CN1108353C - Continuous catalytic reforming combined with zeolitic reforming for increased BTX yield - Google Patents

Continuous catalytic reforming combined with zeolitic reforming for increased BTX yield Download PDF

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CN1108353C
CN1108353C CN97114124A CN97114124A CN1108353C CN 1108353 C CN1108353 C CN 1108353C CN 97114124 A CN97114124 A CN 97114124A CN 97114124 A CN97114124 A CN 97114124A CN 1108353 C CN1108353 C CN 1108353C
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reforming
catalyst
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zeolitic
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CN1216315A (en
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R·S·海兹曼
M·B·鲁斯
J·Y·G·帕克
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环球油品公司
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Abstract

在包括基本上由能够连续再生催化剂颗粒的移动床催化重整区域的连续重整区域再加上含有铂族金属和作用于来自联合重整区域物流的非酸性沸石催化剂的沸石重整区域组成的联合顺序中催化重整石脑油原料。 Comprising a substantially continuously moving bed catalytic reforming regenerated catalyst particles in the continuous-reforming section area plus zeolite reforming region containing a platinum group metal and a nonacidic zeolite from acting on the joint region of the reforming catalyst stream consisting of joint sequence catalytic reforming a naphtha feed. 其独特的联合工艺实现了较高的强度,较高的BTX芳烃产率和/或提高连续重整区域的产量,与现有技术方法相比显示出令人惊奇的效果。 Its unique combination process to achieve a higher strength, higher BTX aromatics yields and / or increased production of the continuous-reforming zone, compared with the prior art method exhibit surprising effect. 该工艺特别适用于改进现有的能够连续再生催化剂的移动床重整装置。 The process is particularly suitable for improving the conventional moving bed reformer catalyst can be continuously regenerated.

Description

用于提高苯、甲苯和二甲苯产量的与沸石重整结合的连续催化重整 For improving the continuous catalytic benzene, toluene and xylene yield in combination with the zeolite reforming reforming

本发明涉及一种用于烃转化的改进方法,具体说是用于汽油沸程馏分烃的催化重整的改进方法。 The present invention relates to an improved process for the conversion of hydrocarbons, particularly improved process for catalytic reforming of gasoline boiling range hydrocarbon fraction.

近年来,出现了使用催化剂移动床进行重整和为避免其失活进行连续再生催化剂移动床的连续催化重整的方法,该方法在新型重整单元操作中占主导地位。 In recent years, the use of moving bed of catalyst and a reforming catalyst in order to avoid a continuous method for the continuous regeneration of the catalyst moving bed for reforming its inactivation, which dominates the new reformer unit operation. 当今世界,为生产用于石油-化学工业或对发动机的爆声具有高阻尼的汽油组分的芳烃中间体的几乎每一个石油炼制厂都采用了对汽油沸程馏分烃原料进行催化重整。 Nowadays, for the production of oil - almost every refinery petroleum chemical industry or gasoline components aromatic intermediate has a high acoustic damping of explosion of the engine are used for the feed gasoline boiling range distillate hydrocarbon catalytic reforming . 对于芳烃的需要量大于芳烃生产原料的供应量。 For the supply of the required amount is greater than the aromatics aromatics feedstock. 然而,由于环境的限制和对高性能内燃机的要求的提高需要提高汽油等级,这种要求也要求提高用汽油辛烷值来度量的汽油组分对爆声的阻尼作用。 However, due to environmental requirements and to improve the internal combustion engine needs to be increased high performance grade gasoline, this requirement is also required to improve the damping effect octane gasoline component with gasoline to measure the sound of the explosion. 因此,在一定的炼油厂内的催化重整装置,常常必需提高其处理能力以满足这些增加芳烃和提高汽油的辛烷值的需要。 Thus, catalytic reforming unit within a refinery, it is often necessary to improve the processing capacity to meet these increasing aromatics and gasoline to improve octane number. 人们希望被应用于连续催化重整工艺的等级提高过程能有效的利用现存的重整和催化-再生设备。 It is desirable to improve the process to be applied to a continuous catalytic reforming process effective level of use of existing reforming and catalyst - reproducing apparatus.

一般情况下,将催化重整应用到富链烷烃和环烷烃的原料中并且通过各种反应进行催化重整:所述的反应是环烷烃脱氢成芳烃,链烷烃脱氢环化成轻质烃,链烷烃和环烷烃的异构化成轻质烃,烷基芳烃的脱烷基化成轻质烃,链烷烃的加氢裂解成轻质烃,并且生成焦炭沉积在催化剂上。 Generally, the catalytic reforming is applied to paraffin-rich feedstock and cyclic alkanes and catalytically reforming various reaction: said reaction is dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins into light hydrocarbons , paraffins and naphthenes isomerization of light hydrocarbons, dealkylation of alkylaromatic hydrocarbons into light hydrocarbons, hydrogenation cracking of paraffins to light hydrocarbons, and coke deposited on the catalyst. 增加芳烃和提高辛烷值的需要使人们的注意力转移到链烷烃-脱氢环化作用上,该作用比其它的芳构化反应,从传统的重整热力学和动力学方面来说不太有利。 Increasing need to improve octane aromatics and people's attention to the paraffin - the cyclization dehydrogenation, the action, from thermodynamic and kinetic aspects is not conventional reforming than other aromatization reactions advantageous. 在最大限度地抑制焦炭产生的同时通过促进脱氢环化反应并且抑制与其竞争的加氢裂解反应来对经过催化重整提高所希望的产品产率产生明显的杠杆作用。 While the maximum inhibition of coke produced by cyclization and dehydrogenation promoting suppress competing hydrocracking reaction on the significant leverage through a catalytic reforming improve the desired product yield. 连续催化重整可以用通过连续再生催化剂产生的高活性催化剂、以较低的压力操作,有效地用于脱氢环化作用。 Continuous catalytic reforming using highly active catalyst can be produced by a continuous catalyst regeneration, lower pressure operation, effective cyclization dehydrogenation.

含有非酸性L-沸石和铂族金属的用于链烷烃的脱氢环化作用的重整催化的有效性在本领域中已被人们所熟知,已经公开了使用这些重整催化剂从链烷烃提余液和环烷烃生产芳烃。 Effectiveness of reforming catalyst containing a non-acidic zeolite and L- cyclization dehydrogenation of paraffins platinum group metal has been well known in the art, it has been disclosed the use of these reforming catalysts stripped from the paraffin raffinate aromatics and naphthenes production. 然而,这种脱氢环化技术在紧张和持续的发展过程中其工业化进程非常缓慢。 However, this dehydrocyclization technology and sustainable development in a tense process of its industrialization process is very slow. 本发明提供一种全新的方法,以补充使用L-沸石技术。 The present invention provides a new approach to supplement the use of L- zeolite technology.

US-A-4,645,586指出使含金属氧化物载体和VIII族金属的双官能团的重整催化剂与原料接触,接着使原料与含有大孔径沸石的,优选L沸石的沸石重整催化剂接触,通过使用第一种传统重整催化剂以提供一产品物流流到第二种非酸性的高选择性催化剂中,克服了现有技术的缺陷。 US-A-4,645,586 noted reforming catalyst containing a metal oxide support and a Group VIII metal and the difunctional material, then contacting the feedstock with a catalyst, preferably a zeolite comprising large pore zeolite is L zeolite reforming, by using the first one conventional reforming catalyst to provide a product stream flows to the second non-acidic, highly selective catalysts, it overcomes the drawbacks of the prior art. 但是该文献中没有建议在BUSS中连续重整。 However, this document does not suggest the BUSS continuous reforming.

US-A-4,985,132指出一种分区域催化重整方法,初始区域内含有在耐熔无机氧化物上的铂-锗的催化剂和在最后催化剂区域含有一与连续催化剂再生系统连接的移动床系统。 US-A-4,985,132 noted that one kind of sub-region of the catalytic reforming process, the initial region containing the refractory inorganic oxide in a platinum - germanium catalyst systems, and moving bed at the last catalyst zone comprises a continuous catalyst regeneration system connection. 然而,没有公开L-沸石成分。 However, there is no disclosure L- zeolite component.

US-A-5,190,638指出以移动床中连续的催化剂再生模式,生产一部分重整物流到第二重整区域的重整,优选使用一种在0.791-0.354mPa(100-500磅/英寸2)含有酸性官能团的催化剂,但是该文献没有公开使用一种非酸性沸石催化剂。 US-A-5,190,638 points out to a moving bed continuous catalyst regeneration mode, a portion of the reformate stream to produce a second reforming zone containing a reforming, it is preferable to use A 0.791-0.354mPa (100-500 lb / in2) the catalyst of acidic functional group, but the document does not disclose the use of a nonacidic zeolitic catalyst.

US-A-3,652,231指出在移动柱中的一种重整催化剂的再生和再调整,但是该文献没有建议双区域的重整。 US-A-3,652,231 stated in the reproduction of one moving column and readjustment of the reforming catalyst, but this document does not suggest the double reforming zone.

本发明的目的是提供一种改善产品产率结构的催化重整方法。 Object of the present invention to provide a catalytic reforming process for improving the product yield structure.

本发明的另一个目的是提高BTX芳烃的产量和连续重整方法的性能。 Another object of the present invention is to improve BTX aromatics yields and performance of a continuous reforming process.

本发明是基于下述的发现,连续催化重整和沸石重整的结合显示大大提高了BTX芳烃产量和使用该方法相对于现有技术获得了突出的改进。 The present invention is based on the discovery described below, the continuous catalytic reforming and zeolitic reforming show greatly improved binding BTX aromatics yields and the use of this method with respect to the prior art obtained outstanding improvement.

本发明的一个宽范围实施方案是一种催化重整方法的结合,在该方法中通过连续催化重整成功的加工烃原料,上述的连续催化重整包括一个连续催化剂再生移动床和在一个含有由非酸性沸石和铂族金属组成的催化剂的沸石重整区域。 A wide range of embodiments of the present invention is a combination of a catalytic reforming process, reforming a hydrocarbon feedstock in the successful processing of the continuous catalytic process by the continuous catalytic reforming comprises a continuous catalyst regeneration in a moving bed and comprising zeolite catalyst by nonacidic zeolite and a platinum group metal composition reforming zone. 优选使用一种催化剂进行连续重整,该催化剂含有一耐熔无机氧化物载体,铂族金属和卤素,而该催化剂至少可半连续的再生和再调整并返回到连续重整反应器。 A catalyst is preferably used for continuous reforming, the catalyst contains a refractory inorganic oxide support, a platinum group metal and halogen, which catalyst is at least semi-continuous regeneration and re-adjusted and returned to the continuous-reforming reactor. 优选非酸性沸石是一L-沸石,最优选的是钾型L-沸石。 Nonacidic zeolite preferably is an L- zeolite, most preferably potassium L- type zeolite. 优选用于一种或二种连续的沸石重整催化剂的铂族金属是铂。 Preferably one or two for the zeolitic reforming catalyst continuously platinum group metal is platinum.

优选在沸石重整区域加工来自连续催化重整的第一种流出物而不用分离游离氢。 Preferably the first processing effluent from continuous catalytic reforming in the zeolitic reforming zone without separation of free hydrogen.

在另一方面,本发明包括添加一沸石重整区域以扩大现有的连续重整加工装置的生产量和/或提高产品质量。 In another aspect, the present invention comprises adding a zeolitic reforming zone to expand the production capacity of existing reformer continuous machining device and / or improve product quality.

图1示出与现有技术的产率比较的本发明的联合方法的BTX-芳烃的产率。 Figure 1 shows the yield of aromatics BTX- integrated process of the present invention compared with the yield of the prior art.

该烃原料含有链烷烃和环烷烃,还可含有芳烃和少量汽油沸程烯烃。 The hydrocarbon feedstock comprises paraffins and naphthenes, aromatics and may also contain a small amount of gasoline boiling range olefins. 可以使用的原料包括直馏石脑油,天然汽油,合成石脑油,热加工汽油,催化裂化汽油,部分重整石脑油或来自提取芳烃的提余液。 Feedstock can be used include straight-run naphthas, natural gasoline, synthetic naphthas, thermal processing gasoline, catalytically cracked gasoline, partially reformed naphthas or raffinates from extraction of aromatics. 蒸馏的范围可是全馏程石脑油,其初沸点一般为40-80℃,终沸点为160-210℃,或者在一个狭窄的范围内具有较低的终沸点。 Distillation range, but the whole range naphtha, which is generally an initial boiling point 40-80 deg.] C, a final boiling point of 160-210 deg.] C, or having a lower end boiling point within a narrow range. 链烷烃原料例如来自中东原油的石脑油,其终沸点在100-175℃较有利于加工,因为该工艺可有效地脱氢环化链烷烃成为芳烃。 Paraffinic feedstock such as naphtha from a Middle Eastern crude oil, a final boiling point of 100-175 deg.] C more favorable process because the process can be effectively dehydrocyclization of paraffins to aromatics. 来自芳烃提取的提余液主要含有可以转变成有价值的BTX芳烃的低值C6-C8石脑油是优选的可供选择替代的烃原料。 Raffinate from aromatics extraction comprising primarily BTX can be converted into valuable low-value C6-C8 aromatic naphtha is preferred to choose an alternative hydrocarbon feedstocks.

本发明的烃原料含有少量的硫化物,一般少于10ppm〔按照元素基准计〕,优选来自含有杂质的原料通过传统的预处理步骤制备烃原料,上述的预处理步骤例如加氢处理,加氢精制,或加氢脱硫作用,将这些杂质如亚硫化物,含氮化合物,氧化物分别转化为H2S,NH3和H2O,它们可通过蒸馏从烃中分出。 Hydrocarbon feedstock to the present invention contains a small amount of a sulfide, usually less than 10ppm according to [] element basis, preferably prepared by conventional hydrocarbon feed pretreatment step feedstock containing impurities from the preprocessing steps such as hydrotreating, refining or hydrogenation desulfurization, these impurities such as sodium sulfide, nitrogen-containing compounds, oxides are converted to H2S, NH3 and H2O, which may be separated from the hydrocarbon by distillation. 优选这种转化使用一种本领域中已知的催化剂,该催化剂含有一种无机氧化物载体和选自元素周期表中的VIB(6)族和VIII(9-10)族的金属〔参见Cotton和Wilkinson,无机化学进展(AdvancedInorganic Chemistry),John Wiley&Sons(第5版,1988)〕。 This conversion preferably uses a catalyst known in the art, the catalyst comprising an inorganic oxide support selected from the Periodic Table of the VIB (6) and Group VIII (9-10) metals Group [see Cotton and Wilkinson, progress in inorganic Chemistry (AdvancedInorganic Chemistry), John Wiley & amp; Sons (5th Edition, 1988)]. 除了传统的氢处理外,预处理步骤还可以包括与能够去除硫化物和其它杂质的吸着剂接触,或者仅包括后者作为可供选择的替代方式进行预处理。 In addition to the conventional hydrotreating, the pretreatment step may further comprise contacting capable of removing sulphides and other impurities sorbent, or only the latter alternative As an alternative pretreatment. 这些吸着剂可以包括但不限于氧化锌,海绵铁,高表面积钠,高表面积氧化铝,活性炭和分子筛。 These sorbents may include but are not limited to, zinc oxide, iron sponge, high surface area sodium, high-surface area alumina, activated carbons and molecular sieves. 用氧化铝-镍吸着剂可以获得优良的结果。 Alumina - Ni sorbent can obtain excellent results. 优选预处理步骤提供一种在现有技术中已经公开的作为希望的重整原料的低硫含量的烃原料,其含硫量例如为1ppm-0.1ppm(100ppb)。 Preferably the pretreatment step of providing a low sulfur content hydrocarbon feedstock reforming raw material A has been disclosed in the prior art as desirable, for example, sulfur content 1ppm-0.1ppm (100ppb).

预处理步骤通过用硫吸着剂结合相对耐硫的重整催化剂可以将烃原料中的硫含量降至很低,耐硫重整催化剂接触污染的原料以便将大部分硫化物转变成为含H2S的排除物流。 Preprocessing step is performed by a relatively sulfur-tolerant reforming catalyst with a sulfur content can be reduced to very low hydrocarbon feedstock, feedstock sulfur-tolerant reforming catalyst with a sulfur sorbent contaminated binding to exclude most of the H2S-containing sulfide is transformed into logistics. 含H2S的物流接触有利的是氧化锌或氧化镁的硫吸着剂以便除去H2S。 Contacting the stream containing H2S is advantageously zinc oxide or magnesium oxide sulfur sorbent to remove H2S. 从而可实现0.1ppm以下的硫含量。 Thereby to achieve a sulfur content of 0.1ppm or less. 在本发明的范围内,预处理步骤包括在现有的重整方法中。 Within the scope of the present invention, in conventional pre-treatment step comprises a reforming process.

每个连续重整区域和沸石重整区域含有一个或多个分别含有催化剂的反应器。 Each successive reforming zone and zeolitic reforming zone containing one or more reactors containing the respective catalysts. 原料可分别以上流、下流模式或以径向流模式接触在每个反应器中的催化剂。 Feed stream may be respectively above, in the downflow mode or in contact with the catalyst in each reactor in a radial flow pattern. 因为现有的重整工艺是在相对低的压力下操作,所以在径向流反应器中的低压力降有利于径向流模式。 Since conventional reforming process is operated at a relatively low pressure, the low pressure in a radial flow reactor drop facilitate radial flow mode.

第一重整条件包括与沸石重整区域一致的压力从100kpa-6MPa(绝对压力),优选100kpa-1Mpa(绝压)。 First reforming conditions comprise a pressure zeolitic reforming zone is consistent from 100kpa-6MPa (absolute pressure), preferably 100kpa-1Mpa (absolute). 操作压力为450kpa或更低可获得优良的结果。 Or lower operating pressure 450kpa obtained excellent results. 通常在含有轻质烃的气体中的游离氢与原料相结合,得到的摩尔比为0.1-10摩尔氢/摩尔C5+烃。 Usually combined in a raw gas containing free hydrogen and light hydrocarbons in the molar ratio of hydrogen to give 0.1 to 10 mol / mole of C5 + hydrocarbons. 相对于第一重整催化剂体积的空速为0.2-10hr-1。 With respect to the volume of first reforming catalyst space velocity 0.2-10hr-1. 操作温度为400-560℃。 The operating temperature was 400-560 ℃.

连续重整区域生产一种富芳烃的第一物流。 Continuous-reforming section to produce an aromatics-enriched first stream. 在原料中的石脑油的大部分转变成为芳烃。 Most transitions in the naphtha feedstock to aromatics. 在原料中的链烷烃基本上被异构化了,加氢裂解了,脱氢环化了,其中重质链烷烃比轻质链烷烃转变的量更多,因此后者在物流中占多数。 Paraffins in the feedstock are isomerized substantially, the hydrocracking, dehydrocyclization, and wherein the heavy paraffins more than the amount of light paraffins transition, so that the latter in the majority stream. C5+物流部分中的芳烃含量相对于烃原料中的芳烃含量提高了至少5(质量)%。 C5 + aromatics content stream portion with respect to the aromatics content of the hydrocarbon feedstock is increased by at least 5 (mass)%. 芳烃组分主要取决于原料组分和操作条件,一般主要由C6-C12芳烃组成。 Aromatic component depends on the operating conditions and raw material component, is generally formed predominately C6-C12 aromatics.

在重整反应中,由于诸如在微粒上沉积的焦炭达到一定程度催化剂不再适用之类机理而导致催化剂颗粒失活。 In the reforming reaction, since such particles are deposited on the coke reaches a certain level the catalyst is no longer applicable such mechanisms leading to deactivation of the catalyst particles. 这种失活催化剂必需在重整工艺中重新使用之前再生和再调整。 Such catalyst deactivation and regeneration readjustment necessary prior to reuse in the reforming process.

由于通过几天的再生循环保持接近新鲜催化剂的高催化剂活性致使连续重整可以在更具强度的条件下进行操作。 Since the regeneration cycle by a few days to maintain high catalyst activity of the fresh catalyst close so that reforming can be operated continuously under conditions more strength. 移动床的优点在于保持生产,同时除去或置换催化剂。 Advantage of the moving bed is to maintain production while the catalyst is removed or replaced. 催化剂微粒由于重力通过在移动床内的一个或多个反应器,并被送到连续再生区域。 The catalyst particles by gravity through the one or more moving bed reactors, and to a continuous regeneration zone. 连续催化剂的再生是在移动床模式中由重力使催化剂微粒下流通过在再生容器中的各种处理区域进行的。 Continuous regeneration of the catalyst is in a moving bed mode, the catalyst particles by gravity in downflow through the various processing performed in the reproduction area of ​​the container. 虽然催化剂通过各种区域的移动常常设定为连续的,实际上是在间隔紧密的各时间点上分别输送相对小量的催化剂微粒意义上的半连续操作。 While moving through the catalyst zone is often set various continuous, semi actually are conveyed on a relatively small amount of fine catalyst particles sense at each time point closely spaced continuous operation. 例如每分钟一批料可以从反应区域的底部排出,排出可以历时1/2分钟;即在一分钟周期内催化剂微粒流动历时1/2分钟。 E.g. batch per minute may be withdrawn from the bottom of the reaction zone, it can be discharged over 1/2 min; i.e., within one minute cycle of the catalyst particles flow over 1/2 minutes. 由于在反应器和再生区域内一般相对于批量体积,装料体积较大,催化剂床可以设计成移动连续的。 Since in the reactor and the regeneration zone relative to the general batch volume, larger charge, the catalyst bed may be designed to move continuously.

在一个连续的再生区域,在一燃烧区域,催化剂微粒与含热氧气流接触,通过氧化除去焦炭。 In a continuous regeneration zone, a combustion zone, catalyst particles in contact with the hot oxygen stream containing coke is removed by oxidation. 通常催化剂再通过干燥区域,通过与热的、干燥的空气流接触除去水。 Typically through the catalyst drying zone, water is removed by drying air flow in contact with the hot. 通过直接接触空气流冷却干燥催化剂。 The catalyst was dried by direct contact with cooling air flow. 优选地,催化剂还可在位于燃烧区域下边的卤化作用区域内通过与含有卤化物的气体接触被卤化。 Preferably, the catalyst also is halogenated by contact with a halide-containing gas in the combustion zone is located in the lower region of the halogenation. 最后,催化剂微粒在还原区域用含氢气体还原,获得再调整的催化剂微粒,并被输送到移动床反应器。 Finally, the catalyst particles in the reduction zone with a hydrogen-containing reducing gas to obtain the catalyst particles of readjustment, and is supplied to the moving bed reactor. 有关连续催化剂再生,特别是有关移动床重整工艺的详细内容被公开在下述,特别是在US-A-3,647,680;US-A-3,652,231;US-A-3,692,496和US-A-4,832,921中。 For continuous catalyst regeneration, particularly detailed information about moving-bed reforming process is disclosed in the following, in particular in US-A-3,647,680; US-A-3,652,231; US-A-3,692,496 and in US-A-4,832,921.

来自连续重整区域的废催化剂微粒在再生区域首先与含热氧气流接触,以除去在重整反应期间积聚在催化剂表面上的焦炭。 The spent catalyst particles from the continuous-reforming zone is first contacted with hot oxygen-containing stream in a regeneration zone to remove accumulated during the reforming reaction of the coke on the catalyst surface. 废催化剂微粒的焦炭含量可多达催化剂重量的20%,但是更典型的是5-7%。 The coke content of spent catalyst particles may be as much as 20% by weight of the catalyst, but more typically 5-7%. 焦炭主要含有碳和少量氢,在局部区域中在450-550℃(可达到600℃)焦炭被氧化成一氧化碳,二氧化碳,和水。 Coke mainly containing carbon and a small amount of hydrogen, in a partial region at 450-550 deg.] C (up to 600 ℃) coke is oxidized to carbon monoxide, carbon dioxide, and water. 用于燃烧焦炭的氧气以通常含有0.5-1.5%体积氧的循环气体的形式进入再生区域的燃烧部分。 Oxygen for combustion of the coke in the form of recycle gas containing usually 0.5 to 1.5% by volume of oxygen into the combustion section of the regeneration zone. 烟道气由下列组分构成,它们是一氧化碳,二氧化碳,水,未反应的氧,氯气,氢氯酸、氧化亚氮,氧化硫,和从燃烧区域收集的氮的一部分从再生区域作为烟道气排出。 Flue gas consists of the following components, which are carbon monoxide, carbon dioxide, water, a portion of the oxygen, chlorine, hydrochloric acid, nitrous oxide, sulfur oxides and nitrogen is collected from the combustion zone unreacted regeneration zone as flue from gas discharge. 剩余部分和少量的含氧补充气体(一般为空气,占总气量约3%)结合以补充消耗的氧气并作为循环气体返回到燃烧区域。 And a minor amount of the remaining portion of oxygen-containing makeup gas (generally air, about 3% of the total gas) to replenish consumed oxygen binding and returned as recycle gas into the combustion zone. 典型的燃烧区域的布置可参见US-A-3,652,231。 A typical arrangement of the combustion zone can be found US-A-3,652,231.

由于催化剂微粒向下移动通过燃烧区与焦炭相伴被脱除,一般通过该区域的中途到达“穿透点”,在该处并非输送的氧气均被消耗掉了。 Since the catalyst particles are removed and downward movement accompanied by coke combustion zone, generally reaching "through points" by the middle of the region, where oxygen delivery are not consumed. 人们已经知道,现有的重整催化剂微粒具有与许多细孔相关的较大的表面积,当催化剂微粒在床内达到穿透点时,在微粒表面保持的焦炭深入细孔内,因此氧化反应以非常缓慢的速率进行。 It is known, conventional reforming catalyst particles have a larger surface area associated with many pores, when the catalyst particles reach the breakthrough point in the bed, the coke in the depth of pores holding fine particle surface, and thus oxidation reaction very slow rate.

在补充气体内的和来自燃烧步骤的水占烟道气的很少量并且被排出,因而在循环气环路内形成一平衡值。 Water and from the combustion step is accounted for a very small amount of flue gas and in the make-up gas is discharged, thereby forming a balance in the recycle gas loop. 视具体情况而定,在循环环路内的水浓度可通过干燥用于补充补充气的空气得到降低,在循环气体环路内安装一用于气体循环的干燥器或者排出来自循环气流的大量的烟道气以降低在循环气体环路内的水平衡值。 As the case may be, the water concentration in the circulation loop can be reduced by the supplemental air dried for make-up gas is mounted inside a dryer for recycle gas loop gas circulation or exhaust gas stream from the recycle of large flue gas to reduce the water balance in the recycle gas loop.

视具体情况而定,催化剂微粒从燃烧区直接进入干燥区,其中的水从微粒的表面和细孔内通过与热气流接触被蒸发掉。 As the case may be, the catalyst particles from the combustion zone directly into the drying zone, wherein water from the pores and the inner surface of the particles is evaporated by contact with hot air. 一般气流被加热到425-600℃并且视具体情况而定在加热之前进行予干燥,以便增加能够被吸收掉的水量。 Usually air stream is heated to 425-600 deg.] C and as the case may be dried prior to heating, so as to increase the amount of water that can be absorbed. 优选干燥气流含有氧气,更优选氧气含量超过空气内氧含量,以便来自催化剂微粒的内孔的焦炭的最后燃烧可以在干燥区域内完成,并使在干燥区域内没有消耗的过量氧气与来自燃烧区的烟道气一起向上流动以补充通过燃烧反应被消耗的氧气。 Preferably the drying gas stream contain oxygen, more preferably more than the oxygen content within the oxygen content of air, so the final combustion of the coke from the inner pores of the catalyst particles can be accomplished in the drying zone, and the excess oxygen not consumed in the drying zone from the combustion zone the upward flow of the flue gas together with supplemental oxygen to be consumed by a combustion reaction. 使催化剂微粒与含有高浓度氧的气体接触,通过提高在催化剂上的铂或其它金属的氧化态,同样有助于催化剂微粒恢复全部活性。 Contacting the catalyst particles with a gas containing a high concentration of oxygen by increasing the oxidation state of the platinum or other metals on the catalyst, the catalyst particles also help restore full activity. 在催化剂微粒离开该区域之前设定干燥区域降低催化剂微粒的湿含量至不大于0.01wt%(按照催化剂的重量计)。 Set drying zone before the catalyst particles leave the region of reduced moisture content of the fine catalyst particles to not more than 0.01wt% (according to the weight of the catalyst).

在视具体情况而定进行的干燥步骤之后,优选催化剂微粒在分离区域与含氯的气体接触以在催化剂的表面上重新分布贵金属。 After drying, as the case may be, of the step, the catalyst particles in the separation zone is preferably contacted with chlorine gas on the surface of the catalyst noble metal redistribution. 为了逆转因暴露于高温下和燃烧区域中的水蒸气而形成的贵金属的聚集需要重新分布。 In order to reverse the aggregation of noble metal due to exposure to high temperature and water vapor in the combustion region formed by the need to re-distribution. 重新分布在425-600℃优选在510-540℃进行。 Redistribution 425-600 deg.] C preferably at 510-540 ℃. 氯气的浓度为气体的0.01-0.2mol%,大量氧气存在有利于促进快速和完全的重新分散铂族金属以得到重新分散的催化剂微粒。 0.01-0.2mol% chlorine concentration of the gas, there is a large amount of oxygen and promoting rapid and complete re-dispersion of the platinum group metal to obtain redispersed catalyst particles.

在用于催化目的之前,通过与一种富氢还原气体接触还原再生和重新分布催化剂以便将催化剂上的贵金属变成单质状态。 Prior to use in catalytic purposes, by reducing the hydrogen-rich gas with one catalytic reduction catalyst for regeneration and re-distribution of the noble metal on the catalyst into elemental state. 虽然氧化催化剂的还原是大部分重整操作的基本步骤,但是,该步骤通常稍稍提前或在反应区内进行并且一般不再被视作再生区域内的设备部分。 Although the redox catalyst is a reforming operation most basic steps, but this step is usually slightly ahead of or in the reaction zone and generally no longer be regarded as the reproducing apparatus portion of the inner region. 用相对纯的氢气还原气体在450-550℃、优选480-510℃进行高度被氧化催化剂的再生以提供一再调整的催化剂。 , Preferably 480-510 deg.] C for regeneration highly oxidized catalyst to provide a catalyst again adjusted with a relatively pure hydrogen reduction gas at 450-550 ℃.

在连续重整区域按装置的制度操作期间,供给该区域的大部分催化剂是已被再生的并按如上描述再调整的第一重整催化剂。 In the continuous-reforming zone by the system during operation of the device, most of the catalyst supplied to the zone that has been regenerated as described above and press the readjusted first reforming catalyst. 到达重整区域的催化剂的一部分可作为补充的供给的第一重整催化剂,以克服特别在重整工艺开始期间失活和细粒的损耗,但是这种量比较少,每次再生循环一般少于0.1%。 As a supplement to the first part of the reforming catalyst reaches the reforming catalyst supply region, particularly to overcome during the reforming process begins deactivation and fines loss, but less than this, generally less per regeneration cycle to 0.1%. 该第一重整催化剂是双官能复合物,其中含有一加氢-脱氢金属,优选在一耐熔载体上的铂族金属组分优选载体是提供用于裂解和异构化的酸位的一种无机氧化物。 The first reforming catalyst is a bifunctional complex, which comprises a hydrogenation - dehydrogenation metal, preferably platinum group metal component on a support preferably refractory support is provided for cracking and isomerization of the acid sites an inorganic oxide. 第一重整催化剂用于在原料中含有石脑油的脱氢以及异构化、裂解和脱氢环化作用。 For naphtha reforming catalyst containing a first dehydrogenation and isomerization, cracking and dehydrocyclization acting in the feedstock.

耐熔的第一重整催化剂载体应是多孔的,吸附性,组成均匀的高表面积材料,对于它的组成来说没有该种材料固有的组成梯度。 The first reforming catalyst support should be a refractory porous, adsorptive, high-surface area material consisting of uniform, there is no inherent compositional gradients for this material is its composition. 在本发明的范围内,耐熔载体含有一种或多种:(1)耐熔无机氧化物例如氧化铝,二氧化硅,二氧化钛,氧化镁,氧化锆,氧化铬,氧化钍,氧化硼或其混合物;(2)合成制备的或天然产生的粘土和可被酸处理的硅酸盐;(3)或是天然产生的或是合成制备的沸石硅铝酸盐晶体,例如呈氢形式或在同金属阳离子交换的形式的FAU,MEL,MFI,MOR,MTW(沸石命名法IUPAC委员会);(4)尖晶石例如MgAl2O4,FeAl2O4,ZnAl2O4,CaAl2O4;和(5)由一种或多种上述各组材料形成的组合体。 Within the scope of the present invention, refractory support containing one or more of: (1) refractory inorganic oxides such as alumina, silica, titania, magnesia, zirconia, chromia, thoria, boria or mixtures thereof; naturally occurring clays or (2) and synthetically produced silicates may be acid-treated; (3) or a naturally occurring or synthetically prepared crystalline aluminosilicate zeolite, e.g. the hydrogen form or in the form of with the metal cation-exchanged form FAU, MEL, MFI, MOR, MTW (IUPAC Commission of zeolite nomenclature); (4), for example, spinel MgAl2O4, FeAl2O4, ZnAl2O4, CaAl2O4; and (5) from one or more each group of materials formed by a combination thereof. 优选用于第一种重整催化剂的耐熔载体是氧化铝,特别优选的是γ-和η-氧化铝。 Preferred refractory support for the first reforming catalyst is alumina, and particularly preferred are γ- η- alumina.

氧化铝粉末可以呈本领域的专业人员熟知的载体材料的任意形状,或者形式,例如球形,挤压物,杆状,丸状,片状,薄片或颗粒形。 Alumina powder can be any shape support material well known skilled in the art, or form, such as spheres, extrudates, rods, pellets, chips, flakes or granular form. 球形微粒可按下述步骤形成,通过使氧化铝粉末与适宜的胶溶酸和水反应转化氧化铝粉末成为氧化铝溶胶并将生成的溶胶和凝胶剂混合物滴入油浴中,形成氧化铝凝胶的球形微粒,接着进行公知的老化,干燥和焙烧步骤生成上述的球形微粒。 Spherical particles formed according to the following step, the alumina powder by a suitable peptizing acid and water to react with an alumina powder to become transformed and the resulting alumina sol and a sol-gel mixture was added dropwise in an oil bath to form alumina spherical particles of the gel, followed by known aging of, the step of generating the above-described drying and calcining the spherical particles. 优选的挤压物形状优选通过将氧化铝粉末和水以及适宜的胶溶剂混合,以形成具有在500℃45-65质量%烧失量的挤压捏塑体,所述的胶溶剂是例如硝酸,乙酸,硝酸铝等材料。 The preferred extrudate form is preferably obtained by mixing alumina powder and water and a suitable peptizing agent to form extruded at 500 ℃ 45-65 having a loss on ignition% by mass of dough, said peptizing agent is nitric acid e.g. , acetic acid, aluminum nitrate material. 通过形状和尺寸适宜的模子挤压生成的捏塑体以形成挤压物颗粒,其后,用公知的方法干燥和焙烧。 Extruded dough shape and size produced by a suitable die to form extrudate particles, thereafter, by a known method of drying and calcining. 作为可供选择替代的方式,通过辊压在旋转盘上的挤压物颗粒由挤压物形成球形颗粒。 As an alternative an alternative embodiment, by rolling on a rotating disc extrudate particles spherical particles formed by the extrudate. 通常颗粒是球形的,直径为1/16-1/8英寸(1.5-3.1mm),虽然颗粒尺寸可以大到1/4英寸(6.35mm)。 Typically the particles are spherical, having a diameter of 1 / 16-1 / 8 inch (1.5-3.1mm), although the particle size may be as large as 1/4 inch (6.35mm). 在特定的再生器中,希望所使用的催化剂颗粒落在相对狭窄的尺寸范围内。 In a particular regenerator, it is desirable to use the catalyst particles to fall within a relatively narrow range of sizes. 优选的催化剂颗粒直径为1/16英寸(3.1mm)。 A preferred catalyst particle diameter of 1/16 inch (3.1mm).

第一重整催化剂的基本组分是一种或多种铂族金属,优选铂组分。 The basic component of the first reforming catalyst is one or more platinum group metals, preferably platinum component. 铂可作为一种化合物或作为一种单质金属存在于催化剂中,所述的化合物以与一种或多种催化剂复合体中的其它成分化学结合的形式例如氧化物,硫化物,卤化物或者卤氧化物存在。 Platinum may be used as a single compound or as a compound of elemental metal present in the catalyst in the form of chemical combination with one or more other ingredients of the catalyst composite body such as an oxide, sulfide, halide, or a halogen the presence of oxides. 当基本上所有的铂以还原状态存在于催化剂复合体中可以获得最佳的结果。 When the best results can be obtained substantially all of the platinum present in the catalyst in a reduced state composite body. 按照单质基准计算,一般铂组分占催化剂组合物的0.01-2质量%,优选0.05-1质量%。 Calculated in accordance with elemental basis, a platinum component typically accounts for 0.01 mass% of the catalyst composition, preferably 0.05 to 1 mass%.

在本发明的范围内,第一重整催化剂含有用以改善优选的铂组分的作用的金属助催化剂。 Within the scope of the present invention, the first reforming catalyst contains a metal promoter to improve the effect of the preferred platinum component. 这些金属改性剂包括IVA(14)族的金属,其它VIII(8-10)族金属,铼,铟,镓,锌,铀,镝,铊及其混合物。 These metal modifiers may include metals (14) Group IVA, other VIII (8-10) metals, rhenium, indium, gallium, zinc, uranium, dysprosium, thallium and mixtures thereof. 当第一重整催化剂含有锡组分时可获得优良的结果。 Excellent results are obtained when the first reforming catalyst contains a tin component. 这种金属改性剂的催化有效量可通过现有技术中的任意已知方法掺合进入催化剂中。 Catalytically effective amounts of such metal modifiers may be incorporated by any method known in the prior art into the catalyst.

该第一重整催化剂可含有卤素组分,卤素组分可是氟,氯,溴或碘或其混合物。 The first reforming catalyst may contain a halogen component, a halogen component but a fluorine, chlorine, bromine or iodine, or mixtures thereof. 氯是优选的卤素组分,一般卤素组分与无机氧化物载体以结合状态存在。 Chlorine is the preferred halogen component, typically a halogen component with the inorganic oxide support is present in a combined state. 优选卤组分良好的分散在整个催化剂中,按照单质基准计算,其含量是最后催化剂的0.2-15wt%。 The halogen component is preferably well dispersed throughout the catalyst, calculated according to a single reference substance, the content is 0.2-15wt% of the final catalyst.

一种视具体情况存在的第一重整催化剂成分是沸石,或晶体铝硅酸盐,然而优选这种催化剂基本不含沸石组分。 An apparent first reforming catalyst component is present in the specific case where a zeolite, or crystalline aluminosilicate, however, this catalyst is preferably substantially free of zeolite component. 按照在US-A-4,741,820公开的,第一重整催化剂含有一种非沸石分子筛。 In accordance with US-A-4,741,820 disclosed a first reforming catalyst contains a zeolitic molecular sieve.

第一重整催化剂一般在100-320℃的温度下干燥0.5-24小时,接着在300-550℃在空气气氛中氧化0.5-10小时。 The first reforming catalyst is generally dried at a temperature of 100-320 deg.] C for 0.5 to 24 hours, followed by oxidation in an air atmosphere at 300-550 ℃ 0.5-10 hours. 已经氧化的催化剂优选在300-550℃和基本无水的条件下被还原0.5-10小时或更长时间。 The catalyst preferably has oxidation is reduced from 0.5 to 10 hours at 300-550 deg.] C and substantially anhydrous conditions, or longer. 在US-A-4,677,094中公开了第一重整催化剂的制备和活化的详细内容。 It discloses the details of the preparation and activation of a first reforming catalyst in US-A-4,677,094.

固定床反应区中或移动床反应区含有沸石催化剂,从而催化剂可以连续的排出和加入。 A fixed bed or a moving bed reaction zone in a reaction zone containing a zeolite catalyst, whereby the catalyst can be continuously added and discharged. 这些可供选择替代的方法是与本领域专业人员熟知的催化-再生相关的,例如:(1)一含有固定床反应器的半再生装置通过提高温度、最后关闭装置以便再生和再活化催化剂来保持强度、操作;(2)一种摇摆反应器装置,随着催化剂失活其中单独的固定床反应器通过歧管配置依次被隔离开,在隔离开的反应器内的催化剂被再生和再活化,同时其它的反应器保持生产状态;(3)连续再生从移动床中排出的催化剂,再活化以及置换上述再活化的催化剂;(4)在相同区域中的含有半再生和连续再生设备的混合系统。 These alternative alternative method is well known to those skilled in Catalytic - regeneration of, for example: (1) a semiregenerative unit containing fixed-bed reactor, by increasing the temperature, and finally closing means to activate the catalyst to be regenerated and reused holding strength, operation; (2) a wobble reactor apparatus, wherein the catalyst deactivation as a separate fixed bed reactor is isolated sequentially disposed through the manifold, the catalyst in the isolated reactor is regenerated and reactivated , while the other reactor is kept production status; (3) continuous regeneration of catalyst withdrawn from a moving bed, reactivation and permutations of the above reactivated catalyst; (4) were mixed in the same region containing semi regeneration and continuous regeneration equipment system. 本发明的优选的实施例是在半再生沸石重整区域内的固定床反应器和在连续重整区域内的具有连续催化剂再生作用的移动床反应器的混合系统。 Preferred embodiments of the present invention is in the semi-regenerative reforming zeolite hybrid systems in the area of ​​the fixed bed reactor and moving bed reactor with continuous catalyst regeneration in the continuous-reforming zone.

在该重整方法中,优选的第一重整催化剂提供总催化剂量的20-90vol%.第一和沸石重整催化剂的相对体积取决于产品的目标和该工艺是否与原有使用的设备相结合。 In the reforming process, preferably a first reforming catalyst to provide 20-90vol% of the total amount of the catalyst. The first and zeolitic reforming catalyst relative volume depends on whether the target device relative to the product and the process used in the original combined. 如果一个全新的工艺装置实际上的生产目的是以相对少量的萘原料最多的生产苯和甲苯,有利的是,沸石重整催化剂含有的大致比例优选为催化剂总量的10-60%。 If the unit is in fact a new production process is the production of benzene and toluene object of a relatively small amount of raw material naphthalene most, it is advantageous that the zeolitic reforming catalyst comprises a substantially ratio is preferably 10 to 60% of the total catalyst. 另一方面,如果一新的沸石重整区域被加入到一个存在的连续重整区域,沸石重整区域最好仅占催化剂总量的相对小的比例以便最大限度地减小新区域对现存的连续重整操作的影响。 On the other hand, if a new zeolitic reforming zone is added to an existing continuous-reforming section, the zeolitic reforming zone is preferably relatively small proportion of the total catalyst in order to minimize only new zone of the existing affect the operation of the continuous reforming. 在后者的情况下,由第一重整催化剂提供该方法催化剂总体积量的55%-95%。 In the latter case, there is provided a method of 55% -95% of the total volume of first reforming catalyst is a catalyst.

本发明特别优选的实施方案是将沸石重整区域加入到现有的连续重整区域即其中设置了是具有催化剂连续再生功能的移动床重整装置的设备。 A particularly preferred embodiment of the invention is a zeolitic reforming zone is added to an existing continuous-reforming section in which the device is provided having a moving bed reforming unit with continuous catalyst regeneration function. 连续再生重整装置需要较多的基本建设投资,一般涉及高强度重整并且包括附加的设备用于连续催化剂再生。 Continuous regeneration reforming unit needs a large capital investment, and generally relates to high-strength reforming include additional devices for continuous catalyst regeneration. 通过增加对转化连续重整生产的第一物流中轻质链烷烃特别有效的沸石重整区域,为整个催化重整操作的改进提供了途径:提高强度,也称芳烃的总产率或产品总辛烷值;通过降低连续重整强度提高连续重整区域的生产量至少5%,优选至少10%,视具体情况而定至少20%,在一些实施例中达30%或更多。 By increasing the conversion of a first continuous stream reforming light paraffins produced in a particularly efficient zeolitic reforming zone, to provide an improved catalytic reforming operation of the whole way: to increase the strength, also known as total yield or product total aromatics octane; by reducing the continuous increase of at least 5% strength reforming production of the continuous-reforming section, preferably at least 10%, as the case may be, at least 20%, 30% or more in some embodiments. 这种降低强度是通过在连续重整区域在较高的空速,较低的氢气对烃的比例和较少的催化剂循环量的条件下进行一次和多次操作实现的。 Such a reduction in strength and is achieved by multiple operations at higher space velocity, conditions and less hydrocarbon ratio lower catalyst circulation in the continuous-reforming zone hydrogen. 然后,通过加工来自沸石重整区域中连续重整区域的第一物流实现所要求的产品质量。 Then, the processing from the zeolitic-reforming zone a first stream of the continuous-reforming zone to achieve the desired product quality.

提高选择性,降低连续重整操作的强度和选择性地转变在第一种物流中的残余链烷烃成为芳烃。 Increasing the selectivity, reduced continuous reforming operation and selectively change the intensity in a first stream of the residual paraffins to aromatics.

来自连续重整区域的第一物流进入用于完成重整反应的沸石重整区域,优选伴随第一物流的游离氢在沸石重整区域内的第一物流加工之前不被分离,即连续的重整区域和沸石重整区域是在相同的氢气环路内。 The first stream enters from the continuous-reforming zone for completion of the reforming reaction zeolitic reforming zone is preferably free hydrogen accompanying the first stream a first stream in the zeolitic reforming zone are not separated prior to the processing, i.e., continuous weight zeolitic reforming zone and the entire region are within the same hydrogen loop. 在本发明的范围内,补充的石脑油原料被加入到第一物流中,作为原料到达沸石重整区域,以得到附加的重整产品。 Within the scope of the present invention, the supplementary naphtha feed is added to the first stream, as the raw material reaches the zeolitic-reforming zone to obtain an additional reformate. 补充的石脑油原料具有的特征是在用于烃原料的那些描述的范围内,最佳的是低沸点的并且最有利的是用于比供到连续重整区域的原料较轻的芳烃的生产的原料。 Supplementary naphtha feed has characteristics within the scope of those used in the description of the hydrocarbon feedstock, it is the best and most advantageously is a low-boiling aromatic hydrocarbons lighter than the starting materials are continuously supplied to the reforming region production of raw materials. 该第一物流和视具体情况存在的补充石脑油原料,在沸石重整区域内在第二重整条件下接触沸石重整催化剂。 The presence of the first stream and the supplementary naphtha feed, as the case, contacts the zeolitic reforming catalyst in the zeolitic reforming zone a second internal reforming conditions.

在沸石重整区域烃原料接触沸石重整催化剂得到一种富芳烃产品,其主要反应是在第一物流中保持的链烷烃的脱氢环化作用。 The reforming zone in the zeolitic reforming a hydrocarbon feedstock in contact with a zeolite catalyst to obtain an aromatic-rich product, cyclization reaction is mainly held in the first stream dehydrogenation of paraffins. 在本发明的沸石重整区域使用的第二重整条件包括压力从100kpa-6MPa(绝压),优选从100kpa-1MPa(绝压),在最后的反应器出口处的压力为450KPa或更低是特别优选的。 Second reforming conditions in the zeolitic-reforming zone of the present invention include a pressure from 100kpa-6MPa (absolute), preferably from 100kpa-1MPa (absolute pressure), the pressure at the outlet of the final reactor is less or 450KPa It is particularly preferred. 以足够的量将游离氢供给到沸石重整区域,所述的量对应于比率0.1-10mol氢每mol烃原料,优选不大于6,更优选不大于5。 A sufficient amount of free hydrogen is supplied to the zeolitic-reforming zone in an amount corresponding to the ratio 0.1-10mol hydrogen per mol of hydrocarbon feedstock, preferably not more than 6, and more preferably not more than 5. 其中游离氢指的是在烃或其它化合物中是没有被结合的分子H2。 Wherein the free hydrogen molecules H2 refers to a hydrocarbon or other compounds that are not bound. 含有的沸石重整催化剂体积对应的液体小时空速从1-40hr-1,优选至少为7hr-1,更优选的为10hr-1或以上。 Volume contained zeolitic reforming catalyst corresponds to a liquid hourly space velocity from 1-40hr-1, preferably at least 7hr-1, more preferably 10hr-1 or more.

被定义为烃原料,游离氢,和任意的伴随游离氢的组分的混合物的最高温度的操作温度一般在260-560℃,选择这个温度以能实现连续重整区域和沸石重整区域相结合的最佳总结果,所述的结果是关于当以化学芳烃的生产为目的产品中的芳烃产率或以汽油生产为目的的性能例如辛烷值。 Is defined as a hydrocarbon feedstock, the highest temperature of the mixture of free hydrogen, and any components accompanying the free hydrogen, generally operating at temperatures 260-560 deg.] C, a temperature selected to achieve the continuous-reforming zone and zeolitic reforming zone combination the best overall results, the result is on when chemical aromatics production is the object of aromatics yields or product in the production of gasoline octane number, for example, for the purpose of performance. 在原料中的烃的类型也对温度的选择有影响,因为沸石重整催化剂用于轻质链烷烃的脱氢环化作用特别有效。 Type of hydrocarbon in the feedstock also influence temperature selection, as the zeolitic reforming catalyst to effect dehydrocyclization of light paraffins is particularly effective. 在早先的连续重整反应器内由于反应吸热伴随着其穿过催化剂床的温度的下降,环烷烃通常在较大程度上得到脱氢处理。 Due to its endothermic heat of reaction accompanied by a decline in temperature across the catalyst bed, naphthene dehydrogenation process generally obtained a large extent in the continuous reforming reactor earlier. 通常初始的反应温度在每个以补充催化剂不可避免的失活为目的的操作周期期间缓慢的升高。 Typically the initial reaction temperature was raised slowly to complement each during the inevitable deactivation of the catalyst for the purpose of operating cycle. 连续重整区域的反应器和沸石重整区域的反应器的温度最好是彼此错开,即在反应器之间是不同的,以便相应于诸如不同芳剂的比值和非芳剂浓度之类变量生产目标产品。 Continuous reforming reaction zone and zeolitic reforming reactor zone temperature is preferably offset from each other, i.e., between the different reactors so as to correspond to a non-aromatic, such as ratios and concentrations of different variables like aromatic agent production target product. 通常沸石重整区域的最高温度低于在连续重整区域的最高温度,但是在沸石重整区域的温度可以较高,这取决于催化剂的条件,和目标产品。 Typically the maximum temperature of the zeolitic reforming zone is lower than the maximum temperature in the continuous-reforming zone, but at higher temperatures the zeolitic reforming zone, depending on the conditions of the catalyst, and the target product.

沸石重整区域可以包括含有沸石重整催化剂的单个反应器,或者包括本领域公知的二个或多个平行的装有阀门的反应器,以便进行可供选择替代的循环再生。 Zeolitic reforming region may comprise a single reactor containing the zeolitic reforming catalyst comprising a two or a plurality of valved or parallel reactors known in the art, an alternative choice for recycling. 在单个的反应器和平行循环反应器之间的选择,取决于反应器体积和需要保持稳定而不会间断的高产率。 The choice between a single reactor and parallel cyclic reactors depends on the reactor volume and the need to maintain a stable and high yield without interruption. 在任何情况下,沸石重整区域的反应器优选装有阀门用于从联合工艺中脱开,以便沸石重整催化剂可以再生或被置换,同时连续重整区域保持操作。 In any case, the reforming reactor is preferably zeolite region with a valve for releasing from the combination process so that the zeolitic reforming catalyst may be regenerated or replaced while the continuous reforming zone remains operation.

在一可供选择替换的实施方案中,在本发明的范围之内,沸石重整区域含有二个或多个反应器和在反应器之间存在中间加热现象,以升高温度和保持脱氢环化条件。 In an alternative embodiment for the selection, within the scope of the present invention, the zeolitic reforming zone comprises two or more reactors in the presence of the phenomenon of intermediate heating between reactors to raise the temperature and maintaining the dehydrogenation cyclization conditions. 这是很有利的,因为在沸石重整区域中发生的主要反应是链烷烃脱氢环化成芳烃和与之同时发生的常见的环烷烃的脱氢,生成的吸热反应可以在出现充分的脱氢环化作用之前产生的重整温度以下冷却反应物。 This is advantageous, since the main reaction occurring in the zeolitic reforming zone is the dehydrocyclization of paraffins into aromatics common dehydrogenation of naphthenes, and simultaneously therewith, the resulting endothermic reaction may occur sufficiently de reforming temperature to produce hydrogen before the cyclization reaction was cooled.

在另一个可供选择替换的实施方案中,通过在该区域反应器内附加内部换热构件在沸石重整区域内保持重整温度。 In an alternative embodiment an alternative embodiment, an additional internal heat exchanger member held by the reforming temperature in the zeolitic reforming zone in the region of the reactor. 优选热交换反应器是径向流布置的并带有在反应器的环形体积内含有的区域形式的流体通道。 Preferably the heat exchange reactor is a radial flow arrangement and with the annular volume of the reactor in the form of a fluid contained within the channel region. 热交换介质和径向接触催化剂流的反应物流最好以逆流布置通过交替出现的通道。 The reaction stream and the heat exchange medium flows radially contacting the catalyst is preferably in countercurrent passage through alternating arrangement. 一种卷材支持薄壁热交换板并提供流动分布和在该通道的内和外周边上的流动1L集室。 One kind of thin-walled heat exchanger plate supporting web and provide a flow distribution and flow collection chamber 1L and the inner periphery of the outer passage.

沸石重整催化剂含有非酸性沸石,碱性金属组分和铂族金属组分。 Zeolitic reforming catalyst contains a non-acidic zeolite, basic metal component and a platinum group metal component. 重要的是,优选为LTL或L-沸石的沸石是非酸性的,因为在沸石中的酸度会降低对产品催化剂的芳烃的选择性。 Importantly, preferably a non-acidic zeolite is LTL or L- zeolite, as acidity in the zeolite reduces the selectivity to aromatics of the finished catalyst. 为了成为非酸性的沸石,非氢形式占据了几乎其全部的阳离子交换位置。 In order to become a non-acidic zeolite, in the form of non-hydrogen occupies almost all of its cation exchange positions. 占用可交换阳离子位置的阳离子优选包括一种或多种碱金属,虽然其它的阳离子形式也可以存在。 Exchangeable cation sites occupied by cations preferably comprises one or more alkali metals, although other cationic forms may also be present. 特别优选的非酸L-沸石是钾形L-沸石。 Particularly preferred non-acid L- L- shaped zeolite is a potassium zeolite.

为了提供一种用于本发明的适宜形式的催化剂,一般情况使一种粘合剂与L-沸石复合在一起。 In order to provide a suitable catalyst for the form of the invention, a binder and so generally L- zeolite composited together. 已有技术揭示任意耐熔的无机氧化物粘合剂均是适宜的,一种或多种二氧化硅,氧化铝或氧化镁是本发明优选的粘合剂材料,特别优选的是非晶体的二氧化硅,当使用从水溶液中作为特细的球形颗粒沉淀的合成的白色二氧化硅粉末时能够获得良好的结果。 Prior art discloses any refractory inorganic oxide binder are appropriate, one or more of silica, alumina or magnesia are preferred binder materials of the present invention, particularly preferred amorphous titanium silicon oxide, when using a synthetic white silica powder precipitated ultrafine spherical particles from the aqueous solution as good results can be obtained. 优选二氧化硅粘合剂是非酸性的,其中硫酸盐含量小于0.3质量%,具有的BET表面积从120-160m2/g。 Preferred non-acidic silica binder, wherein the sulfate content is less than 0.3 mass%, having a BET surface area of ​​from 120-160m2 / g.

可以通过已知技术的任意方法复合L-沸石和粘合剂以形成所希望的催化剂形状,例如钾形L-沸石和非晶体的二氧化硅在加入胶溶剂之前可被混合成为一种均匀的粉末混合物。 Compound L- zeolite and binder may be by any method known in the art to form the desired catalyst shape, such as potassium L- shaped zeolite and amorphous silica prior to addition of a peptizing agent may be blended into a homogenous powder mixture. 加入一种含有氢氧化钠的水溶液以形成可挤压的捏塑体。 An aqueous solution containing sodium hydroxide is added to form an extrudable dough. 优选的捏塑体的温含量为30-50质量%以形成具有能够经受住直接煅烧的令人满意的完整的挤压物。 Content of the dough temperature is preferably 30 to 50% by mass to form a satisfactory able to withstand direct calcination of complete extrudates. 通过适宜形状和尺寸的模子挤压生成的捏塑体,形成挤压颗粒,干燥颗粒并通过已知的方法焙烧。 Extruding dough generated by a suitable shaped and sized die to form extruded granules, particles are dried and calcined by known methods. 通过上述方法形成球形颗粒用于沸石重整催化剂。 Spherical particles formed by the above method for a zeolite reforming catalyst.

一种碱金属组分是一种沸石重整催化剂的基本组成。 An alkali metal component is an essential component of the zeolitic reforming catalyst. 可使用一种或多种碱金属,其中包括锂,钠,钾,铷,铯及其混合物,优选的是钾。 Using one or more alkali metals, including lithium, sodium, potassium, rubidium, cesium, and mixtures thereof, preferably potassium. 优选碱金属几乎占有非酸性L-沸石的所有阳离子可交换的位置。 Preferably an alkali metal exchangeable cations occupy almost all positions L- nonacidic zeolite. 在US-A-4,619,906中公开了表面沉积碱金属的存在。 It discloses the presence of an alkali metal deposited on the surface in the US-A-4,619,906.

铂族金属是沸石重整催化剂的另一基本特征,优选铂组分,铂可以作为化合物或作为单质金属存在于催化剂中,所述的化合物可以呈同一种或多种催化剂复合物中其它成分化学化合的形式例如氧化物,硫化物,卤化物或卤氧化物。 Platinum group metal is another essential feature of the zeolitic reforming catalyst, preferably a platinum component, a platinum as elemental metal or as a compound present in the catalyst, the compound may be in the same chemical ingredients other one or more catalyst composite in the form of a compound such as an oxide, sulfide, halide or oxyhalide. 当基本上所有的铂以还原态存在于催化剂复合物中时可以得到最好的结果。 When substantially all of the platinum present in the catalyst in a reduced state composite can get the best results. 一般情况下铂组分占催化剂复合物的0.05-5质量%,以单质基准计算,优选0.05-2质量%。 Platinum component comprises from 0.05 to 5 mass% in general catalyst composite, calculated based on elemental, preferably 0.05 to 2 mass%. 在本发明的范围内,催化剂可含有能够对优选铂组分产生的效果具有改进作用的其它已知金属组分,。 Within the scope of the present invention, the catalyst may contain the effect of the preferred platinum component can be produced having improved metal components other known effects. 这种金属改性剂包括IVA(14)族金属,其它VIII(8-10)族金属,铼,铟,镓,锌,铀,镝,铊及其混合物。 Such metal modifiers include IVA (14) metals, other VIII (8-10) metals, rhenium, indium, gallium, zinc, uranium, dysprosium, thallium and mixtures thereof. 通过已知的任意方法,将这种金属改性剂的催化有效量结合入催化剂中。 By any known methods, the catalytically effective amounts of such metal modifiers incorporated into the catalyst.

通常最终的沸石重整催化剂在100-320℃干燥0.5-24小时,接着在300-550℃(优选350℃)在空气气氛中氧化0.5-10小时。 The final zeolitic reforming catalyst generally is dried at 100-320 ℃ 0.5-24 hours, followed (preferably 350 deg.] C) oxidation in an air atmosphere at 300-550 ℃ 0.5-10 hours. 优选氧化的催化剂在300-550℃(优选350℃)经受基本无水还原步骤的作用0.5-10小时或更长时间。 Oxidized catalyst is preferably 300-550 deg.] C (preferably 350 deg.] C) is subjected to the action of substantially anhydrous reduction step 0.5 to 10 hours or longer. 还原步骤的持续时间仅仅只是需要还原铂,以避免催化剂的预失活,如果能够保持干燥气氛,可以作为装置启动部分在现场进行。 Duration of the reduction step just need to restore the platinum, in order to avoid pre-deactivation of the catalyst, it can be maintained if a dry atmosphere, the device may be performed in the field as part of started. 在US-A-4,619,906和US-A-4,822,762中公开了沸石重整催化剂实施例的制备和活化的详细内容。 Zeolitic reforming catalyst are disclosed in US-A-4,619,906 and US-A-4,822,762 in the detailed preparation and activation of embodiments.

沸石重整区域生产处在含有氢和轻质烃的重整物流中的富芳烃产品。 Zeolitic reforming in the reforming region production stream containing hydrogen and light hydrocarbons in the aromatic-rich product. 使用本领域中公知的技术和设备,通常,来自沸石重整区域的重整物流通过冷凝区域到达分离区域。 In the art using known techniques and equipment, generally, a zeolite reformate stream from the reforming zone reaches the separation zone by condensation zone. 在分离区域,一般保持在0-65℃,富氢气体从液相中分离出来,最好生成的富氢流体的大部分通过适宜的压缩装置循环返回到重整区域,部分氢可作为纯净产品用于石油炼制厂或化工厂的其它部分。 In the separation zone, typically maintained at 0-65 deg.] C, the hydrogen rich gas separated from the liquid phase out of most of the hydrogen-rich fluid is preferably returned to the reforming zone is generated by a suitable compression means for circulating a part of hydrogen as a pure product used in other parts of the petroleum refinery or chemical plant. 通常,排出来自分离区域的液相并在分馏系统中加工以调节轻质烃的浓度,获得富芳烃产品。 Typically, the liquid is discharged from the separation zone and processed to adjust the concentration of light hydrocarbons in the fractionation system, the aromatic-rich product is obtained.

实施例三个参数在测定重整方法和催化剂性能方面特别有用,在测定用于链烷烃的脱氢环化作用的催化剂方面尤其适用。 Example three parameters are particularly useful in the determination of the reforming process and catalyst performance, especially for the measurement in terms of the catalyst used for cyclization dehydrogenation of paraffins. “活性”是在设定的反应条件下对催化剂转化反应物的能力的度量。 "Activity" is a measure of the ability of the reactants under the reaction conditions of the catalytic converter is set. “选择性”指示催化剂以高产率获取所需产品的能力。 "Selective" indicates the catalyst ability to obtain a high yield of the desired product. “稳定性”是催化剂保持其活性和选择性不随时间变化的能力的度量。 "Stability" is a measure of the catalyst to maintain activity and selectivity without the ability to change with time.

该实施例显示当加工主要含有C6-C8烃的石脑油原料时中试装置试验的比较结果。 This example shows the result when the processing means comparing the test mainly containing C6-C8 hydrocarbons when naphtha feedstock try. 石脑油原料具有下列特征:比重 0.7283ASTMD-86,℃:IBP 7550% 100EP 137体积% 链烷烃 62.0环烷烃 28.5芳烃 9.5对比试验是在相应的条件下,在整个原料中的非芳烃的转化率范围内进行的,将本发明的多个区域联合工艺的结果和已知的密切相关的重整工艺的结果进行了对比。 Naphtha feedstock having the following characteristics: specific gravity 0.7283ASTMD-86, ℃: IBP 7550% 100EP 137 vol% paraffins 62.0 naphthenes 28.5 aromatics 9.5 Comparative tests under the respective conditions, the conversion of non-aromatic hydrocarbons of the feedstock in the whole carried out within the scope of the results combined process of the present invention a plurality of regions and known closely related reforming processes were compared. 根据“BTX芳烃”或苯/甲苯/二甲苯/乙基苯(代表基本的芳烃中间体)和“C8芳烃或二甲苯+乙基苯(一般将其视作目标芳烃中间体,用以确定新的芳烃配合物的大小)的产率确定结果,实施例1根据已知的催化剂A的用途进行重整中间装置试验加工上述C6-C8原料,连续再生催化剂含有在氯化氧化铝上的0.29质量%的铂,和0.30质量%的锡,操作压力为450kpa,液体小时空速为2.5Hr-1,以氢对原料的摩尔比为6供给分子氢。变化温度以便使非芳烃的转化率范围为45-77质量%。这个比较例的转化率沸程馏分BTX芳烃产率绘制在图1中。 According to "the BTX aromatics," or benzene / toluene / xylene / ethylbenzene (representing the basic aromatic intermediates) and "C8 aromatics or xylenes + ethylbenzene (generally considered the target aromatic intermediate which, to determine a new size arene complexes) yield determination result, the intermediate reformate in Example 1 above means the test C6-C8 feedstock processed according to the known use of catalyst a, and continuous regeneration of the catalyst contained 0.29 mass chloride on alumina % platinum and 0.30 mass% of tin, an operating pressure of 450kPa, a liquid hourly space velocity 2.5Hr-1, a molar ratio of hydrogen to feedstock of 6 supplied molecular hydrogen. changes in temperature so that the conversion of non-aromatic hydrocarbons in the range of 45-77 mass%. the conversion of Comparative Example boiling range fraction of BTX aromatics yields plotted in Figure 1.

实施例2根据本发明加工上述C6-C8原料的多区域联合工艺进行重整中间装置试验。 Example 2 Test intermediate reformer unit according to the present invention, the above-described processing of the C6-C8 feedstock multizone combination process. 催化剂A如实施例1中描述,在催化剂B之前装入,催化剂B含有在粘合二氧化硅的L-沸石上的0.82质量%的铂,催化剂A对催化剂B的体积比是75/25。 A catalyst as described in Example 1, was charged before the catalyst B, Catalyst B contained 0.82 mass% platinum on silica-L- zeolite bound, the volume ratio of the catalyst A Catalyst B was 75/25.

石脑油在下流操作中被装载入反应器中,依次接触催化剂A和催化剂B。 Naphtha is loaded into the reactor in a downflow operation sequentially contacting Catalysts A and B. 操作压力为450kpa,总的液体小时空速相对于催化剂混合物为2.5Hr-1,以氢对原料的摩尔比为4.5供给氢,变化温度获得非芳烃的转化率为50-87质量%。 Operating pressure was 450kPa, total liquid hourly space velocity relative to the catalyst mixture 2.5Hr-1, a molar ratio of hydrogen to feedstock of 4.5 hydrogen supply, temperature change rate of conversion of non-aromatic hydrocarbons to obtain 50-87% by mass.

其结果绘制在图1中,并且将其与对比例1中催化剂A的结果进行对比,结果表明,该催化剂混合物明显地提高了芳烃产率,优于对比催化剂A。 The results are plotted in Figure 1, and compare it to the results of catalyst A in Comparative Example 1, the results showed that the catalyst mixture significantly improved the yield of aromatics, than the comparative catalyst A.

实施例3对比催化剂A和本发明联合催化剂A/B的产率结构在原料(C5+产品的分析辛烷值分别为99.5和98.5)中的非芳烃的当量转化率为74%的条件下进行对比,该产率结构选自实施例I和实施例2的转化率范围,被表示为相对于原料的产率(质量)%。 The comparison of Example 3 and comparative catalyst A catalyst of the present invention is combined yield of the structure A / B of the non-aromatic hydrocarbons in the feed conversion ratio of equivalents of (analysis octane C5 + product was 99.5 and 98.5, respectively) was 74% for the yield of the structure is selected from Examples I and the conversion range of the embodiment of Example 2, is expressed as the yield of the raw material (mass)%.

催化剂A 催化剂A/B苯 9.5 13.0甲苯 25.0 31.0 Catalyst A Catalyst A / B Benzene 9.5 13.0 Toluene 25.0 31.0

C8芳烃 25.0 22.0BTX芳烃总量 59.5 66.0氢 3.6 4.0C5+产品 89.4 91.2本发明的联合催化剂证明其芳烃的产率高于比较例10%以上,以及较高的氢产率和较高C5+产率。 C8 Aromatics 59.5 66.0 25.0 22.0BTX total aromatic product hydrogen 3.6 4.0C5 + 89.4 91.2 United Catalysts invention demonstrate its high aromatics yield, as well as higher hydrogen yields and higher C5 + yield of 10% in Comparative Example.

实施例4本发明的联合方法的另一个优点是通过将反应的最后部分改为沸石重整区域进而更有效地利用连续重整区域来实施本发明。 Another advantage of the integrated process of the invention, four embodiments of the present invention is implemented by the last part of the zeolitic reforming zone to the reaction resulting in more efficient use of the continuous-reforming zone. 这个优点在现有的能够连续再生催化剂的连续重整区域的情况中特别有效,所述的连续催化剂再生不能满足对汽油或芳烃不断增大的需要。 This advantage is particularly effective in the case of conventional continuously reproducing continuous-reforming section of the catalyst, the continuous regeneration of the catalyst for gasoline or aromatics can not meet increasing needs. 通过本发明,在这个区域除了转化率被降低以外也提高了原料的通过量,而不会增加催化剂的循环速率和再生速率。 By the present invention, in the region other than the conversion rate is also increased by reducing the amount of raw materials, without increasing the circulation rate and regeneration rate of the catalyst. 通过在同样的氢气环路中含有的沸石重整区域中基本上仅仅加入反应器同时实现较高的生产量来保持联合工艺的总的转化率。 By zeolitic reforming zone contained in the same loop in substantially only the hydrogen added to the reactor while achieving higher overall conversion of the production process to maintain the joint.

通过由上述的中间装置试验得出的实施例说明该实施方案,比较仅有连续重整区域的“初始”的情况和在本发明中增加了沸石重整区域,从而提高了加工装置生产量的情况(初始值为每年1,000,000公吨)。 DESCRIPTION "home" of this embodiment, only comparison of the continuous-reforming section by way of example a case derived by the intermediate apparatus and tested increased the zeolitic-reforming zone in the present invention, thereby improving the production process of the apparatus case (initial value of 1,000,000 metric tons per year).

初始 发明生产量103吨/年 1,000 1,300非芳烃的转化率,质量%*74 65催化剂循环 基本 0.9×基本氢/原料,摩尔 6.0 4.5液体小时空速,hr-1*2.5 3.3产率,103吨/年:C5+产品 894 1185苯 95 169甲苯 250 403 The initial production of the invention 103 tons / year 1,000 1,300 Conversion of nonaromatics, mass% 74 65 * 0.9 × basic catalyst cycle substantially hydrogen / feedstock, mole 6.0 4.5 Liquid hourly space velocity, hr-1 * 2.5 3.3 Yield, 103 t / in: C5 + products 8941185 benzene toluene 250 403 95 169

C8芳烃 250 286BTX芳烃总量 595 858*在连续重整区域沸石重整区域的空速为10hr-1。 250 286BTX total C8 aromatics 595 858 * an aromatic hydrocarbon in the continuous reforming zone space velocity of the zeolitic reforming zone 10hr-1. 通常,催化剂体积和气体循环是加氢处理装置中生产量的限制参数。 Typically, catalyst volume and gas circulation is hydrotreater production limiting parameters. 液体生产量常常可提高20-30%或更多(在几乎无水力去阻塞时)。 Liquid production can usually 20-30% or more (when almost no obstruction to water). 因此,根据说明本发明的上述实施例,增加包括含有非酸性沸石催化剂的反应器的沸石重整区域并与其它设备作可能的小规模改进可以提高BTX芳烃的生产44%。 Thus, according to the above described embodiments of the present invention, including increasing the reforming zone of the reactor containing zeolite non-acidic zeolite catalyst with possible other equipment for small-scale production can be increased to improve 44% BTX aromatics.

Claims (9)

1.一种用于基本在40-210℃范围内进行蒸馏的催化重整石脑油原料的方法,包括在含有已再生的双官能重整催化剂颗粒的连续重整区域,在游离氢存在下和在第一重整条件下接触石脑油原料以生产原始第一流出物流,上述的催化剂含有铂族金属组分,卤素组分和耐熔无机氧化物,上述的第一重整条件包括压力为100kpa-1Mpa,液体小时空速为0.2-10hr-1,氢气对C5+烃的摩尔比为0.1-10,温度为400-560℃,上述原始第一流出物流含有苯-甲苯-二甲苯类芳烃和一基本量的失活的催化剂颗粒,至少半连续地从连续重整区域除去失活的催化剂颗粒,和在含有含氧的气体中的连续再生区域以及在含有含氢气体的还原区域顺序接触至少部分颗粒以获得再调节的催化剂颗粒,其进一步的特征是将连续重整区域的流通量提高至少5体积%,与此同时,提高空速,降低氢气对烃的摩尔 1. A method for catalytically reforming a naphtha feedstock distilling substantially within the range of 40-210 deg.] C, comprising a continuous reforming area of ​​the reformer bifunctional catalyst particles containing regenerated, the presence of free hydrogen and contacting the naphtha feed at reforming conditions to produce a first original first effluent stream, the above-mentioned catalyst contains platinum group metal component, a halogen component and a refractory inorganic oxide, said first reforming conditions comprising a pressure is 100kpa-1Mpa, a liquid hourly space velocity 0.2-10hr-1, the molar ratio of hydrogen to C5 + hydrocarbons of 0.1 to 10, a temperature of 400-560 deg.] C, said original first effluent stream comprising benzene - toluene - xylenes aromatics and a substantial amount of deactivated catalyst particles, at least semi-continuous removal of deactivated catalyst particles from the continuous-reforming section, and a contact in the region of the sequence, and reducing gas containing hydrogen in a continuous regeneration region contained in the oxygen-containing gas to obtain at least part of the particles of the catalyst particles reconditioning, further characterized in that the continuous circulation reforming zone by at least 5% by volume, at the same time, increase the space velocity, reducing hydrogen to hydrocarbon mole ,使其范围在0.1-6,并且不增加相对于基本量的失活的催化剂颗粒以获得来自连续重整区域的改进的第一物流,和在含有沸石重整催化剂的沸石重整区域内在第二重整条件下接触改进的第一物流而不分离氢以获得含有比初始的第一物流至少多出10%苯-甲苯-二甲苯类的富芳烃产品,上述的沸石重整催化剂含有非酸性沸石,一碱金属组分和铂族金属组分,上述的第二重整条件包括压力为100kPa-6MPa,液体小时空速为1-40hr-1和温度为260-560℃。 , So that the range of 0.1-6, and does not increase substantially with respect to the amount of the catalyst particles inactivated for improved continuously from the reforming region of the first stream, and a second zeolitic reforming zone containing a zeolitic internal reforming catalyst under reforming conditions in contact with two improved without separating a first stream containing hydrogen to obtain an at least one more than the initial 10% of the first benzene stream - containing a non-acidic xylenes aromatics rich product, the above-described zeolite reforming catalyst - toluene zeolite, an alkali metal component and a platinum group metal component, said second reforming conditions comprising a pressure of 100kPa-6MPa, a liquid hourly space velocity of 1-40hr-1 and a temperature of 260-560 ℃.
2.权利要求1的方法,其中每个连续重整区域和沸石重整区域的压力在100kPa-1MPa。 2. The method of claim 1, wherein each of the continuous-reforming zone and zeolitic reforming zone pressure of 100kPa-1MPa.
3.权利要求1的方法,其中在每个连续重整区域和沸石重整区域的压力为450kPa或更低。 The method of claim 1, wherein each of the continuous-reforming zone and zeolitic reforming zone a pressure of 450kPa or less.
4.权利要求1的方法,其中在连续重整区域用以获得改进的第一物流的氢对烃的摩尔比不大于5。 Molar ratio of 4. The method of claim 1, wherein the first stream to obtain an improved hydrogen reforming of hydrocarbons in a continuous area not greater than 5.
5.权利要求1的方法,其中沸石重整区域的液体小时空速是至少为7hr-1。 The method of claim 1, wherein the liquid hourly space velocity of the zeolitic reforming zone is at least 7hr-1.
6.权利要求1的方法,其中沸石重整区域的空速是至少为10hr-1。 6. The method of claim 1, wherein the space velocity of the zeolitic reforming zone is at least 10hr-1.
7.权利要求1-6中任一项的方法,其中非酸性沸石含有铂形L沸石。 The method claimed in any one of claim 1, wherein the non-acidic zeolite L type zeolite containing platinum.
8.权利要求1-6中任一项的方法,其中沸石重整催化剂的碱金属组分含有钾组分。 The method claimed in any one of claim 1, wherein the alkali metal component of the zeolitic reforming catalyst contains potassium component.
9.权利要求1-8中任一项的方法,其中沸石重整催化剂的铂族金属组分含有铂组分。 9. The method according to any one of claims 1-8, wherein the platinum group metal component of the zeolitic reforming catalyst comprises a platinum component.
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US4645586A (en) * 1983-06-03 1987-02-24 Chevron Research Company Reforming process
US5190638A (en) * 1991-12-09 1993-03-02 Exxon Research And Engineering Company Moving bed/fixed bed two stage catalytic reforming

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US4645586A (en) * 1983-06-03 1987-02-24 Chevron Research Company Reforming process
US5190638A (en) * 1991-12-09 1993-03-02 Exxon Research And Engineering Company Moving bed/fixed bed two stage catalytic reforming

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