CN1305817C - Preparation of at least one partial oxidation and/or ammoxidation product of propylene - Google Patents

Preparation of at least one partial oxidation and/or ammoxidation product of propylene Download PDF

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CN1305817C
CN1305817C CNB038254107A CN03825410A CN1305817C CN 1305817 C CN1305817 C CN 1305817C CN B038254107 A CNB038254107 A CN B038254107A CN 03825410 A CN03825410 A CN 03825410A CN 1305817 C CN1305817 C CN 1305817C
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gas mixture
propane
method according
propylene
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CN1703387A (en
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C·黑希勒
G-P·申德勒
J·佩佐尔特
C·阿达米
O·马赫哈默
K·J·米勒-恩格尔
H·马尔坦
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巴斯福股份公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D303/00Compounds containing three-membered rings having one oxygen atom as the only ring heteroatom
    • C07D303/02Compounds containing oxirane rings
    • C07D303/04Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/18Preparation of carboxylic acid nitriles by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/03Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase

Abstract

本发明涉及制造至少一种不完全的丙烯氧化和/或氨氧化产物的方法,根据该方法,丙烯是通过脱氢由粗丙烷制造的,并在未反应的丙烷(作为包含<1体积%的1-丁烯的气体混合物2的组分)的存在下对丙烯进行多相催化气相不完全氧化和/或不完全气相氨氧化。 The present invention relates to a method for producing at least an incomplete oxidation of propylene and / or ammoxidation product, according to this method, the propylene by dehydrogenation is manufactured by a thick oxide, propane and unreacted (as containing <1% by volume for heterogeneously catalyzed gas phase propylene in the presence of 1-butene component gas mixture 2) partial oxidation and / or incomplete gas phase ammoxidation.

Description

丙烯的至少一种不完全氧化和/或氨氧化产物的制备 Preparing at least one partial oxidation and / or ammoxidation products of propylene

本发明涉及制备至少一种丙烯的不完全氧化和/或氨氧化产物的方法,在该方法中:a)在第一步中,在氧的存在和/不存在下对粗丙烷进行均相和/或多相催化脱氢和/或氧化脱氢,以生产含有丙烷和丙烯的气体混合物1,并b)如果合适,将存在于在第一步中生成的气体混合物1中的除丙烷和丙烯之外的部分组分从气体混合物1中分离出来并/或转化为其它化合物,从而由气体混合物1生产含有丙烷和丙烯以及除氧、丙烷和丙烯之外的化合物的气体混合物1′,并在至少一个进一步的步骤中,c)将气体混合物1和/或气体混合物1′作为气体混合物2的组分进行存在于气体混合物1和/或气体混合物1′中的丙烯的多相催化气相不完全氧化和/或不完全气相氨氧化。 Incomplete oxidation and / or ammoxidation products of the present invention relates to a method of preparing at least one of propylene, in which method: a) In the first step, a homogeneous crude propane in the presence and absence of oxygen and / / or heterogeneous catalytic dehydrogenation and / or oxydehydrogenation, containing propane and propylene to produce a gas mixture 1, and b) if appropriate, present in addition to propane and propene produced in the first step of a gas mixture part of the components from a gas mixture than in an isolated and / or converted to other compounds, so that a gas mixture containing a produced gas other than the compound of propane and propene, and oxygen, a mixture of propane and propylene 1 ', and at least one further step, c) the gas mixture and / or gas mixture 1 'as the gas mixture present in component 2 is / or gas mixture and the gas mixture 1 1' heterogeneously catalyzed gas-phase propylene in the incomplete oxidation and / or incomplete gas phase ammoxidation.

就本文而言,粗丙烷是不仅含有丙烷和可能的丙烯,而且还含有丙烷和丙烯之外的至少一种、通常至少两种或三种且经常至少四种或五种化合物的含丙烷的气体。 At least one, usually at least two or three or at least four and often containing propane gas purposes herein, crude containing propane and propane is possible not only propylene but also other than propane and propylene contain five compounds . 这些化合物可以通过例如气相色谱之类的色谱法在粗丙烷中检测出来。 These compounds can be, for example, gas chromatography or the like detected by chromatography in the crude by propane.

就本文而言,丙烷的氧化脱氢作用是被存在的氧强制进行且其中没有游离氢作为中间体生成或可检测出来的脱氢作用。 For purposes herein, the oxidative dehydrogenation of propane is forcing oxygen present and in which no intermediate dehydrogenation or generation of free hydrogen as detected. 与吸热进行的常规脱氢作用不同,氧化脱氢是放热的。 Made of different conventional endothermic dehydrogenation, oxidative dehydrogenation is exothermic. 丙烷的氧化脱氢可以在升高的温度下、在均相催化剂的存在下进行(即不存在例如固体催化剂;参见例如US-A3798283)或者在多相催化剂的存在下进行(即在固体催化剂上;参见DE-A2058054和DE-A 19530494)。 Oxidative dehydrogenation of propane can be performed (i.e., for example, the absence of a solid catalyst; see e.g. US-A3798283), in the presence of a homogeneous catalyst at elevated temperature or in the presence of a heterogeneous catalyst (i.e., the solid catalyst ; see DE-A2058054 and DE-A 19530494).

常规脱氢作用基本与此相同,其中脱氢作用是在没有氧的活跃参与的情况下进行的(参见例如EP-A 731077和WO 01/96270)。 Conventional dehydrogenation substantially the same manner, wherein the dehydrogenation is carried out in the absence of active participation of oxygen (see e.g. EP-A 731077 and WO 01/96270). 在这种情况下,生成的主要副产物是氢,而不是氧化脱氢情形中生成的水。 In this case, the major by-product generated is hydrogen, and not generated in the case of oxidative dehydrogenation water.

就本文而言,丙烯的完全氧化是所有存在于丙烯的碳都转化为碳的氧化物(CO、CO2)的转化。 For purposes herein, all complete oxidation of propylene in the propylene carbons are converted into carbon oxides (CO, CO2) are. 本文中,丙烯与分子氧的所有其它反应都包括在术语“不完全氧化”中。 Herein, the propylene with molecular oxygen to all other reactions included in the term "partial oxidation" in the. 氨氧化作用的特征是反应中还涉及氨。 Wherein the ammoxidation reaction is also involved in ammonia.

在本文中,丙烯优选的不完全氧化和/或氨氧化产物是丙烯醛、丙烯酸、氧化丙烯和丙烯腈。 Herein, preferably the propylene partial oxidation and / or ammoxidation product acrolein, acrylic acid, acrylonitrile, and propylene oxide.

丙烯不完全氧化和/或氨氧化的产物是重要的中间体,例如可用于制备聚合物。 And / or products of incomplete oxidation of ammoxidation of propylene are important intermediates, for example, for preparation of the polymer.

这种不完全氧化和/或氨氧化作用是根据本身已知的方法进行的(可以以本身已知的方式控制反应气混合物中氨的量,从而进行基本上只是不完全氧化的反应、或只是不完全氨氧化的反应、或者是这两种反应的重叠)。 Such incomplete oxidation and / or ammoxidation is carried out according to methods known per se (in a manner known per se can control the amount of ammonia in the reaction gas mixture, so that substantially only a reaction of partial oxidation, or just ammoxidation reaction was not complete, or overlapping these two reactions). 它们是在固体(通常是氧化的)催化剂上的多相催化气相反应。 They are in a solid (usually oxidized) heterogeneously catalyzed gas phase reaction on the catalyst.

可以通过举例的方式引述DE-A 2 351 151(丙烯转化为丙烯醛和/或丙烯酸的实例及丙烯转化为丙烯腈的实例)和EP-A 372 972(丙烯转化为氧化丙烯的实例)。 It may be cited (propylene to acrolein and / or acrylic acid from propylene and the examples are examples of conversion of acrylonitrile) and (propylene into propylene oxide Example) 372 972 DE-A 2 351 151 EP-A by way of example.

作为氧化剂,通常使用分子氧。 As the oxidizing agent, generally molecular oxygen. 可以以例如纯态或与在不完全氧化和/或氨氧化反应中基本上为惰性的气体混合的形式(例如空气)将分子氧加入反应气混合物中。 May be, for example, in pure form or with incomplete oxidation and / or ammoxidation reaction is substantially in the form (e.g., air) gas mixing inert gas molecular oxygen added to the reaction mixture. 反应气混合物中的反应物经常还被至少一种惰性气体(例如N2,H2O,CO,CO2,饱和烃,如C1-C5烃(如DE-A 1924431和EP-A 293224中所述的),He和/或Ar等)稀释,以有助于除热并使反应安全进行。 The reaction gas mixture of the reactants is often further at least one inert gas (e.g. N2, H2O, CO, CO2, saturated hydrocarbons, such as C1-C5 hydrocarbons (e.g., 1,924,431 and EP-A 293224 as described in DE-A), He and / or Ar, etc.) is diluted to facilitate heat removal and safe for the reaction. DE-B 2251364特别推荐使用丁烷作为惰性稀释气体。 DE-B 2251364 is particularly recommended to use butane as the inert diluent gas. 如上所述,氨氧化作用的特点是还存在氨。 As described above, oxidation of ammonia still characterized by the presence of ammonia.

与实验室试验和中试工厂试验的情况不同,工业规模上使用的丙烯原料通常不是化学纯净的丙烯,而是含有杂质但纯度较高的粗丙烯(例如“聚合级”或“化学级”;参见DE-A 10131297)。 Unlike the case of laboratory and pilot plant tests, the propylene feedstock is usually not chemically pure propylene which are used on an industrial scale, but containing impurities but higher purity of the crude propylene (e.g., "polymerization grade" or "chemical grade"; see, DE-A 10131297).

这种较纯粗丙烯的离析较为复杂,且花费较多。 This is more complicated than the isolation of pure crude propylene, and spend more. 其通常由粗烷烃开始,且一般包括至少一个通过物理方法从生成的丙烯中将未反应的烷烃分离出去的纯化步骤(参见例如DE-A 3 521 458)。 Typically starting from crude alkanes, and generally includes a purification step (see, e.g. DE-A 3 521 458) at least one alkane will be separated from unreacted propylene produced by physical means. 纯化步骤通常包括除去丙烯之外的烯烃和其它不同于丙烯的副产物,包括最初存在于粗烷烃中的次要组分。 Purification step generally comprises removal of olefins than propylene and other by-products other than propylene, comprising initially present in the crude alkane minor component.

上述分离通常需要大的投资,并且由于烯烃/烷烃的相似性,是非常耗费能量的。 The separation typically requires a large investment, and because of the similarity of olefin / paraffin, it is very energy consuming. 因此,它们通常仅连同精炼裂化装置和蒸汽裂化装置一起使用,并且仅仅因为在随后的聚合(例如制备聚丙烯)中对以这种方式制得的粗丙烯的大部分具有大的需求量(“规模经济”),而且结果价值得到提升,因而才是值得的。 Thus, they are generally used only in conjunction with refinery crackers and steam cracking units together, and only because the subsequent polymerization (prepared, for example, polypropylene) having a large demand for the majority in this way obtained a crude propylene ( " economies of scale "), and the result value would be enhanced, and thus is worth it.

这些进行不完全氧化和/或氨氧化的粗丙烯的比例是次重要的,且实际上是次要的要求,这就是以这种方式生产的粗丙烯用作不完全氧化和/或氨氧化的原料时仍然具有可接受的价格的原因。 The proportion of incomplete oxidation and / or ammoxidation of crude propylene is of secondary importance, and indeed is a secondary requirement, which is produced in this manner is used as crude propylene partial oxidation and / or ammoxidation the reason still has an acceptable price of raw material.

只有当有可能省略部分或全部所述分离时,该原料的价格才可以明显降低。 Only when it is possible to omit some or all of the separation, the raw material price can be significantly reduced.

作为解决该问题的方法,EP-B 938463建议,在第一步中,例如在氧和多相催化剂的存在下将粗丙烷部分脱氢,制造含有丙烯和丙烷的第一气体混合物,将该混合物作为第二气体混合物的组分原样(即不进行中间处理)进行多相催化气相不完全氧化,将存在于第一气体混合物中的丙烯氧化为丙烯醛和/或丙烯酸。 As a method for solving this problem, EP-B 938463 is recommended, in a first step, for example, crude partial dehydrogenation of propane, for producing a first gas mixture comprising propene and propane in the presence of oxygen and a heterogeneous catalyst, the mixture was as such as a component of a second gas mixture (i.e., without intermediate treatment) performed heterogeneously catalyzed gas-phase partial oxidation, the oxidation of propylene in the presence of a first gas mixture of acrolein and / or acrylic acid.

关于所用粗丙烷的纯度问题,EP-B 938463在第三栏第40行以下指出:“原料链烷的纯度没有特别限制。”“而且原料链烷可以是多种链烷的混合物。进料通常会包含至少30摩尔%、优选至少50摩尔%、更优选至少80摩尔%的丙烷。用于本发明方法中的链烷源,即丙烷进料,不是关键的。”在第3栏第17行以下,EP-B 938463还指出:“因此,在回收丙烯醛之后,包含丙烷的非冷凝气体可以不经重要的、额外的纯化步骤而循环使用。”EP-A 117146的教导基本与EP-B 938463的教导相当,不同的是EP-A117146推荐对丙烷进行多相催化脱氢时排除氧。 Problems regarding purity crude propane used, EP-B 938463 in the third column, line 40 that: "alkane-purity raw material is not particularly limited." "And material alkane may be a mixture of paraffinic feed generally. will comprise at least 30 mol%, preferably at least 50 mol%, more preferably at least 80 mol% of propane. alkanoic source for the method of the present invention, i.e., propane feed, is not critical. "line 17 in column 3 or less, EP-B 938 463 also states: "Thus, after recovery of the acrolein, noncondensable gases containing propane may be used without significant, additional purification steps and recycled." EP-a 117146 teaches substantially EP-B 938,463 the teachings, except that EP-A117146 recommended to exclude oxygen during the heterogeneously catalyzed dehydrogenation of propane.

此外,关于上述循环流的问题,EP-A 117146在第11页第14行以下指出:“因为轻质烃和重质烃副产物,例如甲烷、乙烷、乙烯、丁烷和丁烯,在与丙烯醛或C3烃的沸点相差很大的温度下沸腾,因此可通过蒸馏将它们分离。或者,可吹扫包含浓缩量的副产物的物流。”这种循环气吹扫流的可行性还可见于EP-B 938463第11栏第10行。 Further, regarding the circulating flow above problems, EP-A 117146 on page 11, line 14 as indicated below: "Because of the heavy hydrocarbon and light hydrocarbon by-products such as methane, ethane, ethylene, butane and butene, in boiling with acrolein or C3 hydrocarbons boiling temperatures vary greatly, so that they may be separated by distillation. Alternatively, the purge stream may contain concentrated amounts of by-products. "the feasibility of this cycle gas purge flow also It is found in EP-B 938463 at column 11, line 10.

这两个文献都没有认识到在不完全氧化和/或氨氧化之前分离出上述次要组分的必要性。 Both documents do not recognize / or the necessity of separating the above-described minor components in the ammoxidation before and incomplete oxidation.

继EP-B 938463和EP-A 117146之后,WO 01/96270又提出了见解。 Following EP-B 938463 and EP-A 117146, WO 01/96270 also proposed ideas. 例如,它在第4页第10行以下指出:“在本发明方法中,送至氧化阶段B的进料气混合物在上述组分之外当然还可以含有其它组分,例如CO、CO2、H2O、例如He和/或Ar的稀有气体、氢、甲烷、乙烯、丁烷、丁烯、丁炔、戊烷、丙炔、丙二烯和/丙烯醛。”此外,关于用于脱氢步骤的粗丙烷,WO 01/96270在第15页第26行以下指出:“在本发明中,重要的是用于阶段A的丙烷不必是纯丙烷。相反,所用丙烷可以包含最高达50体积%的其它气体,例如乙烷、甲烷、乙烯、丁烷、丁烯、丙炔、乙炔、H2S、SO2、戊烷等。”虽然WO 01/96270也推荐在第一气体混合物进一步用于存在于其中的丙烯的不完全氧化之前,分离出至少一部分存在于在脱氢步骤中生成的并含有丙烷和丙烯的第一气体混合物中的氢,而且在该分离过程中,非必要地分离出丙烷和丙烯之外的其它组分,必要时基 For example, it is page 4, line 10 of the following states: "In the process of the present invention, the feed gas mixture fed to the oxidation stage B may of course also contain other components in addition to the above components such as CO, CO2, H2O , rare gas such as He and / or Ar, hydrogen, methane, ethylene, butane, butene, butyne, pentane, propyne, propadiene and / or acrolein. "Further, with respect to the dehydrogenation step the crude propane, WO 01/96270 at page 15, line 26 indicated the following: "in the present invention, it is important that the propane used in phase a need not be pure propane Rather, the propane may comprise up to 50% by volume of the other. propylene gas, such as ethane, methane, ethylene, butane, butene, propyne, acetylene, H2S, SO2, pentane and the like. "Although WO 01/96270 also recommended for the first gas mixture further present therein previous incomplete oxidation, separating at least a portion is present in the first gas mixture comprising propane and propylene and hydrogen generated in the dehydrogenation step, and the separation process, optionally separated than propane and propylene other components, if necessary, group 全部分离出,而EP-B731077认为,特别优选地,在进一步使用第一气体混合物之前,从这种第一气体混合物中定量除去除丙烷、丙烯和可能的分子氧之外的所有其它组分,但是,任何用于此目的的分离过程对整个过程的经济性都有不利影响,并且,其次,发现一些上述文献推荐的用于这种定量分离的过程是比较不合适的。 All isolated, and that EP-B731077, particularly preferably, prior to further use the first gas mixture, the gas mixture from this first inter quantitative removal of all of the other components other than propane, propylene and possibly molecular oxygen, However, any separation process used for this purpose on the economics of the entire process has an adverse effect, and, secondly, found that some of the above documents recommended for such quantitative separation process is more appropriate. 例如,WO 01/96270第16页下部推荐的吸收/解吸过程属于后一种情况,在近来的检测中发现其相对不适于例如从C3烃中分离C4烃。 For example, the lower recommended WO 01/96270 on page 16 of the absorption / desorption process is of the latter, for example, found that relatively unsuitable for separating C3 hydrocarbons from the C4 hydrocarbons in the recent detection.

在所引现有技术中,没有认识到以下步骤的必要性:在脱氢和/或氧化脱氢步骤之后或甚至在此步骤之前分离出特定的次要组分,从而在氧化和/或氨氧化步骤中当原料由粗丙烯改为粗丙烷时在生成所需目标产物之外减少副产物的生成。 In the cited prior art, there is no awareness of the need of the steps of: after the dehydrogenation and / or oxydehydrogenation steps or even isolate specific secondary components prior to this step, so that oxidation and / or ammonia when the starting material in the oxidation step was changed from rough crude propylene oxide to reduce by-product formation in addition to generating the desired target product. 虽然现有技术意识到随着原料的改变生成的副产物也发生了变化(根据WO 01/96270,例如在不完全氧化时存在丙烷,会增加丙醛和/或丙酸的形成;但是,不从在脱氢过程中生成的丙烯中分离出丙烷的优点并没有被赋予更重要的意义),但这没有被认为是特别关键的,因为预分离通常比目标产物与副产物的分离更为复杂。 While the prior art realize that changing the material generated as a byproduct also changed (according to WO 01/96270, for example, when propane is present in the incomplete oxidation, increases the formation of propionaldehyde and / or propionic acid; however, not produced from propylene in dehydrogenation of propane is separated and advantages not given greater importance), but this is not considered to be particularly critical, because the pre-separation is usually more complex than the separation of the desired product and by-product . 鉴于该背景,还认为在任何情况下都必须进行目标产物与生成的副产物的分离。 Given this background, that also must be separated from the desired product and by-product in any case.

这种意见在例如EP-A 1192987、DE-A 10122027、EP-A 608838、EP-A529853、DE-A 10051419或DE-A 10119933中也可明显地看到,它们推荐在单个反应区(通常在至少两个反应区进行)在催化剂装料上实施本文开始处定义的方法,所述催化剂装料的活性氧化物成分由至少一种含元素Mo、V和Te和/或Sb的多金属氧化物组成。 In this view, for example, EP-A 1192987, DE-A 10122027, EP-A 608838, EP-A529853, DE-A 10051419 or DE-A 10119933 also be apparent, they are recommended in a single reaction zone (usually at least two reaction zone) defined at the beginning of the method described herein on the catalyst charge, the charge of the active catalyst component consists of at least one oxide containing elements Mo, V and Te and / or Sb multimetal oxide composition. 该过程的基础是相关的活性氧化物成分既能够催化由丙烷生成丙烯的氧化脱氢反应(参见例如EP-B938463第4栏第37行以下),又能够催化丙烯的不完全氧化和/氨氧化反应。 The basic process is related both to the active ingredient an oxide generated by the catalytic oxidative dehydrogenation of propane to propylene (see, e.g. EP-B938463 column 4, line 37 or less), but also capable of catalyzing the partial oxidation of propylene and / ammoxidation reaction. 理所当然地,在该过程中气体混合物1原样用于随后进行的不完全氧化和/氨氧化步骤。 Of course, in the process gas mixture was used as a partial oxidation and / or ammoxidation subsequent step.

但是,例如EP-A 1192987在第9页第26行以下建议:“类似地,对链烷的来源没有限制。它可以作为纯净物购得,也可以作为与烯烃和/或其它杂质的混合物购得。此外,链烷(无论其来源如何)和烯烃(无论其来源如何)可以根据需要进行混合。”完全相似地,DE-A 10122027在第3页第35/36行指出:“对于用于本发明方法中的丙烷的纯度没有特别高的要求。”WO 0196271同样认为纯度差别很大的粗丙烷是可用的。 However, for example in EP-A 1192987, page 9, line 26, the following suggestions: "Similarly, there is no limitation on the source of the alkane which is commercially available as a pure substance or as a mixture with an olefin and / or other impurities are commercially available. . Also obtained, alkane (regardless of origin) and the olefin (regardless of origin) may be mixed as needed "completely Similarly, DE-A 10122027 at page 3, lines 35/36 that:". for a purity propane process of the invention is not particularly high requirements. "WO 0196271 also believe that large differences in the purity of the crude propane are available.

现有技术的以上建议的不足之处在于,它们没有解决以下问题:可能存在于廉价粗丙烷中的组分或者在第一步中由这些组分生成的并因而存在于第一气体混合物中的化合物(它们不存在、或仅以痕量存在于通常所用的粗丙烷中,因而其负面作用迄今一直被忽视),在随后进行的多相催化不完全氧化和/氨氧化中,由于降低了催化剂在所需的丙烯不完全氧化和/氨氧化方面的活性和/或选择性而成为催化剂毒物。 The above prior art deficiencies suggested that they do not address the following problems: low cost components may be present in the crude or propane from these components in a first step, and thus there is generated in the first gas mixture compound (they are not present, or only present in trace amounts commonly used crude propane, reducing its negative effects have been neglected so far), and incomplete oxidation / ammoxidation subsequent heterogeneous catalysis, the catalyst is reduced due to the incomplete oxidation and / ammonia oxidation aspect activity and / or selectivity of the desired propylene and become a catalyst poison.

通过认真细致的研究,现已发现C4烃(由4个碳原子和氢构成的化合物)总体上、且特别是其中烯烃代表物(1-丁烯、反-2-丁烯、顺-2-丁烯和异丁烯)的组、且特别是其中1-丁烯形成了这种催化剂毒物。 By careful study has now been found (by the compound 4 carbon atoms and hydrogen) of C4 hydrocarbons in general, and in particular representatives in which the olefin (1-butene, 2-butene, cis-2 butylene and isobutylene) group, wherein 1-butene and in particular the formation of such catalyst poisons. 但是,饱和的代表物及其它不饱和的代表物也具有负面作用。 However, other saturated and the unsaturated representatives representative may also have a negative effect.

然而C4烃(例如正丁烷、异丁烷、反-2-丁烯、顺-2-丁烯、异丁烯、1,3-丁二烯、1,2-丁二烯、1-丁炔和/或2-丁炔)是处处伴随丙烷而存在的化合物,因而通常以较大的量存在于廉价的粗丙烷中。 However, C4 hydrocarbons (e.g. n-butane, isobutane, 2-butene, cis-2-butene, isobutene, 1,3-butadiene, 1,2-butadiene, 1-butyne and / or 2-butyne) is a compound oxide exists always accompanied, and therefore typically relatively large amounts in the crude propane inexpensive. 对于饱和C4烃,情况尤为如此。 The saturated C4 hydrocarbons, particularly the case. 在丙烷不完全脱氢和/或氧化脱氢的条件下,总是由饱和C4烃生成至少一些C4烯烃,尤其是特别麻烦的1-丁烯。 In the dehydrogenation of propane incomplete and / or oxidative dehydrogenation conditions, always generates at least some of the C4 olefins from saturated C4 hydrocarbons, especially the particularly troublesome 1-butene.

本发明的目的是提供本文开始处描述的制备丙烯的至少一种不完全氧化和/氨氧化产物的方法。 Object of the present invention is to provide a preparation described herein at the beginning of at least one of propylene and incomplete oxidation methods / ammonia oxidation products. 与现有技术的方法不同,本发明方法考虑到了上述事实。 Unlike prior art methods, the present invention contemplates a method of the above facts.

我们发现,上述目的通过一种制备丙烯的至少一种不完全氧化和/氨氧化产物的方法得以实现,在该方法中:a)在第一步中,在氧的存在和/不存在下对粗丙烷进行均相和/或多相催化脱氢和/或氧化脱氢,以生产含有丙烷和丙烯的气体混合物1,并b)如果合适,将存在于在第一步中生成的气体混合物1中的除丙烷和丙烯之外的部分组分从气体混合物1中分离出来并/或转化为其它化合物,从而由气体混合物1生产含有丙烷和丙烯以及除氧、丙烷和丙烯之外的化合物的气体混合物1′,并在至少一个进一步的步骤中,c)将气体混合物1和/或气体混合物1′作为气体混合物2的组分进行存在于气体混合物1和/或气体混合物1′中的丙烯的多相催化气相不完全氧化和/或不完全气相氨氧化,其中气体混合物2中1-丁烯的含量≤1体积%。 We have found that the above object is achieved by a process for the preparation of propylene and at least one partial oxidation / ammoxidation product is achieved, in which method: a) In the first step, in the presence of oxygen and / absence of the crude propane homogeneous and / or heterogeneous catalytic dehydrogenation and / or oxydehydrogenation, to produce a gas containing a mixture of propane and propylene, and b) if appropriate, present in the gas mixture generated in the first step 1 components other than the portion other than propane and propylene is separated from a gas mixture out and / or converted to other compounds, thereby producing a compound containing oxygen and propane and propene than propane and propylene from the gas mixture of gas mixture of 1 ', and at least one further step, c) the gas mixture / or gas mixtures 1 and 1' as a component of the gas mixture 2 will be present in the gas mixture and / or a gas mixture of propylene 1 ', 1 heterogeneously catalyzed gas-phase partial oxidation and / or incomplete gas phase ammoxidation, wherein the content of the gas mixture 2 by volume ≤1% of 1-butene.

在发明方法中,基于存在于气体混合物1中的这些组分的量,丙烷和丙烯之外的、在转化为气体混合物1′的过程中从混合物1中分离出来并/或转化为其它化合物的组分的量最高可达5重量%,或最高可达10重量%,或最高可达20重量%,或最高可达30或40重量%,或最高可达60重量%,或最高可达70或80重量%,或最高可达85或90重量%,或最高可达94重量%,或最高可达96或98重量%,或最高可达99重量%或更高。 In the method of the invention, based on the addition amounts of these components are present in a gas mixture of propane and propylene, separating the gas mixture in the conversion process 1 'in and out from a mixture / or converted to other compounds the amount of the component up to 5 wt%, or up to 10 wt%, or up to 20 wt.%, or up to 30 or 40 wt%, or up to 60 wt.%, or up to 70 or 80 wt%, or up to 85 or 90 wt%, or up to 94 wt.%, or up to 96 or 98 wt%, or up to 99 wt% or more.

根据本发明,气体混合物2中1-丁烯的含量≤0.9体积%或≤0.75体积%或≤0.6体积%或≤0.5体积%或≤0.4体积%,特别优选≤0.3体积%,非常特别优选≤0.2体积%并更优选≤0.1体积%或≤0.05体积%或≤0.03体积%或≤0.01体积%。 According to the present invention, the gas mixture in a content of 1-butene or 2 ≤0.9 ≤0.75 vol% vol% vol% or or ≤0.6 ≤0.5 ≤0.4 vol% or vol%, particularly preferably ≤0.3% by volume, very particularly preferably ≤ 0.2% by volume, and more preferably ≤0.1% by volume or volume percent or ≤0.05 ≤0.03 ≤0.01% by volume or volume percent. 在气体混合物2根本不再包含任何1-丁烯的情况下,过程的这种不利影响根本就不再出现。 In the case where the gas mixture did not contain any of 1-butene, this adverse effect did not occur in the process. 但是从经济性的总体评价来看,可能有理由接受气体混合物2中1-丁烯的部分不利影响,并任其在气体混合物2中的含量为≥0.001体积%的值,或≥0.003体积%或≥0.006体积%或在极端情况下≥0.009体积%。 However, the overall evaluation of the economic point of view, there may be reasons to accept the adverse effects of the gas mixture 2 portions of 1-butene, and mixtures thereof, in any of the gas content of 2% by volume of ≥0.001 value, or volume% ≥0.003 or ≥0.006 volume percent or, in extreme cases ≥0.009% by volume.

在本发明的方法中,优选上述限制不仅仅适用于存在于气体混合物2中1-丁烯的量,而且同时各自独立地适用于丁烯的各种其它可能的代表物(即反-2-丁烯、顺-2-丁烯、异丁烯),并非常特别优选同时适用于气体混合物2中丁烯的总量。 In the method of the present invention, preferably, the restriction applies not only to be present in an amount of 1-butene in the gas mixture, and while each independently butene applied to a variety of other representatives of the possible (i.e., trans-2- butene, cis-2-butene, isobutene), and very particularly preferably suitable for the gas mixture while in the total amount of 2-butene. 这意味着适于本发明目的的气体混合物2是例如以下那些,其中:-1-丁烯的含量≤1体积%且丁烯的总含量≤1体积%;或-1-丁烯的含量≤0.5体积%且丁烯的总含量≤1体积%;或-1-丁烯的含量≤0.3体积%且丁烯的总含量≤1体积%;或-1-丁烯的含量≤0.5体积%且丁烯的总含量≤0.75体积%;或-1-丁烯的含量≤0.75体积%且丁烯的总含量≤1体积%;或-1-丁烯的含量≤0.4体积%且丁烯的总含量≤1体积%;或-1-丁烯的含量≤0.2体积%且丁烯的总含量≤1体积%;或-1-丁烯的含量≤0.5体积%且丁烯的总含量≤0.5体积%;等。 This means that the object of the present invention is suitable for the gas mixture 2 is, for example those in which: -1- butene content of ≤1% by volume and the total content of butene ≤1% by volume; or 1-butene content of ≤ butene and 0.5% by volume of the total content of ≤1% by volume; or 1-butene and butene content of ≤0.3% by volume of the total volume content of ≤1%; content of ≤0.5% by volume and 1-butene or the total content ≤0.75% by volume of butene; content ≤0.75% by volume and 1-butene or a butene content of ≤1% by volume of the total; or 1-butene content of ≤0.4% by volume of the total butenes and content of ≤1% by volume; or 1-butene content of ≤0.2% by volume and the total content of butene volume ≤1%; content of ≤0.5% by volume and 1-butene or butene content of the total volume of ≤0.5 %;Wait.

本发明方法基本提供了两种可能的遵守上述限制的途径;其中可以采用二者中的仅一个或同时采用两种途径。 The method of the present invention provides two basic ways possible to comply with these restrictions; both of which may be employed while using only one or two ways.

首先,原料可以是或者根本不含C4烃、或者仅含以下量的C4烃的粗丙烷:根据本发明方法限定气体混合物2中1-丁烯、(总的)丁烯和(总的)C4烃含量的限制得到遵守。 First, the raw material may be or contain no C4 hydrocarbons, or a crude containing only the following amounts of propane C4 hydrocarbons: defining a gas mixture of 1-butene according to the invention, (total) and butene (total) C4 hydrocarbon content restrictions are observed. 粗丙烷中可能的C4烃的什么含量与本发明方法相容特别依赖于本发明方法第一步所采用的边界条件,并可由本领域技术人员在几个在各种情况下受限于这些特定边界条件的预试验中加以确定。 What propane crude C4 hydrocarbon content may be the method of the present invention is compatible with the particular method of the present invention depends on the boundary conditions employed in the first step, and by those skilled in the art in each case several limited to these particular boundary conditions in the pre-test to be determined.

如果必须从商业粗丙烷中分离出C4烃,这可以以自身已知的方式进行,例如通过净化。 If C4 hydrocarbons must be separated from the crude commercial propane, which can be carried out in a manner known per se, for example by purification. 当然,所有其它分离方法,例如吸附/解吸(如压力摇摆吸附)、萃取和/或吸附/解吸,也是可以的。 Of course, all other separation methods, such as adsorption / desorption (e.g. pressure swing adsorption), extraction and / or adsorption / desorption, is also possible.

另外,或者作为选择,可以从气体混合物1中分离出C4烃总体,特别是1-丁烯或丁烯,从而使这些组分的含量在根据本发明将气体混合物1进一步用作气体混合物1′之前处于或低于根据本发明而要遵守的限制。 In addition, or alternatively, may be isolated from the C4 hydrocarbons generally a gas mixture, in particular 1-butene or butene, so that the content of these components in the gas mixture according to the present invention will further be used as a gas mixture 1 ' before at or below the limit of the present invention to follow. 只有在例如通过歧化和/或复分解进行氧化脱氢或脱氢步骤的过程中,例如当由例如丙烷生成了干扰性的C4烃时,才采用该方法。 Only during, for example by means of disproportionation and / or oxidative dehydrogenation or metathesis dehydrogenation step, for example, when interference is generated by the C4 hydrocarbons such as propane, are used only if the method. 特别是当在本发明方法的第一步中采用了DE-A 10211275的部分气体循环法(在进行催化脱氢的情形中)时,这种可能性增大了。 Especially when using the DE-A 10211275 part of the gas circulation method in the first step of the method of the present invention (in the case of carrying out the catalytic dehydrogenation), the possibility is increased. 关于分离方法,可以使用例如DE-A10131297中所述的吸收和解吸的结合或汽提(优选为压力吸收)、压力摇摆吸附、净化和/或萃取。 About separation method, for example, may be used / or extraction of absorption and desorption in the DE-A10131297 binding or stripping (preferably a pressure absorption), pressure swing adsorption, and purification. 在采用汽提的情况下,需要确保不会通过所用的汽提气引入C4烃。 In the case of steam stripping, it is necessary to ensure that no C4 hydrocarbons is introduced through the stripping gas used.

如果借助空气汽提出以富集的形式存在于吸收介质中的丙烷和丙烯(例如在从催化脱氢反应生成的产物气体混合物中进行吸附之后),可以适用本发明方法中的一种,即,如果汽提气的量选择得合适,通过汽提产生的气体混合物1′可直接用于气相不完全氧化和/或不完全气相氨氧化,并因而与气体混合物2是相同的。 (After adsorption for example, from the catalytic dehydrogenation reaction product gas mixture), if made in the form of absorption medium enriched in propane and propylene by an air steam, a method may be applied according to the present invention, i.e., If the amount of stripping gas is selected to be proper, the gas mixture produced by stripping 1 'may be used directly in the gas phase partial oxidation and / or ammoxidation gas incompletely, and thus the gas mixture is the same. 在这种情况下,气体混合物1′中丙烷、丙烯和氧之外的组分的含量通常为35至55体积%。 In this case, the gas mixture other than the content of the component 1 'of propane, propylene and oxygen is usually 35-55% by volume. 如果准备根据本发明制备丙烯醛和/或丙烯酸,这一过程是优选的。 If the preparation according to acrolein and / or acrylic acid of the present invention, this process is preferred.

当然,上述C4烃的去除也可伴随不同于丙烷和丙烯的组分的去除。 Of course, C4 hydrocarbons may be accompanied by removing the removal of propane and propylene is different from the component. 当然在各种情况下还可能分离出部分丙烷和/丙烯。 Of course a portion may also be isolated and propane / propene in each case.

根据本发明,为了限制总的分离费用及由此造成的对经济性的不利影响,所述分离方法宜专门针对C4烃的去除。 According to the present invention, in order to limit the total cost of the separation and the resulting adverse impact on the economics of the separation process should be designed for the removal of C4 hydrocarbons.

这意味着,在正常情况下,在本发明方法中,气体混合物1′将仍包含至少≥0.1体积%、通常≥0.2体积%或≥0.3体积%或≥0.4体积%或≥0.5体积%、经常≥0.6体积%或≥0.8体积%或≥1体积%、或≥2体积%或≥3体积%或≥5体积%、很可能≥10体积%或≥15体积%或≥20体积%或≥25体积%或≥30体积%或≥35体积%的除丙烷和丙烯和氧之外的组分。 This means that, under normal circumstances, in the process of the present invention, the gas mixture 1 'will still contain at least ≥0.1% by volume, typically vol% or ≥0.2 ≥0.3 ≥0.4 vol% or vol% or ≥0.5% by volume, often vol% or ≥0.6 ≥0.8 ≥1 vol% or volume%, or volume% or ≥2% or ≥3 volume ≥5 vol%, ≥10% by volume or likely vol% or ≥15% or ≥25 ≥20 vol vol% or ≥30% or ≥35% by volume by volume of other constituents other than propane and propylene and oxygen.

但是,本发明方法的气体混合物1′中除丙烷和丙烯和氧之外的组分的比例通常为≤80体积%或≤70体积%或≤60体积%或≤50体积%或≤40体积%。 However, the method of the present invention the gas mixture 1 'ratio of the components other than propane and propylene and oxygen is typically ≤80 ≤70 vol.% Or vol.% Or vol% or ≤60 ≤50 ≤40 vol.% Or vol% .

根据本发明,上述分离宜进行得使气体混合物2不仅符合根据本发明是合适的1-丁烯的含量和(如果可适用)其它丁烯异构体的含量及(如果可适用)丁烯总的含量,而且同时具有≤3体积%或≤2.5体积%、优选≤2体积%并非常特别优选≤0.5体积%或≤0.3体积%或≤0.1体积%的总的C4烃含量。 According to the present invention, the separation should be carried out to obtain the gas mixture 2 is not only in the content of 1-butene and of suitable (if applicable) content and other butene isomers (if applicable) in accordance with the present invention butene Total content, but also has ≤3% by volume or ≤2.5% by volume, preferably ≤2 C4 hydrocarbon content of the total volume and very particularly preferably ≤0.5% by volume or ≤0.3% ≤0.1% by volume or volume percent. 这是因为已发现C4烃(特别是正丁烷和/或异丁烷)的存在在丙烯不完全氧化和/或氨氧化过程中通常是不利的。 This is because it has been found that C4 hydrocarbons (especially n-butane and / or isobutane) in the presence of incomplete oxidation of propylene and / or an ammonia oxidation process is generally disadvantageous.

在气体混合物2根本不再包含任何C4烃的情况下,C4烃的不利影响就根本不再显现。 In the case where the gas mixture did not contain any C4 hydrocarbons, C4 hydrocarbons adverse effects on simply no longer appear. 但是从经济性的总体评价来看,可能有理由接受气体混合物2中C4烃的一些不利影响,并任其在气体混合物2中的含量为≥0.05体积%的值,或≥0.07体积%或≥0.09体积%或≥0.1体积%或在极端情况下≥0.2体积%。 However, the overall evaluation of the economic point of view, there may be reasons to accept some adverse effects in a gas mixture of C4 hydrocarbons, and any mixture thereof in gas content of 2% by volume of values ​​≥0.05, or ≥0.07 vol% or ≥ 0.09 vol% or ≥0.1% by volume or, in extreme cases ≥0.2% by volume.

这就意味着本发明的目的特别是在以下情形下实现的:对于气体混合物2,至少根据本发明对1-丁烯的含量施加的限制之一以及同时在本文中对C4烃的总含量施加的限制之一得到了遵守。 This means that the object of the present invention is achieved in particular in the following situations: 2 for the gas mixture, at least one of the limitations on the content of 1-butene of the present invention is applied, and while applying a total content of C4 hydrocarbons according herein one limitation has been complied with.

换言之,根据本发明为合适的气体混合物2包括例如符合以下规格搭配之一的那些:-1-丁烯的含量≤1体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤1体积%且C4烃的总含量≤2体积%;或-1-丁烯的含量≤0.5体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.5体积%且C4烃的总含量≤2体积%;或-1-丁烯的含量≤0.75体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.75体积%且C4烃的总含量≤2体积%;或 In other words, for example, those comprising a mixture of two of the following are suitable specifications for the gas with the present invention: the total content -1- butene content of ≤1% by volume of C4 hydrocarbons and ≤3% by volume; or 1-butene the content of ≤1% by volume and the total content of C4 hydrocarbons ≤2% by volume; or a total content of 1-butene content of ≤0.5% by volume of C4 hydrocarbons and ≤3% by volume; or 1-butene content of ≤0.5 content ≤0.75% by volume and 1-butene or C4; vol% and the total content of C4 hydrocarbons ≤2% by volume; or a total content of 1-butene content ≤0.75% by volume of C4 hydrocarbons and ≤3% by volume the total content of hydrocarbons ≤2% by volume; or

-1-丁烯的含量≤0.4体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.4体积%且C4烃的总含量≤2体积%;或-1-丁烯的含量≤0.4体积%且C4烃的总含量≤1体积%;或-1-丁烯的含量≤0.3体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.3体积%且C4烃的总含量≤2体积%;或-1-丁烯的含量≤0.3体积%且C4烃的总含量≤1体积%;等。 1-butene content of ≤0.4% by volume and the total content of C4 hydrocarbons ≤3% by volume; or 1-butene content of ≤0.4% by volume and the total content of C4 hydrocarbons ≤2% by volume; or-1- alkenyl content ≤0.4% by volume and the total content of ≤1% by volume of C4 hydrocarbons; or 1-butene content of ≤0.3% by volume and the total content of C4 hydrocarbons ≤3% by volume; or 1-butene content of ≤ content of ≤0.3% by volume and the total content of ≤1% by volume of C4 hydrocarbons or 1-butene;; 0.3% by volume and the total content ≤2% by volume of C4 hydrocarbons and the like.

在本明方法中,同时符合至少一个在本文中对气体混合物2中丁烯的总含量施加的限制的气体混合物2是特别有利的。 In the next process, while meeting at least one of the gas limits the total gas mixture of 2-butene content of the applied mixture 2 herein is particularly advantageous.

换言之,适于本发明目的的气体混合物2特别包括符合以下规格搭配之一的那些:-1-丁烯的含量≤1体积%且丁烯的总含量≤1体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.75体积%且丁烯的总含量≤1体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.5体积%且丁烯的总含量≤1体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.3体积%且丁烯的总含量≤1体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.5体积%且丁烯的总含量≤0.75体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.5体积%且丁烯的总含量≤0.5体积%且C4烃的总含量≤3体积%;或-1-丁烯的含量≤0.5体积%且丁烯的总含量≤0.5体积%且C4烃的总含量≤2体积%;等。 In other words, suitable for the purposes of the present invention comprises a gas mixture of the following are in particular those with specifications: -1- butene content of ≤1% by volume and the total content of butene ≤1% by volume and the total content of C4 hydrocarbons ≤ 3% by volume; or content ≤0.75% by volume of 1-butene and butene content of ≤1% by volume of the total and the total content of C4 hydrocarbons ≤3% by volume; or 1-butene content of ≤0.5% by volume and the total content of the total content of ≤1% by volume of butene and C4 hydrocarbons ≤3% by volume; total amount or content of ≤0.3% by volume of 1-butene and butene ≤1% by volume and the total content of C4 hydrocarbons ≤3 % by volume; or the content of ≤0.5% by volume of 1-butene and butene content ≤0.75% by volume of the total and the total content of C4 hydrocarbons ≤3% by volume; or 1-butene content of ≤0.5% by volume and butoxy the total volume of the total content of the alkylene content ≤0.5% by volume and C4 hydrocarbons ≤3%; content or the total content of ≤0.5% by volume of 1-butene and butene content of ≤0.5% by volume of the total C4 hydrocarbons and volume ≤2 %;Wait.

根据本发明,使用以下方法是特别有利的:不仅遵守上述气体混合物2中1-丁烯含量和C4烃总含量和可能的丁烯总含量的组合,而且同时使用含有以下量的除丙烷和丙烯和氧之外的其它组分的气体混合物1′:至少≥0.1体积%或≥0.2体积%或≥0.3体积%或≥0.4体积%或≥0.5体积%或≥0.6体积%或≥0.8体积%或≥1体积%或≥2体积%或≥3体积%或≥5体积%或≥10体积%或≥15体积%或≥20体积%或≥25体积%或≥30体积%(但通常≤80%体积或≤70%体积或≤60%体积或≤50%体积)。 According to the present invention, the following methods are particularly advantageous: not only comply with the gas mixture of composition 2 1-butene content and the total content of C4 hydrocarbons and the total content of butene possible, but at the same time in addition to containing the following amounts of propane and propylene and other components of a gas mixture of oxygen than 1 ':% by volume or at least ≥0.1 ≥0.2 ≥0.3 vol.% or vol.% or vol% or ≥0.4 ≥0.5 ≥0.6 vol% or vol% or ≥0.8% by volume or ≥1 vol% or ≥2% or ≥3 vol% vol% vol or ≥5 vol% or ≥10 or ≥15 or ≥20 vol% vol% vol% or ≥25 or ≥30% by volume (≦ 80% but usually volume or volume or ≤60% ≤70% ≤50% by volume or volume).

在本发明的背景下进行的研究还表明,为了避免在不完全氧化和/或氨氧化中不合意的丙烯的总燃烧,在本发明方法中,气体混合物2中丙烷的含量通常较低是有利的。 Studies carried out in the context of the present invention also shows that in order to avoid incomplete combustion of the total oxidation and / or ammoxidation of propylene is not desirable, in the process of the present invention, the content of the gas mixture of propane 2 is advantageous usually low of. 根据本发明,气体混合物2中丙烷的含量优选为≤60体积%或≤50体积%。 According to the present invention, the content of a gas mixture of propane is preferably 2 vol% or ≤60 ≤50% by volume. 已发现气体混合物2中丙烷的含量为20至40体积%、例如约30体积%是特别有利的。 It has been found in the propane content of the gas mixture 2 is from 20 to 40% by volume, e.g. about 30% by volume is particularly advantageous.

如果忽略在生产腈的情况下使用的任何氨的含量(即也不把任何氨的含量考虑进体积%的基数中),适于本发明方法的气体混合物2因而通常是这样的:首先,遵守根据本发明对其中1-丁烯含量、优选还有丁烯的总含量并特别优选还有C4烃的总含量的限制,且其次,具有以下组分:7至15体积%的O2,5至10体积%的丙烯,15至40体积%的丙烷,通常是25至35体积%,25至60体积%的氮,通常是40至60体积%,总共为1至5体积%的CO、CO2和H2O及0至5体积%的其它成分。 If the content of any ammonia used in the case of producing a nitrile ignored (i.e. the content of any ammonia not take into account the volume% of base), the method of the present invention is adapted to the gas mixture 2 thus generally such that: firstly, compliance according to still limit the total content of 1-butene content which, according to the invention preferably also butene and particularly preferably the total content of C4 hydrocarbons, and secondly, has the following composition: 7-15% by volume to O2,5 10% by volume of propylene, 15 to 40% by volume of propane, usually 25 to 35% by volume, 25 to 60 vol% nitrogen, usually 40 to 60% by volume, a total of 1 to 5% by volume of CO, CO2 and H2O and 0 to 5% by volume of other ingredients.

当使用气体混合物2进行存在于气体混合物2中的丙烯多相催化不完全氧化以制备丙烯醛和/或丙烯酸时,这是特别适用的。 When using a gas mixture of 2 present in the gas mixture of propylene heterogeneous catalysis is not completely oxidized 2 to acrolein and / or acrylic acid, which is particularly suitable.

另外,本发明方法包括的用于丙烯所有多相催化不完全氧化和/或氨氧化的可能的气体混合物2特别包括具有以下组成的那些,这里仍忽略生成腈的任何NH3含量(也是在百分比的基数中):H2O ≤60体积%,通常≤20体积%,一般为0至5体积%;N2≤80体积%,通常≤70体积%,一般为40至60体积%;O2最高可达20体积%,通常为2至20体积%,一般为5至15体积%;CO ≤2体积%,通常≤1体积%,一般为0至0.5体积%; Further, the method of the present invention includes all propylene heterogeneously catalyzed partial oxidation and / or ammoxidation of possible gas mixtures include in particular those having 2, where the content of any NH3 still negligible nitrile of the following composition (in percent is radix): H2O ≤60% by volume, typically ≤20% by volume, typically from 0 to 5 vol%; N2≤80 vol%, typically ≤70 vol%, typically 40 to 60% by volume; the O2 up to 20 vol. %, typically from 2 to 20% by volume, typically 5 to 15 vol%; CO ≤2% by volume, typically ≤1% by volume, typically from 0 to 0.5% by volume;

CO2≤5体积%,通常≤3体积%,一般为0至2体积%;乙烷 ≤10体积%,通常≤5体积%,一般为0至2体积%;乙烯 ≤5体积%,通常≤2体积%,一般为0至0.5体积%;甲烷 ≤5体积%,通常≤2体积%,一般为0至0.2体积%;丙烷 >0,≤50体积%,通常为10至50体积%,一般为20至40体积%;环丙烷 ≤0.1体积%,通常≤0.05体积%,一般为0至150体积ppm;丙炔 ≤0.1体积%,通常≤0.05体积%,一般为0至150体积ppm;丙二烯 ≤0.1体积%,通常≤0.05体积%,一般为0至150体积ppm;丙烯 大于0,≤30体积%,通常≥2、≤20体积%,一般为5至10体积%;H2≤30体积%,通常≤20体积%,一般为0至10体积%;异丁烷 ≤3体积%,优选≤2体积%,经常为0.1至1体积%;正丁烷 ≤3体积%,优选≤2体积%,经常为0.1至1体积%;反- CO2≤5 vol%, typically ≤3% by volume, typically 0-2% by volume; ≤10 vol% of ethane, typically ≤5% by volume, typically 0-2% by volume; ≤5% by volume of ethylene, typically ≤2 vol%, typically from 0 to 0.5% by volume; ≤5% by volume of methane, typically ≤2% by volume, typically from 0 to 0.2% by volume; propane> 0, ≤50% by volume, typically from 10 to 50% by volume, typically 20 to 40% by volume; cyclopropanecarboxylic ≤0.1% by volume, typically ≤0.05% by volume, the volume is generally 0 to 150 ppm; propynyl ≤0.1% by volume, typically ≤0.05% by volume, the volume is generally 0 to 150 ppm; malonic alkenyl ≤0.1% by volume, typically ≤0.05% by volume, the volume is generally 0 to 150 ppm; propylene is greater than 0, ≤30% by volume, usually ≥2, ≤20% by volume, typically 5 to 10 vol%; H2≤30 volume %, typically ≤20% by volume, typically from 0 to 10% by volume; isobutane ≤3% by volume, preferably ≤2% by volume, often 0.1 to 1% by volume; vol% n-butane ≤3, preferably ≤2 volume %, often 0.1 to 1% by volume; trans - 2-丁烯 ≤1体积%,优选≤0.5体积%,经常≥0.003体积%,≤0.1体积%;顺-2-丁烯 ≤1体积%,优选≤0.5体积%,经常≥0.003体积%,≤0.1体积%;1-丁烯 ≤1体积%,优选≤0.5体积%,经常≥0.003体积%,≤0.1体积%;异丁烯 ≤1体积%,优选≤0.5体积%,经常≥0.003体积%,≤0.1体积%;1,3-丁二烯 ≤1体积%,优选≤0.5体积%,经常≥0.003体积%,≤0.1体积%;1,2-丁二烯 ≤1体积%,优选≤0.5体积%,经常≥0至0.01体积%; 2-butene ≤1% by volume, preferably ≤0.5% by volume, often ≥0.003 vol%, ≦ 0.1% by volume; cis-2-butene ≤1% by volume, preferably ≤0.5% by volume, often ≥0.003 vol%, ≤ 0.1% by volume; 1-butene ≤1% by volume, preferably ≤0.5% by volume, often ≥0.003 vol%, ≦ 0.1% by volume; ≤1% by volume of isobutylene, preferably ≤0.5% by volume, often ≥0.003 vol%, ≦ 0.1 vol%; 1,3-butadiene ≤1% by volume, preferably ≤0.5% by volume, often ≥0.003 vol%, ≦ 0.1% by volume; 1,2-butadiene ≤1% by volume, preferably ≤0.5% by volume, often ≥0 to 0.01% by volume;

1-丁炔 ≤0.5体积%,优选≤0.3体积%,经常为0至0.1体积%;且2-丁炔 ≤0.5体积%,优选≤0.3体积%,经常为0至0.1体积%。 1-butyne ≤0.5% by volume, preferably ≤0.3% by volume, frequently from 0 to 0.1% by volume; and 2-butynyl ≤0.5% by volume, preferably ≤0.3% by volume, frequently from 0 to 0.1% by volume.

适于本发明目的的气体混合物2还包括不仅符合上述规格而且同时还符合以下规格的那些:总的其它不饱和C4烃≤0.5体积%,优选≤0.3体积%,经常为0至0.1体积%;总的C5烃≤0.1体积%,通常≤0.05体积%,一般为0至300体积ppm;总的C6-C8烃≤200体积ppm,通常≤150体积ppm,一般为0至30体积ppm;丙酮≤100体积ppm;C1-C4醇≤100体积ppm;C2-C4醛≤100体积ppm;乙炔≤10体积ppm;总的含羰基化合物(以Ni(CO)4计算)≤100体积ppm;离化的氯≤1mg/kg,一般为0至0.2mg/kg;总的含氯化合物以Cl表示≤1mg/kg,一般为0至0.2mg/kg;总的含氟化合物以F表示≤1mg/kg,一般为0至0.2mg/kg;且总的含硫化合物以S表示≤10mg/kg,经常为0至1mg/kg,一般为0至0.1mg/kg;条件是在所有上述情形中,所有丁烯的总含量优选≤1体积%(特别优选≤0.75体积%并非常特别优选≤0.5体积%)并且特别优选同时C4烃的总含量 Those suitable for the purposes of the present invention further comprises a gas mixture not only in the above-described specifications but also meets the following specifications: total other unsaturated C4 hydrocarbons ≤0.5% by volume, preferably ≤0.3% by volume, frequently from 0 to 0.1% by volume; the total volume of ≤0.1% C5 hydrocarbons, typically ≤0.05% by volume, the volume is generally 0 to 300 ppm; total volume of C6-C8 hydrocarbons ≤200 ppm, typically ≤150 ppm by volume, typically from 0 to 30 ppm by volume; acetone ≤ volume 100 ppm; C1-C4 alcohols volume of ≤100 ppm; C2-C4 aldehydes volume of ≤100 ppm; volume of acetylene ≤10 ppm; total carbonyl-containing compound (in 4 calculates Ni (CO)) ≤100 volume ppm; ionizable chloro ≤1mg / kg, typically from 0 to 0.2mg / kg; total chlorine-containing compound represented by Cl ≤1mg / kg, typically from 0 to 0.2mg / kg; total fluorinated compound represented by F ≤1mg / kg, typically from 0 to 0.2mg / kg; and the total sulfur-containing compounds represented by S ≤10mg / kg, often 0 to 1mg / kg, typically from 0 to 0.1mg / kg; with the proviso that in all the above cases, all the D the total content is preferably ≤1% by volume alkylene (particularly preferably ≤0.75% by volume and very particularly preferably ≤0.5% by volume) and particularly preferably at the same time the total content of C4 hydrocarbons ≤3体积%(优选≤2体积%并特别优选≤1体积%)。 ≤3% by volume (preferably ≤2% by volume and particularly preferably ≤1% by volume).

未说明的化合物(组分)优选在本发明的气体混合物2中不存在,即不可检出。 (Component) is preferably a compound not described in the absence of the present invention, the gas mixture 2, i.e., undetectable.

这种气体混合物2一般也可在本发明方法中获得,特别是如果采用所述分离方法将气体混合物1转化为符合根据本发明指定的要求的气体混合物1′,当第一步是使用含>100重量ppm、或≥150重量ppm、或≥200重量ppm的C4烃或例如最高可达6体积%(如0.1体积%或0.5体积%至6体积%)的所述C4烃的粗丙烷进行的时候,特别当它们符合以下规格时:丙烷的含量≥90体积%,通常≥93体积%,一般≥95体积%;丙烷及丙烯的含量≤99.75体积%或≤99.5体积%,通常≤99体积%或≤98体积%,一般≤97体积%;C4烃的总含量≤6体积%,通常≤5体积%,一般≤4体积%;但经常≥0.5体积%或≥1体积%,有时≥2体积%或甚至≥3体积%;1-丁烯的含量≤0.5体积%,通常≤0.3体积%,一般≤0.1体积%;但经常≥5体积ppm,有时≥10体积ppm或甚至≥20体积ppm;丁烯的总含量≤0.5体积%, This gas mixture also generally be obtained in the process of the present invention, in particular if the separation method is the gas mixture is converted to a mixture of 1 line with 'the present invention according to the gas specified requirements, when the first step is containing> the crude propane 100 ppm by weight, or ≥150 ppm by weight, or C4 hydrocarbons ≥200 ppm by weight or volume, for example, up to 6% (e.g., 0.1 vol% or 0.5 vol.% to 6% by volume) of the C4 hydrocarbon performed time, especially when they meet the following specifications: content ≥90% by volume of propane, ≥93% by volume, usually, typically ≥95% by volume; ≤99.75 content of propane and propylene or ≤99.5% by volume% by volume, typically ≤99 vol% or ≤98% by volume, typically ≤97% by volume; the total content of C4 hydrocarbons ≤6% by volume, typically ≤5% by volume, typically ≤4% by volume; vol but often ≥0.5 ≥1% or vol%, the volume of ≥2 % by volume or even ≥3%; 1-butene content of ≤0.5% by volume, typically ≤0.3% by volume, generally ≤0.1% by volume; but often ≥5 ppm by volume, and sometimes even ≥10 ≥20 ppm by volume or ppm by volume; butene total content ≤0.5% by volume, 常≤0.3体积%,一般≤0.1体积%;但经常≥10体积ppm,有时≥20体积ppm或甚至≥30体积ppm;乙烷的含量≤10体积%,通常≤5体积%,一般为0至2体积%;乙烯的含量≤5体积%,通常≤2体积%,一般为0至0.5体积%;甲烷的含量≤5体积%,通常≤2体积%,一般为0至0.2体积%;环丙烷的含量≤0.1体积%;丙烯的含量≤10体积%,通常≤5体积%,一般≤2体积%;丙烷和丙烯之外的C3烃的总含量≤0.3体积%;C5烃的总含量≤O.3体积%;且C6-C8烃的总含量≤600体积ppm。 Often ≤0.3% by volume, generally ≤0.1% by volume; but often ≥10 ppm by volume, and sometimes ≥20 ≥30 ppm by volume or even volume ppm; oxide content of ≤10% by volume, typically ≤5% by volume, typically from 0 to 2 vol%; ethylene content of ≤5% by volume, typically ≤2% by volume, typically from 0 to 0.5% by volume; the content of ≤5% by volume of methane, typically ≤2% by volume, typically from 0 to 0.2% by volume; cyclopropanecarboxylic the content of ≤0.1% by volume; propylene content of ≤10% by volume, typically ≤5% by volume, typically ≤2% by volume; total amount of C3 hydrocarbons other than propane and propylene ≤0.3% by volume; the total content of hydrocarbons ≤O C5 .3% by volume; and the total content of C6-C8 hydrocarbons volume of ≤600 ppm.

适于本发明目的的粗丙烷还包括不仅符合上述规格而且同时还符合以下规格的那些:含氧有机化合物的总含量≤300体积ppm;乙炔的含量≤30体积ppm;离化的氯的含量≤1mg/kg;含氯化合物的总含量以Cl表示≤1mg/kg;含氟化合物的总含量以F表示≤1mg/kg;含硫化合物的总含量以S表示≤10mg/kg(在催化脱氢的情形中,基于存在于其中的丙烷,反应混合物包含1至1000体积ppm、优选1至100体积ppm的含硫化合物(例如H2S和/或二甲硫)可能是有利的,这是因为它们能够,首先,钝化(反应器的)钢组分,例如Ni、Cr和Fe(这可以减少不希望的丙烷的裂化),且其次,活化所用催化剂(参见《低级链烷的催化脱氢》(Catalytic dehydrogenation of lower alkanes),Resasco,DanielE.;Haller,Gary L.,University Oklahoma,USA,Catalysis(1994),11,379-411));条件是1-丁烯的含量优选≤0.1体积%,并特别优选同时丁烯 Suitable for the purposes of the present invention include not only crude propane further meet the above specifications but also those that meet the following specifications: total content of oxygen-containing organic compound volume of ≤300 ppm; a volume content of acetylene ≤30 ppm; chlorine content of ≤ from 1mg / kg; the total content of the chlorine-containing compound represented ≤1mg / kg to Cl; the total content of the fluorine-containing compound represented by F ≤1mg / kg; the total content of sulfur-containing compound represented by S ≤10mg / kg (in catalytic dehydrogenation case, based on the propane present therein, the reaction mixture comprises 1 to 1000 ppm by volume, preferably 1 to 100 ppm by volume of sulfur-containing compounds (e.g. H2S and / or dimethyl sulfide) may be advantageous because they can first, a passivation (reactor) of steel components such as Ni, Cr, and Fe (this may reduce undesirable cracking propane), and secondly, the catalyst activated (see "catalytic dehydrogenation of lower alkanoyl" ( Catalytic dehydrogenation of lower alkanes), Resasco, DanielE;. Haller, Gary L., University Oklahoma, USA, Catalysis (1994), 11,379-411)); with the proviso that 1-butene content is preferably ≤0.1% by volume, and particularly preferably simultaneously butene 总含量≤0.1体积%,并且非常特别优选同时C4烃的总含量≤3体积%或≤2.5体积%或≤2体积%。 The total content of ≤0.1% by volume, very particularly preferably simultaneously, and the total content of C4 hydrocarbons ≤3% by volume or volume percent or ≤2.5 ≤2% by volume.

当这样的气体混合物1作为气体混合物2的组分进行存在于气体混合物1中的丙烯的多相催化气相不完全氧化和/或氨氧化时,在所述条件下定义的粗丙烷的规格一般适于本发明的方法。 When such a mixture as the gas mixture 2 for gas component heterogeneously catalyzed gas phase when present in the gas mixture in a propylene partial oxidation and / or ammoxidation of propane crude specifications defined under the general conditions aptamer in the process of the present invention. 这里,根据本发明,在本发明方法的第一步中,有限的氧化脱氢和/或脱氢转化率具有整体有利的效果,这一事实是有益的。 Here, according to the present invention, in a first step of the method of the present invention, the oxidative dehydrogenation limited and / or dehydrogenation having an integral conversion advantageous effect, the fact is beneficial. 对于存在的各个饱和烃,该转化率一般为≥5摩尔%,但≤30摩尔%,经常≤25摩尔%并常≤20摩尔%。 For each of the saturated hydrocarbons present, the conversion rate is generally ≥5 mol% but ≤30 mol%, and often frequently ≤25 ≤20 mol% mol%.

以上指定的(但还包括所有其它的)适于本发明方法的粗丙烷通常包含至少0.25体积%或至少0.5体积%或至少1体积%、经常至少1.5体积%或至少2体积%并经常至少2.5体积%或至少3体积%的除丙烷和丙烯之外的组分(但这些组分经常≤10体积%,通常≤7体积%并一般≤5体积%)。 Specified above (but including all other) suitable for the process of the present invention generally comprises at least a crude propane 0.25% by volume or at least 0.5% by volume or at least 1% by volume, often at least 1.5 or at least 2% by volume, and often at least 2.5% by volume at least 3% by volume or volume of component (these components are often ≤10% by volume, typically ≤7 vol% and generally ≤5% by volume) than propane and propylene% in addition. 非主要物质的这些含量通常还适用于适于本发明方法的其它粗丙烷,例如不含C4烃的那些。 The content of the non-predominant species also generally applicable to other methods of the invention adapted crude propane, such as those free of C4 hydrocarbons. 但它们可包含≥0.1体积%、或≥0.5体积%、经常最高可达6体积%的C4烃(例如,0.1或0.5体积%到6体积%)。 But they may contain ≥0.1% by volume, or ≥0.5% by volume, frequently up to 6% by volume of C4 hydrocarbons (e.g., 0.1 or 0.5% by volume to 6% by volume). 此外而且同时,它们可包含≥5体积ppm、经常最高可达0.5体积%的丁烯(例如从5体积ppm至0.5体积%)。 Furthermore and at the same, they may contain ≥5 ppm by volume, often up to 0.5% by volume of butene (e.g. from 5 ppm by volume to 0.5% by volume). 而且它们还可同时包含≥5体积ppm、经常最高可达0.5体积%的1-丁烯(例如从5体积ppm至0.5体积%)。 And they may further comprise ≥5 ppm by volume at the same time, often up to 0.5% by volume of butene-1 (e.g. from 0.5 to 5 ppm by volume% by volume).

特别适于本发明目的的粗丙烷还包括不仅符合上述规格而且同时还符合以下规格的那些:Ag≤1μg/kg;Al≤10μg/kg;As≤1μg/kg;Au≤1μg/kg;Ba≤1μg/kg;Be≤1μg/kg;Bi≤1μg/kg;Ca≤2μg/kg;Cd≤1μg/kg;Co≤1μg/kg;Cr≤1μg/kg;Cu≤1μg/kg;Fe≤10μg/kg;Ga≤1μg/kg;Ge≤1μg/kg;Hg≤1μg/kg;In≤1μg/kg;Ir≤1μg/kg;K≤1μg/kg;Li≤1μg/kg;Mg≤1μg/kg;Mn≤1μg/kg;Mo≤1μg/kg;Na≤1μg/kg;Nb≤1μg/kg;Ni≤1μg/kg;Pb≤1μg/kg;Pd≤1μg/kg;Pt≤1μg/kg;Rh≤1μg/kg;Sb≤1μg/kg;Sn≤1μg/kg;Sr ≤1μg/kg;Ta≤1μg/kg;Ti≤1μg/kg;Tl≤1μg/kg;V≤1μg/kg;Zn≤1μg/kg;和Zr≤1μg/kg。 Particularly suitable for the purposes of the present invention further comprises a crude propane not only in the above-described specifications but also those with the following specifications: Ag≤1μg / kg; Al≤10μg / kg; As≤1μg / kg; Au≤1μg / kg; Ba≤ 1μg / kg; Be≤1μg / kg; Bi≤1μg / kg; Ca≤2μg / kg; Cd≤1μg / kg; Co≤1μg / kg; Cr≤1μg / kg; Cu≤1μg / kg; Fe≤10μg / kg; Ga≤1μg / kg; Ge≤1μg / kg; Hg≤1μg / kg; In≤1μg / kg; Ir≤1μg / kg; K≤1μg / kg; Li≤1μg / kg; Mg≤1μg / kg; Mn≤1μg / kg; Mo≤1μg / kg; Na≤1μg / kg; Nb≤1μg / kg; Ni≤1μg / kg; Pb≤1μg / kg; Pd≤1μg / kg; Pt≤1μg / kg; Rh≤ 1μg / kg; Sb≤1μg / kg; Sn≤1μg / kg; Sr ≤1μg / kg; Ta≤1μg / kg; Ti≤1μg / kg; Tl≤1μg / kg; V≤1μg / kg; Zn≤1μg / kg; and Zr≤1μg / kg.

非常特别适于本发明目的的粗丙烷是不仅符合上述规格而且同时还符合以下规格的那些:20℃时的密度=500±2.0kg/m3;20℃时的蒸气压=7.6±0.2bar;水≤10mg/kg;蒸发残留物≤2mg/kg。 Very particularly suitable for purposes of the present invention the crude propane not only meet the above specifications but also those with the following specifications: density at 20 ℃ = 500 ± 2.0kg / m3; 20 ℃ when the vapor pressure = 7.6 ± 0.2bar; water ≤10mg / kg; evaporation residue ≤2mg / kg.

所述规格建立在通过气相色谱法和通过原子吸收光谱法进行的测定上。 Based on the specification by gas chromatography and the measurement was carried out by atomic absorption spectrometry. 蒸发残留物建立在重量分析测定法的基础上。 Evaporation residue based on the weight of the analytical assay. 其通常包含高沸点烃(例如高级石油)。 Which typically comprises high-boiling hydrocarbons (e.g. advanced oil).

未提到的组分优选在粗丙烷中不存在,即不可检出,根据本发明,这是特别适宜的。 Component is not mentioned in the crude preferably absent propane, i.e., undetectable, according to the present invention, which are particularly suitable.

当以再循环模式使用时,本发明的方法是特别重要的。 When used in the recirculation mode, the method of the present invention is particularly important.

在这种情形下,通过已知的分离方法从得自气相不完全氧化和/或氨氧化的产物气体混合物中分离出所需的目标产物,并至少将存在于该产物气体混合物中的未反应的丙烷、通常与其中存在的未反应的丙烯一起再循环至氧化脱氢和/或脱氢步骤和/或再循环至气相不完全氧化和/或氨氧化中。 In this case, from the gas phase partial oxidation by known methods of separation and / or ammoxidation product gas mixture of the desired product was isolated target, and will at least be present in the product gas mixture of unreacted propane, generally recycled with the unreacted propylene present therein to oxidative dehydrogenation and / or the dehydrogenation step and / or recycled to the gas phase partial oxidation and / or ammoxidation. 将目标产物分离之后,通常以这种方式将丙烷和丙烯作为剩余尾气的组分再循环,而无需对该尾气进行中间处理,或者,当进行中间处理(例如在再循环之前分离出其中存在的CO、CO2、H2和/或O2)时,该中间处理也仅具有有限的作用。 After separation of the desired product, usually in such a manner as propane and propene components remaining exhaust gas recirculation, without intermediate processing of the tail gas, or, when intermediate treatment (e.g., where there is isolated prior to recycle CO, CO2, H2 and / or O2) when the intermediate process is also only a limited effect. 例如,甚至当所用粗丙烷仅含很小比例的1-丁烯、其它丁烯和/或其它C4烃(例如C4烃的总含量≥0.01体积%,最高可能达6体积%)时,如果采用气体再循环模式,它们会累积在气体混合物2中,并且它们的浓度会超过根据本发明指定的极限,除非采取特殊的措施。 For example, even when the thick oxide containing only a small percentage of 1-butene with other butene and / or other C4 hydrocarbons (e.g. volume of the total content of C4 hydrocarbons ≥0.01%, the highest possible volume of 6%), if gas recirculation mode, they will accumulate in the gas mixture, and their concentration exceeds the limit specified in accordance with the present invention, unless special measures are taken. 这些措施例如可以包括在分离出目标产物之后,通过精馏和/或通过吸收/解吸和/或汽提和/或通过吸附/解吸和/或通过冷凝和/或通过膜法从剩余的尾气中选择性地分离出C4烃,并仅循环含有其后残留的丙烷和丙烯的尾气。 Such measures may include, after separating the desired product by distillation and / or by absorption / desorption, and / or stripping and / or by adsorption / desorption, and / or by condensation and / or off-gas from the remaining membrane by e.g. selectively separating C4 hydrocarbons, and only thereafter the remaining tail gas containing circulating propane and propylene.

EP-A 938463认为这种分离步骤是不必要的,虽然它推荐原样使用气体混合物1进行不完全氧化,并将基本上任意纯度的粗丙烷用于第一步。 EP-A 938463 that such a separation step is not necessary, although it is recommended to use as a gas mixture incomplete oxidation, and any substantially pure propane for the first step crude.

作为气体再循环模式的替代方案,还可以将所述尾气用于其它用途,以避免不希望的C4烃的累积。 As an alternative gas recirculation mode, the tail gas may also be used for other purposes, in order to avoid undesired accumulation of C4 hydrocarbons. 例如可将它们与存在于其中的丙烷和丙烯一起燃烧以产生电力,和/或用它们制造合成气等等。 For example, they may be present together with the combustion of propane and propylene therein to generate electric power, and / or for producing synthesis gas and the like thereof.

或者,可以根据现有技术中所述的不同的基本方案实施本发明方法。 Alternatively, the method of the present invention may be practiced according to different prior art basic solutions according to.

在最简单的方案中,例如如下列文献教导的那样,在单个反应区内和存在于其中的催化剂装料上实施本发明方法的所有步骤:EP-A 608838、EP-A 529853、DE-A 19835247、EP-A 895809、JP-A 7-232071、JP-A11-169716、EP-A 1192987、JP-A 10-57813、JP-A 2000-37623、JP-A10-36311、WO 00/29105、EP-A 767164、DE-A 10029338、JP-A 8-57319、JP-A 10-28862、JP-A 11-43314、JP-A 11-574719、WO 00/29106、JP-A10-330343、JP-A 11-285637、JP-A 310539、JP-A 11-42434、JP-A 11-343261、JP-A 3423262、WO 99/03825、JP-A 7-53448、JP-A 2000-51693、JP-A11-263745、DE-A 10046672、DE-A 10118814、DE-A 10119933、JP-A2000/143244、EP-A 318295、EP-A 603836、DE-A 19832033、DE-A19836359、EP-A 962253、DE-A 10119933、DE-A 10051419、DE-A10046672、DE-A 10033121、DE-A 101 459 58、DE-A 10122027、EP-A1193240及这些文献中所引参考。 In the simplest embodiment, for example, as taught in the following references, all steps of the method embodiments of the present invention on a single reaction zone and a catalyst charge present therein: EP-A 608838, EP-A 529853, DE-A 19835247, EP-A 895809, JP-A 7-232071, JP-A11-169716, EP-A 1192987, JP-A 10-57813, JP-A 2000-37623, JP-A10-36311, WO 00/29105, EP-A 767164, DE-A 10029338, JP-A 8-57319, JP-A 10-28862, JP-A 11-43314, JP-A 11-574719, WO 00/29106, JP-A10-330343, JP -A 11-285637, JP-A 310539, JP-A 11-42434, JP-A 11-343261, JP-A 3423262, WO 99/03825, JP-A 7-53448, JP-A 2000-51693, JP -A11-263745, DE-A 10046672, DE-A 10118814, DE-A 10119933, JP-A2000 / 143244, EP-A 318295, EP-A 603836, DE-A 19832033, DE-A19836359, EP-A 962253, DE-A 10119933, DE-A 10051419, DE-A10046672, DE-A 10033121, DE-A 101 459 58, DE-A 10122027, EP-A1193240 and these documents are incorporated by reference.

用于催化剂装料中的活性组合物基本上为含有结合在一起的元素Mo、V、两种元素Te和Sb中的至少一种、至少一种选自由Nb、Ta、W、Ti、Al、Zr、Cr、Mn、Ga、Fe、Ru、Co、Rh、Ni、Pd、Pt、La、Bi、B、Ce、Sn、Zn、Si、Na、Li、K、Mg、Ag、Au和In组成的组的元素的多金属氧化物组合物。 A catalyst loading of active composition comprising substantially bound together elements Mo, V, Te and Sb two elements at least one, at least one selected from the group consisting of Nb, Ta, W, Ti, Al, zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, B, Ce, Sn, Zn, Si, Na, Li, K, Mg, Ag, Au and In multimetal oxide composition of the group of elements.

该结合优选含有选自后一元素组的元素Nb、Ta、W和/或Ti,特别优选元素Nb。 The binding element preferably comprises an element selected from the group of Nb, Ta, W and / or Ti, particularly preferably the element Nb.

有关的活性多金属氧化物组合物优选含有化学计量I的上述元素结合:Mo1VbM1cM2d(I),其中M1为Te和/或Sb,M2为至少一种选自由Nb、Ta、W、Ti、Al、Zr、Cr、Mn、Ga、Fe、Ru、Co、Rh、Ni、Pd、Pt、La、Bi、Ce、Sn、Zn、Si、Na、Li、K、Mg、Ag、Au和In组成的组的元素,b为0.01至1,c为>0至1,d为>0至1。 For the above elements active multimetal oxide composition I preferably contains a stoichiometric binding: Mo1VbM1cM2d (I), wherein M1 is Te and / or Sb, M2 is at least one selected from the group consisting of Nb, Ta, W, Ti, Al, zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, Ce, Sn, Zn, Si, Na, Li, K, Mg, Ag, Au and in the group consisting of element, b is from 0.01 to 1, c is> 0 to 1, d is> 0 to 1.

根据本发明,优选M1为Te且M2为Nb、Ta、W和/或Ti。 According to the present invention, preferably M1 and M2 to Te is Nb, Ta, W and / or Ti. M2优选为Nb。 M2 is preferably Nb.

化学计量系数b宜为从0.1至0.6。 Stoichiometric coefficient b is suitably from 0.1 to 0.6. 相应地,化学计量系数c的优选范围是从0.01至1或从0.05至0.4,且d有利的值为从0.01至1或从0.1至0.6。 Accordingly, the preferred range of stoichiometric coefficient c is from 0.01 to 1, or of from 0.05 to 0.4 and d is advantageously from 0.01 to 1 or from 0.1 to 0.6.

如果化学计量系数b、c和d同时处于上述优选的范围,则根据本发明是特别有利的。 If the stoichiometric coefficient b, c and d are simultaneously in the above preferable range, according to the present invention is particularly advantageous.

如果存在于催化剂装料的活性组合物中除氧之外的元素完全是上述元素结合中的一种,则以上所述是特别适用的。 If present in the catalyst composition to the active oxygen charge in the element is a completely incorporated in the above-described elements, the above is particularly suitable.

那么它们特别是式II的活性多金属氧化物组合物:Mo1VbM1cM2dOn(II),其中变量具有为式I指定的含义,且n为由(II)中除氧之外的元素的化合价和出现频率决定的数。 They are particularly of formula II are then active multimetal oxide composition: Mo1VbM1cM2dOn (II), where the variables have the meanings specified for the formula I, the elements other than oxygen and by n (II) valency and frequency of occurrence determined number.

而且,当本发明方法在单区模式下实施时,优选使用如下活性多金属组合物:其首先或者含有上述元素组合中的一种,或者,就除氧之外的元素而言,由它构成而且同时具有如下X-射线衍射图:具有最大值位于衍射角(2θ)22.2±0.5°(h)和27.3±0.5°(i)的反射h和i。 Further, when the method of the present invention in a single mode, is preferably used as the active multimetal composition: it first containing one or combination of the above elements, or, in the terms of the elements other than oxygen, it is composed of while simultaneously having the following X- ray diffraction pattern: a maximum at a diffraction angle (2θ) 22.2 ± 0.5 ° (h) and 27.3 ± 0.5 ° (i) the reflection h and i. 本文中涉及X-射线衍射图的所有数据均基于使用Cu-Kα射线作X-射线而产生的X-射线衍射图(Siemens衍射仪θ-θD-5000,管电压:40kv,管电流:40mA,孔径光阑V20(可变),散射辐射光阑V70(可变),二级单色仪光阑(0.1mm),检测器光阑(0.6mm),测量间隔(2θ):0.02°,每步测量时间:2.4s,检测器:闪烁计数器。 FIG X- ray diffraction (Siemens diffractometer θ-θD-5000, the tube voltage of all data herein relates to X- ray diffraction pattern are based on the use of Cu-Kα ray as X- rays generated by: 40kv, tube current: 40mA, V20 aperture stop (variable), the scattered radiation diaphragm V70 (variable), two monochromator aperture (0.1mm), the detector diaphragm (0.6mm), the measurement interval (2θ): 0.02 °, each step measurement time: 2.4s, detector: scintillation counter.

这些反射的半高宽度可以非常小或者非常明显。 The half width of the reflection can be very small or very obvious.

对于本发明方法来说,在上述活性多金属氧化物组合物中,特别优选除了反射h和i之外,其X射线衍射图还具有最大值在28.2±0.5°(k)处的反射k的那些。 For the method of the present invention, in the above-described active multimetal oxide composition, especially preferred in addition to the reflection h and i, X-ray diffraction pattern further has a maximum reflection k is 28.2 ± 0.5 ° (k) at the Those ones.

在后者中,根据本发明,又优选在X射线衍射图中其反射h是强度最强且半高宽度不超过0.5°的那些,并非常优选其反射i和反射k分别具有≤1°的半高宽度且具有强度Pi和Pk的那些,Pi和Pk符合关系0.2≤R≤0.85,优选0.3≤R≤0.85,更优选0.4≤R≤0.85,特别优选0.65≤R≤0.85,甚至更优选0.67≤R≤0.75并非常特别优选R=0.70至0.75或R=0.72,其中R是由下式定义的强度比:R=Pi/(Pi+Pk)。 In the latter, according to the present invention, and preferably in the X-ray diffraction intensity of the strongest reflection and h is the width at half maximum does not exceed 0.5 ° those, and is preferably reflective and reflective i k ≤1 °, respectively, with the and those having a half-width, intensity Pi and Pi and Pk, Pk satisfies the relationship 0.2≤R≤0.85, preferably 0.3≤R≤0.85, more preferably 0.4≤R≤0.85, particularly preferably 0.65≤R≤0.85, and even more preferably 0.67 ≤R≤0.75 and very particularly preferably of 0.75 or to R = 0.70 R = 0.72, where R is the intensity ratio defined by the formula: R = Pi / (Pi + Pk).

上述X射线衍射图优选不具有其最大值位于2θ=50.0±0.3°的反射。 The X-ray diffraction pattern having no reflection maximum preferably located at 2θ = 50.0 ± 0.3 ° of.

就本文而言,X射线衍射图中反射强度的定义是DE-A 19835247、DE-A 10122027、DE-A 10051419和DE-A 10046672中给出的定义。 For purposes herein, the definition of the X-ray diffraction intensity of the reflection is DE-A 19835247, DE-A 10122027, DE-A 10051419 defined and DE-A 10046672 given. 这同样适用于半高宽度的定义。 The same applies to the definition of half-width.

除了反射h、i和k之外,根据本发明可以有利地使用的活性多金属组合物的上述X射线衍射图还具有其最大值位于以下衍射角(2θ)的反射:9.0±0.4°(l),6.7±0.4°(o)和 In addition to the reflection h, i and k, based on the X-ray diffraction multiple active metal composition of the present invention can be advantageously used also has its maximum at the following diffraction angles (2 [Theta]) reflections: 9.0 ± 0.4 ° (l ), 6.7 ± 0.4 ° (o) and

7.9±0.4°(p)。 7.9 ± 0.4 ° (p).

X射线衍射图具有其最大值位于衍射角(2θ)45.2±0.4°(q)的额外的反射,这样也是有利的。 X-ray diffraction pattern having its maximum additional reflector located in a diffraction angle (2θ) 45.2 ± 0.4 ° (q), so is also advantageous.

X射线衍射图经常还具有位于29.2±0.4°(m)和35.4±0.4°(n)的反射。 X-ray diffraction pattern further has a reflection often located 29.2 ± 0.4 ° (m) and 35.4 ± 0.4 ° (n) a.

式I和式II定义的元素结合物以纯i相存在也是有利的。 Of Formula I and Formula II binding was defined by the elements present in pure phase i also advantageous. 如果催化活性的氧化物组合物还包含k相,其X射线衍射图除上述反射之外还包括其最大值位于以下衍射角(2θ)的反射:36.2±0.4°和50±0.4°(在本文中,术语i相和k相以DE-A 10122027和DE-A 10119933中的定义使用)。 If the catalytically active oxide composition further comprises a phase k, X-ray diffraction graphs except the reflector further comprises a maximum value at the following diffraction angles (2 [Theta]) reflections: 36.2 ± 0.4 ° and 50 ± 0.4 ° (herein , the phase term i and k phase DE-a 10122027 and DE-a 10119933 defined in use).

如果将反射h指定为强度100,就本发明而言,有利的是反射i、l、m、n、o、p、q在相同的强度标下具有下列强度:i:5至95,通常为5至80,经常为10至60;l:1至30;m:1至40;n:1至40;o:1至30;p:1至30,和q:5至60。 If the reflection intensity is designated as 100 h, in terms of the present invention, it is advantageous that the reflection i, l, m, n, o, p, q has the following strength at the same intensity scale: i: 5 to 95, usually 5 to 80, often from 10 to 60; l: 1 to 30; m: 1 to 40; n: 1 to 40; o: 1 to 30; p: 1 to 30, and and q: 5 to 60.

如果X射线衍射图除上述那些之外还具有其它反射,则它们的半峰宽度通常≤1°。 If the X-ray diffraction in addition to those described above also have other reflection, they generally half peak width ≤1 °.

根据本发明使用的式II的活性多金属氧化物组合物的比表面积、或者含有式I的元素组合的多金属氧化物组合物的比表面积通常为1至30平方米/克(BET表面积,氮气),特别当它们具有如上所述的X射线衍射图时尤为如此。 According to the present invention, the specific surface area The specific surface area of ​​formula II used in active multimetal oxide composition of Formula I or a combination of elements comprising multimetal oxide composition is usually 1 to 30 m2 / g (BET surface area, nitrogen ), in particular, especially when they have an X-ray diffraction pattern described above.

所述活性多金属氧化物组合物的制备在这些组合物的上下文中引用的现有技术中有公开。 Preparation of the prior art active multimetal oxide compositions cited in the context of these compositions there is disclosed. 这方面的现有技术参考文献特别包括DE-A 10122027、DE-A 10119933、DE-A 10033121、EP-A 1192987、DE-A 10029338、JP-A2000-143244、EP-A 962253、EP-A 895809、DE-A 19835247、WO 00/29105、WO 00/29106、EP-A 529853、EP-A 608838(在后两种文献的所有实施例中,使用喷雾干燥作为干燥方法,例如在300至350℃的入口温度和100至150℃的出口温度下、逆流或并流进行)。 This prior art references include in particular DE-A 10122027, DE-A 10119933, DE-A 10033121, EP-A 1192987, DE-A 10029338, JP-A2000-143244, EP-A 962253, EP-A 895809 , DE-a 19835247, WO 00/29105, WO 00/29106, EP-a 529853, EP-a 608838 (in all embodiments of the latter two documents, using a spray drying as a drying method, for example, at 300 to 350 deg.] C at inlet temperature and outlet temperature of 100 to 150 deg.] C, the countercurrent or cocurrent flow).

对于本发明方法的单区实施方案,所述活性多金属氧化物组合物可以原样(即以粉末形式)使用,也可以在进行成型获得合适的几何形状之后使用(参见例如DE-A 10051419中的涂覆催化剂和DE-A 10122027中的几何外形方案)。 For embodiments of the method of the present invention a single region, the active multimetal oxide composition as such can (i.e., in powder form) used during molding can be obtained after the use of suitable geometry (see DE-A 10051419, for example, in and the geometry of the coated catalysts of DE-a 10122027). 它们特别可用于制备丙烯醛和/或丙烯酸及用于制备丙烯腈。 They are particularly useful for the preparation of acrolein and / or acrylic acid and for the preparation of acrylonitrile.

单区方案以所用的、能够催化本发明方法所有步骤的催化剂为基础。 Single zone programs to be used, capable of catalysing the process of the invention is based on all the steps of the catalyst.

反应可以在固定催化剂床上进行,也可以在催化剂流化床或移动床上进行。 The reaction may be carried out in a fixed catalyst bed, the catalyst may be performed in a fluidized bed or moving bed. 相应的方法说明可以在现有技术文献中找到。 Corresponding methods described in the prior art can be found in the literature. 如果本发明方法是以例如用于在单区操作模式下制备丙烯酸的固定床反应进行的,反应宜在管中装填了催化剂的壳管式反应器中进行。 If the method of the present invention is a fixed bed reactor for producing acrylic acid, for example, in the single mode operating region, the reaction should be packed with a shell and tube reactor the catalyst in the tube for. 通常将液体(一般是盐熔融物)作为传热介质通过催化剂管的周围。 Typically a liquid (usually molten salts) as a heat transfer medium around the catalyst tubes. 或者,也可以使用热板式反应器,其中催化剂装料以平面排列存在于冷却板之间。 Alternatively, heat may be used a plate reactor, wherein the catalyst charge in a planar alignment exists between the cooling plate.

反应气体混合物相对于盐浴并流或逆流通过反应器中的催化剂管。 With respect to the reaction gas mixture and salt bath or countercurrent flow through the catalyst in the reactor tube. 盐浴本身可以具有与催化剂管纯粹平行的流。 Salt bath and the catalyst itself may have a purely parallel flow. 但是,当然也可以在其上叠加横流。 However, of course, the cross flow may be superimposed thereon. 总体而言,盐浴可以以曲流方式在催化剂管的周围流动,只有在反应器上方观察时,才看到该流与反应气体混合物并流或逆流。 In general, the salt bath can flow around the catalyst tubes in a meandering manner, only when viewed from above the reactor, only to see the flow of the reaction gas mixture cocurrent or countercurrent. 适于本发明方法的壳管式反应器在例如EP-A 700714和EP-A 700893中有公开。 Shell and tube type reactor suitable for the process of the present invention are disclosed in, for example, 700 714 and EP-A 700893 EP-A in.

对于本发明方法的单区方案,反应气体起始混合物的不同的可能组成可以从有关该方法引用的现有技术中获得。 For the single zone embodiment of the method of the present invention, the reaction gas starting mixture of different composition may be obtained from the prior art relating to the process cited therein.

为制备丙烯酸,反应气体起始混合物的组成通常在下述范围(摩尔比):丙烷∶氧∶H2O∶其它成分(主要是惰性稀释气体)=1∶(0.1-10)∶(>0-50)∶(>0-50)。 To prepare the acrylic acid composition of the starting reaction gas mixture is generally in the following ranges (molar ratio): propane: oxygen :H2O: other components (mainly inert diluent gas) 1: = (0.1-10): (> 0-50) : (> 0-50).

上述比率优选为1∶(0.5-5)∶(1-30)∶(1-30)。 1: above ratio is preferably (0.5-5): (1-30): (1-30).

当所述其它成分主要是分子氮时,上述范围是特别适用的。 When the additional components are mainly molecular nitrogen, the above range is particularly suitable. 反应温度一般为250至550℃(如果忽略反应气体混合物中的额外的氨含量,氨氧化的条件与此相当(参见例如EP-A 929853))。 The reaction temperature is generally 250 to 550 deg.] C (the reaction conditions are ignored if additional ammonia content in the gas mixture, the oxidation of ammonia with an equivalent (see, e.g. EP-A 929853)).

丙烷在本发明方法单区方案的固定床催化剂装料上的空间速度可以是例如10至500标准升/升(固定床)·小时。 Propane space velocity in the fixed bed catalyst charge method of the present invention may be a single program area, for example 10 to 500 Nl / l (fixed bed) per hour. 反应气体起始混合物的空间速度通常在100至10000标准升/升·小时的范围,经常在500至5000标准升/升·小时的范围。 Space velocity of the reaction gas starting mixture is usually from 100 to 10,000 standard liters / liter and hour, often 500 to 5000 Nl / liter per hour.

目标产物(例如丙烯酸)可以以本身已知的方式,例如如DE-A10122027中所述那样,从所获产物气体混合物中分离,即,存在于产物气体混合物中的丙烯酸可以例如通过吸收到高沸点惰性疏水性有机溶剂(例如二苯醚和联苯的混合物,其还可以含有例如邻苯二甲酸二甲酯的添加剂)中而分离。 Desired product (e.g., acrylic acid) may be in a manner known per se, for example as described in the above DE-A10122027, isolated from the resulting product gas mixture, i.e., present in the product gas mixture by absorption, for example, acrylic acid can be high boiling point inert hydrophobic organic solvent (e.g. a mixture of diphenyl ether and biphenyl, which may further contain, for example, dimethyl phthalate additives) are separated. 然后对获得的吸收剂与丙烯酸的混合物以本身已知的方式通过精馏、萃取和/或结晶进行处理,制得纯丙烯酸。 The mixture was then absorber and acrylic acid obtained is treated in a manner known per se by rectification, extraction and / or crystallization to give the pure acid. 或者,丙烯酸与产物气体混合物的初步分离也可以如例如DE-A 10053086、DE-A 19627847、DE-A19740253、DE-A 19740252、DE-A 19606877和DE-A 19740253描述的那样通过分凝作用进行。 Alternatively, the initial separation of acrylic acid from the product gas mixture may be as, for example, DE-A 10053086, DE-A 19627847, DE-A19740253, DE-A 19740252, as by fractional condensation DE-A 19606877 and DE-A 19740253 describes the . 然后,所获丙烯酸冷凝物可以进一步纯化,例如通过分级结晶(例如悬浮结晶和/或分层结晶)进行。 Then, the resulting acrylic acid condensate may be further purified, for example by fractional crystallization (e.g., suspension crystallization and / or crystalline layered).

初步分离丙烯酸后仍然残留的尾气混合物特别包含未反应的丙烷和可能未反应的丙烯。 After the initial separation of a mixture of acrylic acid still remaining tail gas comprising propane and propylene may in particular unreacted unreacted.

取决于该尾气混合物和所用氧源(无论是纯氧、含氧惰性气体还是空气)中1-丁烯的含量、丁烯的总含量和C4烃的总含量,该尾气混合物可以就这样再循环。 Depending on the off-gas mixture and the source of oxygen used (either pure oxygen, oxygen-containing inert gas or air) 1-butene content, and the total content of the total content of C4 hydrocarbons butene, so that the exhaust gas mixture may be recycled . 也可以将其分为相同组成的两个部分,并仅将一部分再循环,将另一部分吹出(例如将其送去焚化或作其它用途(如生产合成气))。 May be divided into two portions of identical composition and only a portion is recycled, the other of the outlet (e.g. sent to incineration or other purposes (e.g., the production of synthesis gas)). 当然也可以用尾气混合物的总量进行后一操作。 Of course, an operation may be performed after the total amount of the exhaust gas mixture.

如果尾气混合物中存在较高比例的根据本发明不希望的C4组分和/或较高比例的其它不希望的组分,存在于尾气混合物中的丙烷和任何丙烯可以例如通过分压净化(可适宜地选择分离系数)而分离出,然后再循环至本发明的方法中并与反应气体起始混合物中的粗丙烷和其它组分结合。 If the exhaust gas present in the mixture according to the present invention, a higher proportion of the undesired components C4 and / or other undesirable components higher proportion of exhaust gas present in the mixture of propane and propylene can be any purification, for example by dividing (available the method suitably selected separation factor) and the separated and then recycled to the present invention taken in conjunction with the starting reaction gas mixture of propane and other components of the crude. 但是,对于本发明来说,使尾气与在萃取装置中优先吸收C3烃的疏水性有机溶剂接触(例如使其通过该有机溶剂)可能就足够了。 However, for the present invention, so that the exhaust gas into contact with a hydrophobic organic solvent preferentially absorb C3 hydrocarbons in the extraction apparatus (e.g., passed through the organic solvent) may be sufficient. 然后,吸收的丙烷和可能的丙烯可以通过解吸和/或用空气(无论如何都将需要空气作为氧源)汽提而再次释放出来,并再循环至本发明方法。 Then, propane and propylene may be absorbed by desorption and / or air (air would be needed in any case as an oxygen source) and is released again stripped and recycled to the process of the present invention. 当然,也可以使用DE-A10059122中描述的方法从产物混合物中分离出丙烯酸。 Of course, also possible to use a method described in DE-A10059122 product mixture is separated from the acrylic acid. 当然也可以用细碎的(如胶态的)材料(例如二氧化硅、二氧化钛、氧化铝、氧化锆和氧化铌)稀释推荐用于单区方案的活性多金属氧化物组合物,以用于本发明的方法中。 Of course, use may also be finely divided (e.g. colloidal) material (e.g., silica, titania, alumina, zirconia and niobium oxide) dilution scheme recommended for the active region of a single multi-metal oxide compositions, for use in the present the method of the invention.

稀释剂与活性组合物的质量比最高可达9(稀释剂)∶1(活性组合物),即,可能的质量比有例如6(稀释剂)∶1(活性组合物)和3(稀释剂)∶1(活性组合物)。 And the active mass of diluent composition ratio of up to 9 (diluent) to 1 (active composition), i.e., for example, may be 6 mass ratio (diluent) to 1 (active composition) and 3 (diluent ) to 1 (active composition). 稀释剂可以如DE-A 10122027中描述的那样在煅烧前或煅烧后加入。 As diluents can be added before or after calcination or calcination DE-A 10122027 describes. 当然,如例如JP-A 3-170445中描述的其它催化剂系统也可用于本发明方法的单区方案。 Of course, other catalyst systems as described for example in the JP-A 3-170445 can also be used for a single region of the method of the present invention.

当本发明方法在一个反应区内实现时,这相当于气体混合物1和气体混合物2是相同的。 When the method of the present invention is implemented in a reaction zone, which corresponds to the gas mixture and a gas mixture is the same. 当根据本发明方法对于本发明方法的产物气体混合物中1-丁烯和其它C4烃的含量指定的极限被超出时,特别要利用本发明方法。 When the method according to the present invention has been exceeded for the product gas mixture of the method of the present invention, the content of 1-butene and other C4 hydrocarbons specified limits, in particular to the use of the method of the present invention.

根据本发明,如例如EP-A 938463、EP-A 117146、DE-A 3313573、GB-A 2118939、US-A 3161670、WO 01/96270、EP-A 731077、DE-A19837520、DE-A 19837517、DE-A 19837519、DE-A 19837518、DE-A19837520、DE-A 10131297和DE-A 10211275描述的那样,该方法优选在超过一个的反应区中进行。 According to the present invention, as for example EP-A 938463, EP-A 117146, DE-A 3313573, GB-A 2118939, US-A 3161670, WO 01/96270, EP-A 731077, DE-A19837520, DE-A 19837517, DE-a 19837519, DE-a 19837518, DE-A19837520, DE-a 10131297 and DE-a 10211275 described above, the process is preferably carried out in more than one reaction zone.

“超过一个的反应区”是指,首先且最主要地,本发明方法的至少一个步骤是在至少部分可独立选自本发明方法中其它步骤的条件的条件下进行的,或者,仅在次要程度上,这些至少部分相互独立的反应条件是在反应过程的一个且相同的步骤中实现的(后者是对于一个步骤采用了多区模式(具有可相互独立设置的温度区)的情况,如例如DE-A 19948241、DE-A19927624、DE-A 19910508、DE-A 19910506和DE-A 19948248描述的)。 "More than one reaction zone" means, first and most important, the process of the present invention, at least one step is carried out at least partially independently selected from the conditions of the other process of the invention the step of conditions, or, at times only to the extent, at least partially independent of these reaction conditions are implemented in a case where the same reaction and process steps (for the latter step employs a multi-mode region (region having a temperature can be set independently of each other), and as for example DE-a 19948241, DE-A19927624, DE-a 19910508, DE-a 19910506 and DE-a 19948248 description). 例如,如果本发明方法包括例如两个步骤,第一步中使用的催化剂和催化剂装料可以例如不同于第二步中使用的催化剂和催化剂装料,或者两个步骤可以使用相同的催化剂和催化剂装料,但是两个步骤中的反应温度可以独立地选择或调整。 For example, if the method of the present invention include, for example two steps, the first step catalyst and catalyst loading may be used, for example, and is different from the catalyst used in the catalyst charge in the second step, or the two steps may be using the same catalyst and catalyst charging, but the reaction temperature in the two steps may be independently selected or adjusted. 自然也可使用二者的结合。 Natural combination of the two may also be used.

多区方案的优势在于原则上它可以使反应条件更好地适应本发明方法各个步骤的需要。 Advantages Multi-zone approach is that in principle it can make the reaction conditions to better adapt to the various steps of the method of the present invention.

该优势是从使用分子氧将丙烯多相催化气相不完全氧化为丙烯酸而熟知的。 The advantage of using molecular oxygen from the gas phase propylene heterogeneously catalyzed partial oxidation to acrylic acid and known.

该反应原则上是在两个延反应坐标相继的步骤中进行的,第一步生成丙烯醛,第二步由丙烯醛生成丙烯酸。 The reaction is carried out on the principle of two successive steps in the extension reaction coordinate, the first step acrolein to acrylic acid from acrolein second step.

该反应方案以本身已知的方式提供了在两个串联的氧化区内根据本发明对存在于气体混合物2中的丙烯进行不完全氧化的可能性,这两个氧化区的每一个中使用的氧化催化剂能够被最优化(这种灵活性还可以使丙烯的不完全氧化停止在丙烯醛阶段,并使丙烯醛可以被分离)。 The reaction scheme in a manner known per se provides the possibility of incomplete oxidation of propylene present in the gas mixture 2 in accordance with the invention the oxidation zone in two series, each of the two used in the oxidation zone the oxidation catalyst can be optimized (this flexibility also allows the partial oxidation of propylene to acrolein stop stage, and acrolein may be separated). 在第一氧化区中(丙烯→丙烯醛),通常优选基于含有元素组合Mo-Bi-Fe的多金属氧化物的催化剂,而基于含有元素组合Mo-V的多金属氧化物的催化剂(例如在本文中推荐用于单区方案的那些)通常优选用于第二氧化区(丙烯醛→丙烯酸)。 In a first oxidation zone (propylene → acrolein) is generally preferred based catalyst comprising elements in combination Mo-Bi-Fe multi-metal oxides, and catalysts based on multimetal oxide comprising the elements Mo-V is a combination (e.g. recommended for those herein) single-zone scheme generally preferred for the second oxidation zone (acrolein → acrylic acid). 但原则上这两个反应步骤也可以在单反应区中于单催化剂上进行。 However, these two reaction steps may be carried out in principle on a single catalyst in a single reaction zone.

一般而言,在本发明方法中,第一步宜在独立的反应区中进行。 Generally, in the process of the present invention, the first step should be conducted in a separate reaction zone.

在丙烷氧化脱氢的情形中,这可以使用分子氧将丙烷均相和/或多相催化气相氧化脱氢为丙烯而进行。 In the case of oxidative dehydrogenation of propane, the propane which may be homogeneous and / or heterogeneously catalyzed dehydrogenation to propylene gas phase oxidation is carried out using molecular oxygen. 可以使用空气、纯分子氧或富含分子氧的空气作为分子氧源。 It can be air, pure molecular oxygen or molecular oxygen-enriched air as molecular oxygen source.

如果将反应区配置为均相氧化脱氢,这原则上可如例如US-A3,798,283、CN-A 1105352、Applied Catalysis,70(2)1991,pp.175-187、Catalysis Today 13,1992,pp.673-678和DE-A 19622331中描述的那样进行。 If the reaction zone configured as a homogeneous oxydehydrogenation, this principle may be as described for example US-A3,798,283, CN-A 1105352, Applied Catalysis, 70 (2) 1991, pp.175-187, Catalysis Today 13,1992, pp.673-678 and performed as described in DE-a 19622331. 适宜的氧源是空气。 Suitable oxygen source is air. 均相氧化脱氢的温度宜选择在300至700℃的范围,优选为400至600℃,特别优选为400至500℃。 The temperature of the homogeneous oxydehydrogenation should choose a range of 300 to 700 deg.] C, preferably 400 to 600 ℃, particularly preferably from 400 to 500 ℃. 工作压力可以为0.5至100bar,特别是1至10bar。 Operating pressure may range from 0.5 to 100bar, in particular 1 to 10bar. 停留时间通常为0.1或0.5至20秒,优选为0.1或0.5至5秒。 The residence time is generally from 0.1 or 0.5 to 20 seconds, preferably from 0.1 or 0.5 to 5 seconds.

至于反应器,可以使用例如管式炉或壳管式反应器,例如使用烟道气作为传热介质的逆流管式炉或使用盐熔融物作为传热介质的壳管式反应器。 As for the reactor, can be used, for example a tube furnace or a shell and tube reactor, such as flue gas countercurrent heat transfer medium tube furnace or a shell and tube reactor using a salt melt as the heat transfer medium. 起始混合物中丙烷与氧的比率优选为0.5∶1至40∶1,特别是1∶1至6∶1,更优选2∶1至5∶1。 Starting mixture of propane to oxygen ratio is preferably 0.5 to 40:1, especially 1:1 to 6:1, more preferably 2 to 5:1. 起始混合物可进一步包含其它组分,优选惰性组分(就本文而言,惰性组分优选为反应进行到小于5摩尔%的程度、优选小于3摩尔%并特别优选小于1摩尔%的组分;它们非常特别优选根本不进行反应),例如水、二氧化碳、一氧化碳、氮、稀有气体、其它烃(例如存在于粗丙烷中的次要组分)和/或丙烯等。 Components of the starting mixture may further contain other components, preferably in an inert components (For purposes herein, the inert component is preferably the reaction occurs to an extent less than 5 mole percent, preferably less than 3 mol% and particularly preferably less than 1 mol% ; very particularly preferably they did not react), for example, water, carbon dioxide, carbon monoxide, nitrogen, noble gases, other hydrocarbons (e.g., propane is present in the other coarse secondary components) and / or propylene. 这些组分还可以包括再循环气的组分。 These components may also include components of the recycle gas.

如果丙烷的氧化脱氢是多相催化氧化脱氢,它原则上可以如例如下述文献中描述的那样进行:US-A 4788371、CN-A 1073893、Catalysis Letters23(1994),103-106、W.Zhang,《高等学校化学学报》,14(1993),566、Z.Huang,《石油化工》,21(1992)592、WO 97/36849、DE-A 19753817、US-A3862256、US-A 3887631、DE-A 19530454、US-A 4341664、J.of Catalysis167,560-569(1997)、J.of Catalysis 167,550-559(1997)、Topics in Catalysis3(1996)265-275、US-A 5086032、Catalysis Letters 10(1991),181-192、Ind.Eng.Chem.Res.1996,35,14-18、US-A 4255284、Applied Catalysis A:General,100(1993),111-130、J.of Catalysis 148,56-67(1994)、V.CortésCorberán and S.Vic Bellón (Ed.),New Developments in SelectiveOxidation II,1994、Elsevier Science BV,pp.305-313、3rd World Congresson Oxidation Catalysis、RKGrasselli,STOyama,AMGaffney and JELyons(Ed.),1997,Elsevier Science BV,p.375以下或DE-A 19837520、DE-A 19837517、DE-A 198 If the oxidation is a heterogeneously catalyzed dehydrogenation of propane oxidative dehydrogenation, for example, as it can in principle be carried out as described in the following references: US-A 4788371, CN-A 1073893, Catalysis Letters23 (1994), 103-106, W .Zhang, US-A3862256 "chemical Journal", 14 (1993), 566, Z.Huang, "petrochemical", 21 (1992) 592, WO 97/36849, DE-A 19753817,, US-A 3887631 , DE-A 19530454, US-A 4341664, J.of Catalysis167,560-569 (1997), J.of Catalysis 167,550-559 (1997), Topics in Catalysis3 (1996) 265-275, US-A 5086032 , Catalysis Letters 10 (1991), 181-192, Ind.Eng.Chem.Res.1996,35,14-18, US-A 4255284, Applied Catalysis A: General, 100 (1993), 111-130, J. of Catalysis 148,56-67 (1994), V.CortésCorberán and S.Vic Bellón (Ed.), New Developments in SelectiveOxidation II, 1994, Elsevier Science BV, pp.305-313,3rd World Congresson Oxidation Catalysis, RKGrasselli, STOyama, AMGaffney and JELyons (Ed.), 1997, Elsevier Science BV, p.375 or less, or DE-A 19837520, DE-A 19837517, DE-A 198 37519、DE-A 19837518。 37519, DE-A 19837518. 在这种情况下,也可以用空气作氧源。 In this case, air can also be used as the oxygen source. 但此处氧源经常包含至少90摩尔%的分子氧,通常包含至少95摩尔%的氧。 But here the oxygen source is often comprise at least 90 mol% of molecular oxygen, typically comprising at least 95 mole% oxygen.

对适于多相催化氧化脱氢的催化剂没有特别的限制。 The catalyst is not particularly limited adapted heterogeneously catalyzed oxydehydrogenation. 本领域技术人员已知的且能够将丙烷氧化为丙烯的所有氧化脱氢催化剂都是合适的。 Those skilled in the art all known oxidative dehydrogenation catalysts for propane oxidation and propylene can be are suitable. 特别地,可使用所有在上述文献中提到的氧化脱氢催化剂。 In particular, oxidative dehydrogenation catalysts can be used in all the above mentioned documents. 合适的催化剂包括例如含有MoVNb氧化物或焦磷酸氧钒的氧化脱氢催化剂,如果合适,还含有助催化剂。 Suitable catalysts include, for example, oxidative dehydrogenation catalysts comprising MoVNb oxides or vanadyl pyrophosphate, if appropriate, further containing cocatalyst. 可用的氧化脱氢催化剂的一个实例是还被推荐用于单区方案的催化剂,其包含具有Mo、V、Te、O和X作主要成分的混合金属氧化物,其中X为至少一种选自铌、钽、钨、钛、铝、锆、铬、锰、镓、铁、钌、钴、铑、镍、钯、铂、锑、铋、硼、铟、硅、镧、钠、锂、钾、镁、银、金和铈的元素(参见EP-A 938463和EP-A 167109)。 One example of oxidative dehydrogenation catalyst available is also recommended for single zone embodiment of the catalyst, which comprises a Mo, V, Te, O and X as a main component of the mixed metal oxide, wherein X is at least one selected from niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, gallium, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium, silicon, lanthanum, sodium, lithium, potassium, magnesium, silver, gold, cerium element (cf. EP-a 938463 and EP-a 167109). 其它特别可用的氧化脱氢催化剂是多金属氧化物组合物或DE-A 19753817的催化剂A和DE-A 19838312中的催化剂,其中多金属氧化物组合物或在第一个文献中作为优选催化剂提到的催化剂A是特别有利的。 Particularly useful other oxidative dehydrogenation catalysts are multimetal oxide composition of catalyst A or DE-A and DE-A 19838312 19753817 in the catalyst, wherein the multimetal oxide composition or as mentioned in the first preferred catalysts literature a catalyst to be particularly advantageous. 这意味着特别可用的活性组合物是式III的多金属氧化物组合物:M1aMo1-bM2bOx(III),其中M1=Co、Ni、Mg、Zn、Mn和/或Cu,M2=W、V、Te、Nb、P、Cr、Fe、Sb、Ce、Sn和/或La,a=0.5-1.5,b=0-0.5且x=由(III)中除氧之外的元素的化合价和丰度确定的数。 This means that particularly useful compositions are of Formula III active multimetal oxide compositions: M1aMo1-bM2bOx (III), where M1 = Co, Ni, Mg, Zn, Mn and / or Cu, M2 = W, V, Te, Nb, P, Cr, Fe, Sb, Ce, Sn and / or La, a = 0.5-1.5, b = 0-0.5 x = the valency and (III) of the elements other than oxygen abundance determined number.

原则上,合适的活性组合物(III)可以以简单的方式如下制备:由它们基本组分的合适来源制造非常均匀的、优选细碎的具有对应于它们化学计量的组成的干燥混合物,并于450至1000℃对该混合物进行煅烧。 In principle, suitable active composition (III) may be prepared in a simple manner as follows: Suitable sources of components made from them is substantially uniform, preferably finely divided dry mixture having a composition corresponding to their stoichiometry, and 450 to 1000 ℃ the mixture is calcined. 活性多金属氧化物组合物(III)的基本组分的可能来源是氧化物,和/或可以至少在氧的存在下通过加热转化为氧化物的化合物。 Possible sources of essential components of the multi-active metal oxide composition (III) is an oxide, and / or may at least in the presence of oxygen by heating the compound into an oxide. 这些化合物特别包括卤化物、硝酸盐、甲酸盐、草酸盐、柠檬酸盐、乙酸盐、碳酸盐、氨络合物盐、铵盐和/或氢氧化物。 These compounds include, in particular halides, nitrates, formates, oxalates, citrates, acetates, carbonates, ammine complex salts, ammonium salts and / or hydroxides. 用于制备多金属氧化物组合物(III)的起始化合物的均匀混合可以以干法实现(例如制备成细碎的粉末),或者以湿法实现(例如使用水作液体介质)。 Uniformly mixing the starting compounds for preparing multimetal oxide composition (III) may be used to implement (e.g., prepared as a finely divided powder) in a dry or wet process implemented (e.g., using water as the liquid medium). 多金属氧化物组合物(III)既可以以粉末形式使用,也可以在成型为特定的催化剂外形后使用;在后一种情形下,成型可以在最终煅烧之前或之后进行。 Multi-metal oxide composition (III) may be used in powder form, may be used in molded shape after a specific catalyst;, molding may be performed before or after the final calcination in the latter case. 可以使用全活性催化剂,但粉末状活性组合物或前体组合物的成型也可以通过将其施用到预成型的惰性催化剂载体上而实现。 Full activity of the catalyst may be used, but the powdered active composition or shaped precursor composition may be applied by an inert catalyst support onto which the preform is achieved. 至于载体材料,可以使用常用的多孔或非多孔氧化铝、二氧化硅、二氧化钍、二氧化锆、碳化硅或硅酸盐,载体的体块可以具有规则的或不规则的外形。 As support material, a conventional porous or non-porous alumina, silica, thorium dioxide, zirconium dioxide, silicon carbide or silicates, bulk carrier may have a regular or irregular shape.

在丙烷的多相催化氧化脱氢中,反应温度优选为200至600℃,特别是250至500℃,更优选350至440℃。 In heterogeneous catalytic oxidative dehydrogenation of propane, the reaction temperature is preferably 200 to 600 ℃, in particular 250 to 500 ℃, more preferably 350 to 440 ℃. 工作压力优选为0.5至10bar,特别是1至10bar,更优选1至5bar。 Working pressure is preferably 0.5 to 10bar, in particular 1 to 10bar, more preferably 1 to 5bar. 已发现高于1bar的工作压力,例如1.5至10bar,是特别有利的。 It has been found higher than 1bar operating pressure, for example 1.5 to 10bar, is particularly advantageous. 丙烷的多相催化氧化脱氢通常是在固定催化剂床上进行的。 Heterogeneously catalyzed oxydehydrogenation of propane is usually carried out in a fixed catalyst bed. 后者宜安装在壳管式反应器的管中,如例如EP-A 0700893和EP-A 0700714及这些文献中引用的参考文献中描述的那样。 The latter should be installed in the pipe shell and tube type reactor, such as, for example, reference EP-A 0700893 and EP-A 0700714 and those cited therein described. 反应气体混合物在催化剂床中的平均停留时间宜为0.5至20秒。 The average residence time of the reaction gas mixture in the catalyst bed is suitably from 0.5 to 20 seconds. 丙烷与氧的比率因所需转化率和催化剂的选择性而不同,但宜在0.5∶1至40∶1的范围,特别是1∶1至6∶1,更优选2∶1至5∶1。 Due to oxygen ratio of propane conversion and selectivity of the catalyst may require a different, but preferably in the range of 0.5 to 40:1, particularly 1:1 to 6:1, more preferably 2 to 5:1 . 丙烯的选择性一般随丙烷转化率的增大而降低。 Propylene selectivity generally increases the propane conversion increases. 因此,丙烷至丙烯的反应优选进行得可以在高丙烯选择性下实现较低的丙烷转化率。 Thus, the reaction of propane to propylene is preferably carried out enough to achieve a low conversion of propane at a high propylene selectivity. 丙烷的转化率特别优选在5至40摩尔%的范围,通常在10至30摩尔%的范围。 Propane conversion rate is particularly preferably in the range of 5 to 40 mol%, typically in the range of 10 to 30 mol%. 此处,术语“丙烷的转化率”是指已加入的丙烷(存在于粗丙烷中的丙烷及存在于任何再循环气体中的丙烷的和)在单程中进行反应的比例。 Here, the term "propane conversion" means the ratio of propane has been added (present in the crude propane and propane present in any recycle gas and propane) reacting in a single pass. 生成丙烯的选择性一般为50至98摩尔%,更优选80至98摩尔%。 Selectivity to propylene is usually 50 to 98 mol%, more preferably 80 to 98 mol%. 术语“选择性”是指以摩尔百分比表示的每1mol反应的丙烷生成的丙烯的摩尔数。 The term "selectivity" refers to the number of moles of propane per 1mol reaction generated in mole percent propylene.

在丙烷的氧化脱氢中使用的起始混合物一般包含5至95摩尔%的丙烷(基于100摩尔%的起始混合物)。 The starting mixture used in the oxidative dehydrogenation of propane typically contains 5 to 95 mole% propane (100 mol% based on the starting mixture). 除了丙烷和氧之外,用于多相催化氧化脱氢的起始混合物可进一步包含其它组分,特别是惰性组分,例如二氧化碳、一氧化碳、氮、稀有气体、其它烃(例如存在于粗丙烷中的次要组分)和/或丙烯。 In addition to propane and oxygen, the starting mixture for the heterogeneously catalyzed oxydehydrogenation may further contain other components, in particular the inert components, such as carbon dioxide, carbon monoxide, nitrogen, noble gases, other hydrocarbons (e.g., propane present in the crude the minor component) and / or propylene. 多相氧化脱氢也可以在例如水蒸气的稀释剂的存在下进行。 Multiphase oxidative dehydrogenation may be carried out in the presence of a diluent, for example water vapor.

本领域技术人员已知的任何反应器顺序都可用于进行丙烷的均相氧化脱氢或多相催化氧化脱氢。 Any reactor sequence known to those skilled in the art may be used to perform homogeneous oxidative dehydrogenation of propane or heterogeneously catalyzed oxydehydrogenation. 例如,氧化脱氢可以在单个反应器中或者在串联的两个或更多个反应器中进行,如果需要,可以在串联的反应器之间引入氧。 For example, oxidative dehydrogenation may be conducted in a series of two or more reactors or in a single reactor, if desired, the oxygen can be introduced between the reactors in series. 也可以将均相氧化脱氢或多相催化氧化脱氢相互结合。 It may be homogeneous or heterogeneous catalytic oxidative dehydrogenation oxydehydrogenation combined with each other.

至于可能的组分,由根据本发明进行的丙烷的氧化脱氢获得的产物混合物可以包含例如以下组分:丙烯、丙烷、二氧化碳、一氧化碳、水、氮、氧、乙烷、乙烯、甲烷、丙烯醛、丙烯酸、环氧乙烷、丁烷(如正丁烷或异丁烷)、乙酸、甲醛、甲酸、环氧丙烷和丁烯(如1-丁烯)。 As possible components, the product mixture obtained by the oxidative dehydrogenation of propane according to the present invention may comprise, for example, the following components: propylene, propane, carbon dioxide, carbon monoxide, water, nitrogen, oxygen, ethane, ethylene, methane, propylene aldehydes, acrylic acid, ethylene oxide, butylene (e.g., n-butane or isobutane), acetic acid, formaldehyde, formic acid, propylene oxide and butylene (e.g. 1-butene). 在本发明的丙烷的氧化脱氢中获得的产物混合物通常包含:5至10摩尔%的丙烯、0.1至2摩尔%的一氧化碳、1至3摩尔%的二氧化碳、4至10摩尔%的水、0至1摩尔%的氮、0.1至0.5摩尔%的丙烯醛、0至1摩尔%的丙烯酸、0.05至0.2摩尔%的乙酸、0.01至0.05摩尔%的甲醛、1至5摩尔%的氧、0.1至1.0摩尔%的所述其它组分,其余为量最多的丙烷,以上分别基于100摩尔%的产物混合物。 The product mixture obtained in the oxidative dehydrogenation of propane according to the present invention generally comprise: from 5 to 10 mol% propylene, from 0.1 to 2 mole% carbon monoxide, 1-3 mol% carbon dioxide, 4-10 mole% of water, 0 to 1 mol% nitrogen, 0.1 to 0.5 mol% acrolein, 0-1 mole% acrylic acid, 0.05 to 0.2 mol% of acetic acid, from 0.01 to 0.05 mole% formaldehyde, 1 to 5 mol% oxygen, 0.1 to 1.0 mol% of the other components, the remaining propane in an amount up to, or more based on 100 mol% of the product mixture, respectively.

第一反应区中的丙烷的脱氢一般也可以进行为基本排除氧的丙烷的多相催化脱氢,如DE-A 3313573、WO 01/96270、DE-A 10131297或DE-A10211275中所述那样,或如下所述。 Dehydrogenation of propane in the first reaction zone may generally be substantially exclude oxygen heterogeneously catalyzed propane dehydrogenation, such as DE-A 3313573, WO 01/96270, DE-A 10131297 or DE-A10211275 in the above , or as described below.

由于发生多相催化脱氢反应时体积增大,因而可以通过减小产物的分压提高转化率。 Since the heterogeneously catalyzed dehydrogenation reaction occurs when the volume increases, it is possible by reducing the partial pressure of the product to improve the conversion rate. 这可以以简单的方式实现,例如在减小的压力下和/或通过混入基本惰性的稀释气体(例如通常对脱氢反应为惰性气体的水蒸气)进行脱氢。 This can be achieved in a simple manner, for example under reduced pressure, and / or (e.g. for the dehydrogenation reaction is generally an inert gas, water vapor) by mixing the dehydrogenated substantially inert diluent gas. 用水蒸气进行稀释通常还有另一优势,即减少了所用催化剂的碳化,因为水蒸气会根据煤的气化原理与生成的碳进行反应。 Still another advantage is usually diluted with water vapor, i.e. carbonization of the catalyst used is reduced, since the water vapor generated by the reaction with carbon according to the principle of coal gasification. 水蒸气还可用作随后的氧化和/或氨氧化区(在本文中也简称为分区)中的稀释气体。 Steam can also be used subsequent oxidation and / or ammoxidation zone (herein also referred to as a partition) in a diluent gas. 水蒸气还可以以简单的方式(例如通过冷凝)从得自脱氢的产物混合物中部分或完全分离,如果将可通过这种方式获得的改性产物混合物进一步用于分区,就提供了提高稀释气体N2比例的可能性。 Steam is also possible in a simple manner (e.g., by condensation) from a partially or completely separated from the dehydrogenation product mixture, if the modified product obtained in this manner may be further configured to partition the mixture, it provides improved dilution likelihood ratio of N2 gas. 其它可用于丙烷多相催化脱氢的合适的稀释剂有,例如,CO、甲烷、乙烷、CO2、氮和稀有气体如He、Ne和Ar。 Other suitable diluents may be used for the heterogeneously catalyzed propane dehydrogenation are, for example, CO, methane, ethane, CO2, nitrogen, and noble gases such as He, Ne and Ar. 所有所述稀释剂都既可以独立地使用,也可以以不同的混合物的形式使用。 The diluent may be all can be used independently, it can also be used in the form of different mixtures. 有利的是所述稀释剂一般也是分区中的合适的稀释剂。 Advantageously it said diluent Suitable diluents are generally partition. 如上所述,优选在各反应区中为惰性的(即化学变化进行到小于5摩尔%的程度,优选小于3摩尔%并更优选小于1摩尔%)稀释剂。 As described above, preferably an inert in each reaction zone (i.e., a chemical change occurs to an extent of less than 5 mole percent, preferably less than 3 mol%, and more preferably less than 1 mol%) diluent. 原则上,所有由现有技术已知的脱氢催化剂都适于丙烷的多相催化脱氢。 In principle, all it is known from the prior art dehydrogenation catalysts suitable for the heterogeneously catalyzed propane dehydrogenation. 它们大致可分为两组,即本质上为氧化性的稀释剂(如氧化铬和/或氧化铝)和含有至少一种在一般为氧化性载体上的通常较稀有的金属(如铂)的稀释剂。 They can be roughly divided into two groups, i.e. oxidising diluent (such as chromium oxide and / or alumina) and comprising at least one essentially usually more typically rare metals (such as platinum) on the oxidic support diluent.

特别地,例如可以使用WO 01/96270、EP-A 731077、DE-A 10211275、DE-A 10131297、WO 99/46039、US-A 4788371、EP-A 0705136、WO99/29420、US-A 4220091、US-A 5430220、US-A 5877369、EP-A 0117146、DE-A 19937196、DE-A 19937105和DE-A 19937107中推荐的所有脱氢催化剂。 In particular, for example, using the WO 01/96270, EP-A 731077, DE-A 10211275, DE-A 10131297, WO 99/46039, US-A 4788371, EP-A 0705136, WO99 / ​​29420, US-A 4220091, US-a 5430220, US-a 5877369, EP-a 0117146, DE-a 19937196, DE-a 19937105 and DE-a 19937107 all recommended dehydrogenation catalyst. 特别可使用DE-A 19937107中实施例1、实施例2、实施例3和实施例4描述的催化剂。 In particular DE-A 19937107 can be used in Example 1, Example 2, Example 3 and the catalyst 4 embodiment described embodiment.

它们是含有以下物质的脱氢催化剂:10至99.9重量%的二氧化锆,0至60重量%的氧化铝、二氧化硅和/或二氧化钛,及0.1至10重量%的元素周期表主族I或II的至少一种元素、过渡族III的元素、过渡族VIII的元素、镧或锡,前提是重量百分比的和为100重量%。 They are dehydrogenation catalyst containing the following substances: 10 to 99.9% by weight of zirconium dioxide, from 0 to 60% by weight of alumina, silica and / or titanium dioxide, and 0.1 to 10 wt% of main group I of the Periodic Table or II at least one element of transition group III elements, the elements of transition group VIII, lanthanum or tin, and the proviso that the weight percentages is 100 wt%.

为进行丙烷的多相催化脱氢,由现有技术已知的所有类型的反应器和工艺方案原则上都是可行的。 For the heterogeneously catalyzed dehydrogenation of propane, the principle known from the prior art for all types of reactors and process schemes are possible. 这些工艺方案在例如有关脱氢催化剂方面引述的所有现有技术文献中都有描述。 These prior art processes all programs documents cited in the relevant dehydrogenation catalyst e.g. aspects are described.

在“CatalyticaStudies Division,Oxidative Dehydrogenation andAlternative Dehydrogenation Processes”,Study Number 4192 OD,1993,430 Ferguson Drive,Mountain View,California,94043-5272 USA中,也对适于本发明目的脱氢工艺进行了较为综合的描述。 In the "CatalyticaStudies Division, Oxidative Dehydrogenation andAlternative Dehydrogenation Processes", Study Number 4192 OD, 1993,430 Ferguson Drive, Mountain View, California, 94043-5272 USA, it is also suitable for the dehydrogenation process object of the present invention for a more comprehensive description of.

丙烷的不完全多相催化脱氢的特点是它是吸热的。 Incomplete heterogeneously catalyzed dehydrogenation of propane characteristic is that it is endothermic. 这就意味着必须在多相催化脱氢之前和/或期间将设定所需反应温度必需的热(能)引入反应气体起始混合物中。 This means must be heterogeneously catalyzed dehydrogenation before and / or during the heat setting temperature required for the desired reaction (energy) introduced into the reaction gas starting mixture.

此外,由于需要高反应温度,丙烷的多相催化脱氢通常因生成少量高沸点高分子有机化合物、直至生成沉积在催化剂表面并因而使催化剂失活的碳而遭受损害。 Further, since a high reaction temperature, the heterogeneously catalyzed dehydrogenation of propane is generally due to the formation of small amounts of high boiling point organic polymer, it is deposited until the generated surface of the catalyst and thereby deactivate the catalyst and carbon suffer damage. 为了使这种不利现象最小化,可以用水蒸气稀释将在多相催化脱氢中于升高的温度下通过催化剂表面的含丙烷的反应气体混合物。 In order to minimize this adverse phenomenon, propane-containing reaction gas mixture is passed through the lower surface of the catalyst may be diluted with water vapor at an elevated temperature in the heterogeneously catalyzed dehydrogenation. 在所获条件下,通过煤的气化原理部分或全部除去已沉积的碳。 Obtained under the conditions, the deposited carbon by removing all or part of the principle of coal gasification.

另一种除去已沉积碳化合物的方法是不时地将含氧气体于高温下通过脱氢催化剂,并因而有效烧除已沉积的碳。 Another method for removing carbon compound is deposited from time to time the oxygen-containing gas through the dehydrogenation catalyst at elevated temperature, and thus effectively burn the deposited carbon addition. 但也可以如下显著地抑制碳沉积的生成:在使将要在多相催化剂上脱氢的丙烷于升高的温度下通过脱氢催化剂之前向丙烷中加入分子氢。 However, the following may be significantly suppressed the production of carbon deposition: addition of molecular hydrogen to propane dehydrogenation catalyst before by making to be dehydrogenated over a heterogeneous catalyst for propane at elevated temperature.

当然,也可以向将要在多相催化剂的存在下脱氢的丙烷中加入水蒸气与分子氢的混合物。 Of course, a mixture of steam and molecular hydrogen can also be added to the dehydrogenated in the presence of a heterogeneous catalyst in propane. 向丙烷的多相催化脱氢中加入分子氢还可以减少不希望的作为副产物的丙二烯、丙炔和乙炔的形成。 Was added molecular hydrogen to the heterogeneously catalyzed dehydrogenation of propane can also reduce undesirable byproducts as propadiene, propyne, and acetylene formation.

适于丙烷多相催化脱氢的反应器形式是固定床管式反应器或壳管式反应器,即脱氢催化剂以反应管或一束反应管中的固定床形式存在。 Heterogeneously catalyzed dehydrogenation of propane is adapted to the form of a fixed bed reactor a tube reactor or a shell and tube reactor, i.e. the presence of a dehydrogenation catalyst in a fixed bed reaction tube or a bundle of reaction tubes. 通过例如烃(如甲烷)的气体在反应管四周进行燃烧而加热反应管。 Is heated by a gas, for example, hydrocarbons (such as methane) in a reaction tube of the combustion reaction tube four weeks. 有利的是仅在固定床的第一个约20至30%部分对催化剂管采用这种直接加热形式,而通过在燃烧过程中释放出的辐射热将该床的其余长度加热到所需的反应温度。 Advantageously only the first portion of about 20 to 30% using a fixed bed catalyst in the form of such a direct heating tube, while the remaining length of the bed was heated to the desired reaction released by the combustion process in a radiant heat temperature. 这样,可实现大致等温的反应条件。 Thus, the reaction can be achieved substantially isothermal conditions. 反应管合适的内径为约10至15cm。 Suitable reaction tube inner diameter is about 10 to 15cm. 典型的壳管式反应器具有300至1000个反应管。 Typical shell and tube reactor having a 300 to 1000 reaction tubes. 这些反应管内的温度为300至700℃,优选400至700℃。 The temperature in the reaction tube 300 to 700 ℃, preferably from 400 to 700 ℃. 宜在将反应气体起始混合物加入管式反应器之前将其预加热至反应温度。 Appropriate starting gas before the reaction mixture was added to the tubular reactor which was preheated to the reaction temperature. 产物气体混合物可以以低50至100℃的温度离开反应管。 Product gas mixture leaving the reaction tube may be by 50 to a temperature of 100 deg.] C. 但该出口温度也可以高出或相等。 However, the outlet temperature can be higher than or equal. 在上述步骤中,使用基于氧化铬和/或氧化铝的氧化脱氢催化剂是有利的。 In the above steps, the use of oxidative dehydrogenation catalysts based on chromium oxide and / or alumina is advantageous. 不使用稀释气体、但从基本上仅有的粗丙烷作为起始反应气体开始通常也是有利的。 Dilution gas is not used, but only substantially crude propane as the starting reaction gas starts usually advantageous. 脱氢催化剂通常也以未稀释的形式使用。 Dehydrogenation catalyst usually used in undiluted form.

在大的工业规模上,可以并联运行多个(如三个)这种壳管式反应器。 On a large industrial scale, it can be run in parallel a plurality of (e.g., three) of such shell and tube reactor. 根据本发明,这些反应器中的两个可以进行脱氢而第三个反应器中的催化剂床进行再生,分区中的生产不会被打断。 According to the present invention, two of these reactors may be a third dehydrogenation catalyst bed reactor is regenerated, producing a partition will not be interrupted.

这种工艺在例如由文献获知的BASF-Linde丙烷脱氢方法中是的有利的。 Such a process is known from the literature BASF-Linde propane dehydrogenation process, for example, is advantageous. 但重要的是,根据本发明,使用这种壳管式反应器就足够了。 But it is important, according to the present invention, the use of such shell and tube reactor will suffice.

在Phillips Petroleum Co.开发的“水蒸气活性重整(STAR)方法”中也使用了这种工艺(参见例如US-A 4902849、US-A 4996387和US-A5389342)。 In the Phillips Petroleum Co. Development "steam active reforming (STAR) method" is also used in this process (see e.g. US-A 4902849, US-A 4996387 and US-A5389342). 关于STAR法中的脱氢催化剂,宜使用锌(镁)尖晶石载体上的含助催化剂的铂(参见例如US-A 5073662)。 About the STAR method dehydrogenation catalyst is preferable to use zinc (Mg) containing platinum on spinel of the cocatalyst (see for example US-A 5073662). 其与BASF-Linde丙烷脱氢方法的区别是,在STAR法中使用水蒸气稀释待脱氢的丙烷。 Which differs from BASF-Linde propane dehydrogenation process is the use of water vapor propane to be dehydrogenated is diluted in the STAR process. 水蒸气与丙烷之间的典型摩尔比为4至6。 Typically between a molar ratio of steam to propane 4-6. 反应器出口压力通常为3至8atm,反应温度宜为480至620℃。 The reactor outlet pressure is usually from 3 to 8atm, the reaction temperature is preferably from 480 to 620 ℃. 总的反应气体混合物在催化剂上的典型空间速度为0.5至10h-1(LHSV)。 Typical space velocity of the total reaction gas mixture on the catalyst is from 0.5 to 10h-1 (LHSV).

也可以使用移动床进行丙烷的多相催化脱氢。 A moving bed may be used for the heterogeneously catalyzed dehydrogenation of propane. 例如,移动催化剂床可容纳在径向流反应器中。 For example, a moving catalyst bed may be housed in a radial flow reactor. 在径向流反应器中,催化剂从顶部缓慢向下移动,而反应气体混合物径向流动。 In the radial flow reactor, the catalyst gradually moves downward from the top, while the reaction gas mixture flows radially. 在例如UOP-Oleflex脱氢方法中采用了这种操作模式。 This mode of operation uses, for example, UOP-Oleflex dehydrogenation process. 由于在该方法中反应器是伪绝热地进行的,因而宜使用串联成串的多个反应器(通常最多可达四个反应器)。 Since in this method the reaction is carried out adiabatically pseudo therefore desirable to use a plurality of reactors in series clusters (typically up to four reactors). 这样就可以避免反应器入口处反应气体混合物的温度与反应器出口处温度之间的过大差距(在绝热操作中,反应气体起始混合物起着传热介质的作用,反应温度的下降取决于其热焓),同时仍能获得有吸引力的产率。 This prevents an excessive temperature difference between the reactor outlet and the inlet of the reactor a reaction gas mixture (adiabatic operation, the reaction gas starting mixture acts as a heat transfer medium, depending on the reaction temperature drops its enthalpy), while still obtaining an attractive yield.

当催化剂床离开流动床反应器时,可以将其送去再生,然后再使用。 When leaving the catalyst bed is a fluidized bed reactor, which can be sent for regeneration before use. 在此方法中,所用脱氢催化剂可以是例如基本由球形氧化铝载体上的铂组成的球形脱氢催化剂。 In this method, the dehydrogenation catalyst may be used, for example, a spherical dehydrogenation catalyst consisting essentially of platinum on spherical alumina carrier. 在UOP方案中,为避免催化剂过早老化,向待脱氢的丙烷中加入氢。 In UOP embodiment, in order to avoid premature aging of the catalyst, the propane to be dehydrogenated hydrogen is added. 工作压力通常为2至5atm。 Working pressure is usually 2 to 5atm. 氢与丙烷的摩尔比宜为0.1至1。 The molar ratio of hydrogen to propane is suitably 0.1 to 1. 反应温度优选为550至650℃,且反应气体混合物在催化剂上的空间速度为约2至6h-1。 The reaction temperature is preferably 550 to 650 ℃, and the space velocity of the reaction gas mixture on the catalyst is from about 2 to 6h-1.

在所述固定床方法中,催化剂外形还可以是球形的,但也可以是圆柱形(中空或实心)或其它形状。 In the fixed bed process, the catalyst may also be a spherical shape, but may also be cylindrical (hollow or solid), or other shapes.

作为丙烷多相催化脱氢的另一工艺方案,Proceedings De Witt,Petrochem.Review,Houston,Texas,1992 a,N1描述了在流动床中对丙烷进行多相催化脱氢的可能性,在该方法中丙烷未被稀释。 Another process scheme as a heterogeneously catalyzed dehydrogenation of propane, Proceedings De Witt, Petrochem.Review, Houston, Texas, 1992 a, N1 describes the possibility of heterogeneously catalyzed propane dehydrogenation in a fluid bed, in which method propane undiluted.

根据本发明,例如,两个流动床可以并列操作,从而使得其中一个可以周期性地进行再生而不会对总个过程产生不利影响。 According to the present invention, e.g., two fluidized bed may operate in parallel, so that one may be regenerated periodically without adversely affect the overall process a. 至于活性组合物,可以使用氧化铝上的氧化铬。 As active composition may be used chromium oxide on alumina. 工作压力通常为1至2atm,反应温度一般为550至600℃。 Working pressure is usually 1 to 2 atm, the reaction temperature is generally 550 to 600 ℃. 通过将脱氢催化剂预加热至反应温度将脱氢所需的热引入反应系统。 By the dehydrogenation catalyst preheated to the reaction temperature of the heat required for dehydrogenation introduced into the reaction system. 上述进行脱氢的方法在文献中也被称为Snamprogetti-Yarsintez法。 The method of the above-described dehydrogenation in the literature also referred Snamprogetti-Yarsintez process.

作为上述过程的替代方案,也可以使用ABB Lummus Crest开发的方法进行基本排除氧的丙烷多相催化脱氢(参见Proceedings De Witt,Petrochem.Review,Houston,Texas,1992,P1)。 As an alternative to the above process, you may be used a method developed by ABB Lummus Crest heterogeneously catalyzed dehydrogenation of propane substantial exclusion of oxygen (see Proceedings De Witt, Petrochem.Review, Houston, Texas, 1992, P1).

前述用于基本排除氧的对丙烷脱氢的多相催化方法都是以≥30摩尔%的丙烷转化率进行的(一般≤60摩尔%)(基于通过反应区的单程)。 The heterogeneous catalytic method for the substantial exclusion of oxygen propane dehydrogenation of propane are ≥30 mol% conversion performed (typically ≤60 mol%) (based on single pass through the reaction zone). 本发明的优点是达到≥5摩尔%至≤30摩尔%或≤25摩尔%的丙烷转化率就足够了。 Advantage of the invention is to achieve ≥5 mol% propane conversion to mol% or ≤25 ≤30 mol% is sufficient. 这就意味着丙烷的多相催化脱氢也可以以10至20摩尔%的丙烷转化率进行(转化率基于通过反应区的单程)。 This means that the heterogeneously catalyzed propane dehydrogenation can also be carried out in a propane conversion of from 10 to 20 mol% (based on single pass conversion of the reaction zone). 这特别是因为剩余量的未反应丙烷在后面的分区中基本起着惰性稀释气体的作用,并然后能够基本没有损失地再循环至脱氢区和/或分区。 This is especially because the remaining amount of unreacted propane substantially plays the role of an inert diluent gas in the partition behind, and substantially no loss can then be recycled to the dehydrogenation zone and / or partitions.

为了实现上述丙烷的转化率,在0.3至3atm的工作压力下进行丙烷的多相催化脱氢是有利的。 In order to achieve the above-described conversion of propane, heterogeneously catalyzed dehydrogenation of propane at the operating pressure of 0.3 to 3atm it is advantageous. 用水蒸气稀释将在多相催化剂的存在下脱氢的丙烷也是有利的。 Diluted with steam in the dehydrogenation of propane in the presence of a heterogeneous catalyst is also advantageous. 在这种情况下,水的热容部分地补偿了脱氢作用的吸热本质造成的影响,并且用水蒸气进行稀释减小了原料和产物的分压,这对脱氢反应的平衡位置具有有利影响。 In this case, the heat capacity of the water partly compensates the effect caused by the endothermic nature of the dehydrogenation, and the dilution reduces the partial pressure of water vapor with raw materials and products, which has a position of equilibrium of the dehydrogenation reaction is advantageously influences. 此外,如上所述,使用水蒸气对含有贵金属的脱氢催化剂的运行寿命具有有利的影响。 As described above, the use of steam has a favorable effect on the operating life of the dehydrogenation catalyst comprising a noble metal. 如果需要,也可将分子氢作为另一种组分加入。 If desired, molecular hydrogen can also be added as another component. 分子氢与丙烷的比率一般≤5。 The ratio of molecular hydrogen to propane general ≤5. 水蒸气与丙烷的摩尔比因而可以为(这时丙烷的转化率较低)≥0至30,宜为0.1至2并优选为0.5至1。 The molar ratio of steam to propane may therefore (in which case lower conversion of propane) ≧ 0 to 30, is suitably from 0.1 to 2 and preferably from 0.5 to 1. 已发现具有低丙烷转化率的操作模式的另一优点是,在反应气体通过反应器的单程中仅消耗了较少量的热,而且在通过反应器的单程中较低的反应温度就足以实现转化。 Another advantage has been found to have a mode of operation of the low propane conversion is one way in a reaction gas through the reactor consumes only a relatively small amount of heat, but also lower in a single pass through the reactor the reaction temperature is sufficient to achieve transformation.

因而,较低丙烷转化率下的丙烷脱氢(伪)绝热地进行是有利的。 Accordingly, propane dehydrogenation (pseudo) at low propane conversion is advantageously carried out adiabatically. 这意味着一般先将反应气体起始混合物加热到500至700℃(或550至650℃)(例如通过在围绕它的壁的四周直接燃烧)。 This means that the first reaction gas starting mixture is generally heated to 500 to 700 deg.] C (or 550 to 650 deg.] C) (e.g. surrounded by the direct combustion of its walls). 通过催化剂床的单个绝热过程通常就足以实现所需转化,同时反应气体混合物被冷却约30℃至200℃(取决于转化率和稀释度)。 Single adiabatic catalyst bed is generally sufficient to achieve the desired conversion, while the reaction gas mixture is cooled to about 30 deg.] C to 200 ℃ (depending on conversion and dilution). 从绝热操作模式来看,存在作为传热介质的水蒸气也具有有利影响。 Adiabatic mode of operation from the point of view, the presence of water vapor as the heat transfer medium also have an advantageous effect. 较低的反应温度可以使所用催化剂床的运行寿命更长。 Lower reaction temperatures cause the operating life of the catalyst bed can be used longer.

原则上,较低丙烷转化率下的丙烷多相催化脱氢可以在固定床反应器中或者在移动床或流化床反应器中进行,无论脱氢是绝热操作还是等温操作。 In principle, the heterogeneously catalyzed dehydrogenation of propane at low propane conversion can be carried out in a moving bed or a fluidized bed reactor or in a fixed bed reactor, whether adiabatic dehydrogenation operation or isothermally.

本发明方法值得注意的方面是,单个作为固定床反应器的、反应气体混合物轴向和/或径向流过其中的竖式炉反应器就足以进行本发明方法,特别是在绝热操作中。 Noteworthy aspect of the method of the present invention, as a single fixed bed reactor, the reaction gas mixture of the axial and / or radial flow reactor through which the shaft furnace is sufficient for the method of the present invention, in particular in an adiabatic operation.

在最简单的情况下,这是单个封闭的反应空间,例如容器,其内径为0.1至10m,可以为0.5至5m,其中固定催化剂床安装在支撑装置(如格栅)上。 In the simplest case, this is a single closed reaction space, such as a container, an inner diameter of 0.1 to 10m, may be 0.5 to 5m, wherein the fixed catalyst bed is mounted on a support means (e.g. a grid). 在这种情况下,热的含丙烷的反应气体轴向流过装有催化剂且在绝热操作中被热绝缘的反应空间。 In this case, the heat of propane-containing reaction gas flows axially through the reaction space is thermally insulated and equipped with a catalyst in an adiabatic operation. 催化剂的外形可以是球形或环形或挤出物的形式。 Shape of the catalyst may be spherical or toroidal or extrudates form. 因为在这种情况下可以用非常廉价的设备获得反应空间,因此所有产生特别低的压降的催化剂外形都是优选的。 Because in this case may be a very inexpensive device to obtain a reaction space, all the special shape of the catalyst to produce low pressure drop are preferable. 它们特别是产生大的空体积或构造为例如独石或蜂巢的催化剂外形。 They particularly a large volume of air such as a catalyst or as a monolithic or honeycomb shape. 为了实现含丙烷反应气的径向流动,反应器可以例如包含两个安装在外圆柱形壁内的同心网眼圆柱,催化剂床安装在它们之间的环形间隙中。 Propane gas to achieve radial flow reactor, the reactor may for example comprise two concentric mesh cylinder mounted within the outer cylindrical wall, the catalyst bed is mounted in the annular gap therebetween. 在绝热操作的情形中,外圆柱形壁也可以适宜地热绝缘。 In the case of adiabatic operation, the outer cylindrical wall may be suitably thermally insulated.

用于在单程中具有较低丙烷转化率的丙烷多相催化脱氢的合适催化剂特别是DE-A 19937107中公开的催化剂,特别是所有通过举例公开的那些。 Suitable catalysts for heterogeneous catalysis with lower propane conversion in a single pass of propane dehydrogenation catalyst is particularly disclosed in DE-A 19937107, in particular all those disclosed by way of example.

在延长的操作期间之后,上述催化剂可以以简单的方式再生,例如,在第一再生阶段使先以氮和/或水蒸气(优选的)稀释的空气以300至600℃、通常为400至550℃的入口温度通过催化剂床。 During and after prolonged operation, the catalyst can be regenerated in a simple manner, for example, that the first nitrogen and / or water vapor (preferably) in a first regeneration stage dilution air at 300 to 600 ℃, typically 400-550 inlet temperature ℃ through the catalyst bed. 再生气在催化剂床上的空间速度可以是例如50至10000h-1,且再生气中的氧含量可以为0.5至20体积%。 Regeneration gas space velocity in the catalyst bed can be for example 50 to 10000h-1, and the oxygen content of the regeneration gas may be from 0.5 to 20% by volume.

在随后的另一再生阶段,可以用空气作为在相同再生条件下的再生气。 In another subsequent stage of regeneration, with air as the regeneration gas may be in the same regeneration conditions. 在实践中,有利的是于再生前用惰性气体(例如N2)冲洗催化剂。 In practice, it is advantageous to flush the catalyst prior to regeneration with an inert gas (e.g. N2).

然后,通常可以在相同条件下使用纯分子氢或以惰性气体(优选水蒸气)稀释的分子氢(氢的含量应≥1%)再生催化剂。 Then, generally use pure molecular hydrogen under the same conditions or diluted with an inert gas (preferably steam) molecular hydrogen (hydrogen content should be ≥1%) regenerated catalyst.

在所有情况下,具有较低丙烷转化率(≤30摩尔%)的丙烷多相催化脱氢都可以以与具有高的丙烷转化率(>30摩尔%)的方案中相同的催化剂上的空间速度(总反应气的空间速度及存在于其中的丙烷的空间速度)操作。 Heterogeneously catalyzed dehydrogenation of propane, in each case, with a lower propane conversion (≦ 30 mol%) may be at the same space velocity in the catalyst having high propane conversion rate (> 30 mol%) of the scheme (total reaction gas present in the space velocity and wherein the space velocity of the propane) operation. 该反应气空间速度可以为例如100至10000h-1,通常为300至5000h-1,即经常为约500至3000h-1。 The reaction gas space velocity may be, for example, 100 to 10000h-1, typically 300 to 5000h-1, i.e. often about 500 to 3000h-1.

较低丙烷转化率下的丙烷多相催化脱氢特别可以适宜地在塔盘反应器中进行。 Propane under heterogeneous catalytic dehydrogenation of propane conversion low in particular be suitably carried out in a tray reactor.

这包含超过一个催化脱氧反应的、物理上独立地连续安装的催化剂床。 It contains more than one catalytic deoxygenation reactions, continuously mounted physically separate catalyst beds. 催化剂床的数目可以为1至20,宜为2至8,或3至6。 The number of catalyst beds may be from 1 to 20, is suitably 2-8, or 3-6. 催化剂床宜在径向或轴向上一个接一个地安装。 The catalyst bed should be mounted one after another in a radial or axial direction. 实践中,在这种塔盘反应器中使用固定床型催化剂是有利的。 In practice, using a fixed bed catalyst is advantageous in that the disk reactor column.

在最简单的情形中,固定催化剂床轴向安装在竖炉反应器中或同心网眼圆柱体之间的环形间隙中。 In the simplest case, the fixed catalyst bed is mounted axially in a shaft furnace reactor or in a concentric annular gap between the mesh cylinder. 但也可以将环形间隙设置为一个比一个高的段,并使气体径向通过一个段并进入下一个高于它或低于它的段。 However, the annular gap may be set higher than a segment, and the gas through a radial segment and into the next higher or lower than that of its segments.

反应气体混合物宜在其从一个催化剂床通往下一个催化剂床的途中在塔盘反应器中进行中间加热,例如使其通过以热气加热的热交换器排管,或使其通过以热燃烧气加热的管道。 The reaction gas mixture should be on its way from the catalyst bed leading to a catalyst bed in a reactor in the intermediate tray is heated, for example, passed through a heat exchanger to heat the hot gas discharge tube, or passed through a hot combustion gas heating pipes.

如果塔盘反应器是绝热操作的,为达到合意的丙烷转化率(≤30摩尔%),在将反应气体混合物引入脱氢反应器之前将其预加热至450至550℃并在塔盘反应器内将其保持在该温度范围就足够了,特别是使用DE-A19937107(尤其是通过举例描述的实施方案)中所述催化剂时尤为如此。 If the tray before the reactor is operated adiabatically, to achieve desirable propane conversion (≦ 30 mol%), in the reaction gas mixture introduced into the dehydrogenation reactor which was preheated to 550 to 450 [deg.] C and the reactor trays within to hold it in this temperature range is enough, especially the use of DE-A19937107 especially when (particular embodiments described by way of example) in the catalyst. 这样,就可以以极低的温度进行总的丙烷脱氢,就固定催化剂床两次再生之间的运行期间而言这是特别有利的。 Thus, the overall dehydrogenation of propane can be performed at very low temperatures during operation in terms of a fixed catalyst bed between two regenerations which is particularly advantageous.

更为适宜的方法是催化脱氢自热地进行,即例如以直接方式(自热操作)进行上述中间加热。 More suitable method is to perform autothermal catalytic dehydrogenation, i.e. for example in a direct manner (autothermal operation) heating the above intermediate. 为此,在反应气体混合物流过第一催化剂床之前和/或在后面的催化剂床之间将有限量的分子氧加入反应气体混合物中。 For this reason, before the reaction gas mixture flows through the first catalyst bed and / or between the catalyst beds behind a limited amount of molecular oxygen is added to the reaction gas mixture. 取决于所用脱氢催化剂,这导致了存在于反应气体混合物中的烃、可能已沉积在催化剂表面上的碳或类碳化合物和/或在丙烷多相催化脱氢过程中生成的和/或加入反应气体混合物中的氢的有限燃烧(实践中,安装含有特定地(选择性地)催化塔盘反应器中氢(和/或烃)燃烧的催化剂的催化剂床也是有利的(这种催化剂的实例有US-A 4788371、US-A 4886928、US-A5430209、US-A 5530171、US-A 5527979和US-A 5563314中描述的那些;例如,这种催化剂床可以以包含脱氢催化剂的床之间的交替形式容纳在塔盘反应器中))。 Depending on the dehydrogenation catalyst, which leads to the hydrocarbons present in the reaction gas mixture, it may have been deposited carbon or carbon compound based on the catalyst surface and / or generated in the heterogeneous catalysis of propane dehydrogenation and / or added the reaction gas mixture combustion is limited (in practice, the installation comprising a specific instance (optionally) a catalytic tray reactor the hydrogen (and / or hydrocarbon) a combustion catalyst bed catalyst is also advantageous (such catalysts hydrogen there are US-a 4788371, US-a 4886928, US-A5430209, US-a 5530171, US-a 5527979 and US-a 5563314 as those described in; for instance, this catalyst bed may comprise between dehydrogenation catalyst beds alternate form housed in the tray reactor)). 这样释放的反应热可以使丙烷多相催化以伪自热的方式实际上等温地进行。 Such heat release may be the reaction of propane in a pseudo-heterogeneous catalytic autothermal manner practically isothermally. 这样,如果选择较长的反应气体在催化剂床中的时间,就可以以降低的或基本恒定的温度进行丙烷脱氢,这可以获得两次再生之间的特别长的运行期间。 Thus, if the gas is selected longer reaction time in the catalyst bed, propane dehydrogenation can be carried out at reduced or substantially constant temperature, it is possible to obtain a particularly long period of operation between two regenerations.

一般来说,引入上述类型的氧应使得反应气体混合物中的氧含量为其中存在的丙烷及丙烯量的0.5至30体积%。 In general, the introduction of the type described above should be such that the oxygen content of the oxygen in the reaction gas mixture is 0.5 to 30 volume amounts of propane and propylene present therein%. 关于氧源,可以使用纯分子氧或被例如CO、CO2、N2、稀有气体的惰性气体稀释的氧,特别是空气。 Of the oxygen source, pure molecular oxygen, or may be used e.g. CO, CO2, N2, an inert gas is a noble gas diluted oxygen, in particular air. 所获燃烧气一般具有附加的稀释作用,因而促进了丙烷的多相催化脱氢。 The resulting combustion gases generally have an additional dilution effect, thereby promoting the heterogeneously catalyzed dehydrogenation of propane.

将密闭的内件(如管状内件)安装到催化剂床之间的空间,可以使丙烷的多相催化脱氢更为等温地进行,这些内件在装入塔盘反应器之前最好已被抽空,但这不是必须的。 The closed inner member (inner tubular member) is mounted to the space between the catalyst beds, can be made more heterogeneously catalyzed dehydrogenation of propane carried out isothermally, the inner member prior to loading trays reactor preferably has been taking the time, but this is not necessary. 这些内件还可以安放在各催化剂床内。 The inner member may also be placed in each catalyst bed. 这些内件装有合适的固体或液体,它们在高于特定温度时蒸发或熔融并在该过程中吸收热,然后在温度低于该特定温度时冷凝并释放热。 The inner member is provided with a suitable solid or liquid, and they evaporate or melt in the process absorbs heat above a certain temperature, and then when the specific temperature below the condensation temperature and heat release.

另一种将用于丙烷多相催化脱氢的反应气体起始混合物加热到所需反应温度的方法是利用氧燃烧部分存在于其中的丙烷和/或H2(例如在特定的燃烧催化剂上进行,如简单地使反应气体混合物通过催化剂上和/或催化剂中),并利用这样释放的燃烧热将反应气体混合物加热到所需反应温度。 Another gas starting mixture for the heterogeneously catalyzed propane dehydrogenation reaction was heated to the desired reaction temperature is a method using oxygen combustion section propane present therein and / or H2 (for example, on a particular combustion catalyst, the simple reaction gas mixture on the catalyst and / or catalyst) and the combustion heat thus released will be the reaction gas mixture is heated to the desired reaction temperature. 所获燃烧产物,例如CO2、H2O,以及任何伴随燃烧需要的分子氧的N2有利地构成了惰性气体。 The resulting combustion products such as CO2, H2O, and any associated molecular oxygen required for combustion is advantageously constituted N2 inert gas.

上述的氢燃烧可以特别适宜地以DE-A 10211275中描述的方法进行,即用于气相中丙烷的连续多相催化不完全脱氢的方法,在该方法中:-将其中存在有待脱氢的丙烷的反应气体连续加入反应区,-在反应区中,使反应气体通过至少一个固定催化剂床,在该催化剂床上通过催化脱氢生成了分子氢和在至少不完全程度上的丙烯, Described above can be particularly suitably hydrogen combustion in a method described in DE-A 10211275 is performed, i.e., gas phase in the continuous heterogeneously catalyzed propane dehydrogenation for incomplete, in which method: - in which there is room for the dehydrogenation of the reaction of propane gas to the reaction zone continuously, - in the reaction zone, the reaction gas through at least one fixed catalyst bed, the catalyst bed is generated at least the propylene and molecular hydrogen incomplete extent by catalytic dehydrogenation,

-将含有分子氧的至少一种气体在进入反应区之前和/或之后加入反应气体中,-在反应区中,分子氧部分氧化存在于反应气体中的分子氢,从而生成水蒸气,并-从反应区中取出含有分子氢、水蒸气、丙烯和丙烷的产物气体,其中将取自反应区的产物气体分为具有相同组成的两部分,并将这两部分之一作为循环气再循环至脱氢反应区中,并根据本发明将另一部分进一步用作气体混合物1。 - at least one gas containing molecular oxygen is added before entering the reaction zone and / or after the reaction gas, - in the reaction zone, the partial oxidation of molecular oxygen in the presence of molecular hydrogen in the reaction gas to generate steam, and - remove the product gas containing molecular hydrogen, water vapor, propylene and propane from the reaction zone, wherein the product gas from the reaction zone is divided into two parts having the same composition, and one of the two parts to be recycled as recycle gas the dehydrogenation reaction zone, and another portion of the present invention will further be used as a gas mixture.

如果在粗丙烷之外将含有丙烷和可能的丙烯并出自分区的循环气(如果需要,可从中除去次要组分(例如C4烃,如1-丁烯))加入脱氢区作为另一丙烷源,则该方法是特别优选的。 If possible containing propane and propene and propane from the outside of the coarse partition recycle gas (if necessary, can be removed therefrom subcomponent (e.g. C4 hydrocarbons such as 1-butene)) was added as a further dehydrogenation zone propane source, the method is particularly preferred. 如果循环气代表用于该方法中氢的燃烧的唯一的氧源,那么这是特别适用的。 If the recycle gas represents a unique source of oxygen in the process of combustion of hydrogen, which is then particularly suitable.

在本发明方法中,在丙烷的多相催化脱氢中生成的产物气体混合物一般含有丙烷、丙烯、分子氢、N2、H2O、甲烷、乙烷、乙烯、1-丁烯、其它丁烯和其它C4烃(正丁烷、异丁烷、丁二烯等)、CO和CO2。 In the method of the present invention, produced in the heterogeneously catalyzed dehydrogenation of propane in the product gas mixture typically contains propane, propylene, molecular hydrogen, N2, H2O, methane, ethane, ethylene, 1-butene, butene and other other C4 hydrocarbons (n-butane, iso-butane, butadiene, etc.), CO and CO2. 其一般处于0.3至10atm的压力下,并经常具有400至500℃、在有利的情况下为450至500℃的温度。 Generally at a pressure of 0.3 to 10atm, and often of 400 to 500 ℃, advantageously in the case of a temperature of 450 to 500 deg.] C.

尽管EP-A 117146、DE-A 3313573和US-A 3161670推荐依原样使用丙烷多相催化脱氢中生成的产物气体混合物(气体混合物1)作为送入分区的进料,但是根据本发明通常有利的是,在将其进一步用作送入分区的进料之前,分离出至少部分存在于出自氧化脱氢和/或脱氢的产物气体混合物(气体混合物1)中的任何C4烃(例如1-丁烯、正丁烷、异丁烷、其它丁烯、丁二烯等)。 Although EP-A 117146, DE-A 3313573 and US-A 3161670 were used as recommended by the heterogeneously catalyzed dehydrogenation of propane produced in the product gas mixture (gas mixture 1) is fed as feed to the partition, but according to the present invention advantageously generally that, prior to further use as a feed into the partition, is separated by at least partly in the oxidative dehydrogenation product gas mixture and / or dehydrogenation (gas mixture 1) any C4 hydrocarbons (such as 1 butene, n-butane, isobutane, other butenes and butadiene). 如果氢存在于气体混合物1中,上述分离可以与氢的至少部分分离结合,或预先进行这种氢分离。 If hydrogen is present in a gas mixture, the separation may be at least partially separated hydrogen bonding, or hydrogen in advance of such separation.

例如,后者可以如下实现:使气体混合物1通过仅对分子氢为渗透性的、通常为管状的膜,如果适宜,在其已于间接热交换器中冷却后进行(宜将回收的热用于加热本发明方法需要的原料气)。 For example, the latter can be achieved: 1 mixture by gas only permeable to molecular hydrogen, generally tubular membrane, if appropriate, be (should the recovery of heat used was cooled in an indirect heat exchanger which the method of the present invention requires heating the feed gas). 可以将已通过此方法分离的分子氢(如果需要)部分返还至丙烷的多相催化脱氢,或者将其送去作其它用途。 Separated by this method may be molecular hydrogen (if desired) partially returned to the heterogeneously catalyzed dehydrogenation of propane, or be sent for other purposes. 例如,可以在燃料电池中燃烧。 For example, combustion in a fuel cell.

作为替代方案,可以通过部分冷凝、吸附和/或提纯分离出部分或全部的氢(优选在高于大气压的压力下进行)。 Alternatively, by partial condensation, adsorption and / or purification of the separated part or all of hydrogen (preferably at a pressure above atmospheric pressure). 在本发明方法中,也可以通过用分子氧将氢选择性地(例如多相催化)燃烧而从产物气体混合物(气体混合物1)中除去部分或全部的分子氢。 In the process of the invention, to remove some or all of the molecular hydrogen from the product gas mixture (gas mixture 1) with molecular oxygen can also be selectively hydrogen (e.g., heterogeneous catalytic) combustion. 反应生成的水可以部分或完全分离,也可以留在气体混合物中,因为它可以在分区中起着惰性稀释剂的作用。 The water of reaction may be partially or completely separated, may be left in the gas mixture, as it plays the role of an inert diluent in the partition. 适于此目的的催化剂在例如US-A 4788371、US-A 4886928、US-A 5430209、US-A 55530171、US-A 5527979和US-A 5563314中公开过。 The catalyst suitable for this purpose, for example, US-A 4788371, US-A 4886928, US-A 5430209, US-A 55530171, US-A 5527979 and in US-A 5563314 discloses.

如例如EP-A 832056中所述,也可以例如通过在除脱氢催化剂之外又加入的至少一种可还原的金属氧化物上的氧化,在多相催化脱氢过程中当场有效地进行分子氢的选择性燃烧。 As for example described in EP-A 832056, may be spot effectively molecules heterogeneous catalysis, for example by oxidation of the dehydrogenation process in addition to the dehydrogenation catalyst further added at least one reducible metal oxide is selective hydrogen combustion.

根据本发明,有利的是在将其余的产物气体混合物(气体混合物1′)用作送至分区的进料之前和/或同时,分离出至少10摩尔%、或至少25摩尔%、经常至少35摩尔%、或至少50摩尔%、通常至少75摩尔%或全部量的在多相催化脱氢中生成的分子氢。 According to the present invention, it is advantageous before the remaining product gas mixture (gas mixture 1 ') is used as a feed to the partition and / or simultaneously, separated at least 10 mole%, or at least 25 mole%, usually at least 35 mole%, or at least 50 mol%, typically at least 75 mol% or the total amount generated in the heterogeneously catalyzed dehydrogenation of molecular hydrogen. 如果必要,可以在将气体混合物进一步用于分区之前分离出(如通过冷凝)存在于气体混合物1中的任何水。 If necessary, it can be isolated prior to further partition the gas mixture (e.g., by condensation) any water present in the gas mixture is 1. 当然,如果需要,也可以在分离出分子氢和/或例如1-丁烯等的C4烃的同时,分离出产物气体混合物(气体混合物1)中丙烷和丙烯之外的其它组分。 Of course, if desired, may be separated simultaneously hydrogen molecules and / or the like such as 1-butene in the C4 hydrocarbons separated product gas mixture (gas mixture 1) than the other components of propane and propylene.

实现这一目的的简单可能的方法是,例如,使优选被冷却(优选冷却至10至70℃)的气体混合物1,如在0.1至50atm的压力和0至100℃的温度下,与丙烷和丙烯在其中优先被吸收的(优选高沸点的)有机溶剂(优选疏水性的)接触,例如简单地使所述气体通过该有机溶剂。 Possible simple way to do this is, for example, that the preferably cooled (preferably cooled to 10 to 70 ℃) a gas mixture, such as 0.1 to 50atm at a pressure and a temperature of 0 to 100 deg.] C, and propane where propylene is preferentially absorbed (preferably a high boiling) organic solvent (preferably hydrophobic) contacts, for example, simply passing the gas through the organic solvent. 通过随后的解吸、提纯和/或使用在分区中为惰性的和/或在该反应区中需要作为反应剂的气体(如空气)进行汽提,将丙烷和丙烯一起以纯化的形式回收,并用作送至分区的进料(如上所述,在使用空气进行汽提的情况下,以这种方式产生的气体混合物1′可以与气体混合物2相同,即直接原样用作加入至少一个不完全氧化反应的进料)。 By subsequent desorption, purification and / or inert in the partition and / or a gas (e.g., air) in the reaction zone required as reactant is stripped and the recovered together in a purified form of propane and propylene, and with as a feed to the partition (as described above, in the case of stripping air, the gas mixture produced in this manner 1 'may be the same with the gas mixture 2, i.e., it added directly used as at least a partial oxidation the feed to the reactor). 出自吸收的、可能含有分子氢的尾气可以例如进行膜分离,且如果需要,已分离出的氢可然后用于丙烷的多相催化脱氢中。 By absorption, the exhaust gas may contain molecular hydrogen separation membrane can be, for example, and if desired, the separated hydrogen can then be used in a heterogeneously catalyzed dehydrogenation of propane.

但是,在当前的分离方法中,C3烃/C4烃的分离因数是相对有限的,并且通常不足以满足本发明的要求。 However, during the separation process, the hydrocarbon separation factor C3 / C4 hydrocarbons are relatively limited and usually insufficient to meet the requirements of the invention.

因而,作为上述通过吸收进行的分离步骤的替代方案,通常优选使用压力摇摆吸附或压力提纯,以实现本发明的目的。 Thus, as an alternative to separation by absorption step described above, it is generally preferred to use a pressure or a pressure swing adsorption purification, in order to achieve the object of the present invention.

用于上述吸收式分离的合适的吸收介质原则上是所有能够吸收丙烷和丙烯的吸收介质。 Suitable absorption principle for the absorption-type separation medium is capable of absorbing all the absorption medium propane and propylene. 吸收介质优选是优选疏水性的和/或高沸点的有机溶剂。 Preferred absorption medium is preferably hydrophobic and / or high boiling organic solvent. 该溶剂的沸点(于1atm的大气压力下)宜为至少120℃,优选至少180℃,更优选200至350℃,特别是250至300℃,甚至更优选260至290℃。 The boiling point of the solvent (under atmospheric pressure in the 1atm) should be at least 120 ℃, preferably at least 180 ℃, more preferably 200 to 350 ℃, especially 250 and 300 ℃, and even more particularly 260 to 290 ℃. 其闪点(于1atm的大气压力下)宜高于110℃。 A flash point (under atmospheric pressure of 1atm) should be higher than 110 ℃. 一般来说,相对非极性的有机溶剂,例如优选不含对外起作用的极性基团的脂族烃,或者芳族烃,通常适于作为吸收介质。 Generally, relatively non-polar organic solvents, such as aliphatic hydrocarbon containing no polar group is preferably the external function, or aromatic hydrocarbons, typically suitable as absorption medium. 一般而言,合意的是吸收介质具有非常高的沸点且同时对丙烷和丙烯具有非常高的溶解能力。 In general, it is desirable that the absorption medium with a very high boiling point and simultaneously have very high solubility of the propane and propylene. 合适的吸收介质的实例有脂族烃,如C8-C20烷烃和烯烃;和芳烃,例如来自石蜡蒸馏的中油馏分;和在O原子上有庞大基团的醚;或者它们与可以加入它们中的、例如DE-A 4308087中公开的邻苯二甲酸1,2-二甲酯的极性溶剂的混合物。 Examples of suitable absorption medium are aliphatic hydrocarbons, such as C8-C20 alkanes and alkenes; and aromatic hydrocarbons such as oil fraction from paraffin distillation; and an ether group in a bulky O atom; or they can be added to them and , for example a mixture of polar solvents phthalate disclosed in DE-a 4308087 1,2-dimethyl. 其它合适的吸收介质有苯甲酸和邻苯二甲酸与含有1至8个碳原子的直链烷醇的酯,例如苯甲酸正丁酯、苯甲酸甲酯、苯甲酸乙酯、邻苯二甲酸二甲酯、邻苯二甲酸二乙酯;和传热油,例如联苯、二苯醚、和联苯与二苯醚的混合物、或它们的氯代衍生物;及三芳基烯,例如4-甲基-4'-苄基二苯基甲烷及其异构体2-甲基-2'-苄基二苯基甲烷、2-甲基-4'-苄基二苯基甲烷和4-甲基-2'-苄基二苯基甲烷及这些异构体的混合物。 Other suitable absorbent medium benzoic acid and phthalic acid with a linear alkanol containing 1-8 carbon atoms ester, e.g., n-butyl benzoate, methyl benzoate, ethyl benzoate, phthalate dimethyl, diethyl phthalate; and heat transfer oils, such as biphenyl, diphenyl ether, and a mixture of biphenyl and diphenyl ether, or chlorinated derivatives thereof; and triaryl-ene, 4 e.g. - benzyl-methyl-4'-diphenylmethane isomers and 2'-benzyl-2-methyl-diphenylmethane, 2-methyl-4'-diphenylmethane benzyl and 4- diphenyl methane and mixtures of these isomers 2'-methyl benzyl group. 合适的吸收介质是联苯与二苯醚的溶剂混合物,优选具有共沸组成的混合物,特别是由约25重量%的联苯和约75重量%的二苯醚组成的混合物,例如市售Diphyl(如购自Bayer Aktiengesellschaft的)。 Suitable absorbent medium is a mixture of biphenyl and diphenyl ether solvent, preferably a mixture of azeotropic composition, in particular a mixture consisting of about 25% by weight of biphenyl and about 75% by weight of the diphenyl ether composition, for example a commercially available Diphyl (e.g., commercially available from Bayer Aktiengesellschaft) is. 通常以占整个溶剂混合物0.1至25重量%的量将例如邻苯二甲酸二甲酯的溶剂加入该溶剂混合物。 The total solvent mixture is usually from 0.1 to 25% by weight of dimethyl phthalate for example, a solvent is added to the solvent mixture. 其它特别可用的吸收介质有辛烷、壬烷、癸烷、十一烷、十二烷、十三烷、十四烷、十五烷、十六烷、十七烷和十八烷,已发现十四烷是特别合适的。 Other particularly useful absorption media have octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, seventeen and octadecanes have been found tetradecane is particularly suitable. 有利的是所用吸收介质符合上述沸点要求但同时具有不太高的分子量。 Advantageously the absorption medium meets the above requirements, but at the same time having a boiling point of not too high a molecular weight. 吸收介质的分子量宜≤300g/mol。 Molecular absorption medium should ≤300g / mol. DE-A 3313 573中所述具有8至6个碳原子的链烷烃也是合适的。 DE-A 3313573 in the alkane having 8-6 carbon atoms are also suitable. 合适的商品的实例有Haltermann销售的产品,例如Halpasolsi,如Halpasol 250/340 i和Halpasol 250/275 i,及以PKWF和Printosol的名称销售的印墨油。 Examples of suitable products are Haltermann goods sold, e.g. Halpasolsi, as Halpasol 250/340 i and Halpasol 250/275 i, and the names and Printosol PKWF oil sold under the ink. 优选不含芳族的商品,例如PKWFaf型的商品。 Preferably free of aromatic product, e.g. PKWFaf type products.

对进行吸收的方式没有任何特别的限制。 There is no particular limitation on the way of absorption. 可以使用本领域技术人员熟悉的所有方法和条件。 You can use all the methods and conditions familiar to the person skilled in the art. 气体混合物优选在下列条件下与吸收介质接触:1至50bar、优选2至20bar、更优选5至10bar的压力,0至100℃、特别是30至50℃的温度。 The mixture gas is preferably under the following conditions in contact with an absorption medium: 1 to 50bar, preferably 2 to 20bar, more preferably from 5 to 10bar pressure of 0 to 100 deg.] C, in particular of a temperature of 30 to 50 deg.] C. 吸收可以在塔中进行,也可以在猝冷设备中进行。 Absorption may be performed in a column, it may be performed in the quenching apparatus. 其可以以并流进行,也可以以逆流进行。 Which can be cocurrent, countercurrent may be performed. 合适的吸收塔的实例有板式塔(具有泡罩塔板和/或筛板),具有规整填料(例如,比表面积为100至1000m2/m3或最高达750m2/m3的金属板填料,如Mellapak250 Y)的塔,及包含无规则填料的填料塔(例如用拉西环填充的塔)。 Examples of suitable absorber column with a plate (with bubble trays and / or sieve), having a structured packing (e.g., a specific surface area of ​​100 to 1000m2 / m3 or up to 750m2 / m3 filler metal plate, such as Mellapak 250 Y) of the column, and comprises random packing of a packed column (e.g. column packed with Raschig rings). 但是,也可以使用滴流式塔和喷淋塔、石墨块吸收器、例如厚膜和薄膜吸收器的表面吸收器以及盘式洗涤器、交叉喷淋洗涤器和旋转洗涤器。 However, it is also possible to use trickle towers and spray towers, graphite block absorbers, e.g. thick and thin film surface of the absorber and an absorber pan scrubbers, cross-spray scrubbers and rotary scrubbers. 使吸收在带有或不带内件的泡罩塔中进行也是有利的。 Absorption in a bubble column with or without internals performed also advantageous.

可以通过汽提、闪蒸和/或蒸馏从吸收介质中分离出丙烷和丙烯。 You may flash and / or distillation separation from the absorption medium by stripping out propene and propane.

优选通过汽提和/或解吸从吸收介质中分离出丙烷和丙烯。 Preferably separated by stripping and / or desorption of the absorption medium from propane and propylene. 可以常规方式利用压力和/或温度的变化优选在0.1至10bar、特别是1至5bar、更优选1至3bar的压力和0至200℃、特别是20至100℃、更优选30至70℃、特别优选40至60℃的温度下进行解吸。 Conventional manner using pressure and / or temperature change is preferably from 0.1 to 10bar, in particular 1 to 5bar, pressure is more preferably 1 to 3bar in and from 0 to 200 ℃, in particular 20 to 100 ℃, more preferably 30 to 70 ℃, particularly desorbed at a temperature of preferably from 40 to 60 deg.] C. 适于汽提的气体的实例是水蒸气,但特别优选氧/氮混合物,如空气。 Examples of suitable stripping gas is steam, but particularly preferably oxygen / nitrogen mixture, such as air. 如果使用空气或者氧含量高于10体积%的氧/氮混合物,可有利地在汽提过程之前或进行中加入缩小爆炸范围的气体。 If air or an oxygen content higher than 10% by volume of oxygen / nitrogen mixtures, may advantageously be performed prior to or during the stripping of the gases added to refine the explosive range. 特别可用于此目的的气体是20℃下比热≥29J/mol·K的气体,例如甲烷、乙烷、丙烷、丙烯、苯、甲醇、乙醇及氨、二氧化碳和水。 Especially useful for this purpose than the gas the gas is hot ≥29J / mol · K, such as methane, ethane, propane, propylene, benzene, methanol, ethanol, and ammonia, carbon dioxide and water at 20 ℃. 但根据本发明,应避免用C4烃作这种添加剂。 According to the present invention, however, should be avoided as such additives C4 hydrocarbons. 带有或不带内件的泡罩塔也特别可用于汽提。 A bubble column with or without internals are also particularly useful for stripping.

还可以通过蒸馏或提纯从吸收介质中分离出丙烷和丙烯,在这种情况下,可以使用包含有序填料、随机填料或合适内件的常规塔。 It may also be isolated or purified by distillation from the absorption medium propane and propene, in this case, using conventional column containing ordered packing, random packing or suitable internals. 蒸馏和提纯中优选的条件是0.01至5bar、特别是0.1至4bar、更优选1至3bar的压力和50至300℃、特别是150至250℃的温度(塔底温度)。 Distillation and purification conditions preferably 0.01 to 5bar, in particular 0.1 to 4bar, more preferably 1 to 3bar a pressure of 50 to 300 ℃, in particular the temperature (column bottom temperature) 150 to 250 deg.] C of.

通过汽提从吸收介质获得的气体混合物1′可在用作送至分区的进料之前送往另一处理阶段,从而例如减少被共汽提的吸收介质的损失(如在除沫器和/或深层过滤器中沉淀),并因而同时保护分区不受吸收介质的影响,或者进一步提高C3烃与C4烃的分离。 Obtained by stripping of the gas mixture from the absorption medium 1 'can be sent to a further process stage prior to being fed to the partition used, for example to reduce the losses by absorption co-stripped media (as in the demister and / depth filters or precipitated), and thus at the same time protects the partition from the absorption medium, or to further improve the separation of C3 hydrocarbons and C4 hydrocarbons. 可以通过本领域技术人员已知的所有处理步骤进行吸收介质的这种去除。 This removal may be performed by absorption medium known to those skilled in all processing steps. 就本发明而言优选的这种分离的实施方式是例如用水猝冷出自汽提装置的原料气流。 For the present invention a preferred embodiment this separation is, for example, the feed gas stream by quenching with water stripping device. 在这种情况下,利用水将吸收介质洗出该装载的原料气流,且同时该原料气流负载了水。 In this case, the water absorption medium stream to wash out the loading of the feed, while the feed gas stream loaded with water. 所述洗涤或猝冷可以例如通过逆流喷洒水于解吸塔顶部在液体收集塔板上方进行,或在单独的装置中进行。 The washing or quenching may be carried out, for example, above the liquid collecting tray by spraying water on the top of a countercurrent stripper column, or in a separate device.

为了提高分离效果,可在猝冷区安装可增大猝冷表面积的、在提纯、吸收和解吸领域中的技术人员已知的内件。 In order to improve the separation effect, the surface area of ​​the installation can be increased quenched in quenching zone, purification, absorption and desorption known to persons skilled in the art within the member.

水是优选的洗涤介质,因为它一般不干扰后面的分区。 Water is a preferred washing medium, as it generally does not interfere with the rear partition. 在水从载有丙烷和丙烯的原料气流中洗出吸收介质后,水/吸收介质混合物被送去进行相分离,经处理的原料气流作为气体混合物1′加入分区。 After the water from the feed gas stream containing propane and propene in an absorbent wash medium, water / absorption medium mixture is sent to phase separation, the treated feed gas stream as a gas mixture of 1 'Add partition.

已被汽提不含C3烃的吸收介质、以及在相分离中回收的吸收介质都可重新用于吸收目的。 It has been put vapor absorption medium free of C3 hydrocarbons, as well as absorption medium recovered in the phase separation can be reused for absorption purposes.

气体混合物1和/或由其制造的气体混合物1′现可以本身已知的方式用于至少一个反应区中,以供应使用进料气体混合物2的丙烯至丙烯醛和/或丙烯酸和/或丙烯腈的多相催化气相氧化和/或氨氧化。 1 the gas mixture and / or gas production therefrom mixture 1 'can now be known per se for the at least one reaction zone to supply a mixture of propylene to acrolein and / or acrylic acid and / or 2, using a feed of propylene gas nitriles heterogeneously catalyzed gas-phase oxidation and / or ammoxidation. 至于氧化剂,可以加入纯分子氧、空气、富氧空气或氧与惰性气体的任何其它混合物。 As the oxidizing agent, any other mixtures of pure molecular oxygen, air, oxygen enriched air or oxygen with an inert gas may be added. 如果不完全氧化是将丙烯转化为环氧丙烷,则可以采用例如EP-A 372972中描述的步骤。 If the partial oxidation of propylene is converted to propylene oxide, the steps described in EP-A 372972, for example, may be employed.

如果氧化反应是氧化为丙烯腈的不完全氨氧化,例如可以如DE-A 2351151所述进行。 If the oxidation reaction is incomplete oxidation of acrylonitrile ammoxidation, for example, may be performed as described in DE-A 2351151. 如果是丙烯至丙烯醛和/或丙烯酸的不完全氧化,则在本发明的方法中设定伴随使用气体混合物1和/或1′(也可以使用这二者的混合物,即分离从一个部分进行而不从另一个部分进行)的气体混合物2的组成,使得其处于以下摩尔比范围:丙烷∶丙烯∶N2∶O2∶H2O∶其它=0.5至20∶1∶0.1至40∶0.1至10∶0至20∶0至1。 If the propylene to acrolein and / or acrylic acid incomplete oxidation, is set along a gas mixture 1 and / or 1 '(a mixture of both may be used in the method of the present invention, i.e., a portion separated from without the other part) of the gas mixture consisting of 2, so that it is in the following molar ratio ranges: propane: propene = 0.5 20:1:0.1 :N2:O2:H2O: other to 40:0.1 to 10:0 to 20:0 to 1.

根据本发明,上述摩尔比宜为2至10∶1∶0.5至20∶0.5至5∶0.01至10∶0至1。 According to the present invention, the above molar ratio is suitably from 2 to 10:1:0.5 to 20:0.5 to 5:0.01 to 10:0 to 1.

根据本发明,上述摩尔比还宜为3至6∶1∶1至10∶1至3∶0.1至2∶0至0.5。 According to the invention, the molar ratio of 3 to 6:1:1 further desirable to 10:1 to 3:0.1 to 2-0 to 0.5.

如上所述,使用分子氧进行的丙烯至丙烯酸的多相催化气相不完全氧化在两个步骤中进行,这两个步骤在反应坐标上相互承接,其中第一个步骤生成丙烯醛,第二个步骤由丙烯醛生成丙烯酸。 As described above, the heterophasic propylene catalytic gas phase using molecular oxygen for the partial oxidation to acrylic acid is carried out in two steps, each receiving the two steps on the reaction coordinate, wherein a first step acrolein, the second the step of generating acrylic acid from acrolein.

这种分为两个在时间上相互承接的步骤的反应次序,以本身已知的方式使得本发明方法的分区在这种情况下可以采用两个连续的氧化区的形式,从而使待用的氧化催化剂在这两个氧化区的每一个中可以最优化。 This reaction sequence is divided into two steps in time with each other to undertake, in manner known per se so that the partitioning method of the present invention, in this case in the form of two successive oxidation zone may be employed, so that the inactive the oxidation catalyst can be optimized in each of the two oxidation zone. 例如,基于包含元素组合Mo-Bi-Fe的多金属氧化物的催化剂一般对第一氧化区(丙烯→丙烯醛)是优选的,而基于包含元素组合Mo-V的多金属氧化物的催化剂通常对第二氧化区(丙烯醛→丙烯酸)是优选的。 For example, based on elemental composition of Mo-Bi-Fe oxide catalysts comprising multimetal oxide generally of a first zone (propylene → acrolein) are preferred, while catalysts based on multimetal oxides containing the element combination Mo-V generally a second oxidation zone (acrolein → acrylic acid) are preferred.

许多用于所述两个氧化区的适宜的多金属氧化物催化剂在过去已有描述,并是本领域技术人员熟知的。 Many suitable multimetal oxide catalysts for the two oxidation zones have been described in the past, and are well known to the skilled person. 例如,EP A 253409在第5页参考了合适的美国专利。 For example, EP A 253409 on page 5 of U.S. Patent No. suitable reference.

DE-A 4431957和DE-A 4431949也公开了用于所述两个氧化区的适宜的多金属氧化物催化剂。 DE-A 4431957 and DE-A 4431949 also discloses a suitable multimetal oxide catalysts for the two oxidation zones. 它们特别是上述两个文献中式I的那些。 They are in particular those of formula I above two documents.

对于不完全氧化的第一步,即丙烯至丙烯醛的多相催化气相不完全氧化,如上所述,原则上可以使用所有包含Mo、Bi和Fe的多金属氧化物组合物。 For the first step partial oxidation of propylene to acrolein i.e. heterogeneously catalyzed gas-phase partial oxidation, as described above, it can be used all contain Mo, Bi and Fe multimetal oxide composition principle.

它们特别是DE-A 19955176中式I的活性多金属氧化物组合物、DE-A 19948523中式I的活性多金属氧化物组合物、DE-A 19948523中式I的活性多金属氧化物组合物、DE-A 10101695中式I、II和III的活性多金属氧化物组合物、DE-A 19948248中式I、II和III的活性多金属氧化物组合物、DE-A 19955168中式I、II和III的活性多金属氧化物组合物以及EP-A 700714中描述的活性多金属氧化物组合物。 They are particularly active DE-A 19955176 formula I multimetal oxide composition, DE-A 19948523 formula I as active multimetal oxide composition, DE-A I 19948523 active multimetal oxide composition of formula, DE- a 10101695 of formula I, II and III are active multimetal oxide composition, DE-a 19948248 of formula I, II and III are active multimetal oxide composition, DE-a 19955168 of formula I, II and III activity polymetallic oxide compositions and an active multimetal oxide composition of EP-a 700714 describes.

其它包含Mo、Bi和Fe的适于该氧化步骤的多金属氧化物催化剂是在DE-A 10046957、DE-A 10063162、DE-C 3338380、DE-A 19902562、EP-A 15565、DE-C 2380765、EP-A 807465、EP-A 279374、DE-A 3300044、EP-A 575897、US-A 4438217、DE-A 19855913、WO 98/24746、DE-A 19746210(式II的那些)、JP-A 91/294239、EP-A 293224和EP-A 700714中公开的那些。 Other multi-metal oxide catalyst comprising Mo, Bi and Fe are suitable for this oxidation step in DE-A 10046957, DE-A 10063162, DE-C 3338380, DE-A 19902562, EP-A 15565, DE-C 2380765 , EP-a 807465, EP-a 279374, DE-a 3300044, EP-a 575897, US-a 4438217, DE-a 19855913, WO 98/24746, (those of formula II) DE-a 19746210, JP-a 91 / 294,239, EP-a 293224 and those of EP-a 700714 are disclosed. 特别是这些文献中通过举例提到的实施方案,其中EP-A 15565、EP-A 575897、DE-A 19746210和DE-A 19855913是特别优选的。 In particular these documents mentioned by way of example embodiments, in which EP-A 15565, EP-A 575897, DE-A 19746210 and DE-A 19855913 is particularly preferred. 在本文中,特别可提到的是EP-A 15565中实施例1c描述的催化剂和可以以类似的方式制备但其活性组成为式Mo12Ni6.5Zn2Fe2Bi1P0.0065K0.06Ox·10SiO2的催化剂。 In this context, particular mention may be made of the catalyst described in Example 1c of EP-A 15565 and the embodiment may be prepared in a similar manner but its activity composition formula Mo12Ni6.5Zn2Fe2Bi1P0.0065K0.06Ox · 10SiO2 catalysts. 其它值得特别提到的催化剂是DE-A 19855913中实施例3(化学计量:Mo12Co7Fe3Bi0.6K0.08Si1.6Ox)的外形为5mm×3mm×2mm(外径×高×内径)的全活性中空圆柱体催化剂,以及多金属氧化物II--DE-A 19746210的实施例1描述的全活性催化剂。 Other catalysts are worthy of special mention EXAMPLE 3 DE-A 19855913 In Embodiment: Shape (stoichiometric Mo12Co7Fe3Bi0.6K0.08Si1.6Ox) of 5mm × 3mm × 2mm was (outer diameter × inside diameter × height) of the hollow cylinder fully active catalyst, and a plurality of metal oxide II - DE-a full activity of the catalyst of Example 1 described 19,746,210. 还可以提到US-A 4438217的多金属氧化物催化剂。 It may also be mentioned US-A 4,438,217 a multi-metal oxide catalyst. 当这些中空圆柱体具有5.5mm×3mm×3.5mm或5mm×2mm×2mm或5mm×3mm×2mm或6mm×3mm×3mm或7mm×3mm×4mm的外形时(分别为外径×高×内径),后者是特别适用的。 When the shape of a hollow cylinder having a 5.5mm × 3mm × 3.5mm or 5mm × 2mm × 2mm or 5mm × 3mm × 2mm or or 6mm × 3mm × 3mm of 7mm × 3mm × 4mm (respectively the outside diameter × inside diameter × height) the latter is particularly useful.

许多适于丙烯至丙烯醛步骤的多金属氧化物组合物可以用式IV描述:Mo12BiaFebX1cX2dX3eX4fOn(IV),其中变量具有以下含义:X1=镍和/或钴,X2=铊、碱金属和/或碱土金属,X3=锌、磷、砷、硼、锑、锡、铈、铅和/或钨,X4=硅、铝、钛和/或锆,a=0.5至5,b=0.01至5,优选2至4, Many suitable multimetal oxide composition of propylene to acrolein step may be described by Formula IV: Mo12BiaFebX1cX2dX3eX4fOn (IV), where the variables have the following meanings: X1 = nickel and / or cobalt, X2 = thallium, an alkali metal and / or alkaline earth metal, X3 = zinc, phosphorus, arsenic, boron, antimony, tin, cerium, lead and / or tungsten, X4 = silicon, aluminum, titanium and / or zirconium, a = 0.5 to 5, b = 0.01 to 5, preferably 2 to 4,

c=0至10,优选3至10,d=0至2,优选0.02至2,e=0至8,优选0至5,f=0至10且n=由IV中氧之外的元素的化学价和丰度确定的数。 c = 0 to 10, preferably from 3 to 10, d = 0 to 2 and preferably from 0.02 to 2, e = 0 to 8 and preferably 0 to 5, f = 0 to 10 and n = the elements other than oxygen in IV of valence and abundance of the determined number.

它们可以本身以知的方式制得(参见例如DE-A 4023239),通常成型为未稀释的形式以制造球形、环形或圆柱形,或以涂覆催化剂的形式使用,即涂覆有活性组合物的预成型的惰性载体。 They may be prepared by per se known manner (see e.g. DE-A 4023239), generally shaped to undiluted form to manufacture a spherical, cylindrical, or annular, or in the form of catalyst-coated, i.e., coated with the active composition preformed inert carrier. 当然,它们也可用作粉末形式的催化剂。 Of course, they can also be used as a catalyst in powder form.

原则上,式IV的活性组合物可以以简单的方式如下制备:由它们基本组分的合适来源制造非常均匀的、优选细碎的具有对应于它们化学计量的组成的干燥混合物,并于350至650℃对该混合物进行煅烧。 In principle, active compositions of formula IV may be prepared in a simple manner as follows: a suitable source thereof for producing a very homogeneous basic component, preferably finely divided dry mixture having a composition corresponding to their stoichiometry, and at 350-650 the mixture was calcined ℃. 煅烧可以在惰性气体中进行,也可以在例如空气(惰性气体与氧的混合物)的氧化气氛中或还原气氛(例如惰性气体、NH3、CO和/或H2的混合物)进行。 The calcination can be performed in an inert gas, an oxidizing atmosphere may be, for example, air (a mixture of inert gas and oxygen), or in a reducing atmosphere (e.g. an inert gas, NH3, CO / H2, or a mixture) of. 煅烧时间可以是从数分钟至数小时,并一般随温度上升而缩短。 The calcination time may be from minutes to hours and is generally shorter with increasing temperature. 活性多金属氧化物组合物IV的基本组分的可能来源是氧化物,和/或可以至少在氧的存在下通过加热转化为氧化物的化合物。 Possible sources of essential components of the active multimetal oxide compositions IV are oxides, and / or may at least in the presence of oxygen by heating the compound into an oxide.

除氧化物之外,其它合适的起始化合物特别包括卤化物、硝酸盐、甲酸盐、草酸盐、柠檬酸盐、乙酸盐、碳酸盐、氨络合物盐、铵盐和/或氢氧化物(可以在均匀干燥的混合物中另外混入以下化合物:最迟在后面的煅烧期间分解和/或可以被分解为以气态释放出的化合物的化合物,例如NH4OH、(NH4)2CO3、NH4NO3、NH4CHO2、CH3COOH、NH4CH3CO2和/或草酸铵)。 In addition to oxides, in particular other suitable starting compounds include halides, nitrates, formates, oxalates, citrates, acetates, carbonates, ammine complex salts, ammonium salts and / or hydroxides (may be additionally mixed into a uniform dry mixture following compounds: by the decomposition and / or may be decomposed into a gaseous compound is released during the calcining of the back, for example NH4OH, (NH4) 2CO3, NH4NO3 , NH4CHO2, CH3COOH, NH4CH3CO2 and / or ammonium oxalate).

用于制备多金属氧化物组合物IV的起始化合物的均匀混合可以以干法进行或者以湿法进行。 Uniformly mixing the starting compounds for preparing multimetal oxide compositions IV can be used in a dry or in a wet process. 如果以干法进行,宜将起始化合物用作细粉末,并在混合后进行煅烧,如果合适,还进行压制。 If the dry process, the starting compound should be used as the fine powder, and calcined after mixing, if appropriate, further pressing. 但是均匀混合优选以湿法进行。 However, mixing is preferably carried out in a uniform wet. 在这种情况下,起始混合物通常以水溶液和/或水悬浮液的形式相互混合。 In this case, the starting mixture is generally in the form of an aqueous solution and / or suspension mixed with each other. 特别均匀的干燥混合物是当基本组分源都处于溶解形式时在所述混合过程中获得的。 Particularly homogeneous dry mixture is an essential component when the source is in dissolved form are obtained in the mixing process. 优选用水作为溶剂。 Preferably with water as the solvent. 然后干燥所获含水组合物,优选以100至150℃的出口温度通过喷雾干燥所述含水混合物。 The resulting aqueous composition is then dried, preferably to an outlet temperature of 100 to 150 deg.] C by spray drying said aqueous mixture.

式IV的活性多金属氧化物组合物可以以粉末形式或者在成型为特定的催化剂外形后用于“丙烯→丙烯醛”步骤。 Formula IV multimetal oxide active composition may be in powder form or after formed into a specific shape for the catalyst "propylene → acrolein" step. 成型可以在最终煅烧之前或之后进行。 Molding may be performed before or after the final calcination. 例如,可以通过压制由粉末形式的活性组合物或其未煅烧的和/或部分煅烧的前体制造全活性催化剂,以产生合意的催化剂外形(例如通过压制成片、挤出或柱塞挤出),如果需要,可以加入助剂如石墨或硬脂酸作润滑剂和/或成型助剂;及增强材料,如玻璃微纤维、石棉、碳化硅或钛酸钾。 For example, an active catalyst can be produced by pressing the whole powder form of the active composition or its uncalcined and / or partially calcined precursor catalyst to produce a desirable shape (e.g., extruded into a sheet by pressing, extrusion or ram ), if desired, adding additives, such as graphite or stearic acid as a lubricant and / or a molding aid; and reinforcing materials such as glass microfibers, asbestos, silicon carbide or potassium titanate. 合适的全活性催化剂外形有,例如,外径和长度为2至10mm的实心圆柱形或空心圆柱形。 Suitable active catalysts full profile are, for example, an outer diameter of 10mm and a length of 2 to a solid cylindrical or hollow cylindrical. 在是空心圆柱形的情况下,壁厚宜为1至3mm。 In the case where a hollow cylindrical, wall thickness is suitably 1 to 3mm. 当然,全活性催化剂还可以是球形,此时其直径可以是2至10mm。 Of course, all-active catalyst may also be spherical, with a diameter at this time may be 2 to 10mm.

特别可用的空心圆柱外形是5mm×3mm×2mm(外径×长度×内径),特别是在全活性催化剂的情况下。 Particularly useful are hollow cylindrical shape 5mm × 3mm × 2mm (outside diameter × inside diameter × length), particularly in the case of full activity of the catalyst.

当然,也可以通过施用到预成型的惰性催化剂载体上而实现粉末状活性组合物的成型,或其尚未煅烧的和/或部分煅烧的粉末状前体组合物的成型。 Of course, it can also be achieved molded powdered active composition by administering to the catalyst on an inert support preform, or a molded yet calcined and / or partially calcined powdered precursor composition. 为制造涂覆的催化剂,通常在合适的可旋转容器中涂覆载体,这是由例如DE-A 2909671、EP-A 293859或EP-A 714700获知的。 Making a coated catalyst, is typically coated carrier in a suitable rotatable container, which is made, for example, DE-A 2909671, EP-A 293859 or EP-A 714700 learned. 为涂覆载体,宜将待施用的粉末组合物打湿,并在施用后例如通过热空气再次干燥。 Is coated carrier, it should be administered the wet powder composition, and dried again by hot air, for example after administration. 施用到载体上的粉末组合物的厚度宜为10至1000μm,优选为50至500μm,特别优选150至250μm。 Applied to the thickness of the powder composition on the support is suitably 10 to 1000μm, preferably 50 to 500μm, particularly preferably 150 to 250μm.

至于载体材料,可以使用常用的多孔或非多孔氧化铝、二氧化硅、二氧化钍、二氧化锆、碳化硅或例如硅酸镁或硅酸铝的硅酸盐。 As support material, a conventional porous or non-porous alumina, silica, thorium dioxide, zirconium dioxide, silicon carbide or silicates such as magnesium silicate or aluminum silicate. 对于本发明方法中的所述反应,它们一般基本是惰性的。 For the polymerization process of this invention, they are typically substantially inert. 载体可以具有规则的或不规则的形状,但优选表面粗糙度非常大的形状规则的载体,例如球形或中空圆柱形。 The carrier may have a regular or irregular shape, the surface roughness of the support is preferably a very large regular shape, such as spherical or hollow cylindrical. 使用具有粗糙表面且直径为1至8mm、优选4至5mm的基本为非多孔的球形滑石是适宜的。 Having a rough surface and a diameter of 1 to 8mm, preferably substantially nonporous spherical talc 4 to 5mm is appropriate. 但使用长度为2至10mm、外径为4至10mm的圆柱体作为载体也是适宜的。 However, using a length of 2 to 10mm, an outer diameter of 4 to 10mm cylinder as a carrier are also suitable. 在使用合适的环作为载体的情况下,其壁厚通常为1至4mm。 In the case of using the ring as a suitable carrier, typically a wall thickness of 1 to 4mm. 就本发明方法而言,优选的环形载体的长度为2至6mm,外径为4至8mm,壁厚1至2mm。 In terms of the method of the present invention, the length of the annular carrier is preferably 2 to 6mm, an outer diameter of 4 to 8mm, a wall thickness of 1 to 2mm. 外形为7mm×3mm×4mm(外径×长度×内径)的环也特别可用作本发明的载体。 Shape of 7mm × 3mm × 4mm (outside diameter × inside diameter × length) of the ring is also particularly useful as vectors of the present invention. 当然,待施用到载体表面的催化活性氧化物组合物的细度与所需涂层的厚度相匹配(参见EP-A 714 700)。 Of course, it is applied to the fineness of the surface of the support catalytically active oxide composition of the desired coating thickness matches (see EP-A 714 700).

其它可用于由丙烯生成丙烯醛的活性多金属氧化物组合物是式V的组合物:[Y1a′Y2b′Ox′]p[Y3c′Y4d′Y5e′Y6f′Y7g′Y2h′Oy′]q(V)其中各变量的含义如下:Y1=单独的铋或者铋与碲、锑、锡和铜中的至少一种,Y2=钼或钼与钨,Y3=碱金属、铊和/或钐,Y4=碱土金属、镍、钴、铜、锰、锌、锡、镉和/或汞,Y5=铁或铁与元素铬和铈中的至少一种,Y6=磷、砷、硼和/或锑,Y7=稀土元素、钛、锆、铌、钽、铼、钌、铑、银、金、铝、镓、铟、硅、锗、铅、钍和/或铀,a'=0.01至8,b'=0.1至30,c'=0至4,d'=0至20,e'>0至20,f'=0至6,g'=0至15,h'=8至16,x'、y'=由V中除氧之外的元素的化合价和丰度决定的数,且p、q=比率p/q为0.1至10的数,其具有化学组合物Y1a′Y2b′Ox′的三维区域,所述三维区域因具有不同于其局部环境的组成而与其局部环境区别开来,且其最 Other acrolein from propylene can be used to generate an active multimetal oxide composition is a composition of Formula V: [Y1a'Y2b'Ox '] p [Y3c'Y4d'Y5e'Y6f'Y7g'Y2h'Oy'] q ( V) wherein the meaning of each variable is as follows: Y1 = bismuth alone or with at least one of bismuth, Y2 = molybdenum, tungsten or molybdenum and tellurium, antimony, tin and copper, Y3 = an alkali metal, thallium and / or samarium, Y4 = alkaline earth metal, nickel, cobalt, copper, manganese, zinc, tin, cadmium and / or mercury, at least one = Y5, Y6 = phosphorus, arsenic, boron and / or antimony and elemental chromium or iron and cerium, Y7 = rare earth elements, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and / or uranium, a '= 0.01 to 8, b' = 0.1 to 30, c '= 0 to 4, d' = 0 to 20, e '> 0 to 20, f' = 0 to 6, g '= 0 to 15, h' = 8 to 16, x ', y '= is determined by the valence and abundance of the elements V number other than oxygen, and p, q = the ratio p / q is a number from 0.1 to 10, having a chemical composition Y1a'Y2b'Ox' three-dimensional region, the three-dimensional region has a different composition because of their local environment and distinguish their local environment, and the most 大直径(该区域表面(边界)上两点之间的、并穿过重心的最长连接线)为1nm至100μm,经常为10nm至500nm或1μm至50或25μm。 Large diameter (and through the center of gravity of the longest connecting line between the upper surface of the region (border) points) is 1nm to 100 m, often 10nm to 500nm or 1μm to 50 or 25μm.

特别适宜的多金属氧化物组合物V是Y1是单独的铋的那些。 Particularly suitable multimetal oxide composition V Y1 are those bismuth alone.

其中,又优选具有式VI组成的那些:[Bia”Z2b”Ox”]p”[Z212Z3c”Z4d”Fee”Z5f”Z6g”Z7h”Oy”]q”(VI)其中各变量具有如下含义:Z2=钼或钼与钨,Z3=镍和/或钴,Z4=铊、碱金属和/或碱土金属,Z5=磷、砷、硼、锑、锡、铈和/或铅,Z6=硅、铝、钛和/或锆,Z7=铜、银和/或金,a”=0.1至1,b”=0.2至2,c”=3至10,d”=0.02至2,e”=0.01至5,优选0.1至3,f”=0至5,g”=0至10,h”=0至1,x”、y”=由VI中除氧之外的元素的化合价和丰度决定的数,且p”、q”=比率p”/q”为0.1至5、优选为0.5至2的数,非常特别优选Z2b”=(钨)b”和Z212=(钼)12的组合物VI。 Wherein, further preferably those of formula VI consisting of: [Bia "Z2b" Ox "] p" [Z212Z3c "Z4d" Fee "Z5f" Z6g "Z7h" Oy "] q" (VI) wherein the variables have the following meanings: Z2 = molybdenum or molybdenum and tungsten, Z3 = nickel and / or cobalt, Z4 = thallium, an alkali metal and / or alkaline earth metal, Z5 = phosphorus, arsenic, boron, antimony, tin, cerium and / or lead, Z6 = silicon, aluminum , titanium and / or zirconium, Z7 = copper, silver and / or gold, a "= 0.1 to 1, b" = 0.2 to 2, c "= 3 to 10, d" = 0.02 to 2, e "= 0.01 to 5, preferably from 0.1 to 3, f "= 0 to 5, g" = 0 to 10, h "= 0 to 1, x", y "= determined by the valence and abundance VI elements except for oxygen number, and p ", q" = the ratio p "/ q" is from 0.1 to 5, preferably a number of 0.5 to 2, very particularly preferably Z2b "= (tungsten) b" and Z212 = (Mo) composition VI 12 of .

有利的是,适于本发明目的的多金属氧化物组合物V(多金属氧化物组合物VI)的总的[Y1a′Y2b′Ox′]p含量([Bia”Z2b”Ox”]p”)的至少25摩尔%(优选至少50摩尔%)以三维区域的化学组合物Y1a′Y2b′Ox′[Bia”Z2b”Ox”]p”〕的形式存在,所述三维区域因具有不同于其局部环境的组成而与其局部环境区别开来,且其最大直径为1nm至100μm。 Advantageously, the object of the present invention is suitable for multi-metal oxide compositions V (multi-metal oxide compositions VI) total [Y1a'Y2b'Ox '] p content ([Bia "Z2b" Ox "] p" ) of at least 25 mole% (preferably at least 50 mol%) chemical composition of the three-dimensional region Y1a'Y2b'Ox '[Bia "Z2b" Ox "] p"] is present in the form of the three-dimensional region has a different because of its composition of the local environment and open its local environment difference, and a maximum diameter of 1nm to 100μm.

关于成型,在关于多金属氧化物催化剂IV的部分所述内容适用于多金属催化剂V。 Molded on, in part on the multi-IV metal oxide catalyst suitable for use in multi-metallic catalyst V.

活性多金属氧化物组合物V的制备描述于例如EP-A 575897和DE-A 19855913中。 Preparation of active multimetal oxide composition V are described in, for example, EP-A 575897 DE-A 19855913 and.

特别地,上文推荐的惰性载体材料也可用作稀释合适的固定催化剂床和/或限制其范围的惰性材料,或用作保护催化剂和/加热气体混合物的上游床。 In particular, the preferred inert carrier materials may be used above a suitable dilute fixed catalyst bed and / or limiting the scope of the inert material, or as to protect the catalyst bed and upstream / gas mixture is heated.

在此,可以指出的是,所有已推荐为适于由丙烯生成丙烯醛的步骤的催化剂和多金属氧化物组合物原则上也都是适于由丙烯生成丙烯腈的的不完全氨氧化的。 Here, it may be noted that, in principle, all of the catalyst have been proposed and multimetal oxide compositions are suitable for the step of generating acrolein from propylene are also not fully suitable for the ammoxidation of propylene to produce acrylonitrile.

对于第二步,即由丙烯腈生成丙烯酸的多相催化气相不完全氧化,如上所述,原则上可以使用所有包含Mo和V作活性组合物的多金属氧化物组合物,例如由DE-A 10046928获知的那些。 For the second step, i.e. to form acrylic acid by heterogeneously catalyzed gas-phase acrylonitrile partial oxidation, as described above, may be used for all multi-metal oxide compositions comprising Mo and V as the active principle of the composition, for example, from DE-A 10,046,928 learned those.

许多这种组合物,例如DE-A 19815281中的那些,可以用式VII来描述:Mo12VaX1bX2cX3dX4eX5fX6gOn(VII)其中各变量具有如下含义:X1=W、Nb、Ta、Cr和/或Ce,X2=Cu、Ni、Co、Fe、Mn和/或Zn,X3=Sb和/或Bi,X4=一种或多种碱金属,X5=一种或多种碱土金属,X6=Si、Al、Ti和/或Zr,a=1至6,b=0.2至4,c=0.5至18,d=0至40,e=0至2, Many such compositions, for example, in DE-A 19815281, those of formula VII can be described: Mo12VaX1bX2cX3dX4eX5fX6gOn (VII) where the variables have the following meanings: X1 = W, Nb, Ta, Cr and / or Ce, X2 = Cu , Ni, Co, Fe, Mn and / or Zn, X3 = Sb and / or Bi, X4 = one or more alkali metals, X5 = one or more alkaline earth metals, X6 = Si, Al, Ti and / or Zr, a = 1 to 6, b = 0.2 to 4, c = 0.5 to 18, d = 0 to 40, e = 0 to 2

f=0至4,g=0至40,和n=由VII中除氧之外的元素的化合价和丰度决定的数。 f = 0 to 4, g = 0 to 40 and n = a number determined by the valence and abundance VII elements other than oxygen.

在活性多金属氧化物VII中,根据本发明优选的实施方案是式VII中各变量具有以下含义的那些:X1=W、Nb和/或Cr,X2=Cu、Ni、Co和/或Fe,X3=Sb,X4=Na和/或K,X5=Ca、Sr和/或Ba,X6=Si、Al和/或Ti,a=1.5至5,b=0.5至2,c=0.5至3,d=0至2,e=0至0.2,f=0至1,和n=由VII中除氧之外的元素的化合价和丰度决定的数。 Active multimetal oxides VII in accordance with a preferred embodiment of the invention is of formula VII, the variables have the following meanings that: X1 = W, Nb and / or Cr, X2 = Cu, Ni, Co and / or Fe, X3 = Sb, X4 = Na and / or K, X5 = Ca, Sr and / or Ba, X6 = Si, Al and / or Ti, a = 1.5 to 5, b = 0.5 to 2, c = 0.5 to 3 d = 0 to 2, e = 0 to 0.2, f = 0 to 1, and n = a number determined by the valence and abundance VII elements other than oxygen.

但是,根据本发明非常特别优选的多金属氧化物VII是式VIII所示的那些:Mo12Va′Y1b′Y2c′Y5f′Y6g′On′(VIII)其中Y1=W和/或Nb,Y2=Cu和/或Ni,Y5=Ca和/或Sr,Y6=Si和/或Al,a'=2至4,b'=1至1.5, However, according to the present invention is very particularly preferred multimetal oxide of formula VII are those of VIII: Mo12Va'Y1b'Y2c'Y5f'Y6g'On '(VIII) where Y1 = W and / or Nb, Y2 = Cu and / or Ni, Y5 = Ca and / or Sr, Y6 = Si and / or Al, a '= 2 to 4, b' = 1 to 1.5,

c'=1至3,f'=0至0.5,g'=0至8,和n'=由VIII中除氧之外的元素的化合价和丰度决定的数。 c '= 1 to 3, f' = 0 to 0.5, g '= 0 to 8 and n' = a number determined by the valence and abundance VIII elements other than oxygen.

适于本发明目的的活性多金属氧化物组合物(VII)可以本身已知的方法,例如DE-A 4335973或EP-A 714700中公开的方法制备。 Preparation methods known per se can be suitable for the purposes of the present invention is a multi-active metal oxide composition (VII), for example, DE-A 4335973 or EP-A 714700 are disclosed.

原则上,适于步骤“丙烯醛→丙烯酸”的活性多金属氧化物组合物,特别是式VII所示的那些,可以以简单的方式如下制备:由它们基本组分的合适来源制造非常均匀的、优选细碎的具有对应于它们化学计量的组成的干燥混合物,并于350至600℃对该混合物进行煅烧。 In principle, suitable for the step "acrolein → acrylic acid" active multimetal oxide compositions, in particular those of formula VII may be prepared in a simple manner as follows: Suitable sources of essential components made from them very uniform , preferably finely divided dry mixture having a composition corresponding to the stoichiometry thereof, at 350 to 600 deg.] C and calcining the mixture. 煅烧可以在惰性气体中进行,也可以在例如空气(惰性气体与氧的混合物)的氧化气氛中或在还原气氛(例如惰性气体与例如H2、NH3、CO、甲烷和/或丙烯醛还原气体的混合物,或所述还原气体自身)中进行。 The calcination can be performed in an inert gas, or in a reducing atmosphere may be (e.g. with an inert gas, for example H2, NH3, CO, methane and / or acrolein reducing gas in an oxidizing atmosphere, for example, air (a mixture of inert gas and oxygen) in for mixture, or the reducing gas itself) in. 煅烧时间可以是从数分钟至数小时,并一般随温度上升而缩短。 The calcination time may be from minutes to hours and is generally shorter with increasing temperature. 活性多金属氧化物组合物VII的基本组分的可能来源是氧化物,和/或可以至少在氧的存在下通过加热转化为氧化物的化合物。 Possible sources of essential components of the active multimetal oxide composition VII is an oxide, and / or may at least in the presence of oxygen by heating the compound into an oxide.

用于制备多金属氧化物组合物VII的起始化合物的均匀混合可以以干法进行或者以湿法进行。 Uniformly mixing the starting compounds for preparing multimetal oxide compositions VII can be used in a dry or in a wet process. 如果以干法进行,宜将起始化合物用作细粉末,并在混合后进行煅烧,如果合适,还进行压制。 If the dry process, the starting compound should be used as the fine powder, and calcined after mixing, if appropriate, further pressing. 但是均匀混合优选以湿法进行。 However, mixing is preferably carried out in a uniform wet.

在这种情况下,起始混合物通常以水溶液和/或水悬浮液的形式相互混合。 In this case, the starting mixture is generally in the form of an aqueous solution and / or suspension mixed with each other. 特别均匀的干燥混合物是当基本组分源都处于溶解形式时在所述混合过程中获得的。 Particularly homogeneous dry mixture is an essential component when the source is in dissolved form are obtained in the mixing process. 优选用水作为溶剂。 Preferably with water as the solvent. 然后干燥所获含水组合物,优选以100至150℃的出口温度通过喷雾干燥所述含水混合物。 The resulting aqueous composition is then dried, preferably to an outlet temperature of 100 to 150 deg.] C by spray drying said aqueous mixture.

所获多金属氧化物组合物,特别是式VII所示的那些,可以以粉末形式或者在成型为特定的催化剂外形后用于丙烯醛的氧化。 The resulting multimetal oxide compositions, in particular those of formula VII may be in powder form or formed into shape after a specific catalyst for the oxidation of acrolein. 成型可以在最终煅烧之前或之后进行。 Molding may be performed before or after the final calcination. 例如,可以通过压制由粉末形式的活性组合物或其未煅烧的前体组合物制造全活性催化剂,以产生合意的催化剂外形(例如通过压制成片、挤出或柱塞挤出),如果需要,可以加入助剂如石墨或硬脂酸作润滑剂和/或成型助剂;及增强材料,如玻璃微纤维、石棉、碳化硅或钛酸钾。 For example, the whole can be manufactured by compressing the active catalyst precursor composition from the powder form of the active composition or its uncalcined catalyst to produce a desirable shape (e.g., by compression into tablets, extrusion or ram extrusion), if desired , may be added to aid such as graphite or stearic acid as a lubricant and / or a molding aid; materials, such as glass microfibers, asbestos, silicon carbide or potassium titanate and enhancement. 合适的全活性催化剂外形有,例如,外径和长度为2至10mm的实心圆柱形或空心圆柱形。 Suitable active catalysts full profile are, for example, an outer diameter of 10mm and a length of 2 to a solid cylindrical or hollow cylindrical. 在是空心圆柱形的情况下,壁厚宜为1至3mm。 In the case where a hollow cylindrical, wall thickness is suitably 1 to 3mm. 当然,全活性催化剂还可以是球形,此时其直径可以是2至10mm。 Of course, all-active catalyst may also be spherical, with a diameter at this time may be 2 to 10mm.

当然,也可以通过施用到预成型的惰性催化剂载体上而实现粉末状活性组合物的成型,或其尚未煅烧的粉末状前体组合物的成型。 Of course, it can also be achieved molded powdered active composition by administering to the catalyst on an inert support preform, or a molded Not calcined powdered precursor composition. 为制造涂覆的催化剂,通常在合适的可旋转容器中涂覆载体,这是由例如DE-A 2909671、EP-A 293859或EP-A 714700获知的。 Making a coated catalyst, is typically coated carrier in a suitable rotatable container, which is made, for example, DE-A 2909671, EP-A 293859 or EP-A 714700 learned.

为涂覆载体,宜将待施用的粉末组合物打湿,并在施用后例如借助热空气再次干燥。 Is coated carrier, it should be administered the wet powder composition, for example by means of hot-air drying and again after administration. 施用到载体上的粉末组合物的厚度宜为10至1000μm,优选为50至500μm,特别优选150至250μm。 Applied to the thickness of the powder composition on the support is suitably 10 to 1000μm, preferably 50 to 500μm, particularly preferably 150 to 250μm.

至于载体材料,可以使用常用的多孔或非多孔氧化铝、二氧化硅、二氧化钍、二氧化锆、碳化硅或例如硅酸镁或硅酸铝的硅酸盐。 As support material, a conventional porous or non-porous alumina, silica, thorium dioxide, zirconium dioxide, silicon carbide or silicates such as magnesium silicate or aluminum silicate. 载体可以具有规则的或不规则的形状,但优选表面粗糙度非常大的形状规则的载体,例如具有粗砂涂层的球形或中空圆柱形。 The carrier may have a regular or irregular shape, the surface roughness of the support is preferably a very large regular shape, e.g. grit having a coating of hollow cylindrical or spherical. 使用具有粗糙表面且直径为1至8mm、优选4至5mm的基本为非多孔的球形滑石是适宜的。 Having a rough surface and a diameter of 1 to 8mm, preferably substantially nonporous spherical talc 4 to 5mm is appropriate. 但使用长度为2至10mm、外径为4至10mm的圆柱体作为载体也是适宜的。 However, using a length of 2 to 10mm, an outer diameter of 4 to 10mm cylinder as a carrier are also suitable. 在使用环作为载体的情况下,其壁厚通常为1至4mm。 In the case of using as the support ring, the wall thickness is usually 1 to 4mm. 环形载体优选具有2至6mm的长度,4至8mm的外径和1至2mm的壁厚。 The annular support preferably has a length of from 2 to 6mm, the outer diameter and wall thickness of 1 to 2mm to 8mm to 4. 外形为7mm×3mm×4mm(外径×长度×内径)的环也特别可用作载体。 Shape of 7mm × 3mm × 4mm (outside diameter × inside diameter × length) is particularly useful as a carrier ring. 当然,待施用到载体表面的催化活性氧化物组合物的细度与所需涂层的厚度相匹配(参见EP-A 714700)。 Of course, it is applied to the fineness of the surface of the support catalytically active oxide composition of the desired coating thickness matches (see EP-A 714700).

用于“丙烯醛→丙烯酸”步骤的合适的活性多金属氧化物组合物是如式IX所示的组合物:[D]p[E]q(IX)其中各变量具有如下含义:D=Mo12Va”Z1b”Z2c”Z3d”Z4e”Z5f“6g”Ox”, Suitable active for "acrolein → acrylic acid" step multimetal oxide composition is a composition as shown in Formula IX: [D] p [E] q (IX) wherein the variables have the following meanings: D = Mo12Va "Z1b" Z2c "Z3d" Z4e "Z5f" 6g "Ox",

E=Z712Cuh”Hi”Oy”,Z1=W、Nb、Ta、Cr和/或Ce,Z2=Cu、Ni、Co、Fe、Mn和/或Zn,Z3=Sb和/或Bi,Z4=Li、Na、K、Rb、Cs和/或H,Z5=Mg、Ca、Sr和/或Ba,Z6=Si、Al、Ti和/或Zr,Z7=Mo、W、V、Nb和/或Ta,优选Mo和/或W,a”=1至8,b”=0.2至5,c”=0至23,d”=0 to 50,e”=0至2,f”=0至5,g”=0至50,h”=4至30,i”=0至20,和x”、y”=由IX中除氧之外的元素的化合价和丰度决定的数,和p、q=比率p/q为160∶1至1∶1的非零的数,且组合物IX可如下获得:单独预形成细碎形式的多金属氧化物组合物E(起始组合物1):Z712Cuh”Hi”Oy”(E)然后以所需的比率p∶q将预形成的固体起始组合物1混入以化学计量D包含元素Mo、V、Z1、Z2、Z3、Z4、Z5和Z6的这些元素的源物质的水溶液、水悬浮液或细碎干燥混合物中(起始组合物2):Mo12Va”Z1b”Z2c”Z3d”Z4e”Z5f”Z6g”(D)如果需要,可干燥所获含 E = Z712Cuh "Hi" Oy ", Z1 = W, Nb, Ta, Cr and / or Ce, Z2 = Cu, Ni, Co, Fe, Mn and / or Zn, Z3 = Sb and / or Bi, Z4 = Li , Na, K, Rb, Cs and / or H, Z5 = Mg, Ca, Sr and / or Ba, Z6 = Si, Al, Ti and / or Zr, Z7 = Mo, W, V, Nb and / or Ta , preferably Mo and / or W, a "= 1 to 8, b" = 0.2 to 5, c "= 0 to 23, d" = 0 to 50, e "= 0 to 2, f" = 0 to 5 g "= 0 to 50, h" = 4 to 30, i "= 0 to 20, and x", y "= determined by the valence and abundance of the elements other than oxygen IX, number, and p, q = the ratio p / q is non-zero number of 160:1 to 1:1, IX and the composition can be obtained as follows: pre multimetal oxide composition E (starting composition 1) formed separately in finely divided form: Z712Cuh " the solid starting composition hi "Oy" (E) and then to the desired ratio of pre-formed 1 p:q mixed stoichiometrically D comprises elements Mo, V, Z1, Z2, Z3, Z4, Z5, and Z6 these aqueous source material elements, finely divided aqueous suspension or in a dry mixture (starting composition 2): Mo12Va "Z1b" Z2c "Z3d" Z4e "Z5f" Z6g "(D) if desired, drying the obtained containing 混合物,并于250至600℃煅烧这样获得的干燥前体组合物,以产生合意的催化剂外形。 Mixture was calcined at 250 to 600 deg.] C thus obtained was dried precursor composition, desirable shape to produce a catalyst.

优选的多金属氧化物组合物IX是将预形成的固体起始组合物1于≤70℃混入含水起始起始组合物2中而制备的。 The solid starting composition is preferably a multi-metal oxide compositions IX are mixed in a pre-formed aqueous composition at ≤70 ℃ initial starting 2 was prepared. 制备多金属氧化物组合物IX的详细描述可见于例如EP A 668104、DE-A 19736105、DE-A 10046928、DE-A 19740493和DE-A 19528646。 Detailed description of the preparation of multimetal oxide composition IX is found, for example EP A 668104, DE-A 19736105, DE-A 10046928, DE-A 19740493 and DE-A 19528646.

关于成型,在关于多金属氧化物催化剂VII的部分所述内容适用于多金属催化剂IX。 Molded on, in part on the multi-metal oxide catalyst VII suitable for use in multi-metallic catalyst IX.

其它非常适于步骤“丙烯醛→丙烯酸”的多金属氧化物催化剂是DE-A 19815281所述的那些,特别是该文献描述的式I所示的活性多金属氧化物组合物。 Other very suitable step "acrolein → acrylic acid" is a multi-metal oxide catalyst that DE-A active multimetal oxide composition I shown in the formula 19815281 especially described in this document.

有利的是,对于由丙烯生成丙烯醛的步骤使用全活性催化剂环,而对于由丙烯醛生成丙烯酸的步骤使用涂覆的催化剂环。 Advantageously, for the step of acrolein from propylene using a full ring active catalyst, and for the step from acrolein to acrylic acid using a catalyst-coated rings.

不完全氧化的第一步(由丙烯生成丙烯醛)可以使用上述催化剂在例如DE-A 4431957中描述的单区多管固定床反应器中进行。 The first step of incomplete oxidation (acrolein from propylene) may be performed using the catalyst in the reactor in a single zone, for example, DE-A 4431957 describes a multi-tube fixed bed.

使用氧作为氧化剂。 Using oxygen as the oxidant. 如果选择N2作为惰性稀释气体,使用空气作为氧源是特别适宜的。 If selected as the inert diluent gas N2, using air as oxygen source is particularly suitable.

不完全氧化通常是以1∶(1.0-3.0)∶(5-25)、优选1∶(1.7-2.3)∶(10-15)的丙烯∶氧∶惰性气体(包括水蒸气)体积(标准升)比率进行的。 1: usually incomplete oxidation (1.0-3.0): (5-25), preferably 1: (1.7-2.3): (10-15) propylene: oxygen: inert gases (including water vapor) volume (standard liters ) of ratios. 反应压力通常为1至3 bar,且总的空间速度优选为1500至4000标准升/(升·小时)。 The reaction pressure is generally from 1 to 3 bar, and the total space velocity is preferably from 1500 to 4000 Nl / (1.h). 丙烯的空间速度一般为90至200标准升/(升·小时)。 Propylene space velocity is generally from 90 to 200 standard liters / (liter · hr).

进料气混合物优选从上方流入单区多管固定床反应器中。 The feed gas mixture preferably flows from the upper region of a single multi-tubular fixed bed reactor. 至于传热介质,宜使用盐熔融物,优选由60重量%的硝酸钾(KNO3)和40重量%的亚硝酸钠(NaNO2)组成的、或由53重量%的硝酸钾(KNO3)、40重量%的亚硝酸钠(NaNO2)和7重量%的硝酸钠(NaNO3)组成的盐熔融物。 As heat transfer medium, it is preferable to use a salt melt, preferably from 60% by weight of potassium nitrate (of KNO3) and 40% by weight of sodium nitrite (NaNO2 in) consisting of, or consisting of 53% by weight of potassium nitrate (of KNO3), 40 wt. % of sodium nitrite (NaNO2 in) of sodium nitrite and 7% by weight (of NaNO3) was composed of a molten salt.

从反应器上方观察时,盐熔融物和反应气混合物可以以并流或逆流输送。 When viewed from the top of the reactor, the salt melt and the reaction gas mixture can be conveyed in cocurrent or countercurrent. 盐熔融物优选以曲流的形式在催化剂管的周围通过。 The salt melt is preferably in the form of meanders around the catalyst tubes.

如果进料混合物是从顶部向下通过催化剂管,则宜从底部向上如下装填催化剂管(如果流动方向是从底部向上,装填顺序宜相反): If the feed mixture is from the top downwards through the catalyst tubes, preferably, from the bottom of the catalyst tubes filled up as follows (if the flow direction is from the bottom upwards, the opposite should filling order):

-首先,对于40至60%的催化剂管长度,或者仅有催化剂,或者是催化剂与惰性材料(后者最高可占混合物的20重量%)的混合物(C部分);-接下来,对于20至40%的总管长,或者仅有催化剂,或者是催化剂与惰性材料(后者最高可占混合物的40重量%)的混合物(B部分);和-最后,对于10至20%的总管长,为惰性材料床(A部分),其优选选择得可产生非常小的压降。 - First, 40 to 60% of the catalyst tube length, or only the catalyst, or a mixture of the catalyst with an inert material (which may comprise up to 20 wt% of the mixture) (part C); - Next, to 20 40% of the length of the manifold, or only the catalyst, or a mixture of the catalyst with an inert material (which may comprise up to 40 wt% of the mixture) (part B); and - finally, to 10 to 20% of the length of the manifold, as bed of inert material (a part), which is preferably chosen to be a very small pressure drop.

C部分优选不经稀释。 Part C is preferably undiluted.

如果使用DE-A 10046957实施例1中描述的、或DE-A 10046957实施例3描述的催化剂以及外形为7mm×7mm×4mm(外径×高×内径)的滑石环作惰性材料,上述装填方案是特别适宜的。 If the shape of the catalyst and DE-A 10046957 is described in Example 1, DE-A 10046957 or described in Example 3 of 7mm × 7mm × 4mm (outside diameter × inside diameter × height) of talc as inert material ring, the above-described loading scheme It is particularly suitable. 至于盐浴温度,适用DE-A 4431957中所述内容。 As the salt bath temperature for the content 4,431,957 in DE-A.

但不完全氧化的第一步(由丙烯生成丙烯醛)也可以使用所述催化剂在例如DE-A 19910506中描述的双区多管固定床反应器中进行。 However, the first step of incomplete oxidation (generation of acrolein from propylene) of the catalyst may be used in a two-zone example described in DE-A 19910506 a multitubular fixed bed reactor. 在上述两种情况下,在单程中实现的丙烯转化率通常都≥90摩尔%或≥95摩尔%。 In both cases, the conversion of propylene is usually achieved in a single pass are ≥90 mol%, or ≥95 mol%. 不完全氧化的第二步(由丙烯醛生成丙烯酸)可以使用所述催化剂在例如DE-A 4431949中描述的单区多管固定床反应器中进行。 A second step of incomplete oxidation (from acrolein to acrylic acid) may be performed using the catalyst in a reactor in a single multi-tube zone, for example, DE-A 4431949 describes a fixed bed. 由丙烯生成丙烯醛的氧化反应产生的产物混合物一般原样(即没有分离出次要组分)送入由丙烯醛生成丙烯酸的氧化反应,如果需要,在中间冷却后进行。 The product produced by the oxidation of propylene to acrolein reaction mixture as it is generally (i.e., not isolated secondary components) fed to the oxidation reaction from acrolein to acrylic acid, if necessary, after intermediate cooling.

不完全氧化的第二步所需的氧优选以空气加入,并且一般直接加入来自丙烯氧化反应的产物气体混合物中。 Step desired partial oxidation with air oxygen is preferably added, and is generally added directly to the product gas mixture from the oxidation reaction of propylene.

加入这种丙烯醛氧化反应的进料气混合物一般具有以下组成:丙烯醛∶氧∶水蒸气∶惰性气体的体积比率(标准升)为1∶(1-3)∶(0-20)∶(3-30),优选1∶(1-3)∶(0.5-10)∶(7-18)。 The addition of such an oxidation reaction of acrolein feed gas mixture generally has the following composition: acrolein: oxygen: steam: inert gas volume ratio (standard liters) of 1: (1-3): (0-20): ( 3-30), preferably 1: (1-3): (0.5-10): (7-18).

这里,反应压力一般也是1至3bar,且总的空间速度优选为1000至3800标准升/(升·小时)。 Here, the reaction pressure is generally 1 to 3bar, and the total space velocity is preferably from 1000 to 3800 Nl / (1.h). 丙烯醛的空间速度一般为80至190标准升/(升·小时)。 Acrolein space velocity is generally from 80 to 190 standard liters / (liter · hr).

进料气混合物同样优选从上方流入单区多管固定床反应器中。 Also preferred feed gas mixture flows from the upper region of a single multi-tubular fixed bed reactor. 在第二阶段,所用传热介质同样宜为盐熔融物,优选由60重量%的硝酸钾(KNO3)和40重量%的亚硝酸钠(NaNO2)组成的、或由53重量%的硝酸钾(KNO3)、40重量%的亚硝酸钠(NaNO2)和7重量%的硝酸钠(NaNO3)组成的盐熔融物。 In the second phase, the same heat-transfer medium is a salt melt should, preferably from 60% by weight of potassium nitrate (of KNO3) and 40% by weight of sodium nitrite (NaNO2 in) consisting of, or consisting of 53% by weight of potassium nitrate ( KNO3), 40 wt% of sodium nitrite (NaNO2 in) of sodium nitrite and 7% by weight (of NaNO3) melt salt thereof. 从反应器上方观察时,盐熔融物和反应气混合物可以以并流或逆流输送。 When viewed from the top of the reactor, the salt melt and the reaction gas mixture can be conveyed in cocurrent or countercurrent. 盐熔融物优选以曲流的形式在催化剂管的周围通过。 The salt melt is preferably in the form of meanders around the catalyst tubes.

如果进料混合物是从顶部向下通过催化剂管,则宜从底部向上如下装填催化剂管:-首先,对于50至70%的催化剂管长度,或者仅有催化剂,或者是催化剂与惰性材料(后者最高可占混合物的20重量%)的混合物(C部分);-接下来,对于20至40%的总管长,或者仅有催化剂,或者是催化剂与惰性材料(后者最高可占混合物的40重量%)的混合物(B部分);和-最后,对于5至20%的总管长,为惰性材料床(A部分),其优选选择得可产生非常小的压降。 If the feed mixture is from the top downwards through the catalyst tubes, it is desirable that the following catalyst tubes filled from the bottom up: - First of all, for 50 to 70% of the catalyst tube length, or only the catalyst, or the catalyst with an inert material (the latter the mixture may comprise up to 20 wt%) mixture (part C); - Next, the manifold 20 to 40% longer, or only the catalyst, or the catalyst with an inert material (which may comprise up to 40% by weight of the mixture %) of a mixture (part B); and - finally, to 5 to 20% of the length of the manifold, the bed (a portion) of an inert material, which is preferably chosen to be a very small pressure drop.

C部分优选不经稀释。 Part C is preferably undiluted.

如果流动方向是从底部向上,装填顺序宜相反。 If the flow direction is upward, the sequence should be loaded from the opposite bottom.

如果使用DE-A 10046958预备实施例5中描述的、或DE-A 19815281描述的催化剂以及外形为7mm×7mm×4mm或7mm×7mm×3mm(均为外径×高×内径)的滑石环作惰性材料,上述装填方案是特别适宜的。 If DE-A 10046958 preparation described in Example 5, the catalyst or DE-A 19815281 and shape as described or 7mm × 7mm × 4mm 7mm × 7mm × 3mm (both outside diameter × inside diameter × height) ring as talc an inert material, and the filling solution is particularly suitable. 至于盐浴温度,适用DE-A 4431949中所述内容。 As the salt bath temperature for the content in DE-A 4,431,949. 其一般选择得使单程中实现的丙烯醛的转化率通常≥90摩尔%或≥95摩尔%。 Generally selected so that the acrolein conversion in a single pass is generally achieved ≥95 ≥90 mole% or mole%.

但不完全氧化的第二步(由丙烯醛生成丙烯酸)也可以使用所述催化剂在例如DE-A 19910508中描述的双区多管固定床反应器中进行。 The second step, but not completely oxidized (generated from acrolein acrylic acid) may also be used, for example, the two-zone catalyst in DE-A 19910508 describes a multi-tube fixed bed reactor. 至于丙烯的转化率,适用以上所述的范围。 As for the conversion of propylene, the above-described suitable range. 当该第二步在双区多管固定床反应器中进行时,于第一步直接送入的来自不完全氧化的产物气体混合物(如上所述)同样宜直接用于制造进料气混合物(如果需要,在中间冷却后使用)。 When the second step in the two-zone multi-tubular fixed bed reactor, in the first step directly into the product gas mixture (as described above) from the incomplete oxidation directly suitable for manufacturing the same feed gas mixture ( If necessary, used after intermediate cooling). 不完全氧化的第二步所需的氧优选以空气加入,并且直接加入来自不完全氧化的第一阶段的产物气体混合物中。 Step desired partial oxidation with air oxygen is preferably added, and added directly to the product gas mixture from the first stage of incomplete oxidation.

在直接进一步使用来自不完全氧化的第一步的产物气体混合物供应不完全氧化的第二步的两阶段操作模式中,一般将两个单区多管固定床反应器或两个双区多管固定床反应器串联。 In the second step of the two-stage operation mode of the first step directly further used the partial oxidation product gas mixture supplied from the incomplete oxidation, in general, the two single-zone multi-tubular fixed bed reactor or two two-zone multi-tube fixed bed reactors in series. 混合式串联(单区/双区或相反)也是可行的。 Series hybrid (single-zone / dual zone or vice versa) is also possible.

可在反应器之间安装需要时可以包含惰性床的中间冷却器,所述惰性床起到过滤的作用。 May intercooler inert bed may comprise at installation time required between the reactor, the inert bed functions as filtering. 用于由丙烯生成丙烯酸的不完全氧化的第一步的多管反应器中盐浴温度一般为300至400℃。 For the first step of a multi-tube reactor bath temperature of incomplete oxidation of propylene to acrylic acid is generally from 300 to 400 ℃. 用于由丙烯生成丙烯酸的不完全氧化的第二步(即由丙烯醛生成丙烯酸的不完全氧化)的多管反应器中盐浴温度一般为200至350℃。 For the second step of incomplete oxidation of propylene to acrylic acid (i.e. acrylic acid from acrolein generated incomplete oxidation) of the multi-tube reactor bath temperature is generally 200 to 350 ℃. 此外,通常以下述量将传热介质(优选为盐熔融物)输送通过相关的多管固定床反应器:它们的流入温度与它们的流出温度之间的差别一般≤5℃。 In addition, the following amounts are usually heat transfer medium (preferably a salt melt) conveyed through the associated multi-tubular fixed bed reactor: the temperature thereof between the inflow outflow temperature difference thereof is generally ≤5 ℃. 如上所述,由丙烯生成丙烯酸的不完全氧化的两个步骤也可以如DE-A 10121592所述在一个反应器中的一个装料上进行。 As described above, the propylene to acrylic acid by the two step partial oxidation may also be carried out as the DE-A 10121592 a charge in a reactor.

可再次指出的是,用于第一步(“丙烯→丙烯醛”)的部分进料气混合物(气体混合物2)可以是来自不完全氧化的循环气。 Again be noted that the portion of the feed gas mixture for the first step ( "propylene → acrolein") (the gas mixture) may be derived from the recycle gas is not completely oxidized.

这是从来自不完全氧化的产物气体混合物中分离出目标产物(丙烯醛和/或丙烯酸分离)之后残留的气体,并可作为惰性稀释气再循环至送入由丙烯生成丙烯醛和/或丙烯酸的不完全氧化的第一步和/或第二步的进料中。 This is remaining after the separation of the desired product (acrolein and / or acrylic acid separation) from the product gas mixture from the partial oxidation gas, is recycled to the feeding acrolein and / or acrylic acid from propylene can be used as the inert diluent gas the first step of the incomplete oxidation and / or the feed to the second step.

但是,这种包含丙烷和可能的丙烯的循环气优选再循环至送入本发明方法第一步的进料中。 However, this may comprise propane and propylene is recycled to the circulating gas is preferably fed into the first step of the method of the present invention in the feed.

还可以再次指出的是,本发明的不完全氧化和/或氨氧化可以通过首先使不含氧的反应气混合物从催化剂装料上通过而制备。 Also again it noted that the present invention incomplete oxidation and / or ammoxidation may be prepared by first reacting the reaction of oxygen from the gas mixture through the catalyst charge. 在这种情况下,不完全氧化所需的氧是以晶格氧提供的。 In this case, the incomplete oxidation of oxygen is required to provide the lattice oxygen. 催化剂床在后面的再生步骤中使用含氧气体(如空气、富氧空气或贫氧空气)再生,从而使得它可重新用于不含氧的反应气混合物,等等。 The catalyst bed regeneration step in later oxygen-containing gas (such as air, oxygen-enriched air or oxygen-depleted air) regeneration, so that it can be reused for the reaction gas mixture of oxygen, and the like.

总之,其中催化剂装料延着单个催化剂管在第一反应步骤结束时改变的壳管式反应器(这种适于作为本发明的反应区B的丙烯不完全氧化是例如EP-A 911313、EP-A 979813、EP-A 990636和DE-A 2830765教导的)代表了实现用于由丙烯生成丙烯酸的不完全氧化两个步骤的两个反应区的最简单的方式。 In short, where the catalyst charge casting shell and tube reactor single catalyst tubes change at the end of the first reaction step (reaction of propylene suitable as such a zone B of the present invention, partial oxidation, for example, EP-A 911313, EP- a 979813, EP-a 990636 and DE-a 2830765 teaches a) represents the simplest way to achieve two reaction zones for the partial oxidation of propylene in two steps by the generated acid. 如果需要,反应管中的催化剂装料可被惰性床打断。 If desired, the catalyst charge in the reaction tube can be interrupted by an inert bed.

但是,所述两个氧化区优选以两个串联的壳管式系统的形式实现。 However, the two oxidation zones are preferably implemented in the form of two series of shell and tube system. 它们可安装在一个反应器中,其中由一束管向另一束管的过渡是通过没有容纳在催化剂管中的惰性材料床(宜为可接近的)形成的。 They can be installed in a transition reactor, wherein a bundle of tubes to another beam tube is formed by a bed of inert material is not housed in the catalyst tube (preferably as accessible). 虽然传热介质一般在催化剂管周围流动,但它不接触如上所述安装的惰性床。 Although the heat transfer medium flowing around the catalyst tubes in general, but it does not contact the inert bed installed as described above. 所述两束催化剂管因而宜容纳在彼此物理分离的反应器中。 Thus the two beams should be accommodated in the catalyst tubes physically separated from each other in the reactor. 为了减少离开第一氧化区的产物气体混合物中丙烯醛的任何后燃烧,一般在两个壳管式反应器之间安装中间冷却器。 In order to reduce any oxidation after leaving the first region of the acrolein product gas mixture in the combustion, typically between two shell and tube type reactor equipped with an intercooler. 可以使用例如DE-A 19929487和DE-A 19952964中所述带有盐冷却和/蒸发冷却的板式换热器反应器代替壳管式反应器。 May be used, for example, a plate heat exchanger reactor DE-A 19929487 and DE-A 19952964 and said salts with cooling / evaporative cooling in place of a shell and tube reactor.

第一氧化区中的反应温度一般为300至450℃,优选为320至390℃。 The reaction temperature in the first oxidation zone is generally from 300 to 450 ℃, preferably 320 to 390 ℃. 第二氧化区中的反应温度一般为200至300℃,通常为220至290℃。 The reaction temperature in the second oxidation zone is generally 200 to 300 ℃, usually 220 to 290 ℃. 两个氧化区中的反应压力宜为0.5至5atm,优选1至3atm。 The reaction pressure in both the oxidation zone is suitably from 0.5 to 5atm, preferably 1 to 3 atm. 两个氧化区中氧化催化剂上的反应气体的空间速度(标准升/升·小时)经常为1500至2500h-1,或最高达4000h-1。 Two oxidation zone space velocity of the reaction gas in the oxidation catalyst (Nl / l · hr) often 1500 to 2500h-1, or up to 4000h-1. 丙烯的空间速度可以为100至200标准升/升·小时或更高。 Propylene space velocity may be 100 to 200 Nl / l · hr or higher.

原则上,本发明方法中的两个反应区可以如例如DE-A 19837517、DE-A 19910506、DE-A 19910508和DE-A 19837519所述进行配置。 In principle, two reaction zone of the present invention may be configured as, for example, DE-A 19837517, DE-A 19910506, DE-A 19910508 and DE-A 19837519. 这两个反应区(需要时的多区反应器系统)的外加热通常以本身已知的方式与特定的反应气混合物组合物和催化剂装料相匹配。 The two outer heating the reaction zone (multi-zone reactor system when needed) is generally in a manner known per se to match the specific reaction gas mixture composition and catalyst loading.

所需作为根据本发明需要的分区中氧化剂的全部分子氧可在一开始就全部加入送入分区的进料气混合物中。 As required in accordance with the partition into the partition of the present invention requires the oxidizing agent may be molecular oxygen to all added all at the beginning of the feed gas mixture. 但例如在制备丙烯酸时,当然也可以在第一分区之后加入额外的氧。 However, for example in the preparation of acrylic acid, of course, additional oxygen may be added after the first partition. 在制备丙烯酸的情况下,这后一步骤是优选的。 In the case of production of acrylic acid, after which a step is preferable.

在第一氧化区中(丙烯→丙烯醛),将丙烯∶分子氧的摩尔比率设置为1∶1-3,经常为1∶1.5-2。 In a first oxidation zone (propylene → acrolein), propylene: molecular oxygen molar ratio is set to 1:1-3, often 1:1.5-2. 类似的数值适合于丙烯醛不完全氧化为丙烯酸的第二氧化区中丙烯醛∶分子氧的摩尔比率(优选1∶1.5-1.5)。 The second oxidation zone similar in the values ​​for the partial oxidation of acrolein to acrylic acid, acrolein: molecular oxygen molar ratio of (preferably 1:1.5-1.5).

在两个氧化区中,过量的分子氧对于气相氧化的动力学一般具有有益的效果。 In both the oxidation zone, an excess of molecular oxygen to the gas phase oxidation kinetics general has a beneficial effect. 与根据本发明采用的脱氢反应中的比率相反,不完全氧化中的热动力学受反应剂摩尔比的影响不明显,因为由丙烯生成丙烯酸的多相催化气相不完全氧化是由热力学控制的。 The contrast ratio of the dehydrogenation reaction of the present invention employed in thermodynamic incomplete oxidation is affected by the molar ratio of reactants is not obvious, because propylene to acrylic acid by the heterogeneously catalyzed gas-phase partial oxidation is controlled by thermodynamics . 因而,例如在第一氧化区中,原则上也可以使用相对于分子氧摩尔过量的丙烯。 Thus, for example, in the first oxidation zone, it may also be used in principle with respect to propylene molar excess of molecular oxygen. 在这种情况下,过量的丙烯充当稀释气。 In this case, an excess of propylene to act as a diluent gas.

但是,由丙烯生成丙烯酸的多相催化气相不完全氧化原则上也可以在单一氧化区中进行。 However, propylene to acrylic acid by heterogeneously catalyzed gas-phase partial oxidation in principle also be performed in a single oxidation zone. 在这种情况下,两个反应步骤都在装填了能够催化这两个反应步骤的催化剂的反应器中发生。 In this case, two reaction steps are packed with the occurrence of these two reaction steps capable of catalyzing the catalyst reactor. 当然,催化剂装料也可以在氧化区内延着反应坐标连续或突然地变化。 Of course, the catalyst charge can be extended reaction coordinate continuously or abruptly changes in the oxidation zone. 在两个氧化区串联的形式的、一个根据本发明采用的分区的实施方案中,如果需要,在第一氧化区作为副产物生成的、并存在于离开第一氧化区的产物气体混合物中的碳的氧化物和水蒸气,自然可以在送至第二氧化区之前部分或全部从该产物气体混合物中分离出来。 In the two oxidation zones in series to form a first product gas mixture leaving the oxidation zone in accordance with an embodiment of the carbon partitioning in the present invention employed, if desired, in a first oxidation zone as a by-product, and it is present oxides and water vapor, can naturally be separated from some or all of the product gas mixture prior to the second oxidation zone. 根据本发明,优选不需要这种分离的操作模式。 According to the present invention, preferred mode of operation does not require such a separation.

不完全氧化和/或氨氧化需要的、与气体混合物1或1′在后者加入分区之前混合的分子氧的可能的来源包括纯分子氧和被例如CO2、CO、稀有气体、N2和/或饱和烃的惰性气体稀释的分子氧。 Incomplete oxidation and / or ammoxidation required gas mixture 1 or 1 'which is added prior to the mixing of the partition may include a source of pure molecular oxygen and molecular oxygen are e.g. CO2, CO, noble gases, N2, and / or saturated hydrocarbon inert gas diluted oxygen molecules.

宜用空气作为氧源以满足至少部分对分子氧的需求。 Appropriate to air as the oxygen source to meet at least part of the molecular oxygen.

在本发明方法中,将冷空气引入热的气体混合物1或1′,可直接冷却气体混合物1或1′。 In the process of the invention, the cool air introduced into the hot gas mixture 1 or 1 ', the gas mixture can be directly cooled 1 or 1'.

在制备丙烯醛和/或丙烯酸的情况下,离开根据本发明使用的分区的产物气体混合物一般主要包含目标产物丙烯醛或丙烯酸、或后者与下列物质的混合物:丙烯醛、未反应的分子氧、丙烷、未反应的丙烯、分子氮、以副产物生成的和/或用作稀释气的水蒸气、以副产物生成的和/或用作稀释气的碳的氧化物及少量其它低级醛、低级链烷羧酸(如乙酸、甲酸和丙酸)和马来酐、苯甲醛、芳香羧酸和芳香羧酸酐(如邻苯二甲酸酐和苯甲酸)、可能的其它烃如C4烃(如1-丁烯和可能的其它丁烯)及其它惰性稀释气。 In the case of producing acrolein and / or acrylic acid, the product gas mixture leaving the partition according to the present invention generally comprises a main target product acrolein or acrylic acid, or a mixture of the latter with the following materials: acrolein, unreacted molecular oxygen , propane, unreacted propylene, molecular nitrogen, to a by-product and / or steam as diluent gas, by-product oxides and / or carbon is used as the diluent gas and small amounts of other lower aldehydes, lower alkanoic acid (e.g. acetic acid, formic acid and propionic acid) and maleic anhydride, benzaldehyde, aromatic carboxylic acids and aromatic carboxylic anhydride (e.g., phthalic anhydride and benzoic acid), possibly other hydrocarbons, such as C4 hydrocarbons (e.g. 1-butene and possibly other butenes) and diluted with other inert gas.

目标产物可以以本身已知的方式从产物气体混合物中分离出来,例如通过丙烯酸的部分冷凝、或将丙烯酸吸收进水中或高沸点疏水有机溶剂中、或将丙烯醛吸收进水中或低级羧酸的水溶液中并随后对被吸收的物质进行处理;或者,也可以分级冷凝产物气体混合物;参见例如EP-A 117146、DE-A 4308087、DE-A 4335172、DE-A 4436243、DE-A 19924532和DE-A 19924533。 The target product can be isolated in a manner known per se from the product gas mixture in, for example, by partial condensation of acrylic acid, or to absorb water or high-boiling hydrophobic organic solvent in the acrylic acid or acrolein absorbed in water or a lower carboxyalkyl aqueous acid solution and subsequently substances are absorbed by the process; alternatively, may be fractional condensation product gas mixture; see for example EP-a 117146, DE-a 4308087, DE-a 4335172, DE-a 4436243, DE-a 19924532 and DE-A 19924533. 也可如EP-A 982287、EP-A 982289、DE-A 19924532、DE-A 10115277、DE-A 19606877、DE-A 19740252、DE-A 19627847、DE-A 10053086和EP-A 982288所述分离出丙烯酸。 As also EP-A 982287, EP-A 982289, DE-A 19924532, DE-A 10115277, DE-A 19606877, DE-A 19740252, DE-A 19627847, DE-A 10053086 and EP-A 982,288 the isolated acrylic.

如果需要,也可分离出未反应的丙烯和/或丙烯醛并循环至分区。 If desired, be isolated unreacted propylene and / or acrolein and recycled to the partition.

分离优选如WO/0196271的图7所示进行。 Separation is preferably performed as shown in FIG 7 WO / 0196271 FIG. 同样,目标产物分离出之后残留的残余气体中除丙烯酸和丙烯醛之外的主要组分、所用粗丙烷和所用脱氢/氧化脱氢催化剂都可以单独分离出,并/或与丙烷和循环气(再循环流)一起再循环至加入本发明方法第一步的进料中。 Similarly, the target product remaining after separation of the residual gas in addition to a main component acrylic acid and acrolein, propane, and the crude used for the dehydrogenation / oxidative dehydrogenation catalyst can be separated alone, and / or with the recycle gas and propane (recycle stream) is recycled to the first step of the process of the invention was added in the feed together. 但是,未反应的丙烷当然也可以与未反应的丙烯混合(作为进料循环流)再循环至该进料流中。 However, unreacted propane, of course, may be mixed with the unreacted propylene (as a recycle stream feed) is recycled to the feed stream. 在本发明方法的连续进行的方案中,丙烷就这样连续地转化为丙烯酸和/或丙烯醛。 In the continuous embodiment of the method of the present invention, thus continuously converting propane to acrylic acid and / or acrolein.

如上所述,丙烷和丙烯可以通过吸收进高沸点疏水有机溶剂中从目标产物分离出之后残留的残余气体中分离出来,然后进行解吸和/或汽提(和吸收介质的再使用)。 As mentioned above, propane and propylene can be separated in a hydrophobic organic solvent remaining after the target product is separated from the residual gas by absorption into a high boiling point, followed by desorption and / or stripping (absorption medium and reused). 所述残余气体一般包含O2、CO、CO2、H2O、N2、稀有气体及其它低级醛、低级链烷羧酸(如乙酸、甲酸和丙酸)和马来酐、苯甲醛、芳香羧酸和芳香羧酸酐(如邻苯二甲酸酐和苯甲酸)和烃,如C4烃(如1-丁烯和可能的其它丁烯)。 The residual gas generally comprises O2, CO, CO2, H2O, N2, noble gases and other lower aldehydes, lower alkanecarboxylic acids (e.g. acetic acid, formic acid and propionic acid) and maleic anhydride, benzaldehyde, aromatic carboxylic acids and aromatic carboxylic anhydride (e.g., phthalic anhydride and benzoic acid) and hydrocarbons, such as C4 hydrocarbons (e.g., 1-butene and possibly other butenes). 实现该分离的其它可能的方式有吸附、提纯、膜法和部分冷凝。 Other possible way to achieve adsorption of the separation, purification, membrane and partially condensed. 所述分离过程优选在高于大气压的压力下进行。 The separation process is preferably carried out at a pressure above atmospheric pressure.

如果使用对氧或含氧化合物敏感的脱氢催化剂,需将这些含氧化合物在循环气再循环至加入本发明方法第一步的进料中之前从其中除去。 If removed therefrom prior to use of oxygen or oxygen sensitive compounds dehydrogenation catalyst for an oxygenate these cycle gas recycled to the first step of the process of the invention was added in the feed. 这种氧的去除还可用于避免丙烷在脱氢阶段的总体氧化。 This removal of oxygen may also be generally used to avoid oxidation of propane dehydrogenation stage. DE-A 19937107所述的脱氢催化剂对含氧化合物不敏感(特别是该DE第一次公开的实施例1至4所述的那些)。 According to DE-A 19937107 dehydrogenation catalyst is not sensitive to oxygen-containing compound (in particular to those of the first embodiment 4 of the Example 1 disclosed in the DE).

同样如上所述,进行该分离的另一可能方式是分馏。 Also described above, another possible embodiment is the isolated fractionation. 优选在低温下进行分压蒸馏。 Preferably dividing distillation at low temperatures. 采用的压力可以是例如10至100bar。 Pressure may be employed, for example, 10 to 100bar. 至于提纯塔,可以使用填充有随机填料的塔、板式塔或包含有序填料的塔。 As purification column may be packed with random packing column, a plate column or a column containing ordered packing. 合适的板式塔是具有双流塔板、泡罩塔板或浮阀塔板的塔。 Suitable dual flow tray column having trays, bubble cap trays or valve trays column. 回流比可以是例如1至10。 The reflux ratio may be, for example, from 1 to 10. 进行该分离的其它可能方式有例如压力萃取、压力摇摆吸附、压力洗涤、部分冷凝和压力萃取。 Other possible ways to carry out the extraction separation with a pressure e.g., pressure swing adsorption, pressure washing, extraction pressure and partial condensation.

根据本发明,例如,如果在本发明方法的第一步之后除去了次要组分(如C4烃(如1-丁烯、正丁烷、异丁烷和可能的其它丁烯)),或者干扰性的C4烃没有积累(如当它们在分区中合适的催化剂上燃烧时),当然也可以将全部量的残余气体再循环(作为再循环流)至加入本发明方法第一步的进料中。 According to the present invention, e.g., if the minor component is removed after the first step of the method of the present invention (e.g., C4 hydrocarbons (such as 1-butene, n-butane, isobutane, and possibly other butenes)), or not interfering C4 hydrocarbon accumulation (e.g., when they are burned over a suitable catalyst in the partition), of course, may be the entire amount of residual gas is recycled (as a recycle stream) is added to the first step of the method of the present invention is a feed in. 在这种情况下,用于除丙烷、丙烯和分子氧之外的气体组分的出口可以仅仅仅次于气体混合物1和气体混合物1′之间。 In this case, an outlet for the gas components other than propane, propylene and molecular oxygen in the gas mixture can only after the gas mixtures 1 and 1 'between.

当然也可以在目标产物分离出之后提供其它出口。 Of course, the outlet may be provided after the target additional product isolated. 如果再循环至丙烷脱氢反应的循环气包含一氧化碳,可以在加入新鲜粗丙烷之前将其催化氧化为CO2。 If recycled to the dehydrogenation of propane recycle gas comprises carbon monoxide, can be added prior to the fresh crude propane catalytic oxidation to CO2. 反应释放的反应热可用于加热至脱氢温度。 The reaction heat released to be used for heating the dehydrogenation reaction temperature.

如果要在尾气作为循环气再循环至丙烷的脱氢反应和/或氧化脱氢反应之前从尾气中分离出碳的氧化物,也可以将存在于尾气中的CO催化后燃烧为CO2,因为CO2可以较简单地分离出来(例如用碱液洗涤)。 If the exhaust gas to be separated before the gas is recycled as recycle to the dehydrogenation reaction of propane and / or off-gas from the oxidative dehydrogenation reaction of carbon oxides, may be present in the oxidation of CO in the exhaust gas after combustion is CO2, because CO2 it can be relatively easily separated (e.g., washed with lye). 这种CO的催化后燃烧也可以在脱氢区中进行,例如在上述脱氢催化剂(如DE-A 19937107所述的那些,特别是该DE第一次公开的实施例1至4中所述的那些)上进行。 May be performed in the combustion zone following the catalytic dehydrogenation of CO that, in the above example, the dehydrogenation catalyst (e.g., those described in DE-A, in particular the DE of the first embodiment according to the disclosed embodiments 19,937,107 1-4 It carried on) those.

自然也可以将部分未改变的尾气再循环至丙烷的脱氢反应和/或氧化脱氢反应,并仅从剩余部分中分离出丙烷和丙烯的混合物,并同样将其再循环至丙烷的脱氢反应和/或氧化脱氢反应和/或再循环至分区。 NATURAL portion may be recycled to the exhaust unaltered propane dehydrogenation and oxidative dehydrogenation reaction or / and separating only the remaining portion of the mixture of propane and propylene, and likewise it is recycled to the dehydrogenation of propane reaction and / or oxidative dehydrogenation reaction and / or recycled to the partition. 在后一种情况下,尾气的残余部分宜与气体混合物1或气体混合物1′结合。 In the latter case, the remainder of the exhaust gas mixture should be 1 or gas mixture 1 'binding.

尾气的分馏可以例如以下述方式进行:基本上所有沸点低于丙烯的沸点的组分都在提纯塔中上升的洗涤部分中分离出来,并在塔的顶部除去。 Exhaust fractionation may, for example in the following manner: substantially all components boiling below the boiling point of propylene are separated in the wash column rises partially purified in and removed at the top of the column. 这些组分首先且主要是碳的氧化物CO和CO2及未反应氧和乙烯、甲烷、N2。 These components are first and mainly carbon oxides CO and CO2 and oxygen and unreacted ethylene, methane, N2. 在塔底,可分离出例如较高沸点的C4烃。 At the bottom, can be isolated for example C4 hydrocarbons of higher boiling point.

如果采用丙烷的多相催化氧化脱氢作为本发明方法的第一步,每当按照DE-A 19837520、DE-A 19837517、DE-A 19837519和DE-A 19837518分离出分子氮时,还可以分离出次要组分。 If using heterogeneous catalytic oxidative dehydrogenation of propane as the first step of the method of the present invention, each time according to DE-A 19837520, DE-A 19837517, DE-A 19837519 and DE-A 19837518 separated molecular nitrogen, can also be isolated a minor component.

实施例使用含有丙烯和丙烷的不同的气体混合物2在两个串联的固定床反应器中进行的丙烯的多相催化气相不完全氧化A)一般处理条件的说明1、用于由丙烯生成丙烯醛的不完全氧化步骤的第一固定床反应器所用传热介质:由53重量%的硝酸钾、40重量%的亚硝酸钠和7重量%的硝酸钠组成的盐熔融物。 Described embodiments use different gas containing propylene and propane in a mixture of two propylene two serially connected fixed bed reactors in the gas phase heterogeneously catalyzed partial oxidation A) General process conditions 1, for from propylene to acrolein salt melt of 53% by weight of potassium nitrate, 40% by weight of sodium nitrite and sodium nitrate 7% by weight of the composition: a first fixed bed reactor incomplete oxidation step as a heat transfer medium.

催化剂管的尺寸:总长4200mm,内径26mm,外径30mm,壁厚2mm。 Dimensions of the catalyst tube: total length of 4200mm, an inner diameter of 26mm, outside diameter 30mm, thickness 2mm.

反应器:包含不锈钢双壁圆柱(圆柱形外容器包围的圆柱形导管)。 Reactor: stainless steel comprising a double-walled cylinder (a cylindrical outer container surrounding the cylindrical conduit). 各处壁厚为2至5mm。 The entire wall thickness of 2 to 5mm.

外圆柱的内径为168mm。 The inner diameter of the outer cylinder is 168mm.

导管的内径为约60mm。 The inner diameter of the conduit is about 60mm.

双壁圆柱的顶部和底部分别用盖和底封闭。 The top and bottom, respectively double-walled cylinder is closed with a lid and bottom.

催化剂管容装在圆柱形容器中,使其上端和下端分别伸出盖和底250mm(并密封在盖和底中)。 Catalyst tubes housed in a cylindrical vessel, so that the upper and lower lid and protrude 250mm (and sealed in the cover and in the bottom).

传热介质封闭在圆柱形容器内。 Heat medium enclosed within a cylindrical container. 为了在圆柱形容器内的整个催化剂管长度(3700mm)上于催化剂管的外壁上确保非常均一的热边界条件,通过鼓泡氮将传热介质循环进圆柱形容器中。 For the whole length of the catalyst tubes in the cylindrical container (3700mm) in the outer wall of the catalyst tubes ensures a very uniform thermal boundary conditions, by bubbling nitrogen into the heat transfer medium circulating in a cylindrical container.

传热介质借助上升的氮从底部向上传递,然后在圆柱形导管与圆柱形外容器之间的中间空间向下回落(类似的良好循环也可通过泵送(如螺旋泵)实现)。 Increase the heat transfer medium by means of nitrogen passed from the bottom upwards, and the intermediate space between the cylindrical pipe and a cylindrical outer container dropped downward (similar excellent cycle may also be achieved by pumping (e.g., a screw pump)). 可借助施加至外壁上的电加热将传热介质的温度调整到所需的水平。 May be applied by means of electrical heating to the temperature of the outer wall of the heat transfer medium is adjusted to a desired level. 另外,借助空气进行冷却。 Further, by air cooling.

加入反应器的进料:从反应器上方观察,盐熔融物与反应气混合物(各气体混合物2)逆流传送。 Added to the reactor feed: observation, salt melt and reaction gas mixture (each gas mixture 2) is transferred from the upper countercurrent reactor. 反应气混合物从顶部进入反应器。 The reaction gas mixture enters the reactor from the top. 在各种情况下,其进入反应管时的温度为250℃。 In each case, when the temperature into the reaction tube 250 ℃.

盐熔融物从底部以T入的温度进入圆柱形导管,并从顶部以T出的温度离开圆柱形导管。 The salt melt into the cylindrical conduit from the bottom to the temperature T, and T the temperature in the cylindrical conduit leaving from the top. T入与T出之间的差别为约2℃。 Into the difference between T and T is about 2 ℃.

T平均=(T入+T出)/2。 Average T = (T + T into a) / 2.

催化剂管装料(从顶部向下):A部分:50cm长的滑石环前床,外形为7mm×7mm×4mm(外径×长×内径)。 The catalyst tube charge (from the top down): A Part: 50cm long steatite rings front bed, the shape of 7mm × 7mm × 4mm (outside diameter × inside diameter × length).

B部分:100cm长的催化剂管装料,由30重量%的外形为5mm×3mm×2mm(外径×长×内径)的滑石环和70重量%的来自C部分的全活性催化剂的均匀混合物组成。 Part B: 100cm long catalyst charge tube, the outer shape of 30 wt% of 5mm × 3mm × 2mm (outside diameter × inside diameter × length)% talc ring homogeneous mixture from the full activity of the catalyst C and 70 parts by weight of the composition .

C部分:170cm长的催化剂装料,由如DE-A 10046957实施例1所述的环形(5mm×3mm×2mm,外径×长×内径)全活性催化剂组成。 Part C: 170cm long catalyst charge, such as by the annular DE-A 10046957 (5mm × 3mm × 2mm, the outside diameter × inside diameter × length) of the Example 1 embodiment the whole composition of the catalyst activity.

D部分:50cm长的滑石环后床,外形为7mm×7mm×4mm(外径×长×内径)。 Part D: 50cm long steatite rings of the rear bed, the shape of 7mm × 7mm × 4mm (outside diameter × inside diameter × length).

通过反应器的反应气起始混合物流:都是3860克/升的气体混合物2。 Mixing the starting gas stream through the reactor the reactor: 3860 g are / liter 2 gas mixture.

丙烯在催化剂装料上的空间速度:100标准升/升·小时。 Propylene space velocity on the catalyst charge: 100 Nl / l · hr.

2、中间冷却和氧的中间引入的说明离开第一固定床反应器的产物气混合物用于通过连接管的中间冷却的目的(借助氧的间接冷却)。 2, the intermediate cooling and intermediate introduction of oxygen gas mixture leaving the first fixed bed reactor product for cooling purposes through the intermediate connection pipe (indirect cooling by means of oxygen). 连接管长400mm,内径26mm,壁厚2mm,材料为不锈钢,在其中间部分的200mm装填有直径为6mm的滑石球的惰性床,直接通过法兰与第一固定床反应器的催化剂管相连。 Connecting pipe length 400mm, internal diameter 26mm, wall thickness 2mm, made of stainless steel, in which the intermediate portion is filled with a 200mm diameter steatite spheres of 6mm inert bed, the catalyst is directly connected to the flange of the first fixed bed reactor tube.

在所有情况下,气体混合物都以高于310℃的温度进入连接管,以约140℃的温度离开。 In all cases, the gas mixture are at a temperature higher than 310 deg.] C into the connection pipe at a temperature of about 140 deg.] C to leave. 然后将290标准升/小时的压缩空气作为氧源混入气体混合物中。 Then 290 Nl / h of compressed air as an oxygen source gas mixed into the mixture.

所获进料气混合物以220℃的温度送入用于由丙烯醛生成丙烯酸的不完全氧化步骤的固定床反应器中。 The resulting feed gas mixture is fed at a temperature of 220 deg.] C for partial oxidation step of generating a fixed bed reactor acrylic acid from acrolein.

3、用于由丙烯醛生成丙烯酸的不完全氧化步骤的第二固定床反应器使用配置与用于第一步的反应器相同的固定床反应器。 3, the second fixed bed reactor for the partial oxidation step of generating acrylic acid from acrolein using the configuration of the reactor for the first step of the same fixed bed reactor. 从反应器上方观察,盐熔融物和反应气混合物并流传送。 Viewed from above the reactor, the salt melt and the reaction gas mixture and streaming. 盐熔融物和反应气混合物都从底部进入。 Salt melt and reaction gas mixture are entered from the bottom.

催化剂管装料(从底部向上)为:A部分:20cm长的滑石环前床,外形为7mm×7mm×4mm(外径×长×内径)。 The catalyst tube charge (from the bottom) are: A Part: 20cm long steatite rings front bed, the shape of 7mm × 7mm × 4mm (outside diameter × inside diameter × length).

B部分:100cm长的催化剂装料,由30重量%的外形为7mm×3mm×4mm(外径×长×内径)的滑石环和70重量%的来自C部分的涂覆催化剂的均匀混合物组成。 Part B: 100cm long catalyst charge, a 30% by weight of the outer shape of 7mm × 3mm × 4mm (outside diameter × inside diameter × length) and a homogeneous mixture of talc ring 70 wt% of the coated catalyst from the C moiety.

C部分:200cm长的催化剂装料,由如DE-A 10046928制备实施例5所述的环形(7mm×3mm×4mm,外径×长×内径)涂覆催化剂组成。 Part C: 200cm long catalyst charge, prepared from DE-A 10046928 annular as described in Example 5 (7mm × 3mm × 4mm, outer diameter × inside diameter × length) coated with catalyst.

D部分:50cm长的滑石环后床,外形为7mm×7mm×4mm(外径×长×内径)。 Part D: 50cm long steatite rings of the rear bed, the shape of 7mm × 7mm × 4mm (outside diameter × inside diameter × length).

在所有情况下,进料气混合物都以标称速度4240克/升通过第二反应器。 In all cases, the feed gas mixture are at nominal speed 4240 g / liter through the second reactor. T平均如对于第一固定床反应器的定义。 The average T are as defined for the first fixed bed reactor.

在下列所有实施例中,第一反应器中丙烯的转化率都设置为97.7摩尔%,第二反应器中丙烯醛的转化率都设置为99.3摩尔%。 In all the following examples, the first reactor propylene conversion are set to 97.7 mol%, the second reactor are set acrolein conversion was 99.3 mole%.

需要的T平均(气体混合物2的组成的函数)、丙烯酸的产率AAA(摩尔%)和形成碳的氧化物的选择性SCOx(摩尔%)在各个实施例中具有以下值。 Desired average T (function of the composition of the gas mixture 2), the selectivity of oxide SCOx the AAA acrylic acid yield (mol%) and carbon formation (mol%) having the following values ​​in the various embodiments. 其中SCOx基于在两个反应器上反应的丙烯,是作为气体混合物2的组成的函数实现的。 Wherein the propylene-based SCOx two reactors in the reaction, a mixture consisting of 2 to achieve a function as a gas.

B)实施例1气体混合物2的组成是:6.18体积%的丙烯, B) the mixture of Example 2 is an embodiment of the gas: 6.18 vol% propylene,

33.1体积%的丙烷,12.3体积%的氧,0.15体积%的COx,46.7体积%的N2和1.63体积%H2O。 33.1% by volume of propane, 12.3% by volume of oxygen, 0.15% by volume of COx, 46.7 vol% N2 and 1.63 vol% H2O.

AAA=86.1摩尔%, T平均,第一反应器=316℃。 AAA = 86.1 mol%, T mean the first reactor = 316 ℃.

SCOx=9.2摩尔%, T平均,第二反应器=274℃。 SCOx = 9.2 mol%, T average, the second reactor = 274 ℃.

C)实施例2气体混合物2的组成是:6.04体积%的丙烯,42.3体积%的丙烷,10.4体积%的氧,0.15体积%的COx,39.5体积%的N2和1.60体积%H2O。 Example 2 A gas mixture consisting of 2, C) were: 6.04% by volume of propylene, 42.3% by volume of propane, 10.4% by volume of oxygen, 0.15% by volume of COx, 39.5 vol% N2 and 1.60 vol% H2O.

AAA=85.2摩尔%, T平均,第一反应器=322℃。 AAA = 85.2 mol%, T mean the first reactor = 322 ℃.

SCOx=9.9摩尔%, T平均,第二反应器=278℃。 SCOx = 9.9 mol%, T average, the second reactor = 278 ℃.

D)实施例3气体混合物2的组成是:0.20体积%的乙烷,6.14体积%的丙烯,33.0体积%的丙烷,12.2体积%的氧,0.16体积%的COx,46.6体积%的N2和1.65体积%H2O。 Example 3 A gas mixture D) of Embodiment 2 is composed of: 0.20% by volume of ethane, 6.14% by volume of propylene, 33.0% by volume of propane, 12.2% by volume of oxygen, 0.16% by volume of COx, 46.6 vol% N2 and 1.65 vol% H2O.

AAA=86.1摩尔%, T平均,第一反应器=316℃。 AAA = 86.1 mol%, T mean the first reactor = 316 ℃.

SCOx=9.2摩尔%, T平均,第二反应器=274℃。 SCOx = 9.2 mol%, T average, the second reactor = 274 ℃.

E)实施例4气体混合物2的组成是:0.22体积%的乙烯,6.13体积%的丙烯,33.0体积%的丙烷,12.2体积%的氧,0.16体积%的COx,46.6体积%的N2和1.64体积%H2O。 Example 4 Gas E) Embodiment mixture of 2 are: 0.22 vol% ethylene, 6.13% by volume of propylene, 33.0% by volume of propane, 12.2% by volume of oxygen, 0.16% by volume of COx, 46.6 vol% N2 and 1.64 volume % H2O.

AAA=86.1摩尔%, T平均,第一反应器=316℃。 AAA = 86.1 mol%, T mean the first reactor = 316 ℃.

SCOx=9.2摩尔%, T平均,第二反应器=274℃。 SCOx = 9.2 mol%, T average, the second reactor = 274 ℃.

F)实施例5气体混合物2的组成是:0.20体积%的正丁烷,6.14体积%的丙烯,33.0体积%的丙烷,12.2体积%的氧,0.16体积%的COx,46.6体积%的N2和1.65体积%H2O。 Example 5 Gas Composition F) Embodiment 2 of the mixture is: 0.20% by volume n-butane, 6.14% by volume of propylene, 33.0% by volume of propane, 12.2% by volume of oxygen, 0.16% by volume of COx, 46.6% by volume of N2 and 1.65 vol% H2O.

AAA=85.2摩尔%, T平均,第一反应器=316.5℃。 AAA = 85.2 mol%, T mean the first reactor = 316.5 ℃.

SCOx=9.9摩尔%, T平均,第二反应器=274℃。 SCOx = 9.9 mol%, T average, the second reactor = 274 ℃.

G)实施例6气体混合物2的组成是:2.02体积%的正丁烷,5.98体积%的丙烯,32.4体积%的丙烷,12.0体积%的氧, Example 6 of the gas mixture consisting of 2 G) were: 2.02% by volume n-butane, 5.98% by volume of propylene, 32.4% by volume of propane, 12.0% by volume of oxygen,

0.16体积%的COx,45.8体积%的N2和1.64体积%H2O。 0.16% by volume of COx, 45.8 vol% N2 and 1.64 vol% H2O.

不能再通过在催化剂可以承受的范围内提高T平均保持所需的丙烯转化率。 Can not maintain an average propylene conversion required in the catalyst by increasing the tolerable range T.

H)实施例7气体混合物2的组成是:0.05体积%的1-丁烯,6.16体积%的丙烯,33.0体积%的丙烷,12.3体积%的氧,0.16体积%的COx,46.7体积%的N2和1.70体积%H2O。 H) Example 7 2 gas mixture composition is: 0.05% by volume of 1-butene, 6.16% by volume of propylene, 33.0% by volume of propane, 12.3% by volume of oxygen, 0.16% by volume of COx, 46.7% by volume of N2 and 1.70 vol% H2O.

AAA=85.1摩尔%, T平均,第一反应器=318℃。 AAA = 85.1 mol%, T mean the first reactor = 318 ℃.

SCOx=10摩尔%, T平均,第二反应器=281℃。 SCOx = 10 mol%, T average, the second reactor = 281 ℃.

I)实施例8气体混合物2的组成是:0.09体积%的1-丁烯,6.16体积%的丙烯,32.9体积%的丙烷,12.3体积%的氧,0.15体积%的COx,46.8体积%的N2和1.68体积%H2O。 Example 8 Gas I) Embodiment 2 is a mixture of: 0.09% by volume of 1-butene, 6.16% by volume of propylene, 32.9% by volume of propane, 12.3% by volume of oxygen, 0.15% by volume of COx, 46.8% by volume of N2 and 1.68 vol% H2O.

AAA=85.0摩尔%, T平均,第一反应器=320℃。 AAA = 85.0 mol%, T mean the first reactor = 320 ℃.

SCOx=10.2摩尔%, T平均,第二反应器=287℃。 SCOx = 10.2 mol%, T average, the second reactor = 287 ℃.

J)实施例9 J) Example 9

气体混合物2的组成是:0.20体积%的1-丁烯,6.19体积%的丙烯,32.7体积%的丙烷,12.3体积%的氧,0.18体积%的COx,46.7体积%的N2和1.71体积%H2O。 2 is a gas mixture composition: 0.20% by volume of 1-butene, 6.19% by volume of propylene, 32.7% by volume of propane, 12.3% by volume of oxygen, 0.18% by volume of COx, 46.7 vol% 1.71 vol% N2 and H2O .

不能再通过在催化剂可以承受的范围内提高T平均保持所需的丙烯转化率。 Can not maintain an average propylene conversion required in the catalyst by increasing the tolerable range T.

Claims (73)

1.制备至少一种丙烯的不完全氧化和/或氨氧化产物的方法,在该方法中:a)在第一步中,在氧的存在和/不存在下对粗丙烷进行均相和成多相催化脱氢和/或氧化脱氢,以生产含有丙烷和丙烯的气体混合物1,并b)如果合适,将存在于在第一步中生成的气体混合物1中的除丙烷和丙烯之外的部分组分从气体混合物1中分离出来并/或转化为其它化合物,从而由气体混合物1生产含有丙烷和丙烯以及除氧、丙烷和丙烯之外的化合物的气体混合物1′,并在至少一个进一步的步骤中,c)将气体混合物1和/或气体混合物1′作为气体混合物2的组分进行存在于气体混合物1和/或气体混合物1′中的丙烯的多相催化气相不完全氧化和/或不完全气相氨氧化,其中气体混合物2的1-丁烯的含量≤1体积%。 The method of incomplete oxidation and / or ammoxidation products of at least 1. Preparation of propylene, in which method: a) In the first step, in the presence of oxygen and / crude propane into homogeneous and absence heterogeneously catalyzed dehydrogenation and / or oxydehydrogenation, containing propane and propylene to produce a gas mixture 1, and b) if appropriate, present in the gas mixture generated in the first step in addition to propane and propene than 1 partial separation of components from a gas mixture out and / or converted to other compounds, so that a gas produced by a mixture of a compound containing oxygen and propane and propene than propane and propylene gas mixture ', and at least one a further step, c) the gas mixture 'as a component of the gas mixture 2 will be present in and / or a gas mixture of a gas mixture of 1' 11 and / or gas mixtures heterogeneously catalyzed gas-phase partial oxidation of propylene and / or incomplete gas phase ammoxidation, wherein the gas mixture of the 1-butene content of 2% by volume ≤1.
2.如权利要求1所述的方法,其中气体混合物2的1-丁烯的含量≤0.75体积%。 2. The method according to claim 1, wherein the gas mixture by volume of 1-butene content ≤0.75% 2.
3.如权利要求1所述的方法,其中气体混合物2的1-丁烯的含量≤0.5体积%。 The method according to claim 1, wherein the gas mixture by volume of 1-butene content of ≤0.5% 2.
4.如权利要求1所述的方法,其中气体混合物2的1-丁烯的含量≤0.3体积%。 4. The method according to claim 1, wherein the gas mixture 2 is 1-butene content of ≤0.3% by volume.
5.如权利要求1所述的方法,其中气体混合物2的1-丁烯的含量≤0.1体积%。 5. The method according to claim 1, wherein the gas mixture by volume of 1-butene content of ≤0.1% 2.
6.如权利要求1所述的方法,其中气体混合物2的1-丁烯的含量>0.003体积%。 6. The method according to claim 1, wherein the 1-butene content of the gas mixture 2> 0.003% by volume.
7.如权利要求1所述的方法,其中气体混合物2的1-丁烯的含量>0.001体积%。 7. The method according to claim 1, wherein the 1-butene content of the gas mixture 2> 0.001% by volume.
8.如权利要求1至7任一项所述的方法,其中气体混合物2的反-2-丁烯的含量≤1体积%。 8. The method according to any one of claims 7, wherein the gas mixture by volume 2-butene content of ≤1 2%.
9.如权利要求1至7任一项所述的方法,其中气体混合物2的反-2-丁烯的含量≤0.5体积%。 9. The method according to any one of claims 7, wherein the gas mixture by volume 2-butene content of ≤0.5 2%.
10.如权利要求1至7任一项所述的方法,其中气体混合物2的反-2-丁烯的含量≤0.05体积%。 10. The method according to any one of claims 7, wherein the gas mixture by volume 2-butene content ≤0.05 2%.
11.如权利要求1至7任一项所述的方法,其中气体混合物2的顺-2-丁烯的含量≤1体积%。 11. The method according to any one of claims 1 to claim 7, wherein the gas mixture by volume of cis-2-butene content of ≤1 2%.
12.如权利要求1至7任一项所述的方法,其中气体混合物2的顺-2-丁烯的含量≤0.5体积%。 12. The method according to any one of claims 1 to claim 7, wherein the gas mixture by volume of cis-2-butene content of ≤0.5 2%.
13.如权利要求1至7任一项所述的方法,其中气体混合物2的顺-2-丁烯的含量≤0.05体积%。 13. The method according to any one of claim 1 to claim 7, wherein the gas mixture by volume of cis-2-butene content ≤0.05 2%.
14.如权利要求1至7任一项所述的方法,其中气体混合物2的异丁烯的含量≤1体积%。 14. The method according to any one of claims 7, wherein the content of the gas mixture 2 is ≤1% by volume of isobutylene.
15.如权利要求1至7任一项所述的方法,其中气体混合物2的异丁烯的含量≤0.5体积%。 15. The method according to any one of claims 7, wherein the content of the gas mixture 2 is ≤0.5% by volume of isobutylene.
16.如权利要求1至7任一项所述的方法,其中气体混合物2的异丁烯的含量≤0.05体积%。 16. The method according to any one of claims 7, wherein the content of the gas mixture 2 is ≤0.05% by volume of isobutylene.
17.如权利要求1至7任一项所述的方法,其中气体混合物2中丁烯的总含量≤1体积%。 17. The method according to any one of claims 7, wherein the gas mixture the total content of ≤1% by volume of 2-butene.
18.如权利要求1至7任一项所述的方法,其中气体混合物2中丁烯的总含量≤0.5体积%。 18. The method according to any one of claims 7, wherein the gas mixture the total content of ≤0.5% by volume of 2-butene.
19.如权利要求1至7任一项所述的方法,其中气体混合物2中丁烯的总含量≤0.05体积%。 19. The method according to any one of claims 7, wherein the gas mixture the total content ≤0.05% by volume of 2-butene.
20.如权利要求1至7任一项所述的方法,其中气体混合物2中C4烃的总含量≤3体积%。 The method according to any one of claims 7 to 20. claimed in claim 2 wherein the gas mixture the total content of C4 hydrocarbons ≤3% by volume.
21.如权利要求1至7任一项所述的方法,其中气体混合物2中C4烃的总含量≤2体积%。 21. The method according to any one of claims 1 to 7, wherein the gas mixture the total content of C4 hydrocarbons ≤2% by volume.
22.如权利要求1至7任一项所述的方法,其中气体混合物2中C4烃的总含量≤1体积%。 22. The method according to any one of claims 1 to 7, wherein the total content of the gas mixture 2 by volume ≤1% of C4 hydrocarbons.
23.如权利要求1至7任一项所述的方法,其中气体混合物2中C4烃的总含量>0.05体积%且<3体积%。 23. The method according to any one of claims 1 to 7, wherein the gas mixture the total content of C4 hydrocarbons> 0.05 vol% and <3% by volume.
24.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥0.1体积%的除丙烷、丙烯和氧之外的组分。 The method according to any one of claims 7 to 24. claimed in claim 1 wherein the gas mixture 'comprises ≥0.1% by volume of components other than other than propane, propylene and oxygen.
25.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥0.2体积%的除丙烷、丙烯和氧之外的组分。 25. The method according to any one of claims 1 to 7, wherein the gas mixture 1 'comprises ≥0.2% by volume of components other than other than propane, propylene and oxygen.
26.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥0.3体积%的除丙烷、丙烯和氧之外的组分。 26. The method according to any one of claims 7, wherein the gas mixture 1 'comprises ≥0.3% by volume of components other than other than propane, propylene and oxygen.
27.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥0.5体积%的除丙烷、丙烯和氧之外的组分。 The method according to any one of claims 7 to 27. Claim 1 wherein the gas mixture 'comprises ≥0.5% by volume of components other than other than propane, propylene and oxygen.
28.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥1体积%的除丙烷、丙烯和氧之外的组分。 The method according to any one of claims 7 to 28. claimed in claim 1 wherein the gas mixture 'comprises components other than the addition of ≥1% by volume of propane, propylene and oxygen.
29.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥3体积%的除丙烷、丙烯和氧之外的组分。 29. The method according to any one of claims 7, wherein the gas mixture 1 'comprising components other than the addition of ≥3% by volume of propane, propylene and oxygen.
30.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥5体积%的除丙烷、丙烯和氧之外的组分。 The method according to any one of claims 7 to 30. claimed in claim 1 wherein the gas mixture 'comprises components other than the addition of ≥5 vol% of propane, propylene and oxygen.
31.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥10体积%的除丙烷、丙烯和氧之外的组分。 The method according to any one of claims 7 to 31. claimed in claim 1 wherein the gas mixture 'comprises ≥10% by volume of components other than other than propane, propylene and oxygen.
32.如权利要求1至7任一项所述的方法,其中气体混合物1′包含≥30体积%的除丙烷、丙烯和氧之外的组分。 The method according to any one of claims 7 to 32. claimed in claim 1 wherein the gas mixture 'comprises ≥30% by volume of components other than other than propane, propylene and oxygen.
33.如权利要求1至7任一项所述的方法,其中气体混合物2最高可包含60体积%的丙烷。 The method according to any one of claims 7 to 33. claimed in claim 2 wherein the gas mixture may contain up to 60% by volume of propane.
34.如权利要求1至7任一项所述的方法,其中气体混合物2最高可包含50体积%的丙烷。 7 A method according to any one of claims 1 to 34. claimed in claim 2 wherein the gas mixture may contain up to 50% by volume of propane.
35.如权利要求1至7任一项所述的方法,其中气体混合物2包含20体积%至40体积%的丙烷。 The method according to any one of claims 7 to 35. claimed in claim 2 wherein the gas mixture comprises 20 vol% to 40 vol% propane.
36.如权利要求1至7任一项所述的方法,其中气体混合物2包含:7至15体积%的O2,5至10体积%的丙烯,15至40体积%的丙烷,25至60体积%的氮,总共为1至5体积%的CO、CO2和H2O及0至5体积%的其它组分,其中忽略了任何存在的氨。 25 to 60 volume of 7-15 vol% to 10 vol% O2,5 of propylene, 15 to 40% by volume of propane: 36. A method as claimed in any one of claims 1 to 7, wherein a gas mixture comprising % of nitrogen, for a total of 1 to 5% by volume of CO, CO2 and H2O and 0-5% by volume of other components, which ignores the presence of any ammonia.
37.如权利要求1至7任一项所述的方法,其中气体混合物2包含:H2O≤60体积%,N2≤80体积%,O2>0,≤20体积%,CO≤2体积%,CO2≤5体积%,乙烷≤10体积%,乙烯≤5体积%,甲烷≤5体积%,丙烷>0,≤50体积%,环丙烷≤0.1体积%,丙炔≤0.1体积%,丙二烯≤0.1体积%,丙烯>0,≤30体积%,H2≤30体积%,异丁烷≤3体积%,正丁烷≤3体积%,反-2-丁烯≤1体积%,顺-2-丁烯≤1体积%,1-丁烯≤1体积%,异丁烯≤1体积%,1,3-丁二烯≤1体积%,1,2-丁二烯≤1体积%,1-丁炔≤0.5体积%,2-丁炔≤0.5体积%,其中忽略任何存在的氨。 37. A method according to any one of claims 1 to 7, wherein the gas mixture 2 comprising: H2O≤60 vol%, N2≤80 vol%, O2> 0, ≤20 vol%, CO≤2 vol%, CO2 ≤5% by volume, ≤10% by volume of ethane, ethylene ≤5% by volume, ≤5% by volume of methane, propane> 0, ≤50% by volume, cyclopropane ≤0.1% by volume, ≤0.1% by volume of propyne, propadiene ≤0.1% by volume propylene> 0, ≤30 vol%, H2≤30 vol%, ≤3% by volume of isobutane, n-butane ≤3% by volume ≤1% by volume of 2-butene, cis-2 - butene volume ≤1% ≤1% by volume of 1-butene, isobutene volume ≤1% ≤1% by volume of 1,3-butadiene, 1,2-butadiene ≤1% by volume, 1- ≤0.5% by volume alkynyl, 2-butynyl ≤0.5% by volume, ignoring any ammonia present.
38.如权利要求1至7任一项所述的方法,其中粗丙烷包含≥0.25体积%的除丙烷和丙烯之外的组分。 The method according to any one of claim 7 to claim 38., wherein the volume of the crude propane ≥0.25 comprising components other than propane and propylene percent.
39.如权利要求1至7任一项所述的方法,其中粗丙烷包含≥1体积%的除丙烷和丙烯之外的组分。 The method according to any one of claim 7 as claimed in claim 39., wherein the volume of the crude propane ≥1 comprising components other than propane and propylene percent.
40.如权利要求1至7任一项所述的方法,其中粗丙烷包含≥2体积%的除丙烷和丙烯之外的组分。 40. The method according to any one of claims 1 to 7, wherein the crude propane contains components other than propane and propylene ≥2% by volume.
41.如权利要求1至7任一项所述的方法,其中粗丙烷包含≥3体积%的除丙烷和丙烯之外的组分。 41. The method according to any one of claims 1 to 7, wherein the crude propane contains components other than propane and propylene ≥3% by volume.
42.如权利要求1至7任一项所述的方法,其中粗丙烷最高可包含6体积%的C4烃。 The method according to any one of claim 7 to claim 42., wherein the crude propane may comprise up to 6% by volume of C4 hydrocarbons.
43.如权利要求1至7任一项所述的方法,其中粗丙烷包含0.1至6体积%的C4烃。 The method according to any one of claim 7 to claim 43., wherein the crude propane containing 0.1 to 6% by volume of C4 hydrocarbons.
44.如权利要求1至7任一项所述的方法,其中粗丙烷最高可包含0.5体积%的1-丁烯。 The method according to any one of claim 7 to claim 44., wherein the crude propane may comprise up to 0.5% by volume of 1-butene.
45.如权利要求1至7任一项所述的方法,其中粗丙烷包含5体积ppm至0.5体积%的1-丁烯。 45. The method according to any one of claims 1 to 7, wherein the crude propane containing 5 ppm by volume to 0.5% by volume of 1-butene.
46.如权利要求1至7任一项所述的方法,其中粗丙烷包含总量最高可达0.5体积%的丁烯。 The method according to any one of claims 7 to 46. wherein the maximum total amount of crude propane comprising up to 0.5% by volume of butene.
47.如权利要求1至7任一项所述的方法,其中粗丙烷包含总量为5体积ppm至0.5体积%的丁烯。 47. A method according to any one of claims 1 to 7, wherein the crude propane containing 5 ppm by volume to a total amount of 0.5% by volume of butene.
48.如权利要求1至7任一项所述的方法,其中粗丙烷符合以下规格:丙烷的含量≥90体积%,丙烷及丙烯的总含量≤99体积%,C4烃的总含重≤6体积%,1-丁烯的含量≤0.5体积%,丁烯的总含量≤0.5体积%,乙烷的含量≤10体积%,乙烯的含量≤5体积%,甲烷的含量≤5体积%,环丙烷的含量≤0.1体积%,丙烯的含量≤10体积%,丙烷和丙烯之外的C3烃的总含量≤0.3体积%,C5烃的总含量≤0.3体积%,且C6-C8烃的总含量≤600体积ppm。 1 48. The method according to any one of claims 7, wherein the crude propane meets the following specifications: a content ≥90% by volume of propane, propene and propane, the total content of ≤99% by volume, of the total weight of C4 hydrocarbons containing ≤6 vol%, 1-butene content of ≤0.5% by volume, the total content of ≤0.5% by volume of butene, the content of ≤10% by volume of ethane, ethylene content of ≤5% by volume, the methane content of ≤5% by volume, ring the content of ≤0.1% by volume of propane, propylene content of ≤10% by volume of the total content of ≤0.3 C3 hydrocarbons other than propane and propene volume%, the total content of ≤0.3% by volume C5 hydrocarbons, C6-C8 hydrocarbons and the total content, volume of ≤600 ppm.
49.如权利要求1至7任一项所述的方法,其中第一步中丙烷的转化率≥5摩尔%至≤30摩尔%。 The method according to any one of claim 7 to claim 49., ≥5 mol% to ≤30 mol%, wherein the conversion of propane in the first step.
50.如权利要求1至7任一项所述的方法,其中从得自气相不完全氧化和/或不完全气相氨氧化的产物气体混合物中分离出丙烯的至少一种不完全氧化和/或氨氧化的产物,并至少将未反应的丙烷和丙烯再循环至第一步和/或再循环至气相不完全氧化和/或不完全气相氨氧化。 50. The method according to any one of claims 1 to 7, wherein the gas obtained from the partial oxidation / or product gas mixture of ammonia gas and incomplete oxidation of propylene is separated at least one partial oxidation and / or the product of ammonia oxidation, and at least the unreacted propane and propylene is recycled to the first step and / or recycled to the partial oxidation gas and / or gas-phase ammoxidation incomplete.
51.如权利要求1至7任一项所述的方法,其中所述方法是在反应区中在催化剂装料上进行的,所述催化剂装料的活性组合物由至少一种多金属氧化物组合物组成,所述多金属氧化物组合物含有结合在一起的元素Mo、V、两种元素Te和Sb中的至少一种、至少一种选自由Nb、Ta、W、Ti、Al、Zr、Cr、Mn、Ga、Fe、Ru、Co、Rh、Ni、Pd、Pt、La、Bi、B、Ce、Sn、Zn、Si、Na、Li、K、Mg、Ag、Au和In组成的组的元素。 51. The method according to any one of claims 1 to 7, wherein said process is carried out on the catalyst charge in the reaction zone, the catalyst charge of at least one active composition multimetal oxide the composition composed of the multi-metal oxide composition comprising a combination of elements Mo, V, Te and Sb two elements at least one, at least one selected from the group consisting of Nb, Ta, W, Ti, Al, Zr , Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, B, Ce, Sn, Zn, Si, Na, Li, K, Mg, Ag, Au and in groups of elements.
52.如权利要求51所述的方法,其中所述活性组合物由至少一种多金属氧化物组合物组成,所述多金属氧化物组合物具有元素化学计量I:Mo1VbM1cM2d(I)其中M1为Te和/或Sb,M2为至少一种选自由Nb、Ta、W、Ti、Al、Zr、Cr、Mn、Ga、Fe、Ru、Co、Rh、Ni、Pd、Pt、La、Bi、Ce、Sn、Zn、Si、Na、Li、K、Mg、Ag、Au和In组成的组的元素,b为0.01至1,c为>0至1,且d为>0至1。 52. A method according to claim 51, wherein the active composition of at least one multimetal oxide composition composed of a multi-element metal oxide composition having the stoichiometry I: Mo1VbM1cM2d (I) wherein M1 is Te and / or Sb, M2 is at least one selected from the group consisting of Nb, Ta, W, Ti, Al, Zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, Ce , element group Sn, Zn, Si, Na, Li, K, Mg, Ag, Au and in, b is from 0.01 to 1, c is> 0 to 1, and d is> 0 to 1.
53.如权利要求52所述的方法,其中M1为Te且M2为Nb、Ta、W和/或Ti。 53. The method according to claim 52, wherein M1 and M2 is Te of Nb, Ta, W and / or Ti.
54.如权利要求52所述的方法,其中M2为Nb。 54. The method according to claim 52, wherein M2 is Nb.
55.如权利要求51所述的方法,其中所述活性多金属氧化物的X射线衍射图具有最大值位于衍射角(2θ)22.2±0.5°(h)和27.3±0.5°(i)的反射h和i。 55. The method according to claim 51, wherein the X-ray diffraction pattern of the active multimetal oxide has a reflection maximum at a diffraction angle (2θ) 22.2 ± 0.5 ° (h) and 27.3 ± 0.5 ° (i) the h and i.
56.如权利要求55所述的方法,其中所述X射衍射线图另外具有最大值位于28.2±0.5°的反射k。 56. The method according to claim 55, wherein the further X-rays diffraction diagram has a reflection maximum at k of 28.2 ± 0.5 °.
57.如权利要求55所述的方法,其中反射h在X射衍射线图中强度最大,且其半高宽度不超过0.5°。 57. The method according to claim 55, wherein the maximum intensity of reflection h in X-rays diffraction chart, having a half width and not more than 0.5 °.
58.如权利要求57所述的方法,其中反射i和反射k的半高宽度分别≤1°,且反射k的强度Pk和反射i的强度Pi满足关系0.2≤R≤0.85,其中R是由下式定义的强度比:R=Pi/(Pi+Pk) 58. The method according to claim 57, wherein the half width of the reflection i and of the reflection k each ≤1 °, and the reflection i and the intensity Pk intensity Pi of the reflection k satisfies the relationship 0.2≤R≤0.85, wherein R is intensity ratio defined by the equation: R = Pi / (Pi + Pk)
59.如权利要求51所述的方法,其中所述活性多金属氧化物的X射线衍射图不具有最大值位于2θ=50±0.3°的反射。 59. The method according to claim 51, wherein the X-ray diffraction pattern of the active multimetal oxide having no reflection maximum at 2θ = 50 ± 0.3 ° of.
60.如权利要求1至7任一项所述的方法,其中第一步是在单独的反应区中进行的。 The method according to any one of claim 7 to claim 60., wherein the first step is carried out in separate reaction zones.
61.如权利要求60所述的方法,其中所述第一步是多相催化脱氢。 61. The method according to claim 60, wherein said first step is a heterogeneously catalyzed dehydrogenation.
62.如权利要求60所述的方法,其中从气体混合物1中分离出存在于气体混合物1中的除丙烷和丙烯之外的组分中包含至少一种C4烃的部分。 62. The method according to claim 60, wherein there is separated from the gas mixture to a gas mixture of 1 part of at least one C4 hydrocarbon components other than the one contained propane and propene.
63.如权利要求60所述的方法,其中从气体混合物1中分离出存在于气体混合物1中的除丙烷和丙烯之外的组分中含至少一种丁烯的部分。 63. The method according to claim 60, wherein there is separated from the gas mixture containing at least one of a portion of components other than butene propane and propene in addition to a gas mixture.
64.如权利要求60所述的方法,其中从气体混合物1中分离出存在于气体混合物1中的除丙烷和丙烯之外的组分中至少含1-丁烯的部分。 64. The method according to claim 60, wherein there is separated from the gas mixture 1 to components other than propane and propylene containing at least one other portion of the gas mixture of 1-butene.
65.如权利要求60所述的方法,其中使用活性组分含有元素Mo、Bi和Fe的催化剂进行多相催化气相不完全氧化和/或不完全气相氨氧化。 65. The method according to claim 60, wherein the active ingredient elements containing Mo, Bi and Fe catalyst for heterogeneously catalyzed gas phase partial oxidation and / or incomplete gas phase ammoxidation.
66.如权利要求60所述的方法,其中使用活性组分为式IV所示的多金属氧化物的催化剂进行多相催化气相不完全氧化和/或不完全气相氨氧化:Mo12BiaFebX1cX2dX3eX4fOn(IV)其中各变量具有以下含义:X1=镍和/或钴,X2=铊、碱金属和/或碱土金属,X3=锌、磷、砷、硼、锑、锡、铈、铅和/或钨,X4=硅、铝、钛和/或锆,a=0至5,b=0.01至5,c=0至10,d=0至2,e=0至8,f=0至10和n=由(IV)中氧之外的元素的化学价和丰度确定的数。 66. The method according to claim 60, wherein the active component of the catalyst multimetal oxide represented by the formula IV for heterogeneously catalyzed gas phase partial oxidation and / or partial gas-phase ammoxidation: Mo12BiaFebX1cX2dX3eX4fOn (IV) wherein the variables have the following meanings: X1 = nickel and / or cobalt, X2 = thallium, an alkali metal and / or alkaline earth metal, X3 = zinc, phosphorus, arsenic, boron, antimony, tin, cerium, lead and / or tungsten, X4 = silicon, aluminum, titanium and / or zirconium, a = 0 to 5, b = 0.01 to 5, c = 0 to 10, d = 0 to 2, e = 0 to 8, f = 0 to 10 and n = a ( IV) represents a valence and abundance of the elements other than oxygen determined.
67.如权利要求60所述的方法,其中使用活性组分含有元素Mo和V的催化剂进行多相催化气相不完全氧化。 67. The method according to claim 60, wherein the active component of the catalyst containing the elements Mo and V, for heterogeneously catalyzed gas-phase partial oxidation.
68.如权利要求60所述的方法,其中使用活性组分为式VII所示的多金属氧化物的催化剂进行多相催化气相不完全氧化:Mo12VaX1bX2cX3dX4eX5fX6gOn(VII)其中各变量具有如下含义:X1=W、Nb、Ta、Cr和/或Ce,X2=Cu、Ni、Co、Fe、Mn和/或Zn,X3=Sb和/或Bi,X4=一种或多种碱金属,X5=一种或多种碱土金属,X6=Si、Al、Ti和/或Zr,a=1至6,b=0.2至4,c=0.5至18,d=0至40,e=0至2,f=0至4,g=0至40和n=由VII中除氧之外的元素的化合价和丰度决定的数。 68. The method according to claim 60, wherein the catalyst is a multimetal oxide active component of Formula VII shown in heterogeneously catalyzed gas-phase carried out using partial oxidation: Mo12VaX1bX2cX3dX4eX5fX6gOn (VII) where the variables have the following meanings: X1 = W, Nb, Ta, Cr and / or Ce, X2 = Cu, Ni, Co, Fe, Mn and / or Zn, X3 = Sb and / or Bi, X4 = one or more alkali metals, X5 = one kind or more alkaline earth metals, X6 = Si, Al, Ti and / or Zr, a = 1 to 6, b = 0.2 to 4, c = 0.5 to 18, d = 0 to 40, e = 0 to 2, f = 0 to 4, g = 0 to 40 and n = a number determined by the valence and abundance VII elements other than oxygen.
69.如权利要求1至7任一项所述的方法,其中丙烯不完全氧化和/或氨氧化的产物包含至少一种选自由氧化丙烯、丙烯醛、丙烯酸和丙烯腈组成的组的化合物。 The method according to any one of claims 7 to 69. The claims and / or products of incomplete oxidation of propylene ammoxidation comprising at least one compound selected from the group consisting of propylene oxide, acrolein, acrylic acid and acrylonitrile group.
70.如权利要求1至7任一项所述的方法,其中第一步包括在氧的存在和/不存在下对粗丙烷进行多相催化脱氢,并对气体混合物1进行存在于气体混合物1中的丙烯的多相催化气相氨氧化。 70. The method according to any one of claims 1 to 7, wherein the first step involves the presence of oxygen in the crude heterogeneously catalyzed propane dehydrogenation and the presence / absence of the gas mixture and the gas mixture present in the 1 a heterogeneously catalyzed gas-phase ammoxidation of propylene.
71.如权利要求1至7任一项所述的方法,其中第一步包括在存在和/不存在氧、存在水蒸气的条件下对粗丙烷进行多相催化脱氢,并从在第一步中生成的气体混合物1中冷凝出全部或部分水蒸气以获得气体混合物1′,对气体混合物1′进行存在于气体混合物1′中的丙烯的多相催化气相不完全氧化和/不完全气相氨氧化。 71. The method according to any one of claims 1 to 7, wherein the first step comprises the presence and / or absence of oxygen, the crude heterogeneously catalyzed propane dehydrogenation in the presence of steam, and from the first the gas mixture generated in step 1 all or part of the steam is condensed to obtain a gas mixture of 1 ', gas mixture 1' is present in the gas mixture of propylene heterogeneously catalyzed gas-phase 1 'of the partial oxidation and / or incomplete gas ammonia oxidation.
72.如权利要求1至7任一项所述的方法,其中第一步包括对粗丙烷进行自热式多相催化脱氢。 72. The method according to any one of claims 1 to 7, wherein the first step comprises the crude propane multiphase autothermal catalytic dehydrogenation.
73.如权利要求1至7任一项所述的方法,其中将气体混合物1和/或气体混合物1′作为气体混合物2的组分进行存在于气体混合物1和/或气体混合物1′中的丙烯的多相催化不完全气相氨氧化。 73. The method according to any one of claims 7 to claim 1 wherein the gas mixture and / or gas mixture 1 'as a component of the gas mixture 2 will be present in the gas mixture and / or gas mixture 1' heterogeneously catalyzed gas-phase propylene ammoxidation incomplete.
CNB038254107A 2002-09-27 2003-09-18 Preparation of at least one partial oxidation and/or ammoxidation product of propylene CN1305817C (en)

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