WO2014112712A1 - Procédé de production d'hydrocarbure cyclique à partir d'une substance de transformation de lignine au moyen d'un catalyseur à support de métal noble - Google Patents

Procédé de production d'hydrocarbure cyclique à partir d'une substance de transformation de lignine au moyen d'un catalyseur à support de métal noble Download PDF

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Publication number
WO2014112712A1
WO2014112712A1 PCT/KR2013/010802 KR2013010802W WO2014112712A1 WO 2014112712 A1 WO2014112712 A1 WO 2014112712A1 KR 2013010802 W KR2013010802 W KR 2013010802W WO 2014112712 A1 WO2014112712 A1 WO 2014112712A1
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Prior art keywords
catalyst
lignin
formula
producing
cyclic hydrocarbon
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PCT/KR2013/010802
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English (en)
Korean (ko)
Inventor
이관영
홍윤기
엄희준
이대원
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고려대학교 산학협력단
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Priority claimed from KR1020130144209A external-priority patent/KR101436429B1/ko
Publication of WO2014112712A1 publication Critical patent/WO2014112712A1/fr

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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum

Definitions

  • the present invention relates to a process for producing cyclic hydrocarbons from lignin converting materials using catalysts loaded with precious metals.
  • lignin is a by-product produced in the pulp process and is burned and used as a lower fuel.
  • lignin is converted into gaseous or liquid phase through pyrolysis and used as fuel or feedstock.
  • bio-oil In the case of liquid, it is called “bio-oil” and it is an oxygen-rich (about 40%) aromatic compound. consist of.
  • biooil as a feedstock for chemicals, it is important to properly remove oxygen contained in biooil.
  • hydrodeoxygenation using a catalyst can be converted into a high yield of aromatic chemicals by appropriately removing oxygen from a lignin converting material, and thus many studies have been conducted.
  • US Pat. No. 4,647,704 describes a process for converting lignin into an aromatic phenol via hydrodeoxygenation.
  • the catalyst is a zero-valent or sulfide tungsten-based catalyst, nickel was used as an additive, and the reaction was carried out using silica-alumina or silica-alumina-phosphate as a carrier.
  • Korean Patent No. 10-0587248 discloses that tungsten or molybdenum-based catalysts include phosphorus, nickel, cobalt, iron, ruthenium, and the like, or cobalt, palladium, nickel, platinum catalysts are zinc, rhenium, selenium, tin, germanium, lead, and the like.
  • a method for obtaining phenol from benzene diol using a catalyst comprising was described.
  • the sulfide catalyst becomes active. Therefore, the prior art has dealt with a method of converting guaiacol into aromatic compounds such as phenol and benzene using a lignin model material, guaiacol, as a reactant, and a sulfide catalyst.
  • the aromatic substances of the sulfide molybdenum can be prepared by aromatic chemicals such as phenol and benzene through a hydrogenated deoxygenation reaction, nine under the catalyst of CoMo or NiMo / Al 2 O 3 there was added sulfur child ahkol The conversion reaction of was studied.
  • Guaicol is converted into an aromatic chemical through a continuous reaction in the presence of hydrogen and sulfide catalysts, as shown in Scheme 1 below, and converted to cyclohexane as the benzene ring is hydrogenated.
  • the present invention is a Group 8 precious metal (Pd, Pt, Ru or Rh) supported by gamma alumina in order to obtain a high yield of cyclic hydrocarbons produced after hydrodeoxygenation and hydrogenation from lignin conversion materials containing aromatic hydrocarbons. It is an object to use this contained tungsten oxide or molybdenum oxide catalyst.
  • the present invention provides a catalyst for producing a cyclic hydrocarbon represented by the following formula (1) or (2).
  • M is Pd, Pt, Ru or Rh.
  • the present invention also provides a method for preparing a cyclic hydrocarbon from the lignin conversion material using the catalyst.
  • the catalyst of the present invention enables the production of cyclic hydrocarbons from lignin convertors in high yields and can be used without sulfur treatment to produce cyclic hydrocarbons under relatively simple conditions without contaminating the product.
  • 1 is a graph showing the conversion rate of the guai alcohol according to the type of catalyst.
  • FIG. 2 is a graph showing the production rate of cyclic hydrocarbons converted from guaiacol according to the amount of tungsten added.
  • 3 is a graph showing the results of repeated measurements 10 times to determine the durability of the catalyst of the present invention.
  • Figure 4 is a graph showing the production rate of the cyclic hydrocarbon when the catalyst of the present invention using the lignin converting material, guaiacol, anisol, catechol and phenol as the reactant.
  • the present invention relates to a catalyst for producing a cyclic hydrocarbon represented by the following formula (1) or (2).
  • M is Pd, Pt, Ru or Rh.
  • the catalyst for producing a cyclic hydrocarbon of the present invention is a molybdenum oxide or tungsten oxide catalyst containing a Group 8 noble metal (Pd, Pt, Ru or Rh) supported by gamma alumina.
  • the catalyst uses lignin convertors as reactants to produce cyclic hydrocarbons.
  • the catalyst for producing a cyclic hydrocarbon of the present invention uses alumina having a gamma phase structure as a carrier, and molybdenum oxide (MoO x ) or tungsten oxide (WO x ) is preferably 10 to 45 to the weight of the alumina carrier. It is included in weight percent. Molybdenum oxide or tungsten oxide contained in the alumina carrier is called molybdenum oxide alumina or tungsten oxide alumina, and is represented by the following formula (3) or (4).
  • Group 8 precious metals (Pd, Pt, Ru or Rh) is included in 1 to 5% by weight relative to the weight of the formula (3) or formula (4).
  • the present invention relates to a method for producing a cyclic hydrocarbon from the lignin conversion material using the catalyst for producing a cyclic hydrocarbon of formula (1) or (2).
  • the lignin converting material is converted into a cyclic hydrocarbon through hydrodeoxygenation and hydrogenation.
  • lignin converting material examples include guaiacol, anisol, catechol and phenol, and preferably guaiacol is most used.
  • the guiacol may be dissolved in an organic solvent, and hexane (n-hexane), decane (n-decane), paraxylene (p-xylene), and the like are preferable.
  • guai acol is mainly converted to cyclohexane, and also to cyclohexanol and methoxycyclohexanol.
  • Ammonium metatungstate (Sigma Aldrich) of 10% by weight relative to the weight of the alumina carrier was added to the alumina carrier by the initial wetness method (Incipient Wetness method) and then dried at 80 ° C. for 12 hours.
  • the dried material was calcined at 500 ° C. to obtain tungsten alumina (WO ⁇ / ⁇ -Al 2 O 3 , 10WA) in powder form. Thereafter, the pore volume of tungsten alumina was measured, and palladium of 2 wt% based on the weight of the tungsten alumina was added by an initial wet method. At this time, palladium is added in an aqueous palladium nitrate solution. Thereafter, the mixture was calcined at 500 ° C. to prepare a Pd / WO x / ⁇ -Al 2 O 3 (Pd10WA) catalyst.
  • a Pd / WO x / ⁇ -Al 2 O 3 (Pd20WA) catalyst was prepared in the same manner as in Example 1 except that 20% by weight of ammonium metatungstate was added to the alumina carrier.
  • a Pd / WO x / ⁇ -Al 2 O 3 (Pd35WA) catalyst was prepared in the same manner as in Example 1, except that 35% by weight of ammonium metatungstate was added to the alumina carrier.
  • Ammonium metatungstate (Sigma Aldrich) of 35% by weight relative to the weight of the alumina carrier was added to the alumina carrier by the initial wetness method (Incipient Wetness method) and then dried at 80 ° C. for 12 hours. The dried material was calcined at 500 ° C. to obtain tungsten alumina (WO ⁇ / ⁇ -Al 2 O 3 , 35WA) in powder form.
  • a Pd / ⁇ -Al 2 O 3 (PdAl) catalyst was prepared by adding an aqueous solution of palladium nitrate of 2% by weight based on the weight of the alumina carrier and firing at 500 ° C.
  • CoMo (Criterion Co., Ltd.) catalyst was injected with H 2 S / H 2 gas and reacted at 400 ° C. for 3 hours to prepare a CoMo-S catalyst.
  • Tetraethyl orthosilicate (Si (OC 2 H 5 ) 4 , SigmaAldrich), which is a silicon precursor, was mixed with tertiary distilled water, and a solution having a pH of 2.0 was prepared using nitric acid solution.
  • an aluminum precursor Al (NO 3 ) 3 9H 2 O, SigmaAldrich
  • tertiary distilled water was mixed to prepare a solution. The two solutions were mixed and stirred at 40 ° C. for 1 hour.
  • Ammonium hydroxide (NH 4 OH) was added dropwise to the solution to adjust the pH to 8.5 and then aged at 40 ° C. for 1 hour.
  • Example 1 to 3 Comparative Examples 1 to 4, alumina catalyst ( ⁇ -Al 2 O 3 , Al) and CoMo catalyst were added to the solution in which 3 wt% of guai alcohol was added to a decane solvent. Each solution was prepared by adding g each to make a total volume of 50 mL. Each solution was filled with hydrogen gas at 300 ° C., and the reaction was carried out for 3 hours while maintaining a total pressure of 7 MPa to prepare cyclohexane from guoacol through hydrodeoxygenation and hydrogenation.
  • alumina catalyst ⁇ -Al 2 O 3 , Al
  • CoMo catalyst CoMo catalyst
  • Example 3 Pd35WA
  • Comparative Examples 2 PdAl
  • CoMo-S which are the catalysts of the present invention
  • the catalyst (35WA), alumina catalyst (Al), and CoMo catalyst of Comparative Example 1 showed a conversion rate of 50% or more, and a conversion rate of less than 5% in the reaction without adding a catalyst.
  • the catalysts of Comparative Examples 1 to 3 (Pd10WA, Pd20WA and Pd35WA) including tungsten
  • Experiment was conducted using 2 (PdAl) and the catalyst of Comparative Example 4 (Si-Al).
  • the catalyst of Example 3 (Pd35WA) containing 35% by weight of tungsten produced the most cyclic hydrocarbon cyclohexane, and the catalysts of Examples 1 (Pd10WA) and 2 (Pd20WA) containing 10 and 20% by weight of tungsten.
  • the yield was 60% or more.
  • the catalyst of Comparative Example 4 (Si-Al) showed a lower yield of cyclohexane, and the catalyst of Comparative Example 2 (PdAl) not containing tungsten had a lower yield than the catalysts of Examples 1 to 3 of the present invention. (FIG. 2).
  • Example 3 Using the catalyst (Pd35WA) prepared in Example 3 to prepare a reaction solution in the same manner as in Experiment 1. In order to measure the durability of the catalyst of the present invention, the catalyst was reused 10 times to determine the yield of cyclohexane converted from guai alcohol.
  • the catalyst for producing a cyclic hydrocarbon of the present invention generates a cyclic hydrocarbon from a variety of lignin conversion materials in addition to gua alcohol in high yield.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un catalyseur pour produire un hydrocarbure cyclique représenté par la formule 1 ou la formule 2, et un procédé de production de l'hydrocarbure cyclique à partir d'une substance de transformation de lignine par l'intermédiaire d'une réaction d'hydrodésoxygénation ou d'hydrogénation au moyen du catalyseur. [Formule 1] M/MoOx/γ-Al2O3; [Formule 2] M/WOx/γ-Al2O3, M représentant Pd, Pt, Ru, ou Rh.
PCT/KR2013/010802 2013-01-18 2013-11-26 Procédé de production d'hydrocarbure cyclique à partir d'une substance de transformation de lignine au moyen d'un catalyseur à support de métal noble WO2014112712A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20130006104 2013-01-18
KR10-2013-0006104 2013-01-18
KR1020130144209A KR101436429B1 (ko) 2013-01-18 2013-11-26 귀금속이 담지된 촉매를 사용하여 리그닌 전환 물질로부터 고리모양 탄화수소를 생성하는 방법
KR10-2013-0144209 2013-11-26

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WO2014112712A1 true WO2014112712A1 (fr) 2014-07-24

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR950017873A (ko) * 1993-12-30 1995-07-20 조말수 헤테로 폴리산을 이용한 방향족 화합물의 선택적 고리 수소화방법
US20100043278A1 (en) * 2006-06-09 2010-02-25 Albemarle Netherlands B.V. Catalytic hydrodeoxygenation of an oxygenate feedstock
KR20120035764A (ko) * 2010-10-06 2012-04-16 서울대학교산학협력단 알파 탄소-산소-4 탄소 결합을 포함한 리그닌 화합물 분해용 양이온 치환된 헤테로폴리산 촉매, 상기 촉매에 담지된 귀금속 촉매 및 상기 촉매를 이용한 알파 탄소-산소-4 탄소 결합을 포함한 리그닌 화합물 분해 방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR950017873A (ko) * 1993-12-30 1995-07-20 조말수 헤테로 폴리산을 이용한 방향족 화합물의 선택적 고리 수소화방법
US20100043278A1 (en) * 2006-06-09 2010-02-25 Albemarle Netherlands B.V. Catalytic hydrodeoxygenation of an oxygenate feedstock
KR20120035764A (ko) * 2010-10-06 2012-04-16 서울대학교산학협력단 알파 탄소-산소-4 탄소 결합을 포함한 리그닌 화합물 분해용 양이온 치환된 헤테로폴리산 촉매, 상기 촉매에 담지된 귀금속 촉매 및 상기 촉매를 이용한 알파 탄소-산소-4 탄소 결합을 포함한 리그닌 화합물 분해 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. L. CONTRERAS ET AL.: "Thermal Stability of Pt Nanoparticles Supported on WOx/A12O3 for n-Heptane Hydroconversion", MRS-PROCEEDINGS, vol. 1279, 1 February 2011 (2011-02-01) *

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