CN1081938C - 醚化-氢化方法 - Google Patents
醚化-氢化方法 Download PDFInfo
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- CN1081938C CN1081938C CN96199928A CN96199928A CN1081938C CN 1081938 C CN1081938 C CN 1081938C CN 96199928 A CN96199928 A CN 96199928A CN 96199928 A CN96199928 A CN 96199928A CN 1081938 C CN1081938 C CN 1081938C
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- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- C07C41/01—Preparation of ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- 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
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- 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
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Abstract
一种使用位于醚化区(22)上面的氢化区(24)从醚化产物中除去二烯的方法。生产MTBE,并且也对未反应的C4物料流进行C4物料流所含丁二烯的选择加氢处理。通过管线(101)引入C4物料流并且通过管线(102)引入甲醇,它们在管线(104)处合并,随后通过管线(103)进入蒸馏塔(20),其中C4物料流和甲醇在醚化区(22)接触,在此MTBE蒸馏向下。然后对未反应的C4物料在氢化区(24)进行选择加氢处理,其中塔顶残液(108)中的丁二烯被降低90%以上。这样经过氢化处理的C4物料适合于冷酸烷基化或其中丁二烯有害的其它用途。
Description
背景技术
本发明涉及一种用于生产叔烷基醚的催化蒸馏方法,其中未反应的残液基本上不含有丁二烯,并且较吸引人的是本发明可用于冷酸烷基化方法和其它方法。
相关信息
现有技术中已公知通过伯醇和异烯烃反应来生产叔烷基醚。人们发现,使用蒸馏塔反应器同时进行反应和从反应物中蒸馏出产品特别有益于这种通常具有平衡限制的反应。以下公开的专利中描述了使用蒸馏塔反应器及其改进装置的方法:US专利4,218,011、4,232,177、4,305,254、4,504,687、4,978,807、5,118,873、5,120,403、5,248,836、5,248,837、和5,313,005。催化蒸馏可广泛适用于异烯烃的醚化,这在上述几篇专利中有所描述。
US专利5,431,888公开了一种多功能蒸馏塔反应器,其中用于异烯烃加氢处理以除去二烯烃和硫醇的氢化催化剂堆积在醚化催化剂的下面,所说的异烯烃包含来自流化床催化裂化装置的轻石脑油。
通常,用于甲基叔丁基醚(MTBE)生产方法的烯烃原料是含有正丁烷、异丁烷、正丁烯、异丁烯和一些丁二烯的混合C4物料流。异丁烯(iC4 =)优先和甲醇反应,形成MTBE和主要为惰性的剩余物。未反应的C4物料经常作为原料用于正丁烯和异丁烯反应形成异辛烷的冷酸烷基化方法。使用这种含量的丁二烯不影响醚化作用,任何丁二烯在烷基化方法的原料中存在均会发生反应形成淤泥,造成不希望有的“酸消耗”。因此,人们需要iC4 =醚化的残液中基本上不含有丁二烯。而且将正C4烯烃骨架异构化成异丁烯要求除去丁二烯。
本发明的具体特征是发现了甲醇存在于氢化区中不会不利影响二烯的氢化和催化剂的效果。
发明简述
本发明涉及一种方法,其中使用蒸馏塔反应器,将氢化催化剂制备为蒸馏塔反应器中的蒸馏结构,位于醚化反应的下游。优选氢化在堆积于醚化催化剂上面的床中完成,醚化催化剂制备为蒸馏结构,异烯烃优先和醇在较低的醚化床中反应,并且在较高的氢化床中将二烯氢化。出乎意料的是氢化没有受到氢化区中甲醇的抑制。氢化区中可以存在共沸或者过量的甲醇(通常过量10%以下),但没有感到对二烯的氢化有所阻碍。
本发明优选的实施方案是用于生产甲基叔丁基醚(MTBE)的催化蒸馏方法,由包含异丁烯的反应物在含有正丁烯、丁烷和丁二烯的C4物料流以及甲醇(MeOH)中反应,通过将反应混合物送入反应蒸馏塔中、酸性离子交换树脂催化剂床的下面,所说的酸性离子交换树脂催化剂床构成了第一反应蒸馏区。氢可以随混合的甲醇/C4进料一起送入蒸馏塔反应器。
在第一(较低)反应蒸馏区中,甲醇优先和异丁烯反应形成MTBE,MTBE同时蒸馏向下离开催化床。之后,未反应的和惰性的C4物料沸腾向上进入包含氢化催化剂作为蒸馏结构的第二(较高)反应蒸馏区,在其中丁二烯优先和氢反应,产生丁烯和丁烷。令人惊奇的是甲醇在C4物料中的共沸浓度(约4%)不会影响将催化剂活化后丁二烯的转化。
尤其预料不到的是蒸馏***中使用低氢分压不会造成氢化失败的结果,这个不会造成氢化失败的结果是液相***中发现的高氢分压作为基础能够预料的,而且是世界级范围内的广泛标准。冷凝现象是蒸馏中的恒定因素,据信它可以造成和液相中高压同样或者更好的氢化能力,即将氢引入液体中以便发生氢化过程。
醚化原料可以包含通常为丁烯及戊烯的C4-C6异烯烃和醇,所说的醇可以是C1-C4的一元醇,优选甲醇和乙醇。二烯含有通常为1wt%以下的杂质,并且通常为对应于烃进料馏分的那些二烯。
优选醚化也是催化蒸馏反应,但可以将任何醚化反应器中的流出物,如直通式液相反应器或沸腾反应器,直接送入包含催化蒸馏氢化区的蒸馏反应器中,优选送入氢化区下面的常规蒸馏区。常规蒸馏区可以包含在独立的装置中,并且将塔顶馏出物送入氢化区。
附图简介
图1是实施本发明方法的流程性简化示意图。
图2是表示各种程度的氢进料率和丁二烯浓度下氢化性能的示意图。
优选实施方案的描述
优选实施方案是生产甲基叔丁基醚并且氢化含在用于醚化的C4物料流中的丁二烯的方法,该方法包括以下步骤:
(a)将含有异丁烯和丁二烯的第一物料流、含有甲醇的第二物料流以及含有氢的第三物料流送入蒸馏塔反应器的进料区;
(b)使物料流在含有醚化催化剂的醚化反应蒸馏区中接触,以同时:
(i)优先将至少一部分异丁烯和一部分甲醇反应,形成甲基叔丁基醚,
(ii)蒸馏甲基叔丁基醚向下离开醚化反应蒸馏区,并且
(iii)蒸馏未反应的异丁烯、甲醇、丁二烯和氢向上离开醚化反应蒸馏区;
(c)将未反应的异丁烯、甲醇、丁二烯和氢在含有氢化催化剂的氢化反应蒸馏区接触,以便将一部分丁二烯选择加氢处理成丁烯;
(d)从蒸馏塔反应器的底部引出醚产物;并且
(e)从蒸馏塔反应器引出塔顶馏出物,该塔顶馏出物具有比第一物料流的丁二烯含量低的丁二烯含量。
在氢化反应和在醚化反应中,首先进行催化蒸馏是有利的,因为反应和蒸馏同时发生,起始反应产物和其它物料流成分从反应区尽可能快地除去可以降低副反应发生的可能性。其次,由于所有成分均在沸腾,所以将反应温度控制为***压力下的混合物沸点。反应热量仅仅造成更大程度的沸腾,但在给定的压力下温度基本上没有增加。结果,可以通过调节***的压力实现对反应速率和产品分布的一系列控制。而且,调节生产量(停留时间=液体每小时的空间流速-1)得到进一步控制产品分布,并达到对副反应如低聚反应的一定程度的控制。该反应从催化蒸馏中获得的另一个好处是内回流提供给催化剂洗涤效果,由此降低聚合物的产生和成焦。范围为0.4-5L/D(刚好在催化床下面的液体重量/馏出液重量)的内回流可以达到显著的结果。
用于醚化的催化剂优选为酸性阳离子交换树脂,例如由罗姆和哈斯化学公司提供的大孔树脂15(Amberlyst 15)。这里使用的适宜的催化蒸馏结构包括将阳离子交换树脂颗粒放在布带的多个袋中,布带通过用编结开口筛网的不锈钢金属线固定在蒸馏塔反应器中,金属线将筛网和布带以螺旋线形式缠绕在一起。这样可以满足催化剂需要的流动和防止催化剂的损失。布料可以是任何反应惰性的材料。适合使用棉布或亚麻布,优选纤维玻璃布或“特氟隆”布。
氢化是指氢和碳-碳重键反应成“饱和”化合物。氢化反应很早便为人所知,并且通常在超计大气压和中等温度下使用大过量的氢通过金属催化剂来进行。已知催化氢化反应的金属中有铂、铼、钴、钼、镍、钨和钯。通常,催化剂的市售形式使用这些金属的载体氧化物。在使用之前用还原剂或者在使用过程中通过原料中的氢将氧化物还原成活性形式。这些金属还可以催化其它反应,最值得一提的是升温催化脱氢反应。另外,当增加停留时间时,它们可以促进烯烃化合物自身或和其它烯烃的反应,以生产二聚物或低聚物。
相当长时间以前人们便已知烃化合物的选择加氢作用。1962年9月在Petroleum Division of the American Chemical中出现的“TheSelective Hydrogenation of Pyrolysis Gasoline”中,Peterson等讨论了C4和高级二烯烃的选择加氢。Boitiaux等在“Newest HydrogenationCatalyst”Hydrocarbon Processing,1985年3月,描述了一般性、非纵览性的氢化催化剂的各种用途,包括富含丙烯物料流和气体馏分的选择氢化。目前实际使用的常规液相氢化需要高氢分压,通常超过1378000kgf/m2,且更经常达到最高2756000kgf/m2或2756000kgf/m2以上的范围。在液相氢化中,氢分压主要是***的压力。
优选的氢化催化剂是具有钯含量约0.5wt%的氧化铝载体钯催化剂。氢化催化剂一般以直径为0.80~6.35mm的小球或挤出物的形式提供。本发明氢化反应优选的催化剂结构包括挠性半刚性开口筛网管形材料,例如在结合本发明新近开发的一个或数个实施方案中,使用填充有颗粒催化剂原料的不锈钢金属筛网。最具体说,US专利5,431,890描述的结构是优选用于氢化催化剂的结构,该专利引入此作为参考。其中公开的是一种包状催化蒸馏结构,通过将多个链条或连续筒状结构放在金属网筛如除雾器金属线的顶部,布置成与包的纵向轴呈一定的角度,例如当将金属线网筛卷起时,卷起的结构产生新的和改进的催化蒸馏结构。所说的筒包括填充有颗粒催化原料的挠性半刚性开口筛网管形元件、每1-12英寸长度具有一扣件以形成多个链条的筒型结构。
通常,以实际氢分压至少约0.1psia-70psia以下、优选50psia优选的氢气流随其它反应物送入反应蒸馏塔中。在如上定义的氢分压范围内,由于过量的氢通常被排走,所用的氢气不会多于氢化高级不饱和化合物所必需使用的氢。优选氢分压为约0.1-10psia,且更优选不超过7psia。0.5-5psia范围的氢分压将获得最佳的效果。
该快速方法的一个优点是流化床催化裂化装置(FCCU)产生的C4物料可以不经预处理使用。该C4物料流含有约13.28wt%的异丁烯、多至0.5wt%的丁二烯。物料流中剩余的物质主要为丁烷和正丁烯。
现在根据附图1更详细地描述本发明的一个优选实施方案。反应器10优选是按照US专利4,950,803的描述进行操作的反应器,但可以使用任何预备的反应器构造或根本没有预备的反应器。甲醇通过流送线101送入。且FCCU C4物料通过流送线102送入,二者在流送线104中合并,并且送入包含酸性阳离子交换树脂26床的固定床下流防护反应器10中。
反应器10的流出物通过流送线103流出,并且进入蒸馏塔反应器20。蒸馏塔反应器20具有汽提段28,汽提段28在含有酸性阳离子交换树脂蒸馏结构的醚化反应蒸馏区22的下面,而醚化反应蒸馏区22在含有氢化催化蒸馏结构的氢化反应蒸馏区24的下面。塔还包括位于氢化区24上面的精馏段29。氢气通过进料线中流送线105送入塔20中包含催化剂区的下面,由此在进入氢化区24之前和其它反应物混合。
异丁烯优先和甲醇在醚化反应蒸馏区22中反应,形成甲基叔丁基醚,甲基叔丁基醚沸点高于C4物料,也高于甲醇,因此被蒸馏向下进入汽提段28,在其中任何C4物料和甲醇沸腾返回醚化反应蒸馏区22,以进一步反应。
未反应的C4物料和甲醇共沸物(约4%)沸腾向上进入氢化反应蒸馏区24,在其中丁二烯和氢反应,丁二烯含量降低至约20-100wppm。
从蒸馏塔反应器20的底部通过流送线107将醚排出。塔顶馏出物大部分含有未反应的C4物料,并含有小于约100wppm的丁二烯。当蒸大部分含有未反应的C4物料,并含有小于约100wppm的丁二烯。当蒸馏塔反应器首先开始运行时,将氢化区24中的甲醇浓度保持在约2wt%以下,直至将氢化催化剂活化。在氢化催化剂活化之后,所说浓度可以提高至4wt%的共沸程度。活化时间必须对每种单独的催化剂进行确定。
塔顶馏出物通过流送线108排出,并且将C4物料在冷凝器30中冷凝,在接收器40中收集,在其中将任何未冷凝的物料分离并且通过流送线111排出。可以将一部分C4物料作为回流液通过流送线109返回至塔中或者作为产品通过流送线110排出。塔顶馏出的C4物料包含小于100wppm的丁二烯,某些情况下仅约20wppm。通常将塔顶产物水洗以除去对冷酸烷基化方法同样有害的任何甲醇物质。可以将含有正丁烯C4塔顶馏出物或残液用于冷酸烷基化方法。
各反应蒸馏区的温度依赖于容器的压力。塔顶压力优选在689000-757900kgf/m2之间,并且提供的醚化区温度为32.2-79.4℃,氢化区温度为29.4-76.7℃。
实施例
将反应***构造成如图1所示。催化蒸馏(CD)塔反应器包括用陶瓷填充圈填充的15.24m的汽提段。汽提段的直径在进料点以下为101.6mm,在进料点以上为76.2mm。汽提段的蒸汽穿过具有两个催化蒸馏结构床的76.2mm直径的反应区。较低的为6.096m的反应区,其中用酸性阳离子交换树脂催化剂填充在如上所述的布包中。CD反应器的进料点低于树脂催化剂。在醚化催化剂的正上方是如上所述的用7.62m载于氧化铝上的钯基催化剂填充在金属线网容器中的塔。来自反应区的液体(中间回流)直接向下通过到汽提区,从中取出样品并且通过IR分析甲醇含量。
进入防护床反应器的烃原料为C4FCC。异丁烯浓度平均为12-13wt%。原料中丁二烯平均为0.5wt%(约0.3-0.6wt%)。当需要如图2所示的较高浓度时,进料中加入商品级的1,3-丁二烯。图2显示了在丁二烯不同浓度下氢进料率对丁二烯转化率的影响。氢具有工业用级的纯度(99.95%H2)。硫醇小于2ppm且乙腈浓度平均为20ppm。甲醇具有99.9%的纯度。
在塔顶压力为757900kgf/m2下操作蒸馏塔。在氢化催化剂开始活化之后,将甲醇送入装置中以便在塔顶达到约4wt%的共沸值。
CD反应器醚化区中运转的整个异丁烯转化率平均为90%以上。基于MTBE产率和送入装置中的异丁烯总量,异丁烯的平均转化率计算为98.0%。图2显示了C4残液可以由含有最多为0.5wt%(5000wppm)丁二烯的进料气体流在甲醇的存在下氢化成100wppm含量的丁二烯。下表描述CD反应器中运行的典型状况。
表物料流运行的小时时间 446 926条件压力,PSIA 110 110温度,°FBTMS 285 290催化区(22) 151 156(24) 152-125 154塔顶 125 142物料流 103 105 107 108 103 105 107 108组成,wt%甲烷 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.061乙烷 0.045 0.000 0.000 0.034 0.045 0.000 0.000 0.029乙烯 0.001 0.000 0.000 0.000 0.001 0.000 0.000 0.000丙烷 1.598 0.000 0.000 1.636 1.598 0.000 0.000 0.136丙烯 0.080 0.000 0.000 0.073 0.080 0.000 0.000 0.013异丁烷 27.688 0.000 0.000 33.811 27.688 0.000 0.000 32.280异丁烯 5.291 0.000 0.000 0.107 5.291 0.000 0.008 0.5001-丁烯 12.204 0.000 0.000 4.135 12.204 0.000 0.000 4.4471,3-丁二烯 0.399 0.000 0.000 0.001 0.399 0.000 0.000 0.000正丁烷 8.909 0.000 0.000 12.450 8.909 0.000 0.000 11.751反式-2-丁烯 15.490 0.000 0.000 31.810 15.490 0.000 0.000 31.5212,2-二甲基丙烷 0.004 0.000 0.000 0.000 0.004 0.000 0.000 0.000甲基-环丙烷 0.013 0.000 0.000 0.014 0.013 0.000 0.000 0.016顺式-2-丁烯 11.749 0.000 0.000 14.407 11.749 0.000 0.000 15.2473-甲基-1-丁烯 0.359 0.000 0.059 0.017 0.359 0.000 0.098 0.029异戊烯 0.599 0.000 2.239 0.009 0.599 0.000 2 166 0.0081-戊烯 0.032 0.000 0.122 0.000 0.032 0.000 0.127 0.0002-甲基-1-丁烯 0.016 0.000 0.029 0.013 0.016 0.000 0.041 0.014正戊烷 0.005 0.000 0.017 0.000 0.005 0.000 0.076 0.0002-甲基-1,3-丁二烯 0.003 0.000 0.003 0.000 0.003 0.000 0.004 0.000反式-2-戊烯 0.011 0.000 0.037 0.000 0.011 0.000 0.030 0.000顺式-2-戊烯 0.004 0.000 0.015 0.000 0.004 0.000 0.013 0.0002-甲基-2-丁烯 0.032 0.000 0.481 0.098 0.032 0.000 0.365 0.116反式-1,3-戊二烯 0.000 0.000 0.000 0.000 0.000 0.000 0.078 0.000顺式-1,3-戊二烯 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000二甲醚 0.000 0.000 0.000 0.008 0.000 0.000 0.000 0.013甲醇 2.855 0.000 0.000 1.103 2.855 0.000 0.007 3.725叔丁醇 0.000 0.000 0.098 0.000 0.000 0.000 0.000 0.000甲基-叔丁基醚 12.380 0.000 95.364 0.000 12.380 0.000 95.636 0.000甲基-仲丁基醚 0.015 0.000 0.203 0.000 0.015 0.000 0.085 0.000叔戊基甲基醚 0.010 0.000 1.236 0.000 0.010 0.000 1.097 0.000DIB-1(2,4,4-三甲基- 0.000 0.000 0.008 0.000 0.000 0.000 0.004 0.000DIB-1(2,4,5-三甲基- 0.000 0.000 0.000 0.000 0.000 0.000 0.003 0.000重物质 0.209 0.000 0.048 0.271 0.209 0.000 0.111 0.095未知物质 0.002 0.000 0.039 0.003 0.002 0.000 0.050 0.000流速,lb/小时 120 23.6 92.4 112.2 24.7 91.6H2SCFH 30.1 14.1
Claims (17)
1.一种生产烷基叔烷基醚并且氢化含在异烯烃中的二烯的方法,所说的异烯烃包含于醚化的物料流,该方法包括以下步骤:
(a)将含有异烯烃和二烯的第一物料流、含有醇的第二物料流以及含有氢的第三物料流送入蒸馏塔反应器的进料区;
(b)使物料流在含有醚化催化剂的醚化反应蒸馏区中接触,以:
(i)将至少一部分异烯烃和一部分醇选择性反应,形成烷基叔烷基醚,
(ii)蒸馏,烷基叔烷基醚向下离开醚化反应蒸馏区,并且
(iii)蒸馏,未反应的异烯烃、醇、二烯和氢向上离开醚化反应蒸馏区;
(c)将未反应的异烯烃、醇、二烯和氢在含有氢化催化剂的氢化反应蒸馏区接触,以便将一部分二烯选择加氢处理成烯烃;
(d)从蒸馏塔反应器的底部引出醚产物;并且
(e)从蒸馏塔反应器引出塔顶馏出物,该塔顶馏出物具有比第一物料流的二烯含量低的二烯含量。
2.根据权利要求1的方法,其中所说的烯烃具有4-6碳原子。
3.根据权利要求1的方法,其中所说的醇为具有1-4碳原子的一元醇。
4.根据权利要求1的方法,其中所说的异烯烃包括异丁烯。
5.根据权利要求1的方法,其中所说的异烯烃包括异戊烯。
6.根据权利要求4的方法,其中所说的醇为甲醇、乙醇或其混合物。
7.根据权利要求5的方法,其中所说的醇为甲醇、乙醇或其混合物。
8.根据权利要求1的方法,其中,所说的烷基叔烷基醚为甲基叔丁基醚,所述的醚化的物料流为醚化的C4物料流,所述的异烯烃为异丁烯,所述二烯为丁二烯,所述的醇为甲醇,所述烯烃为丁烯。
9.根据权利要求8的方法,其中所说的第一物料流还包含从蒸馏塔反应器塔顶引出的正丁烯。
10.根据权利要求8的方法,其中塔顶馏出物料流中的丁二烯含量降低为百万分之100重量份,或更少。
11.根据权利要求8的方法,其中在位于蒸馏塔反应器的醚化反应蒸馏区下面的汽提段中,汽提醚产物中的任何未反应甲醇和C4物料。
12.根据权利要求11的方法,其中进入汽提段的醚产物中的甲醇含量为共沸量或更少。
13.根据权利要求1所述的方法,其改进包括将氢化反应蒸馏区置于醚化反应蒸馏区的上面,以氢化C4物料中包含的一部分丁二烯。
14.根据权利要求13的方法,其中C4物料流中的丁二烯含量被降低至百万分之100重量份,或更少。
15.根据权利要求13的方法,其中醚化反应蒸馏区包含催化蒸馏结构的酸性阳离子交换树脂催化剂。
16.根据权利要求13的方法,其中氢化反应蒸馏区包含催化蒸馏结构的含约0.5wt%钯的氧化铝载体钯催化剂。
17.根据权利要求1的方法,其中,步骤c)中所述氢化催化剂制备为蒸馏结构。
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DE (1) | DE69629841T2 (zh) |
ES (1) | ES2203727T3 (zh) |
RO (1) | RO120320B1 (zh) |
RU (1) | RU2165405C2 (zh) |
WO (1) | WO1997028874A1 (zh) |
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US6284104B1 (en) | 1999-03-04 | 2001-09-04 | Catalytic Distillation Technologies | Apparatus and process for hydrogenations |
DE10050625A1 (de) * | 2000-10-12 | 2002-04-18 | Erdoelchemie Gmbh | Strukturierte Mehrzweckpackungen und deren Verwendung |
US6855853B2 (en) * | 2002-09-18 | 2005-02-15 | Catalytic Distillation Technologies | Process for the production of low benzene gasoline |
US7431827B2 (en) * | 2004-10-27 | 2008-10-07 | Catalytic Distillation Technologies | Process for the production of low sulfur, low olefin gasoline |
CN107056570B (zh) * | 2017-03-17 | 2023-05-30 | 濮阳市盛源石油化工(集团)有限公司 | 一种异辛烷精制烷基化原料气的装置及工艺 |
KR102589091B1 (ko) | 2017-07-27 | 2023-10-16 | 사빅 글로벌 테크놀러지스 비.브이. | 연료 첨가제의 제조 방법 |
CN109651063A (zh) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | 异戊烯的制备方法 |
CN109651057A (zh) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | 制备异戊烯的方法 |
CN111801404A (zh) | 2018-03-19 | 2020-10-20 | 沙特基础工业全球技术有限公司 | 生产燃料添加剂的方法 |
KR20200133359A (ko) | 2018-03-19 | 2020-11-27 | 사빅 글로벌 테크놀러지스 비.브이. | 연료 첨가제 제조 방법 |
US11248181B2 (en) | 2018-04-19 | 2022-02-15 | Sabic Global Technologies B.V. | Method of producing a fuel additive |
EP3790854A1 (en) * | 2018-05-07 | 2021-03-17 | SABIC Global Technologies B.V. | Method of producing a fuel additive |
WO2019217050A1 (en) * | 2018-05-07 | 2019-11-14 | Sabic Global Technologies B.V. | Method of producing a fuel additive |
US11697626B2 (en) | 2018-05-18 | 2023-07-11 | Sabic Global Technologies B.V. | Method of producing a fuel additive with a hydration unit |
WO2020058825A1 (en) | 2018-09-18 | 2020-03-26 | Sabic Global Technologies B.V. | Systems and processes for efficient production of one or more fuel additives |
WO2020104967A1 (en) | 2018-11-20 | 2020-05-28 | Sabic Global Technologies B.V. | Process and system for producing ethylene and at least one of butanol and an alkyl tert-butyl ether |
AR120161A1 (es) | 2019-10-07 | 2022-02-02 | Lummus Technology Inc | Coproducción de isobutano y buteno-1 de alta pureza a partir de c₄ mixto |
KR20240027799A (ko) * | 2021-07-20 | 2024-03-04 | 루머스 테크놀로지 엘엘씨 | 촉매 증류에서의 삼관능 공정 |
CN116041151A (zh) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | 一种cpme的合成工艺 |
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- 1996-12-31 RU RU98117137/04A patent/RU2165405C2/ru active
- 1996-12-31 WO PCT/US1996/020896 patent/WO1997028874A1/en active IP Right Grant
- 1996-12-31 ES ES96945327T patent/ES2203727T3/es not_active Expired - Lifetime
- 1996-12-31 JP JP52850097A patent/JP3973690B2/ja not_active Expired - Lifetime
- 1996-12-31 AU AU15229/97A patent/AU710971B2/en not_active Ceased
- 1996-12-31 EP EP96945327A patent/EP0880388B1/en not_active Expired - Lifetime
- 1996-12-31 DE DE69629841T patent/DE69629841T2/de not_active Expired - Lifetime
- 1996-12-31 RO RO98-01286A patent/RO120320B1/ro unknown
- 1996-12-31 CA CA002245581A patent/CA2245581A1/en not_active Abandoned
- 1996-12-31 BR BR9612493A patent/BR9612493A/pt not_active IP Right Cessation
- 1996-12-31 CN CN96199928A patent/CN1081938C/zh not_active Expired - Lifetime
- 1996-12-31 KR KR10-1998-0705571A patent/KR100437966B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
---|---|
DE69629841T2 (de) | 2004-07-29 |
JP2001507671A (ja) | 2001-06-12 |
RO120320B1 (ro) | 2005-12-30 |
EP0880388A1 (en) | 1998-12-02 |
WO1997028874A1 (en) | 1997-08-14 |
AU710971B2 (en) | 1999-09-30 |
JP3973690B2 (ja) | 2007-09-12 |
CA2245581A1 (en) | 1997-08-14 |
KR19990081860A (ko) | 1999-11-15 |
BR9612493A (pt) | 1999-07-20 |
ES2203727T3 (es) | 2004-04-16 |
KR100437966B1 (ko) | 2004-08-16 |
EP0880388B1 (en) | 2003-09-03 |
EP0880388A4 (en) | 2000-12-27 |
DE69629841D1 (de) | 2003-10-09 |
CN1209077A (zh) | 1999-02-24 |
RU2165405C2 (ru) | 2001-04-20 |
AU1522997A (en) | 1997-08-28 |
US5628880A (en) | 1997-05-13 |
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