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KR860003849A - 산화용 촉매 및 그의 제조방법 - Google Patents

산화용 촉매 및 그의 제조방법 Download PDF

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KR860003849A
KR860003849A KR1019850008660A KR850008660A KR860003849A KR 860003849 A KR860003849 A KR 860003849A KR 1019850008660 A KR1019850008660 A KR 1019850008660A KR 850008660 A KR850008660 A KR 850008660A KR 860003849 A KR860003849 A KR 860003849A
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vanadium
catalyst
phosphorus
ene
composite oxide
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푸마갈리 카틀로 (외 1)
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알렉산드로 디 시오
알루수이세 이탈리아 에스·피·에이
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Publication of KR860003849A publication Critical patent/KR860003849A/ko

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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C07C57/145—Maleic acid
    • 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
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Abstract

내용 없음

Description

산화용 촉매 및 그의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
첨부도면은 140℃에서 건조된 V―P―O 복합산화물의 기공반경이 10,000Å 이하인 기공에 대한 체적분포를 나타낸 것임.

Claims (20)

  1. 바나듐 1원자당 인 1―1.3원자로 된 바나듐/인 복합산화물을 함유하고 탄화수소를 말레산 무수물로 산화시키기 위한 촉매에 있어서, 반경 100―1,000Å을 갖는 기공의 기공체적률이 반경 10,000Å 이하를 갖는 기공들의 총기공 체적의 30% 이상인 것을 특징으로 하는 촉매.
  2. 제1항에 있어서, 100―1,000Å의 반경을 갖는 기공의 기공체적률이 10,000Å 이하의 반경을 갖는 기공들의 총기공체적의 40% 이상인 것을 특징으로 하는 촉매.
  3. 제1항 또는 제2항에 있어서, 촉매입자의 90%가 1―5마이크로미터의 직경을 갖는 것을 특징으로 하는 촉매.
  4. 제1항에 있어서, 바나듐 1원자당 인 1.05―1.2원자를 함유하는 것을 특징으로 하는 촉매.
  5. 제1항에 있어서, 바나듐 1원자당 촉진제 0.01―0.3(양호하기로는 0.05―0.15) 원자의 비율로 Li, Ti, Zr, Hf, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, B, Si, Sn, Bi, 또는 이들의 혼합물로부터 선택되는 촉진제를 함유하는 것을 특징으로 하는 촉매.
  6. 제1항 내지 제5항중 어느 하나에 있어서, 바나듐 1원자당 인원자 1―1.3의 비율로 바나듐/인 복합산화물을 함유하고 탄화수소를 말레산 무수물로 산화시키기 위한 촉매에 있어, 인 함유 화합물을 유기용매에 도입한 후, 바나듐 함유 화합물을 바나듐 1원자당 인원자 1―1.3의 비율로 0.5―4시간(양호하기로는 0.8―2시간)동안 연속적으로 가한 다음, 반응시 생성된 물을 반응혼합물로부터 연속적 및 직접적으로 제거하고, 반응혼합물을 분리한후, V―P―O 복합산화물을 고체로 단리시킨 다음 90 내지 150℃에서 건조한후 200 내지 300℃에서 활성화시키는 방법에 의해 제조된 촉매.
  7. 제1항 내지 제6항중 어느 하나에 있어서, 활성화되거나 재활성화할 촉매가 산소분자 부존재하에 300 내지 500℃에서 2―6의 탄소원자를 갖는 가스상 탄화수소성분(양호하기로는 n―부안, 1,3―부타디엔, n―부텐, 부트―1―엔, 시스―부트―2―엔, 트랜스―부트―2―엔 또는 이들의 혼합물)을 복합산화물에 통과시킴으로써 환원되는 것을 특징으로 하는 촉매.
  8. 제1항 내지 제7항중 어느 하나에 있어서, 촉매가 분활성가스 양호하기로는 CO2또는 질소를 함유하는 가스상 탄화수소 성분에 의해 환원되는 것을 특징으로 하는 촉매.
  9. 바나듐/인 복합산화물로 구성되고 탄화수소를 말레산 무수물로 산화시키기 위한 촉매의 제조방법에 있어서, 인함유 화합물을 유기용매에 도입한후, 바나듐함유 화합물을 바나듐 1원자당 인원자 1―1.3의 비율로 0.5―4시간(양호하기로는 0.8―2시간) 동안 연속적으로 가한 다음, 반응시 생성된 물을 반응 혼합물로부터 연속적 및 직접적으로 제거하고, 반응혼합물을 분리한 후, V―P―O 복합산화물을 고체로 단리시킨 다음 90 내지 150℃에서 건조한후 200 내지 300℃에서 활성화시키는 것을 특징으로 하는 산화용 촉매의 제조방법.
  10. 제9항에 있어서, 유기용매로서 C1―C6―알콜, 양호하기로는 메탄올, 에탄올, 프로판올, 부탄올, 1―프로판올, 2―프로판올, 1―부탄올, 2―부탄올, 이소부탄올, 이소―아밀알콜 또는 이들의 혼합물, 더욱 양호하기로는 이소부탄올이 사용되는 것을 특징으로 하는 방법.
  11. 제9항 또는 제10항에 있어서, 사용된 인―함유 화합물이 5가인(양호하기로는 P2O5) 또는 85중량%(양호하기로는 100중량%)의 H3PO4를 함유하는 것을 특징으로 하는 방법.
  12. 제9항에 있어서, 5가 바나듐의 무기화합물 또는 4가 바나듐의 무기화합물, 양호하기로는 V2O5이 바나듐―함유 화합물로서 사용되는 것을 특징으로 하는 방법.
  13. 제9항에 있어서, 바나듐―함유 화합물이 2마이크로미터이하(양호하기로는 1마이크로미터이하)의 입자크기로 사용되는 것을 특징으로 하는 방법.
  14. 제9항에 있어서, 바나듐 1원자당 1.05 내지 1.2원자의 인이 사용되는 것을 특징으로 하는 방법
  15. 제9항에 있어서, Li, Ti, Zr, Ht, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, B, Si, Sn 또는 Bi, 또는 이들의 혼합물로부터 선택되는 촉진제가 촉진제 대 바나듐의 비율 0.01:1 내지 0.3:1, 양호하기로는 0.05:1 내지 0.15:1로 제조과정에 첨가되는 것을 특징으로 하는 방법.
  16. 제9항에 있어서, 촉진제가 탄산염, 질산염, 염화물, 브롬화물, 황산염 또는 아세테이트 같은 염 또는 산화물로서 첨가되는 것을 특징으로 하는 방법.
  17. 제9항에 있어서, 고체가 90 내지 150℃, 양호하기로는 130 내지 140℃에서 건조되는 것을 특징으로 하는 방법.
  18. 제9항에 있어서, 활성화되거나 재활성화할 촉매가 산소분자 부존재하에 300 내지 500℃에서 2―6의 탄소원자를 갖는 가스상 탄화수소 성분, 양호하기로는 n―부탄, 1,3―부타디엔, n―부엔, 부트―1―엔, 시스―부트―2―엔, 트랜스―부트―2―엔 또는 이들의 혼합물을 복합산화물에 통과시킴으로써 환원되는 것을 특징으로 하는 방법.
  19. 제9항에 있어서, 촉매가 불활성가스, 양호하기로는 CO2또는 질소를 함유하는 가스상 탄화수소 성분에 의해 환원되는 것을 특징으로 하는 방법.
  20. 제1항에 있어서, 1,3―부타디엔, n―부탄, n―부텐, 부트―1―엔, 시스―부트―1―엔, 트랜스―부트―2―엔 또는 이들의 혼합물, 양호하기로는 n―부탄올 말레산 무수물로 부분적으로 산화시키기 위해 사용되는 촉매.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019850008660A 1984-11-20 1985-11-20 산화용 촉매 및 그의 제조방법 KR860003849A (ko)

Applications Claiming Priority (2)

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IT23,671A/84 1984-11-20
IT23671/84A IT1177272B (it) 1984-11-20 1984-11-20 Catalizzatore per reazioni di ossidazione e procedimento per la sua produzione

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US (2) US4668652A (ko)
EP (1) EP0182078B1 (ko)
JP (1) JPS61181540A (ko)
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CN (1) CN1005685B (ko)
AR (1) AR240877A1 (ko)
AT (1) ATE60256T1 (ko)
BR (1) BR8505808A (ko)
CA (1) CA1264728A (ko)
DE (1) DE3581496D1 (ko)
ES (1) ES8608927A1 (ko)
IN (1) IN166342B (ko)
IT (1) IT1177272B (ko)
NO (1) NO167552C (ko)
TR (1) TR22772A (ko)
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NO167552B (no) 1991-08-12
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US4713464A (en) 1987-12-15
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DE3581496D1 (de) 1991-02-28
CN85107878A (zh) 1986-05-10
AR240877A2 (es) 1991-03-27
NO854616L (no) 1986-05-21
JPH0582261B2 (ko) 1993-11-18
ATE60256T1 (de) 1991-02-15
CA1264728A (en) 1990-01-23
EP0182078B1 (de) 1991-01-23
IN166342B (ko) 1990-04-14
JPS61181540A (ja) 1986-08-14
EP0182078A2 (de) 1986-05-28
IT8423671A1 (it) 1986-05-20
US4668652A (en) 1987-05-26
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