 그 제조 방법을 제공하는 것이다. As described above, the vanadium-titania wetting gel manufactured by the sol-gel method is manufactured by drying and calcining, thereby having a structure in which the pores of the nanoparticle size are networked and having a low content of the active substance vanadium. It is to provide a vanadia-titania girogel catalyst having a low cost and high efficiency and a method of preparing the same.
본 발명의 또다른 목적은 상기의 바나디아-티타니아 지로젤 촉매를 이용하여 탄화수소화합물의 암옥시화 반응을 진행시킴으로써, 고부가가치의 니트릴화합물을 생성할 수 있게 하는 제조 방법을 제공하는 것이다.
It is still another object of the present invention to provide a method for producing a high-value nitrile compound by performing a dark oxidation reaction of a hydrocarbon compound using the vanadia-titania girogel catalyst.
상기한 바와 같은 목적을 달성하기 위한 본 발명에 따른 바나디아-티타니아 지로젤 촉매는, 나노입자 크기의 기공이 네트워크화된 구조를 가지는 지로젤이고, 바나디아 및 티타니아로 구성되며, 상기 바나디아의 함량이 전체 촉매 중량의 3∼5중량%인 것을 특징으로 한다. 본 발명의 바나디아-티타니아 지로젤 촉매는 바나디아가 잘 분산되어 있고, 티타니아와의 상호작용 정도가 높다. The vanadia-titania girogel catalyst according to the present invention for achieving the above object is a geogel having a networked structure of pores of nanoparticle size, and composed of vanadia and titania, and the content of the vanadia It is characterized by the 3 to 5 weight% of this total catalyst weight. In the present invention, the vanadia-titania girogel catalyst is well dispersed in vanadia and has a high degree of interaction with titania.
본 발명에 따른 바나디아-티타니아 지로젤 촉매에 있어서, 상기 촉매는 크롬, 안티몬, 주석, 철, 비스무스, 및 몰리브덴으로 구성되는 군으로부터 1이상 선택된 금속산화물, 인 또는 칼륨을 더 함유하는 것을 특징으로 한다.In the vanadia-titania girogel catalyst according to the present invention, the catalyst further comprises at least one metal oxide, phosphorus or potassium selected from the group consisting of chromium, antimony, tin, iron, bismuth, and molybdenum. do.
본 발명에 따른 바나디아-티타니아 지로젤 촉매의 제조방법은, 바나듐 산화물 및 티타늄 산화물의 전구체가 되는 알콕사이드 또는 비알콕사이드 무기젤 원료 용액에 산촉매를 첨가하고 일정한 온도를 유지하여 젤을 합성하는 제1단계; 제1단계에서 제조된 젤을 일정온도에서 숙성시키는 제 2단계; 제2단계에서 숙성된 젤을 건조시키는 제3단계; 및 제3단계에서 건조된 지로젤을 불활성 분위기에서 유기물을 제거시키고 공기 또는 산소 분위기에서 열처리하는 제4단계를 포함하여 구성되는 것을 특징으로 한다. In the method for preparing a vanadium-titania girogel catalyst according to the present invention, a first step of synthesizing a gel by adding an acid catalyst to an alkoxide or non-alkoxide inorganic gel raw material solution that is a precursor of vanadium oxide and titanium oxide and maintaining a constant temperature ; A second step of aging the gel prepared in the first step at a predetermined temperature; A third step of drying the gel matured in the second step; And a fourth step of removing the organic matter in the inert atmosphere and heat treating the dried gel in the third step in an air or oxygen atmosphere.
본 발명에 따른 바나디아-티타니아 지로젤 촉매의 제조 방법에 있어서, 상기 제1단계의 무기젤 원료가 비알콕사이드인 경우 에틸렌옥사이드, 프로필렌옥사이드, 및 부틸렌옥사이드로부터 선택되는 1이상의 에폭사이드를 함께 사용하는 것을 특징으로 한다.In the method for preparing a vanadia-titania girogel catalyst according to the present invention, when the inorganic gel raw material of the first step is a non-alkoxide, at least one epoxide selected from ethylene oxide, propylene oxide, and butylene oxide is used together. Characterized in that.
본 발명에 따른 바나디아-티타니아 지로젤 촉매의 제조 방법에 있어서, 상기 제1단계의 산촉매는 염산, 질산, 초산, 및 옥살산으로 이루어진 군으로부터 1이상 선택되는 것을 특징으로 한다.In the method for preparing a vanadia-titania girogel catalyst according to the present invention, the acid catalyst of the first step is selected from the group consisting of hydrochloric acid, nitric acid, acetic acid, and oxalic acid.
본 발명에 따른 바나디아-티타니아 지로젤 촉매의 제조 방법에 있어서, 상기 제1단계는 무기젤 원료에 크롬, 안티몬, 주석, 철, 비스무스, 및 몰리브덴으로 구성되는 군으로부터 1이상 선택된 금속염, 인 또는 칼륨을 더 첨가하는 것을 특징으로 한다.In the method for preparing a vanadia-titania girogel catalyst according to the present invention, the first step is a metal salt, phosphorus or at least one selected from the group consisting of chromium, antimony, tin, iron, bismuth, and molybdenum in the inorganic gel raw material. It is characterized by further adding potassium.
본 발명에 따른 바나디아-티타니아 지로젤 촉매의 제조 방법에 있어서, 상기 제4단계의 열처리 온도는 500~600℃인 것을 특징으로 한다.In the method for producing a vanadia-titania girogel catalyst according to the present invention, the heat treatment temperature of the fourth step is characterized in that 500 ~ 600 ℃.
본 발명에 의한 니트릴화합물의 제조 방법은 상기의 바나디아-티타니아 지로젤 촉매를 이용하여 탄화수소화합물을 암옥시화 반응시키는 것을 특징으로 한다.The method for producing a nitrile compound according to the present invention is characterized by a dark oxidization reaction of a hydrocarbon compound using the vanadia-titania girogel catalyst.
본 발명에 의한 바나디아-티타니아 지로젤 촉매의 제조 방법은 다음과 같다.The method for producing the vanadia-titania girogel catalyst according to the present invention is as follows.
제 1단계에서는 솔-젤법을 이용하여 습윤젤을 형성한다. 바나듐 산화물과 티타늄 산화물의 전구체로 알콕사이드나 비알콕사이드가 사용되며 에탄올이나 메탄올 을 용매로 하여 일정온도를 유지한다. 젤의 구조적 특성을 위해 염산, 질산, 황산, 초산, 옥살산 등의 산촉매를 첨가하며, 양론비에 맞는 물을 넣어 젤화시킨다. 비알콕사이드의 경우 에틸렌옥사이드, 프로필렌옥사이드, 부틸렌옥사이드 등의 에폭사이드를 사용하여 젤화한다. 경우에 따라 크롬, 안티몬, 주석, 철, 비스무스, 몰리브덴 등을 포함한 염이나 인과 칼륨을 첨가할 수 있다.In the first step, the wet gel is formed using the sol-gel method. Alkoxides and non-alkoxides are used as precursors of vanadium oxide and titanium oxide, and the temperature is maintained using ethanol or methanol as a solvent. For the structural properties of the gel, acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and oxalic acid are added, and gelation is performed by adding water suitable for the stoichiometric ratio. In the case of non-alkoxides, gelation is performed using epoxides such as ethylene oxide, propylene oxide and butylene oxide. In some cases, salts or phosphorus and potassium may be added, including chromium, antimony, tin, iron, bismuth and molybdenum.
제 2단계에서는 젤을 숙성시킨다. 밀봉한 상태에서 상온에서 1~30일 가량의 숙성기간을 두어 젤을 안정화 시킨다. 경우에 따라 냉장숙성(4℃)이나 고온숙성(40-60℃)을 하기도 한다. In the second step, the gel is aged. Stabilize the gel with a maturation period of about 1 to 30 days at room temperature in a sealed state. In some cases, refrigeration aging (4 ° C) or high temperature aging (40-60 ° C) may be used.
제 3단계에서는 젤을 건조시킨다. 70~150℃의 온도범위에서 5~50시간 동안 건조시켜 젤 내의 용액을 제거한다. 바람직하게는 90~110℃에서 12~20시간 동안 건조시킨다.In the third step, the gel is dried. Remove the solution in the gel by drying for 5-50 hours in the temperature range of 70 ~ 150 ℃. Preferably it is dried for 12 to 20 hours at 90 ~ 110 ℃.
제 4단계에서는 건조된 지로젤을 열처리한다. 유기물 제거를 위해 헬륨이나 아르곤 분위기에서 300~400℃의 열처리를 하고, 공기나 산소 분위기에서 500~600℃의 온도로 열처리한다. In the fourth step, the dried gel is heat-treated. In order to remove organic matter, heat treatment is performed at 300 to 400 ° C. in helium or argon atmosphere, and at 500 to 600 ° C. in air or oxygen atmosphere.
상술한 바와 같이 제조된 본 발명의 바나디아-티타니아 지로젤 촉매를 이용하여 m-크실렌을 암옥시화 반응시킨다. 고정층 반응기에 촉매를 0.02~1.0g 채워 넣고 m-크실렌을 500~5000ppm 포함하는 산소를 2~20ml/min의 유속으로 흘린다. 암모니아는 산소 대비 0.1~5 몰 비율이 되도록 혼합되어 반응기에 유입되고, 전체 반응 기체의 체류시간은 0.1~2.0초, 반응온도는 280~450℃로 반응을 진행시킨다. 이때 바람직하게는 촉매 0.1g 기준으로 m-크실렌 농도 2000~3000ppm, 산소 유량 5~10ml/min, 산소 대 암모니아 비 2∼3 : 1, 반응온도 350~375℃를 유지한다. 본 발명의 바나디아-티타니아 지로젤 촉매는, 암모니아와 산소가 있는 조건에서 m-크실렌의 탄화수소기를 시안기로 대치시켜 이소프탈로니트릴의 선택성을 높게 한다. The m -xylene is subjected to the dark oxidization reaction using the vanadia-titania girogel catalyst of the present invention prepared as described above. The catalyst is packed in a fixed bed reactor with 0.02 to 1.0 g of oxygen and flows oxygen containing 500 to 5000 ppm of m -xylene at a flow rate of 2 to 20 ml / min. Ammonia is mixed so as to be 0.1 to 5 molar ratios of oxygen and introduced into the reactor, the residence time of the entire reaction gas is 0.1 to 2.0 seconds, and the reaction temperature proceeds at 280 to 450 ° C. At this time, preferably, m -xylene concentration 2000-3000ppm, oxygen flow rate 5-10ml / min, oxygen-ammonia ratio 2-3: 1, and reaction temperature 350-375 degreeC are maintained at 0.1 g of catalysts. In the present invention, the vanadia-titania girogel catalyst replaces a hydrocarbon group of m -xylene with a cyan group under conditions of ammonia and oxygen to increase the selectivity of isophthalonitrile.
하기에서 실시예를 통하여 본 발명을 더 구체적으로 설명한다. 그러나, 아래의 실시예는 본 발명에 대한 이해를 돕기 위해 예시의 목적으로만 제공된 것일 뿐 본 발명의 범주 및 범위가 여기에 한정되지 않음을 밝혀둔다.The present invention will be described in more detail with reference to the following Examples. However, the following examples are provided only for the purpose of illustration in order to facilitate the understanding of the present invention, and the scope and scope of the present invention is not limited thereto.
<실시예 1><Example 1>
티타늄 (IV) 부톡사이드 (Ti[O(CH2)3CH3]4), 물, 질산, 에탄올이 각각 몰비로 1 : 4 : 0.09 : 29.5의 비율이 되도록 용액을 만든다. 여기에 바나듐 트리이소프로폭사이드([(CH3)2CHO]3VO)를 각각 3중량%, 5중량%가 되도록 첨가한다. 일정시간 교반하여 젤이 형성되면 교반을 멈추고 2일간 상온 숙성시킨다. 숙성된 젤을 90℃ 오븐에서 12 시간 이상 건조하여 지로젤을 만들고 금속 산화물 형태가 되도록 하기 위하여 산소 분위기에서 500℃, 4시간 동안 열처리를 한다. The solution is prepared such that titanium (IV) butoxide (Ti [O (CH 2 ) 3 CH 3 ] 4 ), water, nitric acid and ethanol are each in a molar ratio of 1: 4: 0.09: 29.5. Vanadium triisopropoxide ([(CH 3 ) 2 CHO] 3 VO) is added to 3% by weight and 5% by weight, respectively. When the gel is formed by stirring for a certain time, the stirring is stopped and aged at room temperature for 2 days. The aged gel is dried in a 90 ° C. oven for at least 12 hours to form a geogel and heat treated at 500 ° C. in an oxygen atmosphere for 4 hours to form a metal oxide.
도 1은 상기에서 제조된 5중량%바나디아-티타니아 지로젤 촉매의 전자현미경(TEM) 사진이다. 1 is an electron microscope (TEM) photograph of the 5 wt% vaniadia-titania girogel catalyst prepared above.
상기에서 제조된 바나디아-티타니아 지로젤 촉매의 암옥시화 반응 전환율 및 수율을 측정하였다. The conversion and yield of the dark oxidization reaction of the vanadia-titania girogel catalyst prepared above were measured.
구체적으로, 먼저 지로젤 촉매 0.1g을 고정층 반응기에 채운 뒤 300℃부터 425℃까지 25℃ 간격으로 각각 1시간의 반응시간을 두어 반응성을 확인하였다. 반응기로 들어가는 m-크실렌의 양을 일정하게 하기 위하여 순환용 냉각수를 이용하여 10℃로 일정하게 온도를 유지하고, 이 온도에서 m-크실렌이 포화되어 2600~2700 ppm의 농도로 산소가스를 통해 반응기로 주입된다. m-크실렌 포화 산소 혼합 가스는 이후 암모니아와 혼합하여 전체유량이 12.46 ml/min로 반응기에 유입된다. 반응물과 생성물의 탄소의 양론수지를 세우기 위해 가스크로마토그래피를 사용하였다. 반응기로 유입되기 전의 m-크실렌의 농도와 촉매 층을 통과한 m-크실렌의 농도는 모두 가스크로마토그래피로 분석하여 전환율을 얻었고, 반응물의 부반응물인 이산화탄소와 일산화탄소는 메탄화 장치가 부착된 가스크로마토그래피로 분석을 하였다. 촉매 층을 통과하여 암옥시화 반응에 의해 생성된 이소프탈로니트릴은 고상으로 얻어져, 이 생성물은 메탄올 10g에 용해하여 액체크로마토그래피로 분석하였다.Specifically, 0.1 g of the gel gel was fixed in a fixed bed reactor, and the reaction time was confirmed by placing a reaction time of 1 hour at 25 ° C intervals from 300 ° C to 425 ° C. In order to keep the amount of m -xylene into the reactor constant, the temperature is kept constant at 10 ° C. using circulating cooling water, and at this temperature, m -xylene is saturated, and the reactor passes through oxygen gas at a concentration of 2600-2700 ppm. Is injected into. The m -xylene saturated oxygen mixed gas is then mixed with ammonia and introduced into the reactor at a total flow rate of 12.46 ml / min. Gas chromatography was used to establish the stoichiometric balance of the reactants and products. Xylene m that has passed through the concentration and the catalyst layer of the - - m before entering the reactor the concentration of xylene are all got a conversion rate and thereafter analyzed with a gas chromatography, the sub reaction of carbon dioxide and carbon monoxide in the reaction is methanation unit is attached to the gas chromatograph The analysis was done by chromatography. The isophthalonitrile produced by the dark oxidization reaction through the catalyst layer was obtained in the solid phase, and the product was dissolved in 10 g of methanol and analyzed by liquid chromatography.
하기 표 1 및 2는 각각 3중량% 및 5중량%바나디아-티타니아 지로젤 촉매의 암옥시화 반응 실험에서 얻은 전환율과 수율을 정리한 것이다. 여기서, m-크실렌의 전환율은 촉매 반응으로 소모된 m-크실렌의 양에 반응전 m-크실렌의 양을 나누어 준 후 100으로 곱하여 퍼센트 단위로 환산한 값이다. 또한, 수율은 반응물의 전체 탄소에서 생성물로 전환한 탄소의 비율을 백분율로 나타낸 값이다. Tables 1 and 2 below summarize the conversion and yields obtained in the dark oxidization reaction experiments of 3 wt% and 5 wt% Banadia-titania girogel catalysts, respectively. Wherein, m - is the m-xylene conversion of consumption by catalyst reaction is a value converted to a percentage by multiplying by 100 and then divided into a given amount of xylene-I response to the amount of xylene m. In addition, the yield is a value indicating the percentage of carbon converted from the total carbon of the reactants to the product.
상기 표 1 및 2에서 보는 바와 같이, 반응온도가 높아짐에 따라 m-크실렌의 암옥시화 반응성은 증가하여 350℃에서 3중량%바나디아-티타니아 지로젤 촉매의 경우 80%의 전환율을 나타냈으며, 5중량%바나디아-티타니아 지로젤 촉매의 경우 84%의 전환율을 나타냈다. 이소프탈로니트릴은 375℃에서 3중량%바나디아-티타니아 지로젤 촉매의 경우 63%의 수율을, 5중량%바나디아-티타니아 지로젤 촉매의 경우 59%의 수율을 보이며, 최대의 선택도를 나타내었다.As shown in Tables 1 and 2, as the reaction temperature increases, the m -xylene's amoxylation reactivity was increased, indicating a conversion rate of 80% for the 3 wt% vanadia-titania girogel catalyst at 350 ° C. A 5% by weight Banadia-Titania girogel catalyst showed a conversion of 84%. Isophthalonitrile has a yield of 63% for 3 wt% vanadia-titania girogel catalyst and 59% for 5 wt% vanadia-titania girogel catalyst at 375 ° C, showing maximum selectivity. It was.
<실시예 2><Example 2>
실시예 1에서 수행한 내용과 동일한 방법으로 바나디아-티타니아 지로젤 촉매를 제조하였다. 다만, 본 실시예에서는 10중량%의 바나디아를 함유하는 지로젤 촉매를 제조하여 바나디아의 함량에 따른 반응결과를 확인하였다. A Vanadia-titania girogel catalyst was prepared in the same manner as described in Example 1. In this example, however, a Girogel catalyst containing 10% by weight of vanadium was prepared, and the reaction result according to the content of vanadium was confirmed.
상기에서 제조된 10중량%바나디아-티타니아 지로젤 촉매를 사용하여 m-크실렌의 암옥시화 반응을 수행하여 얻어진 전환율과 이소프탈로니트릴 수율은 하기 표 3에 정리하였다. The conversion and isophthalonitrile yields obtained by the dark oxidization reaction of m -xylene using the prepared 10 wt% vanadia-titania girogel catalyst are summarized in Table 3 below.
상기 표 3에서 보는 바와 같이, 반응온도 350℃에서 m-크실렌의 전환율은 97%로 촉매의 반응성은 매우 좋으나, 이소프탈로니트릴 수율은 22%로 낮음을 확인할 수 있다. 그 이유는 m-크실렌이 암모니아보다는 산소와 직접 반응하여 산화에 의해 일산화탄소나 이산화탄소로 전환되었기 때문이다. As shown in Table 3, the conversion of m -xylene is 97% at a reaction temperature of 350 ° C., but the reactivity of the catalyst is very good, but the isophthalonitrile yield is as low as 22%. This is because m -xylene reacted directly with oxygen rather than ammonia and was converted to carbon monoxide or carbon dioxide by oxidation.
상기 결과로부터, 솔-젤 법으로 제조한 촉매가 암옥시화 반응에서 선택성을 갖기 위해서는 바람직한 바나디아의 함량 즉, 3~5중량%의 바나디아 함량이 필요함을 알 수 있다.From the above results, it can be seen that in order for the catalyst prepared by the sol-gel method to have selectivity in the dark oxidization reaction, a preferable vanadium content, that is, a vanadium content of 3 to 5% by weight is required.
<실시예 3><Example 3>
본 실시예에서는 원료물질의 전구체로 비알콕사이드를 사용하여 지로젤 촉매를 제조하였다. In this example, a zeogel catalyst was prepared using non-alkoxide as a precursor of a raw material.
먼저, 티타늄(IV) 트리클로라이드(TiCl4), 물, 프로필렌옥사이드, 질산, 에탄올이 각각 몰비로 1 : 4 : 5 : 0.1 : 30의 비율이 되도록 용액을 만든다. 여기에 바나듐 옥시트리클로라이드 (VOCl3)를 각각 3, 5, 7, 10중량%가 되도록 첨가한다. 일정시간 교반하여 젤이 형성되면 교반을 멈추고 상온 숙성시킨다. 건조 과정과 열처리 과정은 실시예 1에서 수행한 내용과 동일하다. First, a solution is prepared such that titanium (IV) trichloride (TiCl 4 ), water, propylene oxide, nitric acid, and ethanol are in a ratio of 1: 4: 5: 0.1: 30 in molar ratio, respectively. To this is added vanadium oxytrichloride (VOCl 3 ) to 3, 5, 7, 10% by weight, respectively. When the gel is formed by stirring for a certain time, the stirring is stopped and aged at room temperature. The drying process and the heat treatment process are the same as those performed in Example 1.
상기에서 제조된 바나디아-티타니아 지로젤 촉매를 사용하여 실시예 1에서 사용한 것과 동일한 방법으로 암옥시화 반응을 수행하고, 전환율 및 선택도를 측정하였다. 상기에서 제조된 지로젤 촉매의 바나디아 함량에 따른 이소프탈로니트릴 수율은 하기 표 4에 정리하였다. The dark oxidization reaction was carried out in the same manner as in Example 1 using the vanadia-titania girogel catalyst prepared above, and the conversion and selectivity were measured. The yield of isophthalonitrile according to the vanadia content of the prepared girogel catalyst is summarized in Table 4 below.
본 실시예에 의한 지로젤 촉매와 실시예1에서 제조한 촉매의 반응결과는 유사하였다. 상기 표 4에서 보는 바와 같이, 본 실시예에서도 바나디아의 함량이 3~5 중량%일 때, 효능이 높음을 확인할 수 있었다. The reaction results of the Girogel catalyst according to the present example and the catalyst prepared in Example 1 were similar. As shown in Table 4, even in this embodiment, when the content of the vanadium 3 to 5% by weight, it was confirmed that the efficacy is high.
<비교예 1>Comparative Example 1
실시예 1에서 수행한 내용과 동일한 방법으로 3중량%바나디아-티타니아 지로젤 촉매를 제조하였고, 다만 열처리를 함에 있어서, 산소 분위기, 700℃에서 4시간동안 열처리하였다. A 3 wt% vanadia-titania girogel catalyst was prepared in the same manner as described in Example 1, except that the heat treatment was performed for 4 hours at 700 ° C. in an oxygen atmosphere.
상기에서 제조된 지로젤 촉매를 사용하여 암옥시화 반응을 수행하였고, 그 결과 얻어진 m-크실렌의 암옥시화 반응에 따른 전환율과 수율은 하기 표 5에 나타내었다. Amoxy oxidation was carried out using the gel prepared as a gel, and the conversion and yields according to the dark oxidation of m -xylene obtained as shown in Table 5 below.
상기 표 5에서 보는 바와 같이, 반응온도 350℃에서 m-크실렌의 전환율은 15%이고, 이 온도 이하에서는 촉매의 활성이 매우 낮음을 확인할 수 있었다. 이것은 지로젤 촉매의 제조시 열처리 온도가 높아짐에 따라 티타니아의 결정구조가 바뀌는 것에 영향을 받기 때문이다. 따라서, 제조된 지로젤 촉매가 암옥시화 반응에 서 유용하게 사용되기 위해서는, 지로젤 촉매의 제조시 적절한 열처리 온도(500~600℃)가 필요하다는 것을 알 수 있다.As shown in Table 5, the conversion of m -xylene is 15% at the reaction temperature of 350 ℃, it was confirmed that the activity of the catalyst is very low below this temperature. This is because the crystal structure of titania is affected by an increase in the heat treatment temperature during the preparation of the gel polymer. Therefore, it can be seen that the appropriate heat treatment temperature (500-600 ° C.) is required for the preparation of the gel-gel in order for the prepared gel-gel catalyst to be usefully used in the dark oxidization reaction.
<비교예 2>Comparative Example 2
본 비교예에서는 종래의 촉매 제조법으로 많이 사용하고 있는 함침법으로 바나디아-티타니아 촉매를 제조하였다. In this comparative example, the vanadia-titania catalyst was manufactured by the impregnation method which is used a lot in the conventional catalyst preparation method.
바나디아의 전구체로 사용된 암모늄 메타바나데이트를 산과 함께 물에 균일하게 용해하여 상업용 티타니아 (데구사, P-25) 분말에 함침 하였고 증발하여 건조시켰다. 실시예 1에서 수행한 조건과 동일하게 건조, 열처리 하여 촉매를 제조하였으며, 제조된 촉매를 이용하여 암옥시화 반응실험을 진행하였다. Ammonium metavanadate used as a precursor of vanadia was uniformly dissolved in water with acid, impregnated into commercial titania (degussa, P-25) powder, and evaporated to dryness. The catalyst was prepared by drying and heat treatment in the same manner as in Example 1, and the dark oxidization reaction experiment was conducted using the prepared catalyst.
상기에서 제조된 촉매의 바나디아 함량에 따른 이소프탈로니트릴 수율은 하기 표 6에 정리하였다. The isophthalonitrile yield according to the vanadia content of the catalyst prepared above is summarized in Table 6 below.
상기 표 6에서 보는 바와 같이, 325℃에서 m-크실렌의 전환율이 80% , 이소프탈로니트릴 수율이 38%이고, 그 이상의 온도에서는 이소프탈로니트릴의 수율이 급격하게 감소하여 400℃ 에서는 5%이하의 수율을 보였다. 즉, 종래의 방법에 의하여 제조된 촉매의 경우, 반응 온도가 올라갈수록 반응 효율이 급격하게 떨어짐을 확인할 수 있다. As shown in Table 6 above, the conversion of m -xylene is 80% and isophthalonitrile is 38% at 325 ° C, and the yield of isophthalonitrile is drastically decreased at temperatures higher than 5% at 400 ° C. Yield was shown. That is, in the case of the catalyst prepared by the conventional method, it can be seen that the reaction efficiency drops rapidly as the reaction temperature increases.
또한, 실시예 1에서 제조한 지로젤 촉매의 반응결과와는 상이하게, 종래 방법에 의하여 제조된 촉매의 경우, 바나디아 함량이 이소프탈로니트릴 수율에 큰 영향을 미치지 않았다.In addition, unlike the reaction result of the Girogel catalyst prepared in Example 1, in the case of the catalyst prepared by the conventional method, the vanadia content did not significantly affect the isophthalonitrile yield.
본 발명에 의한 바나디아-티타니아 지로젤 촉매는, 탄화수소화합물의 암옥시화 반응에 사용하였을 때, 낮은 바나디아 함량에서도 넓은 반응온도 범위에서 탄화수소화합물의 전환율과 니트릴화합물의 수율 및 선택성을 크게 향상시킬 수 있는 저비용 고효율의 촉매이다. The vanadia-titania girogel catalyst according to the present invention can greatly improve the conversion of hydrocarbon compounds and the yield and selectivity of nitrile compounds at a wide reaction temperature range even at low vanadia content when used in the dark oxidation of hydrocarbon compounds. It is a low cost and high efficiency catalyst.
본 발명에 의한 바나디아-티타니아 지로젤 촉매의 제조시 사용된 솔-젤 법은, 촉매의 활성을 높이기 위하여 소량의 조촉매를 첨가할 경우에도 고분산도로 담지 할 수 있어 물성을 제어하기 쉽고 용이한 장점을 가지고 있다.The sol-gel method used in the preparation of the vaniadia-titania girogel catalyst according to the present invention can be supported with high dispersion even when a small amount of promoter is added to increase the activity of the catalyst, so that it is easy to control physical properties. It has one advantage.
본 발명에 의한 바나디아-티타니아 지로젤 촉매는 m-크실렌의 암옥시화 반응에 국한되지 않고, 파라핀과 올레핀 및 방향족 화합물의 부분산화반응과 암옥시화 반응, NOX의 부분환원 반응과 이산화황의 산화반응에도 유용하게 쓰일 수 있다.The vanadia-titania girogel catalyst according to the present invention is not limited to the amoxylation of m -xylene, but is partially or partially reacted with paraffins, olefins and aromatics, and with the reduction of NO x and sulfur dioxide. It can also be useful for oxidation reactions.
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