JP5731003B2 - クメンの製造方法 - Google Patents
クメンの製造方法 Download PDFInfo
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- JP5731003B2 JP5731003B2 JP2013533886A JP2013533886A JP5731003B2 JP 5731003 B2 JP5731003 B2 JP 5731003B2 JP 2013533886 A JP2013533886 A JP 2013533886A JP 2013533886 A JP2013533886 A JP 2013533886A JP 5731003 B2 JP5731003 B2 JP 5731003B2
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims description 61
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- 239000003054 catalyst Substances 0.000 claims description 37
- 239000010457 zeolite Substances 0.000 claims description 36
- 238000010555 transalkylation reaction Methods 0.000 claims description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 32
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
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- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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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
- 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
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- 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
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- 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
- C07C2529/80—Mixtures of different zeolites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は一般にクメンの製造方法に関する。
本明細書で用いられる用語「流れ」は、直鎖状、分岐状若しくは環状のアルカン、アルケン、アルカジエン、及びアルキン等の種々の炭化水素分子、及び、必要に応じて、水素等の気体、又は重金属等の不純物、並びに硫黄化合物及び窒素化合物等のその他の物質を含むことができる。また、「流れ」は、芳香族及び非芳香族の炭化水素を含むこともできる。さらに、炭化水素分子は、C1、C2、C3・・・Cn(式中、「n」は1つ以上の炭化水素分子中の炭素原子の数を表す)と略記してもよい。更に、上付き記号「+」又は、「−」は、略記された1つ以上の炭化水素の表記と共に用いることができ、例えば、C3+又はC3−であり、これは略記された1つ以上の炭化水素を含む。一例として、「C3+」は、3個以上の炭素の1つ以上の炭化水素分子を意味する。
本明細書で用いられる用語ノルマル「プロピルベンゼン」は、「nPB」と略記してもよい。
本明細書で用いられる用語「ジイソプロピルベンゼン」は、「DIPB」と略記してもよい。
本明細書で用いられる用語「ポリプロピルベンゼン」は、DIPB及びTIPBを含み、「PIPB」と略記してもよい。
本明細書で用いられる用語「重量毎時空間速度」は、「WHSV」と略記してもよい。
本明細書で用いられる用語「ジエチルジフェニルエタン」は、「DEDPE」と略記してもよい。
本明細書で用いられる用語「重質化合物」は、重質芳香族化合物を含んでよく、例えば、1種以上のn−プロピルベンゼン、アミルベンゼン、シメン、ブチルベンゼン、α−メチルスチレン、ヘキシルベンゼン、ヘプチルベンゼン、インデン、テトラリン、ヘキスメトジヒインデン、イソプロジメトテトラ、ジフェニルプロパン及びジフェニルエタン(これらは、必要に応じ、或は更に置換されてもよい)、並びに/又は、蒸留等の工程で、塔側流及び/又は塔底流中等のDIPB及び/又はTIPBと共に分離できる以前に言及されていない他の共通沸騰物が挙げられる。
Rr p+Al1−xExSiyOz
式中、「R」は、プロトン化アミン、プロトン化ジアミン、第4級アンモニウムイオン、ジ第4級アンモニウムイオン、プロトン化アルカノールアミン、及び4級化アルカノールアンモニウムイオンからなる群から選択される少なくとも1種の有機アンモニウム陽イオンである。好ましい有機アンモニウム陽イオンは、非環式のものか、または1つの置換基として環式の基を含まないものである。これらの中で、置換基として少なくとも2つのメチル基を含むものが、特に好ましい。「R」の(Al+E)に対する比は、0.05から5まで変化する「r」で表される。「R」の加重平均価数である「p」の値は、1から2まで変化する。Siの(Al+E)に対する比は、6.5から35まで変化する「y」で表される。元素のEは、四面体配位であり、骨格中に存在し、ガリウム、鉄、クロム、インジウム、及びホウ素からなる群から選択される。Eのモル比率は「x」で表され、0から0.5までの値を有する。一方、「z」はOの(Al+E)に対するモル比であり、式:
z=(r・p+3+4・y)/2
で表される。
これとその他のUZM−8ゼオライト並びに調製方法は、例えば、米国特許第6,756,030B1号に開示されている。
(0.1〜0.3)R:(0.7〜1.0)M2/nO:1Al2O3:(2.5〜4.0)SiO2・YH2O
式中、「R」はエチルアンモニウム酸化物、水素酸化物、及びその互いの混合物から成る群から選択され、「M」は金属であり、「n」はその原子価、及び「Y」は3.5〜5.5の値である。
(0.85〜1.1)M2/nO:Al2O3:xSiO2
式中、「M」は価数「n」を有するカチオンであり、「x」は5.0〜11.0の値を有する。このようなゼオライトは、例えば、米国特許第2008/0171649A1号、同2008/0171901A1号、及び同2008/0171902A1号に開示されている。
以下の実施例により、さらに対象となる触媒を説明する。本発明の態様のこれらの例示説明によって本発明の特許請求の範囲がこれらの実施例の特定の詳細に限定されるものではない。これらの実施例は、工学的計算及び同様の方法の実地操作経験に基づいている。
米国特許第5,013,699号に開示されている市販の蒸製Y型ゼオライトを重量で15%のNH4NO3水溶液中でスラリー化する。十分な量の17重量%HNO3溶液を30分かけて添加し、余分な枠組みのアルミニウムの一部を除去する。その後、スラリーの温度を79℃まで上昇させて90分間保持する。79℃で90分接触させた後、スラリーを濾過し、濾過ケーキを重量で22%の硝酸アンモニウム溶液で洗浄し、続いて過剰量の温脱イオン水で水洗する。得られる濾過ケーキを適切な水分量まで乾燥し、HNO3−解膠アルミナ(商品名CATAPAL Cで販売され、南アフリカのハウテン州のサソールリミテッドの子会社であるサソール北米から入手)と混合し、乾燥基準で、80重量部のゼオライトと20重量部のAl2O3結合剤の混合物を得る。その後、混合物を直径1.59mmの円筒形押出成形品として押出し、乾燥し、600℃で1時間、空気流中で焼成する。触媒の物性は、SiO2:65.2重量%(バルクで乾燥基準)、Al2O3:34.7重量%(乾燥基準)、ナトリウム:Na2O換算で0.04重量%(乾燥基準)、(NH4)2O:0.1重量%(乾燥基準)、単位格子寸法:24.512Å、及び米国特許第US6,756,030B1号のカラム7〜8記載のX線分析に従って実施した絶対XRD強度:69.7である。
大きなビーカー中で、1,006.69gの脱イオン水に160.2gの水酸化ジエチルジメチルアンモニウムを加え、続いて、2.1gの重量で50%のNaOH溶液を加える。次に、51.5gの液体アルミン酸ナトリウムをゆっくり添加し、20分間攪拌する。続いて、178.9gのシリカ(ドイツ、フランクフルトのエボニックデグサ(Evonik Degussa GmbH)により、商品名ULTRASIL(登録商標)で販売)を、ゆっくりとゲルに添加し、20分間攪拌する。次いで、36gのUZM−8種結晶(例えば、米国特許6,756,030B1号に従って作製)をゲルに添加し、更に20分間攪拌する。次いで、ゲルを2リットルの攪拌機付き反応器に移し、160℃まで2時間加熱し、115時間かけて結晶化させる。
米国特許第7,371,010号B2に開示されたβゼオライト等の合成βゼオライトを、まず、アンモニウム交換し、揮発性成分を含まない基準でナトリウム含有量をNa2O換算で500wppm未満に下げ、100℃で乾燥する。アンモニウム変換し、乾燥したβゼオライトを、揮発性成分を含まない基準で、質量で70%のゼオライト及び30%のアルミナを含む直径0.159cmの円筒形ペレットとして押し出す。形成した触媒を110℃で2時間乾燥し、600℃で1時間、回転窯中の空気流で焼成する。
触媒Bで上述のとおり調製した合成UZM−8をアンモニウム交換し、揮発性成分を含まない基準でナトリウム含有量をNa2O換算で500wppm未満に下げる。アンモニウム交換したUZM−8を触媒Cの調製で述べたアンモニウム交換βゼオライトと混合し、70:30重量比とし、次いで直径0.159cmの円筒形に押し出す。押出物を100℃で2時間乾燥する。次に、押出物を450℃で1時間、次いで550℃で更に1時間、空気流中で焼成する。
供給原料は1つ以上の市販トランスアルキル化装置から得られるポリアルキル化ベンゼンにベンゼンを配合することにより調製される。供給原料は芳香族環基のプロピル基に対するモル比が2.0:1.0である典型的なトランスアルキル化供給原料組成物を表す。
触媒及び供給原料を下記の表4に示すように試験する。
上記記載から、当業者は容易に本発明の本質的な特徴を見極めることができ、その趣旨及び範囲から逸脱することなく、本発明を種々の使用法及び条件に適合させるように、本発明の種々の変更及び修正を行うことができる。
Claims (7)
- A)トランスアルキル化供給原料流をトランスアルキル化区域に送る工程と、
B)反応生成物を分離区域に送る工程と、
を含む、クメンを製造するためのポリイソプロピルベンゼンの処理方法であって、
前記分離区域は、ジイソプロピルベンゼン、トリイソプロピルベンゼン、及び1種以上の重質化合物を含む流れを生成し、前記流れは、前記流れの中の前記ジイソプロピルベンゼンと前記トリイソプロピルベンゼンと前記1種以上の重質化合物との重量に対して、少なくとも重量で0.7%の前記1種以上の重質化合物を含み、前記流れの少なくとも一部は前記トランスアルキル化区域に再循環され、
前記トランスアルキル化区域が、UZM−8ゼオライトを含む第1成分とβゼオライトを含む第2成分とを含む触媒を含む、
ポリイソプロピルベンゼンの処理方法。 - 前記トランスアルキル化供給原料流がベンゼン及び前記再循環流を含む、請求項1に記載の方法。
- 前記第1成分の前記第2の成分に対する重量比が1:10〜10:1である、請求項1又は2に記載の方法。
- 前記第1成分の前記第2成分に対する重量比が1:5〜5:1である、請求項1〜3のいずれか一項に記載の方法。
- 前記トランスアルキル化区域が、24.34〜24.58Åの単位セル寸法及び6.5〜20のバルクSi/Al2モル比を有する酸処理水蒸気改質Y型ゼオライトを含む触媒を含む、請求項1〜4のいずれか一項に記載の方法。
- 前記トランスアルキル化区域が、化学的修飾Y型ゼオライトを含む触媒を含む、請求項1〜5のいずれか一項に記載の方法。
- 前記分離区域が、複数の蒸留区域を含む、請求項1〜6のいずれか一項に記載の方法。
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US11951463B2 (en) | 2017-03-29 | 2024-04-09 | ExxonMobil Engineering & Technology Company | Catalyst compositions and their use in aromatic alkylation processes |
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