[go: up one dir, main page]

CN1100772C - 使二氢呋喃类加氢成四氢呋喃类的方法 - Google Patents

使二氢呋喃类加氢成四氢呋喃类的方法 Download PDF

Info

Publication number
CN1100772C
CN1100772C CN96198706A CN96198706A CN1100772C CN 1100772 C CN1100772 C CN 1100772C CN 96198706 A CN96198706 A CN 96198706A CN 96198706 A CN96198706 A CN 96198706A CN 1100772 C CN1100772 C CN 1100772C
Authority
CN
China
Prior art keywords
thf
catalyst
dihydrofuran
palladium
metal
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
CN96198706A
Other languages
English (en)
Other versions
CN1203595A (zh
Inventor
F·J·布罗克尔
R·菲施尔
G·凯比尔
R·宾考斯
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of CN1203595A publication Critical patent/CN1203595A/zh
Application granted granted Critical
Publication of CN1100772C publication Critical patent/CN1100772C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran
    • 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
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • 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
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

在用氢气催化加氢2，5-或2，3-二氢呋喃、得到四氢呋喃的方法中，使用的催化剂是通过蒸发沉积作用或喷涂作用将一种或多种金属沉积到作为载体的金属丝网或金属箔上而得到。

Description

使二氢呋喃类加氢成四氢呋喃类的方法
本发明涉及一种用氢气催化加氢2，5-和2，3-二氢呋喃(DHF)、得到四氢呋喃(THF)的改进方法。
按照EP-A 524216，含有作为副组分的3，4-环氧-1-丁烯和巴豆醛的2，5-二氢呋喃能够在镍和铂催化剂上用氢气氢化，得到THF。按照其实施例1和2，每小时每克镍可分别生成3.6和4.7克THF。
US-A4254039描述了在钯-碳催化剂(在碳上5％的钯)上将2，5-二氢呋喃氢化成THF。在仅有51％的转换率下，每小时每克钯可生成约2克THF。
上述方法的缺点是，使用了活性金属的非负载催化剂或负载催化剂。对于实际催化步骤，仅部分地利用了这些高含量的活性金属。但是，如果减少昂贵的活性成分含量，时空产率变得很低，并且这些方法由此变得不经济。
本发明的目的是，提供一种方法，它在使用较少量活性组合物时，能以高的时空产率使DHF氢化成THF。我们发现，这个目的可通过用催化氢化二氢呋喃生成THF的改进方法达到，其特征在于，使用的催化剂是通过蒸发沉积作用或喷涂作用将一种或多种金属沉积到作为载体的金属丝网或金属箔上而得到。
本发明的催化剂是通过在箔状或丝网状金属载体上蒸发沉积或喷涂活性物质而得到的。人们发现，在德国冶金工作者协会出版的“钢铁清单”中列出的材料号为1.4767、1.4401和1.4301的金属箔或丝网材料特别有用。这些金属载体材料一般通过氧化热处理进行预处理，优选在空气中，温度为600-1100℃，温度优选为750-1000℃，并且接着涂敷活性物质。涂敷步骤后，在空气中完成热活化。为了活化，将已涂敷的金属载体在空气中加热到200-800℃，优选为300-700℃，时间为0.5-2小时。如此生产的催化剂材料可接着成型成整体。在反应器中、在20-300℃、优选为20-200℃的条件下用氢气还原催化剂后，催化剂即可使用。就贵金属催化剂来说，没有预先的活化，反应也可直接发生。
在“Handbook of Thin Film Technology”，Maissel and Glang，McGraw hill，New York，1970，“Thin Film Processes”，J.L.Vossen andW.kern，Academic Press N.Y.和EP-A198435中，详细描述了在减压条件下蒸发沉积和喷涂金属的方法。
原则上讲，合适的活性物质是周期表中的金属和金属元素的组合物，优选元素周期表中第I、VII和VIII副族中的金属，例如镍，铜，钴，钌，铑，钯，铼，铱和铂；特别优选为钯。
在10-250℃、优选为在20-200℃，特别优选为30-150℃条件下进行氢化，并且氢气压力为0.5-300巴，优选为0.7-200巴，特别优选为1-100巴。
在压力装置中有利于进行氢化，例如在管式反应器里、以液相作下流式或上流式操作，或在气相中进行氢化。
反应器进料优选包括纯2，5-或2，3-DHF或它们的混合物，但还可以包括副组分(至多5％重量)如巴豆醛，丁醛，乙烯基环氧乙烷和水和/或惰性稀释剂(至多90％重量)例如THF，二噁烷或醇类如正丁醇。
按照本发明，DHF的氢化作用具有高选择性。产生副产物的量很小，在很低的氢气压力下主要是呋喃。但是，通过蒸馏，可以容易地从THF中分离出呋喃，因此用简单的方法可获得99.99％纯度的THF。
通过US-A5034545，US-A5082956或BE-A674652中描述的方法，可制备二氢呋喃类。
THF是大规模使用的工业产品，例如，作为溶剂或用于聚-THF的原料。
本发明的方法能使活性物质与所形成的THF的重量比高达每小时15000。
                           实施例
起始溶液或产品溶液的组成均用重量％表示。
                           实施例1
在900℃时、在空气中加热具有0.18mm网孔和丝直径0.112mm的1.4767号材料的嗒夫丝网5小时。接着，在电子束蒸发沉积单元中，在载体网的两边蒸发沉积6nm金属钯进行预处理。用晶体振荡器测量涂层厚度，并且使用晶体振荡器控制蒸发沉积速度。蒸发沉积金属钯的量为138mg/m2。将此催化剂网加工成为整体。为此，用钉齿辊将部分网加工成波纹状。将此波纹状网与光滑的网放在一起并卷起。用点焊固定使之成为整体。
                        实施例2
用如实施例1中描述的那样的催化剂网0.112m2制成每个具有20cm高和2cm直径的两个催化剂整料，并且以相当于0.247g钯/升的1.79m2/l的网密度安装在管状反应器中。催化剂首先在150℃用氢气还原2小时。反应器体系冷却后，以具有再循环的上流模式在催化剂上方在50℃和常压下泵入2，5-二氢呋喃和氢气。单位横截面积的物料通过量是250m3/m2h的2，5-二氢呋喃和220m3/m2h的H2。时空产率为0.34kgTHF/升催化剂·小时或1375g THF/克钯·小时。用气相色谱分析原料和氢化产品，得到下列数据：原料：2，5-DHF：99.0％，2，3-DHF：0.1％，THF：0.85％，呋喃：0.05％产品：THF：98.6％，呋喃：1.4％
                          实施例3
用类似于实施例2的方法，以具有再循环的上流模式在80℃和20巴的压力装置中氢化2，5-二氢呋喃。单位横截面积的物料通过量是90m3/m2h的2，5-二氢呋喃和10m3/m2h的H2。时空产率为1.65kg THF/升催化剂·小时。基于相应于0.322g Pd/l安装的2.338m2/l的催化剂网，基于活性物质计的产率为5120g THF/克钯·小时。用气相色谱分析原料和氢化产品，得到下列数据：原料：2，5-DHF：98.99％，2，3-DHF：0.07％，THF：1.01％，呋喃：0.04％产品：THF：99.7％，呋喃：0.3％。

Claims (5)

1.一种在催化剂存在下用氢气对2，5-或2，3-二氢呋喃催化加氢、得到四氢呋喃的方法，其特征在于，使用的催化剂是通过蒸发沉积作用或喷涂作用将一种或多种选自元素周期表第I、VII和VIII族过渡金属的金属沉积到作为载体的金属丝网或金属箔上而得到。
2.按照权利要求1所述的方法，其特征在于，使用催化剂前，在空气中升温活化催化剂。
3.按照权利要求1或2所述的方法，其特征在于，使用的金属载体的材料号为1.4767，1.4401或1.4301。
4.按照权利要求1-3中任何一个所述的方法，其特征在于，在沉积金属前，在空气中将载体加热到600-1100℃。
5.按照权利要求1-4任何一个所述的方法，其特征在于，使用含钯催化剂。
CN96198706A 1995-11-29 1996-11-18 使二氢呋喃类加氢成四氢呋喃类的方法 Expired - Fee Related CN1100772C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19544405A DE19544405A1 (de) 1995-11-29 1995-11-29 Verfahren zur Hydrierung von Dihydrofuranen zu Tetrahydrofuranen
DE19544405.1 1995-11-29

Publications (2)

Publication Number Publication Date
CN1203595A CN1203595A (zh) 1998-12-30
CN1100772C true CN1100772C (zh) 2003-02-05

Family

ID=7778648

Family Applications (1)

Application Number Title Priority Date Filing Date
CN96198706A Expired - Fee Related CN1100772C (zh) 1995-11-29 1996-11-18 使二氢呋喃类加氢成四氢呋喃类的方法

Country Status (17)

Country Link
US (1) US5965751A (zh)
EP (1) EP0863889B1 (zh)
JP (1) JP2000500768A (zh)
KR (1) KR100419594B1 (zh)
CN (1) CN1100772C (zh)
AU (1) AU7627296A (zh)
BR (1) BR9612108A (zh)
CZ (1) CZ164398A3 (zh)
DE (2) DE19544405A1 (zh)
ES (1) ES2158364T3 (zh)
IL (1) IL124340A (zh)
MX (1) MX9804023A (zh)
MY (1) MY115224A (zh)
PL (1) PL326930A1 (zh)
RU (1) RU2168505C2 (zh)
TW (1) TW360647B (zh)
WO (1) WO1997019939A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100623272B1 (ko) * 2005-07-08 2006-09-12 한국과학기술연구원 세 고리형 테트라하이드로퓨란 화합물과 이의 제조방법
CN105833801A (zh) * 2016-05-27 2016-08-10 北京神雾环境能源科技集团股份有限公司 一种用于乙炔加氢制乙烯滴流床的气体除沫器
CN105833803A (zh) * 2016-05-27 2016-08-10 北京神雾环境能源科技集团股份有限公司 一种用于乙炔加氢制乙烯填料鼓泡床的气体除沫器
CN105833806A (zh) * 2016-05-27 2016-08-10 北京神雾环境能源科技集团股份有限公司 一种用于乙炔加氢制乙烯三相流化床的气体除沫器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4254039A (en) * 1980-06-16 1981-03-03 National Distillers & Chemical Corp. Process for the preparation of tetrahydrofuran
EP0198435A2 (de) * 1985-04-17 1986-10-22 BASF Aktiengesellschaft Verfahren zur Herstellung von Katalysatoren für die Abgasentgiftung
US4962210A (en) * 1990-04-02 1990-10-09 Eastman Kodak Company Process for the preparation of high-purity tetrahydrofuran

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH022880A (ja) * 1988-06-17 1990-01-08 Mitsubishi Petrochem Co Ltd 還元ニッケル担持触媒の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4254039A (en) * 1980-06-16 1981-03-03 National Distillers & Chemical Corp. Process for the preparation of tetrahydrofuran
EP0198435A2 (de) * 1985-04-17 1986-10-22 BASF Aktiengesellschaft Verfahren zur Herstellung von Katalysatoren für die Abgasentgiftung
US4962210A (en) * 1990-04-02 1990-10-09 Eastman Kodak Company Process for the preparation of high-purity tetrahydrofuran
EP0524216A1 (en) * 1990-04-02 1993-01-27 Eastman Kodak Co METHOD FOR REPRESENTING HIGH PURITY TETRAHYDROFURANE.

Also Published As

Publication number Publication date
IL124340A0 (en) 1998-12-06
RU2168505C2 (ru) 2001-06-10
JP2000500768A (ja) 2000-01-25
TW360647B (en) 1999-06-11
MX9804023A (es) 1998-09-30
EP0863889B1 (de) 2001-06-06
DE19544405A1 (de) 1997-06-05
ES2158364T3 (es) 2001-09-01
KR100419594B1 (ko) 2004-04-17
BR9612108A (pt) 1999-02-23
CZ164398A3 (cs) 1998-09-16
CN1203595A (zh) 1998-12-30
IL124340A (en) 2000-08-31
WO1997019939A1 (de) 1997-06-05
DE59607053D1 (de) 2001-07-12
PL326930A1 (en) 1998-11-09
KR19990071715A (ko) 1999-09-27
EP0863889A1 (de) 1998-09-16
US5965751A (en) 1999-10-12
MY115224A (en) 2003-04-30
AU7627296A (en) 1997-06-19

Similar Documents

Publication Publication Date Title
CN1066427C (zh) 在固定床钯催化剂上进行炔的部分加氢制备链烯烃
KR100520741B1 (ko) 과산화수소의 제조 방법
JP2004529068A (ja) 構造化担体または一体式担体を有する触媒を使用した非置換またはアルキル基置換の芳香族炭化水素の水素化方法
CN1100772C (zh) 使二氢呋喃类加氢成四氢呋喃类的方法
JPH07179379A (ja) ブテン−２−ジオール−１，４の製造方法および触媒
US6297415B1 (en) Catalytic distillation process
JP2004524273A (ja) 反応蒸留による芳香族炭化水素の水素化方法
AU756102B2 (en) Improved process for the hydrogenation of maleic acid to 1,4-butanediol
US6998366B2 (en) Thin layer catalysts based on Raney alloys, and method for the production thereof
US6380402B2 (en) Preparation of gamma-butyrolactone by catalytic hydrogenation of maleic anhydride
CN1326611C (zh) 含有铼的载附催化剂以及使用该催化剂在液相中氢化羰基化合物的方法
CN1093854C (zh) 乙烯基环氧乙烷选择性加氢制环氧丁烷的方法
CN1096452C (zh) 1,2－环氧丁烷的制备
CA2235042A1 (en) Hydrogenation of dihydrofurans to give tetrahydrofurans
US6464954B2 (en) Method for hydrogenating an anthraquinone compound
SU1726011A1 (ru) Способ приготовлени катализатора гидрировани непредельных органических соединений
KR100483637B1 (ko) 촉매 증류법

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
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee