KR100983740B1 - Oxidative dehydrogenation catalyst, and process for preparing propylene from propane using the same - Google Patents
Oxidative dehydrogenation catalyst, and process for preparing propylene from propane using the same Download PDFInfo
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- KR100983740B1 KR100983740B1 KR1020080136730A KR20080136730A KR100983740B1 KR 100983740 B1 KR100983740 B1 KR 100983740B1 KR 1020080136730 A KR1020080136730 A KR 1020080136730A KR 20080136730 A KR20080136730 A KR 20080136730A KR 100983740 B1 KR100983740 B1 KR 100983740B1
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- South Korea
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- oxidative dehydrogenation
- propane
- dehydrogenation catalyst
- catalyst
- metal
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 51
- 239000001294 propane Substances 0.000 title claims abstract description 50
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000010574 gas phase reaction Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000006356 dehydrogenation reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- -1 CO 2 Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/651—
-
- B01J35/653—
-
- B01J35/657—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
본 발명은 산화 탈수소 촉매, 및 이를 이용한 프로판으로부터 프로필렌의 제조방법에 관한 것이다. 본 발명에 따른 산화 탈수소 촉매는 활성성분의 담지시 높은 분산도를 가지며, 메조 및 매크로 기공의 발달은 물질전달 속도를 높이는 효과를 갖는다. 따라서, 본 발명의 산화 탈수소 촉매를 이용하여 고온에서 수소 존재 하에 프로판을 산화 탈수소 반응시킬 경우 프로판 전환율, 생성물 중의 프로필렌 선택도, 및 프로필렌 수율을 높여 촉매 활성이 매우 높게 나타난다.The present invention relates to an oxidative dehydrogenation catalyst and a process for producing propylene from propane using the same. The oxidative dehydrogenation catalyst according to the present invention has a high dispersion degree when the active ingredient is supported, and the development of meso and macro pores has an effect of increasing the material transfer rate. Therefore, when the oxidative dehydrogenation reaction of propane in the presence of hydrogen at high temperature using the oxidative dehydrogenation catalyst of the present invention, the catalytic activity is very high by increasing the propane conversion rate, propylene selectivity in the product, and propylene yield.
Description
본 발명은 산화 탈수소 촉매, 및 이를 이용한 프로판으로부터 프로필렌의 제조방법에 관한 것이다.The present invention relates to an oxidative dehydrogenation catalyst and a process for producing propylene from propane using the same.
일반적으로, 탄화수소 기체, 특히 프로판의 경우, 백금과 같은 귀금속계 또는 크롬과 같은 산화물계 탈수소 촉매를 사용하여 프로판으로부터 프로필렌을 제조하는 공정이 종래부터 공업적으로 널리 실시되고 있다. 그러나 프로판 탈수소 반응은 흡열 반응이기 때문에, 단열 반응 장치의 반응에서는 반응의 진행과 함께 반응 온도가 저하되므로 프로필렌의 생산량의 증가를 위해서는 추가적인 반응열을 일정하게 공급해 주어야 한다. 또한, 프로판 탈수소 반응은 열역학적으로 최대 프로필렌의 수율이 제한받는 가역반응에 의한 평형 반응이기 때문에 높은 전환율을 얻기 어렵다. 따라서, 프로판과 산화제를 동시에 첨가하여 산화반응에 의해 발생되는 열을 이용하면 탈수소 반응에 비해 공급되는 열량이 줄어들 수 있을 것으로 생각된다. 따라서, 탈수소 반응에서 생성된 수소를 산화 촉매를 사용하여 선택적으로 산 화시키는 산화 공정을, 탈수소 공정에 조합하는 것이 종전부터 제안되어 왔다.In general, in the case of hydrocarbon gases, in particular propane, a process for producing propylene from propane using a noble metal type such as platinum or an oxide type dehydrogenation catalyst such as chromium has been conventionally widely practiced industrially. However, since propane dehydrogenation is an endothermic reaction, the reaction temperature decreases with the progress of the reaction in the adiabatic reaction apparatus, and thus additional heat of reaction must be constantly supplied to increase the yield of propylene. In addition, propane dehydrogenation is difficult to obtain high conversion because it is an equilibrium reaction by reversible reaction in which the yield of maximum propylene is limited thermodynamically. Therefore, it is thought that the amount of heat supplied can be reduced compared to the dehydrogenation reaction by using heat generated by the oxidation reaction by simultaneously adding propane and oxidant. Therefore, it has been proposed in the past to combine an oxidation process for selectively oxidizing hydrogen generated in a dehydrogenation reaction using an oxidation catalyst in a dehydrogenation process.
현재까지 진행된 연구 결과에 의하면, 프로판 산화 탈수소 반응에서는 바나디아(V2O5)계 촉매를 사용한 연구가 많이 진행되었으나, 알루미나 담체를 사용한 경우 40% 이하의 낮은 선택도와 8~9% 정도의 프로필렌 수율을 나타내고 있으며, 비교적 낮은 온도인 350~400℃에서 작용된다(R. Grabowski, Catal. Rev., 48 (2006) 199). 또한 VMgO계 촉매의 경우에도, 60% 이하의 선택도와 20% 이하의 낮은 프로필렌 수율을 나타내고 있다(Owen, O.S. and Kung, H.H. J. Mol. Catal., 79 (1993) 265). 한편, VNbO계 촉매의 경우에는 380~450℃의 반응 조건에서 90%의 높은 선택도를 나타내고 있지만 상대적으로 매우 낮은 전환율을 보인다[Smits, R.H.H., Seshan, K., Leemreize, H., and Ross, J.R.H. Catal. Today, 16 (1993) 513). 최근 들어, 바나디아 및 몰리브데나계 촉매에 알칼리 금속(K, Li, Rb 등)과 전이금속(Ni, Cr, V, Mo, P 등)을 보조 성분으로 사용한 연구가 계속 진행되어 선택도를 향상시키고 있지만, 낮은 반응온도에 의한 상대적인 전환율 감소로 인하여 전체적인 수율 증가는 미미한 실정이다.According to the research results so far, propane oxidative dehydrogenation has been conducted using a vanadia (V 2 O 5 ) -based catalyst, but when using an alumina carrier, low selectivity of less than 40% and propylene of 8-9% Yield is shown and is operated at a relatively low temperature of 350-400 ° C. (R. Grabowski, Catal. Rev., 48 (2006) 199). In the case of the VMgO-based catalyst, the propylene yield shows a selectivity of 60% or less and a low propylene yield of 20% or less (Owen, OS and Kung, HHJ Mol. Catal., 79 (1993) 265). On the other hand, the VNbO-based catalyst shows a high selectivity of 90% under the reaction conditions of 380-450 ° C., but shows a relatively low conversion rate [Smits, RHH, Seshan, K., Leemreize, H., and Ross, JRH Catal. Today, 16 (1993) 513). Recently, studies on using alkali metals (K, Li, Rb, etc.) and transition metals (Ni, Cr, V, Mo, P, etc.) as auxiliary components for vanadia and molybdenum catalysts have been conducted. Although it is improving, the overall increase in yield is insignificant due to the decrease in the relative conversion rate due to the low reaction temperature.
바나디아계 촉매 이외에도 Fe-ZSM-5, Fe-Al-MFI, Fe-Ga-MFI 등의 제올라이트 촉매를 사용하고, 산화제로 N2O를 사용한 경우 500~550℃의 온도에서 프로필렌의 수율이 22-25% 라는 보고가 있다. 또한 600℃에서 CO2 존재 하에 Ga2O3 계열의 촉매를 사용하였을 때, 프로판 전환율 및 프로필렌 선택도가 각각 20~30% 및 90% 이상이라는 보고도 있다. CoMoOx, MgMoOx 등의 촉매는 450~480℃에서 산소를 산화제로 사용 하여 약 20%의 프로판 전환율과 60%의 프로필렌 선택도를 가진다는 결과 또한 발표되었다.In addition to the vanadium-based catalyst, when a zeolite catalyst such as Fe-ZSM-5, Fe-Al-MFI, Fe-Ga-MFI is used and N 2 O is used as the oxidizing agent, the yield of propylene is 22 at a temperature of 500 to 550 ° C. There is a report of -25%. In addition, when using a catalyst of the Ga 2 O 3 series in the presence of CO 2 at 600 ℃, it is also reported that the propane conversion and propylene selectivity is 20-30% and 90% or more, respectively. Catalysts such as CoMoOx and MgMoOx have also been reported to have about 20% propane conversion and 60% propylene selectivity using oxygen as the oxidant at 450-480 ° C.
또한 촉매의 비활성화가 비교적 낮은 백금계 촉매를 산화 탈수소 반응에 적용하는 연구도 지속되고 있다. 이에 관한 기술로, WO 2006/094938호에는 산소를 사용하여 프로판으로부터 프로필렌을 제조하는 공정이 기재되어 있으며, 미국특허 제 5,105,052호에는 Pt/Pd/Al2O3 촉매를 이용하여 프로판/수소/산소의 조건에서 산화 탈수소 반응을 수행하는 공정이 기재되어 있다. 상기 미국특허 문헌에 기재된 산화 탈수소 반응의 경우, 수소가 없을 시 20%의 선택도와 14.6%의 수율을 나타내었으며, 수소 존재 시에는 13.3%의 선택도와 11.8%의 수율을 나타내었다.In addition, studies have continued to apply platinum-based catalysts having relatively low catalyst deactivation to oxidative dehydrogenation. In this regard, WO 2006/094938 describes a process for producing propylene from propane using oxygen and US Pat. No. 5,105,052 using propane / hydrogen / oxygen using a Pt / Pd / Al 2 O 3 catalyst. A process for carrying out an oxidative dehydrogenation reaction under the conditions of is described. In the case of the oxidative dehydrogenation reaction described in the U.S. Patent Literature, it showed 20% selectivity and 14.6% yield in the absence of hydrogen, and 13.3% selectivity and 11.8% yield in the presence of hydrogen.
일반적으로, 산화 탈수소 공정에 사용되는 산화제로는 O2, CO, CO2, N2O, 스팀, 황 화합물 등이 있으며, 특히 O2, CO2, 스팀에 대한 연구가 많이 진행되었다. 이 중 높은 산화력을 지닌 산소는 산소 자체의 환경적 유해성이 없고, 높은 활성을 나타내기 때문에 산소를 이용하는 산화 탈수소 기술에 대해 많은 연구가 이루어져 왔다. 그러나 산화제로 산소를 사용할 경우, 고온에서 탄화수소를 연소시켜 선택도를 저하시키는 단점을 가지고 있다. 또한 탈수소 반응에서의 스팀은 열 운반체로 작용하여 촉매상의 유기 침착물의 가스화를 보조하는데, 이는 촉매의 탄화를 방해하고, 침착된 탄화물을 일산화탄소와 이산화탄소로 전환시킨다. 또한 촉매의 활성 시간을 증가시키며, 스팀에 의해 탈수소화의 반응 평형을 생성물쪽으로 이동시키는 장점이 있다[WO 2006/094938]. 대한민국 등록특허공보 제 10-501842호에는 이산화 탄소 산화제를 사용한 알킬방향족 탄화수소의 촉매 탈수소화 방법에 관하여 기재되어 있으며, 상기 특허에 의하면 이산화탄소는 평형에 의한 제약이 스팀의 경우와 비교하여 거의 없으며, 잠열에 의한 에너지 손실이 없어서 에너지 사용 측면에서 유리한 것으로 평가되고 있다.In general, oxidants used in the oxidative dehydrogenation process include O 2 , CO, CO 2 , N 2 O, steam, sulfur compounds and the like, in particular O 2 , CO 2 , steam has been studied a lot. Among them, oxygen having high oxidizing power has no environmental hazards of oxygen itself and shows high activity, so much research has been made on oxidative dehydrogenation technology using oxygen. However, when oxygen is used as an oxidizing agent, it has a disadvantage of lowering selectivity by burning hydrocarbon at high temperature. In addition, steam in the dehydrogenation reaction acts as a heat carrier to assist in the gasification of organic deposits on the catalyst, which interferes with the carbonization of the catalyst and converts the deposited carbide into carbon monoxide and carbon dioxide. It also increases the activation time of the catalyst and has the advantage of shifting the reaction equilibrium of the dehydrogenation to the product by steam [WO 2006/094938]. Korean Patent Publication No. 10-501842 discloses a method for catalytic dehydrogenation of alkylaromatic hydrocarbons using a carbon dioxide oxidant. According to the patent, carbon dioxide is almost free from restrictions due to equilibrium, and latent heat. It is evaluated to be advantageous in terms of energy use because there is no energy loss.
그러나 대부분의 산화 탈수소 반응의 경우 500℃ 이하의 비교적 낮은 반응온도에서 이루어지기 때문에 반응열을 외부에서 공급해주어야 하는 단점이 있으며, 생성되는 프로필렌의 선택도는 높지만 프로판 전환율이 낮아 단위 시간당의 프로필렌의 수율이 낮은 단점이 있다.However, most of the oxidative dehydrogenation reactions are performed at a relatively low reaction temperature of 500 ° C. or less, and thus, the heat of the reaction must be supplied externally. There is a low disadvantage.
따라서, 고온에서 산화 탈수소화 반응을 수행하면 촉매반응과 동시에 열분해 반응이 발생하여 상기 문제점을 극복할 수 있을 것으로 생각된다. 즉, 프로판과 산화제를 동시에 혼합하여 공급함으로써 산소와 수소의 산화반응에 의해 발생되는 열을 이용할 수 있어 저온 산화 탈수소 반응에 비해 공급되는 반응열이 줄어들게 되고, 반응 평형의 이동에 의해 높은 전환율을 나타낼 수 있을 것으로 생각된다.Therefore, when the oxidative dehydrogenation reaction is performed at a high temperature, it is thought that the pyrolysis reaction occurs at the same time as the catalytic reaction, thereby overcoming the above problems. That is, by simultaneously mixing and supplying propane and oxidant, the heat generated by the oxidation reaction of oxygen and hydrogen can be used, and thus the heat of reaction supplied is reduced compared to the low temperature oxidative dehydrogenation reaction, and high conversion can be exhibited by the shift of the reaction equilibrium. I think there will be.
본 발명자들은 고온에서 수소 존재 하에 탄화수소를 산화 탈수소 반응시켜 전환율, 선택도 및 수율을 높게 나타낼 수 있는 산화 탈수소 촉매에 대해 연구하던 중, 열변형된 알루미나 담체를 사용하여 흡착 담지법으로 산화 탈수소 촉매를 제조하였으며, 상기 제조된 촉매를 이용하여 고온에서 프로판, 수소, 산소 혼합기체를 산화 탈수소 반응을 수행한 결과 전환율, 선택도 및 수율이 높게 나타남을 확인하고, 본 발명을 완성하였다.The present inventors have been studying an oxidative dehydrogenation catalyst which can oxidatively dehydrogenate a hydrocarbon in the presence of hydrogen at a high temperature to exhibit high conversion, selectivity, and yield. After the oxidative dehydrogenation reaction of propane, hydrogen, and oxygen mixture gas was carried out at high temperature using the prepared catalyst, it was confirmed that the conversion, selectivity, and yield were high, thus completing the present invention.
본 발명은 산화 탈수소 촉매, 및 이를 이용한 프로판으로부터 프로필렌의 제조방법을 제공하고자 한다.The present invention is to provide an oxidative dehydrogenation catalyst, and a method for producing propylene from propane using the same.
본 발명은 백금, 보조금속, 알칼리 금속 또는 알칼리토금속, 및 할로겐 성분이 담체에 담지된 형태를 가지며, 백금 성분에 대한 보조금속 성분의 중량비는 0.1~2.0이고, 담체 표면적에 대한 알칼리 금속 또는 알칼리 토금속 성분의 비율은 0.001~0.009 중량%/㎡이고, 백금, 보조금속, 및 알칼리 금속 또는 알칼리토금속에 대한 할로겐 성분의 중량비가 0.5~2.0인 산화 탈수소 촉매를 제공한다.The present invention has a form in which a platinum, an auxiliary metal, an alkali metal or an alkaline earth metal, and a halogen component are supported on a carrier, the weight ratio of the auxiliary metal component to the platinum component is 0.1 to 2.0, and an alkali metal or alkaline earth metal to a carrier surface area. The proportion of the component is 0.001 to 0.009% by weight / m 2, and an oxidative dehydrogenation catalyst is provided in which the weight ratio of the halogen component to platinum, auxiliary metal, and alkali metal or alkaline earth metal is 0.5 to 2.0.
또한, 본 발명은 상기 산화 탈수소 촉매를 이용하여 프로판, 수소, 산소를 함유하는 혼합기체를 600~1000℃의 반응 온도, 0.1~10의 절대기압, 혼합기체와 촉 매와의 액체공간속도(Liquid Hourly Space Velocity; LHSV)가 0.1~30 hr-1인 조건 하에 기상반응시켜 산화 탈수소 반응에 의한 프로판으로부터 프로필렌의 제조방법을 제공한다.The present invention also provides a mixed gas containing propane, hydrogen, and oxygen using a oxidative dehydrogenation catalyst at a reaction temperature of 600 to 1000 ° C., an absolute atmospheric pressure of 0.1 to 10, and a liquid space velocity of the mixed gas and the catalyst. The gas phase reaction is carried out under the condition of Hourly Space Velocity (LHSV) of 0.1 to 30 hr −1 to provide a process for producing propylene from propane by oxidative dehydrogenation.
이하, 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 산화 탈수소 촉매는 촉매 총 중량에 대해 백금 0.05~2.0 중량%, 보조금속 0.05~20.0 중량%, 알칼리 금속 또는 알칼리토금속 0.05~3.0 중량%, 및 할로겐 성분 0.1~5.0 중량%를 담체에 담지시켜 흡착 담지법으로 제조한다.The oxidative dehydrogenation catalyst according to the present invention comprises 0.05 to 2.0% by weight of platinum, 0.05 to 20.0% by weight of auxiliary metal, 0.05 to 3.0% by weight of alkali metal or alkaline earth metal, and 0.1 to 5.0% by weight of halogen component to the carrier. It is prepared by adsorption supporting method.
상기 백금은 주요금속으로 사용되며, 보조금속으로는 주석, 게르마늄, 갈륨, 인듐, 아연 및 망간으로 이루어진 군으로부터 선택된 것을 사용하며, 특히 주석이 바람직하다. 알칼리 금속 또는 알칼리토금속은 칼륨, 나트륨 및 리튬으로 이루어진 군으로부터 선택된 것을 사용한다. 할로겐 성분으로는 염소, 인 및 불소로 이루어진 군으로부터 선택된 것을 사용한다.The platinum is used as the main metal, and the auxiliary metal is selected from the group consisting of tin, germanium, gallium, indium, zinc and manganese, and tin is particularly preferable. Alkali metal or alkaline earth metal is used selected from the group consisting of potassium, sodium and lithium. As the halogen component, one selected from the group consisting of chlorine, phosphorus and fluorine is used.
상기 담체는 알루미나, 실리카 및 이의 혼합성분이 사용될 수 있으며, 바람직하게는 알루미나가 적당하다. 알루미나의 세타상 결정성은 90% 이상이 바람직하다. 감마-알루미나의 경우, 알루미나 자체의 산점으로 인한 부반응성이 크고, 반응 중 알루미나 결정성이 변화하며 비표면적이 감소하는 구조적 특성 변화를 가져오게 된다. 알파-알루미나의 경우, 낮은 비표면적으로 인해 귀금속의 분산도를 낮추고 전체적인 귀금속의 활성면적을 감소시켜 낮은 촉매활성을 나타낸다.The carrier may be used alumina, silica and mixed components thereof, preferably alumina. The theta phase crystallinity of the alumina is preferably 90% or more. In the case of gamma-alumina, the side reactivity due to the acid point of the alumina itself is large, the alumina crystallinity changes during the reaction, and the structural properties of the specific surface area is reduced. In the case of alpha-alumina, the low specific surface area lowers the dispersion of the precious metal and decreases the overall active area of the precious metal, resulting in low catalytic activity.
상기 담체는 비표면적이 70~170㎡/g이고, 5~100㎚의 메조 기공과 100~20,000 ㎚의 매크로 기공을 갖는다. 만일 담체의 비표면적이 70㎡/g 미만이면 금속 활성 성분의 분산도가 낮아지고, 170㎡/g을 초과하면 알루미나의 감마 결정성이 높게 유지되어 부반응성이 증대된다. 담체 기공의 부피와 기공의 크기는 반응물과 생성물의 물질 전달 계수를 결정짓는 주요 인자이며, 화학반응 속도가 빠른 상황에서 물질의 확산 저항은 전체적인 반응속도를 결정짓기 때문에 기공의 크기가 큰 구조체가 촉매의 활성을 높게 유지하는데 유리하다. 또한, 기공의 크기가 큰 담체를 사용하는 것이 코크의 축적에 둔감하게 작용하여 촉매활성 유지에 유리하다.The carrier has a specific surface area of 70 to 170 m 2 / g, and has meso pores of 5 to 100 nm and macro pores of 100 to 20,000 nm. If the specific surface area of the carrier is less than 70 m 2 / g, the dispersibility of the metal active component is lowered. If the specific surface area of the carrier is more than 170 m 2 / g, the gamma crystallinity of the alumina is maintained to increase the side reaction. The volume of the carrier pores and the size of the pores are the major factors that determine the mass transfer coefficients of the reactants and products.In the case of high chemical reaction rate, the diffusion resistance of the material determines the overall reaction rate. It is advantageous to keep the activity of the high. In addition, the use of a carrier having a large pore size acts insensitive to accumulation of coke and is advantageous for maintaining catalytic activity.
본 발명에 따른 촉매는 활성성분의 담지시 높은 분산도를 가지며, 메조 및 매크로 기공의 발달은 물질전달 속도를 높이는 효과를 갖는다. 촉매 내에 존재하는 기공의 크기가 큰 경우, 촉매 상에 발생되는 코크에 의한 활성 감소에 둔감하게 되고, 물질 전달 속도가 높아 액체 공간 속도가 증가할 경우에도 높은 반응 활성을 보이게 된다. 본 발명에 따른 촉매는 알칼리 금속 및 알칼리 토금속, 그리고 할로겐 성분의 양을 제어하여 제조한다. 이들 성분은 알루미나 담체의 알루미늄 원소와 결합되어 알루미나 자체가 갖고 있는 루이스 산의 특성을 감쇠시켜 생성물의 탈착을 용이하게 하며, 그로 인한 코크의 생성을 억제하는 효과를 갖는다. 또한, 알루미나의 결정성 자체에 내재된 산점을 감소시키는 방향으로, 감마의 성상에서 세타 또는 알파의 성상으로 변형 시킴으로써도 동일한 산점 감소의 효과를 보이게 된다.The catalyst according to the present invention has a high dispersion degree when supporting the active ingredient, and the development of meso and macro pores has an effect of increasing the mass transfer rate. When the size of the pores present in the catalyst is large, it is insensitive to the decrease in activity due to the coke generated on the catalyst, and even if the liquid space velocity is increased due to the high mass transfer rate, high reaction activity is exhibited. Catalysts according to the invention are prepared by controlling the amounts of alkali and alkaline earth metals and halogen components. These components are combined with the aluminum element of the alumina carrier to attenuate the characteristics of the Lewis acid possessed by the alumina itself, thereby facilitating the desorption of the product, thereby suppressing the formation of coke. In addition, in the direction of reducing the scattering point inherent in the crystallinity of the alumina, the same scattering effect is also reduced by changing from the properties of gamma to theta or alpha.
본 발명에 따른 프로판으로부터 프로필렌의 제조방법은, 상기 산화 탈수소 촉매를 이용하여 프로판, 수소, 산소를 함유하는 혼합기체를 600~1000℃, 바람직하 게는 600~800℃의 반응 온도, 0.1~10의 절대기압, 바람직하게는 1~5의 절대기압, 혼합기체와 촉매와의 액체공간속도가 0.1~30 hr-1, 바람직하게는 2~20 hr-1인 조건 하에 기상반응시켜 산화 탈수소 반응에 의해 프로판으로부터 프로필렌을 제조한다. 이때, 산화 탈수소 반응에 공급되는 혼합기체 중, 산소의 양은 프로판 총량을 기준으로 0.001~0.2몰, 바람직하게는 0.005~0.1몰, 더욱 바람직하게는 0.005~0.05몰이다. 또한, 공급되는 수소의 양은 프로판 총량을 기준으로 0.2~1.5몰, 바람직하게는 0.4~1.2몰, 더욱 바람직하게는 0.6~1.0몰이다. 이때 공급되는 산소는 순수한 분자상 산소, 공기, 분자상 산소와 공기의 혼합물, 분자상 산소와 질소, CO2 등과 같은 비활성 기체와의 혼합물, 또는 이들의 혼합물과 스팀과의 혼합물 형태로 사용될 수 있으나, 바람직하게는 분자상 산소가 적당하다.In the method for producing propylene from propane according to the present invention, a mixed gas containing propane, hydrogen, and oxygen is reacted at 600 to 1000 ° C, preferably 600 to 800 ° C using the oxidative dehydrogenation catalyst, and 0.1 to 10. Is subjected to gas phase reaction under the condition that the absolute atmospheric pressure of 1 to 5, preferably 1 to 5, and the liquid space velocity of the mixed gas and the catalyst is 0.1 to 30 hr −1 , preferably 2 to 20 hr −1 . Propylene is produced from propane. At this time, the amount of oxygen in the mixed gas supplied to the oxidative dehydrogenation reaction is 0.001 to 0.2 mol, preferably 0.005 to 0.1 mol, more preferably 0.005 to 0.05 mol based on the total amount of propane. The amount of hydrogen supplied is 0.2 to 1.5 mol, preferably 0.4 to 1.2 mol, more preferably 0.6 to 1.0 mol, based on the total amount of propane. In this case, the supplied oxygen may be used in the form of pure molecular oxygen, air, a mixture of molecular oxygen and air, a mixture of inert gas such as molecular oxygen and nitrogen, CO 2 , or a mixture of these with steam. Molecular oxygen is preferable.
본 발명에 따른 프로판으로부터 프로필렌의 제조방법은, 가혹한 고온의 조건에서도 효과적인 프로필렌을 제조하는 방법으로, 본 발명에 따른 산화 탈수소 촉매를 적용할 경우, 프로필렌 생산량의 증대 및 촉매의 활성 저하가 낮다. 즉, 본 발명의 프로필렌의 제조방법은 산소의 산화반응에 의해 발생되는 반응열을 활용할 수 있으며, 반응 평형을 극복하므로써 높은 프로판 전환율을 나타낸다. 또한 반응 조건을 가혹하게 할 경우에도 촉매의 성능 감소가 적으며, 비활성화가 심해진 경우에도 장기 사용 안정성의 측면에서 개선된 효과를 보인다. 또한 공급된 프로판과 함께 기상 반응에 산소를 투입하게 되면 촉매상의 주석 성분과 백금 성분과의 과도한 합금 형성을 줄여 촉매의 활성을 개선시킨다. 또한, 본 발명에 의한 부수적인 효과 로는 촉매상의 코크를 반응 중에 제거하는 기능도 있어 이에 의한 활성 개선 효과도 있다. 산소를 함유한 성분을 사용할 때, 부수적으로 탄화수소 혹은 촉매에 침적된 코크와의 반응에 의한 일산화 탄소의 발생, 물의 부생 등이 가능하며, 이는 효과적으로 코크 발생을 줄이는 기능 측면에서 유용하다.The method for producing propylene from propane according to the present invention is a method for producing propylene that is effective even under severe high temperature conditions. When the oxidative dehydrogenation catalyst according to the present invention is applied, the increase in propylene production and the decrease in activity of the catalyst are low. That is, the method for producing propylene of the present invention can utilize the heat of reaction generated by the oxidation reaction of oxygen, and exhibits high propane conversion rate by overcoming the reaction equilibrium. In addition, even if the reaction conditions are severe, the reduction in the performance of the catalyst is small, and even in the case of severe deactivation shows an improved effect in terms of long-term stability. In addition, when oxygen is introduced into the gas phase reaction with the propane supplied, excessive alloy formation between the tin component and the platinum component on the catalyst is reduced, thereby improving the activity of the catalyst. In addition, as a side effect of the present invention, there is a function of removing coke on the catalyst during the reaction, thereby improving activity. When oxygen-containing components are used, it is possible to generate carbon monoxide by reaction with coke deposited in hydrocarbon or catalyst, by-product of water, etc., which is useful in terms of effectively reducing coke generation.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 실시예에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.
실시예 1Example 1 : 산화 탈수소화 촉매의 제조 : Preparation of Oxidative Dehydrogenation Catalyst
촉매 합성에 사용된 담체로 감마 결정성을 갖고, 평균 지름이 1.65㎜이며, 충진 밀도가 0.56 g/㎖인 구형의 상용 알루미나를 구입하여, 공기 분위기에서 1050℃의 온도로 6시간 동안 열변형하여 세타상으로 변형시켰다. X-ray 분석법을 이용하여 알루미나의 결정성을 측정한 결과, 90% 이상의 세타 결정성을 가지고 있었다.As a carrier used in the synthesis of the catalyst, a spherical commercial alumina having a gamma crystallinity, an average diameter of 1.65 mm, and a packing density of 0.56 g / ml was purchased, and thermally deformed at an air temperature of 1050 ° C. for 6 hours. Transform into theta phase. As a result of measuring the crystallinity of alumina by X-ray analysis, theta crystallinity was more than 90%.
상기 열변형된 알루미나 담체를 사용하여 흡착 담지법으로 촉매를 제조하였다. 주석 염화물(SnCl2) 0.0717g, 염산(HCl) 0.5714g, 질산(HNO3) 0.0714g을 증류수 24g에 넣어 녹인 후, 열변형된 알루미나 20g을 넣어 담지하였다. 담지액은 회전증발기를 이용하여 건조하였으며, 상온에서 1.5시간 동안 25rpm으로 교반한 후, 80℃에서 1.5시간 동안 건조하였다. 완전한 건조를 위하여 105℃ 오븐에서 15시간 동안 건조하고, 700℃ 소성로에서 3시간 동안 열처리하였다. 이후, 주석이 담지된 알루미나 15g을 염화 백금산(H2PtCl6·6H2O) 0.3319g, 염산 0.2143g, 질산 0.0536g이 녹 아있는 증류수 18.0552g에 넣어 담지하였다. 담지액은 회전증발기를 이용하여 건조하였으며, 상온에서 1.5시간 동안 25rpm으로 교반한 후, 감압 상태 80℃에서 1.5시간 동안 25rpm으로 회전시켜 건조하였고, 105℃ 오븐에서 15시간 동안 건조하고, 600℃ 소성로에서 3시간 동안 열처리하였다. 이후, 주석과 백금이 담지된 알루미나 10g을 질산 칼륨(KNO3) 0.1933g, 염산 0.1629g이 녹아있는 증류수 12.1136g에 넣어 담지하였다. 담지액은 회전증발기를 이용하여 건조하였으며, 상온에서 1.5시간 동안 25rpm으로 교반한 후, 감압 상태 80℃에서 1.5시간 동안 25rpm으로 회전시켜 건조하였고, 105℃ 오븐에서 15시간 동안 건조하고, 600℃ 가열로에서 3시간 동안 열처리하여 산화 탈수소화 촉매를 제조하였다. 제조된 촉매의 백금에 대한 주석의 중량비는 0.5이고, 담체 표면적에 대한 칼륨의 비율이 0.006 중량%/㎡, 활성 금속에 대한 Cl 성분의 중량비는 1.3이다.The catalyst was prepared by adsorptive loading using the heat-modified alumina carrier. 0.0717 g of tin chloride (SnCl 2 ), 0.5714 g of hydrochloric acid (HCl), and 0.0714 g of nitric acid (HNO 3 ) were dissolved in 24 g of distilled water, followed by 20 g of heat-modified alumina. The supporting solution was dried using a rotary evaporator, stirred at 25 rpm for 1.5 hours at room temperature, and then dried at 80 ° C. for 1.5 hours. For complete drying it was dried for 15 hours in a 105 ℃ oven, and heat-treated for 3 hours in a 700 ℃ kiln. Then, 15 g of tin-supported alumina was added to 1319 552 g of distilled water in which 0.3319 g of chloroplatinic acid (H 2 PtCl 6 .6H 2 O), 0.2143 g of hydrochloric acid, and 0.0536 g of nitric acid were dissolved. The supporting solution was dried using a rotary evaporator, stirred at 25 rpm for 1.5 hours at room temperature, and then dried at 25 rpm for 1.5 hours at 80 ° C. under reduced pressure, dried for 15 hours in an oven at 105 ° C., and then heated at 600 ° C. in a kiln. Heat treatment for 3 hours at. Thereafter, 10 g of alumina loaded with tin and platinum was placed in 12.1136 g of distilled water in which 0.1933 g of potassium nitrate (KNO 3 ) and 0.1629 g of hydrochloric acid were dissolved. The supporting solution was dried using a rotary evaporator, stirred at 25 rpm for 1.5 hours at room temperature, then dried at 25 rpm for 1.5 hours at 80 ° C. under reduced pressure, dried for 15 hours in an oven at 105 ° C., and heated at 600 ° C. An oxidative dehydrogenation catalyst was prepared by heat treatment in a furnace for 3 hours. The weight ratio of tin to platinum of the prepared catalyst was 0.5, the ratio of potassium to the carrier surface area was 0.006 wt% / m 2, and the weight ratio of Cl component to active metal was 1.3.
비교예 1Comparative Example 1 : 주석 성분이 담지되지 않은 산화 탈수소화 촉매의 제조 : Preparation of Oxidative Dehydrogenation Catalyst without Tin Component
상기 실시예 1에서 얻어진 열변형된 알루미나 15g을 염화 백금산 0.3319g, 염산 0.2143g, 질산 0.0536g이 녹아있는 증류수 18.0552g에 넣어 담지하였다. 담지액은 회전증발기를 이용하여 건조하였으며, 상온에서 1.5시간 동안 25rpm으로 교반한 후, 감압 상태 80℃에서 1.5시간 동안 25rpm으로 회전시켜 건조하였다. 이후 105℃ 오븐에서 15시간 동안 건조하고, 600℃ 소성로에서 3시간 동안 열처리하여 백금 알루미나 촉매를 얻었다. 제조된 촉매의 백금에 대한 Cl 성분의 중량비는 0.9 이다.15 g of the heat-modified alumina obtained in Example 1 was placed in 18.0552 g of distilled water in which 0.3319 g of chloroplatinic acid, 0.2143 g of hydrochloric acid, and 0.0536 g of nitric acid were dissolved. The supporting solution was dried using a rotary evaporator, and stirred at 25 rpm for 1.5 hours at room temperature, and then dried by rotating at 25 rpm for 1.5 hours at 80 ° C under reduced pressure. After drying for 15 hours in an oven at 105 ℃, heat treatment for 3 hours at 600 ℃ kiln to obtain a platinum alumina catalyst. The weight ratio of Cl component to platinum of the prepared catalyst is 0.9.
비교예 2Comparative Example 2 : 주석 성분의 함량이 증가되어 담지된 산화 탈수소화 촉매의 제조 : Preparation of Supported Oxidative Dehydrogenation Catalyst with Increased Tin Content
주석염화물 0.6818g, 염산 0.5714g, 질산 0.0714g을 증류수 24g에 넣어 녹인 후, 상기 실시예 1에서 얻어진 열변형된 알루미나 20g을 넣어 담지하였다. 담지액은 회전증발기를 이용하여 건조하였으며, 상온에서 1.5시간 동안 25rpm으로 교반한 후, 80℃에서 1.5시간 동안 건조하였다. 완전한 건조를 위하여 105℃ 오븐에서 15시간 동안 건조하고, 700℃ 소성로에서 3시간 동안 열처리하였다. 제조된 촉매의 백금에 대한 주석의 중량비는 4.4이고, 활성 금속에 대한 Cl 성분의 중량비는 2.8이다.0.6818 g of tin chloride, 0.5714 g of hydrochloric acid, and 0.0714 g of nitric acid were dissolved in 24 g of distilled water, and 20 g of heat-modified alumina obtained in Example 1 was added thereto. The supporting solution was dried using a rotary evaporator, stirred at 25 rpm for 1.5 hours at room temperature, and then dried at 80 ° C. for 1.5 hours. For complete drying it was dried for 15 hours in a 105 ℃ oven, and heat-treated for 3 hours in a 700 ℃ kiln. The weight ratio of tin to platinum of the prepared catalyst is 4.4, and the weight ratio of Cl component to active metal is 2.8.
실험예 1Experimental Example 1 : 산화 탈수소 촉매의 성능 실험 : Performance Experiment of Oxidative Dehydrogenation Catalyst
본 발명에 따른 산화 탈수소 촉매의 성능을 확인하기 위하여, 하기와 같은 실험을 수행하였다.In order to confirm the performance of the oxidative dehydrogenation catalyst according to the present invention, the following experiment was performed.
상기 실시예 1 및 비교예 1~2에서 제조된 촉매 1.5g을 부피가 7㎖인 석영반응기 내에 각각 충진한 후, 프로판, 수소, 산소 혼합기체를 공급하여 산화 탈수소 반응을 각각 수행하였다. 이때, 수소와 프로판의 비율은 1:1, 프로판과 산소의 비율은 30:1로 고정하였으며, 반응온도는 650℃, 압력은 1.5 절대압력, 액체공간속도는 15hr-1로 유지하면서 산화 탈수소 반응을 수행하였다. 반응 후의 기체 조성은 반 응 장치와 연결된 기체 크로마토그래피로 분석하여 프로판 전환율, 반응 후 생성물 중의 프로필렌 선택도, 프로필렌 수율을 구하였다.After filling 1.5 g of the catalyst prepared in Example 1 and Comparative Examples 1 and 2 into a quartz reactor having a volume of 7 ml, respectively, propane, hydrogen, and oxygen mixed gas were supplied to perform an oxidative dehydrogenation reaction, respectively. At this time, the ratio of hydrogen and propane was fixed at 1: 1, and the ratio of propane and oxygen was set at 30: 1. The reaction temperature was 650 ° C., the pressure was 1.5 absolute pressure, and the liquid space velocity was maintained at 15hr −1 while the oxidative dehydrogenation reaction was carried out. Was performed. The gas composition after the reaction was analyzed by gas chromatography connected to the reaction apparatus to determine the propane conversion, the propylene selectivity in the product after the reaction, and the propylene yield.
결과는 표 1에 나타내었다.The results are shown in Table 1.
표 1에 나타난 바와 같이, 본 발명에 따른 촉매의 프로판 전환율은 40.2%, 생성물 중의 프로필렌 선택도는 78.6%, 프로필렌 수율은 31.6%로 매우 높은 촉매 활성을 나타내었다. 또한 반응시간이 증가함에 따라 촉매 활성도 높게 유지되고 있음을 확인하였다. 반면, 주석 성분이 없는 촉매(비교예 1)는 본 발명의 촉매(실시예 1)에 비해 초기 활성은 비슷하지만 반응시간이 경과함에 따라 활성이 급격히 저하되었다. 또한, 본 발명의 촉매(실시예 1)와 주석 성분의 함량이 증가되어 담지된 촉매(비교예 2)를 비교하면, 주석의 양의 증가한 경우 초기에는 비슷한 활성을 보였지만 반응이 진행됨에 따라 과량의 주석으로 인하여 백금-주석의 합금이 증가되어 활성의 감소가 나타났다.As shown in Table 1, the catalyst according to the present invention exhibited very high catalytic activity: 40.2% propane conversion, 78.6% propylene selectivity in the product, and 31.6% propylene yield. In addition, it was confirmed that the catalytic activity was maintained high as the reaction time increased. On the other hand, the catalyst without the tin component (Comparative Example 1) was similar to the initial activity compared to the catalyst of the present invention (Example 1), but the activity was drastically decreased as the reaction time elapsed. In addition, when comparing the catalyst of the present invention (Example 1) and the content of the tin component supported by the increase of the tin component (Comparative Example 2), the increase in the amount of tin initially showed a similar activity, but as the reaction proceeds, Tin increased the alloy of platinum-tin, indicating a decrease in activity.
실험예 2Experimental Example 2 : 수소의 존재 여부에 의한 산화 탈수소 촉매의 성능 실험 : Performance Experiment of Oxidative Dehydrogenation Catalyst by Presence of Hydrogen
본 발명에 따른 산화 탈수소 촉매의 성능이 수소의 존재에 의해 어떠한 영향을 받는지 확인하기 위하여, 하기와 같은 실험을 수행하였다.In order to confirm how the performance of the oxidative dehydrogenation catalyst according to the present invention is affected by the presence of hydrogen, the following experiment was performed.
상기 실험예 1에서 촉매로 실시예 1에서 제조한 촉매를 사용하고, 혼합기체로 프로판과 산소의 혼합기체를 사용한 것을 제외하고는, 실험예 1과 동일하게 하여 프로판 산화 탈수소 반응을 각각 수행하였다. 이때, 프로판과 산소의 비율은 30:1로 고정하였다.Propane oxidative dehydrogenation was carried out in the same manner as in Experiment 1 except that the catalyst prepared in Example 1 was used as the catalyst in Experimental Example 1, and a mixed gas of propane and oxygen was used as the mixed gas. At this time, the ratio of propane and oxygen was fixed at 30: 1.
결과는 표 2에 나타내었다.The results are shown in Table 2.
표 2에 나타난 바와 같이, 혼합기체 중 수소를 제외한 혼합기체를 본 발명의 촉매를 사용하여 산화 탈수소 반응을 수행한 결과, 프로판 전환율, 생성물 중의 프로필렌 선택도, 및 프로필렌 수율이 매우 낮게 나타나 매우 낮은 촉매 활성을 나타내었다. 따라서, 본 발명의 산화 탈수소 촉매는 프로판 산화 탈수소 반응에서 수소의 존재에 의해 프로판 전환율, 생성물 중의 프로필렌 선택도, 및 프로필렌 수율을 높게 나타내어 매우 높은 촉매 활성을 나타냄을 알 수 있다.As shown in Table 2, oxidative dehydrogenation of the mixed gas excluding hydrogen in the mixed gas was carried out using the catalyst of the present invention. As a result, propane conversion, propylene selectivity in the product, and propylene yield were very low. Activity was shown. Accordingly, it can be seen that the oxidative dehydrogenation catalyst of the present invention exhibits very high catalytic activity due to high propane conversion, propylene selectivity, and propylene yield due to the presence of hydrogen in the propane oxidative dehydrogenation reaction.
본 발명에 따른 산화 탈수소 촉매는 활성성분의 담지시 높은 분산도를 가지며, 메조 및 매크로 기공의 발달은 물질전달 속도를 높이는 효과를 갖는다. 따라 서, 본 발명의 산화 탈수소 촉매를 이용하여 고온에서 수소 존재 하에 프로판을 산화 탈수소 반응시킬 경우 프로판 전환율, 생성물 중의 프로필렌 선택도, 및 프로필렌 수율을 높여 촉매 활성이 매우 높게 나타난다.The oxidative dehydrogenation catalyst according to the present invention has a high dispersion degree when the active ingredient is supported, and the development of meso and macro pores has an effect of increasing the material transfer rate. Accordingly, when oxidative dehydrogenation of propane is carried out in the presence of hydrogen at high temperature using the oxidative dehydrogenation catalyst of the present invention, the catalytic activity is very high by increasing propane conversion, propylene selectivity in the product, and propylene yield.
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| KR101921407B1 (en) * | 2017-01-06 | 2018-11-23 | 효성화학 주식회사 | Dehydrogenation catalysts and preparation method thereof |
| KR101951537B1 (en) * | 2017-01-09 | 2019-02-22 | 효성화학 주식회사 | Composite catalyst support, dehydrogenation catalysts and preparation method thereof |
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| KR101981886B1 (en) * | 2018-02-01 | 2019-05-23 | 효성화학 주식회사 | Dehydrogenation catalyst |
| CN113877577B (en) * | 2020-07-02 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for improving alkane conversion rate |
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