CN1972885B - 用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的催化剂与方法 - Google Patents

用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的催化剂与方法 Download PDF

Info

Publication number
CN1972885B
CN1972885B CN2005800207082A CN200580020708A CN1972885B CN 1972885 B CN1972885 B CN 1972885B CN 2005800207082 A CN2005800207082 A CN 2005800207082A CN 200580020708 A CN200580020708 A CN 200580020708A CN 1972885 B CN1972885 B CN 1972885B
Authority
CN
China
Prior art keywords
carrier
catalyzer
aqueous solution
catalyst
light olefin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2005800207082A
Other languages
English (en)
Other versions
CN1972885A (zh
Inventor
张永清
S·J·格尔登
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.)
Catalytic Solutions Inc
Original Assignee
Catalytic Solutions Inc
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 Catalytic Solutions Inc filed Critical Catalytic Solutions Inc
Publication of CN1972885A publication Critical patent/CN1972885A/zh
Application granted granted Critical
Publication of CN1972885B publication Critical patent/CN1972885B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/12—Fluorides
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/0205—Impregnation in several steps
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/63—Platinum group metals with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/66—Silver or gold
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
    • 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
    • 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
    • C10G2400/22—Higher 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

提供用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的催化剂与方法。与常规的选择性加氢催化剂相比，该催化剂在再生之后保留更高的活性和选择性。该催化剂含有载带在无机载体上的第一组分和第二组分。所述无机载体含有锆、镧系元素或碱土金属的至少一种盐或氧化物。

Description

用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的催化剂与方法
相关申请
根据35U.S.C.119(e)，本申请要求2004年6月23日提交的美国专利临时申请序列号No.60/582559、2004年6月23日提交的美国专利临时申请序列号No.60/582747、2004年6月23日提交的美国专利临时申请序列号No.60/582568和2004年6月23日提交的美国专利临时申请序列号No.60/582534的权益，所有这些在此全文引入作为参考。
技术领域
本发明涉及用于轻质烯烃原料物流内的二烯烃和乙炔选择性加氢的催化剂和方法。
背景技术
轻质烯烃是生产聚合物和化学品的重要原料。通常通过热解或催化裂解炼厂气、乙烷、丙烷、丁烷或类似原料物流，或者通过流化催化裂解原油馏分，来制备轻质烯烃。通过这些方法生产的烯烃原料物流含有少量乙炔和二烯烃。
在轻质烯烃原料物流内的乙炔和二烯烃可引起聚合催化剂中毒或者可产生非所需的化学副产物。因此通常通过在常常包括银组分、钯组分和氧化硅或氧化铝载体且有或无其它促进剂的催化剂上选择性加氢，从轻质烯烃原料物流中除去乙炔和二烯烃。通常希望催化剂基本上将所有的乙炔和二烯烃选择性加氢成单烯烃，而只将少量烯烃转化成链烷烃。
选择性加氢催化剂会随时间失活，这可能是因为低聚物沉积在催化剂上。通过在升高的温度下，使蒸汽和空气相继通过催化剂来再生选择性加氢催化剂将在一定程度上恢复催化剂的活性和选择性。再生的选择性加氢催化剂的催化剂活性和选择性通常低于新鲜的选择性加氢催化剂的活性和选择性。与常规的选择性加氢催化剂相比，仍需要在再生之后保留更高活性和选择性的选择性加氢催化剂组合物。
在常规的选择性加氢催化剂中使用的钯是昂贵的。与常规的选择性加氢催化剂相比，仍需要相对便宜的选择性加氢催化剂。
与常规的选择性加氢催化剂相比，还需要具有更高活性和更长寿命的选择性加氢催化剂。
发明内容
本发明的一个方面提供用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的催化剂。该催化剂含有：选自铜、金、银及其混合物的第一组分，选自镍、铂、钯、铁、钴、钌、铑及其混合物的第二组分，无机载体，和选自锆、镧系元素、碱土金属及其混合物的至少一种无机盐或氧化物。
优选地，通过浸渍、揉制或研磨，将无机盐或氧化物加入到载体中。在一个实施方案中，可以以任何顺序添加无机盐或氧化物、第一组分、第二组分和载体。催化剂可含有至少一种萤石。优选地，在煅烧、使用或再生催化剂之后形成萤石。
在一个实施方案中，第一组分含有钯，和第二组分含有银。无机盐可选自硝酸盐、乙酸盐、氯化物、碳酸盐及其混合物。无机盐或氧化物的重量百分数范围可以是约0.01-50％重量。有利的是，催化剂是多相催化剂。可采用选自铜、金、银、镍、铂、钯、铁、钴、钌、铑、锆、镧系元素、碱土金属及其混合物的至少两种水溶性盐的水溶液制备该多相催化剂。
本发明另一方面提供使轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的方法。该方法包括在本发明催化剂存在下使原料物流与氢气接触。优选地，轻质烯烃原料物流含有碳数介于C2至C6的至少一种烯烃。例如，轻质烯烃原料物流可含有选自乙烯、丙烯、丁烯、戊烯和己烯的至少一种烯烃。优选地，轻质烯烃原料物流是乙烯原料物流。
在一个实施方案中，在约0-250℃的温度下接触。优选地，在约0.01-50bar的压力下接触。
本发明另一方面涉及制备用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的多相催化剂的方法。该方法包括形成选自铜、金、银、镍、铂、钯、铁、钴、钌、铑、锆、镧系元素、碱土金属及其混合物的至少两种水溶性盐的单一水溶液。该方法还包括使单一水溶液与选自氧化硅和氧化铝的无机载体接触，并在形成所述多相催化剂的条件下，煅烧所述无机载体和单一水溶液，其中多相催化剂含有选自锆、镧系元素和碱土金属的至少一种无机盐或氧化物。
优选地，该方法还包括在煅烧之前从单一水溶液中除去水。在一个实施方案中，除去水包括干燥单一水溶液。优选地，无机载体是氧化硅或氧化铝，和水溶性盐是选自硝酸盐、乙酸盐、草酸盐、氢氧化物和碳酸盐的盐。
具体实施方式
用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的常规选择性加氢催化剂当被再生后，将损失活性和选择性。因此本发明的目的是提供具有改进的活性和选择性的催化剂。
因此，本发明的一个方面提供选择性加氢催化剂，其包括在无机载体上的第一组分和第二组分。第一组分可包括银、铜、金或银、铜和金的任何混合物。第二组分可包括钯、镍、铂、铁、钴、钌、铑或其混合物。无机载体可包括氧化硅或氧化铝。
在一个实施方案中，第二组分的至少一部分除了包括在常规选择性加氢催化剂中用作第二组分的钯以外，可另外包括镍、铁、钴、铑或钌，或者用它们替代钯。用作第二组分的镍、铁、钴或钌可能不如常规选择性加氢催化剂中用作第二组分的钯昂贵。与钯相比，镍、铁、钴、钌和铑更不易中毒。硫、砷和其它无机材料可能使催化剂中毒。
本发明的发现是，通过添加选自锆、一种或多种镧系元素、一种或多种碱土金属及其混合物的至少一种无机盐来改性氧化硅或氧化铝载体，将增加选择性加氢催化剂再生之后的活性和/或选择性。在一个实施方案中，本发明的无机盐可以以约0.01％-50％重量或者更优选约0.05％-20％重量的量存在于催化剂上，其中无机盐的百分数以氧化物为基准计算。至少一种无机盐或氧化物可以是萤石，或者可以在煅烧、使用或浸渍之后转化成萤石。无机盐可以是硝酸盐、乙酸盐、氯化物、碳酸盐、任何其它合适的盐或其混合物形式。
对于本发明的目的来说，钇和镧被视为镧系元素。本申请和所附权利要求中的术语镧系元素包括镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥和钇的任何元素。
可通过任何合适的方法，其中包括但不限于用一种或多种盐的溶液浸渍载体；或者揉制或研磨第一组分、第二组分和一种或多种无机盐或与载体，从而将本发明的第一组分、第二组分和无机盐加入到载体中。
可按照任何顺序将第一组分、第二组分和无机盐加入到载体中。第一和第二组分可一起或者分别添加。无机盐可与第一组分和/或第二组分同时加入到载体中。
当煅烧一种或多种无机盐时，该一种或多种无机盐可至少部分转化成氧化物形式。类似地，煅烧第一和/或第二组分可将该组分转化成氧化物。氧化物可以是单一盐的氧化物，或者氧化物可以是混合金属氧化物。在一些情况下，氧化物可在煅烧之后形成萤石。所形成的氧化物的形式可取决于煅烧条件。催化剂的活性和/或稳定性可能也取决于煅烧条件。
一种或多种无机盐和/或第一与第二组分可在使用或再生过程中转化成相应的一种或多种氧化物。
在另一实施方案中，第一组分、第二组分的氧化物或氧化物的混合物或者无机盐可直接加入到催化剂中，而不是或者另外添加盐或盐的混合物到载体中并将其转化成氧化物。可按照任何顺序添加催化剂的所有组分。
本发明的催化剂可以是单相催化剂或者多相催化剂。多相催化剂是含有多个相的催化剂。在一个实施方案中，充分混合多相。可通过形成水溶性盐的单一水溶液，使该水溶液与无机载体接触，除去水，并煅烧载体和水溶性盐，以获得多相催化剂，从而制备多相催化剂(MPC)。与具有相同组成的单相催化剂相比，通常发现多相催化剂具有更高的活性和稳定性。
尽管不希望受理论所束缚，但据认为当通过煅烧水溶性盐的混合物形成多相催化剂时，将形成两相或更多相的多相催化剂的紧密混合物。据认为当多相催化剂暴露于高温下时，多相催化剂中多相的紧密混合物抑制多相的聚集或烧结。
形成多相催化剂的水溶性盐可以是银、铜、金、钯、镍、铂、铁、钴、钌、铑、锆、一种或多种镧系元素、一种或多种碱土金属或其混合物的至少两种水溶性盐。因此，除了包括第一组分和第二组分以外，多相催化剂还可包括稳定载体的组分。多相催化剂含有选自锆、镧系元素、碱土金属及其任何混合物的至少一种无机盐或氧化物。本发明多相催化剂的至少一种无机盐或氧化物可以是或不是形成水溶性盐的水溶液的水溶性盐之一。
可使用任何形式的水溶性盐来形成水溶性盐的水溶液。合适的水溶性盐包括但不限于硝酸盐、乙酸盐、草酸盐、氢氧化物、氧化物、碳酸盐等。
在一个实施方案中，可在形成多相催化剂之前从水溶性盐的水溶液中除去水。可通过加热溶液，通过蒸发除去水。或者，可通过将空气鼓风通过水溶性盐的水溶液而除去水。
可采用沉淀剂沉淀形成多相催化剂所使用的水溶性盐。可煅烧沉淀的水溶性盐，形成多相催化剂。
沉淀剂可以是任何合适的沉淀剂。一些合适的沉淀剂包括但不限于碱金属氢氧化物、氢氧化铵、硝酸和草酸。
在煅烧之前可干燥水溶性盐或沉淀的水溶性盐的混合物。
可通过加热水溶性盐或多相催化剂前体的混合物到足够高以形成多相催化剂的所需相化学的温度，从而由水溶性盐或者干燥的多相催化剂前体的干燥混合物形成多相催化剂。尽管足够高的温度取决于所形成的多相催化剂，但通常加热水溶性盐到约600-900℃的温度，更优选到约700-850℃的温度，以形成多相催化剂。
根据本发明的实施方案，加热水溶性盐的混合物约1-100小时，约2-50小时或者约3-10小时，形成多相催化剂，但时间可以变化，这取决于多相催化剂的配方。鉴于本发明的教导，可由本领域的技术人员在没有过多实验的情况下，确定形成多相催化剂的合适条件。
该催化剂适合于选择性加氢与轻质烯烃混合的炔烃和二烯烃。在本申请的上下文中所使用的术语“轻质烯烃”应理解为是指碳数范围为C2-C6的所有烯烃。因此，术语“轻质烯烃”包括乙烯、丙烯、丁烯、戊烯和己烯。术语“丁烯”、“戊烯”和“己烯”包括丁烯、戊烯和己烯的所有异构体。
可在气相、液相中或者作为气/液混合物形式进行加氢。所使用的氢气量为与二烯烃和/或乙炔反应所需要量的约0.8-5倍，优选约0.95-2倍。
在约500-10000m3/h的空速下，在约0-250℃的温度下和在约0.01-50bar的压力下，进行选择性加氢。
实施例1
如下所述制备催化剂A。用硝酸铈、乙酸氧锆和硝酸镧的水溶液浸渍氧化硅载体。干燥浸渍的载体并煅烧。随后用含有水溶性钯盐和水溶性银盐的水溶液浸渍煅烧过的载体。干燥并煅烧催化剂。
实施例2
以与催化剂A相同的方法制备催化剂B，所不同的是用硝酸锶的水溶液而不是硝酸铈、乙酸氧锆和硝酸镧的水溶液浸渍氧化硅载体。
实施例3
以与催化剂A相同的方法制备催化剂C，所不同的是用只含水溶性钯盐和水溶性银盐的水溶液浸渍氧化硅载体。该催化剂不含锆、镧系元素或碱土金属。
实施例4
以与催化剂A相同的方法制备催化剂D，所不同的是用含有硝酸铁的水溶液替代水溶性钯盐浸渍氧化硅载体。
实施例5
以与催化剂A相同的方法制备催化剂E，所不同的是用含有硝酸钴的水溶液替代水溶性钯盐浸渍氧化硅载体。
实施例6
以与催化剂A相同的方法制备催化剂F，所不同的是用含有硝酸钌的水溶液替代水溶性钯盐浸渍氧化硅载体。
实施例7
以与催化剂A相同的方法制备催化剂G，所不同的是用含有硝酸铑的水溶液替代水溶性钯盐浸渍氧化硅载体。
实施例8
以与催化剂A相同的方法制备催化剂H，所不同的是用除了水溶性钯盐和水溶性银盐外还含有硝酸钴的水溶液浸渍氧化硅载体。催化剂H因此同时含有钯和钴作为第二组分。
实施例9
以与催化剂A相同的方法制备催化剂I，所不同的是将硝酸铈、乙酸氧锆、硝酸镧、水溶性钯盐和水溶性银盐的水溶液分别加入到载体中，并在添加每一溶液之后，煅烧载体和水溶液。
据发现催化剂A含有多相催化剂。催化剂I为单相催化剂。
测试
在10bar压力下在氢气存在下，在约45-120℃的温度下，使含有约1％乙炔的乙烯原料物流与催化剂A接触。该催化剂选择性加氢乙炔。在独立的实验中，在相同的条件下，与催化剂B、催化剂C、催化剂D、催化剂E、催化剂F、催化剂G、催化剂H和催化剂I接触，将含有约1％乙炔的乙烯原料物流选择性加氢。在选择性加氢之后，通过蒸汽/空气再生工艺，分别再生催化剂A、B、C、D、E、F、G、H和I。
与催化剂C相比，催化剂A、B、D、E、F、G、H和I在再生之后保留更高百分数的活性。据发现在催化剂A、B、D、E、F、G、H和I中，在载体上存在选自锆、一种或多种镧系元素、一种或多种碱土金属或其混合物的无机盐改进再生之后选择性加氢催化剂的活性。
催化剂C不含在载体上的选自锆、一种或多种镧系元素、一种或多种碱土金属或其混合物的无机盐。催化剂C的可再生性小于在载体上含有无机盐的催化剂。
与具有相同组成的单相催化剂I相比，多相催化剂A具有更高的活性。与单相催化剂的活性相比，形成多相催化剂改进活性。
采用丙烯、丁烯、戊烯和己烯的原料物流代替前面所述的乙烯原料物流进行其它试验。所有原料物流均含有约1％的乙炔。在10bar压力下在氢气存在下，在约45-120℃的温度下进行试验。催化剂A-I与各种原料物流的趋势类似于用乙烯原料物流获得的趋势。
在不偏离其实质特征的情况下，本发明的实施方案可体现于其它具体形式中。所述实施方案在所有方面均应视为只是例举而不是限制。因此通过所附权利要求而不是前述说明来确定本发明实施方案的范围。基于权利要求的等价含义和范围内的所有变化均包括在其范围内。

Claims (8)

1.一种用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的多相催化剂，该催化剂通过如下步骤制备：
用硝酸铈、乙酸氧锆和硝酸镧的水溶液浸渍无机载体；
干燥所述浸渍的载体和随后煅烧；
随后用含有水溶性钯盐和水溶性银盐的水溶液浸渍所述煅烧过的载体；和
随后干燥并煅烧所述催化剂；
其中所述无机载体是氧化硅。
2.一种用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的方法，该方法包括在催化剂存在下使所述原料物流与氢气接触，其中所述催化剂为通过如下步骤制备的多相催化剂：
用硝酸铈、乙酸氧锆和硝酸镧的水溶液浸渍无机载体；
干燥所述浸渍的载体和随后煅烧；
随后用含有水溶性钯盐和水溶性银盐的水溶液浸渍所述煅烧过的载体；和
随后干燥并煅烧所述催化剂；
其中所述无机载体是氧化硅。
3.权利要求2的方法，其中所述轻质烯烃原料物流包括碳数介于C2至C6的至少一种烯烃。
4.权利要求2的方法，其中所述轻质烯烃原料物流包括选自乙烯、丙烯、丁烯、戊烯和己烯的至少一种烯烃。
5.权利要求2的方法，其中所述接触在0-250℃的温度下进行。
6.权利要求2的方法，其中所述接触在0.01-50bar的压力下进行。
7.权利要求2的方法，其中所述轻质烯烃原料物流是乙烯原料物流。
8.一种制备用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的多相催化剂的方法，该方法包括：
用硝酸铈、乙酸氧锆和硝酸镧的水溶液浸渍无机载体；
干燥所述浸渍的载体和随后煅烧；
随后用含有水溶性钯盐和水溶性银盐的水溶液浸渍所述煅烧过的载体；和
随后干燥并煅烧所述催化剂；
其中所述无机载体是氧化硅。
CN2005800207082A 2004-06-23 2005-06-21 用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的催化剂与方法 Expired - Fee Related CN1972885B (zh)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
US58274704P 2004-06-23 2004-06-23
US58256804P 2004-06-23 2004-06-23
US58255904P 2004-06-23 2004-06-23
US58253404P 2004-06-23 2004-06-23
US60/582,559 2004-06-23
US60/582,747 2004-06-23
US60/582,534 2004-06-23
US60/582,568 2004-06-23
PCT/US2005/021740 WO2006009988A1 (en) 2004-06-23 2005-06-21 Catalysts and processes for selective hydrogenation of acetylene and dienes in light olefin feedstreams

Publications (2)

Publication Number Publication Date
CN1972885A CN1972885A (zh) 2007-05-30
CN1972885B true CN1972885B (zh) 2010-12-08

Family

ID=35207667

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2005800207082A Expired - Fee Related CN1972885B (zh) 2004-06-23 2005-06-21 用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的催化剂与方法

Country Status (5)

Country Link
US (6) US20060166816A1 (zh)
EP (1) EP1786748A1 (zh)
JP (1) JP2008504117A (zh)
CN (1) CN1972885B (zh)
WO (1) WO2006009988A1 (zh)

Families Citing this family (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7348463B2 (en) * 2006-03-27 2008-03-25 Catalytic Distillation Technologies Hydrogenation of aromatic compounds
GB0704603D0 (en) * 2007-03-09 2007-04-18 Ge Healthcare Bio Sciences Ab Packing system and method for chromatography columns
US9597610B2 (en) 2007-03-09 2017-03-21 Ge Healthcare Bioprocess R&D Ab Packing system and method for chromatography columns
US9597611B2 (en) 2007-03-09 2017-03-21 Ge Healthcare Bioprocess R&D Ab Packing system and method for chromatography columns
CN101433841B (zh) * 2007-12-13 2010-04-14 中国石油天然气股份有限公司 一种选择性加氢催化剂及其制备方法
EP2204235A1 (en) 2008-12-19 2010-07-07 Total Petrochemicals Research Feluy Catalyst and process for selective hydrogenation of alkynes and dienes
EP2204236A1 (en) 2008-12-19 2010-07-07 Total Petrochemicals Research Feluy Catalyst and process for hydrogenation of hydrocarbon feedstocks
JP5322733B2 (ja) * 2009-03-31 2013-10-23 Ｊｘ日鉱日石エネルギー株式会社 一酸化炭素の選択的酸化反応用触媒の製造方法
FR2949077B1 (fr) * 2009-08-17 2011-07-22 Inst Francais Du Petrole Procede de preparation d'un catalyseur supporte a base de ni et d'un metal du groupe ib pour l'hydrogenation selective d'hydrocarbures polyinsatures
US8435486B2 (en) * 2010-05-24 2013-05-07 Toyota Jidosha Kabushiki Kaisha Redox material for thermochemical water splitting, and method for producing hydrogen
US20120209042A1 (en) * 2011-02-10 2012-08-16 Saudi Basic Industries Corporation Liquid Phase Hydrogenation of Alkynes
WO2013021506A1 (ja) 2011-08-05 2013-02-14 トヨタ自動車株式会社 熱化学水分解用レドックス材料及び水素製造方法
US9670115B2 (en) * 2012-02-15 2017-06-06 Clariant Corporation Method and system for purifying an ethylene-containing gas stream
US9511353B2 (en) 2013-03-15 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) Firing (calcination) process and method related to metallic substrates coated with ZPGM catalyst
US9511355B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) System and methods for using synergized PGM as a three-way catalyst
US9511350B2 (en) 2013-05-10 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) ZPGM Diesel Oxidation Catalysts and methods of making and using same
US9771534B2 (en) 2013-06-06 2017-09-26 Clean Diesel Technologies, Inc. (Cdti) Diesel exhaust treatment systems and methods
US9545626B2 (en) 2013-07-12 2017-01-17 Clean Diesel Technologies, Inc. Optimization of Zero-PGM washcoat and overcoat loadings on metallic substrate
US9180436B1 (en) 2013-11-19 2015-11-10 Emerging Fuels Technology, Inc. Optimized fischer-tropsch catalyst
US9358526B2 (en) 2013-11-19 2016-06-07 Emerging Fuels Technology, Inc. Optimized fischer-tropsch catalyst
US9511358B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. Spinel compositions and applications thereof
US9475004B2 (en) 2014-06-06 2016-10-25 Clean Diesel Technologies, Inc. Rhodium-iron catalysts
US9731279B2 (en) 2014-10-30 2017-08-15 Clean Diesel Technologies, Inc. Thermal stability of copper-manganese spinel as Zero PGM catalyst for TWC application
CN105732264B (zh) * 2014-12-12 2018-09-04 中国石油天然气股份有限公司 一种甲醇制烯烃中微量乙炔选择加氢方法
US9700841B2 (en) 2015-03-13 2017-07-11 Byd Company Limited Synergized PGM close-coupled catalysts for TWC applications
US9951706B2 (en) 2015-04-21 2018-04-24 Clean Diesel Technologies, Inc. Calibration strategies to improve spinel mixed metal oxides catalytic converters
CN106622245A (zh) * 2015-10-28 2017-05-10 中国石油化工股份有限公司 一种炔烃及二烯烃选择加氢催化剂和一种炔烃及二烯烃选择加氢方法
CN106925279B (zh) * 2015-12-31 2020-05-08 中国石油天然气股份有限公司 一种Fe系选择加氢催化剂、制备方法及其应用
CN106928009B (zh) * 2015-12-31 2019-12-10 中国石油天然气股份有限公司 一种前脱乙烷前加氢除炔方法
US10533472B2 (en) 2016-05-12 2020-01-14 Cdti Advanced Materials, Inc. Application of synergized-PGM with ultra-low PGM loadings as close-coupled three-way catalysts for internal combustion engines
US9861964B1 (en) 2016-12-13 2018-01-09 Clean Diesel Technologies, Inc. Enhanced catalytic activity at the stoichiometric condition of zero-PGM catalysts for TWC applications
CN108246310A (zh) * 2016-12-29 2018-07-06 中国石油天然气股份有限公司 一种Fe-Ag选择加氢催化剂及其制备方法和应用
CN108250017A (zh) * 2016-12-29 2018-07-06 中国石油天然气股份有限公司 一种碳三馏分选择加氢的方法
CN108250011A (zh) * 2016-12-29 2018-07-06 中国石油天然气股份有限公司 一种选择加氢的乙烯精制方法
CN108250025A (zh) * 2016-12-29 2018-07-06 中国石油天然气股份有限公司 一种前脱乙烷前加氢除炔的方法
CN108250030A (zh) * 2016-12-29 2018-07-06 中国石油天然气股份有限公司 一种乙烯物料选择加氢精制方法
US10265684B2 (en) 2017-05-04 2019-04-23 Cdti Advanced Materials, Inc. Highly active and thermally stable coated gasoline particulate filters
CN110639517A (zh) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 丁二烯选择加氢的催化剂以及应用
CN112939717B (zh) * 2019-11-26 2023-01-10 中国石油天然气股份有限公司 一种轻烃裂解碳二馏分选择加氢工艺的除炔方法
CN113477249A (zh) * 2021-06-21 2021-10-08 润和科华催化剂(上海)有限公司 一种乙炔选择性加氢制乙烯的催化剂、制备方法及应用
CN115888727A (zh) * 2022-11-28 2023-04-04 浙江卫星能源有限公司 用于丙炔选择性加氢合成丙烯的镍基耐硫催化剂、制备方法及其应用
CN116764630A (zh) * 2023-07-06 2023-09-19 浙江工业大学 一种氧化铽负载Pd催化剂的制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5585318A (en) * 1995-01-20 1996-12-17 Phillips Petroleum Company Alkyne hydrogenation process
EP0839573A1 (en) * 1996-10-30 1998-05-06 Phillips Petroleum Company Hydrogenation process and catalyst therefor comprising palladium and silver deposited on a spinel support
WO2003015916A1 (fr) * 2000-09-29 2003-02-27 China Petroleum And Chemical Corporation Catalyseur d'hydrocraquage selectif des hydrocarbures insatures, son procede de fabrication et ses applications
CN1409655A (zh) * 1999-12-08 2003-04-09 巴斯福股份公司 用于炔烃和双烯的选择氢化的负载型催化剂

Family Cites Families (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855324A (en) * 1969-11-28 1974-12-17 Exxon Research Engineering Co Hydrogenation of organic compounds
US3673079A (en) * 1970-01-21 1972-06-27 Chevron Res Catalyst manufacture
US3953368A (en) * 1971-11-01 1976-04-27 Exxon Research And Engineering Co. Polymetallic cluster compositions useful as hydrocarbon conversion catalysts
US3893944A (en) * 1972-05-16 1975-07-08 Exxon Research Engineering Co Catalyst for hydrogenation of organic compounds
US3978149A (en) * 1974-08-22 1976-08-31 Exxon Research And Engineering Company Hydrogenation of organic compounds
HU176794B (en) * 1978-06-03 1981-05-28 Chinoin Gyogyszer Es Vegyeszet Process for producing alloy of aluminium of high reducing activity,containing discontinual heterodisperz alloy on the surface
US4484015A (en) * 1981-05-06 1984-11-20 Phillips Petroleum Company Selective hydrogenation
US4404124A (en) * 1981-05-06 1983-09-13 Phillips Petroleum Company Selective hydrogenation catalyst
US4459372A (en) * 1982-08-25 1984-07-10 Uop Inc. Surface-metallated refractory inorganic oxides, method of their preparation and catalyst supported on the oxides
US4496785A (en) * 1983-09-28 1985-01-29 Standard Oil Company (Indiana) Process for reacting alcohols and olefins
FR2670400B1 (fr) * 1990-12-13 1993-04-02 Inst Francais Du Petrole Procede de preparation de catalyseurs multimetalliques.
US5856263A (en) * 1992-08-28 1999-01-05 Union Carbide Chemicals & Plastics Technology Corporation Catalysts comprising substantially pure alpha-alumina carrier for treating exhaust gases
EP0605251A1 (en) * 1992-12-28 1994-07-06 Kabushiki Kaisha Riken Exhaust gas cleaner
US5817896A (en) * 1993-03-26 1998-10-06 The University Court Of The University Of Dundee Catalytic method of replacing halogen in halocarbons
JP3440290B2 (ja) * 1993-08-26 2003-08-25 独立行政法人産業技術総合研究所 排ガス浄化方法
US5426045A (en) * 1993-12-16 1995-06-20 Sea Run Holdings, Inc. Method for culturing mammalian cells in a medium containing fish serum
DE69408957T2 (de) * 1993-12-28 1998-09-17 Riken Kk Vorrichtung und Verfahren zur Reinigung von Abgas
EP0667182A3 (en) * 1994-02-10 1995-10-18 Riken Kk Exhaust gas purifier and method for cleaning exhaust gas.
US5658542A (en) * 1994-07-15 1997-08-19 Kabushiki Kaisha Riken Exhaust gas cleaner and method for cleaning same
US5475173A (en) * 1994-07-19 1995-12-12 Phillips Petroleum Company Hydrogenation process and catalyst therefor
EP0710499A3 (en) * 1994-11-04 1997-05-21 Agency Ind Science Techn Exhaust gas purifier and method for purifying an exhaust gas
US5741468A (en) * 1994-12-28 1998-04-21 Kabushiki Kaisha Riken Exhaust gas cleaner and method for cleaning exhaust gas
DE19506843A1 (de) * 1995-02-28 1996-08-29 Studiengesellschaft Kohle Mbh Mikroporöse amorphe Mischmetalloxide für formselektive Katalyse
US5587348A (en) * 1995-04-19 1996-12-24 Phillips Petroleum Company Alkyne hydrogenation catalyst and process
US6054409A (en) * 1995-06-06 2000-04-25 Institut Francais Du Petrole Selective hydrogenation catalyst and a process using that catalyst
US5637548A (en) * 1995-07-07 1997-06-10 The Dow Chemical Company Preparation of bimetallic catalysts for hydrodechlorination of chlorinated hydrocarbons
EP0761289A3 (en) * 1995-09-08 1997-05-02 Riken Kk Exhaust gas purifiers and exhaust gas purification methods
US6096933A (en) * 1996-02-01 2000-08-01 Phillips Petroleum Company Hydrocarbon hydrogenation and catalyst therefor
AU692723B2 (en) * 1996-02-01 1998-06-11 Phillips Petroleum Company Catalyst composition and process for selecting hydrogenation of diolefins
US5948377A (en) * 1996-09-04 1999-09-07 Engelhard Corporation Catalyst composition
DE19636064A1 (de) * 1996-09-05 1998-03-12 Basf Ag Verfahren zur Hydrierung
EP0933129B1 (en) * 1996-09-11 2003-03-26 Süd-Chemie Catalysts Japan Inc. Catalyst for selective hydrogenation of highly unsaturated hydrocarbon compound in olefin compound
US6239322B1 (en) * 1996-11-07 2001-05-29 Institut Francais Du Petrole Selective hydrogenation catalysts containing palladium, also tin and/or lead, and the preparation and use thereof
US6127310A (en) * 1997-02-27 2000-10-03 Phillips Petroleum Company Palladium containing hydrogenation catalysts
US6365544B2 (en) * 1998-05-22 2002-04-02 Conoco Inc. Fischer-Tropsch processes and catalysts using fluorided alumina supports
US6333294B1 (en) * 1998-05-22 2001-12-25 Conoco Inc. Fischer-tropsch processes and catalysts with promoters
DE19839459A1 (de) * 1998-08-29 2000-03-02 Basf Ag Katalysator und Verfahren zur Selektivhydrierung ungesättigter Verbindungen in Kohlenwasserstoffströmen
DE19840373A1 (de) * 1998-09-04 2000-03-09 Basf Ag Katalysator und Verfahren zur Selektivhydrierung ungesättigter Verbindungen in Kohlenwasserstoffströmen
US6127588A (en) * 1998-10-21 2000-10-03 Phillips Petroleum Company Hydrocarbon hydrogenation catalyst and process
US6511642B1 (en) * 1999-01-12 2003-01-28 Kabushiki Kaisha Toyota Chuo Kenkyusho Porous material, catalyst, method of producing the porous material and method for purifying exhaust gas
GB0212321D0 (en) * 2002-05-29 2002-07-10 Johnson Matthey Plc Catalyst composition
CN1097480C (zh) * 1999-06-25 2003-01-01 中国石油化工集团公司 炔烃选择加氢催化剂
JP3489049B2 (ja) * 1999-07-15 2004-01-19 日産自動車株式会社 排気ガス浄化用触媒
US6417136B2 (en) * 1999-09-17 2002-07-09 Phillips Petroleum Company Hydrocarbon hydrogenation catalyst and process
DE10048219A1 (de) * 2000-02-10 2002-04-11 Sued Chemie Ag Katalysator für die Hydrierung von ungesättigten Kohlenwasserstoffen
US6627571B1 (en) * 2000-03-01 2003-09-30 Symyx Technologies, Inc. Method and system for the situ synthesis of a combinatorial library of supported catalyst materials
US6576588B2 (en) * 2000-04-07 2003-06-10 Catalytic Distillation Technologies Process for selective hydrogenation of alkynes and catalyst therefor
CN1090997C (zh) * 2000-04-30 2002-09-18 中国石油化工集团公司 一种选择加氢除炔多金属催化剂
US6465391B1 (en) * 2000-08-22 2002-10-15 Phillips Petroleum Company Selective hydrogenation catalyst and processes therefor and therewith
US6407280B1 (en) * 2000-09-28 2002-06-18 Rohm And Haas Company Promoted multi-metal oxide catalyst
US6403525B1 (en) * 2000-09-28 2002-06-11 Rohm And Haas Company Promoted multi-metal oxide catalyst
DE10048844A1 (de) * 2000-10-02 2002-04-11 Basf Ag Verfahren zur Herstellung von Platinmetall-Katalysatoren
US6509292B1 (en) * 2001-03-30 2003-01-21 Sud-Chemie Inc. Process for selective hydrogenation of acetylene in an ethylene purification process
US6734130B2 (en) * 2001-09-07 2004-05-11 Chvron Phillips Chemical Company Lp Hydrocarbon hydrogenation catalyst composition, a process of treating such catalyst composition, and a process of using such catalyst composition
JP3855266B2 (ja) * 2001-11-01 2006-12-06 日産自動車株式会社 排気ガス浄化用触媒
US20030134744A1 (en) * 2001-12-19 2003-07-17 Sud-Chemie Inc. Process for production and distribution of a prereduced selective hydrogenation catalyst
US20040192983A1 (en) * 2003-02-18 2004-09-30 Chevron Phillips Chemical Co. Acetylene hydrogenation catalyst with segregated palladium skin
US7115789B2 (en) * 2003-03-28 2006-10-03 Exxon Mobil Chemical Patents Inc. Process for removal of alkynes and/or dienes from an olefin stream
JP4403499B2 (ja) * 2003-06-13 2010-01-27 株式会社豊田中央研究所 水素吸蔵材料
US7045670B2 (en) * 2003-09-03 2006-05-16 Synfuels International, Inc. Process for liquid phase hydrogenation
US20050096217A1 (en) * 2003-10-29 2005-05-05 Sud-Chemie, Inc. Selective hydrogenation catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5585318A (en) * 1995-01-20 1996-12-17 Phillips Petroleum Company Alkyne hydrogenation process
EP0839573A1 (en) * 1996-10-30 1998-05-06 Phillips Petroleum Company Hydrogenation process and catalyst therefor comprising palladium and silver deposited on a spinel support
CN1409655A (zh) * 1999-12-08 2003-04-09 巴斯福股份公司 用于炔烃和双烯的选择氢化的负载型催化剂
WO2003015916A1 (fr) * 2000-09-29 2003-02-27 China Petroleum And Chemical Corporation Catalyseur d'hydrocraquage selectif des hydrocarbures insatures, son procede de fabrication et ses applications

Also Published As

Publication number Publication date
US20100222210A1 (en) 2010-09-02
JP2008504117A (ja) 2008-02-14
EP1786748A1 (en) 2007-05-23
US20090131246A1 (en) 2009-05-21
CN1972885A (zh) 2007-05-30
WO2006009988A1 (en) 2006-01-26
US20080234125A1 (en) 2008-09-25
US20100240936A1 (en) 2010-09-23
US20080242903A1 (en) 2008-10-02
US20060166816A1 (en) 2006-07-27

Similar Documents

Publication Publication Date Title
CN1972885B (zh) 用于轻质烯烃原料物流内的乙炔和二烯烃选择性加氢的催化剂与方法
KR102467896B1 (ko) 고 변환율 및 선택성의 odh 공정
JP4339681B2 (ja) 不飽和オレフィンの選択的水素化のための選択的水素化触媒、及びその使用
US4206134A (en) Ruthenium supported on manganese oxide as hydrocarbon synthesis catalysts in CO/H2 reactions
JP3041442B2 (ja) ゼオライトとガリウムをベースとする触媒の存在下における、天然ガスからの液体炭化水素の製造方法
US3751508A (en) Catalyst for selective hydrogenation of acetylenic hydrocarbon in the concurrent presence of diolefin
US7256153B2 (en) Carrier catalytic converter for the selective hydrogenation of alkines and dienes
RU2547466C1 (ru) Катализатор и способ реформинга
KR20120109998A (ko) 메탄의 산화성 짝반응을 위한 방법
CN108290144A (zh) 沸石催化剂及低级烯烃的制造方法
CN102056666A (zh) 通过再生不含贵金属的相应催化剂使含甲烷的混合物脱氢芳构化的方法
EP1809417B1 (en) Use of a catalyst obtained using chemical liquid deposition in hydrocarbon cracking
JPH0639397B2 (ja) Ｃ▲下３▼及びｃ▲下４▼炭化水素の転化用触媒及びその転化法
JPS58156349A (ja) 排ガス浄化用三元触媒
TW201542512A (zh) 不飽和烴之製造方法
TWI639468B (zh) 穩定之錸系異相催化劑及其應用
JPS6265744A (ja) Ｃ↓３及びｃ↓４炭化水素の転化用触媒組成物ならびに転化方法
CN113856745B (zh) 一种抗Zn流失芳构化催化剂及其制备方法和应用
JPH1094718A (ja) 窒素酸化物の接触還元方法
JP4198208B2 (ja) 低分岐度オクテンの製造方法
RU2161535C2 (ru) Способ приготовления палладиевого катализатора
JP2005066525A (ja) 水素製造用触媒及びそれを用いた水素の製造方法
WO2024138065A1 (en) Decarbonized olefins production using process intensification
WO2020174392A1 (en) Catalyst and method related thereto for the synthesis of hydrocabons from syngas
JPH08323207A (ja) オレフィンの低重合方法、その触媒及び触媒の製造方法

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
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20101208

Termination date: 20110621