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1. 发明授权

KR100599251B1 디메틸에테르 합성용 촉매와 촉매의 제조방법 有权
标题翻译：二甲醚合成催化剂及其制备方法
公开(公告)号：KR100599251B1
公开(公告)日：2006-07-13
申请号：KR1020040066855
申请日：2004-08-24
申请人： 에스케이 주식회사
发明人： 전기원 , 노현석 , 김재우 , 오전근 , 방진환
IPC分类号： B01J29/04 , B01J37/02
CPC分类号： B01J37/0009 , B01J29/06 , B01J29/18 , B01J29/40 , B01J29/7007 , B01J37/0018 , B01J2229/42 , C07C41/09 , C07C43/043
摘要： 본 발명은 디메틸에테르 합성용 촉매와 촉매의 제조방법에 관한 것으로서, 더욱 상세하게는 메탄올을 탈수시켜 디메틸에테르를 고효율로 합성하는데 사용하기 위한 촉매로서 (a) 소수성 제올라이트; (b) 알칼리금속, 알칼리토금속 및 암모늄 중에서 선택된 양이온; (c) 알루미나, 실리카 및 실리카-알루미나 중에서 선택된 촉매성형용 바인더겸 반응희석제가 포함되어 이루어진 신규 조성의 촉매와, 상기한 촉매 제조방법으로서 소수성 제올라이트와 알칼리금속, 알칼리토금속 및 암모늄 중에서 선택된 양이온의 전구물질을 무기 바인더(보헤마이트, 실리카졸 및 클레이 중에서 선택된 1종 또는 2종 이상)의 페이스트에 혼합하여 고온에서 소성하여 제조하는 방법; 소수성 제올라이트에 알칼리금속, 알칼리토금속 및 암모늄 중에서 선택된 양이온의 전구물질을 함침시킨 후 소성하여 얻어진 미립체에, 무기 바인더(보헤마이트, 실리카졸 및 클레이 중에서 선택된 1종 또는 2종 이상)의 페이스트를 혼합하여 고온에서 소성하여 제조하는 방법; 또는 무기 바인더(보헤마이트, 실리카졸 및 클레이 중에서 선택된 1종 또는 2종 이상)의 페이스트에 소수성 제올라이트를 혼합하여 고온에서 소성한 성형물에 암모늄 양이온의 전구물질을 함침시켜 고온에서 소성하여 제조하는 방법을 포함한다.
본 발명에 따른 촉매는 메탄올 또는 합성가스로부터 디메틸에테르 합성용 촉매로 사용되어서는 탄화수소 부산물을 생성시키지 않으면서 높은 촉매 활성이 장시간 유지되어 디메틸에테르를 현저히 높은 수율로 제조할 수 있게 된다.
디메틸에테르, 메탄올, 보헤마이트, 소수성 제올라이트, 실리카졸, 알루미나, 클레이

2. 发明公开

KR1020060033551A 단열반응기에서 미정제 메탄올로부터 디메틸에테르의제조방법 有权
标题翻译：在惰性反应器中从甲醇中制备二甲醚的方法
公开(公告)号：KR1020060033551A
公开(公告)日：2006-04-19
申请号：KR1020040082721
申请日：2004-10-15
申请人： 에스케이 주식회사
发明人： 전기원 , 노현석 , 김재우 , 오전근 , 방진환
IPC分类号： C07C41/09
CPC分类号： C07C41/09 , C07C41/01 , C07C43/043
摘要： The present invention relates a process for preparing dimethyl ether from crude methanol in an adiabatic reactor(s)/and more particularly to a process for preparing dimethyl ether wherein crude methanol containing water is dehydrated by using (1) a catalytic system in which the reactant contacts a catalyst 1 of hydrophobic zeolite partially substituted by a specific metal cation and subsequently a catalyst 2 selected from gamma-alumina or silica-alumina; and (2) an adiabatic reactor(s). In the present invention, the dehydration is accomplished effectively by avoiding the formation or byproducts and the deactivation of catalyst. Therefore, dimethyl ether useful as clean fuel and a raw material in chemical industry can be produced from crude methanol with an enhanced yield in an adiabatic reactor(s).

3. 发明授权

KR100629939B1 단열반응기에서 미정제 메탄올로부터 디메틸에테르의제조방법 有权
标题翻译：在绝热反应器中由粗甲醇制备二甲醚的方法
公开(公告)号：KR100629939B1
公开(公告)日：2006-09-28
申请号：KR1020040082721
申请日：2004-10-15
申请人： 에스케이 주식회사
发明人： 전기원 , 노현석 , 김재우 , 오전근 , 방진환
IPC分类号： C07C41/09
CPC分类号： C07C41/09 , C07C41/01 , C07C43/043
摘要： The present invention relates a process for preparing dimethyl ether from crude methanol in an adiabatic reactor(s)/and more particularly to a process for preparing dimethyl ether wherein crude methanol containing water is dehydrated by using (1) a catalytic system in which the reactant contacts a catalyst 1 of hydrophobic zeolite partially substituted by a specific metal cation and subsequently a catalyst 2 selected from gamma-alumina or silica-alumina; and (2) an adiabatic reactor(s). In the present invention, the dehydration is accomplished effectively by avoiding the formation or byproducts and the deactivation of catalyst. Therefore, dimethyl ether useful as clean fuel and a raw material in chemical industry can be produced from crude methanol with an enhanced yield in an adiabatic reactor(s).

4. 发明公开

KR1020040074519A 메탄올로부터 디메틸에테르의 제조방법 有权
标题翻译：从甲醇制备二甲基甲酰胺的方法
公开(公告)号：KR1020040074519A
公开(公告)日：2004-08-25
申请号：KR1020030010426
申请日：2003-02-19
申请人： 에스케이 주식회사
发明人： 전기원 , 노현석 , 이규호 , 김재우 , 오전근 , 방진환
IPC分类号： C07C41/09
CPC分类号： C07C41/09 , C07C43/043
摘要： PURPOSE: Provided is a method for preparing a dimethylether in high yield, by using dually-filled catalyst system in which gamma-alumina or silica-alumina that is a hydrophilic solid acid catalyst fills the top part of reactor and hydrophobic zeolite catalyst fills the lower part of the reactor. CONSTITUTION: The method comprises the steps of (i) dehydrating a methanol by passing the methanol on the solid acid catalyst, and then (ii) further dehydrating an unreacted methanol and a product of the step(i) by passing them on zeolite that is a hydrophobic solid acid catalyst. The dehydration is effected by using dually-filled catalyst system in which hydrophilic solid acid catalyst fills the top part of reactor and zeolite that is a hydrophobic solid acid catalyst fills the lower part of the reactor. The hydrophilic solid acid catalyst is a gamma-alumina or silica alumina, and the hydrophobic solid acid catalyst is a hydrophobic zeolite having SiO2/Al2O3 ratio of 20-200.
摘要翻译：目的：提供以高产率制备二甲醚的方法，通过使用双重填充的催化剂体系，其中作为亲水性固体酸催化剂的γ-氧化铝或二氧化硅 - 氧化铝填充反应器的顶部，疏水性沸石催化剂填充下部部分反应堆。方法：该方法包括以下步骤：（i）通过使甲醇通过固体酸催化剂使甲醇脱水，然后（ii）使未反应的甲醇和步骤（i）的产物进一步脱水，疏水性固体酸催化剂。脱水通过使用双重填充的催化剂体系进行，其中亲水性固体酸催化剂填充反应器的顶部，作为疏水性固体酸催化剂的沸石填充反应器的下部。亲水性固体酸催化剂是γ-氧化铝或二氧化硅氧化铝，疏水性固体酸催化剂是SiO2 / Al2O3比为20-200的疏水性沸石。

5. 发明授权

KR100501922B1 메탄올로부터 디메틸에테르의 제조방법 有权
标题翻译：从甲醇制备二甲醚的方法
公开(公告)号：KR100501922B1
公开(公告)日：2005-07-18
申请号：KR1020030010426
申请日：2003-02-19
申请人： 에스케이 주식회사
发明人： 전기원 , 노현석 , 이규호 , 김재우 , 오전근 , 방진환
IPC分类号： C07C41/09
CPC分类号： C07C41/09 , C07C43/043
摘要： The present invention relates to a process for preparing dimethyl ether from methanol. More particularly, this invention relates to an improved process for preparing dimethyl ether with high yield useful as a clean fuel as well as a raw material in chemical industry performed via a catalytic system, wherein dehydration of methanol is first carried out by using a hydrophilic solid acid catalyst and then subsequent dehydration of methanol is carried out continuously by using a hydrophobic zeolite solid acid catalyst in the concurrent presence of unreacted methanol, dimethyl ether produced and water.

6. 发明公开

KR1020050029258A 디메틸에테르 합성용 촉매와 촉매의 제조방법 有权
标题翻译：二甲醚合成催化剂及其制备方法
公开(公告)号：KR1020050029258A
公开(公告)日：2005-03-24
申请号：KR1020040066855
申请日：2004-08-24
申请人： 에스케이 주식회사
发明人： 전기원 , 노현석 , 김재우 , 오전근 , 방진환
IPC分类号： B01J29/04 , B01J37/02
CPC分类号： B01J37/0009 , B01J29/06 , B01J29/18 , B01J29/40 , B01J29/7007 , B01J37/0018 , B01J2229/42 , C07C41/09 , C07C43/043
摘要： To provide a novel catalyst used for preparing dimethyl ether at a high yield by using methanol as a raw material and dehydration reacting methanol, and a preparation process of the catalyst. The catalyst for dimethyl ether synthesis by methanol dehydration contains (a) hydrogen(H) type hydrophobic zeolite; (b) cations selected from alkali metal, alkali earth metal and ammonium; and (c) an inorganic binder selected from alumina, silica and silica-alumina. The preparation process of catalyst for dimethyl ether synthesis comprises: a process(1-i) of preparing a paste phase by adding an acidic aqueous solution or water to one or more inorganic binders selected from boehmite, silica sol and clay; a process(1-ii) of extrusion molding the mixture after mixing the paste with hydrophobic zeolite particulate and salts or hydroxide of alkali metals or alkali earth metals; and a process(1-iii) of drying the molded product, and firing the dried molded product at 500 to 800 deg.C.
摘要翻译：以甲醇为原料，通过甲醇脱水反应，提供以高产率制备二甲醚的新型催化剂及催化剂的制备方法。通过甲醇脱水合成二甲醚的催化剂含有（a）氢（H）型疏水性沸石; （b）选自碱金属，碱土金属和铵的阳离子; 和（c）选自氧化铝，二氧化硅和二氧化硅 - 氧化铝的无机粘合剂。用于二甲醚合成的催化剂的制备方法包括：通过向一种或多种选自勃姆石，硅溶胶和粘土的无机粘合剂中加入酸性水溶液或水来制备糊相的方法（1-i）将糊料与疏水性沸石颗粒和碱金属或碱土金属的盐或氢氧化物混合后，将混合物挤出成型的方法（1-ii）和干燥成型体的工序（1-iii），在500〜800℃下烧成干燥后的成型体。

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