ISOTHERMAL CHEMICAL PROCESS

Abstract

Endothermic reactions (those whose heat of reaction is positive) may be controlled in a truly isothermal fashion with external heat input applied directly to the solid catalyst surface itself and not by an indirect means external to the actual catalytic material. This heat source can be supplied uniformly and isothermally to the catalyst active sites solely by conduction using electrical resistance heating of the catalytic material itself or by an electrical resistance heating element with the active catalytic material coating directly on the surface. By employing only conduction as the mode of heat transfer to the catalytic sites, the non-uniform modes of radiation and convection are avoided permitting a uniform isothermal chemical reaction to take place.

Claims

1. A method comprising the steps of: conducting an isothermal endothermic chemical reactions over a heterogeneous catalysts; and heating an electrically conductive catalytic material by electrical resistance whereby said electrically resistance comprises the only heat source for the endothermic process.

2. The method of claim 1, further including the step of: employing an electrical resistance heating device in direct physical contact with an active heterogeneous catalytic agent disposed on the outer surface of said electrically conductive catalytic material; and said electrically conductive catalytic material directly contacting a reacting fluid.

3. The method of claim 1, further including the step of: applying at least one wash coat between said electrical resistance heating device and the said active heterogeneous catalytic agent.

4. The method for carrying out isothermal endothermic reactions as in claims 1, wherein the electrical resistance heating device is heated by means of direct electrical current.

5. The method for carrying out isothermal endothermic reactions as in claims 2, wherein the electrical resistance heating device is heated by means of direct electrical current.

6. The method for carrying out isothermal endothermic reactions as in claims 3, wherein the electrical resistance heating device is heated by means of direct electrical current.

7. The process for manufacture of unsaturated hydrocarbons directly from saturated hydrocarbons according to claims 1 in which the electrical resistance element is Silicon Carbide, graphitic carbon, or a metal from the transition series of elements in the Periodic Table of the Elements.

8. The process for manufacture of unsaturated hydrocarbons directly from saturated hydrocarbons according to claims 1 in which the catalyst is a mixture of chromium oxides wherein the valence of the chromium is +2 to +6.

9. The process for manufacture of chemical products which undergo endothermic reactions for their manufacture. This includes specifically direct dehydrogenation of hydrocarbons (paraffinic or olefinic) to less saturated products and the reaction of ammonia with hydrocarbons to produce cyanic compounds (RCN where R is hydrogen or an organic group).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0033] A better understanding of the present invention will be had upon reference to the following description in conjunction with the accompanying drawings in which like numerals refer to like parts throughout the several views and wherein:

[0034] FIG. 1 is a view of a prior art conventional tubular reactor;

[0035] FIG. 2 shows the complexities of heat transferred from different surfaces to each other by prior art processes;

[0036] FIG. 3 shows the complexities of heat transferred from different surfaces to each other by prior art processes;

[0037] FIG. 4 is shows a prior art induction heated reactor having a reaction zone containing an array of electrically conductive catalyst entities in close proximity to an induction heating device requiring an external source of alternating current electrical power connected to an induction heating device so as to create a region of high intensity alternating magnetic field throughout the reaction zone, thereby heating the catalysts;

[0038] FIG. 5 is a graph showing the typical relationship between the overall Yield and the temperature of operation;

[0039] FIG. 6 shows an electrically conductive Raney Nickel rod of catalytic material;

[0040] FIG. 7 shows an electrically conductive silicon carbide rod having active catalyst particles exposed directly on the surface of the rod; and

[0041] FIG. 8 shows a silicon carbide rod 14 including an Al.sub.2O.sub.3 washcoat and active catalyst particles exposed on the surface of the catalyst rod.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0042] For the purposes of promoting an understanding of the principles of the invention, reference will now be made to the embodiment illustrated in the drawings and specific language will be used to described the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated device, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates.

[0043] As stated earlier, the advantage of truly isothermal reactors lies in the thermal control of the catalyst and reacting fluid to maximize effectiveness of reaction conversion and the minimization of by-products.

[0044] When more than one reaction can take place over the catalyst conversion can be defined as the amount of reactant consumed in the reaction divided by the original amount of reactant:

Conversion=(mols inletmols outlet)/tools inlet

[0045] If all of the mols of reactant are converted to the desired product, it is said that the reaction is 100% selective. However, if additional or side reactions can occur, the Selectivity will be less than 100%. The Selectivity is defined as the mols of reactant going to product divided by the total mols converted.

Selectivity=((mols product out)/(mols reactant converted))100

[0046] The arithmetic product of Conversion and Selectivity is termed Yield.

YieldConversion X Selectivity/100

[0047] In a commercial operation, the total product produced is defined as the Yield and the highest Yield can be achieved only under isothermal conditions because temperature gradients will lower Conversion to maintain a specified Selectivity or they will decrease Selectivity if Conversion is maintained by higher temperature. This is illustrated in FIG. 5 showing the typical relationship between the overall Yield and the temperature of operation.

[0048] In FIG. 5, the rising Yield is due to a more rapid increases in Conversion for the principle product. Yield will reach a maximum at temperature t.sub.max and will reduce with additional temperature because the by-product make increases faster than product increase. For any particular reaction of this sort, it is obvious that any temperature other than t.sub.max will result in lower Yield. This applies equally well to any process in which there is a temperature gradient, T, common to all other reactor designs.

[0049] In some commercial applications, by-product make is of minimal importance. Such an example is the steam reforming of hydrocarbons wherein light hydrocarbon molecules are reacted with steam at high temperatures to produce a mixture of hydrogen, carbon monoxide, carbon dioxide, and steam. This is a highly endothermic reaction occurring over very active nickel based catalyst and is usually performed in a tubular reactor. Because the reaction is endothermic, the equilibrium conversion to product is greater at higher temperatures.

[0050] A possible side reaction is the Boudouard Reaction, two molecules of carbon monoxide reacting to form one molecule of carbon dioxide and one molecule of carbon. Because the elemental carbon formed is a solid, it will build up on the catalyst surface and poison the ability of the catalyst to function. Fortunately, this reaction does not commonly occur in commercial reactors due to the temperature limitation of the reactor tubes (a thermodynamic limitation) and the high partial pressure of steam (a kinetic limitation) employed to further the principle reaction to more favorable equilibrium.

[0051] Because steam reforming can be performed with only small regard to carbon formation, this does not apply to all applications. Specifically, the direct dehydrogenation of hydrocarbons suffers strongly from carbon by-product at commercial operating conditions.

[0052] There are several commercial processes for the direct dehydrogenation of hydrocarbons to olefins all of which must supply the necessary heat of reaction from an external source. For example, the Oleflex and Catofin processes supply heat by means of externally heating the catalyst and subsequent contact with the reacting hydrocarbon fluid. Because the catalyst must be heated to high temperatures (>650 C.), hydrocarbon contact with the catalyst produces coke as a by-product. Heat transfer occurs between the hot catalyst particles and the fluid until all of the externally added heal is consumed by the heat of reaction.

[0053] Under commercial reactor conditions, the dehydrogenation reaction will reach equilibrium at 550-560 C. at the reactor exit but the solid coke is formed in the layers of the catalyst bed which are above 600 C. This is vitally important because it shows that for an isothermal operation at temperatures below 600 C., the process could be carried out on a continuous basis without the buildup of deleterious coke. If, for example, a truly isothermal reactor of the invention were employed for this reaction, not only could the reactor operated in continuous mode but the outlet temperature could likely be increased to 580-590 C. and a significant gain in conversion could be achieved because of the more favorable equilibrium.

[0054] The STAR process operates in a tubular reactor at lower temperatures limiting the conversion to olefin but reducing the amount of coke that is formed. Coke is not eliminated, only reduced along with the conversion. The residual coke that is formed must be removed from the catalyst in a separate process (usually burned off in-situ). As earlier stated, tubular reactors operated for endothermic reactions can have severe temperature differentials in the catalyst bed and a radial temperature profile that can vary 20-25 C. Hence, in all of the commercial processes for direct dehydrogenation of hydrocarbons, solid coke is formed and lowering the operating temperature to reduce the amount of coke formation leads to less than acceptable product.

[0055] All three of the commercial processes suffer from the coke formation caused by external heating features that must be hotter than the final temperature of the fluid. Contact of the hot catalyst above the 650 C. will in every case cause irreversible coke to be formed.

[0056] The ideal reactor for this type of application is a truly isothermal reactor which can control the temperature at a uniform level to maximize the conversion of hydrocarbon to olefin yet at a temperature sufficiently low that coke does not form. Such a temperature can be less than 600 C. where conversion is at least that of current technology and potentially higher. Isothermal temperatures below 600 C. become very attractive economically as the Yield will not suffer from Selectivity loss at higher temperatures.

[0057] Under such conditions, the process can be continuous without the need for cyclic regeneration as in the CATOFIN example or a separate reactor for burning off coke and heating the catalyst as in the OLEFLEX process. Because the temperatures can be easily controlled below the coke forming temperature, it can avoid any coke deposition as in the Star process because there are no hot tube walls to heat the catalyst bed.

[0058] In the above examples, a desired continuous process would suffer catastrophic failure if the side reaction (coking) were to occur on the surface of the catalyst. Under these circumstances, for maximum conversion of saturated hydrocarbon to olefin, the precise kinetics of the principle and side reactions must be known. Referring to the explanation of kinetic control (vida infra), it is important to characterize the activation energies, E.sub.a, for each reaction. This is the important characteristic of a catalyst which responds to the rate effect by temperature. With the exact knowledge of the individual reaction kinetics, dehydrogenation of hydrocarbons can be effectively carried out in the temperature region where the reaction rate of coke formation is negligible and the conversion to olefin is maximized.

Examples of Application of the Isothermal Chemical Process

[0059] The following examples describe preferred embodiments of the invention. Other embodiments within the scope of the claims herein will be apparent to one skilled in the art from consideration of the specification or practice of the invention as disclosed herein. It is intended that the specification, together with the examples, be considered exemplary only, with the scope and spirit of the invention being indicated by the claims which follow the examples. In the examples all percentages are given on a weight basis unless otherwise indicated.

[0060] For a truly isothermal reaction to take place, the surface of the catalyst particles where adsorption, reaction, and desorption of reactants and products occurs must be continuously at the same temperature. These small catalytic particles where chemical reaction occurs are well known in the industry as active sites and I have found the only way to achieve such a constant temperature at all of the catalyst surfaces and active sites is by means of an electrical resistance element which serves as the catalyst itself or which serves as a physical support for the individual catalyst active sites. In this way, an applied electrical potential across the electrical resistance element will increase the temperature of the element and any catalytic active sites directly attached to the element to a constant and controlled temperature. It is then a simple application of the appropriate electrical current to maintain the temperature of the catalyst surface, where all of the reaction is taking place, at a fixed, desirable temperature. This method relies on the uniformity of conductive heat transfer directly to the catalyst active sites and does not rely on the irregular and inconsistent heat transfer mechanisms of radiation and convection.

Example 1

[0061] Example 1 illustrates an application where the electrical resistance heating element acted as the catalyst itself and no other components were required except the applied electrical current.

[0062] The electrically conductive rod 12 of catalyst material shown in FIG. 6 is used as an electrical resistance element. For example, the conductive rod 12 may comprise solid nickel metal or a RANEY NICKEL sometimes referred to a skeletal catalyst or sponge-metal catalyst which is a product produced by W.R. Grace and Company. RANEY NICKEL is a proven catalyst made by forming an alloy of aluminum and nickel metals. The aluminum is leached from the alloy with a caustic solution leaving only metallic nickel with a high B.E.T. surface area. Because nickel is a conductor of electricity, an applied voltage across a nickel surface will serve to increase the temperature of the catalytic nickel uniformly.

[0063] More particularly, the NiAl alloy is prepared by dissolving nickel in molten aluminum followed by cooling (quenching). Depending on the Ni:Al ratio, quenching produces a number of different phases. During the quenching procedure, small amounts of a third metal or promoter, such as zinc or chromium, are added to enhance the activity of the resulting catalyst. The promoter changes the mixture from a binary alloy to a ternary alloy, which can lead to different quenching and leaching properties during activation. In the activation process, the alloy, usually as a fine powder, is treated with a concentrated solution of sodium hydroxide forming sodium aluminate (Na[Al(OH)4]). The surface area of Raney nickel tends to decrease with increasing leaching temperature due to structural rearrangements within the alloy that may be considered analogous to sintering, where alloy ligaments would start adhering to each other at higher temperatures, leading to the loss of the porous structure. During the activation process, Al is leached out of the NiAl3 and Ni2Al3 phases that are present in the alloy, while most of the Al remains, in the form of NiAl. The removal of Al from some phases but not others is known as selective leaching. The NiAl phase provides the structural and thermal stability of the catalyst. The catalyst is resistant to decomposition. Raney nickel is available as a finely divided gray powder. Each Microscopic particle of powder is a three-dimensional mesh, with pores of irregular size and shape of which the vast majority are created during the leaching process. Raney nickel is notable for being thermally and structurally stable, as well has having a large BET (Brunauer-Emmett-Teller) surface area. These properties are a direct result of the activation process and contribute to a relatively high catalytic activity. The surface area is typically determined via a BET measurement using a gas that will be preferentially adsorbed on metallic surfaces, such as hydrogen. Using this type of measurement, almost all the exposed area in a particle of the catalyst has been shown to have Ni on its surface implying a large surface is available for reactions to occur simultaneously, which is reflected in an increased catalyst activity.

[0064] A high catalytic activity, coupled with the fact that hydrogen is absorbed within the pores of the catalyst during activation, makes Raney nickel a useful catalyst for many hydrogenation reactions. Its structural and thermal stability (i.e., it does not decompose at high temperatures) allows its use under a wide range of reaction conditions.

[0065] Raney Nickel is a useful catalyst for many reactions both exothermic (hydrogenation of hydrocarbons) and endothermic (steam reforming of hydrocarbons) reactions. Of course, it serves no purpose to heat the catalyst for exothermic reactions but for the example reaction of steam reforming of hydrocarbons, it has special application. This special application applies to the temperature limitations of traditional isothermal tubular reformers. In these units, the process gas (steam and hydrocarbon) pass through the interior of long steel tubes containing catalyst particles. These catalyst particles typically have a refractory base onto which have been deposited very small particles of nickel metal.

[0066] An advantage to the use of electrical resistance heating is that much higher temperatures are possible than can be applied through steel tubes. Outer wall temperatures of the containment tubes are limited for the highest grade stainless steel to about 1000 C. Of course, for the endothermic steam reforming reaction, much more favorable equilibrium conversions lie at higher temperatures and much higher temperatures are easily achievable with electrical resistance elements. For this application, electrically heated nickel or Raney Nickel rods could be operated at temperatures up to the softening point of the metal although an increase in outlet temperature of 50-100 C. would be much for favorable for conversion.

Example 2

[0067] Example 1 illustrated an application where the electrical resistance heating element acted as the catalyst itself and no other components were required except the applied electrical current.

[0068] In commercial catalytic reactors, this is rarely the case. Most active catalysts are themselves not electrical conductors in the same category as metallic nickel or perhaps another catalytically active metal (Pt, Pd, etc). Many catalysts are combinations of metal oxides, chlorides, or sulfides and are effectively electrical insulators.

[0069] FIG. 7 shows an electrically conductive silicon carbide rod 14 having active catalyst particles 16 exposed directly on the surface of the rod.

[0070] For such materials, it is necessary to precipitate these active components onto the surface of an electrical conductive material, which could be a metal as previously described or, more practically, an element such as silicon carbide. Applying active catalyst to the surface of a solid silicon carbide rod (or other shape) permits electrical current to be passed through it creating heat by electrical resistance. Because the outer temperature of the electrical resistance heating element is constant, the temperature of the catalytic active sites on the surface is constant as well. The isothermal temperature of the desired reaction is then easily controlled by simply varying the electrical current through the electrical resistance heating element.

[0071] In addition to silicon carbide, most metals in their metallic state and electrically conductive forms of carbon may also be used as electrical heating elements upon which catalytic elements may be adhered.

[0072] The heat of chemical reaction on the catalyst surface can be supplied and balanced by the electrical heating resistance element such that the surfaces of the catalytic components remain at constant temperature.

[0073] This is the very definition of an isothermal reaction and has application to many chemical reactions including the example given above for direct dehydrogenation of hydrocarbons. Because an effective catalyst for this process is Cr.sub.2O.sub.3 (usually deposited on a refractory support), the use of SiC rods as a support for the Cr.sub.2O.sub.3 is ideal. Cr.sub.2O.sub.3 itself is not electrically conductive and could not be used in the application of Brunson but can easily be deposited onto the surface of a SiC rod heated by electrical resistance. Because the SiC will be at a constant temperature, the catalytic material directly adhering to the surface will also be at constant temperature and truly isothermal reaction will occur with the benefits described heretofore.

Example 3

[0074] FIG. 6 shows a silicon carbide rod 14 including an Al.sub.2O.sub.3 washcoat 18 and active catalyst particles 16 exposed on the surface of the catalyst rod.

[0075] Catalytic components, such as finely divided metal crystallites of elemental nickel for the steam reforming reaction, are more active when dispersed on an inert carrier material such as aluminum oxides or silicon oxides. Because the nickel crystallites are more active on alumina, it is clear that a layer of aluminum oxide may also be chemically precipitated on the surface of an electrical resistance heating element in a uniform layer and the nickel added onto the aluminum oxide in like fashion. This, in effect, creates what is known in the industry as a wash coat of support material on another material more desirable for mechanical integrity or enhanced catalytic activity. Using the electrical resistance heating element as the base material, wash coats of other catalyst support materials can be applied as is common practice in the art. This in no way alters the efficacy of the invention. If the wash coat contributes thermal resistance to the flow of conductive heat from the electrical resistance heating element to the catalyst particles, the temperature of the active catalyst particles may be maintained simply with addition electrical current through the electrical resistance heating element.

[0076] The foregoing detailed description is given primarily for clearness of understanding and no unnecessary limitations are to be understood therefrom, for modification will become obvious to those skilled in the art upon reading this disclosure and may be made upon departing from the spirit of the invention and scope of the appended claims. Accordingly, this invention is not intended to be limited by the specific exemplifications presented herein above. Rather, what is intended to be covered is within the spirit and scope of the appended claims.