KR940013595A - Highly Active Residual Catalyst - Google Patents

Highly Active Residual Catalyst Download PDF

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KR940013595A
KR940013595A KR1019920024982A KR920024982A KR940013595A KR 940013595 A KR940013595 A KR 940013595A KR 1019920024982 A KR1019920024982 A KR 1019920024982A KR 920024982 A KR920024982 A KR 920024982A KR 940013595 A KR940013595 A KR 940013595A
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diameter
pore volume
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pores
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KR100241174B1 (en
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에스. 드렐켈 리챠드
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윌리암 제랄드 덕
셰브런 리써치 앤드 테크놀로지 캄파니
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • B01J35/63—Pore volume
    • 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
    • B01J35/647—2-50 nm
    • 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
    • B01J35/66—Pore distribution
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

본 발명은 촉매활성이 개선된 촉매, 이 촉매를 제조하는 방법 및 금속-함유 중질 공급원료를 수소화 탈황시키기 위해 이 촉매를 사용하는 방법에 관한 것이다. 이 촉매는 직경이 70 내지 130Å인 세공이 세공용적의 70용적%를 차지하며 알루미나로 이루어진 지지체상의 VIB족 및 VIII족 금속 또는 금속화합물을 함유한다.The present invention relates to a catalyst having improved catalytic activity, a process for preparing the catalyst and a process for using the catalyst for hydrodesulfurization of a metal-containing heavy feedstock. The catalyst comprises 70% by volume of pores having a diameter of 70 to 130 mm 3 and occupies 70% by volume of the pore volume and contains Group VIB and Group VIII metals or metal compounds on a support made of alumina.

Description

고활성 잔유 촉매Highly Active Residual Catalyst

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음As this is a public information case, the full text was not included.

제 1 도는 본발명 촉매의 세공직경분포를 나타낸다,1 shows the pore diameter distribution of the catalyst of the present invention,

제 2 도는 선행기술 촉매의 세공직경분포를 나타낸다,2 shows the pore diameter distribution of the prior art catalyst,

제 3 도는 760°F+ 아랍중질 상압잔유의 0.35 액체시간당 공간속도 공급물 유속에서 55%의 미량탄소잔유(MCR) 전화율을 유지시키는데 필요한 반응기 온도를 나타낸다.3 shows the reactor temperature needed to maintain a 55% trace carbon residue (MCR) conversion rate at 0.35 liquid hourly space velocity feed flow rate of 760 ° F + Arab heavy atmospheric residue.

Claims (23)

알루미나 지지체; 및 VIB족 및 VIII족 원소의 금속, 산화물 및 황화물로 이루어진 그룹중에서 선택된 VIB족 성분 및 VIII족 성분으로 이루어지며; 상기 지지체의 세공용적이 g당 약 0.5 내지 약 1.1㎤ 범위이고, 직경이 70 내지 130Å인 세공의 세공용적이 70% 이상이며, 직경이 300Å 이상인 세공의 세공용적이 5% 미만이고, 세공직경이 1000Å 이상인 세공의 세공용적이 2% 미만임을 특징으로 하는, 중유의 수소화 탈황에 개선된 활성을 나타내는 촉매조성물.Alumina support; And a Group VIB component and a Group VIII component selected from the group consisting of metals, oxides and sulfides of Group VIB and Group VIII elements; The pore volume of the support ranges from about 0.5 to about 1.1 cm 3 per g, the pore volume of the pores having a diameter of 70 to 130 mm 3 is 70% or more, the pore volume of the pores having a diameter of 300 mm 3 or more is less than 5%, and the pore diameter is A catalyst composition exhibiting improved activity for hydrodesulfurization of heavy oil, characterized in that the pore volume of pores of 1000 kPa or more is less than 2%. (a) 주로 알파-알루미나 1수화물을 함유하는 해교가능한 입자상고체를 산수용액과 혼합시켜 약 3.0 내지 4.5범위의 pH로 되게함으로써 상기 입자상 고체를 처리하고; (b) 처리된 고체중에 산의 당량당 염기의 양을 약 0.2 내지 약 0.5당량의 범위로 함유하는 질소염기의 수용액을 혼합시켜 혼합된 산의 적어도 일부를 중화시키고; (c) 중화되거나 부분적으로 중화된 고체를 성형시키고; (d) 성형된 고체를 약 150°F 내지 1700°F 범위의 온도에서 건조시키고 소성시켜 완결시킴으로써 제조되며, 세공용적이 g당 0.5㎤ 이상이고, 세공직경이 70 내지 130Å 범위인 세공의 세공용적이 70% 이상이며, 직경이 300Å 이상인 세공의 세공용적이 5% 미만이고, 세공직경이 1000Å 이상인 세공의 세공용적이 2% 미만인 다공성 지지체를, 열에 의해 금속산화물로 분해될 수 있는 VIB족 및 VIII족 금속화합물로 이루어진 그룹중에서 선택된 하나이상의 촉매물질 또는 촉매물질 전구체를 함유하는 수용액으로 함침시킨 후, 건조시키고, 생성된 함침시킨 지지체를 소성시킴을 특징으로 하여, 중유의 수소화 탈황용 고활성촉매를 제조하는 방법.(a) treating the particulate solid by mixing the peptizable particulate solid containing predominantly alpha-alumina monohydrate with an acid aqueous solution to a pH in the range of about 3.0 to 4.5; (b) neutralizing at least a portion of the mixed acid by mixing an aqueous solution of nitrogen base containing in the range of about 0.2 to about 0.5 equivalents of base per equivalent of acid in the treated solid; (c) forming a neutralized or partially neutralized solid; (d) prepared by drying the molded solid at a temperature in the range of about 150 ° F. to 1700 ° F., and calcining to complete, pore volume of pores having a pore volume of at least 0.5 cm 3 per g and a pore diameter in the range of 70 to 130 mm 3. Group VIB and Group VIII, which can decompose a porous support having a pore volume of less than 5% and a pore volume of less than 2% with a pore diameter of 300 mm or more and less than 2% with a pore diameter of 1000 mm or more to a metal oxide by heat. After impregnating with an aqueous solution containing at least one catalyst material or catalyst material precursor selected from the group consisting of a group metal compound, it is dried, and the resulting impregnated support is calcined. How to manufacture. 중유를 수소화 탈황조건하에서; 세공용적이 g당 약 0.5 내지 약 1.1㎤ 이고, 직경이 70 내지 130Å인 세공의 세공용적이 70% 이상이며, 직경이 300Å 이상인 세공의 세공용적이 5% 미만이고, 세공직경이 1000Å 이상인 세공의 세공용적이 2% 미만인 알루미나 지지체; 및 VIB족 및 VIII족 원소의 금속, 산화물 및 황화물로 이루어진 그룹중에서 선택된 VIB족 성분 및 VIII족 성분으로 이루어진 촉매와 접촉시킴을 특징으로 하여, 중유를 수소화 탈황시키는 방법.Heavy oil under hydrodesulfurization; The pore volume is about 0.5 to about 1.1 cm 3 per g, the pore volume of the pore having a diameter of 70 to 130 mm 3 is 70% or more, the pore volume of the pore having a diameter of 300 mm 3 or more is less than 5%, and the pore diameter is 1000 mm 3 or more An alumina support having a pore volume of less than 2%; And contacting a catalyst comprising a Group VIB component and a Group VIII component selected from the group consisting of metals, oxides and sulfides of Group VIB and Group VIII elements. 제 1 항에 있어서, 직경이 70 내지 130Å인 세공의 세공용적이 80% 이상인 촉매조성물.The catalyst composition according to claim 1, wherein the pore volume of pores having a diameter of 70 to 130 mm 3 is 80% or more. 제 1 항에 있어서, VIB족 및 VIII족 화합물이 코발트, 니켈 및 몰리브덴의 화합물로 이루어진 그룹중에서 선택됨을 추가의 특징으로 하는 촉매조성물.The catalyst composition of claim 1, wherein the Group VIB and Group VIII compounds are selected from the group consisting of compounds of cobalt, nickel and molybdenum. 제 1 항에 있어서, 세공용적의 5% 미만이 140Å 이상의 직경을 갖는 세공인 촉매조성물.The catalyst composition according to claim 1, wherein less than 5% of the pore volumes are pores having a diameter of 140 mm 3 or more. 제 1 항에 있어서, 1000Å 이상의 직경을 갖는 세공이 세공용적의 1% 미만을 구성하는 촉매조성물.The catalyst composition of claim 1, wherein the pores having a diameter of 1000 mm 3 or more constitute less than 1% of the pore volume. 제 2 항에 있어서, 산용액이 질산, 염산, 플루오로화수소산 및 브롬화수소산의 산용액중에서 선택되는 방법.3. The process according to claim 2, wherein the acid solution is selected from acid solutions of nitric acid, hydrochloric acid, hydrofluoric acid and hydrobromic acid. 제 2 항에 있어서, 알파-알루미나 1수화물의 크기가 약 500마이크론 이하의 범위인 방법.The method of claim 2, wherein the size of the alpha-alumina monohydrate is in the range of about 500 microns or less. 제 2 항에 있어서, 질소염기의 일반식이 R3N 또는 R3NHOH이고, 모든 R그룹이 동일 또는 상이하며, 수소 및 탄소원자수 1 내지 3의 알킬 그룹으로 이루어진 그룹중에서 선택되는 방법.The method of claim 2, wherein the general formula of the nitrogen base is R 3 N or R 3 NHOH, all R groups are the same or different and are selected from the group consisting of hydrogen and alkyl groups of 1 to 3 carbon atoms. 제 2 항에 있어서, 수용액이 코발트염 또는 니켈염 및 헤테로폴리몰리브덴산의 용액이며 함침이 1단계로 수행되는 방법.The process according to claim 2, wherein the aqueous solution is a solution of cobalt salt or nickel salt and heteropolymolybdic acid and the impregnation is carried out in one step. 제 1 항에 있어서, 니켈 및 몰리브덴을 각각 약 3중량% 및 9중량%로 함유함을 추가의 특징으로 하는 촉매조성물.The catalyst composition of claim 1, further comprising about 3 wt% and 9 wt% nickel and molybdenum, respectively. 제 2 항에 있어서, 질소염기의 용액이 산의 당량당 약 0.35당량 미만의 양의 염기를 함유하는 방법.The method of claim 2 wherein the solution of nitrogen base contains less than about 0.35 equivalents of base per equivalent of acid. 제 2 항에 있어서, 촉매에서 직경이 70 내지 130Å인 세공의 세공용적이 80% 이상인 방법.The process according to claim 2, wherein the pore volume of the pores having a diameter of 70 to 130 mm 3 in the catalyst is at least 80%. 제 2 항에 있어서, 촉매가 VIB족 및 VIII족 화합물이 코발트, 니켈 및 몰리브덴의 화합물로 이루어진 그룹중에서 선택됨을 추가의 특징으로 하는 방법.3. The process of claim 2, wherein the catalyst is further selected from the group consisting of compounds of Group VIB and Group VIII, consisting of compounds of cobalt, nickel and molybdenum. 제 2 항에 있어서, 세공용적의 5% 미만이 140Å 이상의 직경을 갖는 세공인 방법.The method of claim 2, wherein less than 5% of the pore volumes are pores having a diameter of at least 140 mm 3. 제 2 항에 있어서, 1000Å 이상의 직경을 갖는 세공이 세공용적의 1% 미만을 구성하는 방법.The method of claim 2, wherein the pores having a diameter of 1000 mm 3 or more constitute less than 1% of the pore volume. 제 2 항에 있어서, 촉매가 니켈 및 몰리브덴을 각각 약3중량% 및 9중량%로 함유함을 추가의 특징으로 하는 방법.3. The process of claim 2, wherein the catalyst further contains about 3% by weight and 9% by weight of nickel and molybdenum, respectively. 제 3 항에 있어서, 촉매에서 직경이 70 내지 130Å인 세공의 세공용적이 80% 이상인 방법.4. The process according to claim 3, wherein the pore volume of the pores having a diameter of 70 to 130 mm 3 in the catalyst is at least 80%. 제 3 항에 있어서, 촉매가 VIB족 및 VIII족 화합물이 코발트, 니켈 및 몰리브덴의 화합물로 이루어진 그룹중에서 선택됨을 추가의 특징으로 하는 방법.4. The process of claim 3, wherein the catalyst is further selected from the group consisting of compounds of Group VIB and Group VIII, consisting of compounds of cobalt, nickel and molybdenum. 제 3 항에 있어서, 세공용적의 5% 미만이 140Å 이상의 직경을 갖는 세공인 방법.4. The method of claim 3, wherein less than 5% of the pore volume is pores having a diameter of at least 140 mm 3. 제 3 항에 있어서, 1000Å 이상의 직경을 갖는 세공이 세공용적의 1% 미만을 구성하는 방법.4. The method of claim 3 wherein the pores having a diameter of at least 1000 mm 3 make up less than 1% of the pore volume. 제 3 항에 있어서, 촉매가 니켈 및 몰리브덴을 각각 약 3중량% 및 9중량%로 함유함을 추가의 특징으로 하는 방법.4. The process of claim 3, wherein the catalyst further contains about 3 weight percent and 9 weight percent nickel and molybdenum, respectively. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019920024982A 1992-12-22 1992-12-22 Hydrodesulfurization catalyst of heavy oil and process for preparing thereof KR100241174B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101402093B1 (en) * 2006-08-11 2014-05-30 상하이 리서치 인스티튜트 오브 페트로케미칼 테크놀로지 시노펙 Alumina having a complex pore structure, and catalyst and process for selective hydrogenation of cracking gasoline

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101402093B1 (en) * 2006-08-11 2014-05-30 상하이 리서치 인스티튜트 오브 페트로케미칼 테크놀로지 시노펙 Alumina having a complex pore structure, and catalyst and process for selective hydrogenation of cracking gasoline

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