Title of Invention

OXIDATION REACTOR AND PROCESS FOR THE OXIDATION OF FLUIDS

Abstract

The invention relates to an oxidation reactor and process suited to operate the said reactor which houses a multitude of gas-tight and oxygen conductive membrane elements the external surfaces of which are arranged on the side of a reaction chamber to be filled with catalyst and which constitute, in conjunction with the membrane elements penetrable by oxygenous gas, a connection between the distribution chamber and a collection chamber and/or discharge section of the reactor. The reactor is characterized in that one or several spacer pieces establish a defined minimum distance between the external surface of a membrane element and the catalyst in the reaction chamber.

Full Text

An oxidation reactor and process [0001] The invention relates to an oxidation reactor and an oxidation process suited to operate the said reactor, which houses a multitude of gas-tight and oxygen conductive membrane elements, the external surfaces of which are arranged on the side of a reaction chamber suitable to be filled with catalyst and which constitute, in conjunction with the membrane elements penetrable by oxygenous gas, a connection between the distribution chamber and a collecting chamber and/or discharge section of the reactor. The reactor is characterised in that one or several spacer pieces establish a defined minimum distance between the external surface of the membrane and the catalyst of the reaction chamber. [0002] Synthesis gas, i.e. gas mixtures with the main components CO and H2 (and if nec- essary for the specific production and purification step, with further components such as CO2, H2, N2 and inert ingredients) is produced in accordance with the state-of-the-art tech- nology mainly by two methods: endothermic steam reforming of hydrocarbons (such as methane) and derivated compounds according to the equation and by direct conversion of these compounds with the aid of oxygen in a partial oxidation (at least in a formal sense) according to the following equation: [0003] Oxygen required for partial oxidation may, for instance, originate from a cryogenic air fractionation plant. [0004] In the case of the state-of-the-art steam reforming used in the production of syn- thesis gas, a major disadvantage is due to the high investment costs as well as the large amount of heat released during plant operation. With regard o the partial oxidation accord- ing to equation (2), however it is necessary to consider the input of expensive oxygen as a demerit because the said oxygen is supplied by a separate ir fractionation plant. As the purity requirements do not allow a content of nitrogen in the synthesis gas obtained at a later stage, the addition of an as oxidizing agent is not feasible [0005] It would be a real economic benefit if it were possible to add the oxygen required for synthesis gas production without additional process step, i.e. direct oxygen feed by means of a conductive membrane into the oxidation reactor, and if even air could be used as feedstock for the O2 needed. [0006] In this context, laboratory scale processes are known which use so-called concur- rently conductive membranes (in US patent 6,077,323 also named: mixed conducting membrane) for synthesis gas production. These concurrently conductive materials are still in the development stage and they are compounds which under appropriate operating conditions exhibit a conducting capacity for electrons and oxygen ions to a significant ex- tent in each case. Materials which are exclusively oxygen ions conductive, hence without permeability to electrons, and which require charge balancing via an external power circuit, are of minor importance only. [0007] In case such type of materials are used to form gas-tight or almost gas-tight mem- branes and then they undergo heating up to the operating temperature, an oxygen flux will be established across the membrane, provided there is a partial pressure gradient be- tween the feed side and the permeative side as stated below, thereby exploiting defective lattice sections: [0008] Each O2 molecule originating from the permeative side and sent into the reaction chamber will release a charge of 4 e , which is transported to the feed side counter-current to the oxygen flux. [0009] In this case the transport of the oxygen takes place in the ionic form, i.e. there is a theoretical oxygen-specific selectivity of the membrane to an indefinite extent. Thus, a membrane that is free of defective sectors and air being used as the oxygen supplier per- mits the separation of the oxygen from the residual air constituents such as nitrogen. [0010] According to the a: ve information, it is known in the present state of the art that oxidation reactions can take place with the aid of oxygen consuctive materials, with a reac- tor being used to divide the reactor into two chambers by means of a concurrently conduc- tive membrane. During o\ ation an oxygen containing gas or gas mixture is fed on the one side of the membrane membrane module, while the opposite side of the membrane (hereinafter referred to as external surface or permeative side) is provided with the fluid to be oxidised. US 5,820,655 A, for example, describes the use of such a membrane reactor. Oxygen carrying gases such as water vapour, CO2 or preferably air are exploited. During operation, oxygen permeates the membrane from the side with a higher partial pressure of the oxygen and then it reacts with the oxidisable fluid that is present on the opposite side. In the case of synthesis gas production, the preferred oxidisable fluid is hydrocarbon such as methane or natural gas with a high methane content water vapour being typically added to preclude coking. [0011] Since the oxygen constantly undergoes reaction, the oxygen partial pressure on the permeative side is below the partial pressure of the oxygen on the feedside so that further oxygen continues to permeate. This is why air with a more or less indefinite pres- sure can be used on the feed side, while a considerably higher pressure simultaneously prevails on the permeative side. The minimum limit for the oxygen partial pressure is set to be higher than that on the permeative side. [0012] In order to obtain acceptable reaction velocities and consequently integral selectivi- ties on the permeative side, for instance, in the synthesis gas production, it is a typical practice to use an appropriate catalyst in the reaction chamber of the reactor. Documents EP 0 999 180 A2, EP 1 035 072 A1, US 6,077,323 or US 6,695,983 describe typical ex- amples of that application At the specified operating conditions, oxygen permeates the membrane from the feed side and is converted on the opposite permeative side. The driv- ing force for this permeation is the difference in partial pressure of the oxyen on the two sides of the membrane. As this pressure is constantly maintained by the oxygen undergo- ing a permanent reaction, it is possible to perform the synthesis gas production with the aid of air on the feed side and a hydrocarbon/water vapour mixture on the permeative side, thereby using air at atmospheric pressure or a pressure that only slightly exceeds the said pressure. [0013] The mixed conductive materials are typically ceramic materials which on account of an oxygen defective structure under appropriate operating conditions, possess the ability of conducting oxygen ions. Appropriate operating conditions in this case are understood to mean a sufficiently high temperature of > 600°C as well as an oxygen partial pressure dif- ference via the ceramic material. Such materials may typically originate from the group of perowskite (ABO3) or perove skite-related structures, fluorite structures (AO2), aurivillius structures ([Bi202][An-1BnOx) or Brownmillerite structures (A2B2O5). Composite materials of ion and electron conductive materials may also be suitable Typical examples of oxygen conductive materials or material classes quoted in the technical literature are: La1 x(Ca,Sr,Ba)xCo1-yFeyO3-δ, Ba(Sr)Co1-xFexO3-δ, Sr(Ba)Ti(Zr)1-x-y, CoyFexO3-δ, La1-xSrxGa1-yFeyO3-δ, La0,5Sr0. 5MnO3-δ, LaFe(Ni)O3-δ, La0.9Sr0.1FeO3-δ or BaCoxFeyZr1-x-yO3-δ. (A. Thursfield, I. S. Metcalfe, J. Mat. Sci., 2004, 14, 275-2485). [0014] Furthermore, multiphase composite materials may for example be exploited, too. Materials that are suitable t, technical applications are those with as high an oxygen per- meability as possible. Typics; values in this case approximate >0.1 Nm3 / (m2 h) oxygen. [0015] A certain problem, however, is the chemical and mechanical stability of the mem- branes. The specialist skilled in the art is for example in a position to calculate the balance oxygen partial pressure of a synthesis gas stream of standard composition to be bars at 900°C and 30 bars total pressure. [0016] On the other hand, the materials used as mixed conductive materials are normally oxidic ceramics which tend to cause a reduction and consequently destruction of the crys- tal structure in a range that is below the oxygen partial pressure depending on the con- stituents of the membrane Thus, a specialist skilled in the art can for example, easily cal- culate that CoO usually contained in such materials will be reduced to form elemental Co at a temperature of 900°C and the above mentioned oxygen partial pressure of bars. This theoretical evaluation can also be substantiated by means of a test series as described in the example c>= comparison. [0017] A further peril originating from such high oxygen partial pressure gradients may emanate from tensions chemically induced. Depending on the level of the respective oxy- gen partial pressure on either side of the membrane, different oxygen defective structures will develop within the crystal lattice of the membrane. This will inevitably lead to different crystal lattice constants on the feed and permeative side of the membrane. The mechani- cal load thus induced which is also named chemically induced tension may perhaps cause a destruction of the membrane. [0018] Example of comparison 1 Test samples of materia!? Ba(Co,Fe,Zr)O3-δ suitable for concurrently conductive mem- branes, hereinafter referred to as BCFZ (Journal of Membrane Science, 2005, 258, 1-4), were exposed to a synthesis gas atmosphere at a temperas re of 850°C and a pressure of 1 bar, the chemical compesition of the atmosphere was as ested below: [0020] After the said period the crystal structure of the test pieces was determined by X- Ray Diffraction (XRD) depending on the dwelling time. Fig. 1 shows the results of the comparison. The relative intensity for the six dwelling times selected for the membrane was plotted in relation to the diffraction angle (Theta). The new peaks of relative intensity that occurred vis-a-vis the 0 h value during prolonged dwelling time revealed, inter alia, that elemental Co as well as various independent oxide phases had formed. Simultane- ously the peaks crucial for the Perovskite phase disappeared. It became obvious that a rather short period of only 50 h caused a degradation of the crystal structure which leads to a disruption of the intended functionality of the membrane, i.e. to local decomposition. [0021] In addition to the destruction of the membrane, the presence of air on one side of the membrane entailed the formation of various different lattice constants on either side of the membrane, which caused mechanical load as a result of chemically induced tensions (F. Boroomand, E. Wessel, H. Bausinger, K. Hilpert, Solid State Ionics, 2000, 129, 251- 258; S. B. Adler, J. Am. Ceram. Soc, 2001, 84, 2117-2119) [0022] On the empirical as well as theoretical bases one must therefore fear that a ce- ramic membrane of the BCFZ composition will be destroyed when being used for the syn- thesis gas production so that hitherto no industrial exploitation has taken place although the material properties are essentially appropriate for the application. [0023] In addition it cannot be precluded that placing the catalyst material in direct contact with the membrane at the required temperature of > 800°C; will cause solids reactions in the contact area of the surfaces involved, which would contribute to a degradation or local destruction of the membrane. [0024] EU 0,999,180 A2 reveals a possibility of avoiding this destruction. The addition of oxygenates such as CO2 or water vapour on the permeative side of the membrane is rec- ommended in this document. This measure increases the balance oxygen partial pressure on the permeative side of the membrane to a value above the limit normally leading to a reduction of the membrane. However, the high investment costs and operating expenditure required for the necessary gas recycle system within the plant and for the narrow variation margin of the balance oxygen partial pressure are a real problem. In the case of the typical balance oxygen partial pressures of 10-10 bars that can be obtained on the permeative side, the membrane materials are in fact no longer reduced but nevertheless chemically induced tensions continue to occur. Hence, the return of the oxygenates is essentially un- suitable for improving the reduction stability and simultaneously the mechanical stability and, moreover, such measure also decreases the plant economy of this process. [0025] From the state-of-the-art viewpoint the objective is to develop an oxidation reactor with an oxygen conducting membrane that has a high reduction stability and a high me- chanical stability, the membrane being stable against the catalyst, without causing a deg- radation of the crystal structure which leads to a disruption of the intended functionality of the membrane by a local decomposition, because it is assumed that placing the catalyst material in direct contact with the membrane at the required temperature of > 800°C will cause solid reactions in the contact area of the surfaces involved, which will contribute to a degradation or local destruction of the membrane. [0026] The aim of the present invention is achieved by an oxidation reactor that is pro- vided with a feed line for piping the oxygen bearing gas to a distribution chamber or a header element. In addition the said reactor is equipped with a feed line for raw gas to be completely or partially oxidised, the said line being connected to a reaction chamber which has a multitude of gas-tight oxygen conducting membrane elements. [0027] With reference to the oxygen transport the membrane elements have an inlet sur- face area and an outlet surface area, the latter being defined as external surface located on the side of the reaction chamber. The membrane elements ensure the connection be- tween the distribution chamber or collecting chamber and/or discharge section. During operation the oxygen bearing gas can flow through the reactor in the following order: inlet, distribution chamber, membrane element, collecting chamber and/or outlet section, the reaction chamber being filled with catalyst. [0028] One or several subcer elements are used to establish a defined minimum space between the external surface of the membrane elements nd / or a bundle of such ele- ments on the one side a: the catalyst space on the othe rhe said bundle or group may consist of parallel or twis or drilled membrane element; The catalyst is fillable and can be filled into the reaction chamber, and the spacer elements are catalytically active com- ponents which oxidise in the membrane contact sections during the specified reactor op- eration and thus become inert, and are placed in contact with the outlet area of the mem- brane. [0029] It is recommended that the above mentioned spacer elements of the reactor de- scribed in this document be formed as prefabricated pieces that enclose the bundle or group or be arranged in advanced position towards the reaction chamber. The prefabri- cated blocks may be made of the bulk type and/or as single element such as a jacket pipe. In this case, the inert material has either a pore volume or a perforated section that is smaller than the fines portion of the catalyst packing. [0030] In a further embodiment the spacer elements may consist of one or several materi- als which are directly applied to the external membrane surface. Spacer elements of such a type with a porous structure, the volume of which is smaller than the fines content of the bulk catalyst material, retain the catalyst in such a manner that it comes not into direct con- tact with the oxygen conducting membrane. [0031] A comparable method of retaining the catalyst is to form the spacer elements as catalytically active components which oxidise in the intended sections during the specified reactor operation and thus become inert and which are placed opposite the outlet area of the membrane and/or are arranged to come into slight contact. [0032] The shape of the spacer elements made in accordance with the invention is either regular or of an irregular structure. The said spacers can also be enhanced by providing them with one or several catalytically active surfaces, the ideal shape of the spacers being such that the surfaces pointing towards the reaction chamber are provided with a catalyti- cally active material coat or consist of the said material. [0033] The present invention also encompasses an oxidation reactor which essentially complies with the type of reactor described above but which by adequate shaping of the catalyst in the reaction chamber provides for a minimum distance between the external surface of the membrane element or a group or bundle of membrane elements and the catalyst itself. A particularly advantageous embodiment of the catalyst provides for a bar type or surface type shape . [0034] The oxidation receptor can be further improved by gluing or sintering one side of the catalyst to fix it adequately to the plate. In the case of such a design it is common practice to arrange in parallel the membrane and the catalyst and to obtain by this method a de fined distance with accurate centreline. [0035] A beneficial embodiment of the invention provides for membrane elements installed in the above mentioned oxidation reactors and made of one or several material that orgi- nate from group of Perovskite (ABO3), Perovskite-related structures, fluorite structures (AO2), Aurivillius structures ([Bi2O2]An-1BnOx]) or Brownmillente structures (A2B205). A type of membrane that is particularly suited for the 02 transport and consequently for the utiliza- tion in oxidation reactors is either made of one material or several materials which can be described by the formulae listed below: La1.x(Ca,Sr,Ba)xCo1_yFey03.8, Ba(Sr)Co1.xFexO3.5, Sr(Ba)Ti(Zr)1.x.yCoyFexO3-8, BaCoxFeyZri.x.y03-5, LaLxS^Ga^FeyOM, La2NixFey04-8, Lao,5Sro,5MnO3.5, LaFe(Ni)03.8 oder La0,9Sr0,iFeO3.6. [0036] An ideal version of such membrane elements exhibits an oxygen permeability which at approx. 950°C and an oxygen partial pressure difference of >0.1 bar between the free gas phases located on the two sides of the membrane approximates an average value of > 0.1 Nm3/(m2h). [0037] Moreover, the invention also encompasses a process for the oxidation of fluids in an oxidation reactor that is constructed in line with the design types described above, with the reaction chamber being filled with a catalyst: oxygen or an oxygan-bearing gas is admitted via the inlet into the distribution chamber of the oxidation reactor, a gas or gas mixtire to be oxidised is piped into the reaction chamber, - the temperature in the reaction chamber ranging from 200 to 1200°C, preferably from 500 to 1000°C and in the ideal version from 700 to 900 °C and furthermore, - at a pressure between 1 - 200 bars, preferably 10 - 70 bars and in the ideal ver- sion 30 to 60 bars [0038] A beneficial embodiment of the invention provides for an oxidation process in which the gas to be oxidised preferably has a content of methane or natural gas with a high methane portion, which may also contain non-oxidisable ingredients. [0039] Moreover, the invention also encompasses the us«; of the above mentioned oxida= tion process in a configuration dedicated to the production of synthesis gas with the main ingredients H2 and CO. The present invention also covers he use of the oxidation process as described in this document in order to perform the oxidative dehydration of alkanes, oxidative methane coupling, partial oxidation of higher hydrocarbon derivatives or selective oxidation of constituents of gas mixtures. 1 Oxidation reactor with direct oxygen feed by means of a conductive membrane con- tained in the oxidation reactor and an enhanced efficacy, encompassing: • a feed line (5) for oxygenous gas, which communicates with the distribution chamber (12) or distribution element, • a feed line (6) intended for raw gas to be partly or completely oxidised and communicating with the reaction chamber (2), • a multitude of gas-tight and oxygen conductive membrane elements (1) be- ing arranged in the reaction chamber (2), the external surfaces of said ele- ments (1) forming inlet and outlet surfaces - referred to the gas transport - the outlet surfaces being provided on the side of the reaction chamber (2) and constituting, in conjunction with the membrane elements (1), • a connection between the distribution chamber (12) and collecting chamber (13) and/or discharge section of the reactor, oxygenous gas passing through the said parts, and the reaction chamber (2) remaining suitable for accommodating a catalyst packing (4,9), • one or several spacer elements (3) establishing a defined minimum dis- tance between the external surface of the membrane element (1) and the catalyst bed (4,9) in the reaction chamber (3), characterised in thai • the catalyst (4,9) is tillable and can be filled into the reaction chamber (2), and • the spacer elements (3) are catalytically active components which oxidise in the membrane contact sections during the specified reactor operation and thus becomeinert, and which are placed in contact with the outlet area of the membrane (1). 2 Oxidation reactor as claimed in claim 1, wherein the spacer elements (3) establish a defined minimum distance between the external surfaces of a bundle or group of membrane elements (1) and the catalyst bed (4,9) in the reaction chamber. 3 Oxidation reactor as claimed in any of the preceding claims 1 or 2, wherein the said spacer elements (3) are prefabricated blocks which enclose the membrane elements (1) individually or the respective bundle or group (1) in the direction towards the reac- tion chamber (2), the said blocks (3) being of bulk type and / or individual elements such as a jacket pipe 4 Oxidation reactor as claimed in any of the preceding claims 1 to 3, wherein the spacer elements (3) are of a regular or irregular structure. 5 Oxidation reactor as claimed in any of the preceding claims 1 to 4, wherein the spacer elements (3) are provided with one or several catalytically active surfaces, the ideal shape of the spacers (3) being such that the surfaces pointing towards the reaction chamber (2) are provided with a catalytically active material. 6 Oxidation reactor as claimed in any of the preceding claims 1 to 5, wherein the shape of the spacer elements (3), which are catalytically active components, in the reaction chamber (2) are formed in such a manner that a defined minimum distance is secured between the external surface of the membrane element (1) or a group of membrane elements (1) and the catalyst (4) in the reaction chamber (2). 7 Oxidation reactor as claimed in claim 6, wherein the catalyst (4) be shaped as bar- type or surface type elements (1). 8 Oxidation reactor as claimed in any of the preceding claims 6 or 7, wherein the cata- lyst (4) is glued or sintered to at least one side of the plate. 9 Oxidation reactor as claimed in the preceding claims 1 to 8, wherein the membrane elements (1) be made from one or several materials originating from the group of Perovskite (ABO3), Perovskite-related structures, fluorite structures (AO2), Aurivillius structures ([Bi2O2][An-1BnOx]) or Brownmillerite structures (A2B2O5). 10 Oxidation reactor as claimed in any of the preceding claims 1 to 8, wherein the mem- brane elements (1) be formed from one or several materials which can be described by one of the formulae listed below: 11 Oxidation reactor as claimed in any of the preceding claims 1 to 8, wherein the mem- brane elements (1) exhibit an oxygen permeability which at 950°C and an oxygen par- tial pressure difference of > 0.1 bar between free gas phases located on the two sides of the membrane (1) approximates an average value of > 0.1 Nm3/(m2h). 12 Process for the oxidation of fluids with direct oxygen feed by means of a conductive membrane contained in the oxidation reactor and an enhanced efficacy, characterised in that • a reactor that is constructed in line with the design types described in the preceding claims 1 to 11, the reaction chamber (2) being filled with a cata- lyst (9), • oxygen or an oxygen-bearing gas is admitted via the inlet into the distribu- tion chamber (12) of the oxidation reactor, • a gas or gas mixture to be oxidised is piped into the reaction chamber (2), • the temperature in the reaction chamber (2) ranging from 200 to 1200°C, preferably from 500 to 1000°C and in the ideal version from 700 to 900 °C and furthermore, • at a pressure between 1 and 200 bars, preferably 10-70 bars and in the ideal version 30 to 60 bars. 13 Process for the oxidation of fluids as claimed in claim 12, wherein the gas to be oxi- dised also contains non-oxidisable constituents which preferably are methane or natu- ral gas with a high content of methane. 14 Process for the oxidation of fluids as claimed in the preceding claims 12 or 13, wherein a gas or gas xture to be oxidised is piped into the reaction chamber (2) so that synthesis gas with e main components H2 and CC produced. 15 Process for the oxidation of fluids as claimed in the preceding claims 12 or 13, wherein an oxidative dshydration of alkanes, oxidative ethane coupling, partial oxi- dation of higher hydrocarbons and/or hydrocarbon derivates or selective oxidation of constituents of gas mixtures is performed. ABSTRACT AN OXIDATION REACTOR AND A PROCESS FOR THE OXIDATION OF FLUIDS The invention relates to an oxidation reactor and process suited to operate the said reactor which houses a multitude of gas-tight and oxygen conductive membrane elements the external surfaces of which are arranged on the side of a reaction chamber to be filled with catalyst and which constitute, in conjunction with the membrane elements penetrable by oxygenous gas, a connection between the distribution chamber and a collection chamber and/or discharge section of the reactor. The reactor is characterized in that one or several spacer pieces establish a defined minimum distance between the external surface of a membrane element and the catalyst in the reaction chamber.

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02355-kolnp-2008-abstract.pdf

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02355-kolnp-2008-description complete.pdf

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02355-kolnp-2008-international search report.pdf

02355-kolnp-2008-pct request form.pdf

2355-KOLNP-2008-(21-08-2012)-CORRESPONDENCE.pdf

2355-KOLNP-2008-(24-04-2012)-ABSTRACT.pdf

2355-KOLNP-2008-(24-04-2012)-AMANDED CLAIMS.pdf

2355-KOLNP-2008-(24-04-2012)-DESCRIPTION (COMPLETE).pdf

2355-KOLNP-2008-(24-04-2012)-DRAWINGS.pdf

2355-KOLNP-2008-(24-04-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

2355-KOLNP-2008-(24-04-2012)-FORM-1.pdf

2355-KOLNP-2008-(24-04-2012)-FORM-2.pdf

2355-KOLNP-2008-(24-04-2012)-FORM-3.pdf

2355-KOLNP-2008-(24-04-2012)-OTHERS.pdf

2355-KOLNP-2008-CORRESPONDENCE 1.2.pdf

2355-KOLNP-2008-CORRESPONDENCE 1.3.pdf

2355-KOLNP-2008-CORRESPONDENCE OTHERS 1.1.pdf

2355-KOLNP-2008-EXAMINATION REPORT.pdf

2355-KOLNP-2008-FORM 18.pdf

2355-KOLNP-2008-FORM 3.pdf

2355-KOLNP-2008-FORM 5.pdf

2355-KOLNP-2008-GPA.pdf

2355-KOLNP-2008-GRANTED-ABSTRACT.pdf

2355-KOLNP-2008-GRANTED-CLAIMS.pdf

2355-KOLNP-2008-GRANTED-DESCRIPTION (COMPLETE).pdf

2355-KOLNP-2008-GRANTED-DRAWINGS.pdf

2355-KOLNP-2008-GRANTED-FORM 1.pdf

2355-KOLNP-2008-GRANTED-FORM 2.pdf

2355-KOLNP-2008-GRANTED-SPECIFICATION.pdf

2355-KOLNP-2008-INTERNATIONAL PUBLICATION.pdf

2355-KOLNP-2008-INTERNATIONAL SEARCH REPORT.pdf

2355-KOLNP-2008-OTHERS 1.1.pdf

2355-KOLNP-2008-OTHERS.pdf

2355-KOLNP-2008-PCT REQUEST FORM.pdf

2355-KOLNP-2008-REPLY TO EXAMINATION REPORT.pdf

2355-KOLNP-2008-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

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