CN103987454A - 醇选择性脱水成二烷基醚和联合醇制汽油方法 - Google Patents

醇选择性脱水成二烷基醚和联合醇制汽油方法 Download PDF

Info

Publication number
CN103987454A
CN103987454A CN201280062144.9A CN201280062144A CN103987454A CN 103987454 A CN103987454 A CN 103987454A CN 201280062144 A CN201280062144 A CN 201280062144A CN 103987454 A CN103987454 A CN 103987454A
Authority
CN
China
Prior art keywords
catalyst
alcohol
under
product
less
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.)
Pending
Application number
CN201280062144.9A
Other languages
English (en)
Inventor
T·W·比特尔
S·J·麦卡锡
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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 ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of CN103987454A publication Critical patent/CN103987454A/zh
Pending legal-status Critical Current

Links

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
    • 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
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • 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
    • B01J29/82—Phosphates
    • B01J29/83—Aluminophosphates (APO compounds)
    • B01J35/30—
    • B01J35/31—
    • B01J35/61—
    • B01J35/613—
    • B01J35/615—
    • B01J35/633—
    • B01J35/635—
    • B01J35/647—
    • B01J35/67—
    • 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
    • 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
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/28—Phosphorising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/36—Steaming
    • 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
    • B01J2229/37—Acid treatment
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • Y02P20/10—Process efficiency
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

方法涉及将C1-C4醇转化成汽油和/或柴油沸程产物的联合方法，所述方法包括：使C1-C4醇进料在选择性脱水条件下与包含γ-氧化铝且在催化剂的四面体配位铝部位上基本不含末端羟基的催化剂接触以形成二烷基醚脱水产物；和使二烷基醚脱水产物与沸石转化催化剂在转化条件下接触以形成汽油和/或柴油沸程烃产物。

Description

醇选择性脱水成二烷基醚和联合醇制汽油方法
发明领域
本公开内容涉及醇选择性脱水成二烷基醚，以及包括该选择性脱水作为第一步骤的联合醇制汽油形成方法。
发明背景
甲醇选择性脱水制备二甲醚作为甲醇转化成汽油和柴油沸程烃中的第一步骤是商业上重要的反应。类似地，高级醇如乙醇的选择性脱水在合成大量商业上重要的二烷基醚如二乙醚中是重要的。
如例如美国专利No.4,536,485所述，醇选择性脱水的现有方法使用固体酸催化剂，例如氧化铝、二氧化硅、氧化铝-二氧化硅混合物和结晶铝硅酸盐，例如沸石。然而，除所需醚产物外，这些固体酸催化剂通常产生不理想的副产物，例如焦炭、甲烷、二氧化碳和氢气。副产物形成通常降低选择性并可在绝热反应器内潜在地触发危险的温度剧增。因此，副产物形成可通过调整醇进料的水浓度以控制反应器出口温度而保持为低的。然而，提高醇进料的水浓度可降低每反应器程的醇平衡转化率，并可降低总选择性脱水方法效率。
根据本发明，现在发现可通过选择四面体配位铝部位上基本不含末端羟基的γ-氧化铝形式作为选择性脱水催化剂而将C1-C4醇如甲醇甚至在醇进料中相对低水浓度下选择性地脱水成二烷基醚而不明显形成副产物或反应器温度剧增，如通过催化剂的IR光谱中基本不存在～3770cm-1下的吸收带所测定。
发明概述
一方面，本发明在于将C1-C4醇转化成汽油和/或柴油沸程产物的联合方法，所述方法包括：使C1-C4醇进料在选择性脱水条件与包含γ-氧化铝且在催化剂的四面体配位铝部位上基本不含末端羟基的催化剂接触以形成二烷基醚脱水产物；和使二烷基醚脱水产物与沸石转化催化剂在转化条件下接触以形成汽油和/或柴油沸程烃产物。
方便地，选择性脱水催化剂的γ-氧化铝具有在～3770cm-1下小于0.010cm/mg的归一化吸收率。
另外或者作为选择，选择性脱水催化剂可具有小于1的α值。
另外或者作为选择，选择性脱水催化剂在用于在～350℃、约大气压力和～2.4hr-1的重时空速下使2-甲基-2-戊烯异构化时可产生其中2,3二甲基-2丁烯与4-甲基-2-戊烯的重量比小于0.2的异构化产物。
另外或者作为选择，脱水条件可包括约250至约500℃的温度和约100至约7000kPa的压力。
另外或者作为选择，C1-C4醇进料包含小于15重量％水。
在特定实施方案中，醇可包含甲醇或者为甲醇，因此，二烷基醚可包含二甲醚或者为二甲醚，在这种情况下，转化步骤在其产物中有利地形成汽油和柴油沸程烃。
应当指出，本申请涉及各自于2011年10月17日提交的美国临时申请Nos.61/548,015、61/548,038、61/548,044、61/548,052、61/548,057和61/548,064，通过引用将其各自的全部内容并入本文中至描述本文所述本发明的任何部分所需的程度。本申请还涉及5个其它共同未决国际(PCT)申请，其各自在与其相同日期提交且要求前述美国临时专利申请的益处，并分别标题为“磷改性沸石催化剂的制备方法”、“磷改性沸石催化剂的制备方法”、“磷改性沸石催化剂”、“磷改性沸石催化剂”和“磷改性沸石催化剂”，通过引用将其各自的全部内容进一步并入本文中至描述本文所述本发明的任何部分所需的程度。
附图简述
图1显示绘出实施例1的甲醇脱水方法中的甲醇转化率和二甲醚和甲烷产量相对于温度的图。
图2显示绘出在实施例1的甲醇脱水方法中产生的甲烷的重量分数相对于温度的图，其中将～10重量％水加入或不加入甲醇进料中。
图3显示绘出对于实施例2的甲醇脱水方法中所用不同的γ-氧化铝催化剂，产生的甲烷的重量分数相对于温度的图。
图4显示对比用实施例3的2-甲基-2-戊烯异构化方法中所用的不同γ-氧化铝催化剂得到的产物分布的图。
图5显示对实施例2的甲醇脱水方法中所用不同γ-氧化铝催化剂的路易斯酸部位浓度进行比较的图。
图6对比在～150℃下吡啶吸附，其后在～150℃下抽空～30分钟以后，与在～450℃下在真空下除气～2小时以后，实施例2的甲醇脱水方法中所用γ-氧化铝催化剂的不同IR光谱。
图7显示对于实施例2的甲醇脱水方法中所用不同的γ-氧化铝催化剂，在～440℃下的甲烷形成相对于～3771cm-1下的羟基浓度的图。
实施方案详述
本文描述将C1-C4醇转化成汽油和/或柴油沸程产物的联合方法。作为第一步骤，联合方法包括使用包含γ-氧化铝且在选择性脱水催化剂的四面体配位铝部位上基本不含末端羟基的催化剂将醇选择性脱水成二烷基醚。第二步骤可有利地包括使二烷基醚脱水产物与沸石转化催化剂在转化条件下接触以形成汽油和/或柴油沸程烃产物。
醇脱水通常可在约250至约500℃的温度和约100至约7000kPa的压力下进行。在较高操作温度下，发现选择性脱水催化剂上强路易斯酸度的存在可导致非选择性醇分解成焦炭、甲烷、二氧化碳和氢气副产物，倾向于导致收率的损失、减活以及商业反应器中可能的危险温度提高。通过选择不具有强路易斯酸度且在四配位氧化铝部位上基本不含末端[OH-]基团的氧化铝(在吡啶IR谱中通过～3770cm-1下的吸收带表示)，醇分解可明显降低而不会负面地影响醇脱水反应。特别地，发现当选择性脱水催化剂的γ-氧化铝具有在～3770cm-1下小于10cm/g的归一化IR吸收率时得到有利结果。
如本文所用，术语“在～3770cm-1下的归一化吸收率”在本文中用于意指包含γ-氧化铝的选择性脱水催化剂的吡啶FTIR谱中集中在约3770cm-1的吸收率与包含γ-氧化铝的选择性脱水催化剂的背景谱线图中集中在约3770cm-1的相应吸收率之间的差，除以每单位面积的试样重量。在该试验中，背景FTIR谱在约～450℃下在真空，包括约1.3mPa或更小的压力P下除气至少～1小时以后，在～20至～80℃的温度T下取得。吡啶FTIR谱在(i)在约～450℃下在真空，包括约1.3mPa或更小的压力P下除气至少～1小时，(ii)将试样冷却至约150℃，(iii)使试样在约18托(约2.4kPa)的吡啶分压下在约150℃下吸收吡啶至少～20分钟，(iv)将试样在约150℃和所述压力P下抽空至少～20分钟，和(v)然后将试样冷却至所述温度T以后在相同温度T下取得。
本文所用优选催化剂中强路易斯酸度的不存在可方便地通过研究在催化剂用于使2-甲基-2-戊烯异构化时的产物分布而证明：
因此，如G.M.Kramer和G.B.McVicker，Acc.Chem.Res.19(1986)，第78页所述，催化剂上强酸部位的存在可倾向于有利于产生2,3二甲基-2丁烯：
而中等强度的部位可倾向于有利于3-甲基-2-戊烯：
且弱酸部位可倾向于有利于4-甲基-2-戊烯：
特别地，发现在～350℃、大气压力和～2.4hr-1的重时空速下使2-甲基-2-戊烯异构化时，有利的结果可在本发明选择性脱水方法中使用γ-氧化铝得到，可产生其中2,3-二甲基-2-丁烯与4-甲基-2-戊烯的重量比可以为小于0.2，例如小于0.05的异构化产物。
优选本发明方法中所用选择性脱水催化剂可具有小于1的α值。α值可以为与标准二氧化硅-氧化铝催化剂相比，沸石催化剂的酸活性的度量。α试验描述于美国专利No.3,354,078；the Journal of Catalysis，第4卷，第527页(1965)；第6卷，第278页(1966)；和第61卷，第395页(1980)中，通过引用将其各自关于该描述的内容并入本文中。其中所用试验的实验条件包括～538℃的恒定温度和可变的流速，如the Journal of Catalysis，第61页，第395页中详细描述的。
本文所述选择性醇脱水方法可在水的存在下进行，但醇进料的水浓度可低于用常规催化剂所需的，由此有利地提高每反应器程的醇的平衡转化率，和/或提高总方法效率。通常，C1-C4醇进料可包含小于15重量％水，例如小于10重量％水、小于7重量％水或小于4重量％水。另外或者作为选择，C1-C4醇进料可包含至少0.5重量％水，例如至少2重量％水。
本发明方法可用于将多种醇选择性脱水成它们相应的二烷基醚，但方法通常可用于具有1-6个碳原子，优选1-4个碳的正醇，尤其是甲醇和/或乙醇。通过使用本文所述选择性脱水催化剂，可将链烷烃副产物的量降至选择性脱水转化产物的小于1重量％。在特定实施方案中，醇可包含甲醇或者为甲醇，且二烷基醚可包含二甲醚或者为二甲醚。通常，联合方法可进一步包括使至少一部分二烷基醚(例如二甲醚)选择性脱水产物与沸石转化催化剂在转化条件下接触以形成汽油和/或柴油沸程烃产物的转化步骤。
另外或者作为选择，本发明可包括以下实施方案中的一个或多个。
实施方案1.将C1-C4醇转化成汽油和/或柴油沸程产物的联合方法，所述方法包括：使C1-C4醇进料在选择性脱水条件下与包含γ-氧化铝且在催化剂的四面体配位铝部位上基本不含末端羟基的催化剂接触以形成二烷基醚脱水产物；和使二烷基醚脱水产物与沸石转化催化剂在转化条件下接触以形成汽油和/或柴油沸程烃产物。
实施方案2.实施方案1的方法，其中选择性脱水催化剂的γ-氧化铝具有在～3770cm-1下小于10cm/g的归一化IR吸收率。
实施方案3.前述实施方案中任一项的方法，其中选择性脱水催化剂具有小于1的α值。
实施方案4.前述实施方案中任一项的方法，其中选择性脱水催化剂在～350℃、约大气压力和约2.4的重时空速下使2-甲基-2-戊烯异构化时产生其中2,3二甲基-2丁烯与4-甲基-2-戊烯的重量比小于0.2的异构化产物。
实施方案5.前述实施方案中任一项的方法，其中选择性脱水条件包括约250至约500℃的温度和约100至约700kPa的压力。
实施方案6.前述实施方案中任一项的方法，其中C1-C4醇进料包含小于15重量％水。
实施方案7.前述实施方案中任一项的方法，其中二烷基醚产物包含小于1重量％相应链烷烃。
实施方案8.前述实施方案中任一项的方法，其中C1-C4醇包含甲醇或者为甲醇，且其中二烷基醚包含二甲醚或者为二甲醚。
实施方案9.实施方案8的方法，其中转化步骤产生包含汽油和柴油沸程烃的产物。
现在参考以下非限定性实施例和附图更特别地描述本发明。
实施例
实施例1
在～100％甲醇在～55psig(～380kPag)、～10hr-1WHSV和～380℃、～400℃、～420℃和～440℃的多个温度下脱水中测试在本文中指定为催化剂1的市售γ-氧化铝的～50g试样。结果显示于图1中。每种情况下，将甲醇脱水成二甲醚和甲醇的平衡混合物。然而，显著量的甲烷由甲醇分解形成，在较高温度下特别如此。
随着将～10重量％水加入甲醇进料中而重复该方法，结果显示出图2中，所述图还绘出碳化硅对照(无甲醇脱水或分解)结果。可以看出甲醇进料的水含量提高至～10重量％显著降低非选择性甲醇分解和甲烷形成。然而，甲烷形成仍高于所需的。
实施例2
重复实施例1的方法，但使用下表1中汇总的三种不同的市售γ-氧化铝，以进行～100％甲醇的脱水。结果显示于图3中，并证明最好的结果显示用催化剂3得到。
表1
*TPAA＝程序升温氨吸附
在例行α试验中在标准条件(在流过保持在～1000℉下的反应器的He载气中的～100托己烷蒸气压力)下用正己烷裂化测量筛分γ-氧化铝试样的酸性活性。α试验由经～30分钟的4个均匀间隔测量组成。将数据绘出，并相对于定义具有1的α值的二氧化硅-氧化铝计算相对裂化速率。结果显示于上表1中。
实施例3
在塞流反应器中研究2-甲基-2-戊烯(2M2P)在实施例2中所用各催化剂下的气相异构化。在反应以前将～0.1g的量的各催化剂在～723K下在流动氦气中预处理约1小时。反应起初在～473K下进行～1小时，同时使～15mL/min的在氦气中的～7体积％2M2P流在约大气压力经过催化剂。然后将进料变换成氦气，并将催化剂冷却至～448K，然后冷却至～423K。在～473K、～448K和～423K下转换进料以后～10分钟取出催化剂试样。通过用FID检测器GC分析产物，结果汇总于图4中。
可以看出催化剂1显示出为最酸性的氧化铝，其具有约50％的中和强酸部位，而催化剂3的氧化铝显示出几乎不具有强酸部位，和总体上比其它氧化铝更少的酸部位。
实施例4
对于吸附吡啶的IR测量，将实施例2所用催化剂试样研磨并压成薄自持型片。片比重为约20–35mg/cm2。将各片放入装配有CaF2窗的IR透射池中。将IR比色杯加热并抽空。对于试样处理，将比色杯连接在高真空歧管上。可使用涡流分子泵在歧管中实现通过电离压力计测量的～2×10-6托(～0.3mPa)的压力。吡啶的吸附由连接在歧管上的玻璃瓶进行。吡啶分压通过BaratronTM测量。对于IR测量，将试样皿转移至NicoletTM670FTIR分光计中。光谱以～2cm-1分辨率进行，累积约512扫描。
在载入各片以前，将IR比色杯在流动空气中在～520℃下以约50ml/min的流速除气以除去痕量吡啶，其可能吸附在先前实验的比色杯的壁上。然后将催化剂片放入再生比色杯中并在～450℃下抽空～2小时以除去物理吸着的水并使试样活化。将试样在约2×10-6托(～0.3mPa)的最终压力下真空冷却至～80℃。在该状态下，将比色杯从歧管上分离并由除气试样取得光谱。该光谱称为背景谱线图。
对于吡啶的吸附，将比色杯再连接在歧管上，并使吡啶在室温(～23℃)下用其蒸气平衡～20分钟，导致约18托(～2.4kPa)的吡啶分压。在此期间，关闭比色杯上的阀并将试样加热至～150℃。在比色杯温度达到～150℃以后，关闭液体吡啶瓶上的阀，并使吡啶蒸气扩大到池中。使试样在～150℃下暴露于吡啶蒸气下～30分钟，然后在～150℃下抽空另外～30分钟，随后在真空下冷却至～80℃。最终压力为～5×10-6至～1×10-5托。取得具有吸附吡啶的催化剂的试样光谱。在～150℃下吡啶吸附和抽空以后吸附在试样上的吡啶的量称为弱和强结合吡啶的总量，其分别相当于弱和强路易斯酸部位的量。
在～150℃下吡啶吸附和随后在～150℃下将池抽空以后，将池再连接在歧管上并在～450℃下继续抽空～30分钟。在冷却至～80℃以后，收集另一试样光谱。在～450℃下抽空以后保留在试样上的吡啶的量称为强结合吡啶，其相当于强路易斯酸部位的量。
选择具有在～1450cm-1与～1455cm-1之间的峰位置的路易斯结合吡啶的19b环振动带评估路易斯酸部位。该带的基线定义为带的高频与低频侧的最小值之间的线性曲线。路易斯带结合到～1470cm-1和～1420cm-1的极限之间，并将综合极限设置与限定基线的点一致。在该研究中没有观察到具有在～1540cm-1与～1545cm-1之间的峰位置的吡啶离子的19a环振动带，其相当于布朗斯台德(Bronsted)酸部位。每g试样，路易斯结合吡啶的量使用方程式1)和2)中给出的比尔-朗伯法则计算：
1)Ai/εi＝c*d
2)Ai/εi＝n/Q
其中：
Ai：综合吸收率[cm-1]
εi：综合摩尔消光系数[cm/μmol]
c：吸附于片中的吡啶的浓度[μmol/cm3]
d：片厚度[cm]
Q：片的几何表面积[cm2]
n：吡啶的量[μmol]
综合摩尔消光系数从文献中采用，对路易斯结合吡啶而言为εL≈2.22cm/μmol。更改方程式1)并除以片质量m[mg]，得到方程式3)：
3)n/m＝(Ai*Q)/(εi*m)
其表述每g试样吸附的毫摩尔吡啶的量。
包含羟基且具有～3770cm-1至～3772cm-1的OH拉伸频率的特定路易斯酸-布朗斯台德碱对的浓度由吡啶吸附时～3771cm-1下的吸收率变化测定。
通过片比重归一化获得方程式4：
4)c[OH～3771cm-1]＝A[～3771cm-1，py～150℃]–A[～3771cm-1，vac～450℃]/(m/Q)
差示光谱[py～150℃]-[vac～450℃]产生相对于与OH拉伸方案相邻的高频区在～3771cm-1的OH带位置上的最小值。～3771cm-1带的密度定义为～3771cm-1下的最小值与～3850cm-1下的基线之间的吸收率差。如方程式4中所定义，～3771cm-1下的相应羟基浓度具有单位[cm/mg试样]。
图5显示在～150℃下吡啶吸附和抽空以后路易斯酸部位的总数量，和随后在～450℃下抽空以后评估的强结合吡啶的量。可以看出路易斯部位的总数以催化剂4<催化剂3<催化剂2≈催化剂1的顺序提高，而强路易斯酸部位的量遵循催化剂4≈催化剂3<催化剂2≈催化剂1的顺序。通过吸附吡啶的IR没有检测到布朗斯台德酸部位。
图6显示从在～150℃下吡啶吸附和随后抽空以后取得的试样光谱中减去在～450℃下真空除气～2小时以后的背景光谱而形成的氧化铝试样的OH拉伸频率范围内的不同光谱。
观察到吡啶通过在～3771cm-1下与羟基H键合而相互作用，产生转移至较低频率的扰动羟基的新OH带。H键合导致～3771cm-1下的带消失。因此，H键合在～150℃下吡啶吸附以后取得的试样光谱与在～450℃下除气以后取得的背景谱线图之间的差示光谱中产生在～3771cm-1下的未扰动OH拉伸频率位置上的负带。
图7显示～3771cm-1下羟基浓度与在DME反应器中在～440℃下在氧化铝下制备的重量％甲烷之间关系。催化剂将甲醇转化成甲烷的活性随着在～3771cm-1下的羟基浓度近似线性地提高。
尽管通过参考特定实施方案描述和阐述了本发明，本领域技术人员理解本发明本身适用于本文未必阐述的变化方案。为此，则应仅参考所附权利要求书以确定本发明的真实范围。

Claims (9)

1.将C1-C4醇转化成汽油和/或柴油沸程产物的联合方法，所述方法包括：
使C1-C4醇进料在选择性脱水条件下与包含γ-氧化铝且在催化剂的四面体配位铝部位上基本不含末端羟基的催化剂接触以形成二烷基醚脱水产物；和
使二烷基醚脱水产物与沸石转化催化剂在转化条件下接触以形成汽油和/或柴油沸程烃产物。
2.根据权利要求1的方法，其中选择性脱水催化剂的γ-氧化铝具有在～3770cm-1下小于10cm/g的归一化IR吸收率。
3.根据权利要求1或2的方法，其中选择性脱水催化剂具有小于1的α值。
4.根据前述权利要求中任一项的方法，其中选择性脱水催化剂在～350℃、约大气压力和约2.4的重时空速下使2-甲基-2-戊烯异构化时产生其中2,3二甲基-2丁烯与4-甲基-2-戊烯的重量比小于0.2的异构化产物。
5.根据前述权利要求中任一项的方法，其中选择性脱水条件包括约250至约500℃的温度和约100至约700kPa的压力。
6.根据前述权利要求中任一项的方法，其中C1-C4醇进料包含小于15重量％水。
7.根据前述权利要求中任一项的方法，其中二烷基醚产物包含小于1重量％相应链烷烃。
8.根据前述权利要求中任一项的方法，其中C1-C4醇为甲醇，且其中二烷基醚为二甲醚。
9.根据权利要求8的方法，其中转化步骤产生包含汽油和柴油沸程烃的产物。
CN201280062144.9A 2011-10-17 2012-10-16 醇选择性脱水成二烷基醚和联合醇制汽油方法 Pending CN103987454A (zh)

Applications Claiming Priority (13)

Application Number Priority Date Filing Date Title
US201161548015P 2011-10-17 2011-10-17
US201161548064P 2011-10-17 2011-10-17
US201161548052P 2011-10-17 2011-10-17
US201161548038P 2011-10-17 2011-10-17
US201161548057P 2011-10-17 2011-10-17
US201161548044P 2011-10-17 2011-10-17
US61/548,057 2011-10-17
US61/548,052 2011-10-17
US61/548,015 2011-10-17
US61/548,044 2011-10-17
US61/548,064 2011-10-17
US61/548,038 2011-10-17
PCT/US2012/060372 WO2013059164A2 (en) 2011-10-17 2012-10-16 Selective dehydration of alcohols to dialkylethers and integrated alcohol-to-gasoline processes

Publications (1)

Publication Number Publication Date
CN103987454A true CN103987454A (zh) 2014-08-13

Family

ID=47089187

Family Applications (6)

Application Number Title Priority Date Filing Date
CN201280062144.9A Pending CN103987454A (zh) 2011-10-17 2012-10-16 醇选择性脱水成二烷基醚和联合醇制汽油方法
CN201280061236.5A Pending CN103987456A (zh) 2011-10-17 2012-10-16 制备磷改性的沸石催化剂的方法
CN201280051136.4A Active CN104114277B (zh) 2011-10-17 2012-10-16 磷改性沸石催化剂
CN201280061246.9A Pending CN103987457A (zh) 2011-10-17 2012-10-16 制备磷改性的沸石催化剂的方法
CN201280051056.9A Pending CN103889574A (zh) 2011-10-17 2012-10-16 磷改性的沸石催化剂
CN201280051031.9A Pending CN103945939A (zh) 2011-10-17 2012-10-16 磷改性沸石催化剂

Family Applications After (5)

Application Number Title Priority Date Filing Date
CN201280061236.5A Pending CN103987456A (zh) 2011-10-17 2012-10-16 制备磷改性的沸石催化剂的方法
CN201280051136.4A Active CN104114277B (zh) 2011-10-17 2012-10-16 磷改性沸石催化剂
CN201280061246.9A Pending CN103987457A (zh) 2011-10-17 2012-10-16 制备磷改性的沸石催化剂的方法
CN201280051056.9A Pending CN103889574A (zh) 2011-10-17 2012-10-16 磷改性的沸石催化剂
CN201280051031.9A Pending CN103945939A (zh) 2011-10-17 2012-10-16 磷改性沸石催化剂

Country Status (8)

Country Link
US (6) US20130123557A1 (zh)
EP (1) EP2768609A1 (zh)
JP (2) JP2015501209A (zh)
CN (6) CN103987454A (zh)
CA (3) CA2852667A1 (zh)
SG (7) SG11201401256WA (zh)
WO (6) WO2013059162A1 (zh)
ZA (1) ZA201403600B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146236B (zh) * 2015-05-15 2019-06-18 内蒙古丰汇化工有限公司 由甲醇两步法制备烃类产品的方法

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3080040A1 (en) 2013-12-13 2016-10-19 Exxonmobil Research And Engineering Company Vehicle powertrain with onboard catalytic reformer
US10159963B2 (en) 2013-12-20 2018-12-25 Exxonmobil Research And Engineering Company Catalyst for conversion of oxygenates to aromatics
WO2015094697A1 (en) 2013-12-20 2015-06-25 Exxonmobil Chemical Patents Inc. Conversion of methanol to olefins and para-xylene
CA2968890C (en) * 2014-12-22 2021-07-06 Exxonmobil Research And Engineering Company Conversion of organic oxygenates to hydrocarbons
WO2016105888A1 (en) 2014-12-22 2016-06-30 Exxonmobil Research And Engineering Company Conversion of oxygenates to aromatics
CA2951911A1 (en) * 2015-12-17 2017-06-17 Gilead Sciences, Inc. Tank-binding kinase inhibitor compounds
CN110023458A (zh) 2016-12-07 2019-07-16 埃克森美孚研究工程公司 用于生产芳烃的组合烯烃和氧合物转化
WO2018106396A1 (en) 2016-12-07 2018-06-14 Exxonmobil Research And Engineering Company Integrated oxygenate conversion and olefin oligomerization
KR102500247B1 (ko) 2017-01-19 2023-02-15 엑손모빌 테크놀로지 앤드 엔지니어링 컴퍼니 가변 촉매 조성물에 의한 산소화물의 탄화수소로의 전환
US11918974B2 (en) * 2018-04-30 2024-03-05 The Regents Of The University Of Colorado Functionalization of zeolites
CA3108901A1 (en) * 2018-08-27 2020-03-05 Exxonmobil Research And Engineering Company Molecular sieves and a process for making molecular sieves
CN110876956B (zh) * 2018-09-06 2021-08-27 中国科学院大连化学物理研究所 一种用于乙醇脱水制乙烯反应zsm-11分子筛催化剂的改性方法
US11084983B2 (en) 2019-01-24 2021-08-10 Exxonmobil Research And Engineering Company Fluidized bed conversion of oxygenates with increased aromatic selectivity
EP4301699A1 (en) * 2021-03-02 2024-01-10 Basf Corporation Phosphorus modified uzm-35, methods of preparation, and methods of use thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931349A (en) * 1974-09-23 1976-01-06 Mobil Oil Corporation Conversion of methanol to gasoline components
US4665249A (en) * 1984-12-19 1987-05-12 Mobil Oil Corporation Method for feeding an MTG conversion reactor
CN101492349A (zh) * 2009-03-13 2009-07-29 清华大学 一种节能环保型甲醇脱水联产燃精二甲醚的生产工艺
CN101723775A (zh) * 2008-11-04 2010-06-09 杭州林达化工技术工程有限公司 甲醇或/和二甲醚制烃类的方法和设备

Family Cites Families (99)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6503410A (zh) 1963-02-21 1965-09-20
US3442795A (en) 1963-02-27 1969-05-06 Mobil Oil Corp Method for preparing highly siliceous zeolite-type materials and materials resulting therefrom
USRE28341E (en) 1964-05-01 1975-02-18 Marshall dann
US3308069A (en) 1964-05-01 1967-03-07 Mobil Oil Corp Catalytic composition of a crystalline zeolite
US3354078A (en) 1965-02-04 1967-11-21 Mobil Oil Corp Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide
US3293192A (en) 1965-08-23 1966-12-20 Grace W R & Co Zeolite z-14us and method of preparation thereof
US3702886A (en) * 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
US3709979A (en) 1970-04-23 1973-01-09 Mobil Oil Corp Crystalline zeolite zsm-11
US3832449A (en) 1971-03-18 1974-08-27 Mobil Oil Corp Crystalline zeolite zsm{14 12
US3766093A (en) 1972-01-07 1973-10-16 Mobil Oil Corp Treatment of organic cationcontaining zeolites
US3894104A (en) 1973-08-09 1975-07-08 Mobil Oil Corp Aromatization of hetero-atom substituted hydrocarbons
US4016245A (en) 1973-09-04 1977-04-05 Mobil Oil Corporation Crystalline zeolite and method of preparing same
CA1040187A (en) 1973-09-07 1978-10-10 Mobil Oil Corporation Method of preparing a crystalline aluminosilicate zeolite
US3941871A (en) 1973-11-02 1976-03-02 Mobil Oil Corporation Crystalline silicates and method of preparing the same
US3923636A (en) 1974-06-03 1975-12-02 Texaco Inc Production of lubricating oils
NZ178543A (en) * 1974-09-23 1978-04-03 Mobil Oil Corp Conversion catalyst, crystalline alumin osilicate zeolite containing phosphorus
US3906054A (en) * 1974-09-23 1975-09-16 Mobil Oil Corp Alkylation of olefins
US3972832A (en) 1974-09-23 1976-08-03 Mobil Oil Corporation Phosphorus-containing zeolite catalyst
US4044065A (en) 1974-09-23 1977-08-23 Mobile Oil Corporation Conversion utilizing a phosphorus-containing zeolite catalyst
US3972983A (en) 1974-11-25 1976-08-03 Mobil Oil Corporation Crystalline zeolite ZSM-20 and method of preparing same
US4016218A (en) 1975-05-29 1977-04-05 Mobil Oil Corporation Alkylation in presence of thermally modified crystalline aluminosilicate catalyst
CA1064890A (en) 1975-06-10 1979-10-23 Mae K. Rubin Crystalline zeolite, synthesis and use thereof
US4143084A (en) * 1976-07-19 1979-03-06 Mobil Oil Corporation Di-alkylbenzene isomer mixtures
PL199748A1 (pl) * 1976-07-19 1978-04-24 Mobil Oil Corp Sposob selektywnego wytwarzania p-dwualkilobenzenow
US4035430A (en) * 1976-07-26 1977-07-12 Mobil Oil Corporation Conversion of methanol to gasoline product
EP0007126A1 (en) * 1978-07-06 1980-01-23 Union Carbide Corporation Cumene synthesis process
US4234231A (en) 1978-12-06 1980-11-18 Mobil Oil Corporation Method for restoring a leached formation
US4197413A (en) * 1978-12-14 1980-04-08 Mobil Oil Corporation Production of 3-methylphenol
US4423266A (en) * 1980-10-08 1983-12-27 Mobil Oil Corporation Extending isomerization catalyst life by treating with phosphorous and/or steam
US4356338A (en) * 1979-07-27 1982-10-26 Mobil Oil Corporation Extending catalyst life by treating with phosphorus and/or steam
US4401556A (en) 1979-11-13 1983-08-30 Union Carbide Corporation Midbarrel hydrocracking
US4400571A (en) * 1981-04-27 1983-08-23 Uop Inc. Hydrocarbon isomerization process
DE3117135A1 (de) 1981-04-30 1982-11-18 Bayer Ag, 5090 Leverkusen Kristallines alumosilicat, verfahren zu dessen herstellung sowie dessen verwendung zur katalytischen umwandlung von methanol und/oder dimethylether in kohlenwasserstoffe
US4429176A (en) * 1982-02-08 1984-01-31 Mobil Oil Corporation Active zeolite catalysts of improved stability
US4409132A (en) * 1982-03-18 1983-10-11 Mobil Oil Corporation Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion
US4404414A (en) * 1982-09-28 1983-09-13 Mobil Oil Corporation Conversion of methanol to gasoline
DE3370469D1 (en) * 1982-11-16 1987-04-30 Hoechst Ag Aluminium silicates with a zeolite structure and process for their preparation
DK149326C (da) 1984-01-10 1986-09-15 Haldor Topsoe As Fremgangsmaade til fremstilling af katalysatorer til anvendelse ved ethersyntese
US4556477A (en) 1984-03-07 1985-12-03 Mobil Oil Corporation Highly siliceous porous crystalline material ZSM-22 and its use in catalytic dewaxing of petroleum stocks
JPS6115848A (ja) * 1984-06-30 1986-01-23 Agency Of Ind Science & Technol リン酸カルシウム変性ゼオライト型触媒による低級オレフインの製造方法
US4582815A (en) * 1984-07-06 1986-04-15 Mobil Oil Corporation Extrusion of silica-rich solids
US4560542A (en) * 1984-12-06 1985-12-24 Exxon Research And Engineering Co. Method for the preparation of zeolites using a low water low alkali metal content gel
US4590321A (en) 1985-06-12 1986-05-20 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4665251A (en) 1985-06-12 1987-05-12 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4826667A (en) 1986-01-29 1989-05-02 Chevron Research Company Zeolite SSZ-25
US4954325A (en) 1986-07-29 1990-09-04 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis and use
IT1205681B (it) 1987-05-26 1989-03-31 Eniricerche Spa Materiale sintetico cristallino poroso contenente ossidi di silicio e boro
US5250277A (en) 1991-01-11 1993-10-05 Mobil Oil Corp. Crystalline oxide material
GB9101456D0 (en) * 1991-01-23 1991-03-06 Exxon Chemical Patents Inc Process for producing substantially binder-free zeolite
AU652222B2 (en) * 1991-03-12 1994-08-18 Mobil Oil Corporation Preparation of cracking catalysts, and cracking process using them
US5110776A (en) * 1991-03-12 1992-05-05 Mobil Oil Corp. Cracking catalysts containing phosphate treated zeolites, and method of preparing the same
US5171921A (en) * 1991-04-26 1992-12-15 Arco Chemical Technology, L.P. Production of olefins
JPH04371231A (ja) * 1991-06-18 1992-12-24 N E Chemcat Corp 排気ガス浄化用触媒
US5236575A (en) 1991-06-19 1993-08-17 Mobil Oil Corp. Synthetic porous crystalline mcm-49, its synthesis and use
EP0568913A3 (en) * 1992-05-03 1995-03-22 Dalian Chemical Physics Inst Process for the conversion of methanol into light olefins and catalyst used therefor.
CN1039392C (zh) * 1992-09-22 1998-08-05 中国科学院大连化学物理研究所 甲醇转化为轻烯烃的催化剂和反应工艺
CA2112190C (en) 1992-12-24 2000-02-22 Hiroshi Miura Process for removing nitrogen oxides from oxygen rich exhaust gas
JPH06238131A (ja) * 1992-12-24 1994-08-30 Tosoh Corp 窒素酸化物の除去方法
US5362697A (en) 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
US5457078A (en) 1993-11-29 1995-10-10 Mobil Oil Corporation Manufacture of improved zeolite Beta catalyst
US5993642A (en) * 1994-11-23 1999-11-30 Exxon Chemical Patents Inc. Hydrocarbon conversion process using a zeolite bound zeolite catalyst
CN1049406C (zh) 1995-10-06 2000-02-16 中国石油化工总公司 具有mfi结构含磷和稀土的分子筛
ES2124154B1 (es) 1995-11-08 1999-12-01 Univ Politecnica De Valencia C Metodo de preparaciion y propiedades cataliticas de un solido microporoso con alta superficie externa.
ES2105982B1 (es) 1995-11-23 1998-07-01 Consejo Superior Investigacion Zeolita itq-1
KR0165014B1 (ko) * 1996-03-11 1999-01-15 선우현범 섬유상 제올라이트 zsm-5 및 그 제조 방법
US6423879B1 (en) 1997-10-02 2002-07-23 Exxonmobil Oil Corporation Selective para-xylene production by toluene methylation
US6417421B1 (en) 1998-03-03 2002-07-09 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and process therefor and therewith
US6187983B1 (en) * 1998-04-29 2001-02-13 Exxon Chemical Patents Inc Converting oxygenates to olefins in the presence of electromagnetic energy
US20020049133A1 (en) * 1999-03-02 2002-04-25 Michael S. Ziebarth High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith
US6835863B2 (en) * 1999-07-12 2004-12-28 Exxonmobil Oil Corporation Catalytic production of light olefins from naphtha feed
EP1116519A1 (en) 2000-01-12 2001-07-18 Akzo Nobel N.V. Solid-state phosphorous activation of crystalline porous silicates
US7125818B2 (en) * 2002-10-08 2006-10-24 Exxonmobil Research & Engineering Co. Catalyst for wax isomerate yield enhancement by oxygenate pretreatment
US6756030B1 (en) 2003-03-21 2004-06-29 Uop Llc Crystalline aluminosilicate zeolitic composition: UZM-8
US7060864B2 (en) 2003-09-30 2006-06-13 Saudi Basic Industries Corporation Toluene methylation process
CN1257769C (zh) 2003-10-31 2006-05-31 中国石油化工股份有限公司 一种含磷和金属组分的mfi结构分子筛及其应用
US7399727B2 (en) 2004-04-23 2008-07-15 Saudi Basic Industries Corporation Zeolite catalyst and method
US7285511B2 (en) 2004-04-23 2007-10-23 Saudi Basic Industries Corporation Method of modifying zeolite catalyst
US7375048B2 (en) * 2004-04-29 2008-05-20 Basf Catalysts Llc ZSM-5 additive
KR100632563B1 (ko) 2004-09-10 2006-10-09 에스케이 주식회사 접촉 분해용 고체산 촉매 및 이를 이용하여 전범위납사로부터 경질 올레핀을 선택적으로 제조하는 공정
US7304194B2 (en) 2005-05-05 2007-12-04 Saudi Basic Industries Corporation Hydrothermal treatment of phosphorus-modified zeolite catalysts
US7368410B2 (en) 2005-08-03 2008-05-06 Saudi Basic Industries Corporation Zeolite catalyst and method of preparing and use of zeolite catalyst
CN100391610C (zh) * 2005-08-15 2008-06-04 中国石油化工股份有限公司 含分子筛的催化裂解流化床催化剂
BRPI0505365A (pt) 2005-12-01 2007-09-25 Petroleo Brasileiro Sa processo de obtenção de zeólitas mais resistentes à desativação hidrotérmica
US7662737B2 (en) 2005-12-22 2010-02-16 Saudi Basic Industries Corporation Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof
CN101134172B (zh) 2006-08-31 2010-10-27 中国石油化工股份有限公司 一种烃类转化催化剂
CN1915821A (zh) * 2006-09-06 2007-02-21 北京盛大京泰化学研究所 一种磷改性的zsm－5分子筛的制备方法
EP2025402A1 (en) * 2007-07-31 2009-02-18 Total Petrochemicals Research Feluy Phosphorus modified molecular sieves, their use in conversion of organics to olefins
US7563740B2 (en) * 2006-12-19 2009-07-21 Lyondell Chemical Technology, L.P. Direct epoxidation process
EP2036873A1 (en) * 2007-09-12 2009-03-18 Total Petrochemicals Research Feluy Use of phosphorus modified molecular sieves in conversion of organics to olefins
JP5355910B2 (ja) * 2008-03-13 2013-11-27 旭化成ケミカルズ株式会社 シリカ成形体
TW200918486A (en) * 2007-09-18 2009-05-01 Asahi Kasei Chemicals Corp Process for production of propylene
EP2082801A1 (en) 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Process for obtaining modified molecular sieves
US8846559B2 (en) * 2008-11-03 2014-09-30 Saudi Basic Industries Corporation Stable shape-selective catalyst for aromatic alkylation and methods of using and preparing
WO2010133436A1 (en) * 2009-05-19 2010-11-25 Shell Internationale Research Maatschappij B.V. Process for the manufacture of a formulated oxygenate conversion catalyst, formulated oxygenate conversion catalyst and process for the preparation of an olefinic product
US8062987B2 (en) * 2009-10-05 2011-11-22 Saudi Basic Industries Corporation Phosphorus-containing zeolite catalysts and their method of preparation
CN102049293B (zh) 2009-10-27 2012-11-14 中国石油化工股份有限公司 Zsm-5/a1po4-5双结构分子筛和甲醇制汽油的催化剂和方法
US8906224B2 (en) * 2009-12-23 2014-12-09 Exxonmobil Research And Engineering Company Sweet or sour service catalytic dewaxing in block mode configuration
TWI473651B (zh) * 2010-11-25 2015-02-21 Asahi Kasei Chemicals Corp Silica shaped body, method for producing the same, and production method of propylene using silica molded body
JP2012139640A (ja) * 2010-12-28 2012-07-26 Jx Nippon Oil & Energy Corp 単環芳香族炭化水素製造用触媒および単環芳香族炭化水素の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931349A (en) * 1974-09-23 1976-01-06 Mobil Oil Corporation Conversion of methanol to gasoline components
US4665249A (en) * 1984-12-19 1987-05-12 Mobil Oil Corporation Method for feeding an MTG conversion reactor
CN101723775A (zh) * 2008-11-04 2010-06-09 杭州林达化工技术工程有限公司 甲醇或/和二甲醚制烃类的方法和设备
CN101492349A (zh) * 2009-03-13 2009-07-29 清华大学 一种节能环保型甲醇脱水联产燃精二甲醚的生产工艺

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A.B. MOHAMMED SAAD ET AL: ""Comparative study of the effects of sodium impurity and amorphisation on the Lewis acidity of γ-alumina"", 《APPLIED CATALYSIS A: GENERAL》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146236B (zh) * 2015-05-15 2019-06-18 内蒙古丰汇化工有限公司 由甲醇两步法制备烃类产品的方法

Also Published As

Publication number Publication date
US20130123557A1 (en) 2013-05-16
SG11201401522XA (en) 2014-05-29
CA2852667A1 (en) 2013-04-25
SG11201401523QA (en) 2014-05-29
US20130102825A1 (en) 2013-04-25
WO2013059169A1 (en) 2013-04-25
CA2852669C (en) 2020-09-15
SG11201401253XA (en) 2014-05-29
SG10201602933TA (en) 2016-05-30
EP2768609A1 (en) 2014-08-27
US20130096355A1 (en) 2013-04-18
JP2015501209A (ja) 2015-01-15
US20130096358A1 (en) 2013-04-18
WO2013059162A1 (en) 2013-04-25
JP2014531981A (ja) 2014-12-04
SG11201401524TA (en) 2014-05-29
ZA201403600B (en) 2018-11-28
CA2852780A1 (en) 2013-04-25
WO2013059161A1 (en) 2013-04-25
SG11201401256WA (en) 2014-05-29
WO2013059176A1 (en) 2013-04-25
CA2852669A1 (en) 2013-04-25
US20130281753A1 (en) 2013-10-24
CN103987456A (zh) 2014-08-13
CN104114277B (zh) 2017-02-15
US20130102824A1 (en) 2013-04-25
JP6295199B2 (ja) 2018-03-14
US9821299B2 (en) 2017-11-21
WO2013059164A3 (en) 2013-10-31
WO2013059164A2 (en) 2013-04-25
SG11201401258PA (en) 2014-05-29
WO2013059161A8 (en) 2014-08-28
CN103987457A (zh) 2014-08-13
CN103889574A (zh) 2014-06-25
WO2013059172A1 (en) 2013-04-25
CN103945939A (zh) 2014-07-23
CN104114277A (zh) 2014-10-22

Similar Documents

Publication Publication Date Title
CN103987454A (zh) 醇选择性脱水成二烷基醚和联合醇制汽油方法
Wu et al. Ethylene formation from ethanol dehydration using ZSM-5 catalyst
Rownaghi et al. Yield of gasoline-range hydrocarbons as a function of uniform ZSM-5 crystal size
Kim et al. Gas-phase dehydration of glycerol over silica–alumina catalysts
Zhang et al. Enhancement in the aromatic yield from the catalytic fast pyrolysis of rice straw over hexadecyl trimethyl ammonium bromide modified hierarchical HZSM-5
Pathak et al. Catalytic conversion of glycerol to value added liquid products
Di et al. A ZSM-5/MCM-48 based catalyst for methanol to gasoline conversion
Schreiber et al. Hydrodeoxygenation of fatty acid esters catalyzed by Ni on nano-sized MFI type zeolites
Yu et al. Bifunctional Pd/Al-SBA-15 catalyzed one-step hydrogenation–esterification of furfural and acetic acid: A model reaction for catalytic upgrading of bio-oil
Jing et al. Direct dehydration of 1, 3-butanediol into butadiene over aluminosilicate catalysts
US9902663B2 (en) Method for dehydrating a mixture containing ethanol and isopropanol
US20100144907A1 (en) Process for conversion of synthesis gas to hydrocarbons using a zeolite-methanol catalyst system
Migliori et al. Methanol to dimethylether on H-MFI catalyst: The influence of the Si/Al ratio on kinetic parameters
CN106215970B (zh) Hzsm-5分子筛催化剂的改性处理方法及应用
Deischter et al. Aromatisation of bio-derivable isobutyraldehyde over HZSM-5 zeolite catalysts
CN107848939A (zh) 以乙醛作为主要副产物的生产丙烯酸的新型方法
Gołąbek et al. Ethylene formation by dehydration of ethanol over medium pore zeolites
Lü et al. The effect of P modification on the acidity of HZSM-5 and P-HZSM-5/CuO-ZnO-Al2O3 mixed catalysts for hydrogen production by dimethyl ether steam reforming
CN101081801B (zh) 一种制取小分子烯烃的方法
He et al. Fabrication of extra–framework Al in ZSM–5 to enhance light olefins production in catalytic cracking of n–pentane
Vlasenko et al. Insight into the active site nature of zeolite H-BEA for liquid phase etherification of isobutylene with ethanol
US20160184810A1 (en) Dehydration catalyst and method of making and using the same
US9902662B2 (en) Method for dehydrating a mixture containing ethanol and n-propanol
Xia et al. Fe–Al isomorphous and self-pillared ZSM-5 nanosheet catalyst for cracking of n-heptane with enhanced selectivity of light olefins
CN109174169A (zh) 一种乙醇脱水制乙烯的改性分子筛催化剂及其应用

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140813