[go: up one dir, main page]

CN113498360B - 用于从c4-c7碳氢化合物生产轻质烯烃的催化剂 - Google Patents

用于从c4-c7碳氢化合物生产轻质烯烃的催化剂 Download PDF

Info

Publication number
CN113498360B
CN113498360B CN201980092892.3A CN201980092892A CN113498360B CN 113498360 B CN113498360 B CN 113498360B CN 201980092892 A CN201980092892 A CN 201980092892A CN 113498360 B CN113498360 B CN 113498360B
Authority
CN
China
Prior art keywords
catalyst
zeolite
core
shell
layered double
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.)
Active
Application number
CN201980092892.3A
Other languages
English (en)
Other versions
CN113498360A (zh
Inventor
C·瓦塔纳吉
C·罗道姆
A·蒂瓦萨西
S·彭派尼克
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.)
PTT Global Chemical PCL
Original Assignee
PTT Global Chemical PCL
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
Priority claimed from TH1801008085A external-priority patent/TH1801008085A/th
Application filed by PTT Global Chemical PCL filed Critical PTT Global Chemical PCL
Publication of CN113498360A publication Critical patent/CN113498360A/zh
Application granted granted Critical
Publication of CN113498360B publication Critical patent/CN113498360B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • 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
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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
    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/73—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline having a two-dimensional layered crystalline structure, e.g. layered double hydroxide [LDH]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/77—Compounds characterised by their crystallite size
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/06—Sulfides
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/08—Halides
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • 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
    • 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
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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
    • C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
    • 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
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Nanotechnology (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明涉及用于从C4‑C7碳氢化合物通过催化裂解反应生产轻质烯烃的催化剂和通过所述催化剂生产轻质烯烃的方法，其中所述催化剂具有核‑壳结构，所述核‑壳结构包含硅/铝摩尔比为2‑250的沸石核和层状双氢氧化物壳(LDH)。本发明的催化剂提供底物向产物的高转化百分比和对轻质烯烃产物的高选择性。

Description

用于从C4-C7碳氢化合物生产轻质烯烃的催化剂
技术领域
化学涉及用于从C4-C7碳氢化合物生产轻质烯烃的催化剂。
背景技术
轻质烯烃，例如乙烯和丙烯，是重要的聚合物(例如聚乙烯、聚丙烯等)的生产中重要的石油化工前体。目前，轻质烯烃的工业化生产使用通过热蒸汽裂解分离自天然气的石脑油或乙烷的分子分解作为主要方法。所述方法要求高温，其耗能高，并且也在系统中造成大量炼焦积聚。因此，为了维护不得不经常中止方法。通过石脑油化合物的催化裂解来生产轻质烯烃是为了增加轻质烯烃产率的替代方法，其使用低反应温度并且减少在系统中炼焦积聚。
迄今，已有关于通过石脑油化合物的催化裂解生产烯烃技术的报告。例如，来自Honeywell UOP LLC的研究人员(US7981273B2、US8157985B2和US20100105974A1)已经发展了铝硅酸盐或沸石催化剂，通过添加钾、钠、有机铵阳离子化合物和镓，来用于碳氢化合物，包括石脑油化合物，催化裂解为烯烃化合物，其中有机铵阳离子化合物具有多种类型，例如乙基三甲基铵(ETMA)、二乙基二甲基铵(DEDMA)以及四乙基铵(TEA)等。通过混合不同类型催化剂，也出现了催化剂的发展，其中第一组使用的沸石例如菱沸石、毛沸石、镁碱沸石和ZSM-22等，与第二组例如硅/铝比在200以上的纳米-硅沸石混合。
此外，来自ExxonMobil Oil Corporation的研究人员(US6222087B1和US20050070422A1)已经研究和发展用于通过C4-C7碳氢化合物的催化裂解生产轻质烯烃的催化剂，其中所研究的催化剂为沸石，例如ZSM-22、ZSM-35、SAPO-34、ZSM-5和ZSM-11，包含硅/铝比在300以上的沸石。此外，还有混合含磷的和金属氧化物(例如镓、钛和锆)以为了增加丙烯化合物的产率。
为了以最高效率通过催化裂解生产轻质烯烃，当与副反应相比时，特别是副反应为轻质烷烃产物(例如甲烷、乙烷和丙烷)，所使用的催化剂必须提供对轻质烯烃产物的最高选择性轻质烯烃产物。因而，为了提供对轻质烯烃产物的最高选择性和为了减少催化剂失活等发展催化剂，用于所述方法的催化剂不断发展。
用于通过以沸石催化剂催化裂解碳氢化合物来生产轻质烯烃的催化剂，其发展是有趣的。沸石化合物是结晶的铝硅酸盐，是一种在石油和石油化工产业可用于多种用途的催化剂，例如吸附剂、离子交换剂以及作为催化剂或载体使用的多相催化剂。沸石突出的性能在于，针对应用反应的性质、热和化学稳定性(chemicals stability)可调节的pH，以及择形性。因此，可应用所述包含如下催化剂：合适的酸位点和孔，其具有对所需轻质烯烃产物的选择性的特性。
然而，工业中常规沸石的使用仍有局限，例如低催化效率、快速退化以及困难且复杂的再生催化剂的方法。对所述常规沸石造成局限的主要因素为质量传递和扩散限制，其由沸石结构中的孔尺寸造成，在大的沸石结晶结构中孔尺寸非常小(埃等级)，造成临界质量传递。这对前驱体在活性位点的反应造成困难，并可能由于通过中间体的重整反应形成大量焦炭而造成催化剂失活。此外，在通过碳氢化合物的催化裂解生产轻质烯烃的方法中，为了获得轻质烯烃产物的高选择性，常规沸石的使用局限来自其他原因，例如在外表面上的活性位点的副反应。
WO2018157042公开具有核-壳结构的催化剂组合物和所述催化剂的制备方法，其中核和壳材料为中孔材料，其中核包含至少一种选自TS-1、硅沸石、硅沸石-1、BETA、ZSM-5、AIPO-5、MCM-41和SAPO的材料，并进一步包含金属，例如铂、金、钯、铜、镍、铁、钴、钌、锑、铋或金属氧化物。壳包含至少一种选自微孔沸石、多孔二氧化硅、氧化铝、氧化钛、二氧化锆、碳、金属有机框架(MOF)、沸石咪唑酯框架(ZIF)或共价有机框架(COF)的材料。然而，该研究未报道所述催化剂在轻质烯烃生产方法中的应用。
WO2018108544公开在从丙烷生产轻质烯烃的方法中使用的催化剂组合物，其中所述催化剂包含两种物理混合的组分。第一种组分包含层状双氢氧化物形式的固体载体，其选自具有脱氢活性金属(例如铂)的二氧化铝、二氧化硅、二氧化锆、二氧化钛、氧化镁、氧化钙或其混合物。作为共组分的第二部分包含无机载体，其选自具有过渡金属的氧化铝、二氧化硅、二氧化锆、二氧化钛、沸石或其混合物，其中过渡金属选自钼、钨、铼或其混合物。
WO2017009664A1公开具有核-壳结构的催化剂的特征和所述催化剂的制备方法。核材料为硅酸盐、硅酸铝、硅酸钒、硅酸铁、磷酸硅-铝(SAPO)或磷酸铝(AIPO)。壳材料为层状双氢氧化物。然而，所述专利没有提到所述催化剂在任何生产方法中的应用。
从上述提到的原因，本发明目的在于制备用于从C4-C7碳氢化合物通过催化裂解生产轻质烯烃的催化剂和使用所述催化剂生产轻质烯烃的方法，其中所述催化剂具有包含沸石核和层状双氢氧化物壳的核-壳结构，以适于在具有如下的轻质烯烃生产中的应用：对轻质烯烃的高选择性、小量副产物(例如甲烷、乙烷和丙烷)和增加催化反应的稳定性。此外，相比于没有进一步加入任何金属组分的在先研究，所述催化剂提供良好的轻质烯烃的生产效率。
发明内容
本发明涉及用于从C4-C7碳氢化合物通过催化裂解生产轻质烯烃的催化剂和通过所述催化剂生产轻质烯烃的方法，其中所述催化剂具有核-壳结构，所述核-壳结构包含硅/铝(Si/Al)摩尔比为2-250的沸石核和层状双氢氧化物壳(LDH)。
附图说明
图1示出本发明的样品和对比样品的晶体特征。
图2A)和B)示出本发明Cat 2的样品，电子扫描显微镜和电子透射显微镜的结果。
图3示出通过X-射线光电子能谱(XPS)，对于本发明Cat 2的样品，根据晶体尺寸变化的元素组分百分比。
图4A)和B)分别示出本发明Cat 1和Cat 2的样品，对于戊烷的催化裂解，随时间的轻质烯烃产物选择性。
图5示出本发明的样品和对比样品，对于戊烷的催化裂解，轻质烯烃产物选择性的百分比。
图6示出本发明的样品和对比样品，对于戊烷的催化裂解，轻质烯烃产物产率的百分比。
图7示出本发明的样品和对比样品，对于戊烷的催化裂解，产物选择性的百分比。
具体实施方式
本发明涉及用于从C4-C7碳氢化合物通过催化裂解生产轻质烯烃的催化剂，根据以下实施方案进行描述。
除非另外说明，本文描述的任何方面意指包括对本发明其他方面的应用。
除非另外说明，本文使用的技术术语或科学术语具有如本领域技术人员所定义。
本文命名的任何工具、设备、方法或化学品意味着通过本领域普通技术人员通常使用的工具、设备、方法或化学品，除非另外说明它们仅是本发明中的特定的工具、设备、方法或化学品。
在权利要求或说明书中使用带有“包含”的单数名词或单数代词意味着“一个”以及也包括“一个或更多”、“至少一个”和“一个或超过一个”。
尽管在权利要求中没有特别声明，本申请中公开的所有组合物和/或方法以及权利要求，旨在涵盖如下的实施方案的任何行动、性能、修饰或调整：没有任何显著不同于本发明实验，并且根据本领域普通技术人员获得与本发明实施方案同样的具有实用性的对象和结果。因此，本发明实施方案的可替代或相似的对象，包括本领域技术人员清楚看到的任何小的修饰或调整，应解释为如所附权利要求中出现的发明的精神、范围和概念上的保留。
本申请中，术语“约”意味着本文出现或说明的任何数值可以因任何设备、方法或个人使用所述设备或方法的误差改变或偏离。
以下示出发明实施方案，但并不意图限制本发明的任何范围。
本发明涉及用于从C4-C7碳氢化合物通过催化裂解生产轻质烯烃的催化剂和使用所述催化剂生产烯烃的方法，其中所述催化剂具有核-壳结构，所述核-壳结构包含硅/铝摩尔比为2-30的沸石核和层状双氢氧化物壳(LDH)。
在一个实施方案中，沸石核是分级沸石，其包含尺寸为0.3-0.6nm的微孔、尺寸为2-10nm的中孔和尺寸为50nm以上的大孔，其中基于总孔体积，中孔和大孔的比例为15-60％或更多。
在一个实施方案中，所述沸石的硅/铝摩尔比为2-250。优选地，所述沸石的硅/铝摩尔比为15-30。最优选地，所述沸石的硅/铝摩尔比为15。
在一个实施方案中，所述沸石选自ZSM-5、FAU、MOR、BETA或FER沸石，优选为ZSM-5。
在一个实施方案中，所述沸石的晶体尺寸为100-3000nm。
在一个实施方案中，层状双氢氧化物包含II族金属和III族金属作为主要组分，优选为镁(Mg)和铝(Al)。
在一个实施方案中，所述层状双氢氧化物的镁/铝摩尔比为1-3。优选地，摩尔比为1-2。
在一个实施方案中，所述层状双氢氧化物的厚度为100-1000nm。
优选地，本发明的催化剂包含分级沸石核和包含镁和铝的层状双氢氧化物壳，其中所述催化剂的壳/核质量比为1:1-1:7，优选1:2-1:6。
在另一个实施方案中，已改进本发明的催化剂的性能，用于轻质烯烃的生产，例如产物选择性、生产产率和前驱体到轻质烯烃产物的转化，还包含根据元素周期表的IIA、IIIA、VA、IIB、IIIB、VIB、和VIII族金属，可选自但不限于镧、锶、钯、磷、铂、镓或锌。
在一个实施方案中，本发明的催化剂可根据以下步骤制备：
(a)制备包含用于制备沸石和软模板的化合物的溶液；
(b)在确定的温度和时间下，对从步骤(a)获得的混合物进行水热法，以将所述混合物转化为分级沸石；
(c)制备包含用于制备层状双氢氧化物壳的化合物的溶液；
(d)制备包含从步骤(b)获得的沸石和碳酸钠的溶液；
(e)控制溶液的pH时，将从步骤(c)制备的溶液滴加到从步骤(d)制备的溶液上；
(f)搅拌从步骤(e)获得的混合物约1小时，并且在搅拌条件下用去离子水持续涤约再1小时，然后在搅拌条件下用丙酮持续洗涤约10-14小时；
(g)离心从步骤(f)获得的用丙酮洗涤的混合物，以分离合成的催化剂；
(h)干燥从步骤(g)获得的催化剂；和
(i)通过离子交换法，使获得的样品与硝酸铵(NH4NO3)溶液接触，使用100毫升硝酸铵溶液至1克催化剂，在80℃温度下接触约2小时，然后干燥且重复3次，并且最后在550℃温度下煅烧约6-8小时。
特征在于，步骤(a)中的软模板为季铵盐，可选自但不限于四烷基铵盐，所述四烷基铵盐选自四丙基铵氢氧化物和四丁基铵氢氧化物。
在一个实施方案中，用于制备沸石的化合物为选自异丙醇铝、铝酸钠或硫酸铝的铝化合物，和选自原硅酸四乙酯、硅酸钠或硅胶的二氧化硅化合物的混合物。
在一个实施方案中，步骤(b)在130-180℃的温度下操作。
在另一个实施方案中，本发明的催化剂的制备方法可进一步包含干燥和煅烧步骤。
干燥可通过使用烘箱一般干燥、真空干燥、搅拌干燥和旋转蒸发仪进行。
煅烧可在大气压条件下和在约350-650℃的温度下进行约4-10小时，优选为在约350-400℃的温度下约5-6小时。
在另一个实施方案中，本发明涉及本发明的催化剂在通过C4-C7碳氢化合物的催化裂解生产轻质烯烃的方法中的用途。
在一个实施方案中，C4-C7碳氢化合物的催化裂解可发生，其中使C4-C7碳氢化合物的进料与本发明的催化剂在适于反应的条件下接触，可在固定床系统中操作。
C4-C7碳氢化合物的催化裂解可发生在约450-650℃，优选为约550-600℃的温度下，在大气压-5巴下，最优选为在大气压下。
在一个实施方案中，C4-C7碳氢化合物选自丁烷、戊烷、己烷或庚烷，优选为戊烷。
在一个实施方案中，使用所述催化剂通过C4-C7碳氢化合物的催化裂解获得的产物为轻质烯烃，优选为乙烯和丙烯。
在催化裂解中碳氢化合物进料的重时空速(WHSV)为约1-50小时-1，优选为约2-7小时-1。
一般地，本领域技术人员可以修饰C4-C7碳氢化合物的催化裂解的反应条件，使其适于进料的类型和组分、催化剂和反应器系统。
以下实施例仅为说明本发明的实施方案，不以任何方式限制本发明的范围。
催化剂的制备
催化剂的制备可根据以下方法进行。
沸石核的制备
制备包含铝酸钠和原硅酸四乙酯的溶液，其中硅/铝摩尔比为15。使用四丙基铵氢氧化物作为沸石的模板。然后，对获得的混合物进行水热法，在约130-180℃的温度下约2-4天，以将所述混合物转化为沸石。
然后，用去离子水洗涤获得的沸石，直到pH低于9。获得的物质在约100-120℃温度下干燥约12-24小时。然后，在约500-650℃温度下进行煅烧约8-12小时以去除模板。获得为白色粉末的分级沸石。
层状双氢氧化物壳的制备
制备层状双氢氧化物的前驱体溶液，其包含2.4-4.8毫摩尔硝酸镁和1.2-2.4毫摩尔硝酸铝。然后，将制备的溶液滴加到包含0.2-0.5克碳酸钠和0.5克确定类型的沸石的混合物上。控制pH为约10。
然后，搅拌所述混合物约1小时并用去离子水洗涤。然后，加入丙酮并搅拌10-14小时。最后，根据Chunping et al.(Chemical Science,2016,7(2),1457-61)公开的方法在真空烘箱中干燥混合物。
然后，通过离子交换法，对合成的沸石和层状双氢氧化物混合物材料催化剂进行从钠离子到质子离子的离子交换。获得的沸石和层状双氢氧化物的混合物材料的催化剂在约80℃温度下溶解在0.1摩尔硝酸铵(NH4NO3)溶液中，搅拌约2小时，用纯水洗涤。干燥获得的沸石。然后，获得的沸石在约350℃温度下煅烧约6小时以去除污染物。
对比样品Cat A(ComZSM5)
使用商业可得的硅/铝摩尔比为15的ZSM-5纳米-沸石作为对比样品Cat A。
对比样品Cat B(ZSM5)
通过上述沸石核的制备的方法，制备本发明Cat B的样品。
对比样品催化剂C(ComZSM5-Mg-Al(imp))
通过将对比样品A与镁和铝盐溶液接触来制备对比样品催化剂C，通过注入法，使用10毫升的硝酸镁和硝酸铝，在0.4-1摩尔的浓度和80℃温度下接触1-3小时。然后，通过旋转蒸发仪干燥并且烘箱内在100℃温度下干燥24小时。然后，样品在350℃温度煅烧6小时。
本发明Cat 1的样品(ComZSM5-LDH(ex))
通过将对比样品Cat A作为核并且通过如上所述本发明的催化剂的制备方法，制备本发明Cat 1的样品，以获得具有沸石核和层状双氢氧化物壳的催化剂。
本发明Cat 2的样品(ZSM5-LDH(ex))
通过将对比样品Cat B作为核并且通过如上所述本发明的催化剂的制备方法，制备本发明Cat 2的样品，以获得具有沸石核和层状双氢氧化物壳的催化剂。
C4-C7碳氢化合物的催化裂解用于生产轻质烯烃产物的测试
C4-C7碳氢化合物的催化裂解用于生产轻质烯烃的测试可在以下条件下进行。
催化裂解通过使用约0.2-0.4克催化剂在在固定床反应器中操作。反应前，使催化剂与流速约10-50毫升/分的氮气接触约1-3小时。然后，C5碳氢化合物在约1.25克/小时流速下进料。在约500-600℃的温度、大气压和约2-5小时-1的重时空速(WHSV)下持续反应。
然后，通过随时测量与催化剂反应后前驱体的变化和其他组分的形成，来监测反应，其使用连接到固定床反应器的出口的气相色谱法，使用火焰离子化检测器(FID)作为检测器，以及GASPRO毛细管柱用于分析所述物质的各组分。
图1示出本发明的样品和对比样品的晶体特征，示出本发明Cat 1和Cat 2的样品，其沸石和层状双氢氧化物的核和壳结构。
此外，使用扫描电子显微镜(SEM)和透射电子显微镜(TEM)以示出晶体特征。结果在图2中示出，其说明本发明的沸石为晶体尺寸约100-3000nm的分级沸石。从微孔、中孔和大孔的比表面积测试，发现催化剂Cat A和Cat B都具有微孔、中孔和大孔的尺寸分布，其中相比于总孔体积，中孔和大孔的比例大于或等于15-60％。此外，催化剂Cat A和Cat B的分级因子(HF)为约0.04。这表明这两种催化剂具有分级结构。分级因子可按以下方程式计算。
因此，为了证实本发明的样品，其沸石和层状双氢氧化物的核-壳结构，通过X-射线光电子能谱(XPS)分析根据晶体尺寸变化的镁和硅的浓度百分比。结果在图3中示出。
为了研究包含分级沸石核和层状双氢氧化物壳的催化剂，对从C4-C7碳氢化合物通过催化裂解的轻质烯烃的生产效率的影响，研究本发明催化剂的样品和对比样品。结果在图4到图7中示出。
图4示出本发明的样品，随时间的轻质烯烃产物选择性的效率。发现相比于对比样品，本发明的催化剂给出更好的效率，其中相比于其他类型的催化剂，本发明Cat 2的样品示出最高的戊烷转化并且具有更高的轻质烯烃产物选择性。
图5示出本发明的样品和对比样品的轻质烯烃产物选择性的效率。发现相比于对比样品，本发明的催化剂给出更好的效率，其中相比于其他类型的催化剂，本发明Cat 2的样品示出更高的戊烷转化并且具有更高的轻质烯烃产物选择性。
图6示出本发明的样品和对比样品的轻质烯烃产物产率的效率。发现相比于对比样品，本发明的催化剂给出更好的效率，其中相比于其他类型的催化剂，本发明Cat 2的样品示出更高的戊烷转化并且具有更高的轻质烯烃产物的产率百分比。
图7示出本发明的样品和对比样品的产物选择性的效率。发现相比于其他类型的催化剂，本发明Cat 2的样品示出更高的戊烷转化并且具有更高的轻质烯烃产物选择性，包括具有更低的轻质烷烃产物选择性。
从上述结果，可以认为，发明的包含分级沸石核和层状双氢氧化物壳的催化剂，给出对于C4-C7碳氢化合物的催化裂解的轻质烯烃产物产率的高转化百分比和选择性，如本发明目的中所述。
本发明的最佳方式
本发明的最佳方式如具体实施方式提供。

Claims (17)

1. 一种用于从C4-C7碳氢化合物生产轻质烯烃的催化剂，其中所述催化剂具有核-壳结构，所述核-壳结构包含硅/铝摩尔比为2-250的沸石核和层状双氢氧化物壳，并且所述沸石为包含尺寸为0.3-0.6 nm的微孔、尺寸为2-10 nm的中孔和尺寸为50 nm以上的大孔的分级沸石，其中相比于总孔体积，所述中孔和大孔的比例为15-60%；其中所述C4-C7碳氢化合物选自丁烷、戊烷、己烷或庚烷。
2.根据权利要求1所述的催化剂，其中所述沸石的硅/铝摩尔比为15-30。
3.根据权利要求2所述的催化剂，其中所述沸石的硅/铝摩尔比等于15。
4.根据权利要求1所述的催化剂，其中所述沸石选自ZSM-5、FAU、MOR、BETA或FER型沸石。
5. 根据权利要求1所述的催化剂，其中所述沸石核的晶体尺寸为100-3000 nm。
6.根据权利要求1所述的催化剂，其中所述层状双氢氧化物的金属组分为II族金属和III族金属。
7.根据权利要求6所述的催化剂，其中所述层状双氢氧化物的金属组分为镁和铝。
8.根据权利要求7所述的催化剂，其中所述层状双氢氧化物的镁/铝摩尔比为1-3。
9.根据权利要求8所述的催化剂，其中所述层状双氢氧化物的镁/铝摩尔比为1-2。
10. 根据权利要求1所述的催化剂，其中所述层状双氢氧化物的厚度为100-1000 nm。
11.根据权利要求1所述的催化剂，其中所述催化剂包含壳:核质量比为1:1-1:7的核和壳。
12.根据权利要求11所述的催化剂，其中所述催化剂包含壳:核质量比为1:2-1:6的核和壳。
13.一种通过C4-C7碳氢化合物的催化裂解反应生产轻质烯烃的方法，其使用权利要求1所述的催化剂。
14.根据权利要求13所述的方法，其中所述方法在450-650°C的温度和1大气压-5巴操作。
15.根据权利要求13所述的方法，其中所述C4-C7碳氢化合物为戊烷。
16.根据权利要求13-15中任一项所述的方法，其中产物为轻质烯烃。
17.根据权利要求16所述的方法，其中产物为乙烯和丙烯。
CN201980092892.3A 2018-12-26 2019-12-03 用于从c4-c7碳氢化合物生产轻质烯烃的催化剂 Active CN113498360B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
TH1801008085 2018-12-26
TH1801008085A TH1801008085A (th) 2018-12-26 ตัวเร่งปฏิกิริยาสำหรับการผลิตโอเลฟินส์ขนาดเล็กจากสารประกอบไฮโดรคาร์บอนที่ มีจำนวนคาร์บอน 4 ถึง 7 อะตอม
PCT/TH2019/000063 WO2020218980A1 (en) 2018-12-26 2019-12-03 Catalyst for producing light olefins from c4-c7 hydrocarbons

Publications (2)

Publication Number Publication Date
CN113498360A CN113498360A (zh) 2021-10-12
CN113498360B true CN113498360B (zh) 2024-06-14

Family

ID=72941692

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980092892.3A Active CN113498360B (zh) 2018-12-26 2019-12-03 用于从c4-c7碳氢化合物生产轻质烯烃的催化剂

Country Status (7)

Country Link
US (1) US11801499B2 (zh)
EP (1) EP3902629A4 (zh)
JP (1) JP7467475B2 (zh)
KR (1) KR20210098543A (zh)
CN (1) CN113498360B (zh)
SG (1) SG11202106867WA (zh)
WO (1) WO2020218980A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7440012B2 (ja) * 2019-12-27 2024-02-28 ピーティーティー グローバル ケミカル パブリック カンパニー リミテッド ４～７個の炭素原子を有する炭化水素の接触分解から軽質オレフィンを製造するための触媒、およびその触媒を使用して軽質オレフィンを製造するための工程
US11857951B2 (en) * 2020-10-09 2024-01-02 Iowa State University Research Foundation, Inc. Pore-encapsulated catalysts for selective hydrogenolysis of plastic waste
CN112366328B (zh) * 2020-11-09 2024-06-07 重庆大学 一种部分有序二维超晶体铂合金催化层的制备方法
US12030843B2 (en) 2021-01-05 2024-07-09 Iowa State University Research Foundation, Inc. Catalytic upcycling of polyolefins via versatile alkylaluminums
US20250018381A1 (en) * 2022-04-07 2025-01-16 Ptt Global Chemical Public Company Limited A catalyst for light olefins production and a process of light olefins production by using a catalyst thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106608789A (zh) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 碳四烯烃催化裂解生产丙烯的方法
CN107438482A (zh) * 2015-01-30 2017-12-05 Smh有限公司 用于生产烯烃的复分解催化剂和方法
CN107848817A (zh) * 2015-07-16 2018-03-27 Scg化学有限公司 无机多孔骨架‑层状双氢氧化物核‑壳材料

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8518820D0 (en) * 1985-07-25 1985-08-29 British Petroleum Co Plc Chemical process
ID29487A (id) * 1998-09-28 2001-08-30 Bp Chemical Corp Proses untuk pembuatan olefin dengan menggunakan zeolit pentasil didasarkan katalis
US6222087B1 (en) 1999-07-12 2001-04-24 Mobil Oil Corporation Catalytic production of light olefins rich in propylene
US7326332B2 (en) 2003-09-25 2008-02-05 Exxonmobil Chemical Patents Inc. Multi component catalyst and its use in catalytic cracking
JP4157946B2 (ja) * 2004-03-23 2008-10-01 独立行政法人物質・材料研究機構 金属水酸化物／ゼオライト複合体及びそれから成る吸着剤
US8137533B2 (en) 2008-10-24 2012-03-20 Uop Llc Mixture of catalysts for cracking naphtha to olefins
US8157985B2 (en) 2009-06-22 2012-04-17 Uop Llc Process for catalytic cracking of hydrocarbons using UZM-35HS
US7981273B2 (en) 2009-06-22 2011-07-19 Uop Llc Process for catalytic cracking of hydrocarbons using UZM-35
CN102744093A (zh) * 2011-04-22 2012-10-24 中国石油天然气股份有限公司 一种分子筛的稀土改性方法
EP2975013A1 (en) * 2013-04-03 2016-01-20 Scg Chemicals Co. Ltd. Catalyst for converting paraffin to olefin
US9489822B2 (en) 2015-03-18 2016-11-08 Google Inc. Systems and methods of privacy within a security system
EP3318327A4 (en) * 2015-07-02 2019-02-27 Dalian Institute Of Chemical Physics Chinese Academy of Sciences CATALYST AND METHOD FOR THE PRODUCTION OF LIGHT OLEFINS DIRECTLY FROM SYNTHESEGAS BY A UNIVERSAL PROCESS
GB201512452D0 (en) * 2015-07-16 2015-08-19 Scg Chemicals Co Ltd Inorganic porous framework -layered double hydroxide core-shell materials as catalyst supports in ethylene polymerisation
CN106475134B (zh) * 2016-09-22 2019-05-17 华东师范大学 一种水滑石为壳/分子筛为核的核壳催化剂及其制备和应用
JP2020500711A (ja) 2016-12-13 2020-01-16 エスエムエイチ カンパニー，リミテッド 炭化水素変換触媒系
WO2018157042A1 (en) 2017-02-27 2018-08-30 Sabic Global Technologies B.V. Encapsulated hierarchical zeolite catalyst composition, method of manufacture and use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107438482A (zh) * 2015-01-30 2017-12-05 Smh有限公司 用于生产烯烃的复分解催化剂和方法
CN107848817A (zh) * 2015-07-16 2018-03-27 Scg化学有限公司 无机多孔骨架‑层状双氢氧化物核‑壳材料
CN106608789A (zh) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 碳四烯烃催化裂解生产丙烯的方法

Also Published As

Publication number Publication date
EP3902629A4 (en) 2022-10-05
EP3902629A1 (en) 2021-11-03
KR20210098543A (ko) 2021-08-10
US20210322961A1 (en) 2021-10-21
CN113498360A (zh) 2021-10-12
WO2020218980A1 (en) 2020-10-29
JP7467475B2 (ja) 2024-04-15
JP2022516081A (ja) 2022-02-24
US11801499B2 (en) 2023-10-31
SG11202106867WA (en) 2021-07-29

Similar Documents

Publication Publication Date Title
CN113498360B (zh) 用于从c4-c7碳氢化合物生产轻质烯烃的催化剂
Álvaro-Muñoz et al. Microwave-assisted synthesis of plate-like SAPO-34 nanocrystals with increased catalyst lifetime in the methanol-to-olefin reaction
EP3475393B1 (en) Processes for high severity fluid catalytic cracking systems
Gao et al. Modified seeding method for preparing hierarchical nanocrystalline ZSM-5 catalysts for methanol aromatisation
Kianfar et al. Zeolite catalyst based selective for the process MTG: a review
Álvaro-Muñoz et al. Aluminium chloride: A new aluminium source to prepare SAPO-34 catalysts with enhanced stability in the MTO process
CN109967118B (zh) 一种用于甲醇转化制芳烃的hzsm-5分子筛催化剂的原位改性方法
JP5588973B2 (ja) 結晶質メタロシリケートの製造方法
WO2019177958A2 (en) Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes
JP5588972B2 (ja) 結晶質メタロシリケートの製造方法
CN112794338A (zh) Zsm-5分子筛及其制备方法和应用
Ghazimoradi et al. Synthesis of fluorinated ZSM-5 catalysts: fluoride effect on structure properties and coke resistance in n-hexane catalytic cracking
KR100996976B1 (ko) 장수명 ｍｔｏ 반응용 촉매 및 이의 제조방법
CN114433197B (zh) 一种用于烯烃异构化反应的负载金属催化剂及其制备方法
EP1479662B1 (en) Process for conversion of oxygenates to hydrocarbons and composition of use therein
CN101181692A (zh) 骨架改性酸-碱双功能zsm-5沸石催化剂及其制备方法
Magaji et al. Catalytic Cracking of Liquefied Petroleum Gas (LPG) to Light Olefins Using Zeolite‐Based Materials: Recent Advances, Trends, Challenges and Future Perspectives
Xu et al. Synthesis of core–shell SAPO-34@ SAPO-18 composites by the epitaxial growth method and their catalytic properties for the MTO reaction
KR101695105B1 (ko) Ga-제올라이트 촉매 나노 입자, 이를 제조하는 방법 및 이를 이용한 방향족화 방법
Yazdani et al. Mixing‐assisted hydrothermal synthesis of nanostructured ZnAPSO‐34 used in conversion of methanol to light olefins: Effect of agitation RPM on catalytic properties and performance
US11517885B2 (en) Catalyst for producing olefins from dehydrogenation of alkane and a method for producing olefins using said catalyst
Firdaus et al. Catalytic conversion of n-Dodecane to lower olefins hydrogen carriers over bran-shaped modified MCM-22 zeolite catalyst: SiO2/Al2O3 ratio effects
RU2288034C1 (ru) Способ конверсии углеводородов, катализатор для его осуществления с микро-мезопористой структурой и способ приготовления катализатора
KR20230145993A (ko) 경질 올레핀을 제조하기 위한 촉매 및 상기 촉매를 사용함으로써 경질 올레핀을 제조하는 방법
KR20240142490A (ko) 경질 올레핀 및/또는 방향족 물질의 생성을 위한 mfi 제올라이트 및 이의 용도

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant