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WO2007032188A1 - Catalyseur acide solide - Google Patents

Catalyseur acide solide Download PDF

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Publication number
WO2007032188A1
WO2007032188A1 PCT/JP2006/316558 JP2006316558W WO2007032188A1 WO 2007032188 A1 WO2007032188 A1 WO 2007032188A1 JP 2006316558 W JP2006316558 W JP 2006316558W WO 2007032188 A1 WO2007032188 A1 WO 2007032188A1
Authority
WO
WIPO (PCT)
Prior art keywords
surface area
high surface
acid catalyst
organic compound
solid acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/316558
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English (en)
Japanese (ja)
Inventor
Michikazu Hara
Mai Okamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Institute of Technology NUC
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Tokyo Institute of Technology NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Institute of Technology NUC filed Critical Tokyo Institute of Technology NUC
Priority to JP2007535411A priority Critical patent/JP5114712B2/ja
Publication of WO2007032188A1 publication Critical patent/WO2007032188A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J35/80—Catalysts, in general, characterised by their form or physical properties characterised by their amorphous structures

Definitions

  • the present invention relates to a novel high-performance solid acid catalyst and a method for producing the same.
  • the catalyst of the present invention is useful for producing chemical products with energy saving and high efficiency.
  • Sulfuric acid is an indispensable catalyst for the production of various petrochemical products, raw materials for chemical products, general-purpose chemicals, and pharmaceuticals.
  • Much energy and labor are required for separation of sulfuric acid and products by neutralization, etc., and waste acid treatment, which is not a catalyst that can be repeatedly recycled.
  • waste acid treatment which is not a catalyst that can be repeatedly recycled.
  • more than 15 million tons of sulfuric acid is consumed as a “non-recyclable catalyst” annually, and enormous energy waste and waste discharge have a great impact on the environment.
  • sulfuric acid is highly toxic and corrosive, the effort required to ensure safety and maintain the plant cannot be ignored!
  • Solid acids that can be used repeatedly, are easy to separate and recover, and have low toxicity (solid acids) are one of the keywords that clear this issue.
  • An ideal solid acid that can replace sulfuric acid is (1) has a high density of strong acid sites that function in any solvent and atmosphere, including water, and (2) is thermally and chemically stable. (3) It is an inexpensive material that can be synthesized from ordinary raw materials by a simple method. Since such materials can also be used as proton conductors for polymer electrolyte fuel cells, research and development is proceeding at a rapid pace. The power with which solid acids are currently used in various fields. These are SiO -A10, zeolite,
  • Solid acids of inorganic oxides such as hydrous niobic acid (Nb 0 ⁇ ⁇ 0) and polymers such as ion exchange resin
  • this material can take in a large amount of hydrophilic molecules into the Balta, and the Balta can be used as a reaction field, there is an acid-catalyzed reaction with hydrophilic molecules as reactants! High in acid-catalyzed reactions using as a solvent! It shows catalytic activity (Non-patent Document 1).
  • this material cannot incorporate hydrophobic molecules into the barta, so only the surface sulfonic acid groups are involved in the reaction.
  • due to its small surface area (usually less than 50 m 2 g "1), some acid-catalyzed reactions with hydrophobic molecules as reactants cannot show sufficient catalytic activity. .
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-238311
  • Patent Document 2 International Publication No. 2005/029508 Pamphlet
  • Non-Patent Document 1 Chemistry of Materials, (2006), 18 (13), 3039-3045.
  • the present invention has been made under the technical background as described above. Even in an acid-catalyzed reaction using a hydrophobic molecule as a reactant, sufficient catalytic activity for amorphous carbon having a sulfonic acid group introduced therein can be obtained. It aims at providing the means for making it exhibit.
  • the present invention has been completed based on the above findings. That is, the present invention provides the following (1) to (8).
  • a solid acid catalyst comprising a high surface area support and amorphous carbon into which a sulfonic acid group fixed thereto is introduced.
  • high surface area support is a solid acid catalyst as claimed in and having a 50 m 2 g- 1 or more specific surface area (1).
  • Amorphous carbon into which a sulfonic acid group has been introduced has a sulfonic acid density of 0.5 mmol / g or more, and the integrated intensity ratio of D band to G band in the Raman spectrum is 0.1 to 0.7.
  • the solid acid catalyst according to any one of (1) to (4).
  • a method for producing a solid acid catalyst comprising a step of fixing an organic compound to a high surface area support and a step of heat-treating the organic compound fixed to the high surface area support in concentrated sulfuric acid or fuming sulfuric acid.
  • a step of partially carbonizing the organic compound is included between the step of fixing the organic compound to the high surface area support and the step of heat-treating the organic compound fixed to the high surface area support in concentrated sulfuric acid or fuming sulfuric acid.
  • (6) The method for producing a solid acid catalyst according to (6).
  • the acid catalyst of the present invention can exhibit sufficient catalytic activity even in a reaction in which a hydrophobic molecule is used as a reactant, unlike the catalyst of sulfonic acid group-introduced amorphous carbon alone.
  • a hydrophobic molecule is used as a reactant, unlike the catalyst of sulfonic acid group-introduced amorphous carbon alone.
  • the solid acid catalyst of the present invention comprises a high surface area support and sulfonic acid group-introduced amorphous carbon fixed thereto.
  • the solid acid catalyst of the present invention can only be used with a high surface area support and amorphous carbon with sulfonic acid group introduction, but may contain other elements.
  • the high surface area carrier may be any one as long as it can fix the sulfonic acid group-introduced amorphous carbon.
  • the material of the high surface area carrier is not particularly limited, and examples thereof include oxide solids such as silica, alumina, and titanium, or mesoporous materials such as these oxide solids, activated carbon, and the like.
  • the specific surface area of the high surface area carrier is not particularly limited as long as the amorphous carbon having sulfonic acid group introduced therein can exhibit catalytic activity even for hydrophobic molecules, but it is preferably 50 m 2 g- 1 or more. More preferably, it is 100 m 2 g— 1 or more.
  • High surface area carriers usually have many pores. The pore diameter is not particularly limited, but is preferably 1 to 50 nm. In addition, the pores may penetrate the carrier or may penetrate! /.
  • the sulfonic acid group-introduced amorphous carbon is not particularly limited as long as it has an acid catalyst ability.
  • “sulfonic acid group-introduced amorphous carbon” refers to carbon having a sulfonic acid group and having no crystal structure, or an incomplete crystal structure and not having power.
  • a preferable sulfonic acid group-introduced amorphous carbon for example, carbon in which both G band and D band are detected in a spectrum by Raman spectroscopy, and the integrated intensity of D band and G band.
  • examples thereof include carbon having a ratio (I (D) / I (G)) of 0.1 to 0.7. If the integral intensity ratio is less than 0.3, the solid does not become a solid with a small number of aggregated six-membered carbon rings, and if it exceeds 0.7, the dalaphen sheet becomes large and the sulfonic acid density decreases, so that it does not function as a catalyst.
  • the integral intensity ratio may be 0.1 to 0.7, but is preferably 0.1 to 0.65, more preferably 0.1 to 0.6.
  • the D band, the G band, and their integrated intensities are defined as follows.
  • the D band is Alg breathing mode vibration in a carbon six-membered ring, and its peak Appears at 1350cm- 1 to 1360cm- 1 .
  • the G band is an E2g mode vibration of a carbon six-membered ring, and its peak top appears at 1580cm- 1 to ⁇ 5cm- 1 .
  • the Raman spectrum which is the sum of both peaks, was split into two peaks with Gaussian or Gaussian bite Renzian, and the integrated intensities of the D and G bands obtained were used as the integrated intensities.
  • the sulfonic acid density of the sulfonic acid group-introduced amorphous carbon is preferably 0.5 mmol / g or more, more preferably 1.0 mmol / g or more, and 3.0 mmol / g or more. Further preferred.
  • the upper limit of the sulfonic acid density is not particularly limited, but is preferably 8 mmol / g or less.
  • the solid acid catalyst of the present invention can be used as a catalyst for an acid catalyst reaction using a hydrophobic molecule as a reactant, but is not limited to this, as a catalyst for an acid catalyst reaction using a hydrophilic molecule or the like as a reactant. May be used.
  • acid-catalyzed reactions using hydrophobic molecules as reactants include ⁇ -methylstyrene, 2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-4-methyl-2-pentene. This includes the reaction to form, an alkylation to produce isooctane by adding isobutane to isobutene, and Friedel-Crafts alkylation.
  • the solid acid catalyst of the present invention is produced by a method comprising a step of fixing an organic compound on a high surface area carrier and a step of heat-treating the organic compound fixed on the high surface area carrier in concentrated sulfuric acid or fuming sulfuric acid. be able to.
  • aromatic hydrocarbons can be used, but other organic compounds such as glucose, sugar (sucrose), natural products such as cellulose, polyethylene, and polyacrylamide.
  • Such synthetic polymer compounds may be used.
  • benzene, naphthalene, anthracene, perylene, coronene, etc. can be used as the aromatic hydrocarbon, which may be a polycyclic aromatic hydrocarbon or a monocyclic aromatic hydrocarbon.
  • naphthalene can be used.
  • Only one type of organic compound may be used, or two or more types may be used in combination.
  • it is not always necessary to use a purified organic compound for example, heavy oil containing aromatic hydrocarbons, Pitch, tar, asphalt, etc. may be used.
  • the method for fixing the organic compound to the high surface area carrier is not particularly limited.
  • the organic compound is dissolved or dispersed in an appropriate solvent or dispersion medium, and the high surface area carrier is impregnated with the solution or the like.
  • the organic compound can be fixed to the high surface area carrier by removing the solvent and the like.
  • the organic compound may be fixed to the high surface area support under normal pressure, but when the pores of the high surface area support do not penetrate the support, it is preferably performed under low pressure. This is because, when the pores do not penetrate the support, the organic compound may not diffuse to the deep part of the pores under normal pressure due to air blockage in the pores.
  • the “low pressure” here is not particularly limited as long as it is within a range in which the above-mentioned problem of diffusibility of the organic compound can be improved, but is usually about 0.9 to 0.01 atm.
  • the heat treatment of the organic compound in concentrated sulfuric acid or fuming sulfuric acid can be performed, for example, in the same manner as described in International Publication No. 2005/029508.
  • the heat treatment temperature is not particularly limited as long as it is a temperature at which a reaction such as partial carbonization, cyclization, condensation, and sulfonation of an organic compound proceeds, but industrially, it is 50 to 350 ° C, preferably 80 to 200. ° C.
  • the treatment temperature is less than 50 ° C, the organic compound may not be sufficiently condensed and carbonized, and the formation of carbon may be insufficient.
  • Sulfonic acid groups may not be sufficiently introduced, and the treatment temperature is 350 ° C. If it exceeds C, thermal decomposition of the sulfonic acid group may occur.
  • the heat treatment time can be appropriately selected depending on the organic compound to be used, the treatment temperature, and the like, but is usually 1 to 50 hours, preferably 5 to 20 hours.
  • the amount of concentrated sulfuric acid or fuming sulfuric acid to be used is not particularly limited, but is usually 2.6 to 50.0 mol, preferably 6.0 to 36.0 mol, with respect to 1 mol of the organic compound.
  • Partial carbonization can be performed by heating an organic compound in an inert gas stream such as nitrogen or argon. The heating temperature at this time is usually 100 to 600 ° C, and the treatment time is usually 1 minute to 20 hours.
  • the specific surface area of this composite was 610 m 2 g- 1 , which was 38% of its weight. % was confirmed by powder X-ray diffraction and weight change due to carbon combustion, 0.95 mmol of sulfone per amorphous carbon introduced in this composite. In addition, it was confirmed that the sulfonic acid group-introduced amorphous carbon had a Raman spectrum.
  • the integrated intensity ratio (I (D) / I (G)) of D band and G band in Kuttle was 0.68 o
  • the sulfonic acid density was measured as follows. Since almost all of the sulfur element contained in the sulfonic acid group-introduced amorphous carbon is due to the sulfonic acid group, sulfur analysis in the sample was conducted by elemental analysis by combustion (SX- Elements Micro Analyzer YS-10 (yanaco)). The amount of sulfonic acid was determined. The integral intensity ratio of the D band and G band in the Raman spectrum was determined as follows. The sample powder was placed on the sample holder of the NRS-2100 triple monochromator Raman spectrophotometer (JASCO) and the Raman spectrum was measured.
  • JASCO NRS-2100 triple monochromator Raman spectrophotometer
  • the Raman spectrum in which both the D band and G band are observed is split into two bands, the Gaussian or Gaussian Lorentzian, into the D band and the G band, and the resulting integrated intensities of the D band and G band are obtained.
  • the integrated intensity was used.
  • Carbonaceous powder was obtained by heating 20 g of D-glucose in a nitrogen gas stream at 400 ° C for 15 hours. This powder was heated at 150 ° C. for 15 hours with stirring in 200 ml of 15 wt% fuming sulfuric acid to obtain a black powder. By repeatedly washing this with distilled water, the sulfuric acid in the material was removed to obtain amorphous carbon with sulfonic acid group introduction.
  • the integrated intensity ratio (I (D) / I (G)) of the D band and G band in the surface area, sulfonic acid density, and Raman spectrum of this sulfonic acid group-introduced amorphous carbon is 2m 2 g- 1 respectively. 1.5 mmol / g and 0.59.

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

Abstract

La présente invention concerne un catalyseur acide comprenant un support avec une grande surface et, de fixé à celui-ci, un carbone amorphe ayant un groupe sulfonate introduit dans celui-ci. Ce catalyseur acide est solide, facilitant de ce fait la séparation entre le catalyseur et le produit. En outre, ce catalyseur acide fonctionne comme un catalyseur même dans des réactions où les réactifs sont des molécules hydrophobes, de sorte que l'utilisation de celui-ci dans une large gamme de réactions soit réalisable.
PCT/JP2006/316558 2005-09-16 2006-08-24 Catalyseur acide solide Ceased WO2007032188A1 (fr)

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Application Number Priority Date Filing Date Title
JP2007535411A JP5114712B2 (ja) 2005-09-16 2006-08-24 固体酸触媒

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US71736805P 2005-09-16 2005-09-16
US60/717,368 2005-09-16

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008123530A1 (fr) * 2007-03-27 2008-10-16 Nippon Oil Corporation Procédé de fabrication d'un catalyseur acide solide comprenant un matériau carboné qui comporte un groupement sulfonate et utilisation du catalyseur acide solide
JP2011011201A (ja) * 2008-09-12 2011-01-20 Kanagawa Acad Of Sci & Technol 炭素系固体酸及びその製造方法
JP2012005382A (ja) * 2010-06-23 2012-01-12 Equos Research Co Ltd バイオマス加水分解反応装置
CN102500415A (zh) * 2011-12-02 2012-06-20 南开大学 由纤维素制备的碳微球催化剂及其应用
CN103285883A (zh) * 2013-06-28 2013-09-11 黑龙江大学 一种碳基磺酸固体酸催化剂的制备方法
CN103934027A (zh) * 2014-04-24 2014-07-23 南京德灿化学有限公司 一种固体酸催化剂及其制备方法和应用
JP2019026518A (ja) * 2017-07-31 2019-02-21 学校法人 芝浦工業大学 酸基含有アモルファスカーボンの製造方法、酸基含有アモルファスカーボン、及びセルロースの糖化方法
WO2023182349A1 (fr) 2022-03-23 2023-09-28 株式会社エーピーアイ コーポレーション Procédé de production d'ester d'acide salicylique
CZ310488B6 (cs) * 2023-12-19 2025-08-06 ORLEN Unipetrol RPA s.r.o Kyselý katalyzátor z odpadních surovin a způsob jeho výroby

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000313889A (ja) * 1999-04-30 2000-11-14 Agency Of Ind Science & Technol 芳香族炭化水素又は芳香族炭化水素を含む炭化水素に含まれる芳香族炭化水素の水素化異性化処理方法及びその水素化異性化処理方法に使用される触媒
JP2004238311A (ja) * 2003-02-05 2004-08-26 Japan Science & Technology Agency 多環式芳香族炭素系固体強酸
WO2005029508A1 (fr) * 2003-09-16 2005-03-31 The Circle For The Promotion Of Science And Engineering Carbone amorphe sulfone, procede de production de ce carbone et utilisation correspondante

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6035088A (ja) * 1983-08-06 1985-02-22 Fuji Sekiyu Kk 各種炭素源のスルホン化方法
JPH11135109A (ja) * 1997-10-28 1999-05-21 Mitsui Mining Co Ltd リチウムイオン二次電池負極用非晶質炭素材、及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000313889A (ja) * 1999-04-30 2000-11-14 Agency Of Ind Science & Technol 芳香族炭化水素又は芳香族炭化水素を含む炭化水素に含まれる芳香族炭化水素の水素化異性化処理方法及びその水素化異性化処理方法に使用される触媒
JP2004238311A (ja) * 2003-02-05 2004-08-26 Japan Science & Technology Agency 多環式芳香族炭素系固体強酸
WO2005029508A1 (fr) * 2003-09-16 2005-03-31 The Circle For The Promotion Of Science And Engineering Carbone amorphe sulfone, procede de production de ce carbone et utilisation correspondante

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008123530A1 (fr) * 2007-03-27 2008-10-16 Nippon Oil Corporation Procédé de fabrication d'un catalyseur acide solide comprenant un matériau carboné qui comporte un groupement sulfonate et utilisation du catalyseur acide solide
JP5360719B2 (ja) * 2007-03-27 2013-12-04 Ｊｘ日鉱日石エネルギー株式会社 スルホン酸基含有炭素質材料からなる固体酸触媒の製造方法およびその用途
JP2011011201A (ja) * 2008-09-12 2011-01-20 Kanagawa Acad Of Sci & Technol 炭素系固体酸及びその製造方法
JP2012005382A (ja) * 2010-06-23 2012-01-12 Equos Research Co Ltd バイオマス加水分解反応装置
CN102500415A (zh) * 2011-12-02 2012-06-20 南开大学 由纤维素制备的碳微球催化剂及其应用
CN103285883A (zh) * 2013-06-28 2013-09-11 黑龙江大学 一种碳基磺酸固体酸催化剂的制备方法
CN103934027A (zh) * 2014-04-24 2014-07-23 南京德灿化学有限公司 一种固体酸催化剂及其制备方法和应用
JP2019026518A (ja) * 2017-07-31 2019-02-21 学校法人 芝浦工業大学 酸基含有アモルファスカーボンの製造方法、酸基含有アモルファスカーボン、及びセルロースの糖化方法
JP7038991B2 (ja) 2017-07-31 2022-03-22 学校法人 芝浦工業大学 酸基含有アモルファスカーボンの製造方法
WO2023182349A1 (fr) 2022-03-23 2023-09-28 株式会社エーピーアイ コーポレーション Procédé de production d'ester d'acide salicylique
KR20240161106A (ko) 2022-03-23 2024-11-12 가부시키가이샤 에이피아이 코포레이션 살리실산에스테르의 제조 방법
CZ310488B6 (cs) * 2023-12-19 2025-08-06 ORLEN Unipetrol RPA s.r.o Kyselý katalyzátor z odpadních surovin a způsob jeho výroby

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JPWO2007032188A1 (ja) 2009-03-19

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