JP5192493B2 - ゼオライト・カオリン触媒組成物 - Google Patents
ゼオライト・カオリン触媒組成物 Download PDFInfo
- Publication number
- JP5192493B2 JP5192493B2 JP2009544367A JP2009544367A JP5192493B2 JP 5192493 B2 JP5192493 B2 JP 5192493B2 JP 2009544367 A JP2009544367 A JP 2009544367A JP 2009544367 A JP2009544367 A JP 2009544367A JP 5192493 B2 JP5192493 B2 JP 5192493B2
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- catalyst composition
- kaolin
- binder
- catalyst
- 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.)
- Expired - Fee Related
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/16—Clays or other mineral silicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
三首の丸底フラスコ中で0.5714gの硝酸ガリウムを200mlの脱塩水中に溶解させた。Si/Al比が20である、NH4形態にある乾燥ZSM−5を10g加えた。この混合物を90〜95℃に加熱し、24時間に亘り300rpmで撹拌した。
500mlのテフロン(登録商標)ビーカー内で50.46gの三ケイ酸ナトリウムを200mlの脱塩水に加え、激しく撹拌した。これとは別に、50mlの脱塩水中の13.34gの硝酸アルミニウムの溶液、15mlの脱塩水中の硝酸ガリウム溶液、および50mlの脱塩水中の20.19gの臭化テトラプロピルアンモニウム(TPABr)溶液を調製した。三ケイ酸ナトリウムの撹拌溶液に、硝酸アルミニウム、硝酸ガリウムおよびTPABrの透明な溶液を次々にゆっくりと加えた。さらに、最後に35mlの水を加えた。この混合物のpHを、濃H2SO4および脱塩水の1:1の混合物を加えることによって、9.0に調節した。pHを調節した後、激しい撹拌を30〜45分間続けた。混合物を500mlのSS316オートクレーブに移し、封止し、結晶化を行うために、72時間に亘り400rpmの定速で撹拌しながら170℃に加熱した。
1. La交換カオリン結合剤(C−1)
0.187gの硝酸ランタン六水和物を120mlの脱塩水中に溶解させた。6gのカオリンを加えた。還流設備で24時間に亘り95〜98℃で加熱しながら、この組成物を磁気撹拌子を用いて撹拌した。
硝酸Laの交換を行わずに、上述した1のか焼プロセスを、カオリンに繰り返した。
0.187gの硝酸ランタンを10mlの脱塩水中に溶解させた。それに6gのα−Al2O3を加えてスラリーを調製し、これを、加熱しながら撹拌して、水を蒸発させた。得られたペーストを120℃で乾燥させて、1質量%のLaの公称添加量のα−Al2O3を得た。
α−Al2O3それ自体を、修飾せずに、結合剤として選択した。
ゼオライトAまたはBを1種類の担体Cと2:1の比で完全に混合することによって、異なるゼオライト化合物(AまたはB)および異なる担体(C−1からC−4)を含むいくつかの触媒組成物を粒子形態で調製した。その混合物を10トンの圧力で加圧して、ペレットを製造した。圧縮した触媒組成物を粉砕し、篩い分けした。0.25から0.5mmの粒子を含有する分画および0.5から1.00mmの粒子を含有する分画を、さらに使用するために選択した。
組合せAC−1(本発明による)と比較のための組合せAC−2、AC−3およびAC−4の各々から2gの触媒粒子(粒径0.25〜0.5mm)を、下降流式固定床マイクロ触媒反応装置内に装填し、以下のようにして前処理した:
工程1: 630℃で25ml/分の無水分気流に1時間に亘り曝露した;
工程2: 600℃で80ml/分のN2流量中の5.0体積%の水蒸気に1時間に亘り曝露した;
工程3: 500℃で25ml/分の水素流に1時間に亘り曝露した。
実施例4で調製した組合せBC−1の0.25〜0.5mmの触媒組成物粒子をプロパン転化に用いた。
実施例6の手法を、触媒組成物BC−2について繰り返した。
実施例6の手法を、触媒組成物BC−3について繰り返した。
実施例6の手法を、触媒組成物BC−4について繰り返した。
Claims (7)
- Ga含有ゼオライトおよび結合剤を含む、低級アルカンを芳香族炭化水素に転化する反応に使用するための触媒組成物であって、前記結合剤がLa修飾カオリンであることを特徴とする触媒組成物。
- 前記ガリウムが、ゼオライトとガリウムの合計に対して、多くとも0.95質量%の量で含まれることを特徴とする請求項1記載の触媒組成物。
- 前記カオリンが酸処理されていないことを特徴とする請求項1または2記載の触媒組成物。
- 低級アルカンを芳香族炭化水素に転化する方法であって、請求項1から3いずれか1項記載の触媒組成物を使用することを特徴とする方法。
- 前記芳香族炭化水素が、ベンゼン、トルエンおよびキシレンを少なくとも45質量%含むことを特徴とする請求項4記載の方法。
- 前記低級アルカンがC2〜C6アルカンであることを特徴とする請求項4または5記載の方法。
- 前記低級アルカンを含む供給流を、500〜600℃の温度で前記触媒組成物に接触させる工程を含むことを特徴とする請求項4から6いずれか1項記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IN26DE2007 | 2007-01-03 | ||
IN0026/DEL/2007 | 2007-01-03 | ||
PCT/EP2007/010763 WO2008080517A1 (en) | 2007-01-03 | 2007-12-05 | Zeolite-kaolin catalyst composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2010514564A JP2010514564A (ja) | 2010-05-06 |
JP5192493B2 true JP5192493B2 (ja) | 2013-05-08 |
Family
ID=39276193
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009544367A Expired - Fee Related JP5192493B2 (ja) | 2007-01-03 | 2007-12-05 | ゼオライト・カオリン触媒組成物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US8252710B2 (ja) |
EP (1) | EP2104565B1 (ja) |
JP (1) | JP5192493B2 (ja) |
CN (1) | CN101568382B (ja) |
AT (1) | ATE552906T1 (ja) |
EA (1) | EA015026B1 (ja) |
TW (1) | TW200924843A (ja) |
WO (1) | WO2008080517A1 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9266100B2 (en) * | 2010-05-20 | 2016-02-23 | Saudi Basic Industries Corporation | Pre-carburized molybdenum-modified zeolite catalyst and use thereof for the aromatization of lower alkanes |
EP2734297A1 (en) | 2011-07-21 | 2014-05-28 | Saudi Basic Industries Corporation | Catalyst for the preparation of aromatic hydrocarbons and use thereof |
WO2013102475A1 (en) | 2012-01-04 | 2013-07-11 | Saudi Basic Industries Corporation | Catalyst for the preparation of aromatic hydrocarbons and use thereof |
EP2692438A1 (en) | 2012-08-02 | 2014-02-05 | Saudi Basic Industries Corporation | Catalyst composition for the production of aromatic hydrocarbons |
US10131853B2 (en) | 2014-02-25 | 2018-11-20 | Saudi Basic Industries Corporation | Process for producing BTX from a mixed hydrocarbon source using pyrolysis |
EP3110920B1 (en) * | 2014-02-25 | 2018-07-25 | Saudi Basic Industries Corporation | Process for producing btx from a mixed hydrocarbon source using coking |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4508839A (en) * | 1981-08-27 | 1985-04-02 | Ashland Oil, Inc. | Catalyst for the conversion of carbo-metallic containing oils |
US4482531A (en) * | 1983-04-29 | 1984-11-13 | Mobil Oil Corporation | Synthesis of ZSM-12 zeolite |
DE3373671D1 (en) * | 1983-07-04 | 1987-10-22 | Mobil Oil Corp | Process for converting propane to aromatics over zinc-gallium zeolite |
JPS61204042A (ja) * | 1985-01-14 | 1986-09-10 | エンゲルハ−ド・コ−ポレ−シヨン | 耐バナジウム性ゼオライト流動クラツキング触媒 |
US4629818A (en) * | 1985-04-22 | 1986-12-16 | Mobil Oil Corporation | Aromatization catalyst for a refinery off gas stream |
GB8706503D0 (en) * | 1987-03-19 | 1987-04-23 | British Petroleum Co Plc | Aromatic hydrocarbons |
US5173463A (en) * | 1988-09-06 | 1992-12-22 | Petroleo Brasileiro, S.A.-Petrobras | Kaolin containing fluid cracking catalyst |
US5248642A (en) * | 1992-05-01 | 1993-09-28 | W. R. Grace & Co.-Conn. | Catalytic cracking catalysts and additives |
US5284643A (en) * | 1992-12-10 | 1994-02-08 | Mobil Oil Corp. | Gallium-containing zeolite MCM-22 |
US6077495A (en) * | 1997-03-03 | 2000-06-20 | Engelhard Corporation | Method, composition and system for the controlled release of chlorine dioxide gas |
US5965474A (en) * | 1997-04-29 | 1999-10-12 | Mobil Oil Corporation | FCC metal traps based on ultra large pore crystalline material |
US5883034A (en) * | 1997-07-09 | 1999-03-16 | Phillips Petroleum Company | Hydrocarbon conversion catalyst composition and processes therefor and therewith |
CN1123389C (zh) * | 1998-08-26 | 2003-10-08 | 中国科学院大连化学物理研究所 | 低碳烯烃水合制低碳醇用催化剂制备及应用 |
CN1111090C (zh) * | 1999-11-19 | 2003-06-11 | 中国科学院山西煤炭化学研究所 | 用于烃类芳构化反应的双组份改性沸石催化剂 |
-
2007
- 2007-12-05 EP EP07856529A patent/EP2104565B1/en not_active Not-in-force
- 2007-12-05 CN CN2007800481334A patent/CN101568382B/zh not_active Expired - Fee Related
- 2007-12-05 WO PCT/EP2007/010763 patent/WO2008080517A1/en active Application Filing
- 2007-12-05 EA EA200900932A patent/EA015026B1/ru not_active IP Right Cessation
- 2007-12-05 JP JP2009544367A patent/JP5192493B2/ja not_active Expired - Fee Related
- 2007-12-05 AT AT07856529T patent/ATE552906T1/de active
- 2007-12-05 US US12/448,738 patent/US8252710B2/en not_active Expired - Fee Related
- 2007-12-11 TW TW096147278A patent/TW200924843A/zh unknown
Also Published As
Publication number | Publication date |
---|---|
CN101568382A (zh) | 2009-10-28 |
EA200900932A1 (ru) | 2010-02-26 |
CN101568382B (zh) | 2011-06-29 |
EA015026B1 (ru) | 2011-04-29 |
ATE552906T1 (de) | 2012-04-15 |
EP2104565A1 (en) | 2009-09-30 |
WO2008080517A1 (en) | 2008-07-10 |
US8252710B2 (en) | 2012-08-28 |
TW200924843A (en) | 2009-06-16 |
EP2104565B1 (en) | 2012-04-11 |
US20100029999A1 (en) | 2010-02-04 |
JP2010514564A (ja) | 2010-05-06 |
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