KR100588948B1 - Catalyst for making dimethylether, method of preparing the same and method of preparing dimethylether using the same - Google Patents
Catalyst for making dimethylether, method of preparing the same and method of preparing dimethylether using the same Download PDFInfo
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- KR100588948B1 KR100588948B1 KR1020040019439A KR20040019439A KR100588948B1 KR 100588948 B1 KR100588948 B1 KR 100588948B1 KR 1020040019439 A KR1020040019439 A KR 1020040019439A KR 20040019439 A KR20040019439 A KR 20040019439A KR 100588948 B1 KR100588948 B1 KR 100588948B1
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 129
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000018044 dehydration Effects 0.000 claims abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 208000005374 Poisoning Diseases 0.000 claims abstract description 17
- 231100000572 poisoning Toxicity 0.000 claims abstract description 17
- 230000000607 poisoning effect Effects 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- -1 phosphate compound Chemical class 0.000 claims 2
- 239000000243 solution Substances 0.000 description 19
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 239000010457 zeolite Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011973 solid acid Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- 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 디메틸에테르 제조용 혼합촉매, 이의 제조방법 및 이를 이용한 디메틸에테르의 제조방법에 관한 것으로, 좀 더 구체적으로 금속 질산염 용액과 탄산나트륨 용액을 혼합한 메탄올의 합성촉매 및 H-ZSM-5의 산점을 금속 이온으로 피독 처리하여 산도를 조절한 메탄올의 탈수촉매로 구성되며, 상기 탈수촉매의 실리카/알루미나 비율은 25 내지 140이며, 상기 금속 이온의 피독 처리시 금속 이온의 양은 상기 알루미나에 대해 원자비율로 0.3∼0.7 범위인 디메틸에테르 제조용 혼합촉매, 이의 제조방법 및 이를 이용한 디메틸에테르의 제조방법에 관한 것이다.The present invention relates to a mixed catalyst for preparing dimethyl ether, a method for preparing the same, and a method for preparing dimethyl ether using the same, and more specifically, to a synthetic catalyst of methanol mixed with a metal nitrate solution and a sodium carbonate solution, and an acid point of H-ZSM-5. It is composed of a dehydration catalyst of methanol adjusted to the acidity by poisoning with metal ions, the silica / alumina ratio of the dehydration catalyst is 25 to 140, the amount of metal ions in the poisoning treatment of the metal ions in an atomic ratio with respect to the alumina It relates to a mixed catalyst for preparing dimethyl ether in the range of 0.3 to 0.7, a method for preparing the same, and a method for preparing dimethyl ether using the same.
본 발명에 따른 혼합촉매를 사용하여 수소, 일산화탄소 및 이산화탄소를 함유하는 합성가스로부터 디메틸에테르를 제조할 경우, 2000시간 이상 높은 일산화탄소 전환율을 유지하는 한편 초기반응부터 장시간 선택적으로 디메틸에테르를 제조할 수 있는 장점이 있다.When the dimethyl ether is prepared from the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide using the mixed catalyst according to the present invention, it is possible to selectively prepare dimethyl ether for a long time from the initial reaction while maintaining a high carbon monoxide conversion rate over 2000 hours. There is an advantage.
디메틸에테르, 수소, 일산화탄소, 이산화탄소, 혼합가스, 촉매Dimethyl ether, hydrogen, carbon monoxide, carbon dioxide, mixed gas, catalyst
Description
도 1은 본 발명에 의한 촉매를 사용하여 디메틸에테르를 제조할 경우의 메탄올의 변환율 및 디메틸에테르의 선택성에 대한 그래프이다.1 is a graph showing the conversion of methanol and the selectivity of dimethyl ether when a dimethyl ether is prepared using the catalyst according to the present invention.
도 2는 본 발명의 비교예 1에 의해 제조된 촉매를 사용하여 디메틸에테르를 제조할 경우의 메탄올의 변환율 및 디메틸에테르의 선택성에 대한 그래프이다.2 is a graph showing the conversion of methanol and the selectivity of dimethyl ether when dimethyl ether is prepared using the catalyst prepared according to Comparative Example 1 of the present invention.
본 발명은 디메틸에테르 제조용 촉매, 이의 제조방법 및 이를 이용한 디메틸에테르의 제조방법에 관한 것으로, 좀 더 구체적으로, 수소, 일산화탄소 및 이산화탄소를 함유하는 합성가스로부터 메탄올을 합성하고 메탄올의 탈수반응을 통해 디메틸에테르를 제조하기 위하여 금속질산염 용액과 탄산나트륨을 혼합한 메탄올 합성촉매와 고체산의 산점을 금속 이온으로 피독 처리하여 산도를 조절한 탈수촉매를 포함하는 디메틸에테를 제조용 촉매 및 이를 이용한 디메틸에테르의 제조방법에 관한 것이다.The present invention relates to a catalyst for preparing dimethyl ether, a method for preparing the same, and a method for preparing dimethyl ether using the same. More specifically, dimethyl ether is synthesized from a synthesis gas containing hydrogen, carbon monoxide, and carbon dioxide, and dehydration of methanol. In order to prepare the ether, a catalyst for preparing a dimethyl ether comprising a methanol synthesis catalyst mixed with a metal nitrate solution and sodium carbonate and a dehydration catalyst whose acidity is adjusted by poisoning the acid point of a solid acid with metal ions, and the preparation of dimethyl ether using the same It is about a method.
디메틸에테르는 그 물리적, 화학적 특성이 LPG와 유사하거나 오히려 여러 면에서 우수하여 에어로졸 추진체, 디젤 연료의 대체물질 및 화학반응의 중간체로 사용할 수 있어 최근 주목받고 있는 산소 함유 화합물이다. Dimethyl ether is an oxygen-containing compound that has recently attracted attention because its physical and chemical properties are similar to, or rather superior to, LPG, and can be used as an aerosol propellant, a substitute for diesel fuel, and an intermediate of chemical reactions.
디메틸에테르를 합성하는 전형적인 방법은 메탄올을 진한 황산 촉매와 반응시키는 방법인데, 이 방법은 황산을 재생하는데 많은 비용이 들고 황산의 특성상 반응중에 생기는 물과 반응하여 폭발을 일으킬 위험이 있어 비용과 안전상 많은 문제점이 있다. 이러한 단점을 극복하면서 디메틸에테르를 공업적 규모로 생산하는 주된 방법은 고정베드 반응기(fixed bed reactor)에서 고체산 탈수촉매를 이용하여 메탄올을 탈수시키고 그 생성물을 증류하여 에어로졸 분야에서 요구되는 정도의, 고순도의 디메틸에테르를 회수하는 방법이다. A typical method of synthesizing dimethyl ether is to react methanol with a concentrated sulfuric acid catalyst, which is expensive to regenerate sulfuric acid and, due to the nature of sulfuric acid, there is a risk of explosion by reacting with water generated during the reaction. There is a problem. While overcoming these shortcomings, the main method for producing dimethyl ether on an industrial scale is to dehydrate methanol using a solid acid dehydration catalyst in a fixed bed reactor and distill the product to the extent required by the aerosol field. It is a method of recovering high purity dimethyl ether.
그러나 디메틸에테르가 가장 주목받고 있는 용도인 디젤연료의 대체물질로 사용되기 위해서는 보다 싼값으로 공급되어야 하는데, 산 촉매의 존재하에서 메탄올의 탈수반응을 통하여 얻어지는 디메틸에테르는 메탄올을 합성가스로부터 합성한 후 이를 산 촉매 반응을 통해 합성하는 것이기 때문에 메탄올 보다 가격 면에서 훨씬 비싸고, 열역학적으로 메탄올 합성 반응은 그 특성상 전환율이 제한된다.However, in order to be used as a substitute for diesel fuel, which is the most noticeable use, dimethyl ether has to be supplied at a lower price. Dimethyl ether obtained by dehydration of methanol in the presence of an acid catalyst is synthesized from methanol after synthesis of methanol. It is much more expensive than methanol because it is synthesized through acid catalysis, and thermodynamically, methanol synthesis has limited conversion due to its characteristics.
이를 해결하기 위해 메탄올 합성 촉매와 탈수반응 산 촉매를 혼합한 혼성 촉매를 사용하여 합성가스로부터 직접 디메틸에테르를 합성하는 방법이 개발되었다. 혼성 촉매를 사용하는 디메틸에테르 합성 공정은 탈수반응을 통해 생성물인 메탄올이 제거되고 탈수반응과정에서 생긴 물이 수성반응을 통해 제거되어 촉매의 특성이 개선되고 일산화탄소의 전환율과 디메틸에테르의 수율이 증가하게 된다. 즉, 합성 가스로부터 직접 디메틸에테르를 합성하는 반응과정에서 혼성 촉매상에서는 동시에 세가지 반응 (메탄올 합성 반응, 수성 반응 및 탈수 반응)이 진행되며 동시에 진행되는 각 반응은 다른 반응의 문제점을 화학적으로 제거해주는 효과를 나타낸다.In order to solve this problem, a method of synthesizing dimethyl ether directly from syngas using a hybrid catalyst mixed with a methanol synthesis catalyst and a dehydration acid catalyst has been developed. The dimethyl ether synthesis process using a hybrid catalyst removes methanol as a product through dehydration and the water generated during the dehydration process is removed through an aqueous reaction to improve the properties of the catalyst and increase the conversion of carbon monoxide and the yield of dimethyl ether. do. That is, three reactions (methanol synthesis reaction, aqueous reaction, and dehydration reaction) are simultaneously performed on the hybrid catalyst in the process of synthesizing dimethyl ether directly from the synthesis gas, and each reaction performed simultaneously chemically removes the problems of other reactions. Indicates.
수소와 탄소산화물로부터 디메틸에테르를 직접 합성하는 방법을 포함하여 많은 제조방법들이 문헌에 발표되어 있다. 고정베드 반응기에서 메탄올 촉매 및 탈수 촉매를 함께 사용하여 수소, 일산화탄소 및 이산화탄소를 함유하는 합성가스로부터 직접 디메틸에테르를 제조하는 방법이 개시된 특허 문헌으로는, 독일특허 제291,937호, 미국특허 제5,254,596호, 미국특허 제4,417,000호, 미국특허 제4,177,167호, 제4,375,424호 및 제4,098,809호, 유럽특허 제164,156호 및 제409,086호, 영국특허 제2,093,365호, 제2,097,382호 및 제2,099,327호, 독일특허 제3,220,547호, 제3,201,155호, 제3,118,620호, 제2,757,788호, 및 제2,362,944호, 및 덴마크특허 제6031/87호 및 제2169/89호 등을 들 수 있다. Many preparation methods have been published in the literature, including the direct synthesis of dimethyl ether from hydrogen and carbon oxides. Patents disclosed for producing dimethyl ether directly from a synthesis gas containing hydrogen, carbon monoxide and carbon dioxide using a methanol catalyst and a dehydration catalyst together in a fixed bed reactor are described in German Patent Nos. 291,937, 5,254,596, U.S. Pat.Nos. 4,417,000, U.S. Pat. 3,201,155, 3,118,620, 2,757,788, 2,362,944, and Danish patents 6031/87 and 2169/89.
메탄올 합성 반응의 촉매로는, 구리 금속을 기본으로 하고 아연, 알루미나, 크롬 또는 티타늄 등의 물질을 이용하여 지지체를 변화시키거나 산화물을 여러 가지 비율로 혼합한 삼상 촉매가 주로 사용되며, 이 촉매는 수성 반응 및 역수성 반응에도 활성을 나타낸다. 또한, 메탄올의 탈수반응에는 산 촉매가 주로 사용되며, 그 예로는 알루미나, 제올라이트, 실리카/알루미나, 금속 염, 이온교환수지, 혼합된 금속산화물 등이 있다. 상기 혼성 촉매를 사용하는 디메틸에테르 합성 공정에서는 혼성 촉매 중의 산 촉매의 특성이 반응물인 합성가스의 전환 및 생성물의 선택도와 수율에 큰 영향을 미치게 된다.As a catalyst for the methanol synthesis reaction, a three-phase catalyst based on a copper metal and using a material such as zinc, alumina, chromium or titanium to change a support or mixed with oxides in various ratios is mainly used. It is also active in the aqueous reaction and in the reverse reaction. In addition, an acid catalyst is mainly used for the dehydration reaction of methanol, and examples thereof include alumina, zeolite, silica / alumina, metal salts, ion exchange resins, mixed metal oxides, and the like. In the dimethyl ether synthesis process using the hybrid catalyst, the properties of the acid catalyst in the hybrid catalyst have a great influence on the conversion of the synthesis gas as a reactant and the selectivity and yield of the product.
최근에는 이러한 산 촉매와 메탄올 합성 촉매를 물리적으로 혼합하여 사용하는 대신 유효성분을 함침법으로 합성한 촉매를 사용하는 방법도 제시되었다. 예를 들어, 미국특허 제5,254,596호에서는 테트라이소프로필티타네이트를 암모니아로 침전시킨 후 여과하고 이를 질산아연 6 수화물 및 질산 제2철에 함침시켜 ZnxTiyOz 형태의 촉매를 제조하고 이를 사용하여 합성가스로부터 디메틸에테르를 합성하였다. 또한, 미국특허 제4,328,129호에서는 감마-알루미나 지지체에 3중량%의 로듐과 6.5 중량%의 몰리브덴을 담지시킨 촉매를 사용하여 230psi, 220∼280℃의 조건하에서 합성가스로부터 반응물 조성 CO:H2 = 1:2인 경우에는 일산화탄소 기준으로 27.1 내지 57.3 %의 디메틸에테르와 메탄올로의 전환율을 얻었으며, 반응물 조성 CO:H2 = 1:1인 경우에는 28.2 내지 42.2 %의 전환율을 얻었다. Recently, a method of using a catalyst synthesized by impregnating an active ingredient instead of physically mixing such an acid catalyst and a methanol synthesis catalyst has also been proposed. For example, US Pat. No. 5,254,596 discloses tetraisopropyl titanate with ammonia, followed by filtration and impregnation with zinc nitrate hexahydrate and ferric nitrate to prepare a ZnxTiyOz type catalyst and use it to synthesize dimethyl from synthesis gas. Ether was synthesized. In addition, US Pat. No. 4,328,129 discloses a reactant composition CO: H 2 = from the synthesis gas under conditions of 230 psi, 220-280 ° C using a catalyst loaded with 3% by weight of rhodium and 6.5% by weight of molybdenum on a gamma-alumina support. In the case of 1: 2, conversion of 27.1 to 57.3% of dimethyl ether and methanol based on carbon monoxide was obtained. In the case of reactant composition CO: H 2 = 1: 1, conversion of 28.2 to 42.2% was obtained.
또한, 미국특허 제4,375,424호에서는 감마-알루미나를 질산구리와 질산아연 용액에 담구어 촉매를 제조하였으며, 1700psi, 100∼275℃, 3000의 GHSV, 반응물의 조성 CO:H2 = 1:1에서 CO 전환율 5.8∼70.4% 및 디메틸에테르 전환율 2.8∼94.4%를 얻었다.In addition, US Patent No. 4,375, 424 prepared a catalyst by immersing gamma-alumina in a solution of copper nitrate and zinc nitrate, 1700psi, 100-275 ° C., GHSV of 3000, CO at the composition CO: H 2 = 1: 1. Conversion rates of 5.8 to 70.4% and dimethyl ether conversion of 2.8 to 94.4% were obtained.
한편, 디메틸에테르 합성에 사용되는 산 촉매의 성능을 개선하려는 연구도 많이 행해져왔는데, 대부분의 경우는 부산물을 생성시키는 강산점을 알칼리금속으로 피독시키거나 열처리 방법을 사용하여 산점의 양을 조절하여 부반응을 최대한 억제하거나, 또는 활성 원소를 감마-알루미나에 담지시켜 디메틸에테르의 수율과 선택도를 향상시키려는 시도였다. 그의 한 예로서, 미국특허 제4,595,785호에서는 감마-알루미나에 1%의 티타니아를 담지시킨 촉매를 사용하여 1034kPa, 400℃에서 메탄올의 탈수반응을 수행하여 57.5%의 디메틸에테르, 20%의 메탄올 및 22.5%의 물을 포함하는 응축 생성물을 얻었다. 한국 공개특허 제2000-0002477호에서는 포름알데히드로 개질된 산 촉매를 합성가스로부터 디메틸에테르 합성에 사용할 때 높은 일산화탄소 전환율과 디메틸에테르 선택도 및 수율을 얻고자 노력하였으나 포름알데히드와 함께 알칼리 성분으로 처리하기 때문에 여전히 일산화탄소 전환율이 낮아지는 문제점이 있다.On the other hand, many studies have been conducted to improve the performance of the acid catalyst used in the synthesis of dimethyl ether. In most cases, side reactions are performed by poisoning strong acid sites that generate by-products with alkali metals or by adjusting the amount of acid sites by heat treatment. It was attempted to improve the yield and selectivity of dimethyl ether by inhibiting maximally or supporting the active element in gamma-alumina. As an example, US Pat. No. 4,595,785 discloses dehydration of methanol at 1034 kPa, 400 ° C. using a catalyst having 1% titania loaded on gamma-alumina to give 57.5% dimethyl ether, 20% methanol and 22.5. A condensation product containing% water was obtained. Korean Patent Laid-Open Publication No. 2000-0002477 attempts to obtain high carbon monoxide conversion, dimethyl ether selectivity and yield when a formaldehyde-modified acid catalyst is used for synthesizing dimethyl ether from syngas, but treating with an alkali component with formaldehyde. There is still a problem that the carbon monoxide conversion rate is low.
듀보이스(J. L. Dubois) 등은 Cu/ZnO/Al2O3 촉매와 Y형 제올라이트의 혼합촉매를 사용하여 이산화탄소와 수소로부터 디메틸에테르와 메탄올을 함께 제조한 바 있다(Chem. Lett., 1115(1992)). 이 방법에서는 상업용의 HY형 제올라이트를 그대로 사용하였으나 HY형 제올라이트는 너무 강한 산점(pKa -8.2)을 보유하여 메탄, 에탄, 프로판 등의 탄화수소 부산물을 생성시키는 문제가 있다. 부산물로 생성된 탄화수소는 낮은 분자량의 알칸류로서 생성물로서의 가치가 작을 뿐만 아니라, 반응 후 생성물의 분리시 이산화탄소와의 분리가 어려운 문제가 있다. 한국 공개특허 제1999-0031451호에서는 이러한 문제점들을 해결하고자 적절한 금속 양이온으로 치환시켜 강산점의 세기가 pKa 값으로서 대략 -6.0 에서 -3.0이 되도록 처리한 Y형 제올라이트를 CuO/ZnO계 촉매와 함께 이산화탄소의 수소화 반응에서 촉매로 사용하였을 때 탄화수소 부산물을 생성치 않으면서도 비교적 높은 촉매 활성을 나타냈으나 다량의 메탄올이 생성되어 디메틸에테르 혼합물로의 선택성이 낮아지는 문제점 이 있다.JL Dubois et al. Have prepared a mixture of dimethyl ether and methanol from carbon dioxide and hydrogen using a mixed catalyst of a Cu / ZnO / Al 2 O 3 catalyst and a Y-type zeolite (Chem. Lett., 1115 (1992). )). In this method, the commercial HY zeolite is used as it is, but the HY zeolite has a strong acid point (pKa -8.2), thereby generating hydrocarbon by-products such as methane, ethane, and propane. The hydrocarbon produced as a by-product is not only low in value as a product of alkanes of low molecular weight, but also has a problem in that it is difficult to separate from carbon dioxide in the separation of the product after the reaction. In Korean Patent Laid-Open Publication No. 1999-0031451, a Y-type zeolite treated with a CuO / ZnO-based catalyst with a CuO / ZnO-based catalyst treated with a suitable metal cation so that the strength of the strong acid point is approximately -6.0 to -3.0 as a pKa value is solved. When used as a catalyst in the hydrogenation of showed a relatively high catalytic activity without generating hydrocarbon by-products, but a large amount of methanol is generated there is a problem that the selectivity to the dimethyl ether mixture is lowered.
이에 본 발명에서는 상술한 문제를 해결하기 위하여 광범위한 연구를 수행한 결과, 금속질산염 용액과 탄산나트륨 용액을 혼합한 메탄올 합성촉매와 H-ZSM-5 촉매의 산점을 금속 이온으로 피독 처리하여 산도를 조절한 메탄올 탈수촉매를 혼합한 혼합촉매를 제조하여, 기존의 촉매에 비하여 장시간 높은 일산화탄소 전환율을 안정적으로 유지하는 한편 초기반응부터 장시간동안 탄화수소류와 메탄올 등의 부반응이 없이 선택적으로 디메틸에테르를 제조할 수 있었으며, 본 발명은 이를 기초로 완성되었다.Accordingly, in the present invention, as a result of extensive research to solve the above problems, the acidity of the methanol synthesis catalyst and the H-ZSM-5 catalyst mixed with the metal nitrate solution and the sodium carbonate solution was poisoned with metal ions to adjust the acidity. By preparing a mixed catalyst mixed with a methanol dehydration catalyst, dimethyl ether could be selectively produced without side reactions such as hydrocarbons and methanol for a long time, while maintaining a high carbon monoxide conversion rate for a long time as compared to a conventional catalyst. The present invention has been completed based on this.
따라서, 본 발명의 목적은 수소, 일산화탄소 및 이산화탄소를 함유하는 합성가스로부터 장시간동안 안정적이며 선택적으로 디메틸에테르를 제조할 수 있는 디메틸에테르 제조용 혼합 촉매를 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a mixed catalyst for producing dimethyl ether, which is capable of producing dimethyl ether stably and selectively for a long time from a synthesis gas containing hydrogen, carbon monoxide and carbon dioxide.
본 발명의 다른 목적은 상기 디메틸에테르 제조용 혼합촉매의 제조방법을 제공하는 데 있다.Another object of the present invention to provide a method for producing a mixed catalyst for the production of dimethyl ether.
본 발명의 또 다른 목적은 상기 방법으로 제조된 디메틸에테르 제조용 혼합촉매를 사용하여 디메틸에테르를 제조하는 방법을 제공하는 데 있다.Still another object of the present invention is to provide a method for preparing dimethyl ether using a mixed catalyst for preparing dimethyl ether prepared by the above method.
상기 본 발명의 목적을 달성하기 위한 디메틸에테르 제조용 혼합촉매는 금속 질산염 용액과 탄산나트륨 용액을 혼합한 메탄올의 합성촉매 및 H-ZSM-5의 산점을 금속 이온으로 피독 처리하여 산도를 조절한 메탄올의 탈수촉매로 구성되며, 상기 탈수촉매의 실리카/알루미나 비율은 25 내지 140이며, 상기 금속 이온의 피독 처리 시 금속 이온의 양은 상기 알루미나에 대해 원자비율로 0.3∼0.7 범위인 것으로 구성된다.The mixed catalyst for the production of dimethyl ether to achieve the object of the present invention is a synthetic catalyst of methanol mixed with a metal nitrate solution and a sodium carbonate solution and the acid point of H-ZSM-5 by poisoning with metal ion dehydration of methanol adjusted the acidity It is composed of a catalyst, the silica / alumina ratio of the dehydration catalyst is 25 to 140, the amount of metal ions in the poisoning treatment of the metal ions is composed of 0.3 to 0.7 in the atomic ratio with respect to the alumina.
본 발명의 다른 목적을 달성하기 위한 상기 디메틸에테르 제조용 혼합촉매의 제조방법은 금속 질산염 용액과 탄산나트륨 용액을 pH 7이 되도록 혼합시켜 메탄올 합성촉매를 제조하는 단계; H-ZSM-5의 산점을 금속이온으로 피독처리시켜 메탄올 탈수촉매를 제조하는 단계; 및 상기 합성촉매 및 탈수촉매를 1 : 0.25∼2로 혼합시키는 단계를 포함하며, 상기 탈수촉매의 실리카/알루미나 비율은 25 내지 140이며, 상기 금속 이온의 피독 처리시 금속 이온의 양은 상기 알루미나에 대해 원자비율로 0.3∼0.7 범위로 구성된다.Method for producing a mixed catalyst for the production of dimethyl ether to achieve another object of the present invention comprises the steps of mixing the metal nitrate solution and sodium carbonate solution to pH 7 to prepare a methanol synthesis catalyst; Preparing a methanol dehydration catalyst by poisoning the acid point of H-ZSM-5 with metal ions; And mixing the synthetic catalyst and the dehydration catalyst at 1: 0.225 to 2, wherein the silica / alumina ratio of the dehydration catalyst is 25 to 140, and the amount of metal ions in the poisoning treatment of the metal ions is relative to the alumina. It consists of 0.3-0.7 in atomic ratio.
상기 본 발명의 또 다른 목적을 달성하기 위한 상기 혼합촉매를 사용하여 디메틸에테르를 제조하는 방법은 상기 방법으로 제조된 혼합촉매의 존재하에서, 수소, 일산화탄소 및 이산화탄소를 함유하는 합성가스를 200 내지 350℃의 반응온도, 10 내지 70기압의 반응압력 및 500 내지 20,000h-1의 공간속도에서 반응시키는 것으로 구성된다.Method for producing a dimethyl ether using the mixed catalyst for achieving the another object of the present invention is a synthesis gas containing hydrogen, carbon monoxide and carbon dioxide in the presence of a mixed catalyst prepared by the method 200 to 350 ℃ And a reaction temperature of 10 to 70 atm and a space velocity of 500 to 20,000 h −1 .
이하 본 발명을 좀 더 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
전술한 바와 같이, 본 발명의 디메틸에테르 제조용 혼합촉매는 메탄올 합성촉매와 메탄올 탈수촉매로 이루어진다.As described above, the mixed catalyst for preparing dimethyl ether of the present invention comprises a methanol synthesis catalyst and a methanol dehydration catalyst.
상기 메탄올 합성촉매는 금속질산염 용액과 탄산나트륨 용액을 포함한다. 상 기 금속질산염 용액은 Cu(NO3)2·3H2O, Zn(NO3)2·6H 2O, 및 Al(NO3)3·9H2O로 구성된다. The methanol synthesis catalyst includes a metal nitrate solution and a sodium carbonate solution. The group of metal nitrate solution is composed of Cu (NO 3) 2 · 3H 2 O, Zn (NO 3) 2 · 6H 2 O, and Al (NO 3) 3 · 9H 2 O.
상기 금속질산염 용액와 탄산나트륨 용액은 최종 혼합물이 pH 7로 유지되도록 혼합하는 것이 바람직하다.The metal nitrate solution and sodium carbonate solution is preferably mixed so that the final mixture is maintained at pH 7.
본 발명에 의하면, 상기 메탄올 탈수촉매는 탈수반응에 유효한 고체산의 산점을 금속 이온으로 피독 처리하여 고체산의 산도를 조절하여 사용한다. According to the present invention, the methanol dehydration catalyst is used by controlling the acidity of the solid acid by poisoning the acid point of the solid acid effective for the dehydration reaction with metal ions.
본 발명에 의하면, 상기 고체산 촉매는 실리카/알루미나 비율이 25∼140인 H-ZSM-5 촉매 중에서 선택하여 사용하는 것이 바람직하다. 상기 실리카/알루미나 비율이 25미만이면 촉매가 잘 만들어지지 않는 경향이 있고, 140을 초과하면 산점이 거의 없어서 반응성이 없게 되는 문제가 있다.According to the present invention, the solid acid catalyst is preferably selected from H-ZSM-5 catalysts having a silica / alumina ratio of 25 to 140. If the silica / alumina ratio is less than 25, the catalyst tends not to be made well, and if it exceeds 140, there is a problem that there is almost no acid point, resulting in inactivity.
상기 금속 이온은 Na, K, Li, Rb, Cs, Mg, Ca, Sr, Ba 이온, 이들의 산화물 또는 이들의 인산화합물을 사용하여 통상의 이온교환 방법에 의해 피독 처리한다.The metal ions are poisoned by a conventional ion exchange method using Na, K, Li, Rb, Cs, Mg, Ca, Sr, Ba ions, oxides thereof, or phosphoric acid compounds thereof.
본 발명에 따르면, H-ZSM-5 촉매의 강한 산점을 충분하게 피독 처리하기 위해서 금속 이온의 양은 H-ZSM-5의 알루미나에 대해 원자 비율로 0.3 내지 0.7 범위로 담지시키는 것이 바람직하다. 메탄올의 탈수반응 활성도는 산점의 양에 의존하기 때문에 상기 비율이 0.3 미만이면 강한 고체산점이 일부 존재하므로 활성이 강하여 디메틸에테르에서 탈수반응이 더욱 진행되어 탄화수소와 같은 부산물이 생성되거나 코크가 생성되는 것을 억제할 수 없는 문제점이 있으며, 0.7을 초과하면 탈수반응 활성도가 너무 낮아서 촉매로서의 기능을 수행하지 못하는 단점이 있다.According to the present invention, in order to sufficiently poison the strong acid point of the H-ZSM-5 catalyst, the amount of metal ions is preferably supported in the range of 0.3 to 0.7 in atomic ratio with respect to the alumina of H-ZSM-5. Since the dehydration activity of methanol depends on the amount of acid point, if the ratio is less than 0.3, there is some strong solid acid point, so the activity is strong, so that the dehydration reaction proceeds further in dimethyl ether to produce by-products such as hydrocarbons or coke. There is a problem that cannot be suppressed, and if it exceeds 0.7, the dehydration activity is too low to perform a function as a catalyst.
상기 메탄올 합성촉매 및 탈수촉매는 1 : 0.25∼2의 비율로 혼합하는 것이 .선택성과 전환율 면에서 바람직하다.It is preferable to mix the methanol synthesis catalyst and the dehydration catalyst in a ratio of 1: 0.2.25 to 2.the selectivity and the conversion rate.
한편, 상기 혼합촉매를 사용하고, 수소, 일산화탄소 및 이산화탄소를 함유하는 합성가스로부터 디메틸에테르를 제조하기 위한 반응온도는 200∼350℃, 반응압력은 10∼70 기압, 공간속도는 500∼20,000h-1의 범위가 바람직하다. 이때, 200℃ 미만일 경우에는 전환율이 낮아지는 문제점이 있으며, 350℃ 초과하면 선택성이 저하되므로 바람직하지 못하다. On the other hand, the use of the catalyst mixture, and the reaction temperature for the production of dimethyl ether from synthesis gas containing hydrogen, carbon monoxide and carbon dioxide is 200~350 ℃, the reaction pressure is 10 to 70 atm,
또한, 반응압력은 10기압 미만이면 열역학적으로 디메틸에테르 생성에 불리하고, 70 기압을 초과하면 반응 운전상의 문제점 때문에 적절하지 못하다. 상기 혼합가스의 공간속도는 500h-1 미만이면 반응 생산성이 너무 낮아지고, 20,000h-1을 초과하면 촉매와의 접촉시간이 짧아지기 때문에 전환율이 낮아지는 문제가 있다. In addition, if the reaction pressure is less than 10 atm, thermodynamically disadvantageous to the production of dimethyl ether, and if it exceeds 70 atm, it is not suitable due to problems in the reaction operation. The space velocity of the mixed gas has a problem that the low conversion rate, since the contact time with the catalyst is reduced when the reaction productivity is too low to less than 500h -1, it exceeds 20,000h -1.
반응기로는 기상의 고정층 반응기 또는 유동층 반응기가 이용될 수 있고, 이 중에서 어느 것을 사용해도 동일한 효과를 얻을 수 있다.As a reactor, a gaseous fixed bed reactor or a fluidized bed reactor may be used, and any one of them may achieve the same effect.
이하 실시예를 통해 본 발명을 좀 더 구체적으로 설명하지만 본 발명의 범주가 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the scope of the present invention is not limited thereto.
실시예 1Example 1
혼합 촉매는 다음과 같이 메탄올 합성촉매와 탈수반응촉매를 각각 제조한 후에 이를 물리적으로 혼합하는 방식으로 제조하였다. 메탄올 합성촉매는 금속질산염 용액과 탄산나트륨 용액을 혼합하여 공침방법으로 만든다. 금속질산염 수용액은 Cu(NO3)2·3H2O 53g과 Zn(NO3)2·6H2O 41g 및 Al(NO3)3·9H2O 52g을 증류수에 녹여 500㎖로 만든다. 탄산나트륨 용액은 Na2CO3·10H2O 139g을 증류수에 녹여 500㎖를 만들었다. 상기의 금속질산염 용액과 탄산나트륨 용액을 pH 7이 되도록 혼합하여 침전을 만든 후 침전물을 여과하고 증류수로 씻어주어 침전물을 얻었다. The mixed catalyst was prepared by physically mixing the methanol synthesis catalyst and the dehydration reaction catalyst, respectively, as follows. Methanol synthesis catalyst is made by coprecipitation method by mixing metal nitrate solution and sodium carbonate solution. The aqueous metal nitrate solution is prepared by dissolving 53 g of Cu (NO 3 ) 2 · 3H 2 O, 41 g of Zn (NO 3 ) 2 · 6H 2 O, and 52 g of Al (NO 3 ) 3 · 9H 2 O in distilled water to make 500 ml. Sodium carbonate solution was dissolved in 139g Na 2 CO 3 · 10H 2 O in distilled water to make 500ml. After mixing the metal nitrate solution and sodium carbonate solution to pH 7 to form a precipitate, the precipitate was filtered and washed with distilled water to obtain a precipitate.
얻은 침전물은 120℃에서 건조시키고, 공기 중 350℃에서 5시간 소성시켜 CuO/ZnO/Al2O3 촉매를 얻었다.The obtained precipitate was dried at 120 ° C. and calcined at 350 ° C. for 5 hours in air to obtain a CuO / ZnO / Al 2 O 3 catalyst.
탈수반응촉매는 H-ZSM-5 제올라이트(실리카/알루미나 = 30) 10g을 0.1N NaNO3 수용액 100㎖에 넣고 80℃에서 24시간 동안 교반시킨 후, 여과하고 증류수로 세척한 후 이를 120℃에서 12시간 건조하고 500℃에서 12시간 소성하여 NaH-ZSM-5형 제올라이트(Na/알루미나 원자비=0.7)를 얻었다.The catalyst for dehydration was put 10 g of H-ZSM-5 zeolite (silica / alumina = 30) in 100 ml of 0.1 N NaNO 3 aqueous solution, stirred at 80 ° C. for 24 hours, filtered and washed with distilled water, followed by 12 at 120 ° C. It dried for time and baked at 500 degreeC for 12 hours, and obtained NaH-ZSM-5 type zeolite (Na / alumina atomic ratio = 0.7).
상기의 CuO/ZnO/Al2O3 촉매 0.6g과 NaH-ZSM-5형 제올라이트 0.4g을 취하여 균일하게 혼합한 후 고정층 반응기에 충전하였다. 이 상태에서 10% 수소가 함유된 수소와 질소의 혼합가스를 50㎖/분의 유속으로 흘려주면서 300℃의 온도에서 혼합촉매를 환원 전처리 하였다. 디메틸에테르 제조반응은 일산화탄소와 수소의 혼합가스(H2:CO = 3:2의 부피비)를 50기압, 280℃의 조건에서, 1,500h-1의 공간속도로 상기의 혼합촉매층에 통과시켜 주었으며, 얻어진 반응결과는 하기 표 1에 나타내었다.0.6 g of the above CuO / ZnO / Al 2 O 3 catalyst and 0.4 g of NaH-ZSM-5 zeolite were mixed and uniformly mixed, and then charged into a fixed bed reactor. In this state, the mixed catalyst was reduced pretreatment at a temperature of 300 ° C. while flowing a mixture gas of hydrogen and nitrogen containing 10% hydrogen at a flow rate of 50 ml / min. In the dimethyl ether production reaction, a mixed gas of carbon monoxide and hydrogen (volume ratio of H 2 : CO = 3: 2) was passed through the mixed catalyst layer at a space velocity of 1,500 h -1 at 50 atm and 280 ° C. The obtained reaction results are shown in Table 1 below.
실시예 2Example 2
상기 실시예 1과 동일한 방법으로 혼합촉매를 제조하되, 탈수반응촉매는 H-ZSM-5 제올라이트(실리카/알루미나 = 30) 10g을 0.002N NaNO3 수용액 100㎖에 넣어서 얻은 NaH-ZSM-5형 제올라이트(Na/알루미나 원자비 = 0.3)를 사용하였으며, 얻어진 반응결과는 하기 표 1에 나타내었다.A mixed catalyst was prepared in the same manner as in Example 1, but the dehydration reaction catalyst was obtained by adding 10 g of H-ZSM-5 zeolite (silica / alumina = 30) to 100 ml of 0.002N NaNO 3 aqueous solution. (Na / alumina atomic ratio = 0.3) was used, and the reaction results are shown in Table 1 below.
실시예 3Example 3
상기 실시예 1과 동일한 방법으로 실시하되, 탈수반응촉매는 H-ZSM-5 제올라이트(실리카/알루미나=30) 10g을 0.1N Mg(NO3)2·2H2O 수용액 100㎖에 넣어서 얻은 MgH-ZSM-5형 제올라이트(Mg/알루미나 원자비 = 0.3)를 사용하였으며, 얻어진 반응결과는 하기 표 1에 나타내었다.The dehydration reaction catalyst was carried out in the same manner as in Example 1, except that 10 g of H-ZSM-5 zeolite (silica / alumina = 30) was added to 100 ml of 0.1 N Mg (NO 3 ) 2 .2H 2 O aqueous solution. ZSM-5 type zeolite (Mg / alumina atomic ratio = 0.3) was used, and the reaction results obtained are shown in Table 1 below.
실시예 4Example 4
상기 실시예 1과 동일한 방법으로 실시하되, 일산화탄소와 수소를 촉매층에 통과시켜 반응시킬 때의 반응온도를 250℃의 조건으로 하였다. 얻어진 반응결과는 하기 표 1에 나타내었다.The reaction was carried out in the same manner as in Example 1, but the reaction temperature at the time of reacting carbon monoxide and hydrogen through the catalyst layer was set at 250 ° C. The obtained reaction results are shown in Table 1 below.
실시예 5Example 5
상기 실시예 1과 동일한 방법으로 실시하되, 이산화탄소와 수소를 촉매층에 통과시켜 반응시킬 때의 공간속도를 4,500h-1로 하였다. 얻어진 반응결과는 하기 표 1에 나타내었다. The same method as in Example 1 was carried out, but the space velocity at the time of reacting carbon dioxide and hydrogen through the catalyst layer was 4,500 h −1 . The obtained reaction results are shown in Table 1 below.
실시예 6Example 6
상기 실시예 1과 동일한 방법으로 실시하되, 이산화탄소와 수소를 촉매층에 통과시켜 반응시킬 때의 반응압력을 30기압으로 하였다. 얻어진 반응결과는 하기 표 1에 나타내었다. The reaction was carried out in the same manner as in Example 1 except that the reaction pressure was 30 atm when the carbon dioxide and hydrogen were allowed to pass through the catalyst layer. The obtained reaction results are shown in Table 1 below.
비교예 1Comparative Example 1
상기 실시예 1과 동일한 방법으로 혼합촉매를 제조하되, 탈수반응촉매는 H-ZSM-5 제올라이트(실리카/알루미나=30) 10g을 0.1N NaNO3 수용액 100㎖에서 2회 이온교환하여서 얻은 NaH-ZSM-5형 제올라이트(Na/알루미나 원자비 = 0.9)를 사용하였으며, 얻어진 반응결과는 하기 표 1에 나타내었다.A mixed catalyst was prepared in the same manner as in Example 1, except that 10 g of H-ZSM-5 zeolite (silica / alumina = 30) was ion exchanged twice in 100 ml of 0.1 N NaNO 3 aqueous solution. -5 type zeolite (Na / alumina atomic ratio = 0.9) was used, and the reaction results obtained are shown in Table 1 below.
비교예 2Comparative Example 2
상기 실시예 1과 동일한 방법으로 혼합촉매를 제조하되, 탈수반응촉매는 이온교환되지 않은 H-ZSM-5 제올라이트(실리카/알루미나=30)를 사용하였으며, 얻어진 반응결과는 하기 표 1에 나타내었다.A mixed catalyst was prepared in the same manner as in Example 1, but a dehydration reaction catalyst was used without ion-exchanged H-ZSM-5 zeolite (silica / alumina = 30), and the reaction results obtained are shown in Table 1 below.
상기 표 1은 실시예 1∼6과 비교예 1∼2의 반응결과를 나타낸 것이다. 본 발명의 실시예 및 비교예에 의한 반응결과에 따르면 수소, 일산화탄소 및 이산화탄소를 함유하는 합성가스로부터 디메틸에테르를 제조하는 혼합 촉매의 성분 중에 탈수반응에 유효한 H-ZSM-5 촉매의 산점을 통상의 이온교환 방법에 의해 적당히 피독 처리하여 고체산의 산도가 적절하게 조절된 촉매를 사용하고, 주어진 반응온도, 반응압력 및 공간속도에서 반응을 시키면 비교적 높은 일산화탄소 전환율과 고 선택적으로 디메틸에테르를 제조할 수 있다는 것을 알 수 있다. Table 1 shows the reaction results of Examples 1 to 6 and Comparative Examples 1 and 2. According to the reaction results according to the examples and comparative examples of the present invention, the acid point of the H-ZSM-5 catalyst effective for dehydration reaction in the components of the mixed catalyst for preparing dimethyl ether from the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide is conventional. By using the catalyst with proper acidity of solid acid by appropriate poisoning treatment by ion exchange method and reacting at given reaction temperature, reaction pressure and space velocity, it is possible to prepare relatively high carbon monoxide conversion and high selectivity of dimethyl ether. It can be seen that there is.
반면에 비교예 2에서 보는 바와 같이 피독처리하지 않은 고체산 촉매를 사용할 시에는 피독처리한 것에 비하여 더욱 높은 일산화탄소 전환율을 보이는 반면 디메틸에테르의 선택성은 다소 감소하는 문제점이 있다. 한편, 비교예 1에서 보는 바와 같이 고체산 촉매에 피독처리를 많이 하면 일산화탄소 전환율이 크게 감소하는 문제점이 있다.On the other hand, as shown in Comparative Example 2, when using a non-poisoned solid acid catalyst shows a higher carbon monoxide conversion compared to the poisoning process, the selectivity of dimethyl ether has a problem that is slightly reduced. On the other hand, as shown in Comparative Example 1 there is a problem that the carbon monoxide conversion rate is greatly reduced when the poisoning treatment to a large amount of the solid acid catalyst.
도 1 및 도 2에서는 실시예 1 및 비교예 2에서 제조한 촉매에 대하여 촉매의 안정성을 비교하기 위하여 2000 시간 동안 반응을 유지시키면서 일산화탄소 전환율과 디메틸에테르의 선택성의 변화를 도시한 것이다. 1 and 2 show the change in carbon monoxide conversion and selectivity of dimethyl ether while maintaining the reaction for 2000 hours to compare the catalyst stability of the catalysts prepared in Examples 1 and 2.
비교예 2에서 보는 바와 같이 피독처리하지 않은 고체산촉매를 사용할 시에는 피독처리한 것에 비하여 초기에는 높은 일산화탄소 전환율을 보이지만 시간이 흐름에 따라 전환율이 급격하게 감소하는 경향을 보이고 있다. 한편 실시예 1에서 보는 바와 같이 Na/알루미나 원자비가 0.7 이 되도록 피독처리한 고체산촉매를 사용할 시에는 높은 일산화탄소 전환율을 보이면서도 시간이 흐름에 따라 전환율이 유지되는 경향을 보이고 있다. As shown in Comparative Example 2, when the non-toxic poisoning catalyst is used, the carbon monoxide conversion is initially higher than that of the poisoning treatment, but the conversion rate rapidly decreases with time. On the other hand, as shown in Example 1, when using a solid acid catalyst poisoned so that the Na / alumina atomic ratio is 0.7, while showing a high carbon monoxide conversion rate, the conversion rate is maintained over time.
상술한 바와 같이, 본 발명에 따른 디메틸에테르 제조용 혼합촉매를 사용하여 수소, 일산화탄소 및 이산화탄소를 함유하는 합성가스로부터 디메틸에테르를 제 조할 경우, 2000시간 이상 높은 일산화탄소 전환율을 유지하는 한편 초기반응부터 장시간 선택적으로 디메틸에테르를 제조할 수 있어 금후 산업적으로 실용 가능성이 매우 클 것으로 기대된다.As described above, when the dimethyl ether is prepared from the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide by using the mixed catalyst for preparing dimethyl ether according to the present invention, it maintains a high carbon monoxide conversion rate of 2000 hours or more and is selective from the initial reaction for a long time. Since dimethyl ether can be produced, it is expected to be very practical in the future.
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