CN1333737A - 在硫化床反应器中从甲醇制备低级烯烃的催化方法 - Google Patents

在硫化床反应器中从甲醇制备低级烯烃的催化方法 Download PDF

Info

Publication number
CN1333737A
CN1333737A CN99815451A CN99815451A CN1333737A CN 1333737 A CN1333737 A CN 1333737A CN 99815451 A CN99815451 A CN 99815451A CN 99815451 A CN99815451 A CN 99815451A CN 1333737 A CN1333737 A CN 1333737A
Authority
CN
China
Prior art keywords
catalyzer
reaction
zeolite
methanol
reactor
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.)
Granted
Application number
CN99815451A
Other languages
English (en)
Other versions
CN1163458C (zh
Inventor
G·鲍伯
R·加奈
D·伊万尼斯库
G·伊格纳提斯库
R·伯伊鲁
R·伯杰加
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.)
KASAL CHEMICAL AG
Original Assignee
KASAL CHEMICAL AG
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26653545&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1333737(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by KASAL CHEMICAL AG filed Critical KASAL CHEMICAL AG
Publication of CN1333737A publication Critical patent/CN1333737A/zh
Application granted granted Critical
Publication of CN1163458C publication Critical patent/CN1163458C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
    • C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • 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
    • 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
    • C10G3/62—Catalyst regeneration
    • 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
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/703—Activation
    • 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
    • C10G2400/20—C2-C4 olefins
    • 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
    • Y02P20/584—Recycling of catalysts
    • 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
    • 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
    • Y02P30/40—Ethylene production

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

通过在基于SAPO－34沸石的微球状催化剂上、在流化床反应器－再生器系统中发生持续的反应－再生,将甲醇转化成具有93－100%转化度和大于90%选择性的C2－C4低分子烯烃,其中大于80%是乙烯和丙烯。通过反应温度和进料空间速度的改变而在相对较大的范围,0.69－1.36,内改变乙烯/丙烯的比例。

Description

在流化床反应器中从甲醇制备低级烯烃的催化方法
发明背景
发明领域
本发明涉及一种在具有持续的催化剂再生的流化床反应器中，使用SAP0-34沸石将甲醇转化为烯烃的方法。
发明背景技术
低级烯烃，即乙烯和丙烯，是聚合物生产的重要原料。
工业中，乙烯和丙烯是在所谓的烃热解工艺中通过C2-C4链烷烃和石油馏分的蒸汽裂化得到的。将来随着石油储备的不足，烯烃需求量持续上升，使得研究人员对源自非石油原料的新的烯烃生产技术感兴趣。
C2-C4烯烃生产的其中一个更吸引人的方法是基于甲醇的催化转化，因为甲醇是在先进的技术中制造的，该先进的技术具有高达800,000mt/年单线的能力，并具有广泛的原料可利用性，像天然气体包括甲烷、煤和可再生的生物物质。
仅仅在源于莫比尔石油(Mobil Oil)公司研究人员的高硅沸石ZSM-5合成之后，甲醇转化成具有工业可接受产率的低级烯烃才变为可能(美国专利3,702,886)。这之后，许多其他类型的沸石也在甲醇至烯烃的反应中被测试，如ZSM-34(美国专利4079096)，丝光沸石(罗马尼亚专利87685，美国专利3244766)，菱钾废石(美国专利4079096)，砷-硅酸盐(德国申请公开2830830)，硼-硅酸盐(德国申请公开2830787)。在基于合成铝-硅酸盐的许多专利，如美国专利4062905，3979472，3911041和德国申请公开2755299，2615150中也要求了甲醇至烯烃的转化。
这些催化剂在烯烃中显示出低选择性，且其必须在470-570℃下，用空气周期性地再生。
为了提高烯烃的选择性和增加催化利的有效循环，大量研究了改变沸石和反应条件的许多方法。通过沸石的硅化作用(美国专利4100219，4145315)，由铝提取增加Si/Al的原子比例(美国专利4447669，德国申请公开2935863)，用Cs，Ba，Pb，Tl(美国专利4066714)，B，Mg(美国专利4049573，德国专利3300892)，Hf，Zr(美国专利4481376，德国申请公开3300982)浸渍或离子交换，用惰性材料稀释催化剂(美国专利4025572)，用蒸汽(英国专利2127036)或HF(美国专利4486617)的部分钝化，而得到了令人感兴趣的结果。用Mg-Mg或Mg-Sb的复杂处理(罗马尼亚专利87413)已经给出了良好的结果。改变某些反应参数，例如在大气压下的使用(美国专利4025575)，进料的蒸汽稀释(美国专利4083889)或用空气(美国专利4433189)、氧气(美国专利4049735)和乙醛(美国专利4374295)稀释。
源于联合碳化物公司研究人员的称作SAPO-沸石(美国专利4310440，4440871)的Si-Al-P沸石的合成已经打开了甲醇转化至烯烃，MTO方法的前景。中国的研究人员第一次证明了SAPO-34沸石，在实践中，它是直到甲醇总计转化为89％的C2-C4烯烃得到的，其中57-59％为乙烯且乙烯/丙烯的摩尔比为2.24-2.31(应用催化，Vol.40，Nr.1-2，1988，p.316)。由于催化剂的焦化有效循环仅仅为1-2小时。
美国专利4440871中合成的SAPO-34沸石的使用提出了与有关热和蒸汽稳定性和烯烃选择性相反的文献数据。必须强调的是沸石的合成是用昂贵的材料，如异丙醇铝，氢氧化四乙铵或奎宁环进行的。由于铵离子交换和补充煅烧步骤的必要性反应混合物用NaOH中和使得SAPO-34的生产技术变得复杂。
热分析(Gr.Pop等，催化的发展，Bucharest，1，1993，p，l)显示出结晶小于4微米的SAPO-34沸石具有良好的热和蒸汽稳定性。
在具有固定的床层催化剂的管式反应器中和流化床中具有催化剂再生的流化床反应器中实现MTO-过程。将蒸发的甲醇进料与沸石催化剂混合，装料到提升管接触区域的底部，以形成穿过提升管向上流的混悬液(美国专利4328384)。在甲醇至烯烃的反应中，具有固定床层催化剂的反应器有许多不利之处，因为反应热的除去是困难的且频繁的催化剂再生使生产能力降低。在有效循环中，逐渐增加的在催化剂上沉积的焦炭持续改变了反应产物组成。
流化床反应器和持续的催化剂再生消除了这些不利条件，但是在提升管反应器中不能够实现最佳的反应条件。
流化床反应中的动力研究已经显示出在大约2秒的较短反应时间内，有最大量的乙烯形成。(C.Tsakiris等，Proc.IFAC Symposium DYCORD92 College Park，Maryland，April 1992)，这在提升管反应器中是不能够得到的。提升管反应器中决定产物选择性的两个重要反应参数，接触时间和温度，不能够很好地控制。
发明概述
本发明消除了这些困难，因为催化剂是从廉价原料，如工业氧化铝，含水的硅溶胶和模板(template)中得到的，磷酸四乙基铵是“在原位”制备的：由溴乙烷和三乙胺制备。甲醇的转化和持续的催化剂再生是在没有提升管的流化床反应器中进行的，将甲醇进料注入到紧密的床层催化剂中。
发明详述
催化剂的合成仅仅是用廉价的，工业原料即三乙胺，溴乙烷，浓磷酸，大于70％重量，水合氧化铝和硅溶胶制备的，所有均具有非常低的、0.01％以下的Na含量，进行的。可以用氨水稳定浓的硅溶胶。在本专利条件的情况下，通过Si-Al-P无定形凝胶的水热处理，在相对较短的沸石化处理时间内，得到SAPO-34沸石的活性的、H形式。在350-580℃煅烧除去有机模板之后，所得到的沸石作为催化剂使用。在二氧化硅基质中，在400-450℃下将沸石雾化成微球。在结晶，煅烧，雾化步骤中的无定形凝胶细合物和反应条件，可以确保得到用于甲醇转化至烯烃的活性和选择性催化剂，其具有适宜于流化床过程的颗粒化曲线和良好的热和机械耐受性。
甲醇转化至主要为乙烯和丙烯的低级烯烃的过程，是在包括反应器-再生器系统的流化床中进行的，其具有焦化催化剂从反应器到再生器的和再生催化剂从再生器到反应器的持续循环。将甲醇进料和再生空气注入到催化剂的紧密床层中。这个系统确保催化剂床层中的恒定温度和大约2秒的接触时间。反应器和再生器提升管仅仅防止流的转向。由于提升管中蒸汽或氮气的净化，通过吸附进反应器中的甲醇和烃及吸附进再生器中的氧气净化催化剂。由此避免了再生器中的燃烧而导致的甲醇损失。也可以通过吸附进再生器中催化剂上的氧气来避免反应器中甲醇的燃烧。通过再生器中吸附在催化剂上的氧气可以避免反应器中甲醇的燃烧。催化剂的净化确保在反应产物中非常低的碳氧化物，这对于烯烃分离的成本具有补充降低作用。为了恒定保持催化剂的活性，可从反应器或再生器中除去较小的量，同时加入等量的新催化剂。反应器和再生器具有接收甲醇转化和焦燃烧的热反应的内部装置。
下列实施例举例说明，但是不限制本发明。
实施例
实施例1
通过已知的方法从三乙胺，溴乙烷和73％磷酸制备25％的四乙胺磷酸盐水溶液。
在软化水中悬浮65％Al2O3水合氧化铝和40％三羟铝石，并在搅拌条件下加料到于3500l高压釜的磷酸四乙基铵溶液中，然后加入用氨水稳定的28％SiO2，硅溶胶。用磷酸将最终的悬浮液PH固定在6.3-6.5。
混悬液中组分的摩尔比为：
P2O5∶Al2O3∶SiO2∶TEAOH＝1∶1.5∶0.37∶1.1
在6个连续的步骤中进行沸石化：结晶的第一个步骤在198-205℃时从15％的整个悬浮液开始。20小时之后，在30-40℃冷却高压并加入一新的量的混悬液。在相同的条件下继续沸石化过程。该操作被重复5次。整个沸石化过程，包括步骤间的冷却，大约是100小时。
通过XRD技术的所得产品的分析对照，显示出多于90％的SAPO-34沸石和大约7％未反应的三羟铝石。
表1列出了在所得SAPO-34沸石的XRD-光谱中的特征带，和用于对照的美国专利4440871中报道的SAPO-34光谱。
表1.XRD-光谱中的特征带(Cu灯，Cu kα＝1.5418)
            美国专利4440871     样品，实施例1
    2θ     d，    100Xi/IO  2θ  d，  100Xi/IO
    9.45-9.65     9.36-9.17     81-100  9.63  9.18     100
    12.8-13.05     6.92-6.78     8-20  12.87  6.88     18
    13.95-14.20     6.35-6.24     8-23  14.17  6.25     21
    16.0-16.2     5.54-5.47     25-54  16.16  5.4     47
    17.85-18.15     4.97-4.89     11-26  18.3  4.89     22
    19     4.67     0-2    -    -     -
    20.55-20.9     4.32-4.25     44-100  20.67  4.3     97
    22.05-22.50     4.03-3.95     0-5  22.33  3.98     4
    23.0-23.15     3.87-3.84     2-10  23.15  3.84     8
    24.95-25.4     3.57-3.51     12-87  25.38  3.52     26
    25.8-26.0     3.45-3.43     14-24  25.97  3.43     17
    27.5-27.7     3.243-3.220     1-4  27.68  3.22     4
    28.05-28.4     3.181-3.143     1-12  28.4  3.14     4
    29.2-29.6     3.058-3.018     3-9  29.15  3.06     4
    30.5-30.7     2.931-2.912     19-75  30.67  2.91     29
    31.05-31.4     2.880-2.849     15-28  31.25  2.86     22
    32.2-32.4     2.780-2.763     1-5  32.42  2.76     3
    33.4-33.85     2.683-2.648     0-6  33.66  2.66     4
    34.35-34.65     2.611-2.589     4-15  34.48  2.6     7
    36.0-36.5     2.495-2.462     2-11  36.33  2.47     4
    38.8-38.9     2.321-2.315     0-2  38.8  2.32     2
    39.6-39.7     2.276-2.070     2-4  39.76  2.27     5
微晶体的大小在1-3微米之间(图1)。图2显示通过在空气和蒸汽中煅烧，沸石是稳定的。
在沸石化阶段，产生了具有16.7％固体的沸石混悬液，该固体以6.71/m2小时的滤过速度而被分离。用软化水清洗和空气干燥后，得到具有57％湿度的沸石糊剂。
以沸石：SiO260-40的重量比，将用氨水稳定的28％SiO2硅溶胶与沸石的潮湿糊剂混合，用40％硝酸固定PH在6.3，并在进口400-450℃和出口175-180℃、压力下用热空气雾化。注入压力为4-4.5巴，雾化器以50kg/hour的生产力干燥催化剂。最终在两个恒定的水平，350-400℃3小时和580℃10小时，以100℃/min的加热速度煅烧催化剂。催化剂的冷却时间是4小时。催化剂制备使用的所有原料具有0.01％以下的Na含量。图3显示出所得到的微球状催化剂具有良好的流动性能和颗粒化曲线。
图4是具有流化床层催化剂系统的反应-再生流程图，该流化床层催化剂系统是用于甲醇转化至烯烃，MTO方法，本发明一部分的。根据图4，反应器R1填充100l催化剂，再生器R2具有30l催化剂。通过进行流化形成紧密的流体床层催化剂2-2’和上部的分界面3-3’。在R1中将紧密的流化床层催化剂的温度固定在440℃，在R2中固定在480-610℃。R1和R2中的温度是通过内部热交换器9-9’中的循环加热-冷却剂控制的。甲醇和再生空气是通过连接5-5’和筛网4-4’分别以1001/小时和1000Nl/小时进料的。
反应器和再生器之间的催化剂循环是通过用氮气作为提升用气体通过转移线12-12’进行的。通过用调节器11-11’，它充当催化剂流速调节阀门10-10’，保持恒定的压降而在R1和R2中得到催化剂床层的自动控制水平。在R1和R2的顶部排出输送的催化剂和反应产品，并在旋风分离器系统6-7和6’-7’中分离。穿过管线8-8’，输送的催化剂在反应器-再生器反应区域中循环。在每48小时中，大约2kg催化剂从分离旋风器7或7’的底部排出，用等量的新催化剂通过装料装置15或15’替换。从而补偿催化剂的不可逆钝化。
管线13中的焦化的催化剂具有4.3重量％的焦，管线13’中的再生催化剂具有1.7重量％的焦保留水平。在热交换器14中冷却从旋风分离器7中排出的反应产物，并在分离器16中分离成不凝结(uncondensed)的烃部分和液体部分，该液体部分包含工艺水，二甲醚和未转化的甲醇。将气态烃部分输送到常规的烯烃分离单位中。通过蒸馏从液体部分中分离出甲醇和二甲醚并将其循环至反应器R1中。
将在热交换器16’中冷却之后并在柱14’中洗涤的再生气体排到大气中。
表2给出了物流组成。
表2.实施例1中得到的流出物组成
    组分 不凝结的有机相容器16，重量％ 液相容器16，重量％ 再生气体，退出旋风分离器7’，重量％
    氧      -      -     1.5
    氮      -      -     82.7
    一氧化碳      -      -     4.3
    二氧化碳      -      -     11
    氢     0.2      -     0.5
    甲烷     1.6      -     -
    乙烷     0.3      -     -
    乙烯     46.8      -     -
    丙烷     2.5      -     -
    丙烯     40      -     -
    丁烷     0.53      -     -
    1-丁烯     1.74      -     -
    异-丁烯     0.71      -     -
    2-丁烯     4.04      -     -
    C5+烃     1.58      -     -
    甲醇      -     0.5     -
    二甲醚      -      -     -
    水      -     99.5     -
实施例2
使用实施例1的装置和催化剂，通过温度和空间速度的改变，而在相对较大的0.69-1.29范围内，改变乙烯/丙烯的比例。
表3中给出了一些举例结果。
表3.不同反应条件中的反应产品组成
    实验号     1  2  3     4   5     6
                                a.反应条件
    温度℃     400  405  410  435  470     490
    LHSV，h-1     1.1  0.6  1  1.9  1.5     2.7
                               b.不凝结的有机相分析，重量％
    氢     0.08  0.23  0.13  0.12  0.71     0.1
    碳氧化物      -   -   -  0.14  0.21      -
    甲烷     0.62  1.78  0.81  1.12  2.42     0.91
    乙烷     0.26  0.9  0.42  0.64   -      -
    乙烯     28.3  48.5  34.1  43  42.45     36.8
    丙烷     2.3  5.3  2.4  2.43  5.9     2.27
    丙烯     41.2  35.7  42.9  42  32.95     45.4
    丁烷     0.9  0.88  0.8  0.68  0.8     0.72
    1-丁烯     1.94  1.19  1.75  1.63  1.94     1.7
    异-丁烯     0.77  1.23  0.75  0.44  1.04     0.2
    2-丁烯     7.22  2.56  6.68  4.87  7.13     5.2
    C5+烃     2.41  0.95  2.84  1.58  4.45     1.75
    二甲醚     14  0.78  6.42  1.35   -     4.95
                                  c.液相分析，重量％
    二甲醚     1.5   -  0.5   -   -      -
    甲醇     12  3  9  1.5  0.1     1.5
    水     86.5  97  90.5  98.5  99.9     98.5
                             d.催化剂上沉积的焦，重量％
    反应器R1存在(exist)     4.9  5  4.8  4.5  4.6     4.7
    再生器R2存在(exit)     1.2  2.8  0.6  0.9  1.2     1.9
    e.乙烯/丙烯的比例     0.69  1.36  0.79  1.02  1.29     0.81
    f.甲醇的转化     93.3  98.3  95  99.2  100     99.2
参考文献
1.Brent M.Lok，Celeste M.Messina，Robert L.Pation，Richard T.Gajek，Thomas R.Catnnan，Edith M.Flanigen(联合碳化物公司)，美国专利第4440871号(1984年4月3日)，国际分类号B01J27/14；美国分类号502/241。
2.Ajit V.Sapre(莫比尔公司)，美国专利第4590320号(1986年5月20日)，国际分类号C07C1/20；美国分类号585/324；585/315。
3.Nicholas Davidiuk，James Haddad(莫比尔公司)，美国专利第4328384号(1982年5月4日)，国际分类号C07C1/20；美国分类号585/469；585/639；585/733。

Claims (4)

1.使用在基质中的微球状SAPO-34沸石作为催化剂，通过甲醇转化生产低分子烯烃的方法，包含：使用磷酸四乙基铵作为结晶剂，在不存在Na+的情况下通过水热处理制备沸石，在400-490℃和0.6-2.7h-1液体空间速度下的流化床层催化剂中，通过在紧密的催化剂床层中的注入进料，将甲醇转化为低级烯烃。
2.权利要求1的方法，其中通过用空气在480-610℃下连续再生，和新的催化剂的加入，同时将等量的使用过的催化剂从反应-再生系统中回收，保持催化剂活性和选择性的恒定。
3.权利要求1，2的方法，其中分离未反应的甲醇和二甲醚并在反应阶段中再循环。
4.权利要求1，2，3的方法，其中通过反应温度和进料的空间速度的改变，在0.69-1.36的范围内改变反应产物中乙烯/丙烯的比例。
CNB998154512A 1997-10-02 1999-01-11 在流化床反应器中从甲醇制备低级烯烃的催化方法 Expired - Lifetime CN1163458C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RO97-01829A RO114524B1 (ro) 1997-10-02 1997-10-02 Procedeu de fabricare a oleofinelor cu greutate moleculara mica prin conversia catalitica in strat fluidizat a metanolului
PCT/RO1999/000001 WO2000041986A1 (en) 1997-10-02 1999-01-11 Catalytic process for the preparation of light olefins from methanol in a fluidised bed reactor

Publications (2)

Publication Number Publication Date
CN1333737A true CN1333737A (zh) 2002-01-30
CN1163458C CN1163458C (zh) 2004-08-25

Family

ID=26653545

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB998154512A Expired - Lifetime CN1163458C (zh) 1997-10-02 1999-01-11 在流化床反应器中从甲醇制备低级烯烃的催化方法

Country Status (17)

Country Link
US (1) US6710218B1 (zh)
EP (1) EP1140743B1 (zh)
JP (1) JP2002534487A (zh)
CN (1) CN1163458C (zh)
AT (1) ATE305912T1 (zh)
AU (1) AU768633B2 (zh)
BR (1) BR9916757A (zh)
CA (1) CA2359501C (zh)
DE (1) DE69927604T2 (zh)
EA (1) EA005667B1 (zh)
ES (1) ES2259470T3 (zh)
NO (1) NO20013401L (zh)
NZ (1) NZ512738A (zh)
PL (1) PL193075B1 (zh)
RO (1) RO114524B1 (zh)
TR (1) TR200102007T2 (zh)
WO (1) WO2000041986A1 (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101778928A (zh) * 2007-06-12 2010-07-14 Ifp公司 通过植物油加氢处理制成的具有高乙烯、丙烯和聚合物收率的蒸汽裂化原料的生产
CN101225013B (zh) * 2008-01-31 2010-12-29 中国天辰工程有限公司 甲醇、二甲醚转化制取低碳烯烃气体产物的分离装置及方法
CN101943689A (zh) * 2010-07-09 2011-01-12 神华集团有限责任公司 用于成型催化剂水热处理与固定流化床催化剂评价的装置
CN101130469B (zh) * 2006-08-23 2011-04-13 中国科学院大连化学物理研究所 一种甲醇制取低碳烯烃过程中再生热量的回收方法
CN101048355B (zh) * 2004-11-01 2011-06-15 环球油品公司 烯烃生成工艺中的外第二级旋风分离系统
CN101239873B (zh) * 2007-02-07 2011-07-13 中国石油化工股份有限公司 含氧化合物转化制低碳烯烃的方法
CN102665903A (zh) * 2009-10-13 2012-09-12 道达尔炼油与销售部 由杂原子有机化合物生产c10+烃的方法

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6166282A (en) * 1999-08-20 2000-12-26 Uop Llc Fast-fluidized bed reactor for MTO process
WO2001025150A1 (en) * 1999-10-01 2001-04-12 Pop, Grigore Process for the synthesis of silicoaluminophosphate molecular sieves
AU779140B2 (en) * 1999-11-18 2005-01-06 Exxon Chemical Patents Inc. Method for the synthesis of molecular sieves
JP2002191980A (ja) * 2000-12-11 2002-07-10 Uop Llc 立方晶形態を有する金属アルミノリン酸塩モレキュラーシーブ及び同モレキュラーシーブ用いるメタノールからオレフィンへの転化方法
DK1214974T3 (da) * 2000-12-13 2008-09-29 Uop Llc Metalloaluminiumphosphatmolekylsigte med kubisk krystalmorfologi og methanol til olefinfremgangsmåde under anvendelse af sigten
ES2192923B1 (es) * 2001-01-30 2004-10-01 Universidad Politecnica De Valencia Material cristalino microporoso (itq-19) con caracteristicas laminares, su procedimiento de preparacion y su uso como catalizador en procesos de conversion catalitica de compuestos organicos.
US6812372B2 (en) * 2001-03-01 2004-11-02 Exxonmobil Chemical Patents Inc. Silicoaluminophosphate molecular sieve
BR0116944B1 (pt) * 2001-03-22 2011-11-16 catalisador e processo para converter metanol em olefinas leves.
US7084319B2 (en) 2003-12-05 2006-08-01 Exxonmobil Chemical Patents Inc. Catalyst fluidization in oxygenate to olefin reaction systems
US7371915B1 (en) * 2004-06-25 2008-05-13 Uop Llc Conversion of oxygenate to propylene using moving bed technology
US7408092B2 (en) * 2004-11-12 2008-08-05 Uop Llc Selective conversion of oxygenate to propylene using moving bed technology and a hydrothermally stabilized dual-function catalyst
US7829750B2 (en) 2004-12-30 2010-11-09 Exxonmobil Chemical Patents Inc. Fluidizing a population of catalyst particles having a low catalyst fines content
US7829030B2 (en) 2004-12-30 2010-11-09 Exxonmobil Chemical Patents Inc. Fluidizing a population of catalyst particles having a low catalyst fines content
US20070059236A1 (en) * 2005-09-09 2007-03-15 Broach Robert W Molecular sieves with high selectivity towards light olefins in methanol to olefin conversion
EP2004776A1 (en) 2006-03-31 2008-12-24 ExxonMobil Chemical Patents Inc. Product recovery in gas-solids reactors
US7744746B2 (en) 2006-03-31 2010-06-29 Exxonmobil Research And Engineering Company FCC catalyst stripper configuration
ITMI20061231A1 (it) * 2006-06-26 2007-12-27 Eni Spa Proxcesso e materiali zeolitici per la separazione di gas
JP5050466B2 (ja) * 2006-09-21 2012-10-17 三菱化学株式会社 プロピレンの製造方法
CN101157593B (zh) 2007-03-07 2010-09-22 中国科学院大连化学物理研究所 由甲醇或/和二甲醚生产低碳烯烃的方法
US20080260631A1 (en) 2007-04-18 2008-10-23 H2Gen Innovations, Inc. Hydrogen production process
EP2022565A1 (en) * 2007-07-06 2009-02-11 Casale Chemicals S.A. Process for preparing silicoaluminoposphate (SAPO) molecular sieves, catalysts containing said sieves and catalytic dehydration processes using said catalysts
CN101229921B (zh) * 2007-11-16 2010-09-01 南开大学 Sapo-46硅磷酸铝分子筛的合成方法
US8419835B2 (en) 2010-08-10 2013-04-16 Uop Llc Apparatuses and methods for gas-solid separations using cyclones
RU2505356C2 (ru) * 2011-12-27 2014-01-27 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) Способ получения катализатора и способ синтеза олефинов c2-c4 в присутствии катализатора, полученного этим способом
CN103288570B (zh) * 2013-04-28 2015-01-21 神华集团有限责任公司 一种甲醇制烯烃的装置及其方法
CN104437611A (zh) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 无粘结剂纳米ZSM-5/β共生沸石分子筛催化剂
CN104437614B (zh) * 2013-09-24 2018-04-06 中国石油化工股份有限公司 无粘结剂ZSM‑5/β共结晶分子筛催化剂及其制备方法和用途
CN104437610A (zh) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 无粘结剂纳米ZSM-5/β共生分子筛催化剂
CN103878016B (zh) * 2013-09-30 2017-01-18 洛阳市科创石化科技开发有限公司 一种用于甲醇制备丙烯的复合分子筛催化剂及其用途
JP6230722B2 (ja) * 2013-12-03 2017-11-15 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ メタノール及び／又はジメチルエーテルから低級オレフィンを製造する反応装置
WO2016094171A1 (en) * 2014-12-11 2016-06-16 Uop Llc Elevated pressure 'high value' mto process for improved sapo performance
CN105126903A (zh) * 2015-07-29 2015-12-09 太原大成环能化工技术有限公司 废旧甲醇制烯烃催化剂细粉的再利用方法
CN111974462A (zh) * 2020-09-01 2020-11-24 大唐国际化工技术研究院有限公司 再利用废mtp催化剂的方法
EP4082659A4 (en) * 2020-10-16 2023-04-26 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences REGENERATION DEVICE, DEVICE FOR PRODUCTION OF LOW CARBON OLEFINS AND USES THEREOF
CN114602547B (zh) * 2020-12-08 2023-08-15 中国科学院大连化学物理研究所 一种复合型催化剂及其制备方法、应用

Family Cites Families (76)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3244766A (en) 1961-06-06 1966-04-05 Norton Co Catalytic production of olefins
US3702886A (en) 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
US3911041A (en) 1974-09-23 1975-10-07 Mobil Oil Corp Conversion of methanol and dimethyl ether
US3979472A (en) 1975-03-28 1976-09-07 Mobil Oil Corporation Process for manufacturing hydrocarbons
US4025575A (en) 1975-04-08 1977-05-24 Mobil Oil Corporation Process for manufacturing olefins
US4025576A (en) 1975-04-08 1977-05-24 Mobil Oil Corporation Process for manufacturing olefins
US4066714A (en) 1975-12-08 1978-01-03 Mobil Oil Corporation Manufacture of light olefins
US4049573A (en) 1976-02-05 1977-09-20 Mobil Oil Corporation Zeolite catalyst containing oxide of boron or magnesium
US4100219A (en) 1976-03-31 1978-07-11 Mobil Oil Corporation Silica-modified zeolite catalyst and conversion therewith
US4025572A (en) 1976-05-12 1977-05-24 Mobil Oil Corporation Manufacture of hydrocarbons
US4062905A (en) 1976-08-02 1977-12-13 Mobil Oil Corporation Manufacture of light olefins
US4079096A (en) 1976-11-04 1978-03-14 Mobil Oil Corporation Manufacture of light olefins
US4049735A (en) 1976-12-09 1977-09-20 Mobil Oil Corporation Use of elemental oxygen to inhibit elution of antimony from an antimony-ZSM-5 catalyst
DE2755299A1 (de) 1976-12-20 1978-06-22 Asea Ab Zylinderfoermiger langgestreckter ofen zur behandlung von material unter hoher temperatur und hohem druck
US4145315A (en) 1976-12-23 1979-03-20 Mobil Oil Corporation Silica-modified zeolite catalyst
US4083889A (en) 1977-05-26 1978-04-11 Mobil Oil Corporation Process for manufacturing ethylene
DE2830830A1 (de) 1978-07-13 1980-01-31 Basf Ag Kristalline arsensilikate
DE2830787B2 (de) 1978-07-13 1981-02-19 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von stickstoffhaltigen kirstallinen Metallsilikaten mit Zeolithstniktur
NZ191302A (en) 1978-09-05 1981-10-19 Mobil Oil Corp Producing hydrocarbon mixture from alcohol feed using crystalline aluminosilicate zeolite catalyst
US4328384A (en) 1979-10-30 1982-05-04 Mobil Oil Corporation Fluid zeolite catalyst conversion of alcohols and oxygenated derivatives to hydrocarbons by controlling exothermic reaction heat
DE3024536A1 (de) 1980-06-28 1982-02-04 Hoechst Ag, 6000 Frankfurt Aluminiumsilikat-katalysator
US4310440A (en) 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
FR2519335B1 (fr) 1982-01-04 1986-05-02 Azote & Prod Chim Production d'hydrocarbures a partir de methanol en presence de catalyseurs du type zeolithe
US4433189A (en) 1982-03-18 1984-02-21 Mobil Oil Corporation Catalytic conversion of methanol to light olefins
US4374295A (en) 1982-04-15 1983-02-15 Mobil Oil Corporation Catalytic conversion of methanol to light olefins
US4440871A (en) 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
US4480145A (en) 1982-09-16 1984-10-30 Mobil Oil Corporation Catalysts for the conversion of methanol to ethylene plus gasoline
US4499327A (en) 1982-10-04 1985-02-12 Union Carbide Corporation Production of light olefins
US4677243A (en) 1982-10-04 1987-06-30 Union Carbide Corporation Production of light olefins from aliphatic hetero compounds
DE3243520A1 (de) 1982-11-25 1984-05-30 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von c(pfeil abwaerts)2(pfeil abwaerts)- bis c(pfeil abwaerts)4(pfeil abwaerts)-olefinen aus methanol/dimethylether
DE3300892A1 (de) 1983-01-13 1984-07-19 Claudius Peters Ag, 2000 Hamburg Hammer fuer einen hammerbrecher
US4499315A (en) 1983-11-15 1985-02-12 Union Carbide Corporation Conversion of certain hydrocarbons using silicoaluminophosphate catalysts
US4590320A (en) 1984-08-31 1986-05-20 Mobil Oil Corporation Conversion of methanol to olefins in a tubular reactor with light olefin co-feeding
JPS62501426A (ja) 1984-12-18 1987-06-11 ユニオン　カ−バイド　コ−ポレ−シヨン シリコアルミノホスフエ−トモレキユラ−シ−ブを使用する水素化分解触媒及び方法
US4752651A (en) 1986-06-16 1988-06-21 Union Carbide Corporation Production of light olefins
US4861938A (en) 1987-07-07 1989-08-29 Uop Chemical conversion process
US4973792A (en) 1987-07-07 1990-11-27 Uop Chemical conversion process
US4873390A (en) 1987-07-07 1989-10-10 Uop Chemical conversion process
US4814541A (en) 1987-07-07 1989-03-21 Uop Chemical conversion process
US4849575A (en) 1987-11-25 1989-07-18 Uop Production of olefins
US5095163A (en) * 1991-02-28 1992-03-10 Uop Methanol conversion process using SAPO catalysts
DE4137013A1 (de) 1991-11-11 1993-05-13 Basf Ag Verfahren zur herstellung von aminen durch reduktive aminierung
US5126308A (en) 1991-11-13 1992-06-30 Uop Metal aluminophosphate catalyst for converting methanol to light olefins
NO174341B1 (no) 1991-12-23 1994-04-21 Polymers Holding As Fremg for fremst av krystallinske mikroporose SiAl-fosfater med kontrollert Si-innh, krystallinske mikroporose SiAl-fosfater med forbedret stabilitet mot deaktivering og en anv av disse ved fremstilling av olefiner fra metanol
JP2724420B2 (ja) 1992-05-27 1998-03-09 エクソン・ケミカル・パテンツ・インク 酸素化物の転化における酸抽出されたモレキュラーシーブ触媒の使用
WO1993024431A1 (en) 1992-05-27 1993-12-09 Exxon Chemical Patents Inc. Production of high purity olefins
US5744680A (en) 1995-08-10 1998-04-28 Uop Process for producing light olefins
US5817906A (en) 1995-08-10 1998-10-06 Uop Llc Process for producing light olefins using reaction with distillation as an intermediate step
US5888921A (en) 1995-10-25 1999-03-30 Abb Lummus Global Inc. Binary molecular sieves having a core and shell of different structures and compositions
US5962762A (en) 1995-12-13 1999-10-05 Sun; Hsian-Ning Use of transition metal containing small pore molecular sieve catalysts in oxygenate conversion
US6040264A (en) 1996-04-04 2000-03-21 Exxon Chemical Patents Inc. Use of alkaline earth metal containing small pore non-zeolitic molecular sieve catalysts in oxygenate conversion
ES2230610T3 (es) 1996-05-29 2005-05-01 Exxonmobil Chemical Patents Inc. Catalizador de conversion de hidrocarburos y su uso.
US5925586A (en) 1996-12-31 1999-07-20 Exxon Chemical Patents, Inc. Phosphorus modified small pore molecular sieve catalysts, and their use in the production of light olefins
US5952538A (en) 1996-12-31 1999-09-14 Exxon Chemical Patents Inc. Use of short contact time in oxygenate conversion
TW412510B (en) 1996-12-31 2000-11-21 Exxon Chemical Patents Inc Oxygenate conversions using small pore non-zeolitic molecular sieve catalysts
US5925800A (en) 1996-12-31 1999-07-20 Exxon Chemical Patents Inc. Conversion of oxygenates to hydrocarbons with monolith supported non-zeolitic molecular sieve catalysts
US6051746A (en) 1997-06-18 2000-04-18 Exxon Chemical Patents Inc. Oxygenate conversions using modified small pore molecular sieve catalysts
US5914433A (en) 1997-07-22 1999-06-22 Uop Lll Process for producing polymer grade olefins
TWI234556B (en) * 1997-07-23 2005-06-21 Mitsubishi Gas Chemical Co Catalysts for methanol conversion reactions
US6455749B1 (en) 1997-10-03 2002-09-24 Exxonmobil Chemical Patents, Inc. Method for increasing light olefin yield by conversion of a heavy hydrocarbon fraction of a product to light olefins
US6137022A (en) 1997-12-03 2000-10-24 Exxon Chemical Patents Inc Process for increasing the selectivity of a reaction to convert oxygenates to olefins
US6005155A (en) 1997-12-03 1999-12-21 Exxon Chemicals Patents Inc. Modification of molecular sieve catalyst for reduced methane production during conversion of oxygenates to olefins
US5912393A (en) 1997-12-09 1999-06-15 Uop Llc Metallo aluminophosphate molecular sieve with novel crystal morphology and methanol to olefin process using the sieve
US6207872B1 (en) 1997-12-09 2001-03-27 Uop Llc Metallo aluminophosphate molecular sieve with cubic crystal morphology and methanol to olefin process using the sieve
US6046373A (en) 1998-04-29 2000-04-04 Exxon Chemical Patents Inc. Catalytic conversion of oxygenates to olefins
US6429348B1 (en) 1998-05-05 2002-08-06 Exxonmobil Chemical Patents, Inc. Method for selectively producing propylene by catalytically cracking an olefinic hydrocarbon feedstock
CA2302955C (en) 1998-07-02 2007-12-18 Christiaan P. Van Dijk Modified catalyst and a method of using same for conversion of methanol into olefins
US6482999B2 (en) 1999-02-17 2002-11-19 Exxonmobil Chemical Patents, Inc. Method for improving light olefin selectivity in an oxygenate conversion reaction
US6051745A (en) 1999-03-04 2000-04-18 Phillips Petroleum Company Silicoaluminophosphate material, a method of making such improved material and the use thereof in the conversion of oxygenated hydrocarbons to olefins
US6472569B1 (en) 1999-04-16 2002-10-29 Phillips Petroleum Company Silicoaluminophosphate material, a method of making such improved material and the use thereof in the conversion of oxygenated hydrocarbons to an olefin and/or an ether
US6046371A (en) 1999-05-05 2000-04-04 Phillips Petroleum Company Silicoaluminophosphate material, a method of making such improved material and the use thereof in the conversion of oxygenated hydrocarbons to olefins
US6316683B1 (en) 1999-06-07 2001-11-13 Exxonmobil Chemical Patents Inc. Protecting catalytic activity of a SAPO molecular sieve
US6395674B1 (en) 1999-06-07 2002-05-28 Exxon Mobil Chemical Patents, Inc. Heat treating a molecular sieve and catalyst
US6225254B1 (en) 1999-06-07 2001-05-01 Exxon Mobil Chemical Patents Inc. Maintaining acid catalyst sites in sapo molecular sieves
US6166282A (en) 1999-08-20 2000-12-26 Uop Llc Fast-fluidized bed reactor for MTO process
WO2001025150A1 (en) 1999-10-01 2001-04-12 Pop, Grigore Process for the synthesis of silicoaluminophosphate molecular sieves

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101048355B (zh) * 2004-11-01 2011-06-15 环球油品公司 烯烃生成工艺中的外第二级旋风分离系统
CN101130469B (zh) * 2006-08-23 2011-04-13 中国科学院大连化学物理研究所 一种甲醇制取低碳烯烃过程中再生热量的回收方法
CN101239873B (zh) * 2007-02-07 2011-07-13 中国石油化工股份有限公司 含氧化合物转化制低碳烯烃的方法
CN101778928A (zh) * 2007-06-12 2010-07-14 Ifp公司 通过植物油加氢处理制成的具有高乙烯、丙烯和聚合物收率的蒸汽裂化原料的生产
CN104725177A (zh) * 2007-06-12 2015-06-24 Ifp新能源公司(法国) 通过植物油加氢处理制成的具有高乙烯、丙烯和聚合物收率的蒸汽裂化原料的生产
CN104725177B (zh) * 2007-06-12 2016-11-30 Ifp新能源公司 通过植物油加氢处理制成的具有高乙烯、丙烯和聚合物收率的蒸汽裂化原料的生产
CN101225013B (zh) * 2008-01-31 2010-12-29 中国天辰工程有限公司 甲醇、二甲醚转化制取低碳烯烃气体产物的分离装置及方法
CN102665903A (zh) * 2009-10-13 2012-09-12 道达尔炼油与销售部 由杂原子有机化合物生产c10+烃的方法
CN101943689A (zh) * 2010-07-09 2011-01-12 神华集团有限责任公司 用于成型催化剂水热处理与固定流化床催化剂评价的装置
CN101943689B (zh) * 2010-07-09 2012-11-28 神华集团有限责任公司 用于成型催化剂水热处理与固定流化床催化剂评价的装置

Also Published As

Publication number Publication date
CA2359501C (en) 2008-10-07
PL193075B1 (pl) 2007-01-31
EP1140743A1 (en) 2001-10-10
EA200100727A1 (ru) 2002-06-27
DE69927604D1 (de) 2006-02-16
AU2079299A (en) 2000-08-01
EP1140743B1 (en) 2005-10-05
NO20013401D0 (no) 2001-07-09
ATE305912T1 (de) 2005-10-15
PL349783A1 (en) 2002-09-09
NZ512738A (en) 2003-08-29
AU768633B2 (en) 2003-12-18
CA2359501A1 (en) 2000-07-20
CN1163458C (zh) 2004-08-25
TR200102007T2 (tr) 2001-12-21
JP2002534487A (ja) 2002-10-15
WO2000041986A1 (en) 2000-07-20
US6710218B1 (en) 2004-03-23
BR9916757A (pt) 2001-09-25
EA005667B1 (ru) 2005-04-28
ES2259470T3 (es) 2006-10-01
RO114524B1 (ro) 1999-05-28
DE69927604T2 (de) 2006-07-13
NO20013401L (no) 2001-07-09

Similar Documents

Publication Publication Date Title
CN1163458C (zh) 在流化床反应器中从甲醇制备低级烯烃的催化方法
AU780552B2 (en) Process to control conversion of C4+ and heavier stream to lighter products in oxygenate conversion reactions
US9573860B2 (en) Process to make olefins from oxygenates
EP2547638B1 (en) Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts
US9561990B2 (en) Process to make olefins from oxygenates
US9573859B2 (en) Process to make olefins and aromatics from organics
TW200303237A (en) Molecular sieve compositions, catalyst thereof, their making and use in conversion processes
WO2009156436A2 (en) Process to make olefins from organics
CN1894175A (zh) 催化反应的改进或与催化反应相关的改进
CN102884026A (zh) 制备烯烃的方法
KR101494229B1 (ko) 중간생성물의 실시간 모니터링을 통한 메탄올로부터 경질올레핀 제조용 순환유동층 공정의 효율적 운전
EP2374781A1 (en) Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts
CN1915935A (zh) 提高丙烯选择性的方法
US11453622B2 (en) Catalytic conversion of alcohols and/or ethers to olefins
KR100598270B1 (ko) 유동층 반응기에서 메탄올로부터 경질 올레핀 제조방법
EP2366682A1 (en) Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts
CN108325477B (zh) 一种用于含氧化合物转化的串级移动床反应系统和应用方法
CN108329186B (zh) 一种串级移动床的甲醇转化方法
CN108314601B (zh) 一种用于含氧化合物转化的串级移动床反应系统和方法
RU2409538C2 (ru) Непрерывный способ селективного превращения оксигената в пропилен с использованием технологии подвижного слоя и гидротермически стабилизированной бифункциональной катализаторной системы

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20040825

CX01 Expiry of patent term