DEHYDROGENATION PROCESS AND CATALYST

Abstract: C₃ and/or C₄ hydrocarbons (in particular propane and butanes) are converted to less saturated hydrocarbons (in particular ethylene and propylene) in the presence of a catalyst consisting essentially of either (a) zinc oxide and manganese oxide or (b) zinc oxide, manganese oxide and calcium oxide. Compositions of matter (a) and (b), as defined above, are provided in accordance with this invention.

Description: In one aspect, the present invention relates to a process for converting C₃ and C₄ hydrocarbons to less saturated hydrocarbons. In another aspect, this invention relates to novel compositions of matter which are useful as catalysts in a process for converting C₃ and C₄ hydrocarbons to less saturated hydrocarbons. Processes for the catalytic conversion of C₃ and C₄ hydrocarbons to less saturated hydrocarbons are known, and have been described in U.S. Patents 4,621,163; 4,621,162, 4,620,051 and 4,613,722. EP-A1 0 012 800 discloses a method of producing butane-2,3-dione by catalytic oxidation of isobutanal in the gas phase, where the catalyst comprises manganese oxide and at least one oxide of zinc or titanium. However, there is an ever present need to develop new catalysts which are more effective in these hydrocarbon conversion processes than known catalyst compositions. Summary of the Invention It is an object of this invention to provide a process for converting C₃ and C₄ hydrocarbons to less saturated hydrocarbons (i.e., hydrocarbons containing less bound hydrogen than the feed hydrocarbons). It is another object to provide novel compositions of matter which are useful as catalyst compositions in a process for converting C₃ and C₄ hydrocarbons to less saturated hydrocarbons. Other objects and advantages will be apparent from the detailed description and the appended claims. In accordance with this invention, a process for converting C₃ and/or C₄ hydrocarbons (in particular propane and butanes) to less saturated hydrocarbons (in particular ethylene and propylene) is provided as defined in the claims. The process comprises contacting a feed comprising at least one hydrocarbon containing 3 or 4 carbon atoms per molecule (in particular propane or n-butane or isobutane or mixtures thereof) with a solid catalyst composition consisting essentially of a material selected from the group consisting of (a) zinc oxide and at least one manganese oxide, and (b) zinc oxide, at least one manganese oxide and calcium oxide, under such conditions as to convert at least a portion of the feed hydrocarbon(s) to at least one less saturated hydrocarbon. Preferably, the number of carbon atoms per molecule of the formed less saturated hydrocarbon(s) is less than that of the feed hydrocarbon(s). In a preferred embodiment, zinc oxide is the support material and the major component in catalyst compositions (a) and (b), and manganese oxide is a minor component. In another preferred embodiment, the feed comprises (more preferably consists essentially of) n-butane. In still another preferred embodiment, steam is also present during the hydrocarbon conversion process. Further in accordance with this invention, a composition of matter is provided as defined in the claims. The composition consists essentially of (i) zinc oxide as carrier (support material) and major component, (ii) at least one manganese oxide as first minor component, and (iii) calcium oxide as second minor component. This composition of matter consisting essentially of (i), (ii) and (iii) is effective as catalyst composition for converting C₃ and C₄ hydrocarbons to less saturated hydrocarbons. Detailed Description of the Invention The hydrocarbon feed, in accordance with the present invention, can include any hydrocarbon gas containing significant amounts of C₃ and/or C₄ hydrocarbons, particularly propane, n-butane (normal butane) and isobutane, with n-butane being presently preferred. Other normally gaseous components, or even normally liquid components which vaporize at operating conditions, can also be present if they are not detrimental to the process. Suitable feedstocks for the process of the present invention can be obtained from any source, including natural gas, refinery off-gases and the like, as has been described in U.S. Patent 4,620,051. The process of the present invention can be carried out in fixed, moving, fluidized, ebulating or entrained bed reactors. For experimental purposes and, obviously, to permit accurate measurement and precise control of the process variables, the runs hereinafter set forth in the examples were conducted in a fixed bed reactor. During operation it has been found that small amounts of the feedstock are converted to coke, which is then deposited on the catalyst and contributes to a decline in catalyst activity and selectivity to ethylene. Accordingly, it is desirable to periodically regenerate the catalyst by conventional techniques of carbon removal, such as heating with an oxygen-containing gas, preferably air. During such regeneration, it may also be desirable to use inert gas or steam dilution to control coke burn-off, as is also well known to those skilled in the art. In accordance with the present invention, the addition of steam to the feed hydrocarbon is preferred because it extends the effective life of the catalyst between regenerations. Preferably, free oxygen is substantially absent during the hydrocarbon conversion process of this invention, so as to minimize the formation of CO and CO₂. Furthermore, the catalyst can also be pretreated, before use in the process of this invention, with inert gases (e.g., N₂) or steam or hydrogen gas, while the catalyst composition is being heated to the desired reaction temperature, as has been described in U.S. Patent 4,620,051. Any suitable reaction conditions for the hydrocarbon conversion process of this invention can be employed. Preferred reaction conditions are those that cause dehydrogenative cracking of the feed hydrocarbon(s) (e.g., of propane to ethylene, and of butanes to propylene and ethylene). The gas hourly space velocity (GHSV) of the feed gas generally is in the range of from 100 to 3,000 cc hydrocarbon feed/cc catalyst/hour, and preferably is in the range of from 500 to 1,000 cc/cc/hour. The operating pressure generally is in the range of from 0.7 to 690 kPa (0.1 psia to 100 psia), and preferably is in the range of from 6.9 to 413 kPa (1 psia to 60 psia). If steam is present, the volume ratio of steam to hydrocarbon in the feed generally is in the range of from 0.1:1 to 10:1, and more preferably is in the range of from 0.3:1 to 5:1. The reaction temperature generally is in the range of from 550°C to 800°C, preferably is in the range of from 600°C to 770°C, and more preferably is in the range of from about 620°C to 700°C. The reaction product of the process of this invention generally contains propylene, ethylene, propane, ethane, methane, free hydrogen and carbon oxides. The components of the reaction product (in particular the desirable C₂ and C₃ olefins) can be separated and recovered by any of the conventional separation means (such as cryogenic distillation, membrane separation, absorption, and the like). Unconverted C₃ and/or C₄ feed hydrocarbons can be separated from the components of the reaction product, and can be recycled to the reactor (conversion zone) of the conversion process of this invention. A solid composition of matter, which is used as catalyst in the hydrocarbon conversion process of this invention, can be prepared by any suitable method. The composition of matter, a mixture of zinc oxide and at least one manganese oxide (i.e., MnO and/or Mn₂O₃ and/or Mn₃O₄ and/or MnO₂, and the like), can be prepared by mixing zinc oxide and at least one dissolved suitable manganese compound, preferably dissolved in water, drying the obtained mixture, and then calcining the dried mixture (preferably at 750°C to 800°C, in a free oxygen containing gas atmosphere, such as air) so as to substantially convert the manganese compound(s) to manganese oxide. Non-limiting examples of suitable manganese compounds are Mn(NO₃)₂, Mn(II) carboxylates such as Mn(CH₃CO₂)₂, Mn(HCO₃)₂, Mn(HSO₄)₂, hydrates of the above compounds, and mixtures of the above compounds. The composition of matter can be shaped (e.g., by extrusion or pelletizing) and sieved to a desired particle size. Generally, the first composition of matter of this invention contains 0.1 to 30 weight-% Mn (expressed as element), preferably 0.5 to 10 weight-% Mn. The composition of matter of this invention, consisting essentially of zinc oxide, at least one manganese oxide and calcium oxide, can be prepared by mixing zinc oxide, at least one dissolved suitable manganese compound (preferably dissolved in water) and at least one dissolved suitable calcium compound (preferably dissolved in water), drying the obtained mixture, and then calcining the dried mixture (preferably at 750°C to 800°C, in a free oxygen containing atmosphere such as air), so as to substantially convert the manganese compound(s) to manganese oxide and the calcium compound(s) to calcium oxide. Examples of suitable manganese compounds are listed above. Non-limiting examples of suitable calcium compounds are Ca(NO₃)₂, calcium carboxylates such as Ca(CH₃CO₂)₂, CA(HCO₃)₂, hydrates of the above compounds, and mixtures of the above compounds. The composition of matter can be shaped and sieved, as described above. Generally, the composition of matter of this invention contains 0.1 to 30 weight-% Mn and 0.1 to 20 weight-% Ca, preferably 0.5 to 10 weight-% Mn and 0.5 to 10 weight-% Ca. The weight percentage of oxides of Mn and Ca in the second catalyst composition is less than 50 weight-% (with the balance of more than 50 weight-% being zinc oxide). The following examples are presented to further illustrate this invention and are not to be considered as unduly limiting the scope of this invention. Example I This example illustrates the preparation of manganese oxide containing catalyst compositions which are effective as butane cracking catalysts. Catalyst Composition A was a control catalyst composition, in accordance with U.S. Patent 4,621,163, consisting essentially of manganese oxide as minor component and magnesium oxide as support material. Catalyst Composition A contained 4 weight-% Mn. It was prepared by mixing, in an electric blender, 150 grams of Mg(OH)₂, 39.1 grams of a 50-weight aqueous solution of Mn(NO₃)₂ and enough distilled water to provide a thick paste. The material was dried at 120°C, and then calcined in air at 775°C for 4 hours. The calcined material was ground and sieved, and a 0.84 to 0,43 mm (20-40 mesh) fraction was collected. Catalyst Composition B was a control catalyst composition, substantially in accordance with U.S. Patent 4,159,970, consisting essentially of manganese oxide as minor component and calcium oxide as support material. Catalyst Composition B contained 4 weight-% Mn. It was prepared by impregnation of Ca(OH)₂ with a 50 weight-% aqueous solution of Mn(NO₃)₂. The obtained material was dried at 120°C and then calcined in air at 775°C for 3 hours. Catalyst Composition C (used in the process of this invention) consisted essentially of manganese oxide as minor component and zinc oxide as support material. Catalyst Composition C contained 4 weight-% Mn. It was prepared by mixing 100 grams zinc oxide, 26 grams of an aqueous 50 weight-% Mn(NO₃)₂ solution and enough water to obtain a thick paste. The material was dried overnight at 115°C and calcined in air at 775°C. Catalyst Composition D (Invention) consisted essentially of manganese oxide and calcium oxide as minor components, and zinc oxide as support material. Catalyst Composition D contained 4 weight-% Mn and 3 weight-% Ca. It was prepared substantially in accordance with the procedure for Catalyst Composition C except that Ca(NO₃)₂·4H₂O was used in addition to Mn(NO₃)₂. Example II This example illustrates n-butane cracking tests at various temperatures and in the presence of steam, utilizing the catalyst compositions described in Example I. A gaseous feed mixture of n-butane and steam was introduced into a 15 mm ID quartz tube at a rate of 100 mℓ n-butane per minute and 100 mℓ steam per minute. The quartz tube reactor was filled with either 25 mℓ of Catalyst Composition A or B, or 15 mℓ of Catalyst Composition C, described in Example I. The temperature of the reactor was gradually increased from 620°C to 720°C during each test. The gaseous effluent was sampled every 5 minutes and analyzed by means of a Hewlett-Packard 5880 gas chromatograph. Test results are summarized in Table I. Test data summarized in Table I indicate that Mn/ZnO (Catalyst Composition C) was more effective than Mn/MgO (Catalyst Composition A) and Mn/CaO (Catalyst Composition B) for selectively converting n-butane to the desirable olefins (ethylene and propylene), at reaction temperatures of up to about 700°C. Example III This example illustrates the beneficial effect of the presence of calcium oxide in a manganese oxide/zinc oxide catalyst composition. Test conditions were essentially the same as those described in Example II, except that the reaction temperature was about 750-770°C. Test results are summarized in Table II. Test data summarized in Table II indicate that Catalyst Composition D (manganese oxide + calcium oxide + zinc oxide) was more effective than Catalyst Composition C (manganese oxide + zinc oxide) in converting n-butane to ethylene, at a reaction temperature of about 750°C. Based on these test results, it is concluded that this beneficial effect of CaO will also prevail at temperatures at or below about 700°C.

Claims: A process for converting hydrocarbons to less saturated hydrocarbons comprising the step of contacting a feed comprising at least one hydrocarbon containing 3 or 4 carbon atoms per molecule with a solid catalyst composition consisting essentially of a material selected from the group consisting of (a) zinc oxide and at least one manganese oxide, and (b) zinc oxide, at least one manganese oxide and calcium oxide, under such contacting conditions as to convert at least a portion of said at least one hydrocarbon contained in said feed to at least one less saturated hydrocarbon. A process in accordance with claim 1, wherein said at least one hydrocarbon contained in said feed is selected from the group consisting of propane, n-butane and isobutane; said solid catalyst composition consists essentially of (i) zinc oxide as carrier and major component and (ii) at least one manganese oxide as minor component; and said at least one less saturated hydrocarbon contains fewer carbon atoms per molecule than said at least one hydrocarbon contained in said feed. A process in accordance with claim 2, wherein said at least one hydrocarbon contained in said feed is n-butane and said at least one less saturated hydrocarbon is selected from the group consisting of ethylene and propylene. A process in accordance with claim 2, wherein said solid catalyst composition contains 0.1 to 30 weight-% Mn. A process in accordance with claim 1, wherein said at least one hydrocarbon contained in said feed is selected from the group consisting of propane, n-butane and isobutane; said solid catalyst composition consists essentially of (i) zinc oxide as carrier and major component, (ii) at least one manganese oxide as first minor component and (iii) calcium oxide as second minor component; and said at least one less saturated hydrocarbon contains fewer carbon atoms per molecule than said at least one hydrocarbon contained in said feed. A process in accordance with claim 5, wherein said at least one hydrocarbon contained in said feed is n-butane and said at least one less saturated hydrocarbon is selected from the group consisting of ethylene and propylene. A process in accordance with claim 5, wherein said solid catalyst composition contains 0.1 to 30 weight-% Mn and 0.1 to 20 weight-% Ca. A process in accordance with claim 1, wherein said contacting conditions comprise a temperature in the range of from 600 to 770°C, and a pressure in the range of from 6.9 to 413 kPa (1 to 60 psia). A process in accordance with claim 1, wherein said contacting is carried out in the presence of steam. A process in accordance with claim 9, wherein the volume ratio of steam to said at least one hydrocarbon in said feed is in the range of from 0.1:1 to 10:1. A composition of matter consisting essentially of (i) zinc oxide, (ii) at least one manganese oxide and (iii) calcium oxide. A composition of matter in accordance with claim 11 consisting essentially of (i) zinc oxide as carrier and major component, (ii) at least one manganese oxide as first minor component and (iii) calcium oxide as second minor component. A composition of matter in accordance with claim 11 containing 0.1 to 30 weight-% Mn, 0.1 to 20 weight-% Ca, and more than 50 weight-% zinc oxide as balance. A composition of matter in accordance with claim 11 containing 0.5 to 10 weight-% Mn, 0.5 to 10 weight-% Ca, and more than 50 weight-% zinc oxide as balance. A composition of matter in accordance with claim 11 having been prepared by a process comprising the steps of mixing zinc oxide with at least one dissolved manganese compound and at least one dissolved calcium compound, drying the obtained mixture, and calcining the dried mixture under such conditions as to substantially convert said at least manganese compound to at least one manganese oxide and said at least one calcium compound to calcium oxide.

Inventors: DELZER, GARY ALBERT, KOLTS, JOHN HENRY
Applicants: PHILLIPS PETROLEUM COMPANY
Application year: 1989
Main classification: C07C4
IPC codes: C07C11, C07C5, C07C4, C07B61, B01J23