KR20040086431A - 지지된 은 촉매 및 이 촉매를 사용한 에폭시화 방법 - Google Patents
지지된 은 촉매 및 이 촉매를 사용한 에폭시화 방법 Download PDFInfo
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- KR20040086431A KR20040086431A KR20047013119A KR20047013119A KR20040086431A KR 20040086431 A KR20040086431 A KR 20040086431A KR 20047013119 A KR20047013119 A KR 20047013119A KR 20047013119 A KR20047013119 A KR 20047013119A KR 20040086431 A KR20040086431 A KR 20040086431A
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- KR
- South Korea
- Prior art keywords
- carrier
- catalyst
- alumina
- mixture
- pore volume
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 56
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 37
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- 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 67
- 150000001336 alkenes Chemical class 0.000 claims abstract description 59
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- 239000002245 particle Substances 0.000 claims abstract description 39
- 238000009826 distribution Methods 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 150000002832 nitroso derivatives Chemical class 0.000 description 1
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- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
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- 235000017281 sodium acetate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
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Abstract
Description
담체 | 표면적(㎡/g) | 물 흡수량(g/g) | 세공 부피(ml/g) | 세공 크기 분포 | ||
< 0.2 ㎛(v%) | 0.2 내지 10 ㎛(v%; ml/g) | > 10 ㎛(v%) | ||||
A | 2.04 | 0.42 | 0.41 | 5 | 92; 0.37 | 3 |
B | 2.11 | 0.49 | 0.42 | 9 | 72; 0.30 | 19 |
C | 2.51 | 0.55 | 0.56 | 3 | 95; 0.53 | 2 |
D* | 0.73 | 0.40 | 0.40 | < 1 | 64; 0.26 | 36 |
*비교용 담체 |
촉매 | 세슘 함량(mmol/kg) | 선택성(%) | 온도(℃) |
A* | 5.4 | 82.5 | 224 |
B* | 5.3 | 81.9 | 232 |
D** | 3.0 | 81.9 | 240 |
*본 발명의 촉매**비교용 촉매 |
Claims (17)
- 담체, 및 촉매의 중량에 대해 적어도 10 g/kg의 양으로 이 담체 상에 침착된 은을 함유한 촉매로서, 상기 담체가 적어도 1 ㎡/g의 표면적, 및 0.2 내지 10 ㎛ 범위인 직경의 세공이 총 세공 부피의 적어도 70%를 나타내고 이러한 세공은 함께 담체의 중량에 대해 적어도 0.27 ml/g의 세공 부피를 제공하는 정도의 세공 크기 분포를 갖는 것을 특징으로 하는 촉매.
- 제1항에 있어서, 담체가 0.2 내지 10 ㎛ 범위인 직경의 세공이 총 세공 부피의 75% 초과를 나타내고 이러한 세공은 함께 담체의 중량에 대해 적어도 0.28 ml/g의 세공 부피를 제공하는 정도; 10 ㎛를 초과하는 직경의 세공이 총 세공 부피의 20% 미만을 나타내는 정도; 및 0.2 ㎛ 미만인 직경의 세공이 총 세공 부피의 10% 미만을 나타내는 정도의 세공 크기 분포를 갖는 것을 특징으로 하는 촉매.
- 제2항에 있어서, 담체가 0.2 내지 10 ㎛ 범위인 직경의 세공이 총 세공 부피의 90% 초과를 나타내고 이러한 세공은 함께 담체의 중량에 대해 적어도 0.3 ml/g의 세공 부피를 제공하는 정도; 10 ㎛를 초과하는 직경의 세공이 총 세공 부피의 10% 미만을 나타내는 정도; 및 0.2 ㎛ 미만인 직경의 세공이 총 세공 부피의 7% 미만을 나타내는 정도의 세공 크기 분포를 갖는 것을 특징으로 하는 촉매.
- 제1항 내지 제3항 중 어느 한 항에 있어서, 담체가 0.28 내지 0.8 ml/g 범위의 총 세공 부피 및 최대 2.9 ㎡/g의 표면적, 구체적으로는 0.3 내지 0.7 ml/g 범위의 총 세공 부피 및 1 내지 2.6 ㎡/g 범위의 표면적을 갖는 것을 특징으로 하는 촉매.
- 제1항 내지 제4항 중 어느 한 항에 있어서, 담체가 적어도 95 wt%의 α-알루미나를 포함하고, 0.3 내지 0.8 g/g 범위의 물 흡수량 및 1.4 내지 2.6 ㎡/g 범위의 표면적을 갖는 것을 특징으로 하는 촉매.
- 제1항 내지 제5항 중 어느 한 항에 있어서, 은이 촉매의 중량에 대해 50 내지 500 g/kg, 구체적으로는 50 내지 400 g/kg, 보다 구체적으로는 50 내지 250 g/kg의 양으로 담체 상에 침착되는 것을 특징으로 하는 촉매.
- 제1항 내지 제6항 중 어느 한 항에 있어서, 담체가 결정질의 실리카 함유 조성물 형성 억제제를 포함한 실리카 함유 조성물을 주성분으로 하는 결합 물질을 포함하는 것을 특징으로 하는 촉매.
- 제7항에 있어서, 담체는 적어도 95 wt%의 알루미나 함량을 갖고, 결합 물질은 수화 알루미나, 비결정질 실리카 화합물, 및 알칼리 금속 화합물을 주성분으로하는 것을 특징으로 하는 촉매.
- 제1항 내지 제8항 중 어느 한 항에 있어서, 은 외에 담체 상에 침착되는, 질소, 황, 인, 붕소, 플루오르, IA족 금속, ⅡA족 금속, 레늄, 몰리브덴, 텅스텐, 크로뮴, 티타늄, 하프늄, 지르코늄, 바나듐, 탈륨, 토륨, 탄탈, 니오븀, 갈륨, 및 게르마늄과 이들의 혼합물의 그룹에서 선택된 추가 성분 중 1종 이상을 함유하는 것을 특징으로 하는 촉매.
- 제1항 내지 제9항 중 어느 한 항에 있어서, 은 외에 담체 상에 침착되는, 레늄, 몰리브덴, 텅스텐, IA족 금속, 및 질산염 또는 아질산염 형성 화합물 중 1종 이상을 함유하는 것을 특징으로 하는 촉매.
- 제9항 또는 제10항에 있어서, IA족 금속이 리튬, 칼륨, 루비듐 및 세슘 중에서 선택되는 것을 특징으로 하는 촉매.
- 제1항 내지 제11항 중 어느 한 항에 있어서,a) 적어도 1 ㎡/g의 표면적, 및 0.2 내지 10 ㎛ 범위인 직경의 세공이 총 세공 부피의 적어도 70%를 나타내고 이러한 세공은 함께 담체의 중량에 대해 적어도 0.27 ml/g의 세공 부피를 제공하는 정도의 세공 크기 분포를 갖는 담체를 선택하는 단계; 및b) 상기 담체 상에, 촉매의 중량에 대해 적어도 10 g/kg의 양으로 적어도 은을 침착시키는 단계를 포함하는 촉매 제조 방법.
- a) 10 ㎛ 초과 100 ㎛ 이하의 평균 입자 크기(d50)를 갖는 제1 α-알루미나 미립자 50 내지 90 wt%; 및b) 1 내지 10 ㎛의 평균 입자 크기(d50)를 갖는 제2 α-알루미나 미립자 10 내지 50 wt%를 포함한 혼합물을 형성시키는 단계로서, wt%는 혼합물내 총 α-알루미나의 중량을 기준으로 한 것인 단계, 및 상기 혼합물을 소성(燒成)하여 담체를 형성시키는 단계를 포함하는 방법으로 수득한 담체 상에 은을 침착시키는 단계를 포함하는 촉매 제조 방법.
- 제13항에 있어서, 담체는 적어도 95 wt%의 알루미나 함량을 갖고, 혼합물은,a) 혼합물내 총 α-알루미나의 중량에 대해 65 내지 75 wt%인, 11 내지 60 ㎛의 평균 입자 크기(d50)를 갖는 제1 α-알루미나 미립자;b) 혼합물내 총 α-알루미나의 중량에 대해 25 내지 35 wt%인, 2 내지 6 ㎛의 평균 입자 크기(d50)를 갖는 제2 α-알루미나 미립자;c) 혼합물내 총 α-알루미나의 중량에 대한 산화 알루미늄으로서 계산한, 수화 알루미나 2 내지 5 wt%;d) 혼합물내 총 α-알루미나의 중량에 대한 산화 실리콘으로서 계산한, 비결정질 실리카 화합물 0.2 내지 0.8 wt%; 및e) 혼합물내 총 α-알루미나의 중량에 대한 알칼리 금속 산화물로서 계산한, 알칼리 금속 화합물 0.05 내지 0.3 wt%를 포함하며, 상기 혼합물로 성형체를 만들어 이 성형체를 1250 내지 1500℃의 온도에서 소성하는 것을 특징으로 하는 촉매 제조 방법.
- 제1항 내지 제11항 중 어느 한 항의 촉매 존재하에, 또는 제12항 내지 제14항 중 어느 한 항의 방법으로 수득한 촉매 존재하에, 올레핀을 산소와 반응시키는 단계를 포함하는 올레핀 에폭시화 방법.
- 제15항에 있어서, 올레핀이 에틸렌인 것을 특징으로 하는 올레핀 에폭시화 방법.
- 제15항 또는 제16항의 올레핀 에폭시화 방법으로 수득한 산화 올레핀을 1,2-디올, 1,2-디올 에테르, 또는 알칸올아민으로 전환시키는 단계를 포함하는, 산화 올레핀을 사용하여 1,2-디올, 1,2-디올 에테르, 또는 알칸올아민을 제조하는 방법.
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-
2003
- 2003-02-25 AU AU2003217756A patent/AU2003217756B2/en not_active Ceased
- 2003-02-25 BR BRPI0307958-9B1A patent/BR0307958B1/pt active IP Right Grant
- 2003-02-25 CN CNB2007101263803A patent/CN100553763C/zh not_active Expired - Lifetime
- 2003-02-25 RU RU2004128458/04A patent/RU2342190C2/ru active
- 2003-02-25 CA CA2477069A patent/CA2477069C/en not_active Expired - Lifetime
- 2003-02-25 MX MXPA04008167A patent/MXPA04008167A/es not_active Application Discontinuation
- 2003-02-25 US US10/374,287 patent/US20030162984A1/en not_active Abandoned
- 2003-02-25 EP EP03713718A patent/EP1511563B1/en not_active Expired - Lifetime
- 2003-02-25 JP JP2003570981A patent/JP4335692B2/ja not_active Expired - Lifetime
- 2003-02-25 WO PCT/US2003/005902 patent/WO2003072246A2/en active Application Filing
- 2003-02-25 CN CNB038061961A patent/CN100408168C/zh not_active Expired - Lifetime
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2004
- 2004-08-20 ZA ZA200406645A patent/ZA200406645B/xx unknown
- 2004-08-23 KR KR1020047013119A patent/KR101001503B1/ko active IP Right Grant
- 2004-11-30 IN IN2399DE2004 patent/IN2004DE02399A/en unknown
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2007
- 2007-04-12 US US11/734,516 patent/US20070184973A1/en not_active Abandoned
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2009
- 2009-03-10 US US12/401,086 patent/US20090177016A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP1511563A2 (en) | 2005-03-09 |
CN101085425A (zh) | 2007-12-12 |
CA2477069C (en) | 2012-08-21 |
RU2342190C2 (ru) | 2008-12-27 |
CA2477069A1 (en) | 2003-09-04 |
BR0307958B1 (pt) | 2013-07-09 |
AU2003217756A1 (en) | 2003-09-09 |
RU2004128458A (ru) | 2005-04-10 |
IN2004DE02399A (ko) | 2005-04-01 |
MXPA04008167A (es) | 2004-11-26 |
JP2005518276A (ja) | 2005-06-23 |
US20090177016A1 (en) | 2009-07-09 |
BR0307958A (pt) | 2004-12-21 |
CN1642637A (zh) | 2005-07-20 |
JP4335692B2 (ja) | 2009-09-30 |
WO2003072246A2 (en) | 2003-09-04 |
AU2003217756B2 (en) | 2008-11-20 |
EP1511563B1 (en) | 2012-11-28 |
KR101001503B1 (ko) | 2010-12-14 |
US20070184973A1 (en) | 2007-08-09 |
ZA200406645B (en) | 2006-05-31 |
CN100553763C (zh) | 2009-10-28 |
US20030162984A1 (en) | 2003-08-28 |
WO2003072246A3 (en) | 2004-01-08 |
CN100408168C (zh) | 2008-08-06 |
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