TECHNICAL FIELD

[0001 ] The present development is a method that can be useful in purifying raw gas or off-gas streams from steam crackers or fluid catalytic crackers (FCC). By the method of the present development, acetylene, methylacetylene, nitrogen oxides, and oxygen are simultaneously removed from a raw gas feed stream that comprises ethylene, hydrogen, and CO without significant loss of ethylene, using a supported Ruthenium-based catalyst. The catalyst may comprise between 0.01 wt. % to 5 wt. % ruthenium distributed on a support selected from alumina or other commonly known catalyst support materials.

BACKGROUND ART

[0002] Catalytic cracking processes, such as fluid catalytic cracking (FCC) and deep catalytic cracking (DCC), have been widely used in industry for many years to produce transportation fuels, such as gasoline and diesel. The off-gases from the FCC and DCC processes contain valuable products such as ethylene and propylene. However, these off-gas streams contain relatively dilute concentrations of olefins and it is generally perceived as not being economically feasible to recover the olefins by conventional means, such as fractionation. Thus, most refineries use the off-gas as fuel gas.

[0003] Recently, the recovery of these relatively high value olefins from off- gas streams has gained increasing interest. For example, U.S. Patent 5,981 ,818 describes a process for recovery of dilute olefins from off-gases. Besides valuable olefins, FCC / DCC off-gases also contain detrimental impurities such as acetylenes and di-olefins. These impurities need to be removed from the off-gas streams in order to utilize the high value olefins in downstream processes. Typically, acetylenes and dienes found in olefin streams are commercially removed by a selective hydrogenation process.

[0004] Most selective acetylene hydrogenation operations at the commercial scale use Palladium-based catalysts. In addition to hydrocarbons, an off-gas stream often contains nitrogen oxides, oxygen, sulfur, and other impurities. The Pd-based catalysts have high activity and selectivity for selective hydrogenation of acetylene and dienes; but they are very sensitive to sulfur and some other poisons. Moreover, the Pd-based catalysts are not known to be particularly effective for removal of nitrogen oxides and / or oxygen.

[0005] Nickel catalysts have also been used in selective hydrogenation of acetylene and dienes. Nickel catalysts are resistant to sulfur poisoning, but are not selective toward hydrogenation of acetylene. Most commonly, while acetylene is removed, significant amounts of olefins are also hydrogenated to saturated hydrocarbons. Nickel-based catalysts also tend to form nickel carbonyl when the carbon monoxide level is high in the feed gas stream, particularly at low temperatures. Nickel carbonyl is a highly volatile, highly toxic substance that can deposit in downstream equipment and pose a significant safety hazard to workers in the area.

[0006] U.S. Patent 2,747,970 teaches and claims a process of removing carbon monoxide and carbon dioxide from a gas stream using a catalyst consisting of 0.01 wt. % to 2.0 wt. % ruthenium on an activated earth metal oxide, such as activated alumina. The process comprises directly contacting the gas stream with the supported catalyst while maintaining a reaction temperature of at least 120°C until the carbon content of the CO and CO ₂ is substantially completely converted to methane. However, the process does not teach that the same catalyst and method can be used to remove acetylene, methylacetylene, butadiene, NO, and O ₂ from an ethylene gas stream without risk of loss of ethylene. The prior art which does teach the use of ruthenium catalysts for purification of ethylene streams typically cites the ruthenium catalysts as examples of ineffective catalysts for such applications. For example, in U.S. Patent 4,299,800, a catalyst comprising 0.5 wt. % ruthenium on alumina was evaluated for oxygen removal from a feed stream containing ethylene. At low temperatures (50 ⁰ C), oxygen removal was low and ethylene conversion was essentially non-detectable. However, at higher temperatures (200°C), oxygen removal reached 99.4%, but with concomitant ethylene conversion (loss) of 1 1 .2%, as compared to less than 5% ethylene conversion when using silver, gold or vanadium on alumina.

[0007] Thus, there is a need for a process for removing oxygen, acetylenes, and nitrogen oxides from off-gas streams wherein the ethylene is not converted to lower value hydrocarbons during the purification process and wherein the purified ethylene-containing gas stream comprises less than about 1 ppm each of acetylenes, nitrogen oxides and oxygen.

DISCLOSURE OF EMBODIMENTS OF THE INVENTION

[0008] In one embodiment, a method for the purification of ethylene-containing feed streams from steam crackers or fluid catalytic crackers (FCC) is described, wherein the feed streams further comprise hydrogen, carbon monoxide, nitrogen oxides, oxygen, and acetylenes. The method comprises contacting an ethylene- comprising gas stream with a Ru-based catalyst. The process results in an ethylene-containing product stream comprising less than about 1 ppm acetylenes, less than about 1 ppm nitrogen oxides and less than about 1 ppm oxygen. Purification of the feed stream occurs with minimal loss of ethylene. [0009] In another embodiment, a method for removing oxygen, acetylenes, and nitrogen oxides from ethylene-containing feed streams is described, which further comprise hydrogen and carbon monoxide. The method comprises contacting an ethylene-comprising gas stream with a Ru-based catalyst comprising between 0.01 wt. % to 5 wt. % ruthenium distributed on a carrier to produce an ethylene- containing product that is essentially free of acetylenes, nitrogen oxides and oxygen.

MODES FOR CARRYING OUT EMBODIMENTS OF THE INVENTION [0010] The ethylene-containing feed stream may be the off-gas stream from any steam cracker, fluid catalytic cracker, or similar process. Typically, the off-gas stream includes hydrogen gas, carbon monoxide, oxygen, nitrogen oxides, ethane, ethylene and acetylene.

[001 1 ] The ruthenium-based catalyst may be any catalyst comprising ruthenium distributed on a typical catalyst support material, such as, without limitation, aluminas, titanias, zirconias, silicas, metal aluminates, aluminosilicates, spinels and combinations thereof. Methods of preparing supported ruthenium catalysts are well-known in the art. Optionally, the catalyst may further include promoters, such as, without limitation, silver, gold, copper, zinc, bismuth, lead or combinations thereof. In an exemplary embodiment, the catalyst comprises ruthenium distributed on an alumina support wherein the ruthenium is distributed on the support with a ruthenium salt solution. [0012] In one embodiment, the catalyst comprises ruthenium distributed on an alumina support wherein the ruthenium is distributed on the support by impregnating an alumina support with a ruthenium salt solution. The catalyst may comprise between 0.01 wt. % to 5 wt. % ruthenium. In other embodiments, the catalyst may comprise, or consist essentially of, 0.01 wt. % to 1 wt. % ruthenium, 0.1 wt. % to 0.5 wt. % ruthenium; 0.15 wt. % to 0.30 wt. % ruthenium, a minimum of 0.15 wt. % ruthenium, or a minimum of 0.3 wt. % ruthenium on any type of support, including alumina.

[0013] In an alternative embodiment, the catalyst comprises ruthenium distributed on an alumina support wherein the support has a BET surface area of at least 3 m ² /g, and preferably has a BET surface area of about 3 m ² /g to about 200 m ² /g. Alternatively, the catalyst may comprise ruthenium on a low surface area support, ruthenium on a medium surface area support, or ruthenium on a high surface area support. In general, a support having a BET surface area between 1 m ² /g -10 m ² /g can be classified as a low surface area support. Medium surface area supports typically range between 10 m ² /g - 60 m ² /g while high surface area supports generally have a BET surface area greater than 60 m ² /g. With respect to alumina, the ranges for low, medium and high surface areas are 1 m ² /g -10 m ² /g, 30 m ² /g -60 m ² /g , and greater than 60 m ² /g, respectively. In another embodiment, the support is a medium surface area alumina support.

[0014] In other embodiments, the ruthenium is distributed on the outer layer of an alumina carrier in such a manner as to remain on the outer layer of the support. "Distributed on the outer layer" of the support means that the ruthenium may be located within any part of about a 300 μm distance that extends from the exterior surface of any part of the support towards the center of the support. The depth of the ruthenium distributed on the outer layer of the support may be constant or may vary, especially in places where pores are located on the exterior surface of the support.

[0015] The process comprises directly contacting the gas stream with the supported catalyst while maintaining a reaction temperature of at least 120°C until the acetylene content decreases to less than one (1 ) ppm and the nitrogen oxide content decreases to less than one (1 ) ppm and the oxygen content decreases to less than one (1 ) ppm. Alternatively, the process may comprise contacting the gas stream with the supported catalyst until the product stream is essentially free of impurities that may include acetylene, nitrogen oxides, oxygen and combinations thereof. In other embodiments, the removal of the acetylene, nitrogen oxide and oxygen contents may be either higher or lower, depending a number of factors including laws and regulations governing the operation of the FCC/DCC plant and/or the design of the plant.

[0016] The catalyst may be reduced or sulfided before use. The catalyst may be reduced after being loaded into the reactor and before introduction of the ethylene-containing gas stream by feeding hydrogen or a hydrogen-containing gas through the catalyst at a temperature of at least 100°C for at least one minute. The catalyst may be sulfided after being loaded into the reactor and before introduction of the ethylene-containing gas stream by feeding a sulfur-containing gas stream through the catalyst at a temperature of at least 150°C for at least one minute.

Industrial applicability

[0017] The above described embodiments may be used to purify ethylene- containing feed streams from steam crackers, fluid catalytic crackers (FCC), or any type of hydrocarbon feed stream that includes hydrogen, carbon monoxide, oxygen, and acetylenes.

Examples

[0018] As representative examples, several catalysts were acquired and evaluated for removal of impurities from an ethylene feed stream. These examples are presented to further explain the invention and are not intended, or to be taken, to limit the scope of the invention.

[0019] Catalyst samples evaluated:

Catalyst 1 / Commercial Pd-based catalyst, OleMax 250; obtained from Sϋd-

Chemie Inc., Louisville, Kentucky.

Catalyst 2: 0.15% ruthenium on a low surface area (3.6 m ² ^ alumina carrier;

Catalyse 3: 0.15% ruthenium on a medium surface area (37 m ² /gj alumina carrier;

Catalyst 4: 0.15% ruthenium on a high surface area (165 m ² /gj alumina carrier; Catalyst 5: 0.30% ruthenium on a high surface area (165 m ² /g) alumina carrier.

[0020] Catalyst samples evaluations:

The prepared catalysts are tested in a continuous flow reactor by loading approximately 50 cc of catalyst into the reactor and then feeding a contaminated ethylene-containing feed stream through the loaded catalyst. For testing purposes, in general, the reactor temperature is adjusted to a temperature of from about 120°C to about 300 °C, the carbon monoxide content is held between about 0.05 wt. % and 5 wt. %, and the sulfur content is held below about 50 ppm. The hydrogen partial pressure is held between about 0.05 MPa and 2 MPa with a gas hourly space velocity of from about 500 hr ^"1 to 10,000 hr ^"1 ; more preferably, the hydrogen partial pressure is held between about 0.10 MPa and 1 MPa with a gas hourly space velocity of from about 1000 hr ^"1 to 5,000 hr ^"1 ; and most preferably, the hydrogen partial pressure is held between about 0.10 MPa and 0.3 MPa with a gas hourly space velocity of from about 1500 hr ^"1 to 3500 hr ^"1 and with a hydrogen concentration from about 5% to about 15%.

[0021 ] Catalysts 1 - 4 are tested in the continuous flow reactor. Approximately

50 cc of catalyst is loaded into the reactor, the reactor temperature is adjusted to a predetermined temperature (as indicated in Table 1 ), and an ethylene-containing feed stream contaminated with oxygen, acetylene, and nitric oxide is fed through the reactor at a gas hourly space velocity of 2500 hr- ¹ while the pressure is held at 1 .9 MPa. Gas samples from an inlet and outlet reactor are analyzed using an on-line gas chromatograph and the findings are summarized in Table 1 .

Table 1

[0022] As indicated in Table 1 , the palladium catalyst and the ruthenium catalysts all effectively retain ethylene and hydrogen in the gas stream, although the ruthenium catalysts retain a higher relative percentage of these gases than is observed with the palladium catalyst. Further, the palladium catalyst and the ruthenium catalysts all effectively reduce the levels of acetylene and nitrogen oxides present in the feed stream. However, the ruthenium catalysts are significantly more effective at removing oxygen from the feed stream than the palladium catalyst. Also, most likely because the ruthenium catalysts are less active for hydrogenation of ethylene than the palladium catalyst, less ethane is produced when the ethylene- containing feed stream contacts the ruthenium catalysts than when the feed stream contacts the palladium catalyst.

[0023] Catalyst 5 is tested in the continuous flow reactor at various reactor temperatures, and with additional carbon monoxide or hydrogen sulfide in the feed stream. Approximately 50 cc of catalyst is loaded into the reactor, the reactor temperature is adjusted to a predetermined temperature (as indicated in Table 2), and an ethylene-containing feed stream contaminated with oxygen, acetylene and optionally, nitric oxide or carbon monoxide or hydrogen sulfide, is fed through the reactor at a gas hourly space velocity of 2500 hr ^"1 while the pressure is held at 1 .9 MPa. Gas samples from an inlet and outlet reactor are analyzed using an on-line gas chromatograph and the findings are summarized in Table 2.

Table 2

[0024] As indicated in Table 2, even under adverse conditions of relatively high levels of CO and hydrogen sulfide, the ruthenium catalyst effectively retains ethylene and hydrogen in the gas stream. Further, the ruthenium catalyst effectively reduces the levels of acetylene and oxygen present in the feed stream, and produces relatively low quantities of unwanted ethane.

[0025] Thus, by contacting an ethylene-containing feed stream that further comprises hydrogen, carbon monoxide, oxygen, acetylene, and nitric oxide with a supported ruthenium catalyst, wherein the catalyst comprises between 0.01 wt. % to 5 wt. % ruthenium, in a continuous flow reactor with the catalyst held at a temperature of at least about 120°C, acetylenes, nitrogen oxides and oxygen can be removed from the gas stream with a minimal loss of ethylene.

[0026] It Is understood that one skilled in the art may alter the embodiments shown and described herein without departing from the scope of the invention. For example, it is anticipated that the reactor pressure and the gas hourly space velocity may be adjusted by those skilled in the art to accommodate different sized reactors.