KR950000639A - 불포화 알데하이드 및 불포화 카복실산의 제조방법 - Google Patents
불포화 알데하이드 및 불포화 카복실산의 제조방법 Download PDFInfo
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- KR950000639A KR950000639A KR1019940014514A KR19940014514A KR950000639A KR 950000639 A KR950000639 A KR 950000639A KR 1019940014514 A KR1019940014514 A KR 1019940014514A KR 19940014514 A KR19940014514 A KR 19940014514A KR 950000639 A KR950000639 A KR 950000639A
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- Prior art keywords
- gas phase
- catalytic oxidation
- phase catalytic
- catalyst
- molybdenum oxide
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- 238000004519 manufacturing process Methods 0.000 title claims 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 238000007254 oxidation reaction Methods 0.000 claims abstract 27
- 230000003647 oxidation Effects 0.000 claims abstract 26
- 230000003197 catalytic effect Effects 0.000 claims abstract 23
- 239000007789 gas Substances 0.000 claims abstract 23
- 238000000034 method Methods 0.000 claims abstract 18
- 239000003054 catalyst Substances 0.000 claims abstract 17
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract 16
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 8
- 238000002156 mixing Methods 0.000 claims abstract 7
- 150000001299 aldehydes Chemical class 0.000 claims abstract 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 5
- 239000001301 oxygen Substances 0.000 claims abstract 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract 3
- 230000001172 regenerating effect Effects 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 6
- 229910052742 iron Inorganic materials 0.000 claims 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 3
- 229910052787 antimony Inorganic materials 0.000 claims 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 3
- 229910052785 arsenic Inorganic materials 0.000 claims 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims 3
- 229910052797 bismuth Inorganic materials 0.000 claims 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 3
- 229910052796 boron Inorganic materials 0.000 claims 3
- 229910052792 caesium Inorganic materials 0.000 claims 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 3
- 229910052791 calcium Inorganic materials 0.000 claims 3
- 239000011575 calcium Substances 0.000 claims 3
- 239000010941 cobalt Substances 0.000 claims 3
- 229910017052 cobalt Inorganic materials 0.000 claims 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 3
- 239000011133 lead Substances 0.000 claims 3
- 239000011777 magnesium Substances 0.000 claims 3
- 229910052749 magnesium Inorganic materials 0.000 claims 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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 claims 3
- 239000000203 mixture Substances 0.000 claims 3
- 229910052750 molybdenum Inorganic materials 0.000 claims 3
- 239000011733 molybdenum Substances 0.000 claims 3
- 238000000465 moulding Methods 0.000 claims 3
- 229910052759 nickel Inorganic materials 0.000 claims 3
- 229910052698 phosphorus Inorganic materials 0.000 claims 3
- 239000011574 phosphorus Substances 0.000 claims 3
- 229910052700 potassium Inorganic materials 0.000 claims 3
- 239000011591 potassium Substances 0.000 claims 3
- 229910052701 rubidium Inorganic materials 0.000 claims 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 3
- 229910052710 silicon Inorganic materials 0.000 claims 3
- 239000010703 silicon Substances 0.000 claims 3
- 229910052714 tellurium Inorganic materials 0.000 claims 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims 3
- 229910052716 thallium Inorganic materials 0.000 claims 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims 3
- 239000011135 tin Substances 0.000 claims 3
- 229910052718 tin Inorganic materials 0.000 claims 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 3
- 229910052721 tungsten Inorganic materials 0.000 claims 3
- 239000010937 tungsten Substances 0.000 claims 3
- 229910052725 zinc Inorganic materials 0.000 claims 3
- 239000011701 zinc Substances 0.000 claims 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims 2
- 239000012495 reaction gas Substances 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000005078 molybdenum compound Substances 0.000 claims 1
- 150000002752 molybdenum compounds Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
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- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
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- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
본 발명은 (ⅰ) 일반식 MoaBibFecAeBfCfDgOx의 복합 산화물을 포함한 촉매, 및 (ⅱ) 그 자체로 가스상 접촉 산화반응에 거의 불활성인 몰리브덴 산화물의 존재하에 프로필렌, 이소부틸레 또는 3급 부탄올을 산소분자와 가스상 접촉 산화반응시킴을 포함하는 불포화 알데하이드 및 불포화 카복실산의 제조방법 ; 가스상 접촉 산화반응으로 인해 성능저하된 촉매를 몰리브덴 산화물과 혼합한 후 상기 촉매를 재사용하는 방법 및 성능저하된 촉매를 몰리브덴 산화물과 혼합하여 상기 촉매를 재생시키는 방법에 관한 것이다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (14)
- (ⅰ) 하기 일반식으로 나타내지는 복합 산화물을 포함한 촉매 및 (ⅱ) 그 자체로 가스상 접촉 산화반응에 거의 불활성인 몰리브덴 산화물의 존재하에 프로필렌, 이소부틸렌 또는 3급 부탄올을 산소 분자와 가스상 접촉 산화반응시켜 상응하는 불포화 알데하이드 및 불포화 카복실산을 제조함을 포함하는, 불포화 알데하이드 및 카복실산의 제조방법 :MoaBibFecAeBfCfDgOx상기식에서, Mo, Bi, Fe 및 O는 각각 몰리브덴, 비스무쓰, 철 및 산소를 나타내고, A는 니켈 및/또는 코발트를 나타내고, B는 망간, 아연, 칼슘, 마그네슘, 주석 및 납으로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, C는 인, 붕소, 비소, 텔루륨, 텅스텐, 안티몬, 및 규소로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, D는 칼륨, 루비듐, 세슘 및 탈륨으로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, a가 12일때, 0〈b≤10, 0〈c≤10, 1≤d≤10, 1≤e≤10, 0≤f≤20 및 0〈g≤2이고, x는 각각의 원소의 산화상태에 따른 값을 갖는다.
- 제 1 항에 있어서, 상기 불포화 알데하이드 및 불포화 카복실산이 아크롤레인 및 아크릴산, 또는 메타크롤레인 및 메타크릴산인 방법.
- 제 1 항에 있어서, 그 자체로 상기 가스상 접촉 산화반응에 거의 불활성인 상기 몰리브덴 산화물이 몰리브덴 화합물을 550 내지 700℃의 온도에서 소성시켜 제조한 몰리브덴 산화물인 방법.
- 제 1 항에 있어서, 그 자체로 상기 가스상 접촉 산화방응에 거의 불활성인 상기 촉매 및 상기 몰리브덴 산화물이 상기 촉매와 상기 몰리브덴 산화물의 혼합물로부터 형성된 성형물의 형태로 사용되는 방법.
- 제 1 항에 있어서, 상기 가스상 접촉 산화반응을 고정상 다관형 반응기에서 수행하는 방법.
- 제 5 항에 있어서, 상기 몰리브덴 산화물이 고정상 다관형 반응기의 반응가스 유입부에 존재하는 방법.
- 가스상 접촉 산화반응으로 인해 성능저하된 촉매를 그 자체로 상기 가스상 접촉 산화반응에 거의 불활성인 몰리브덴 산화물과 혼합한 후 사용함을 특징으로 하며, 하기 일반식으로 나타내지는 복합 산화물을 포함한 촉매의 존재하에 프로필렌, 이소부틸렌 또는 3급 부탄올을 산소 분자와 가스상 접촉 산화반응시켜 불포화 알데하이드 및 카복실산을 제조하는 방법 :MoaBibFecAeBfCfDgOx상기식에서, Mo, Bi, Fe 및 O는 각각 몰리브덴, 비스무쓰, 철 및 산소를 나타내고, A는 니켈 및/또는 코발트를 나타내고, B는 망간, 아연, 칼슘, 마그네슘, 주석 및 납으로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, C는 인, 붕소, 비소, 텔루륨, 텅스텐, 안티몬 및 규소로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, D는 칼륨, 루비듐, 세슘 및 탈륨으로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, a가 12일때, 0〈b≤10, 0〈c≤10, 1≤d≤10, 0≤e≤10, 0≤f≤20 및 0≤g≤2이고, x는 각각의 원소의 산화상태에 따른 값을 갖는다.
- 제 7 항에 있어서, 상기 가스상 접촉 산화반응을 고정상 다관형 반응기에서 수행하는 방법.
- 제 8 항에서 있어서, 상기 혼합을, 상기 가스상 접촉 산화반응으로 인해 성능저하된 성형된 촉매를 분쇄하고, 이를 그 자체로 상기 가스상 접촉 산화반응에 거의 불활성인 상기 몰리브덴 산화물의 분말과 블렌딩하고, 이 혼합물을 성형시켜 수행하는 방법.
- 제 8 항에 있어서, 상기 혼합을, 상기 가스상 산화반응으로 인해 성능저하된 성형된 촉매를 그 자체로 상기 가스상 접촉 산화반응에 거의 불활성인 상기 몰리브덴 산화물을 함유한 성형물과 블렌딩하여 수행하는 방법.
- 제 9 항에 있어서, 그 자체로 상기 가스상 접촉 산화반응에 거의 불활성인 상기 몰리브덴 산화물을 상기 가스상 접촉 산화반응으로 인해 성능 저하된 촉매를 기준으로 3 내지 20중량%의 양으로 사용하는 방법.
- 제10항에 있어서, 그 자체로 상기 가스상 접촉 산화반응에 거의 불활성인 상기 몰리브덴 산화물을 상기 가스상 접촉 산화반응으로 인해 성능 저하된 촉매를 기준으로 5 내지 40중량%의 양으로 사용하는 방법.
- 제 8 항, 제 9 항 또는 제10항에 있어서, 반응가스의 유입부에 존재하고 상기 가스상 접촉 산화반응으로 인해 성능저하된 상기 촉매의 일부를 그 자체로 상기 가스상 접촉 산화반응에 거의 불활성인 상기 몰리브덴 산화물과의 혼합물로 사용하는 방법.
- (ⅰ) 프로필렌, 이소부틸렌 또는 3급 부탄올을 산소분자와 가스상 접촉 산화반응시키는데 사용되고 이 반응으로 인해 성능저하되는, 하기 일반식으로 나타내지는 복합 산화물을 포함한 촉매 및 (ⅱ) 그 자체로 상기 가스상 접촉 산화반응에 거의 불활성인 몰리브덴 산화물을 혼합함을 포함하는, 촉매의 재생방법 :MoaBibFecAeBfCfDgOx상기식에서, Mo, Bi, Fe 및 O는 각각 몰리브덴, 비스무쓰, 철 및 산소를 나타내고, A는 니켈 및/또는 코발트를 나타내고, B는 망간, 아연, 칼슘, 마그네슘, 주석, 및 납으로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, C는 인, 붕소, 비소, 텔루륨, 텅스텐, 안티몬 및 규소로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, D는 칼륨, 루비듐, 세슘 및 탈륨으로 이루어진 그룹중에서 선택된 하나 이상의 원소를 나타내고, a가 12일때, 0〈b≤10, 0〈c≤10, 1≤d≤10, 0≤e≤10, 0≤f≤20 및 0〈g≤2이고, x는 각각의 원소의 산화상태에 따른 값을 갖는다.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
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JPS55113730A (en) * | 1979-02-26 | 1980-09-02 | Mitsubishi Petrochem Co Ltd | Preparation of acrolein and acrylic acid |
JPS5756044A (en) * | 1980-09-20 | 1982-04-03 | Mitsui Toatsu Chem Inc | Method for reactivation of catalyst |
DE3217700A1 (de) * | 1981-05-15 | 1982-12-02 | Nitto Chemical Industry Co., Ltd., Tokyo | Verfahren zur verbesserung der aktivitaet von tellur enthaltenden metalloxidkatalysatoren |
DE3311521A1 (de) † | 1982-07-17 | 1984-01-19 | Skw Trostberg Ag, 8223 Trostberg | Verfahren zur reaktivierung von molybdaenhaltigen katalysatoren |
JPS5976544A (ja) * | 1982-10-26 | 1984-05-01 | Nitto Chem Ind Co Ltd | 鉄・アンチモン系金属酸化物触媒の再生方法 |
JPS5976543A (ja) * | 1982-10-26 | 1984-05-01 | Nitto Chem Ind Co Ltd | 鉄・アンチモン系金属酸化物触媒の再生法 |
EP0456837B1 (en) * | 1989-12-06 | 1996-10-09 | Nippon Shokubai Co., Ltd. | Process for producing methacrolein and methacrylic acid |
DE4023239A1 (de) * | 1990-07-21 | 1992-01-23 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von propen oder iso-buten zu acrolein oder methacrolein |
DE19623416A1 (de) † | 1996-06-12 | 1997-12-18 | Basf Ag | Teilchenförmige Pfropfcopolymerisate und diese enthaltende thermoplastische Formmassen mit verbesserter Einfärbbarkeit |
-
1994
- 1994-06-24 KR KR1019940014514A patent/KR100277241B1/ko not_active IP Right Cessation
- 1994-06-24 DE DE69407669T patent/DE69407669T3/de not_active Expired - Lifetime
- 1994-06-24 CN CN94107759A patent/CN1062550C/zh not_active Expired - Fee Related
- 1994-06-24 EP EP94109830A patent/EP0630879B2/en not_active Expired - Lifetime
- 1994-06-27 US US08/266,190 patent/US5602280A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0630879A1 (en) | 1994-12-28 |
EP0630879B1 (en) | 1998-01-07 |
KR100277241B1 (ko) | 2001-02-01 |
CN1062550C (zh) | 2001-02-28 |
DE69407669T2 (de) | 1998-09-10 |
DE69407669T3 (de) | 2002-04-25 |
CN1099024A (zh) | 1995-02-22 |
US5602280A (en) | 1997-02-11 |
DE69407669D1 (de) | 1998-02-12 |
EP0630879B2 (en) | 2001-04-11 |
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