RU2804309C2 - Methods of selective hydrogenation - Google Patents

Abstract

FIELD: hydrogenation.

SUBSTANCE: invention is related to a method for operating a selective hydrogenation reactor, wherein the reactor contains one or more catalyst beds, each of which contains an ionic liquid catalyst composition suitable for the selective hydrogenation of acetylene in a process gas containing at least 10 mol.% ethylene, at least 1 ppm. mol of acetylene and at least 5 mol.% hydrogen. The method includes producing one or more catalyst layers at no more than the first temperature, wherein the catalyst layer is in contact with the first gas containing less than 2 mol.% hydrogen, wherein the first gas is non-reactive in the presence of a catalyst at the first temperature; heating one or more catalyst beds in the presence of the first gas to at least the second temperature, wherein the second temperature at least 20°C is higher than the first temperature, wherein the first gas is unreactive in the presence of the catalyst at the second temperature; and thereafter replacing the first gas in contact with the catalyst composition by introducing a process gas stream to be hydrogenated in the selective hydrogenation reactor while the catalyst bed is at at least a second temperature; and allowing the process gas to flow through the catalyst bed until the acetylene concentration leaving the selective hydrogenation reactor is less than 1 ppm. mol. The invention is also related to variants of methods for starting a reactor for selective hydrogenation.

EFFECT: starting a reactor for hydrogenation does not require either pre-loading CO into the reactor or increasing the pressure in it when using an inert gas, and/or which can be carried out over a short period of time.

19 cl, 7 ex, 1 tbl, 9 dwg

Description

Cross reference to related applications

This application claims the benefit of priority to U.S. Provisional Patent Application No. 62/749,456, filed October 23, 2018, which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE DISCLOSURE

Field of technology to which the invention relates

This disclosure generally relates to hydrogenation processes and hydrogenation catalysts. More specifically, the present disclosure relates to methods for the selective hydrogenation of acetylene, for example, in upstream processes; to methods for starting a reactor for selective hydrogenation, for example, in technological processes at the initial stage of processing; and hydrogenation catalysts suitable for use in such processes.

State of the art

Olefins are important monomers in the production of plastics. For example, to produce polyethylene and polypropylene, respectively, ethylene and propylene are polymerized. Olefins such as ethylene and propylene are typically produced from petroleum products by thermal or catalytic cracking of hydrocarbons. However, cracking produces a crude olefin mixture that may contain acetylene, which may interfere with downstream polymerization of ethylene and propylene. It may be desirable to "scrub" a given process gas to selectively convert acetylene to ethylene without undergoing significant reduction of any olefins present or acetylene itself to form alkanes.

There are two main reactor configurations for the selective hydrogenation of acetylene in ethylene-enriched streams—so-called downstream (or downstream) processes and upstream processes. In a downstream configuration, the feedstock to the selective hydrogenation reactor typically consists primarily of C2 hydrocarbons, and stoichiometric amounts of hydrogen relative to acetylene are added to a given gaseous feedstream stream to ensure the presence of an optimal concentration of hydrogen (typically in the case of being in the range of 1% - 4%, in % (mol.)) in the stream of feedstock supplied to the reactor. Typically, carbon monoxide is not present in amounts greater than 2 ppm in the feed stream; In some conventional processes, CO is added separately to the reactor inlet stream. In the initial processing configuration, the feedstock to the selective hydrogenation reactor typically contains a large excess of hydrogen, for example, 10 - 35 mol% hydrogen, together with carbon monoxide, acetylenes, olefins and other hydrocarbons. In the structure of an ethanol stripper (deethanizer) at the initial stage of processing, the feedstock supplied to the reactor contains a stream of C2 and lighter compounds, while in the installation of a depropanizer column (depropanizer) at the initial stage of processing the feedstock supplied to the reactor contains C3 and lighter hydrocarbons . In such feed streams, carbon monoxide is generally present at concentrations ranging from less than 100 ppm. up to 3000 ppm

Typically, upstream selective hydrogenation of the acetylene present in the olefin-enriched mixture is carried out using optionally promoted palladium shell catalysts. However, the activity of the hydrogenation catalyst under process conditions must be carefully limited to avoid thermal runaway (a runaway feedback loop in which the heat from the exothermic hydrogenation reaction increases the temperature of the catalyst, which in turn increases the rate of the hydrogenation reaction, allowing producing even more heat, etc.), which may result in unwanted over-reduction of ethylene to form ethane and even a reactor shutdown due to an uncontrolled increase in temperature in the reactor. Thus, conventional selective hydrogenation processes are limited at the initial processing stage by strict temperature control, which is maintained below a certain temperature (eg, runaway temperature). Conventional selective hydrogenation processes are limited early in the processing by using gas hourly space velocity (GSV) to ensure that the temperature due to the exothermic hydrogenation reaction required to purify acetylene does not increase excessively so that it does not approach the temperature which may result in uncontrolled thermal conditions.

In addition, reactors for such conventional selective hydrogenation processes at the initial stage of processing, in particular the corresponding reactors containing fresh catalyst, must be started with particular care to avoid the occurrence of uncontrolled thermal conditions. Typically, as will be understood, the initial contact of the catalyst layer with a stream of process gas (ie, containing hydrogen, olefin and acetylene) must be done at a low temperature to avoid runaway conditions. But at such low temperatures, acetylene recovery is typically incomplete, and thus the acetylene concentration in the reactor effluent is greater than the product specifications allow. Thereafter, with a simultaneous flow of process gas, the temperature of the catalyst bed is very slowly increased to the desired reaction temperature at which the acetylene concentration meets specifications. The temperature rise is often on the order of a degree Celsius per hour, and thus the start-up procedure can take more than twenty hours to ensure a product output that meets specifications. During the startup period, out-of-spec reactor effluent is often sent to a flare.

In addition to strict temperature control, it is common to pre-load the reactor with CO during startup and pressurize it using non-reactive gases before heating the catalyst. The composition of the gaseous mixture in the reactor slowly shifts towards the process gas (ie, containing hydrogen, acetylene and one or more olefins). This startup process not only presents safety issues due to the use of large amounts of CO gas on site, but it is also costly due to material costs, lost production time, and treatment/disposal of the reactor outlet product before the reactor is in operation. in full working order.

Accordingly, there remains a need for a process for selectively hydrogenating acetylene at high throughput and/or at low CO concentrations, but without undue risk of thermal runaway. There also remains a need for a method of starting a hydrogenation reactor that does not require either preloading CO into the reactor or pressurizing it using an inert gas, and/or that can be carried out over a short period of time.

Summary of the Invention

The inventors of the present invention have discovered that the catalysts described herein have particularly advantageous properties that enable new processes for the selective hydrogenation of acetylene.

Accordingly, one aspect of the disclosure of the invention is a method for the selective hydrogenation of acetylene, the method comprising contacting a catalyst composition comprising a porous support, palladium and at least one ionic liquid with a process gas containing

ethylene present in the process gas in an amount of at least 10% (mol.);

acetylene present in the process gas in an amount of at least 1 ppm;

hydrogen present in the process gas in an amount of at least 5% (mol.); And

from 0 ppm up to 190 ppm carbon monoxide;

wherein at least 90% of the acetylene present in the process gas is hydrogenated, and no more than 1 mol% of the total acetylene and ethylene present in the process gas is converted to ethane.

Another aspect of the disclosure of the invention is a method for the selective hydrogenation of acetylene, the method comprising contacting a catalyst composition containing a porous support, palladium and at least one ionic liquid with a process gas containing

ethylene present in the process gas in an amount of at least 10% (mol.);

acetylene present in the process gas in an amount of at least 1 ppm;

hydrogen present in the process gas in an amount of at least 5% (mol.); And,

at least 600 ppm carbon monoxide;

wherein at least 90% of the acetylene present in the process gas is hydrogenated and no more than 1 mol% of the total amount of acetylene and ethylene present in the process gas is converted into ethane.

Another aspect of the disclosure of the invention is a method for the selective hydrogenation of acetylene, the method comprising contacting a catalyst composition containing a porous support, palladium and at least one ionic liquid with a process gas containing

ethylene present in the process gas in an amount of at least 10% (mol.);

acetylene present in the process gas in an amount of at least 1 ppm;

hydrogen present in the process gas in an amount of at least 5% (mol.); And

wherein the process gas is contacted with the catalyst at a total hourly gas space velocity (THSV) of at least 7,100 h ⁻¹ (e.g., ranging from 7,500 h ⁻¹ to 40,000 h ⁻¹ ) based on total volume catalyst layer; And

wherein at least 90% of the acetylene present in the process gas is hydrogenated and no more than 1 mol% of the total amount of acetylene and ethylene present in the process gas is converted into ethane.

Another aspect of the disclosure of the invention is a method of operating a reactor for selective hydrogenation, wherein the reactor contains one or more beds of catalyst, each of which contains a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing at least 10% (mol.) ethylene, at least 1 ppm. acetylene and at least 5% (mol.) hydrogen, the method comprising

providing each catalyst layer at no more than a first temperature, wherein the catalyst layer of catalyst is in contact with a first gas, wherein the first gas is unreactive in the presence of the catalyst at the first temperature;

in the presence of a first gas, heating each layer of catalyst to at least a second temperature, wherein the second temperature is at least 10 degrees greater than the first temperature, wherein the first gas is unreactive in the presence of the catalyst at the second temperature; and after that

changing the composition of the gas in contact with the catalyst from the first gas to the process gas stream while the catalyst bed is at at least a second temperature; And

allowing the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

In certain such embodiments, the first temperature is in the range of 31 - 50°C, for example, 31 - 45°C or 31 - 40°C. In other such embodiments, the first temperature is in the range of 35 - 50°C, for example, 35 - 45°C or 35 - 40°C. And in other such embodiments, the first temperature is in the range of 40 - 50, for example, 40 - 45°C.

Another aspect of the disclosure of the invention is a method of operating a reactor for selective hydrogenation, wherein the reactor contains one or more beds of catalyst, each of which contains a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing at least 10% (mol.) ethylene, at least 1 ppm. acetylene and at least 5 mol% hydrogen, the method comprising:

providing the reactor with each layer of catalyst characterized by its catalyst being in contact with a first gas, wherein the first gas is unreactive in the presence of the catalyst at a first temperature, wherein the catalyst has not been brought into contact in the reactor with a carbon monoxide containing gas having a carbon monoxide concentration greater than 100 hours ./million; And

introducing a current of process gas into one or more catalyst beds and refraining from adding carbon monoxide to the process gas.

Such methods may further include increasing the catalyst bed temperature for each catalyst bed from no more than a first temperature to at least a second temperature (e.g., before, during, or after changing the gas in contact with the catalyst with transition from the first gas to the process gas).

Another aspect of the disclosure of the invention is a method of operating a reactor for selective hydrogenation, wherein the reactor contains one or more beds of catalyst, each of which contains a catalyst suitable for selective hydrogenation of acetylene in a process gas containing at least 10% (mol .) ethylene, at least 1 ppm. acetylene and at least 5% (mol.) hydrogen, the method comprising

obtaining each catalyst layer at no more than a first temperature, the catalyst layer being in contact with a gas;

in the presence of process gas, heating each catalyst layer to at least a second temperature, wherein the second temperature is at least 20 degrees greater than the first temperature, and heating each catalyst layer is carried out at a rate in the range of at least 3°C/hour; And

allowing the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

Another aspect of the disclosure of the invention is a method of operating a reactor for selective hydrogenation, wherein the reactor contains one or more beds of catalyst, each of which contains a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing at least 10% (mol.) ethylene, at least 1 ppm. acetylene and at least 5% (mol.) hydrogen, the method comprising

drying one or more catalyst layers at a temperature of at least 50°C; after that

cooling each dried catalyst layer to a first temperature in the range of 31 – 50°C, for example, 31 – 45°C, or 31 – 40°C, or 35 – 45°C, or 35 – 40°C, or 40 – 50° C, or 40 - 45 ° C, and introducing the catalyst of each catalyst layer into contact with the process gas at the first temperature; after that

in the presence of process gas, heating each catalyst layer to at least a second temperature, the second temperature being at least 20 degrees greater than the first temperature; And

allowing the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

Another aspect of the invention is a hydrogenation catalyst composition comprising:

a porous carrier present in the composition in an amount within the range of 90% (wt.) to 99.9% (wt.);

palladium present in the composition in an amount within the range of 0.02% (wt.) to 0.5% (wt.), or from 0.03% (wt.) to 0.4% (wt.), or from 0.04% (wt.) to 0.3% (wt.) based on the mass of the element; And

one or more ionic liquids present in the composition in a combined amount up to 10% by weight.

Another aspect of the invention is a hydrogenation catalyst composition comprising:

porous carrier present in the composition in an amount within the range of 90% (wt.) to 99.9% (wt.) and characterized by a BET determined surface area of not more than 10 m ² /g and volume pores of at least 0.1 ml/g;

palladium present in the composition in an amount within the range of at least 0.02% (wt.) based on the weight of the element; And

one or more ionic liquids present in the composition in a combined amount up to 10% by weight.

Another aspect of the invention is a hydrogenation catalyst composition comprising:

a porous carrier present in the composition in an amount within the range of 90% (wt.) to 99.9% (wt.);

palladium present in the composition in an amount within the range of at least 0.02% (wt.) based on the weight of the element; And

one or more ionic liquids present in the composition in a combined amount of up to 10% by weight,

wherein the hydrogenation catalyst has a BET surface area of not more than 10 m ² /g and a pore volume of at least 0.05 ml/g.

These hydrogenation catalyst compositions may advantageously be used in the methods described herein.

Given the disclosure herein, other aspects of the disclosure will be apparent to those skilled in the relevant art.

Brief description of drawings

Figure 1 is a set of graphs showing the concentration of acetylene and ethylene in the product outlet for the process described herein (left) and the product outlet for a conventional process (right).

Figure 2 is a graph showing ethylene selectivity (left y-axis) for the process described herein (middle line) and a conventional process (bottom line) over several variations in CO concentration (top line, right y-axis) .

Figure 3 is a set of graphs showing acetylene conversion (left) and ethylene selectivity (right) for various processes described herein.

Figure 4 is a set of graphs showing acetylene conversion (left) and ethylene selectivity (right) for various processes described herein.

Figures 5, 6, 7 and 8 are plots of reactor temperatures for the run experiments of Example 6.

Figure 9 is a plot of acetylene reduction selectivity versus CO concentration under isothermal conditions for a catalyst as described herein and a comparative catalyst.

Detailed Description of the Invention

The disclosure of the invention relates to methods for the selective hydrogenation of acetylene (C ₂ H ₂ ) by contacting an acetylene-containing process gas with a catalyst composition containing a porous support, palladium and one or more ionic liquids and optionally promoters such as silver, gold, zinc, tin , lead, gallium, cadmium, copper, bismuth, sodium, cesium or potassium. As determined by the inventors of the present invention, such catalysts can unexpectedly provide improved performance of hydrogenation systems by allowing acetylene to be selectively hydrogenated without thermal runaway under a wider range of conditions than previously contemplated.

For example, in certain aspects of the disclosure, CO may be present in the process gas, if at all, in only a relatively small amount (e.g., ranging from 0 to 190 ppm or 0 to 175 ppm or 0 to 150 ppm in terms of moles). This can enable processes to be carried out without adding CO to the low CO feedstock, thereby simplifying operation and improving plant safety.

In other aspects, the CO in the process gas may be present in a relatively high amount (eg, at least 600 ppm or in the range of 600 ppm to 20,000 ppm or 600 ppm). ./million to 10,000 ppm). This may allow the use of process gases that have high CO levels. In various aspects, the process gas may be contacted with the catalyst composition at a relatively high gas hourly space velocity (GSV) (e.g., at least 7,100 h ⁻¹ , at least 10,000 h ⁻¹ , or at least , 12500 hour ^{- 1} , for example, in the range from 7100 hour ^{- 1} to 40000 hour ^{- 1} or in the range from 10000 hour ^{- 1} to 40000 hour ^{- 1} or in the range from 12500 hour ^{- 1} to 40000 hour ^{- 1} ). As determined by the inventors of the present invention, the catalysts described herein can be used at unexpectedly high rates of reaction components without causing runaway conditions. And in certain embodiments, selective hydrogenation is carried out at a relatively high temperature, which allows for increased reaction rates and increased productivity. As demonstrated by the disclosure, such selective hydrogenation processes can advantageously provide the desired selective acetylene conversion at a relatively low ethylene (ethene; C ₂ H ₄ ) conversion without causing uncontrolled thermal conditions.

Accordingly, one aspect of the invention is a process for the selective hydrogenation of acetylene, the method comprising contacting a catalyst composition with a process gas. The catalyst composition contains a porous support, palladium and one or more ionic liquids. The gaseous mixture includes ethylene present in the process gas in an amount of at least 15% (mol.); acetylene present in the process gas in an amount of at least 1 ppm; hydrogen present in the process gas in an amount of at least 5% (mol.); and from 0 to 190 ppm. carbon monoxide. At least 90% of the acetylene present in the process gas is hydrogenated, and selective hydrogenation is carried out without causing uncontrolled thermal conditions. Yet another aspect of the invention is a method for selectively hydrogenating acetylene, the method comprising contacting the catalyst composition with a process gas. The catalyst composition contains a porous support, palladium and one or more ionic liquids. The gaseous mixture includes ethylene present in the process gas in an amount of at least 15% (mol.); acetylene present in the process gas in an amount of at least 1 ppm; hydrogen present in the process gas in an amount of at least 5% (mol.); and at least 600 ppm. carbon monoxide. At least 90% of the acetylene present in the process gas is hydrogenated, and selective hydrogenation is carried out without causing uncontrolled thermal conditions. In certain such embodiments, contacting is carried out at OCSG within the range of 2000 h ^-1 to 40,000 h ^-1 .

The term runaway heat describes a process in which the heat released by a catalyzed exothermic reaction (such as hydrogenation) increases the temperature of the catalyst, which increases the rate of the catalyzed reaction. In turn, the amount of heat released as a result of the accelerated reaction increases, which further increases the temperature of the catalyst. As will be appreciated by those skilled in the art, in the case of acetylene hydrogenation, this uncontrolled thermal process results in increased production of ethane (C ₂ H ₆ ). Accordingly, the term "thermal runaway" as used herein describes a process that hydrogenates at least 90% of the acetylene present in the process gas and converts no more than 1% of the acetylene to ethane. mol.) from the total amount of acetylene and ethylene present in the process gas. That is, from the acetylene present in the process gas introduced into the process, at least 90% of this amount is hydrogenated. Ethylene and acetylene are typical components of process gases that can be overreduced to form ethane; as noted by the inventors of the present invention, the amount of this undesirable overreduction can be reduced by using the catalysts and methods herein. Thus, the phrase “not more than 1% (mol.) of the total amount of acetylene and ethylene present in the process gas is converted to ethane” means that the amount of ethane leaving the process increases by no more than 1% (mol. .) when calculating the total level of content in the gas product at the outlet of the reactor in comparison with the process gas at the inlet. For example, if the inlet process gas stream has 20 mol% ethane, then the outlet stream contains no more than 21 mol% ethane.

As used herein, selectivity is defined as the fraction of acetylene that is converted to ethylene, that is, (ethylene gain)/(acetylene loss).

Another aspect of the disclosure of the invention is a method for the selective hydrogenation of acetylene, the method comprising contacting the catalyst composition with a process gas at a HOC value of at least 7100 h ^-1 (for example, within the range of 7500 h ^-1 up to 40,000 hours ^{– 1} ). CHOSG values are determined by referring to the volume of the catalyst bed(s). The catalyst composition contains a porous support, palladium and one or more ionic liquids. The process gas includes ethylene present in the process gas in an amount of at least 15% (mol.); acetylene present in the process gas in an amount of at least 1 ppm; and hydrogen present in the process gas in an amount of at least 2% (mol.). At least 90% of the acetylene present in the process gas is hydrogenated, and selective hydrogenation is carried out without the occurrence of uncontrolled thermal conditions (that is, no more than 1% (mol.) of the total amount of acetylene and ethylene present in the process gas is converted to ethane process gas). As determined by the inventors of the present invention, the high selectivity of the catalysts described herein can allow operation at unexpectedly high space velocities. In certain such embodiments, the process gas includes up to 20,000 ppm. carbon monoxide.

Contacting the process gas can be accomplished using a wide variety of equipment familiar to those skilled in the art. For example, the catalyst composition may be contained in a single layer in a reactor vessel or may be distributed among multiple layers within a reactor. The reaction system may include one or more reactor vessels connected in series. The feedstock feed to the reaction zone may flow vertically from bottom to top or top to bottom through the catalyst bed in a typical plug flow reactor, or horizontally through the catalyst bed in a radial flow type reactor. The reaction vessels can be adiabatic reactors including intercoolers, or cooled reactors, for example, tubular isothermal reactors, where the catalyst is in the tubes or the cooling medium is in the tubes. In some embodiments, at least 90% of the acetylene present in the process gas can be hydrogenated by contacting the catalyst composition contained in a single bed. In other embodiments, at least 90% of the acetylene present in the process gas may be hydrogenated by contacting the catalyst composition distributed among the plurality of layers. The process gas may be produced as a single stream or may be produced as a plurality of streams (eg, a hydrogen stream and a hydrocarbon feed stream) that are combined in a reactor.

As determined by the inventors of the present invention, processes that are advantageously as otherwise described herein can provide advantageous performance characteristics, for example, to otherwise conventional olefin processing systems. For example, methods that fall within the description of the invention in other respects herein may be carried out for the purpose of selectively hydrogenating acetylene contained in a crude cracked olefin stream (i.e., a hydrocarbon gas feedstock feedstock) or system overhead stream for separating C ₃ hydrocarbons (ie, the depropanizer) or C ₂ hydrocarbons (ie, the depanner) from the olefin stream. In yet another example, methods that are consistent with the description of the invention in other respects herein can be carried out for the purpose of selectively hydrogenating acetylene contained in a refinery off-gas stream. Accordingly, in various embodiments that are consistent with the invention described elsewhere herein, the process gas is obtained from a cracking process effluent stream, from a depanner overhead stream, from a depanter overhead stream, or from a refinery effluent gas stream. .

In certain embodiments of the methods, which correspond to the description of the invention in other respects herein, selective hydrogenation is carried out at a temperature within the range from 20°C to 140°C. In certain desirable embodiments, the selective hydrogenation is carried out at a temperature within the range of 40°C to 100°C, for example, 40°C to 90°C or 50°C to 100°C or 50°C to 90°C . But technological processes can be carried out over a wide range of temperatures. For example, in certain such embodiments, selective hydrogenation is carried out at a temperature within the range of 20°C to 130°C, for example, in the range of 20°C to 120°C or 20°C to 110°C or 20°C up to 100°C or from 20°C to 90°C. In other such embodiments, selective hydrogenation is carried out at a temperature within the range of 40°C to 140°C, for example, 40°C to 130°C or 40°C to 120°C or 40°C to 110°C . In other such embodiments, selective hydrogenation is carried out at a temperature within the range of 50°C to 140°C, for example, 50°C to 130°C or 50°C to 120°C or 50°C to 110°C . In other such embodiments, selective hydrogenation is carried out at a temperature within the range of 60°C to 140°C, for example, 60°C to 130°C or 60°C to 120°C or 60°C to 110°C or from 60°C to 100°C or from 60°C to 90°C.

Advantageously, as determined by the inventors of the present invention, the process gas of processes that are otherwise described herein may include carbon monoxide (CO) in an amount within a relatively wide range. For example, as noted by the inventors of the present invention, prior art processes typically include some carbon monoxide in the process feed to the extent of adding carbon monoxide to a process feed that does not contain sufficient carbon monoxide. The purpose of carbon monoxide is to alter the activity of the catalyst so that the process does not run out of control and produce more ethane than is desired. Conventional catalysts were understood to have reduced selectivity for acetylene hydrogenation, particularly at reduced carbon monoxide concentrations, and thus it was understood that the addition of carbon monoxide was desirable to maintain the relatively small amount of ethane in the process outlet product. process. In contrast, as determined by the inventors of the present invention, the catalysts described herein can provide high selectivity without runaway even at low CO concentrations. Accordingly, in certain embodiments of methods that are consistent with the invention otherwise described herein, CO in the process gas is present in an amount of up to 190 ppm, for example, in the range of 1 ppm million up to 190 ppm, for example in the range of 5 ppm. up to 190 ppm or from 10 ppm up to 190 ppm or from 25 ppm up to 190 ppm or from 50 ppm up to 190 ppm or from 100 ppm up to 190 ppm In certain embodiments of methods that are otherwise described herein, the CO in the process gas is present in an amount of up to 180 ppm, for example, in the range of 1 ppm. up to 180 ppm, for example in the range from 5 ppm. up to 180 ppm or from 10 ppm up to 180 ppm or from 25 ppm up to 180 ppm or from 50 ppm up to 180 ppm or from 100 ppm up to 180 ppm In certain embodiments of methods that are as otherwise described herein, the CO in the process gas is present in an amount of up to 170 ppm, for example, within the range of 1 ppm. up to 170 ppm, for example in the range of 5 ppm. up to 170 ppm or from 10 ppm up to 170 ppm or from 25 ppm up to 170 ppm or from 50 ppm up to 170 ppm or from 100 ppm up to 170 ppm In certain embodiments of methods that are consistent with the invention otherwise described herein, the CO in the process gas is present in an amount of up to 160 ppm, for example, within the range of 1 ppm. up to 160 ppm, for example in the range of 5 ppm. up to 160 ppm or from 10 ppm up to 160 ppm or from 25 ppm up to 160 ppm or from 50 ppm up to 160 ppm or from 100 ppm up to 160 ppm In certain embodiments of methods that are as otherwise described herein, the CO in the process gas is present in an amount of up to 150 ppm, for example, in the range of 1 ppm. up to 150 ppm, for example in the range of 5 ppm. up to 150 ppm or from 10 ppm up to 150 ppm or from 25 ppm up to 150 ppm or from 50 ppm up to 150 ppm or from 100 ppm up to 150 ppm In certain embodiments of methods that are consistent with the invention otherwise described herein, the CO in the process gas is present in an amount of up to 140 ppm, for example, within the range of 1 ppm. up to 140 ppm, for example in the range of 5 ppm. up to 140 ppm or from 10 ppm up to 140 ppm or from 25 ppm up to 140 ppm or from 50 ppm up to 140 ppm or from 100 ppm up to 140 ppm In certain embodiments of methods that are consistent with the invention otherwise described herein, the CO in the process gas is present in an amount of up to 130 ppm, for example, within the range of 1 ppm. up to 130 ppm, for example in the range of 5 ppm. up to 130 ppm or from 10 ppm up to 130 ppm or from 25 ppm up to 130 ppm or from 50 ppm up to 130 ppm or from 100 ppm up to 130 ppm In certain embodiments of methods that are otherwise described herein, the CO in the process gas is present in an amount of up to 120 ppm, for example, in the range of 1 ppm. up to 120 ppm, for example in the range from 5 ppm. up to 120 ppm or from 10 ppm up to 120 ppm or from 25 ppm up to 120 ppm or from 50 ppm up to 120 ppm In certain embodiments of methods that are otherwise described herein, the CO in the process gas is present in an amount of up to 110 ppm, for example, within the range of 1 ppm. up to 110 ppm, for example in the range from 5 ppm. up to 110 ppm or from 10 ppm up to 110 ppm or from 25 ppm up to 110 ppm or from 50 ppm up to 110 ppm In certain embodiments of methods that are otherwise described herein, the CO in the process gas is present in an amount of up to 100 ppm, for example, in the range of 1 ppm. up to 100 ppm, for example in the range from 5 ppm. up to 100 ppm or from 10 ppm up to 100 ppm or from 25 ppm up to 100 ppm or from 50 ppm up to 100 ppm In certain embodiments of methods that are consistent with the invention otherwise described herein, the CO in the process gas is present in an amount of up to 90 ppm, for example, within the range of 1 ppm. up to 90 ppm, for example in the range from 5 ppm. up to 90 ppm or from 10 ppm up to 90 ppm or from 25 ppm up to 90 ppm or from 50 ppm up to 90 ppm In certain embodiments of methods that are consistent with the invention otherwise described herein, the CO in the process gas is present in an amount of up to 80 ppm, for example, within the range of 1 ppm. up to 80 ppm, for example in the range from 5 ppm. up to 80 ppm or from 10 ppm up to 80 ppm or from 25 ppm up to 80 ppm or from 50 ppm up to 80 ppm In certain embodiments of methods that are consistent with the invention otherwise described herein, the CO in the process gas is present in an amount of up to 50 ppm, for example, within the range of 1 ppm. up to 50 ppm, for example in the range from 5 ppm. up to 50 ppm or from 10 ppm up to 50 ppm or from 25 ppm up to 50 ppm In certain embodiments of methods that are otherwise described herein, substantially no CO is present in the process gas.

Namely, in certain embodiments of methods that are consistent with the invention otherwise described herein, carbon monoxide is not added to the gaseous feed stream to produce process gas. That is, unlike many conventional methods, in certain embodiments that are consistent with the invention otherwise described herein, there is no need to maintain a background concentration of CO in the process gas in order to maintain sufficiently low exothermicity due to ethylene hydrogenation. Rather, the catalysts described herein are highly selective for the hydrogenation of acetylene to ethylene, even at low CO concentrations, and thus there is little risk of thermal runaway due to ethylene reduction at such low CO concentrations.

As noted by the inventors of the present invention, process gas having a high CO content may be the result of variations in an upstream process step, and it would also be desirable to carry out hydrogenation continuously throughout and/or after such process. variations. As noted by the inventors of the present invention, the catalysts described herein can achieve continuous production without runaway performance of gases within specifications for a downstream process at high CO levels up to up to 20,000 ppm, even taking into account the significantly increased temperatures that are typically required for such CO concentrations (ie, compared to the temperatures required to purify acetylene at low CO levels). Namely, as described in Example 7 below, the catalysts described herein can exhibit relatively invariant acetylene selectivity even at elevated CO concentrations. In certain embodiments that are consistent with the invention described elsewhere herein, the CO in the process gas is present in an amount of at least 600 ppm. (e.g. at least 800 ppm or at least 1000 ppm or at least 1500 ppm or at least 2000 ppm) . For example, in certain embodiments that are consistent with the invention described elsewhere herein, CO in the process gas is present in an amount ranging from 600 ppm. up to 20,000 ppm For example, in certain such embodiments, the CO in the process gas is present in an amount ranging from 600 ppm. up to 15,000 ppm or from 600 ppm up to 10,000 ppm or from 600 ppm up to 5000 ppm or from 600 ppm up to 2500 ppm or from 600 ppm up to 1500 ppm or from 700 ppm up to 1200 ppm or from 800 ppm up to 1200 ppm or from 900 ppm up to 1200 ppm or from 700 ppm up to 1000 ppm or from 800 ppm up to 1100 ppm In other such embodiments, the CO in the process gas is present in an amount ranging from 800 ppm. up to 20,000 ppm or from 800 ppm up to 15,000 ppm or from 800 ppm up to 10,000 ppm or from 800 ppm up to 5000 ppm or from 800 ppm up to 2500 ppm or from 800 ppm up to 1500 ppm In other such embodiments, the CO in the process gas is present in an amount in the range of 1000 ppm. up to 20,000 ppm or from 1000 ppm up to 15,000 ppm or from 1000 ppm up to 10,000 ppm or from 1000 ppm up to 5000 ppm or from 1000 ppm up to 2500 ppm In other such embodiments, the CO in the process gas is present in an amount ranging from 1500 ppm. up to 20,000 ppm or from 1500 ppm up to 15,000 ppm or from 1500 ppm up to 10,000 ppm or from 1500 ppm up to 5000 ppm In other such embodiments, the CO in the process gas is present in an amount ranging from 2000 ppm. up to 20,000 ppm or from 2000 ppm up to 15,000 ppm or from 2000 ppm up to 10,000 ppm or from 2000 ppm up to 5000 ppm

However, in other embodiments, the process gas may have a different CO concentration. For example, in certain embodiments (e.g., with an OSH value of at least 7500 h ^-1 , at least 10000 h ^-1 , at least 15000 h ^-1 , or at least 20000 h ^{-1 1} ) the concentration of CO in the process gas reaches up to 1200 ppm, for example, up to 1000 ppm. or up to 500 ppm. or is in the range of 10 ppm. up to 1200 ppm or in the range of 10 ppm. up to 500 ppm or in the range of 50 ppm. up to 1200 ppm or in the range of 50 ppm. up to 500 ppm or in the range of 100 ppm. up to 1200 ppm or in the range of 100 ppm. up to 500 ppm

Advantageously, as determined by the inventors of the present invention, the process gas of processes that correspond to the description of the invention in other respects herein can be contacted with the catalyst composition at a relatively high rate (for example, at least 7100 hours ^{- 1} or within the range of 7500 h ^{- 1} to 40,000 h ^{- 1} ), which, in the desired case, increases productivity. As determined by the inventors of the present invention, as a result of the high selectivity of the catalysts described herein, advantageously, the processes described herein can be carried out at high throughput while maintaining selectivity and without promoting runaway. Accordingly, the methods described herein can be carried out in a selective hydrogenation reactor (i.e., comprising a single catalyst bed or multiple catalyst beds) characterized by a relatively small volume (i.e., compared to conventional processes in in order to achieve the same overall rate of product formation). Accordingly, in certain embodiments that are consistent with the invention otherwise described herein, the process gas is contacted with the catalyst at a HOSH value of at least 7100 h ^{- 1} , for example, within the range of 7100 hour ^{– 1} to 40000 hour ^{– 1} or from 7100 hour ^{– 1} to 30000 hour ^{– 1} or from 7100 hour ^{– 1} to 20000 hour ^{– 1} . In certain embodiments that are consistent with the invention described in other respects herein, the process gas is contacted with the catalyst at a HOSG value of at least 7500 h ^-1 , for example, within the range of 7500 h ^-1 to 40000 hour ^{– 1} or from 7500 hour ^{– 1} to 30000 hour ^{– 1} or from 7500 hour ^{– 1} to 20000 hour ^{– 1} . In certain embodiments, which are consistent with the description of the invention in other respects herein, the process gas is contacted with the catalyst at a HOC value of at least 10,000 h ^–1 , for example, within the range of 10,000 h ^–1 to 40000 hour ^{– 1} or from 10000 hour ^{– 1} to 30000 hour ^{– 1} or from 10000 hour ^{– 1} to 20000 hour ^{– 1} . In certain embodiments, which are consistent with the description of the invention in other respects herein, the process gas is contacted with the catalyst at a HOC value of at least 15,000 h ^–1 , for example, within the range of 15,000 h ^–1 to 40000 hour ^{– 1} or from 15000 hour ^{– 1} to 30000 hour ^{– 1} or from 15000 hour ^{– 1} to 20000 hour ^{– 1} . In certain embodiments, which are consistent with the description of the invention in other respects herein, the process gas is contacted with the catalyst at a HOC value of at least 20,000 h ^–1 , for example, within the range of 20,000 h ^–1 to 40000 hour ^{– 1} or from 20000 hour ^{– 1} to 30000 hour ^{– 1} . CHOSG values are determined by referring to the total volume of the catalyst bed(s).

As noted above, the processes described herein are carried out such that at least 90% of the acetylene present in the process gas is hydrogenated (i.e., the acetylene conversion is at least 90 %). For example, in certain embodiments of methods that fall within the description of the invention in other respects herein, at least 92.5% or at least 95% or at least 96% or at least , 97% or at least 97.5% or at least 98% or at least 98.5% or at least 99% of the acetylene present in the process gas. In certain embodiments of the methods, which correspond to the description of the invention in other respects herein, substantially all of the acetylene present in the process gas is hydrogenated.

As noted above, in various aspects, processes that are consistent with the description of the invention in other respects herein can be carried out without thermal runaway, that is, converting no more than 1 mol% of the total amount to ethane. acetylene and ethylene present in the process gas. For example, in certain embodiments of processes that are otherwise described herein, no more than 0.9 mol% or no more than 0.8 mol% or no more are converted to ethane , than 0.7 mol% or not more than 0.6 mol% or not more than 0.5 mol% of the total amount of acetylene and ethylene present in the process gas, (then is, the amount of ethane product at the exit from the technological process does not increase by more than 0.8% (mol.) or 0.7% (mol.) or 0.6% (mol.) or 0.5% (mol.). ) when calculated on the total level of content in the process gas compared to the introduced process gas). For example, in certain embodiments of processes that are otherwise described herein, no more than 0.2 mol%, such as no more than 0.1 mol%, or not more than 0.05% (mol.) of the total amount of acetylene and ethylene present in the process gas. In certain embodiments of methods that are otherwise described herein, substantially no portion of the total acetylene and ethylene present in the process gas is converted to ethane.

Stated differently, the amount of ethane in the selectively hydrogenated product of processes that are otherwise described herein may include an amount of ethane that is no more than 1 mol% greater than the amount of ethane in the process gas ( that is, before being contacted with a catalyst composition that complies with the invention otherwise described herein). For example, in certain embodiments, the amount of ethane in the selectively hydrogenated product of a process that is otherwise described herein is no more than 0.9 mol% greater or no more than 0.8% greater. (mol.) greater or no more than 0.7% (mol.) greater or no more than 0.6% (mol.) greater or no more than 0.5% (mol.) greater than the amount of ethane in the process gas. In certain embodiments, the amount of ethane in the selectively hydrogenated process product, which is as otherwise described herein, is no more than 0.2 mol% greater, such as no more than 0.1% (mol.) greater than or not more than 0.05% (mol.) greater than the amount of ethane in the process gas. In certain embodiments, the amount of ethane in the selectively hydrogenated process product, which is as otherwise described herein, is substantially the same as the amount of ethane in the process gas.

In accordance with the above description of the invention, using the selective hydrogenation methods described herein, a wide range of process gases can be treated. For example, in certain embodiments of methods that are consistent with the invention otherwise described herein, ethylene in the process gas is present in an amount of at least 15 mole percent. For example, in certain embodiments, ethylene in the process gas is present in an amount ranging from 15 mol% to 70 mol%, or from 15 mol% to 60 mol%, or from 15 mol% .) up to 50% (mol.). In certain embodiments that are consistent with the invention described elsewhere herein, ethylene in the process gas is present in an amount of at least 20 mol%, for example, ranging from 20 mol% to 70% (mol.) or from 20% (mol.) to 60% (mol.) or from 20% (mol.) to 50% (mol.). In certain embodiments that are consistent with the invention described elsewhere herein, ethylene in the process gas is present in an amount of at least 30 mol%, for example, ranging from 30 mol% to 70% (mol.) or from 30% (mol.) to 60% (mol.) or from 30% (mol.) to 50% (mol.).

Acetylene in the process gas composition may be present in a wide range of quantities depending on the specific source of the process gas. In certain embodiments of the methods, which are consistent with the description of the invention in other respects herein, acetylene in the process gas is present in an amount of at least 10 ppm, at least 50 ppm, at at least 100 ppm or at least 500 ppm, for example in an amount ranging from 10 ppm. up to 2% (mol.) or from 10 ppm. up to 1% (mol.) or from 10 ppm. up to 0.5% (mol.) or from 50 ppm. up to 2% (mol.) or from 50 ppm. up to 1% (mol.) or from 50 ppm. up to 0.5% (mol.) or from 100 ppm. up to 2% (mol.) or from 100 ppm. up to 1% (mol.) or from 100 ppm. up to 0.5% (mol.) or from 500 ppm. up to 2% (mol.) or from 500 ppm. up to 1% (mol.) or from 500 ppm. up to 0.5% (mol.). In certain embodiments of methods that are as otherwise described herein, acetylene in the process gas is present in an amount of at least 0.1 mol%, such as at least 0.5% (mol.) or at least 1% (mol.), for example, ranging from 0.1% (mol.) to 2% (mol.) or from 0.5% (mol.) to 2 % (mol.) or from 1% (mol.) to 2% (mol.) or from 0.1% (mol.) to 1.5% (mol.) or from 0.5% (mol.) to 1.5% (mol.) or from 1% (mol.) to 1.5% (mol.) or from 0.1% (mol.) to 1% (mol.) or from 0.5% (mol. .) up to 1% (mol.).

Hydrogen in the process gas can be produced at a wide range of concentrations. Those skilled in the art will select the amount of hydrogen that will allow the required reduction of acetylene to occur and, for example, to ensure that the desired amount of hydrogen is available for a subsequent process step. In certain embodiments that are consistent with the invention described elsewhere herein, hydrogen in the process gas is present in an amount of at least 5 mol%, at least 6 mol%, at least at least 7 mol%, at least 8 mol%, at least 9 mol% or at least 10 mol%, for example in the range of 5 % (mol.) to 50% (mol.) or from 5% (mol.) to 35% (mol.) or from 5% (mol.) to 20% (mol.) or from 5% (mol.) up to 15% (mol.) or from 8% (mol.) to 50% (mol.) or from 8% (mol.) to 35% (mol.) or from 8% (mol.) to 20% (mol. .) or from 8% (mol.) to 15% (mol.) or from 10% (mol.) to 50% (mol.) or from 10% (mol.) to 35% (mol.) or from 10 % (mol.) to 20% (mol.) or from 10% (mol.) to 15% (mol.).

As will be appreciated by those skilled in the art, other components may be present in the process gas of processes that are otherwise described herein. For example, the process gas may include one or more components typically present in the crude olefin stream produced by cracking, such as, for example, C ₁ components (eg, including methane, carbon monoxide and carbon dioxide), C ₂ components (for example, including ethylene, ethane and acetylene) and C ₃ components (for example, including propane, propylene, propadiene and methyl acetylene) and C ₄ components (for example, including 1,3-butadiene). However, in certain embodiments, the process gas will contain no more than 10 mol% (e.g., no more than 5 mol%, no more than 2 mol%), or no more than 1 % (mol.)) carbon-containing components other than _C1 components (for example, methane, carbon monoxide and carbon dioxide), _C2 components (for example, ethylene, ethane and acetylene) and _C3 components (for example, propylene, propane, methyl acetylene and propadiene). In certain embodiments, the process gas will contain no more than 20 mol% (e.g., no more than 15 mol%, no more than 10 mol%, or no more than 5 mol%). mol.)) carbon-containing components other than ethylene, ethane, acetylene, carbon monoxide and carbon dioxide. And in certain embodiments, the process gas will contain no more than 5 mol% (eg, no more than 2 mol%) carbonaceous components other than ethylene, ethane, acetylene, carbon monoxide, and carbon dioxide.

Various gas streams can be combined to produce process gas. For example, a hydrogen-containing gas stream may be added to another gas stream to produce a process gas. Gas streams can be combined in a reactor to produce process gas, which is a combination of the introduced gas streams.

As noted above, in various aspects, the methods of the invention include contacting the catalyst composition with a process gas. Accordingly, another aspect of the invention is a catalyst composition comprising a porous support, palladium and one or more ionic liquids. In certain embodiments, which are consistent with the invention described elsewhere herein, the catalyst composition comprises a porous support selected from alumina, silica, titanium dioxide, and any mixture thereof. In certain such embodiments, alumina, silica, titanium dioxide, and any mixture thereof in the catalyst composition are present in a total amount ranging from 90% by weight to 99.9% by weight, based on the oxide, calculated on a calcined substance. For example, in certain embodiments that are consistent with the invention described elsewhere herein, the catalyst composition comprises a porous support selected from alumina, silica, titanium dioxide, and any mixture thereof, and present in the catalyst composition in an amount ranging from 92.5% (wt.) to 99% (wt.) or from 95% (wt.) to 99.9% (wt.) or from 97.5% (wt.) to 99.9% (wt. ). In certain such embodiments, the porous support is a mixture of alumina and silica. In other such embodiments, the porous support is an alumina, such as alpha alumina.

As used herein, the term “oxide,” including, for example, “mixed oxide,” “alumina,” “silica,” and the like, includes oxides in all forms and crystalline phases. For example, the term "aluminum oxide" includes Al ₂ O ₃ , Al ₂ O _x , where x is within the range of 1 to 3, and so on. Unless otherwise indicated, regardless of the actual stoichiometry of the oxide, for purposes of mass percentage determinations, oxides are converted to the most stable oxide. For example, as will be appreciated by those skilled in the art, non-stoichiometric alumina or even another form of aluminum can still be converted to Al ₂ O ₃ . In addition, unless otherwise indicated, the compositions are described based on the material immediately after calcination.

In certain embodiments that are consistent with the invention described elsewhere herein, the surface area of the porous support determined using the BET method is within the range of 2 m ² /g to 10 m ² /g. As will be understood by those skilled in the art, the "BET surface area" of a material refers to the specific surface area of the material and is determined using the ASTM D3663 Standard Test Method for Surface Area of Catalysts and Catalysts. Carriers"). For example, in certain embodiments that are consistent with the description of the invention in other respects herein, the surface area of the porous support determined using the BET method is within the range of 2 m ² /g to 9 m ² /g or 2 m ² /g up to 8 m ² /g or from 2 m ² /g to 7 m ² /g or from 2 m ² /g to 6 m ² /g or from 2 m ² /g to 5 m ² /g or from 3 m ² /g to 10 m ² /g or from 4 m ² /g to 10 m ² /g or from 5 m ² /g to 10 m ² /g or from 6 m ² /g to 10 m ² /g or from 2 m ² /g to 6 m ² /g or from 3 m ² /g to 7 m ² /g or from 4 m ² /g to 8 m ² /g or from 5 m ² /g to 9 m ² /g. Surface areas determined using the BET method of no more than 10 m ² /g can be obtained by calcining the support to a relatively high degree.

In certain embodiments that are consistent with the invention otherwise described herein, the pore volume (as determined using the mercury incorporation porosimetry method of ASTM D4284) of the porous support is at least 0.10 ml/g , for example, is within the range of 0.10 ml/g to 1.0 ml/g. For example, in certain embodiments that are consistent with the invention described elsewhere herein, the pore volume of the porous support (as determined using the mercury intercalation porosimetry method in accordance with ASTM D4284) is in the range of 0.10 ml/ g to 0.80 ml/g or from 0.20 ml/g to 0.80 ml/g or from 0.30 ml/g to 0.80 ml/g or from 0.20 ml/g to 0.70 ml/g or from 0.30 ml/g to 0.70 ml/g.

The metal-impregnated porous support (i.e., including the porous support, palladium, and any promoters present, but not the ionic liquid) may similarly have a relatively high surface area, for example, at least 0.10 ml/g (according to determined using the mercury incorporation porosimetry method in accordance with ASTM D4284). For example, in certain embodiments that are consistent with the invention described elsewhere herein, the metal-impregnated porous support has a pore volume of at least 0.15 ml/g, at least 0.20 ml/g, or even 0.25 ml/g. In various embodiments, which are consistent with the invention described in other respects herein, the metal impregnated porous support has a pore volume in the range of 0.10 ml/g to 1.0 ml/g, for example, from 0.10 ml/g to 0.80 ml/g or from 0.10 to 0.60 ml/g or from 0.10 to 0.40 ml/g or from 0.10 to 0.30 ml/g. In other embodiments, which are consistent with the description of the invention in other respects herein, the metal impregnated porous support has a pore volume in the range of 0.15 ml/g to 1.0 ml/g, for example, from 0.15 ml/g to 0.80 ml/g or from 0.15 to 0.60 ml/g or from 0.15 to 0.40 ml/g or from 0.15 to 0.30 ml/g. In other embodiments, which are consistent with the description of the invention in other respects herein, the metal impregnated porous support has a pore volume in the range of 0.20 ml/g to 1.0 ml/g, for example, from 0.20 ml/g to 0.80 ml/g or from 0.20 to 0.60 ml/g or from 0.20 to 0.40 ml/g or from 0.20 to 0.35 ml/g. In other embodiments, which are consistent with the invention described in other respects herein, the metal impregnated porous support has a pore volume in the range of 0.25 ml/g to 1.0 ml/g, for example, from 0.25 ml/g to 0.80 ml/g or from 0.25 to 0.60 ml/g or from 0.25 to 0.40 ml/g or from 0.20 to 0.35 ml/g.

The inventors of the present invention have identified several advantages when the metal-impregnated porous support also has a relatively low BET surface area (i.e., no more than 10 m ² /g or the more specific range described above) coupled with a high pore volume Namely, in certain embodiments that are consistent with the invention otherwise described herein, the porous support has a relatively low BET-determined surface area (i.e., no more than 10 m ² /g or a more specific range, described above), but a relatively high pore volume (ie, greater than 0.1 ml/g, for example, within the range of 0.10 ml/g to 1.0 ml/g or the more specific range described above). This allows the material, after impregnation with an ionic liquid as described herein, to retain a certain pore volume even in the presence of the ionic liquid.

For example, in certain embodiments that are consistent with the invention described elsewhere herein, the catalyst composition itself (i.e., including the porous support, palladium and any promoters and ionic liquid present) is characterized by a relatively high pore volume (determined using mercury porosimetry) in accordance with ASTM D4284) of at least 0.05 ml/g. In certain embodiments that are consistent with the invention described elsewhere herein, the catalyst composition has a pore volume of at least 0.10 ml/g, at least 0.15 ml/g, or even 0.20 ml/g. In various embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition has a pore volume in the range of 0.05 ml/g to 1.0 ml/g, for example, from 0.05 ml/g to 0. 80 ml/g or from 0.05 to 0.60 ml/g or from 0.05 to 0.40 ml/g or from 0.05 to 0.30 ml/g. In other embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition has a pore volume in the range of 0.10 ml/g to 1.0 ml/g, for example, from 0.10 ml/g to 0. 80 ml/g or from 0.10 to 0.60 ml/g or from 0.10 to 0.40 ml/g or from 0.10 to 0.30 ml/g. In other embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition has a pore volume in the range of 0.10 ml/g to 1.0 ml/g, for example, from 0.10 ml/g to 0. 80 ml/g or from 0.10 to 0.60 ml/g or from 0.10 to 0.40 ml/g or from 0.10 to 0.30 ml/g. In other embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition has a pore volume in the range of 0.15 ml/g to 1.0 ml/g, for example, from 0.15 ml/g to 0. 80 ml/g or from 0.15 to 0.60 ml/g or from 0.15 to 0.40 ml/g or from 0.15 to 0.30 ml/g. In other embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition has a pore volume in the range of 0.20 ml/g to 1.0 ml/g, for example, from 0.20 ml/g to 0. 80 ml/g or from 0.20 to 0.60 ml/g or from 0.20 to 0.40 ml/g or from 0.20 to 0.35 ml/g. Such materials can be prepared by using a relatively small amount of ionic liquid, for example up to 4% by weight or up to 3% by weight depending on the pore volume of the support.

In certain embodiments, as otherwise described herein, the catalyst composition contains palladium in an amount of at least 0.02% by weight (ie, based on the weight of the element). For example, in certain such embodiments, the catalyst composition contains palladium in an amount of at least 0.03% by weight or at least 0.04% by weight or at least 0. 05% (wt.) or at least 0.06% (wt.) or at least 0.07% (wt.) or at least 0.08% (wt.) or, at least 0.09% (wt.) or at least 0.1% (wt.) or at least 0.11% (wt.) or at least 0.12% (wt.) or at least 0.13% (wt.) or at least 0.14% (wt.) or at least 0.15% (wt.). In certain such embodiments, the catalyst composition contains palladium in an amount of no more than 0.5% by weight (e.g., no more than 0.4% by weight or no more than 0.3% ( wt.) or not more than 0.2% (wt.)). For example, in certain embodiments that are consistent with the invention described elsewhere herein, the catalyst composition contains palladium in an amount ranging from 0.02 wt% to 0.5 wt%, or 0.02 % (wt.) to 0.45% (wt.) or from 0.03% (wt.) to 0.4% (wt.) or from 0.03% (wt.) to 0.35% (wt. .) or from 0.04% (wt.) to 0.3% (wt.) or from 0.04% (wt.) to 0.25% (wt.).

In certain embodiments, which correspond to the description of the invention in other respects herein, palladium is localized on the surface of the support in the so-called shell configuration of the catalyst. “Surface localized” materials are characterized by a substantially higher concentration (eg, being at least 100% greater) at the surface of the material (including the surface of internal pores) than in the interior of the material. As will further be understood by those skilled in the art, the "surface" of the composition does not consist solely of the outermost surface of the atoms of the composition, but rather includes a surface layer on the outside of the composition. For example, the palladium-containing shell on the carrier in certain embodiments may have a thickness of up to 1 mm. The thickness of the shell in certain embodiments, which correspond to the description of the invention in other respects herein, is in the range of 100 - 800 microns.

In certain embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition further comprises at least one promoter selected from silver, gold, zinc, tin, lead, gallium, cadmium, copper, bismuth , sodium, cesium or potassium. For example, in certain such embodiments, the catalyst composition contains a silver promoter. In other such embodiments, the catalyst composition contains a gold or zinc promoter. In certain embodiments that are consistent with the invention described in other respects herein, at least one promoter (e.g., silver) in the catalyst composition is present in a total amount of at least 0.02% by weight ( that is, based on the weight of the element) or at least 0.04% (wt.) or at least 0.06% (wt.) or at least 0.08% (wt. ) or at least 0.1% (wt.) or at least 0.12% (wt.) or at least 0.14% (wt.) or at least 0 .16% (wt.) or at least 0.18% (wt.) or at least 0.2% (wt.) or at least 0.22% (wt.) or at least 0.24% (wt.) or at least 0.26% (wt.) or at least 0.28% (wt.) or at least 0.3 % (wt.). In certain such embodiments, the catalyst composition contains at least one promoter in a total amount of no more than 0.6% by weight (e.g., no more than 0.45% by weight) or no more than 0.3% (wt.)). In certain embodiments, which are consistent with the description of the invention in other respects herein, at least one promoter (eg, silver) is present together with palladium in the shell layer. In certain embodiments, the weight ratio between palladium and promoter metal is within the range of 1:5 to 3:1, for example, within the range of 1:4 to 2:1, or within the range of 1:3 to 1:1.

In certain embodiments, which are consistent with the invention described elsewhere herein, the catalyst composition contains at least one ionic liquid in a total amount of up to 10% by weight. For example, in certain embodiments that are consistent with the invention described elsewhere herein, the catalyst composition contains at least one ionic liquid in a total amount ranging from 0.01% by weight to 10% by weight. ), for example, from 0.01% (wt.) to 8% (wt.) or from 0.01% (wt.) to 6% (wt.) or from 0.01% (wt.) to 4% (wt.) or from 0.01% (wt.) to 3% (wt.) or from 0.01% (wt.) to 2% (wt.) or from 0.01% (wt.) to 1 % (wt.). In certain embodiments that are consistent with the invention described elsewhere herein, the ionic liquid is present in an amount ranging from 0.05% by weight to 10% by weight, for example, from 0.05% by weight. ) to 8% (wt.) or from 0.05% (wt.) to 6% (wt.) or from 0.05% (wt.) to 4% (wt.) or from 0.05% (wt. .) to 3% (wt.) or from 0.05% (wt.) to 2% (wt.) or from 0.05% (wt.) to 1% (wt.). In certain embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition contains at least one ionic liquid in a total amount ranging from 0.1% (wt.) to 10% (wt.), for example, from 0.1% (wt.) to 8% (wt.) or from 0.1% (wt.) to 6% (wt.) or from 0.1% (wt.) to 4% (wt. .) or from 0.1% (wt.) to 3% (wt.) or from 0.1% (wt.) to 2% (wt.) or from 0.1% (wt.) to 1% ( mass). In certain embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition contains at least one ionic liquid in a total amount ranging from 0.2% (wt.) to 10% (wt.), for example, from 0.2% (wt.) to 8% (wt.) or from 0.2% (wt.) to 6% (wt.) or from 0.2% (wt.) to 4% (wt. .) or from 0.2% (wt.) to 3% (wt.) or from 0.2% (wt.) to 2% (wt.) or from 0.2% (wt.) to 1% ( mass). In certain embodiments, which are consistent with the description of the invention in other respects herein, the catalyst composition contains at least one ionic liquid in a total amount ranging from 0.5% (wt.) to 10% (wt.), for example, from 0.5% (wt.) to 8% (wt.) or from 0.5% (wt.) to 6% (wt.) or from 0.5% (wt.) to 4% (wt. .) or from 0.5% (wt.) to 3% (wt.) or from 0.5% (wt.) to 2% (wt.).

As will be appreciated by those skilled in the art, the term "ionic liquid" generally refers to a class of poorly coordinated salts characterized by a relatively low melting point, such as, for example, less than 100°C. In certain embodiments that are consistent with the invention otherwise described herein, the ionic liquid comprises a compound having the formula:

[A] _n ⁺ [Y] _n ^– ,

where n is 1 or 2;

[Y] _n ^– selected from tetrafluoroborate ([BF ₄ ] ⁻ ); hexafluorophosphate ([PF ₆ ] ⁻ ); dicyanamide ([N(CN) ₂ ] ⁻ ); halides (Cl ^- , Br ^- , F ^- , I ^- ); hexafluoroantimonate ([SbF ₆ ] ⁻ ); nitrate ([NO ₃ ] ⁻ ); nitrite ([NO ₂ ] ⁻ ); anionic metal complexes (for example, [CuCl ₄ ] ₂ ⁻ , [PdCl ₄ ] ₂ ⁻ , [AuCl ₄ ] ⁻ ); acetate ([CH ₃ COO] ⁻ ); trifluoroacetate ([F ₃ CCOO] ⁻ ); hexafluoroarsenate ([AsF ₆ ] ⁻ ); sulfate ([SO ₄ ] ₂ ⁻ ); hydrogen sulfate ([R'-SO4] ⁻ ); alkyl sulfate ([R'-SO4] ⁻ ); tosylate ([C ₇ H ₇ SO ₃ ] ⁻ ); trifluoromethanesulfonate ([CF ₃ SO ₃ ] ⁻ ); nonafluorobutanesulfonate ([C ₄ F ₉ SO ₃ ] ⁻ ); triperfluoroethylene trifluorophosphate ([PF ₃ (C ₂ F ₅ ) ₃ ] ⁻ ); tricyanomethide ([C(CN) ₃ ] ⁻ ); tetracyanoborate ([B(CN) ₄ ] ⁻ ; thiocyanate ([SCN] ⁻ ); carbonate ([CO ₃ ] ₂ ⁻ ); carboxylate ([R'-COO] ⁻ ); sulfonate ([R'SO ₃ ] ⁻ ) ; dialkyl phosphate ([R'PO ₄ R''] ⁻ ), alkyl phosphonate ([R'HPO ₃ ] ⁻ ), and bisulfonylimide ([(R'-SO ₂ ) ₂ N] ⁻ ) (for example, bis(trifluoromethylsulfonyl)imide ); where each of R' and R'' independently represents a linear or branched C ₁ - C ₁₂ aliphatic or alicyclic alkyl; C ₅ - C ₁₈ aryl; C ₅ - C ₁₈ aryl-substituted C ₁ - C ₆ alkyl; or C ₁ – C ₆ alkyl-substituted C ₅ – C ₁₈ aryl, wherein alkyl is optionally substituted with one or more halogen atoms;

[A] ⁺ is selected from quaternary ammonium cations, described by the formula [NR ¹ R ² R ³ R] ⁺ , phosphonium cations, described by the formula [PR ¹ R ² R ³ R] ⁺ , sulfonium cations, described by the formula [SR ¹ R ² R ] ⁺ , guanidinium cations described by the formula:

imidazolium cations, described by the formula:

where the imidazole is optionally substituted with one or more groups selected from C ₁ - C ₆ alkyl; C ₁ – C ₆ alkoxy; C ₁ – C ₆ aminoalkyl; _C5 – _C12 aryl; and C ₅ – C ₁₂ aryl-substituted C ₁ – C ₆ alkyl; pyridinium cations, described by the formula:

where the pyridine is optionally substituted with one or more groups selected from C ₁ - C ₆ alkyl; C ₁ – C ₆ alkoxy; C ₁ – C ₆ aminoalkyl; _C5 – _C12 aryl; and C ₅ – C ₁₂ aryl-substituted C ₁ – C ₆ alkyl; pyrazolium cations, described by the formula:

where the pyrazole is optionally substituted with one or more groups selected from C ₁ - C ₆ alkyl; C ₁ – C ₆ alkoxy; C ₁ – C ₆ aminoalkyl; _C5 – _C12 aryl; and C ₅ – C ₁₂ aryl-substituted C ₁ – C ₆ alkyl; and triazolium cations, described by the formula:

where the triazole is optionally substituted with one or more groups selected from C ₁ - C ₆ alkyl; C ₁ – C ₆ alkoxy; C ₁ – C ₆ aminoalkyl; _C5 – _C12 aryl; and C ₅ – C ₁₂ aryl-substituted C ₁ – C ₆ alkyl; where each of R ¹ , R ² , R ³ independently represents a hydrogen atom; C ₁ – C ₂₀ alkyl; C ₃ - C ₈ heteroaryl, optionally substituted by one or more representatives selected from C ₁ - C ₆ alkyl and a halogen atom; C ₃ - C ₈ heteroaryl-substituted C ₁ - C ₆ alkyl, wherein heteroaryl is optionally substituted with one or more representatives selected from C ₁ - C ₆ alkyl and a halogen atom; polyether, described by the formula [-CH ₂ CH ₂ O] _n R ^a , where n is within the range of 1 - 50000, and R ^a is selected from C ₁ - C ₂₀ alkyl; C ₅ - C ₁₂ aryl, optionally substituted with one or more representatives selected from C ₁ - C ₆ alkyl and a halogen atom; and C ₅ - C ₁₂ aryl-substituted C ₁ - C ₆ alkyl, wherein aryl is optionally substituted with one or more representatives selected from C ₁ - C ₆ alkyl and a halogen atom; and where R is selected from C ₁ - C ₂₀ alkyl; C ₄ - C ₈ heteroaryl-substituted C ₁ - C ₆ alkyl, wherein heteroaryl is optionally substituted with one or more representatives selected from C ₁ - C ₆ alkyl and a halogen atom; and C ₄ - C ₁₂ aryl-substituted C ₁ - C ₆ alkyl, wherein aryl is optionally substituted with one or more representatives selected from C ₁ - C ₆ alkyl and a halogen atom.

For example, in certain such embodiments, [A] _n ⁺ is selected from 1-butyl-1-methylpyrrolidinium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1- ethyl-3-methylpyridinium, 1-methyl-3-octylimidazolium, ethyldimethyl(2-methoxyethyl)ammonium, tributylmethylammonium, tricyclohexyltetradecylphosphonium. In certain such embodiments, [Y] _n ^is selected from bis(trifluoromethylsulfonyl)imide, dicyanamide, ethyl sulfate, methylphosphonate, methylsulfate, octyl sulfate, tetracyanoborate, tetrafluoroborate, tricyanomethide, trifluoromethanesulfonate, and tris(pentafluoroethyl)trifluorophosphate.

In certain embodiments that are consistent with the description of the invention in other respects herein, the at least one ionic liquid is selected from 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-butyl-1-trifluoromethanesulfonate methylpyrrolidinium, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tricyanomethide, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium tetrafluoroborate, ethyl sulfate 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium methylphosphonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium tetracyanoborate, tris( 1-butyl-1-methylpyrrolidinium pentafluoroethyl)trifluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium tricyanomethide, 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-ethyl tetracyanoborate -3-methylimidazolium, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, 1-methyl-3-octylimidazolium trifluoromethanesulfonate, ethyldimethyl(2-methoxyethyl)ammonium tris(pentafluoroethyl)trifluorophosphate, tributylmethylammonium dicyanamide, tris(pentafluoroethyl)trifluorophosphate tricyclohex yltetradecylphosphonium and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

As will be appreciated by those skilled in the art, other components may be present in a catalyst composition that is otherwise described herein. However, in certain embodiments that are consistent with the invention described elsewhere herein, the total amount of porous support, palladium, promoters, and ionic liquid is at least 90% by weight or at least 92.5 % (wt.) or at least 95% (wt.) or at least 97.5% (wt.) or at least 98% (wt.) or at least 99 % (wt.) or at least 99.5% (wt.) or at least 99.9% (wt.) of the catalyst composition.

As will be appreciated by those skilled in the relevant art, a catalyst composition which otherwise complies with the description of the invention herein can be prepared using conventional methods, for example, by performing one or more impregnation steps including impregnation (e.g. using a method of achieving initial wetting or a method of over-soaking) a porous support with an impregnating solution containing one or more ionic liquids or palladium and optionally a promoter (for example, silver), each impregnation step being followed by a drying or calcination step.

In certain embodiments of the production of catalyst compositions described herein, the ionic liquid or mixtures of multiple ionic liquids are dissolved or suspended in a solubilizing agent suitable for use for the purpose, such as, for example, water, alcohols, acetone, and the like, or in a mixture of dissolving agents and is continuously applied to the pre-prepared catalyst inside the reaction chamber using a nozzle. To do this, the dissolving agent is continuously removed from the reaction chamber throughout the process. In order to achieve uniform coating of the substrate, the substrate material is continuously fluidized using process gas in a process known as fluidized bed coating. In addition, suitable coating processes for use are dip coating or spray coating using a paint spray gun or a paint spray dry gun.

Leaving aside the application of ionic liquid using coating technologies, the same can also be accomplished by solution or slurry impregnation. To do this, an ionic liquid or a mixture of several ionic liquids is dissolved or suspended in a suitable solubilizing agent (mixture) and subsequently contacted with a preformed catalyst. The dissolving agent is then removed under vacuum or at elevated temperature (or both) by exposing the system to air or using a gas stream. The amount of solvent agent used may be equal to or less than or greater than the pore volume of the catalyst used.

The amount of ionic liquid used in certain desirable embodiments is equal to or less than the pore volume of the catalyst used. After application of the ionic liquid, the system is left with an externally dry solid coated with the desired amount of ionic liquid. The pore volume of the resulting catalyst composition is reduced by the volume of the ionic liquid. Relative to the total mass of the catalyst, 0.1 - 10% (wt), preferably 0.2 - 6% (wt), and especially preferably 0.3 - 4% (wt) of the ionic liquid are used. The distribution of the ionic liquid on the macroscopic form of the substrate in the form of a solid, granulate or powder can be freely controlled by choosing the coating conditions. Depending on the choice of conditions on the substrate, the result may be the formation of so-called eggshell, egg white, egg yolk or uniform distribution for ionic liquid. In addition, any concentration gradient for the ionic liquid can be created on the substrate. The ionic liquid is preferably applied to the surface of the substrate in the form of a thin shell. The thickness of the ionic liquid shell on the support surface of the catalysts described herein is typically in the range of 10 to 2000 microns, preferably in the range of 100 to 1000 microns, and particularly preferably in the range of 100 to 800 microns.

The resulting catalyst can be used without imposing restrictions on the target reaction. The reduction of the metal particles required to activate the catalyst can occur either before or after the ionic liquid coating.

The catalyst, for example, can be reduced before or after the addition of an ionic liquid or mixture of ionic liquids. Those skilled in the art will know the methods used for reduction, which may include, for example, wet chemical methods using a reducing agent such as, for example, NaBH ₄ , LiAlH ₄ , hydrazine (hydrazine hydrate), hypophosphite, formic acid or its salts (formates). In addition, reduction can be promoted in the gas phase by using hydrogen (pure hydrogen or a mixture containing hydrogen; preferably the hydrogen concentration is greater than 1 mol% in N ₂ or other inert gases) within the temperature range 20 – 200°C, preferably 50 – 150°C.

The reduced metal particles obtained in this manner generally have a diameter within the range of 1 to 60 nm, preferably within the range of 1 to 30 nm, and particularly preferably within the range of 2 to 20 nm.

Likewise, the hydrogenation catalyst may be regenerated after placing an ionic liquid thereon, for example while in a bed in a reactor, by contacting it with a hydrogen-containing gas as described above. For example, the ionic liquid may be impregnated onto the catalyst in a process where the catalyst is synthesized, and the catalyst may then be transported and stored at the site while reduction is carried out in the catalyst bed in an acetylene reduction reactor.

However, in other embodiments, the hydrogenation catalyst is not pre-reduced prior to contact with the process gas.

It may be advantageous to dry the catalyst prior to use to reduce the amount of any adsorbed water. Drying can be carried out using a dry inert gas (for example, nitrogen, hydrogen, residual methane, ethane) at a temperature (for example, at least 50 °C, for example in the range of 50 - 100 °C) and for a period of time a period of time (eg, ranging from five hours to two days) until the temperature of the drying gas effluent stream drops below the desired dew point temperature, eg, less than -60°C.

After any hydrogenation and drying steps, it is desirable to reduce the temperature of the catalyst to the first temperature to start the flow of reaction gas. As determined by the inventors of the present invention, the catalysts described herein, due to their high acetylene selectivity (and thus relatively low ethylene reduction rate), can be run at a relatively elevated temperature. Startup for conventional catalysts (like Catalyst C of the Examples) was typically carried out at a low temperature of 30° C. or less. Namely, as determined by the inventors of the present invention, the catalysts described herein can be first contacted with the process gas at higher temperatures, for example, in the range of 31 - 50°C. In certain embodiments, the catalysts described herein may first be contacted with a process gas at a temperature in the range of 31 to 45°C or 31 to 40°C. In other such embodiments, the catalysts described herein may be first contacted with a process gas at a temperature in the range of 35 - 50°C, for example, 35 - 45°C or 35 - 40°C. And in other such embodiments, the catalysts described herein may first be contacted with a process gas at a temperature in the range of 40 - 50°C, for example, 40 - 45°C, 31 - 40°C, or in the range of 35 - 40°C.

Certain catalysts suitable for use in the methods described herein are described in US Patent Application Publication No. 2013/0102819, which is hereby incorporated by reference in its entirety.

In various aspects and embodiments, methods that fall within the description of the invention in other respects herein can be carried out in a selective hydrogenation reactor containing a catalyst bed or sequence of catalyst layers containing a catalyst composition (e.g., a catalyst composition that is consistent with the description of the invention otherwise herein) capable of selectively hydrogenating acetylene.

In yet another aspect, as determined by the inventors of the present invention, upstream selective hydrogenation reactors can be run without many of the undesirable aspects of conventional processes (e.g., long periods of time for flaring process gas, precharging CO into the catalyst, or adding CO to the process stream throughout startup) even in the presence of a “fresh” catalyst composition (eg, freshly installed or regenerated in the reactor, reduced or unreduced, and yet not yet exposed to the process gas). As will be appreciated by those skilled in the art, such a startup process can desirably reduce material costs, reduce reactor downtime, and reduce reactor effluent waste (i.e., product exiting the reactor before the reactor will be in full operating mode).

Accordingly, another aspect of the disclosure of the invention is a method of operating a reactor for hydrogenation, wherein the reactor contains one or more catalyst beds, each of them containing a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing at least at least 10 mol% ethylene, at least 1 ppm. acetylene and at least 5 mol% hydrogen (eg, and at least 10 ppm CO). The method includes preparing each catalyst layer at no more than a first temperature, wherein the catalyst layer of the catalyst is in contact with a first gas, wherein the first gas is unreactive in the presence of the catalyst at the first temperature. In the presence of the first gas, each catalyst bed is heated in the catalyst bed to at least a second temperature, wherein the second temperature is at least 10 degrees higher (e.g., at least 20 degrees higher, 30 degrees greater, at least 40 degrees greater, at least 50 degrees greater, or even at least 60 degrees greater) than the first temperature, the first gas being non-reactive in the presence of the catalyst at the second temperature . The composition of the gas in contact with the catalyst in each layer changes from the first gas to the process gas flow while the catalyst layer is at at least a second temperature. The process gas is allowed to flow through each catalyst bed until an acetylene concentration at the reactor outlet (i.e., the corresponding outlet that functions as the outlet for the reacted process gas) is less than 1 ppm. (eg, less than 0.5 ppm). Thus, the temperature of the catalyst bed can be increased while it is in contact with the first gas so that the process gas does not need to be vented to a flare while the catalyst beds are reaching temperature. In certain embodiments, the acetylene concentration at the reactor outlet is no more than 1 ppm. for 6 hours, for example, for 5 hours, for 4 hours, for 3 hours, or even for two hours, introducing the process gas into one or more catalyst beds. The catalyst materials described herein may allow the introduction of process gas when the catalyst bed(s) are at an elevated temperature and thereby reduce the amount of process gas flowing through the catalyst bed(s) during startup.

In yet another aspect (in combination with the aspect described above or separately), the disclosure of the invention provides a method of running a selective hydrogenation reactor without pretreating the catalyst using CO and without adding CO to the process gas. For example, in one embodiment, a method of operating a selective hydrogenation reactor as described above includes providing the reactor with each catalyst bed characterized by its catalyst being in contact with a first gas, wherein the first gas is unreactive in the presence of the catalyst at a first temperature where the catalyst is at the reactor was not brought into contact with a gas containing carbon monoxide having a carbon monoxide concentration greater than 100 ppm. After this, a flow of process gas is introduced into one or more catalyst layers. The critical point is to avoid adding carbon monoxide to the process gas. Accordingly, the method is carried out without adding significant amounts of CO to the process (ie, as a result of pre-treatment or as a result of addition to the process gas). As determined by the inventors of the present invention, the use of the catalysts described herein can provide the ability to start in the absence of carbon monoxide, which can represent significant improvements in terms of safety, process complexity and production costs. In certain embodiments, such processes also include increasing the temperature of the catalyst bed for each catalyst layer from no more than a first temperature to at least a second temperature. The temperature(s) of the catalyst bed may be increased before or after introduction of the process gas. In other embodiments, the process gas is introduced while simultaneously increasing the temperature(s) of the catalyst bed. Once the temperature is increased, the process gas can flow through one or more catalyst beds until the reactor effluent reaches a level of less than 1 ppm. acetylene (eg, less than 0.5 ppm acetylene).

The first temperature may, for example, be the reactor startup temperature, for example, the temperature of the reactor system when it is not in operation. In certain embodiments, the first temperature is no more than 50°C, for example, in the range of 31 - 50° C or 35 – 50°C or 40 – 50°C or 45 – 50°C. In certain embodiments, the first temperature is no more than 45°C, for example, in the range of 31 - 45°C or 35 - 45°C or 40 - 45°C. In certain embodiments, the first temperature is no more than 40°C, for example, in the range of 31 - 40°C or 35 - 40°C. But in other embodiments, the first temperature is even lower, for example, no more than 30°C or even in some embodiments, no more than 25°C.

The second temperature may, for example, be the operating temperature of the reactor, for example, the temperature at which the reactor effluent (for the particular process gas and other conditions used) has an acetylene concentration of no more than 1 ppm. (eg, no more than 0.5 ppm). Thus, the second temperature may be the temperature of the hydrogenation reaction, which corresponds to the above description of the invention. In certain embodiments, the second temperature is within the range of 40°C to 140°C. In certain desirable embodiments, the second temperature is within the range of 40°C to 100°C, such as 40°C to 90°C or 50°C to 90°C. But other second temperatures are also possible. In some embodiments, the second temperature is within the range of 20°C to 130°C, for example, in the range of 20°C to 120°C or 20°C to 110°C or 20°C to 100°C or from 20°C to 90°C. In some embodiments, the second temperature is within the range of 40°C to 140°C, such as 40°C to 130°C, or 40°C to 120°C, or 40°C to 110°C. In some embodiments, the second temperature is within the range of 50°C to 140°C, such as 50°C to 130°C, or 50°C to 120°C, or 50°C to 110°C. In some embodiments, the second temperature is within the range of 60°C to 140°C, such as 60°C to 130°C or 60°C to 120°C or 60°C to 110°C or 60 °C to 100°C or from 60°C to 90°C. The methods described herein can be used when there are significant differences between the first temperature and the second temperature, for example, being at least 30°C, at least 40°C, at least 50°C, or even , at least 60°C.

Increasing the temperature from no more than the first temperature to at least the second temperature can advantageously be carried out relatively quickly. For example, in certain embodiments that are consistent with the invention described elsewhere herein, the temperature of each catalyst layer is increased from no more than a first temperature to at least a second temperature over a period of time of no more than 10 hours , for example, no more than six hours, for example, being in the range of 2 - 10 hours, 4 - 10 hours or 3 - 6 hours. The rate of temperature change may, for example, be in the range of 3 – 15°C/hour, for example, in the range of 3 – 12°C/hour or 6 – 15°C/hour or 6 – 12°C/hour.

In accordance with the above description of the invention, the process gas includes ethylene, acetylene and hydrogen. The process gas may contain certain amounts of these materials and any other components that otherwise fall within the description of the invention in any embodiment herein. In certain embodiments, the process gas includes at least 10 ppm. CO.

The first gas is non-reactive in accordance with the above description of the invention. In certain embodiments, the first gas includes no more than 1 ppm. acetylene (eg, no more than 0.5 ppm). A wide range of substances can be used as the first gas, individually or in mixtures. The first gas is non-reactive on the catalyst bed at the first temperature and the second temperature. Accordingly, the first gas in certain embodiments includes small amounts (or does not include) hydrogen and/or small amounts (or does not include) a recoverable hydrocarbon. In certain embodiments, the first gas includes less than 2% hydrogen, such as less than 1% hydrogen. Gases like nitrogen and fuel gas can be used.

In the various methods described above, each catalyst layer changes from being in contact with a first gas to being in contact with a process gas. The first gas in the reactor may be present at a relatively lower pressure than the process gas source such that by admitting the process gas into the reactor without opening the reactor outlet, it can be mixed with the first gas to obtain the full reaction pressure. Desirably, the pressure difference is small enough such that the process gas is substantially diluted when first admitted to the reactor. For example, in one example of one embodiment ^, the first reactor gas pressure may be in the range of 200 - 300 psi (1379 - 2068 kPa), while the process gas pressure may be in the range of 400 - ⁵⁰⁰ psi ( 2758 – 3447 kPa). Immediately after the first gas and process gas are mixed in the reactor, a gas flow may be established to allow gas to leak out of the reactor. It goes without saying that, as will be appreciated by those skilled in the art, the specific manner in which process gas is introduced into the reactor will depend on the reactor structure and process.

In certain desirable embodiments, which are consistent with the invention described elsewhere herein, the process gas itself can be used to increase the reactor pressure to the reactor pressure at which the selective hydrogenation process is carried out. That is, in certain embodiments there is no need to pre-pressure when using an inert gas up to the process pressure. More precisely, process gas can be used to increase the pressure in the reactor up to the process pressure. Advantageously, the high selectivity of the catalysts described herein makes it possible to obtain initial reactor pressure using process gas with a much reduced risk of thermal runaway.

As determined by the inventors of the present invention, the catalysts described herein can be brought up to process temperature more quickly than prior catalysts as a result of their high selectivity for acetylene hydrogenation. Accordingly, another aspect of the disclosure of the invention is a method of operating a selective hydrogenation reactor, wherein the reactor contains one or more catalyst beds, each of them containing a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing, at least 10 mol% ethylene, at least 1 ppm. acetylene and at least 5 mol% hydrogen, the method comprising preparing each catalyst layer at no more than a first temperature, the catalyst of the catalyst layer being in contact with a gas; in the presence of process gas, heating each catalyst layer to at least a second temperature, wherein the second temperature is at least 20 degrees greater than the first temperature, and heating each catalyst layer is carried out at a rate in the range of at least 3°C/hour; and allowing process gas to flow through the catalyst bed until an acetylene concentration at the reactor outlet is less than 1 ppm. In certain embodiments, the rate is in the range of 3 - 20°C/hour, for example, 3 - 15°C/hour or 3 - 12°C/hour. In certain embodiments, the rate is in the range of 6 - 20°C/hour, for example, 6 - 15°C/hour or 6 - 12°C/hour. In certain embodiments, the rate is in the range of 9 - 20°C/hour, for example, 9 - 15°C/hour.

The catalysts described above with respect to hydrogenation methods may be suitable for use in the starting methods described herein.

As is typically the case, the methods described herein may further include, prior to introducing the process gas into the bed or contacting the catalyst composition with the process gas, reducing the catalyst (eg, using a stream of hydrogen-containing gas).

Another aspect of the invention is a hydrogenation catalyst composition comprising: a porous support present in the composition in an amount ranging from 90% by weight to 99.9% by weight; palladium present in the composition in an amount within the range of 0.02% (wt) to 0.5% (wt) (for example, from 0.04% (wt) to 0.15% (wt)) in terms of the mass of the element; and one or more ionic liquids present in the composition in a combined amount of up to 10% by weight. In certain embodiments, the catalyst composition further includes at least one promoter (e.g., silver) present in the composition in an amount ranging from 0.05% by weight to 0.25% by weight. , for example, from 0.08% (wt.) to 0.25% (wt.) or from 0.1% (wt.) to 0.25% (wt.) based on the weight of the element.

The amount of palladium in the catalyst composition may be, for example, within the range of 0.05% (wt.) to 0.2% (wt.) or from 0.05% (wt.) to 0.15% (wt.) or from 0.07% (wt.) to 0.2% (wt.) or from 0.07% (wt.) to 0.15% (wt.) or 0.08% (wt.) to 0, 2% (wt.) or from 0.08% (wt.) to 0.15% (wt.) or 0.1% (wt.) to 0.2% (wt.) or from 0.1% ( wt.) to 0.15% (wt.) or 0.11% (wt.) to 0.2% (wt.) or from 0.11% (wt.) to 0.15% (wt.). As determined by the inventors of the present invention, a catalyst characterized by relatively large amounts of palladium, when suitable for use, can provide high conversion and high selectivity without causing runaway behavior.

Another aspect of the invention is a hydrogenation catalyst composition comprising a porous support present in the composition in an amount ranging from 90% by weight to 99.9% by weight; palladium present in the composition in an amount of at least 0.02% (wt.), (for example, ranging from 0.04% (wt.) to 0.15% (wt.)) calculated on the mass of the element; and one or more ionic liquids present in the composition in a combined amount of up to 10% by weight. In certain embodiments, the catalyst composition further includes at least one promoter (e.g., silver) present in the composition in an amount ranging from 0.05% by weight to 0.25% by weight. , for example, from 0.08% (wt.) to 0.25% (wt.) or from 0.1% (wt.) to 0.25% (wt.) based on the weight of the element. In this aspect, the carrier has a BET surface area of no more than 10 m ² /g and a pore volume of at least 0.1 ml/g. The surface area and pore volume of the support determined using the BET method may otherwise correspond to the above description of the invention.

Another aspect of the invention is a hydrogenation catalyst composition comprising: a porous support present in the composition in an amount ranging from 0.90% by weight to 99.9% by weight; palladium present in the composition in an amount within the range of at least 0.02% (wt.) based on the weight of the element; and one or more ionic liquids present in the composition in a combined amount of up to 10% by weight, wherein the hydrogenation catalyst has a BET-determined surface area of not more than 10 m ² /g and a pore volume , constituting at least 0.05 ml/g. As determined by the inventors of the present invention, impregnation with a relatively small amount of ionic liquid can maintain a significant pore volume in the catalyst, that is, such that the pores accessible using the mercury porosimetry method are not completely filled.

In certain such embodiments, the hydrogenation catalyst composition contains palladium in an amount of at least 0.03 wt% or at least 0.04 wt% or at least 0.05 % (wt.) or at least 0.06% (wt.) or at least 0.07% (wt.) or at least 0.08% (wt.) or, according to at least 0.09% (wt.) or at least 0.1% (wt.) or at least 0.11% (wt.) or at least 0.12% ( wt.) or at least 0.13% (wt.) or at least 0.14% (wt.) or at least 0.15% (wt.). In certain such embodiments, the hydrogenation catalyst composition contains palladium in an amount of no more than 0.5% by weight (e.g., no more than 0.4% by weight or no more than 0.3% (wt.) or not more than 0.2% (wt.)). For example, various embodiments include palladium in an amount ranging from 0.02 wt% to 0.5 wt%, or 0.02 wt% to 0.45 wt%, or from 0.03% (wt.) to 0.4% (wt.) or from 0.03% (wt.) to 0.35% (wt.) or from 0.04% (wt.) to 0, 3% (wt.) or from 0.04% (wt.) to 0.25% (wt.).

Such hydrogenation catalysts may advantageously include a promoter which is as otherwise described herein.

In certain desirable embodiments, such hydrogenation catalysts have a BET surface area within the range of 2 m ² /g to 10 m ² /g, for example, within the range of 2 m ² /g to 9 m ² /g or from 2 m ² /g to 8 m ² /g or from 2 m ² /g to 7 m ² /g or from 2 m ² /g to 6 m ² /g or from 2 m ² /g to 5 m ² / g or from 3 m ² /g to 10 m ² /g or from 4 m ² /g to 10 m ² /g or from 5 m ² /g to 10 m ² /g or from 6 m ² /g to 10 m ² /g or from 2 m ² /g to 6 m ² /g or from 3 m ² /g to 7 m ² /g or from 4 m ² /g to 8 m ² /g or from 5 m ² /g to 9 m ² /g.

In certain desirable embodiments, such hydrogenation catalysts have a pore volume in the range of 0.05 ml/g to 1.0 ml/g, for example, 0.05 ml/g to 0.4 ml/g. In certain such embodiments, the hydrogenation catalyst has a pore volume in the range of 0.10 ml/g to 1.0 ml/g, for example, 0.10 ml/g to 0.80 ml/g, or 0.10 to 0 .60 ml/g or from 0.10 to 0.40 ml/g or from 0.10 to 0.30 ml/g or in the range from 0.20 ml/g to 1.0 ml/g, e.g. 0.20 ml/g to 0.80 ml/g or from 0.20 to 0.60 ml/g or from 0.20 to 0.40 ml/g or from 0.20 to 0.35 ml/g or in the range of 0.40 ml/g to 1.0 ml/g, for example 0.40 ml/g to 0.80 ml/g or 0.40 to 0.60 ml/g.

Desirably, the catalysts of the invention include an amount of ionic liquid that does not completely fill the pore volume of the support. For example, in certain embodiments that are consistent with the invention described elsewhere herein, the difference between the pore volume of the support and the pore volume of the catalyst (i.e., including palladium, any promoters, and ionic liquid) is in the range of 10 - 90% of carrier pore volume. In certain such embodiments, this difference is in the range of 20 - 90% of the pore volume of the carrier, for example, 30 - 90% or 40 - 90%. In certain such embodiments, this difference is in the range of 10 - 80% of the pore volume of the carrier, for example, 20 - 80% or 30 - 80% or 40 - 80%. In certain such embodiments, this difference is in the range of 10-70% of the pore volume of the carrier, for example, 20-70% or 30-70% or 40-70%. In certain such embodiments, this difference is in the range of 10 - 60% of the pore volume of the carrier, for example, 20 - 60% or 30 - 60% or 40 - 60%.

The catalysts of the invention may include a wide range of amounts of ionic liquid. For example, in certain embodiments that are consistent with the invention described elsewhere herein, the ionic liquid is present in an amount ranging from 0.1% by weight to 10% by weight, for example, from 0.1% ( wt.) to 8% (wt.) or from 0.1% (wt.) to 6% (wt.) or from 0.1% (wt.) to 4% (wt.) or from 0.1% (wt.) to 3% (wt.) or from 0.1% (wt.) to 2% (wt.) or from 0.1% (wt.) to 1% (wt.), for example, from 0 .2 to 3% (wt.) or 0.5 – 4% (wt.).

Catalysts consistent with these aspects of the disclosure may otherwise be consistent with the above description of the invention with respect to catalysts suitable for use in the methods of the disclosure. In addition, catalysts consistent with this aspect of the disclosure can be used in any of the methods that correspond to the description of the invention in other respects herein.

The processes and materials described herein may be particularly suitable for use in upstream applications. However, as will be appreciated by those skilled in the relevant applications, they can be used in a wide range of other applications, particularly in relevant applications in which the risk of runaway (eg due to high hydrogen concentrations) is problematic.

EXAMPLES

The examples that follow are illustrative of specific embodiments of the invention and various uses thereof. They are presented for purposes of explanation only and should not be construed as limiting the invention.

Example 1. Preparation of a selective hydrogenation catalyst

A porous carrier based on alpha-alumina (4 mm tablets), characterized by a surface area of 5 ± 2 m ² /g determined using the BET method, was impregnated with aqueous solutions of a silver salt and a palladium salt and calcined at a minimum of 260°C in air in for 2 hours. The level of silver in the aqueous silver salt solution and the level of palladium in the palladium salt solution were adjusted to produce a final calcined impregnated support containing 0.050 ± 0.005 wt% palladium and 0.070 ± 0.005 wt% silver. Palladium was localized within the outer layer of 500 μm of the porous support. The pore volume of the metal impregnated carrier was 0.26 ml/g.

The calcined impregnated support was further impregnated with an aqueous solution containing approximately 0.5 wt% ionic liquid (IL) on the dry impregnated support. The resulting material was dried at up to 150°C for 2 hours to obtain catalyst A1. The catalyst had a pore volume of 0.23 ml/g.

Catalyst A2 was prepared in a manner similar to that of catalyst A1. Comparative catalyst C was also obtained, which does not contain IL and is characterized by a level of Pd introduction that is even lower than the corresponding characteristic for catalysts A1 and A2.

Table 1. Catalyst compositions

No. Pd (% (mass)) Ag (% (wt.)) IL (% (wt.)) A1 0.05 0.07 0.5 A2 0.08 0.11 0.5 C 0.02 0.05 0.0

Example 2 Selective hydrogenation

The catalysts prepared in accordance with Example 1 were placed in a 15 ml catalyst bed in a reactor tube. The catalyst was reduced in a stream of hydrogen at an hourly gas space velocity of >500 h ^{– 1} and 94°C for one hour before introducing the gaseous mixture of the feedstock into the reactor. A gaseous mixture containing 200 ppm was passed over the catalyst layer. CO, 19% (mol.) H ₂ , 0.35% (mol.) C ₂ H ₂ , 30% (mol.) C ₂ H ₄ , 45% (mol.) CH ₄ and diluting nitrogen, at CHOSG 7000 hour ^{- 1 and} a total pressure of 500 psig (3447 kPa (g)). The catalyst bed was heated using a water bath at intervals ranging from 2 to 5°C, starting at 40°C. The acetylene and ethane concentrations were monitored at the reactor outlet and are demonstrated in Figure 1. As demonstrated in Figure 1, the temperature at which the acetylene concentration at the reactor outlet decreases to 25 ppm (ie, the activity indicator; _T1 ) is similar for catalysts A1 and C, but the operating range for catalyst A1 (i.e., the difference between the runaway temperature _T2 (the temperature at which the ethane concentration at the reactor outlet reaches 2% (mol)) and T ₁ ) is significantly greater than the corresponding characteristic for catalyst C, respectively, 71 °C compared to 21 °C.

Example 3. CO level drop test

The catalysts prepared in accordance with Example 1 were placed in a 15 ml catalyst bed in a reactor tube. The catalyst was reduced in a stream of hydrogen at an hourly gas space velocity of >500 h ^{– 1} and 94°C for one hour before introducing the gaseous mixture of the feedstock into the reactor. A gaseous mixture containing 200 ppm was passed over the catalyst layer. CO, 0.5% (mol.) C ₂ H ₂ , 19% (mol.) H ₂ , 26% (mol.) C ₂ H ₄ , 40% (mol.) CH ₄ and diluting nitrogen, at CHOSG 7000 hour ^{– 1} . The catalyst bed was heated to a temperature sufficient to produce acetylene concentrations in the range of 20 to 30 ppm at the reactor outlet. Ethylene selectivity for the process was continuously monitored at the reactor outlet and is demonstrated in Figure 2.

At 25 and 45 hours in operation, the CO concentration in the gaseous mixture was briefly reduced to 60 ppm. without reducing the temperature of the reactor bed. At 285 hours of operation, the CO concentration in the gaseous mixture was increased to 340 ppm, and the reactor bed temperature was adjusted to obtain 95% acetylene conversion. Subsequently, the CO concentration was reduced to 60 ppm and then increased to 200 ppm. At 308 hours in operation mode, the cycle implemented at 285 hours in operation mode was repeated. As demonstrated by the results shown in Figure 2, the recovery of ethylene selectivity for catalyst A1 after variations in CO concentration is significantly better than the corresponding performance for catalyst C. In addition, as demonstrated by the results, the selectivity for catalyst A1 remains greater than the corresponding performance for catalyst C at both high and low CO concentrations.

Example 4 Selective Hydrogenation

The catalysts prepared in accordance with Example 1 were placed in a 15 ml catalyst bed in a reactor tube. The catalyst was reduced in a stream of hydrogen at an hourly gas space velocity of >500 h ^{– 1} and 94°C for one hour before introducing the gaseous mixture of the feedstock into the reactor. A gaseous mixture containing 350 ppm was passed over the catalyst bed. CO, 17% (mol.) H ₂ , 0.69% (mol.) C ₂ H ₂ , 47% (mol.) C ₂ H ₄ , 11% (mol.) CH ₄ , 4% (mol.) propylene, 0.098 ppm propadiene, 0.13 ppm methyl acetylene and 130 ppm. 1,3-butadiene, at either 4500 h ^–1 or ^13,000 h ^–1 hOSG and 500 psig (3447 kPa(g)) total pressure. The catalyst bed was heated using a water bath at 5°C intervals. Acetylene conversion and ethylene selectivity were continuously monitored at the reactor outlet and are shown in Figure 3. Namely, the associated temperature increase required to maintain the desired acetylene conversion at 13,000 h ^-1 vs. 4,500 h ^-1 OSH. is in the range of 10 – 12 °C for catalyst C, but only in the range of 8 – 10 °C for catalyst A1. In addition, at 13,000 h ^–1 , the ethylene selectivity of catalyst A1 remained greater than 95% with an acetylene conversion rate of as much as 95%, and the ethylene selectivity of catalyst A1 remained greater than 50% while maintaining an acetylene conversion rate of more than 99%.

Example 5 Selective Hydrogenation

The catalysts prepared in accordance with Example 1 were placed in a 15 ml catalyst bed in a reactor tube. The catalyst was reduced in a stream of hydrogen at an hourly gas space velocity of >500 h ^{- 1} and 94 °C for one hour before introducing the gaseous mixture of the feedstock into the reactor. A gaseous mixture containing 200 ppm was passed over the catalyst layer. CO, 19% (mol.) H ₂ , 0.35% (mol.) C ₂ H ₂ , 30% (mol.) C ₂ H ₄ , 45% (mol.) CH ₄ and diluting nitrogen, with HOSG or 7000 h ^{- 1} or 28,000 h ^{- 1} and a total pressure of ⁵⁰⁰ psig (3447 kPa (g)). The catalyst bed was heated using a water bath at intervals ranging from 2 to 5 °C, starting at 40 °C. Acetylene conversion and ethylene selectivity were continuously monitored at the reactor outlet and are shown in Figure 4. Specifically, the ethylene selectivity for catalyst A2 at 28,000 h ⁻¹ was similar to that for catalyst C at only 7,000 h ⁻¹ , i.e. , the operational productivity was approximately 4 times greater for catalyst A2.

Example 6. Starting the reactor without pre-treatment using CO

Commercial selective hydrogenation units typically require upstream processing of the catalyst bed to pre-treat the catalyst bed with CO at start-up, which prevents reactor temperature runaways when process gas is first introduced into the reactor due to non-selective hydrogenation of ethylene to ethane.

A sequence of start-up tests using catalyst A1 without CO gas pretreatment was performed in a laboratory scale test facility and compared to a base case involving catalyst pretreatment using CO gas. The tests were carried out at CHOSG values of 7000 h ^{– 1} .

The comparative start-up process in the laboratory scale trial included recovery using H ₂ at 94°C for 1 hour followed by a purge as part of the pre-treatment using CO before all gaseous feedstock was brought into operation. In this comparative test, 1% CO in CH ₄ gas was used to purge the system for 20 minutes at 30°C and to increase the reactor pressure to 35 bar, after which a gaseous feed containing 0. 02% CO, 20% _H2 , 3500 ppm. C ₂ H ₂ and 27% C ₂ H ₄ . The temperature of the water bath was maintained at 30°C while simultaneously monitoring the temperatures of the top and bottom of the catalyst bed throughout the test. The data is shown in Figure 5. The first temperature point occurred when the pressure began to increase using just CO/CH ₄ gas. The increase in pressure when using CO/CH ₄ occurred within 1 – 2 minutes. Initially, there was a short-term heat release in the range of 2 – 3°C for ~ 5 minutes. The introduction of gaseous feedstock at 30° C. and 35 bar did not result in significant heat generation. After 15 minutes of reaching stable catalyst bed temperatures, a gas sample was analyzed at the reactor outlet. The ethane concentration at the outlet was stable at 120 ppm, which was derived from the inlet feedstock.

Thereafter, the start-up test was repeated in substantially the same manner, but replacing the CO/CH ₄ pretreatment with the N ₂ pretreatment, followed by introducing the gaseous feedstock at atmospheric pressure and increasing the reactor pressure while using the gaseous feedstock. initial raw material at a consumption in the form of POSG 7000 hour - 1. The temperature of the water bath was maintained at 30°C, and the top and bottom temperatures were monitored throughout the test. It took ~10 minutes to reach the target pressure of 35 bar. The data is shown in Figure 6.

During the 10 minute pressurization period, heat generation ranging from 2 to 3°C was observed, and both top and bottom temperatures returned to less than 30°C after the gas flow stabilized at 35 bar when analyzing a gas sample at the outlet from a reactor demonstrating the presence of more than 2% ethane. This initial formation of ethane was due to the absence of any current from the reactor while the pressure was increased until the reactor reached 35 bar. As demonstrated by continuous analysis of the outlet sample, after the inlet and outlet currents were stabilized at 25 bar, the ethane level at the reactor outlet dropped to approximately 120 ppm, indicating that there was no sustained ethane production in the reactor .

Another start-up test was conducted, this time with the purge lowered using N ₂ between hydrogen reduction and feed gas injection. Instead, the catalyst was purged using a gaseous feed containing 0.02% CO, 20% _H2 , 3500 ppm. With ₂ H ₂ and 27% C ₂ H ₄ for 20 minutes until the pressure increases up to 35 bar using gaseous feedstock. This was done to simulate pre-startup gas recirculation under plant conditions. Temperature measurements began at the beginning of the pressure increase; The data is shown in Figure 7. During the 20 minutes of purging, no change in temperature was observed using the feedstock. The temperatures of both the top and bottom began to increase as the pressure increased, and the top temperature slightly exceeded the bottom temperature. Ethane production during this temperature spike was approximately 10%. Eventually, after 10 minutes, the temperatures returned to normal. Throughout the test, ethane production continued to decrease until stability was achieved at 120 ppm.

Finally, for catalyst C, a start-up procedure using a purge feed gas was used in accordance with the above description of the invention. Figure 8 shows the change in bed temperature of this catalyst and ethane production throughout the startup test. Temperature measurements began immediately after the introduction of the feedstock. The top temperature began to increase before the pressure increased, exceeding the bottom temperature at the beginning of the pressure increase. The top temperature dropped slightly after increasing the pressure and establishing a continuous gas flow, but after that it continued to increase until it stabilized at 36°C. The top temperature did not return to less than 30°C. Ethane production over this time period was stable at ~16%, indicating a stable uncontrolled thermal regime.

Thus, as demonstrated by the run-up experiments described above, catalysts incorporating ionic liquids can provide little risk of thermal runaway, even in the absence of CO pretreatment.

Example 7 Carbon Monoxide Insensitivity

A sensitivity study to carbon monoxide concentration was conducted under isothermal conditions. Namely, the selectivity for catalyst A1 was relatively insensitive to carbon monoxide concentrations, while the selectivity for catalyst C was much more sensitive to carbon monoxide concentrations. Under adiabatic conditions, increased heat generation resulting from increased hydrogenation of ethylene at lower CO concentrations further reduces selectivity, potentially leading to runaway exotherms. Namely, as these data demonstrate, the catalysts described herein can be used under a wide range of conditions, even at low CO concentrations.

The specific details demonstrated herein are presented by way of example only and for purposes of illustrative discussion of preferred embodiments of the present invention and are provided for the purpose of offering what appears to be the most suitable and readily understandable description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to demonstrate the structural details of the invention in more detail than is necessary for a fundamental understanding of the invention, and the description of the invention, taken in conjunction with the drawings and/or examples, will make it obvious to those skilled in the art. Several forms of the invention may be practiced. Thus, as should be understood prior to the description of the disclosed processes and devices, the aspects described herein are not to be limited by particular embodiments, apparatus or configurations, and it goes without saying that as such they may vary. As should also be understood, the terminology used herein is intended for purposes of describing specific aspects only and, unless specifically defined herein, is not intended to be limiting.

The terms “one”, “that”, “given” and similar references used in the context of the description of the invention (especially in the context of the following claims) are to be taken to cover both the singular and the plural if only this document will not indicate otherwise or be clearly inconsistent with the other based on context. The listing of value ranges in this document is intended simply to act as a shorthand way to individually refer to each individual value that falls within the range. Unless otherwise indicated herein, each distinct meaning is included in the specification as if it were individually mentioned herein. Ranges herein are expressed as from “about” one specific value and/or to “about” another specific value. In a representation expressing such a range, the other aspect includes an expression from one particular value and/or to another particular value. Likewise, when expressing values as approximations, using the preceding term "approximately", as should be clear, the specific meaning forms another aspect. As will further be understood, the endpoints of each of the ranges are meaningful both with respect to the other endpoint and independently of the other endpoint.

All methods described herein may be carried out in any suitable order of steps unless otherwise stated herein or otherwise is clearly inconsistent with the context. The use of any and all examples or exemplary language (eg, “such as”) provided herein is intended merely to better explain the invention and is not intended to limit the scope of the invention otherwise claimed. Nothing in the specification should be construed as indicating any unclaimed element essential to the practice of the invention.

Unless the context clearly requires otherwise, throughout the specification and claims, the words “comprise,” “comprising,” and the like are to be taken in an inclusive sense as opposed to an exclusive or exhaustive sense; in other words, in the sense of the phrase “including but not limited to the following.” Words using the singular or plural also include the plural and singular, respectively. In addition, the words “herein,” “above,” and “below,” and words of similar meaning, when used in this application, shall refer to this application as a whole and not to any specific portions of the application.

As will be appreciated by those skilled in the relevant art, each embodiment disclosed herein may include, consist essentially of, or consist of the following: its specific specified element, step, ingredient, or component. As used herein, the transitional terms “comprise” or “comprises” have the meaning “includes, but is not limited to, the following” and provide the possibility of including unspecified elements, steps, ingredients or components even in significant quantities. The transitional phrase "consisting of" excludes any element, step, ingredient or component not specified. The transitional phrase "consisting essentially of" limits the scope of the embodiment to the specified elements, steps, ingredients or components and their respective representatives that do not significantly affect the embodiment.

Unless otherwise indicated, all numbers expressing amounts of ingredients, properties such as molecular weight, reaction conditions, and the like, used in the specification and claims are to be understood in all cases as modified by the term “about.” Accordingly, unless otherwise stated, the numerical parameters set forth in the specification and the accompanying claims are approximations that may vary depending on the desired properties sought by the present invention. At the very least, and not as an attempt to limit the scope of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be considered in light of the number of significant numerical digits presented and using normal rounding techniques. Where there is a need for further clarity, the term "about" has the meaning reasonably assigned to it by those skilled in the art when used in connection with a stated numerical value or range, that is, when referring to a value that is slightly greater or less than that stated. within the normal ranges of uncertainty and imprecision of the relevant state of the art.

Although the numerical ranges and parameters representing the broad scope of the invention are approximations, the numerical values presented in the specific examples are given as accurately as possible. However, any numerical value by its very nature includes certain errors, necessarily resulting from the presence of standard deviation encountered in the measurements during their respective tests.

Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limiting. Each element of the group may be specified and claimed individually or in any combination with other elements of the group or other elements appearing herein. As is contemplated, one or more elements from a group may be included or excluded from the group for reasons of convenience and/or patentability. If any such inclusion or exclusion occurs, the specification is deemed to include the group that corresponds to the modification of the invention, thereby satisfying the written description of all Markush groups used in the appended claims.

This document describes certain embodiments of the present invention, including the best mode for carrying out the invention known to the inventors. It goes without saying that after reading the above description of the invention, variations with respect to these described embodiments should be obvious to those skilled in the relevant field of technology. It is expected by the inventor that those skilled in the art will make use of such variations in accordance with particular circumstances, and the inventors contemplate carrying out the invention in practice and in other ways compared to what is specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter set forth in the claims appended hereto that are permitted by applicable law. In addition, any combination of the elements described above in all their possible variations is covered by the invention, unless otherwise indicated or clearly inconsistent with the other based on the context.

In addition, throughout the presentation of this description of the invention, numerous references have been made to patents and printed publications. Each of the cited references and printed publications is individually incorporated herein in its entirety by reference.

Finally, as should be understood, the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. It is within the scope of the invention that other modifications may be used. Thus, by way of example, and not by way of limitation, in accordance with the provisions set forth herein, alternative configurations of the present invention may be used. Accordingly, the present invention is not limited by provisions that exactly correspond to what is demonstrated and described in the invention.

Additional embodiments of the disclosure are provided in the embodiments listed below, which may be combined in any number and in any manner that are logically and technically consistent.

Embodiment 1. A method for the selective hydrogenation of acetylene, the method comprising contacting a catalyst composition containing a porous support, palladium and at least one ionic liquid with a process gas containing

ethylene present in the process gas in an amount of at least 10% (mol.);

acetylene present in the process gas in an amount of at least 1 ppm;

hydrogen present in the process gas in an amount of at least 5% (mol.); And

from 0 ppm up to 190 ppm carbon monoxide;

wherein at least 90% of the acetylene present in the process gas is hydrogenated and no more than 1 mol% of the total amount of acetylene and ethylene present in the process gas is converted to ethane.

Embodiment 2. A method for the selective hydrogenation of acetylene, the method comprising contacting a catalyst composition containing a porous support, palladium and at least one ionic liquid with a process gas containing

ethylene present in the process gas in an amount of at least 10% (mol.);

acetylene present in the process gas in an amount of at least 1 ppm;

hydrogen present in the process gas in an amount of at least 5% (mol.); And,

at least 600 ppm carbon monoxide;

wherein at least 90% of the acetylene present in the process gas is hydrogenated and no more than 1 mol% of the total amount of acetylene and ethylene present in the process gas is converted into ethane.

Embodiment 3. The method corresponding to embodiment 1 or 2, where the process gas is brought into contact with the catalyst at an hourly gas space velocity (GSV) within the range of 2000 h ^{- 1} to 40,000 h ^{- 1} .

Embodiment 4: A method for selectively hydrogenating acetylene, the method comprising contacting a catalyst composition comprising a porous support, palladium and one or more ionic liquids with a process gas containing

ethylene present in the process gas in an amount of at least 10% (mol.);

acetylene present in the process gas in an amount of at least 1 ppm; And

hydrogen present in the process gas in an amount of at least 5% (mol.);

wherein the process gas is contacted with the catalyst at an hourly gas space velocity (GSV), based on the total catalyst bed volume (i.e., in a single bed or multiple beds), of at least 7100 h ^{- 1} (e.g., located in the range from 7500 hour ^{– 1} to 40000 hour ^{– 1} ); And

wherein at least 90% of the acetylene present in the process gas is hydrogenated and no more than 1 mol% of the total amount of acetylene and ethylene present in the process gas is converted to ethane.

Embodiment 5. The method according to claim 4, wherein carbon monoxide in the process gas is present in an amount up to 20,000 ppm, for example, up to 10,000 ppm. or up to 5000 ppm. or up to 2500 ppm. or up to 1200 ppm. or up to 1000 ppm.

Embodiment 6. A method according to claim 4, wherein carbon monoxide in the process gas is present in an amount up to 100 ppm. or up to 500 ppm. or up to 1000 ppm. or up to 5000 ppm. or in the range of 10 ppm. up to 5000 ppm or in the range of 10 ppm. up to 1200 ppm or in the range of 10 ppm. up to 500 ppm or in the range of 50 ppm. up to 5000 ppm or in the range of 50 ppm. up to 1200 ppm or in the range of 50 ppm. up to 500 ppm or in the range of 75 ppm. up to 1200 ppm or in the range of 75 ppm. up to 500 ppm

Embodiment 7. The method according to any of embodiments 1, 3 and 4, wherein the carbon monoxide in the process gas is present in an amount up to 190 ppm, for example, up to 175 ppm. or within the range of 1 ppm. up to 190 ppm or in the range of 5 ppm. up to 190 ppm or from 10 ppm up to 190 ppm or from 25 ppm up to 190 ppm or from 50 ppm up to 190 ppm or from 75 ppm up to 190 ppm or from 1 ppm up to 175 ppm or from 5 ppm up to 175 ppm or from 10 ppm up to 175 ppm or from 25 ppm up to 175 ppm or from 50 ppm up to 175 ppm or from 100 ppm up to 175 ppm

Embodiment 8. The method according to any of embodiments 1, 3 and 4, wherein carbon monoxide in the process gas is present in an amount up to 150 ppm, for example, up to 140 ppm, for example, within the range of 1 ppm. up to 150 ppm or from 5 ppm up to 150 ppm or from 10 ppm up to 150 ppm or from 25 ppm up to 150 ppm or from 50 ppm up to 150 ppm or from 75 ppm up to 150 ppm or from 1 ppm up to 140 ppm or from 5 ppm up to 140 ppm or from 10 ppm up to 140 ppm or from 25 ppm up to 140 ppm or from 50 ppm up to 140 ppm or from 75 ppm up to 140 ppm

Embodiment 9. The method according to any of embodiments 1, 3 and 4, wherein carbon monoxide in the process gas is present in an amount up to 125 ppm, for example, up to 115 ppm, for example, within the range of 1 ppm. up to 125 ppm or from 5 ppm up to 125 ppm or from 10 ppm up to 125 ppm or from 25 ppm up to 125 ppm or from 50 ppm up to 125 ppm or from 75 ppm up to 125 ppm or from 1 ppm up to 115 ppm or from 5 ppm up to 115 ppm or from 10 ppm up to 115 ppm or from 25 ppm up to 115 ppm or from 50 ppm up to 115 ppm or from 75 ppm up to 115 ppm

Embodiment 10. The method according to any of embodiments 1, 3 and 4, wherein carbon monoxide in the process gas is present in an amount up to 110 ppm, for example, up to 100 ppm, for example, within the range of 1 ppm. up to 110 ppm or from 5 ppm up to 110 ppm or from 10 ppm up to 110 ppm or from 25 ppm up to 110 ppm or from 50 ppm up to 110 ppm or from 75 ppm up to 110 ppm or from 1 ppm up to 100 ppm or from 5 ppm up to 100 ppm or from 10 ppm up to 100 ppm or from 25 ppm up to 100 ppm or from 50 ppm up to 100 ppm

Embodiment 11. The method according to any of embodiments 1, 3 and 4, wherein carbon monoxide in the process gas is present in an amount up to 95 ppm, for example, up to 90 ppm, for example, within the range of 1 ppm. up to 95 ppm or from 5 ppm up to 95 ppm or from 10 ppm up to 95 ppm or from 25 ppm up to 95 ppm or from 50 ppm up to 95 ppm or from 1 ppm up to 90 ppm or from 5 ppm up to 90 ppm or from 10 ppm up to 90 ppm or from 25 ppm up to 90 ppm or from 50 ppm up to 90 ppm

Embodiment 12. The method according to any of embodiments 1, 3 and 4, wherein carbon monoxide in the process gas is present in an amount up to 85 ppm, for example, up to 80 ppm, for example, within the range of 1 ppm. up to 85 ppm or from 5 ppm up to 85 ppm or from 10 ppm up to 85 ppm or from 25 ppm up to 85 ppm or from 50 ppm up to 85 ppm or from 1 ppm up to 80 ppm or from 5 ppm up to 80 ppm or from 10 ppm up to 80 ppm or from 25 ppm up to 80 ppm or from 50 ppm up to 80 ppm

Embodiment 13. A method according to any of embodiments 1 through 12, wherein carbon monoxide is not added to the gaseous feed stream to produce a process gas.

Embodiment 14. The method according to any of embodiments 2 to 4, wherein the carbon monoxide in the process gas is present in an amount within the range of 600 ppm. up to 20,000 ppm or from 600 ppm up to 15,000 ppm or from 600 ppm up to 12500 ppm or from 700 ppm up to 10,000 ppm or from 800 ppm up to 7500 ppm or from 900 ppm up to 5000 ppm or from 700 ppm up to 5000 ppm or from 800 ppm up to 5000 ppm

Embodiment 15. The method according to any of embodiments 2 to 4, wherein the carbon monoxide in the process gas is present in an amount ranging from 800 ppm. up to 20,000 ppm or from 800 ppm up to 15,000 ppm or from 800 ppm up to 10,000 ppm or from 800 ppm up to 5000 ppm or from 800 ppm up to 2500 ppm or from 800 ppm up to 1500 ppm

Embodiment 16. The method according to any of embodiments 2 to 4, wherein the carbon monoxide in the process gas is present in an amount ranging from 1000 ppm. up to 20,000 ppm or from 1000 ppm up to 15,000 ppm or from 1000 ppm up to 10,000 ppm or from 1000 ppm up to 5000 ppm or from 1000 ppm up to 2500 ppm

Embodiment 17. The method according to any of embodiments 2 to 4, wherein the carbon monoxide in the process gas is present in an amount within the range of 1500 ppm. up to 20,000 ppm or from 1500 ppm up to 15,000 ppm or from 1500 ppm up to 10,000 ppm or from 1500 ppm up to 5000 ppm

Embodiment 18. The method according to any of embodiments 2 to 4, wherein the carbon monoxide in the process gas is present in an amount within the range of 2000 ppm. up to 20,000 ppm or from 2000 ppm up to 15,000 ppm or from 2000 ppm up to 10,000 ppm or from 2000 ppm up to 5000 ppm

Embodiment 19. A method according to any one of embodiments 1, 2 and 4 to 18, wherein the process gas is contacted with the catalyst at a HOSG value of at least 7100 h ^-1 , for example, within the range of 7100 hour ^{– 1} to 40000 hour ^{– 1} or from 7100 hour ^{– 1} to 30000 hour ^{– 1} or from 7100 hour ^{– 1} to 20000 hour ^{– 1} .

Embodiment 20. A method according to any one of embodiments 1, 2 and 4 to 18, wherein the process gas is contacted with the catalyst at a HOC value of at least 7500 h ^-1 , for example, within the range of 7500 hour ^{– 1} to 40000 hour ^{– 1} or from 7500 hour ^{– 1} to 30000 hour ^{– 1} or from 7500 hour ^{– 1} to 20000 hour ^{– 1} .

Embodiment 21. A method according to any of Embodiments 1, 2 and 4 through 18, wherein the process gas is contacted with the catalyst at a HOSH value of at least 10,000 h ^-1 , for example, within the range of 10,000 hour ^{– 1} to 40000 hour ^{– 1} or from 10000 hour ^{– 1} to 30000 hour ^{– 1} or from 10000 hour ^{– 1} to 20000 hour ^{– 1} .

Embodiment 22. A method according to any one of embodiments 1, 2 and 4 through 18, wherein the process gas is contacted with the catalyst at a HOSG value of at least 12,500 h ^-1 , for example, within the range of 12,500 hour ^{– 1} to 40000 hour ^{– 1} or from 12500 hour ^{– 1} to 30000 hour ^{– 1} or from 12500 hour ^{– 1} to 20000 hour ^{– 1} .

Embodiment 23. A method according to any one of embodiments 1, 2 and 4 to 18, wherein the process gas is contacted with the catalyst at a HOSH value of at least 15,000 h ^-1 , for example, within the range of 15,000 hour ^{– 1} to 40000 hour ^{– 1} or from 15000 hour ^{– 1} to 30000 hour ^{– 1} or from 15000 hour ^{– 1} to 20000 hour ^{– 1} .

Embodiment 24. A method according to any one of embodiments 1, 2 and 4 to 18, wherein the process gas is contacted with the catalyst at a HOSH value of at least 20,000 h ^-1 , for example, within the range of 20,000 hour ^{– 1} to 40000 hour ^{– 1} or from 20000 hour ^{– 1} to 30000 hour ^{– 1} .

Embodiment 25. The method according to any of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 20°C to 140°C.

Embodiment 26. The method according to any of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 40°C to 100°C.

Embodiment 27. The method according to any of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 40°C to 90°C.

Embodiment 28. The method according to any of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 50°C to 90°C.

Embodiment 29. The method according to any of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 50°C to 100°C.

Embodiment 30. The method according to any of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 20°C to 130°C, for example, in the range of 20°C to 120°C or 20°C up to 110°C or from 20°C to 100°C or from 20°C to 90°C.

Embodiment 31. A method according to any one of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 40°C to 140°C, for example 40°C to 130°C or 40°C to 120 °C or from 40°C to 110°C.

Embodiment 32. The method according to any of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 50°C to 140°C, for example, from 50°C to 130°C or from 50°C to 120 °C or from 50°C to 110°C.

Embodiment 33. The method according to any of embodiments 1 to 24, wherein the selective hydrogenation is carried out at a temperature within the range of 60°C to 140°C, for example 60°C to 130°C or 60°C to 120 °C or from 60°C to 110°C or from 60°C to 100°C or from 60°C to 90°C.

Embodiment 34. A method according to any of embodiments 1 through 33, wherein at least 95% of the acetylene present in the process gas is hydrogenated, for example, at least 96% or at least 97% or at least 97.5% acetylene present in the process gas.

Embodiment 35. A method according to any of embodiments 1 through 33, wherein at least 98% of the acetylene present in the process gas is hydrogenated, for example, at least 98.5% or at least 99% of the acetylene present in the process gas.

Embodiment 36. A method according to any of embodiments 1 through 33, wherein substantially all of the acetylene present in the process gas is hydrogenated.

Embodiment 37. The process according to any of embodiments 1 to 36, wherein the amount of ethane in the selective hydrogenation product is no more than 1 mol% greater than the amount of ethane in the process gas.

Embodiment 38. The method according to any of embodiments 1 to 36, wherein the amount of ethane in the selective hydrogenation product is no more than 0.9 mol%, for example, no more than 0.8 mol% .), greater than the amount of ethane in the process gas.

Embodiment 39. The method according to any of embodiments 1 to 36, wherein the amount of ethane in the selective hydrogenation product is no more than 0.7 mol%, for example, no more than 0.6 mol% .), greater than the amount of ethane in the process gas.

Embodiment 40. The process according to any of Embodiments 1 to 36, wherein the amount of ethane in the selective hydrogenation product is no more than 0.5 mol% greater than the amount of ethane in the process gas.

Embodiment 41. The process according to any of Embodiments 1 to 36, wherein the amount of ethane in the selective hydrogenation product is no more than 0.2 mol% greater than the amount of ethane in the process gas.

Embodiment 42. The process according to any of embodiments 1 to 36, wherein the amount of ethane in the selective hydrogenation product is no more than 0.1 mol% greater than the amount of ethane in the process gas.

Embodiment 43. The process according to any of embodiments 1 to 36, wherein the amount of ethane in the selective hydrogenation product is no more than 0.05 mol% greater than the amount of ethane in the process gas.

Embodiment 44. A method according to any of Embodiments 1 to 44, wherein the ethylene in the process gas is present in an amount ranging from 10 mol% to 70 mol% or from 15 mol% to 60% (mol.) or from 15% (mol.) to 50% (mol.).

Embodiment 45. The method according to any of embodiments 1 to 44, wherein the ethylene in the process gas is present in an amount of at least 20 mol%, for example, ranging from 20 mol% to 70% (mol.) or from 20% (mol.) to 60% (mol.) or from 20% (mol.) to 50% (mol.).

Embodiment 46. The method according to any of embodiments 1 to 44, wherein ethylene in the process gas is present in an amount of at least 30 mol%, for example, ranging from 30 mol% to 70% (mol.) or from 30% (mol.) to 60% (mol.) or from 30% (mol.) to 50% (mol.).

Embodiment 47. The method according to any of embodiments 1 through 47, wherein the acetylene in the process gas is present in an amount of at least 10 ppm, for example, at least 50 ppm.

Embodiment 48. The method according to any of embodiments 1 through 47, wherein the acetylene in the process gas is present in an amount of at least 100 ppm, for example, at least 500 ppm.

Embodiment 49. The method according to any of embodiments 1 through 47, wherein the acetylene in the process gas is present in an amount ranging from 10 ppm. up to 2% (mol), for example from 10 ppm. up to 1% (mol.) or from 10 ppm. up to 0.5% (mol.).

Embodiment 50. The method according to any of embodiments 1 through 47, wherein the acetylene in the process gas is present in an amount ranging from 50 ppm. up to 2% (mol), for example from 50 ppm. up to 1% (mol.) or from 50 ppm. up to 0.5% (mol.).

Embodiment 51. The method according to any of embodiments 1 through 47, wherein the acetylene in the process gas is present in an amount ranging from 100 ppm. up to 2% (mol.), for example from 100 ppm. up to 1% (mol.) or from 100 ppm. up to 0.5% (mol.).

Embodiment 52. The method according to any of embodiments 1 through 47, wherein the acetylene in the process gas is present in an amount ranging from 500 ppm. up to 2% (mol.) or from 500 ppm. up to 1% (mol.) or from 500 ppm. up to 0.5% (mol.).

Embodiment 53. The method according to any of embodiments 1 to 47, wherein the acetylene in the process gas is present in an amount of at least 0.1 mol%, for example, at least 0.5% ( mol.) or at least 1% (mol.).

Embodiment 54. The method according to any of embodiments 1 to 47, wherein the acetylene in the process gas is present in an amount ranging from 0.1 mol% to 2 mol%, for example, 0.5% ( mol.) to 2% (mol.) or from 1% (mol.) to 2% (mol.) from 0.1% (mol.) to 1.5% (mol.) or from 0.5% ( mol.) to 1.5% (mol.) or from 1% (mol.) to 1.5% (mol.) or from 0.1% (mol.) to 1% (mol.) or from 0, 5% (mol.) to 1% (mol.).

Embodiment 55. The method according to any of embodiments 1 to 54, wherein the hydrogen in the process gas is present in an amount of at least 6 mol% or at least 7 mol% or, at least 8% (mol.) or at least 9% (mol.) or at least 10% (mol.).

Embodiment 56. The method according to any of embodiments 1 to 54, wherein the hydrogen in the process gas is present in an amount ranging from 5 mol% to 50 mol%, for example, from 5 mol% to 35% (mol.) or from 5% (mol.) to 20% (mol.) or from 5% (mol.) to 15% (mol.) or from 8% (mol.) to 50% (mol.) ) or from 8% (mol.) to 35% (mol.) or from 8% (mol.) to 20% (mol.) or from 8% (mol.) to 15% (mol.) or from 10% (mol.) to 50% (mol.) or from 10% (mol.) to 35% (mol.) or from 10% (mol.) to 20% (mol.) or from 10% (mol.) to 15% (mol.).

Embodiment 57. A method as in any one of Embodiments 1 through 56, wherein the process gas is obtained from a cracking process effluent stream, from a depropanizer overhead stream, from a depanter overhead stream, or from a refinery effluent gas stream.

Embodiment 58. A method according to any of embodiments 1 through 57, wherein the process gas contains no more than 10 mol% (e.g., no more than 5 mol% or no more than 2% ( mol.) or not more than 1% (mol.)) carbon-containing components other than C ₁ components (for example, methane, carbon monoxide and carbon dioxide), C ₂ components (for example, ethylene, ethane and acetylene) and C ₃ components (for example, propane, propylene, propane, methyl acetylene and propadiene).

Embodiment 59. A method according to any of Embodiments 1 through 57, wherein the process gas contains no more than 20 mol% (e.g., no more than 15 mol%, no more than 10% ( mol.) or not more than 5% (mol.)) carbon-containing components other than ethylene, ethane, acetylene, carbon monoxide, carbon dioxide and methane.

Embodiment 60. The method according to any of embodiments 1 through 59, wherein the catalyst composition contains a porous support selected from alumina, silica, titanium dioxide, and mixtures thereof and present in the catalyst composition in an amount ranging from 90% ( wt.) to 99.9% (wt.), for example, from 92.5% (wt.) to 99.9% (wt.) or from 95% (wt.) to 99.9% (wt.) or from 97.5% (wt.) to 99.9% (wt.).

Embodiment 61: The method according to Embodiment 60, wherein the porous support is an alumina-based porous support, for example, an alpha-alumina-based porous support.

Embodiment 62. The method according to any of embodiments 1 to 61, wherein the catalyst composition contains palladium in an amount of at least 0.02% (wt.), for example, within the range of 0.02% ( wt.) to 0.5% (wt.) or from 0.03% (wt.) to 0.4% (wt.) or from 0.04% (wt.) to 0.3% (wt.) .

Embodiment 63. The method according to any of embodiments 1 through 62, wherein the catalyst composition contains at least one ionic liquid in a total amount of up to 10% by weight.

Embodiment 64. The method according to any of embodiments 1 to 62, wherein the catalyst composition contains at least one ionic liquid in an amount ranging from 0.5 wt% to 4 wt% or 0 .5% (wt.) to 3% (wt.) or from 0.5% (wt.) to 2% (wt.).

Embodiment 65. The method according to any of embodiments 1 to 64, wherein the thickness of the ionic liquid shell on the outer surface of the catalyst is in the range of 10 to 2000 μm, for example, 100 to 1000 μm or 100 to 800 μm.

Embodiment 66. A method according to any of Embodiments 1 to 65, wherein the at least one ionic liquid is selected from 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-butyl-1 trifluoromethanesulfonate -methylpyrrolidinium, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tricyanomethide, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium methylphosphonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium tetracyanoborate, Tris 1-butyl-1-methylpyrrolidinium (pentafluoroethyl)trifluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium tricyanomethide, 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-tetracyanoborate ethyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, 1-methyl-3-octylimidazolium trifluoromethanesulfonate, ethyldimethyl(2-methoxyethyl)ammonium tris(pentafluoroethyl)trifluorophosphate, tributylmethylammonium dicyanamide, tris(pentafluoroethyl)trifluorophosphate tricycle ohexyltetradecylphosphonium and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Embodiment 67: A method of operating a reactor for selective hydrogenation, wherein the reactor contains one or more beds of catalyst, each of them containing a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing at least 10% (mol. ) ethylene, at least 1 ppm. acetylene and at least 5% (mol.) hydrogen, the method comprising

providing each catalyst layer at no more than a first temperature, wherein the catalyst layer of catalyst is in contact with a first gas, wherein the first gas is unreactive in the presence of the catalyst at the first temperature;

in the presence of a first gas, heating each layer of catalyst to at least a second temperature, wherein the second temperature is at least 20 degrees greater than the first temperature, wherein the first gas is unreactive in the presence of the catalyst at the second temperature; and after that

changing the composition of the gas in contact with the catalyst from the first gas to a flow of process gas while simultaneously maintaining the catalyst bed at at least a second temperature; And

allowing process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

Embodiment 68. The method of Embodiment 67, wherein the acetylene concentration at the reactor outlet is less than 1 ppm. within six hours (eg, within four hours or even within two hours) of introducing the process gas into one or more catalyst beds.

Embodiment 69. The method of Embodiment 67 or Embodiment 68, wherein the catalyst of each catalyst bed in the reactor is not contacted with carbon monoxide in an amount greater than 100 ppm, and where the method includes refraining from adding monoxide to the process gas. carbon.

Embodiment 70: A method of operating a reactor for selective hydrogenation, wherein the reactor contains one or more beds of catalyst, each of them containing a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing at least 10% (mol. ) ethylene, at least 1 ppm. acetylene and at least 5% (mol.) hydrogen, the method comprising

providing each catalyst layer at no more than a first temperature, wherein the catalyst layer of the catalyst is in contact with a process gas;

in the presence of process gas, heating each catalyst layer to at least a second temperature, wherein the second temperature is at least 20 degrees greater than the first temperature, and heating each catalyst layer is carried out at a rate in the range of at least 3°C/hour; And

allowing process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

Embodiment 71. The method of Embodiment 70, where the speed is in the range of 3 - 20 °C/hour, for example, 3 - 15 °C/hour or 3 - 12 °C/hour.

Embodiment 72. The method of Embodiment 70, where the speed is in the range of 6 - 20 °C/hour, for example, 6 - 15 °C/hour or 6 - 12 °C/hour.

Embodiment 73. The method of Embodiment 70, where the speed is in the range of 9 - 20 °C/hour, for example, 9 - 15 °C/hour.

Embodiment 74: A method of operating a reactor for selective hydrogenation, wherein the reactor contains one or more beds of catalyst, each of them containing a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing at least 10% (mol). ) ethylene, at least 1 ppm. acetylene and at least 5% (mol.) hydrogen, the method comprising:

providing the reactor with each layer of catalyst characterized by its catalyst being in contact with a first gas, wherein the first gas is unreactive in the presence of the catalyst at a first temperature, wherein the catalyst has not been brought into contact in the reactor with a carbon monoxide containing gas having a carbon monoxide concentration greater than 2000 hours ./million; And

introducing a current of process gas into one or more catalyst beds and refraining from adding carbon monoxide to the process gas.

Embodiment 75. The method of Embodiment 74 further comprising increasing the catalyst bed temperature for each catalyst bed from no more than a first temperature to at least a second temperature.

Embodiment 76: The method of Embodiment 75 wherein the catalyst bed temperature(s) are increased prior to introducing the process gas.

Embodiment 77. The method of claim 75, wherein the temperature(s) of the catalyst bed is increased after introducing the process gas.

Embodiment 78. The method of claim 75, wherein the process gas is introduced while increasing the temperature(s) of the catalyst bed.

Embodiment 79. The method of any one of embodiments 75 through 78, further comprising, after increasing the temperature to at least a second temperature, flowing process gas through one or more catalyst beds until the reactor effluent reaches a content level of less than 1 ppm (eg, less than 0.5 ppm) acetylene.

Embodiment 80. The method according to any of embodiments 67 to 79, where the first temperature is not more than 50°C, for example, is in the range of 31 to 50°C or 35 to 50°C or 40 to 50°C or 45 – 50°С.

Embodiment 81. The method according to any of embodiments 67 to 79, wherein the first temperature is no more than 45°C, for example, in the range of 31 to 45°C or 35 to 45°C or 40 to 45°C.

Embodiment 82. The method according to any of embodiments 67 to 79, where the first temperature is no more than 40°C, for example, in the range of 31 to 40°C or 35 to 40°C.

Embodiment 83. The method according to any of embodiments 67 to 79, wherein the first temperature is no more than 30°C or no more than 25°C.

Embodiment 84: A method of operating a reactor for selective hydrogenation, wherein the reactor contains one or more beds of catalyst, each of them containing a catalyst suitable for use in the selective hydrogenation of acetylene in a process gas containing at least 10% (mol. ) ethylene, at least 1 ppm. acetylene and at least 5% (mol.) hydrogen, the method comprising

drying one or more catalyst layers at a temperature of at least 50°C; after that

cooling each dried catalyst layer to a first temperature in the range of 31 - 50°C and introducing the catalyst of each catalyst layer into contact with the process gas at the first temperature; after that

in the presence of process gas, heating each catalyst layer to at least a second temperature, the second temperature being at least 20 degrees greater than the first temperature; And

allowing process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

Embodiment 85: The method according to Embodiment 84, wherein the first temperature is within the range of 35°C to 50°C, for example, 40°C to 50°C or 45°C to 50°C.

Embodiment 86. The method according to embodiment 84, where the first temperature is within the range of 31°C to 45°C, for example, from 35°C to 45°C or from 40°C to 45°C.

Embodiment 87. The method corresponding to embodiment 84, where the first temperature is within the range of 31°C to 40°C, for example, from 35°C to 40°C.

Embodiment 88. The method according to any of embodiments 67 to 87, wherein the second temperature is within the range of 40°C to 140°C.

Embodiment 89. The method according to any of embodiments 67 to 87, wherein the second temperature is within the range of 40°C to 100°C.

Embodiment 90. The method according to any of embodiments 67 to 87, wherein the second temperature is within the range of 40°C to 90°C.

Embodiment 91. The method according to any of embodiments 67 to 87, wherein the second temperature is within the range of 50°C to 90°C.

Embodiment 92. The method according to any one of embodiments v, where the second temperature is within the range of 50°C to 100°C.

Embodiment 93. The method according to any of embodiments 67 to 87, wherein the second temperature is within the range of 20°C to 130°C, for example, in the range of 20°C to 120°C or 20°C to 110 °C or from 20°C to 100°C or from 20°C to 90°C.

Embodiment 94. A method according to any one of embodiments 67 to 87, wherein the second temperature is within the range of 40°C to 140°C, for example, 40°C to 130°C or 40°C to 120°C or from 40°C to 110°C.

Embodiment 95. A method according to any of embodiments 67 to 87, wherein the second temperature is within the range of 50°C to 140°C, for example, 50°C to 130°C or 50°C to 120°C or from 50°C to 110°C.

Embodiment 96. A method according to any one of embodiments 67 to 87, wherein the second temperature is within the range of 60°C to 140°C, for example, 60°C to 130°C or 60°C to 120°C or from 60°C to 110°C or from 60°C to 100°C or from 60°C to 90°C.

Embodiment 97. A method according to any of embodiments 67 to 96, wherein the second temperature is at least 30° C. higher (eg, at least 40° C. higher) than the first temperature.

Embodiment 98. A method according to any of embodiments 67 to 96, wherein the second temperature is at least 50° C. higher (eg, at least 60° C. higher) than the first temperature.

Embodiment 99. A method according to any of embodiments 67 to 98, wherein the temperature of each catalyst bed is increased from no more than the first temperature to at least a second temperature over a period of time of no more than 10 hours, for example , no more than six hours.

Embodiment 100. The method according to any of embodiments 67 to 69, 74 to 83, and 88 to 99, wherein the first gas comprises no more than 1 ppm. acetylene (eg, no more than 0.5 ppm).

Embodiment 101. A method according to any of embodiments 67 through 100, wherein the process gas includes at least 10 ppm. CO.

Embodiment 102. A method according to any of embodiments 67 through 100, wherein the process gas complies with the inventive description in other respects with respect to one or more embodiments 1 through 66.

Embodiment 103. A method according to any one of Embodiments 67 through 69, 74 through 83, and 88 through 102, wherein each catalyst layer is changed from being in contact with a first gas to being in contact with a process gas over a period of time of no more than 10 hours, for example no more than six hours, for example, being in the range of 2 - 10 hours, 4 - 10 hours or 3 - 6 hours.

Embodiment 104. A method according to any of embodiments 67 through 104, wherein the catalyst is as described in one or more embodiments 1 through 66.

Embodiment 105. A method consistent with any of Embodiments 67 through 104, further comprising, prior to introducing the process gas into the bed or contacting the catalyst composition with the process gas, reducing the catalyst (eg, using a stream of hydrogen-containing gas).

Embodiment 106: A hydrogenation catalyst composition comprising:

a porous carrier present in the composition in an amount within the range of 90% (wt.) to 99.9% (wt.);

palladium present in the composition in an amount within the range of 0.02% (wt) to 0.5% (wt) (for example, within the range of 0.03% (wt) to 0.4% (wt) .) or from 0.04% (wt.) to 0.3% (wt.)) based on the mass of the element; And

one or more ionic liquids present in the composition in a combined amount up to 10% by weight.

Embodiment 107 The catalyst composition of Embodiment 106, wherein the palladium in the composition is present in an amount ranging from 0.02% by weight to 0.5% by weight, for example, from 0.02% by weight. ) to 0.4% (wt.) or from 0.02% (wt.) to 0.3% (wt.) or from 0.02% (wt.) to 0.2% (wt.) or 0 .02% (wt.) to 0.15% (wt.).

Embodiment 108. The catalyst composition of Embodiment 106, wherein the palladium in the composition is present in an amount ranging from 0.04% by weight to 0.5% by weight, for example, from 0.04% by weight. ) to 0.4% (wt.) or from 0.04% (wt.) to 0.3% (wt.) or from 0.04% (wt.) to 0.2% (wt.) or 0 .04% (wt.) to 0.15% (wt.).

Embodiment 109. The catalyst composition of Embodiment 106, wherein the palladium in the composition is present in an amount ranging from 0.05% by weight to 0.5% by weight, for example, from 0.05% by weight. ) to 0.4% (wt.) or from 0.05% (wt.) to 0.3% (wt.) or from 0.05% (wt.) to 0.2% (wt.) or 0 .05% (wt.) to 0.15% (wt.).

Embodiment 110. The catalyst composition of Embodiment 106, wherein the palladium in the composition is present in an amount ranging from 0.06% by weight to 0.5% by weight, for example, from 0.06% by weight. ) to 0.4% (wt.) or from 0.06% (wt.) to 0.3% (wt.) or from 0.06% (wt.) to 0.2% (wt.) or 0 .06% (wt.) to 0.15% (wt.).

Embodiment 111. The catalyst composition of Embodiment 106, wherein the palladium in the composition is present in an amount ranging from 0.08% by weight to 0.5% by weight, for example, from 0.08% by weight. ) to 0.4% (wt.) or from 0.08% (wt.) to 0.3% (wt.) or from 0.07% (wt.) to 0.2% (wt.) or 0 .07% (wt.) to 0.15% (wt.).

Embodiment 112: A hydrogenation catalyst composition comprising:

porous carrier present in the composition in an amount within the range of 90% (wt.) to 99.9% (wt.) and characterized by a BET determined surface area of not more than 10 m ² /g and volume pores of at least 0.1 ml/g;

palladium present in the composition in an amount within the range of at least 0.02% (wt.) based on the weight of the element; And

one or more ionic liquids present in the composition in a combined amount up to 10% by weight.

Embodiment 113 The hydrogenation catalyst of Embodiment 112 comprising palladium in an amount of at least 0.03% by weight or at least 0.04% by weight or at least 0.05% (wt.) or at least 0.06% (wt.) or at least 0.07% (wt.) or at least 0.08% (wt.) or at least 0.09% (wt.) or at least 0.1% (wt.) or at least 0.11% (wt.) or at least 0. 12% (wt.) or at least 0.13% (wt.) or at least 0.14% (wt.) or at least 0.15% (wt.).

Embodiment 114: The hydrogenation catalyst of Embodiment 112 comprising palladium in an amount of no more than 0.5% by weight (e.g., no more than 0.4% by weight) or no more than 0 .3% (wt.) or not more than 0.2% (wt.)).

Embodiment 115: The hydrogenation catalyst of Embodiment 112 containing palladium in an amount within the range of 0.02 wt% to 0.5 wt% or 0.02 wt% to 0.45 % (wt.) or from 0.03% (wt.) to 0.4% (wt.) or from 0.03% (wt.) to 0.35% (wt.) or from 0.04% ( wt.) to 0.3% (wt.) or from 0.04% (wt.) to 0.25% (wt.).

Embodiment 116: The catalyst composition of any of embodiments 106 through 115 further comprising at least one promoter (e.g., silver, gold, zinc, tin, lead, gallium, cadmium, copper, bismuth, sodium, cesium or potassium) present in the composition in an amount within the range of 0.05% (wt.) to 0.25% (wt.), for example, from 0.08% (wt.) to 0.25% (wt.). ) or from 0.1% (wt.) to 0.25% (wt.) based on the mass of the element.

Embodiment 117: The hydrogenation catalyst of any one of embodiments 106 to 116, wherein the porous support has a BET-determinable surface area within the range of 2 m ² /g to 10 m ² /g.

Embodiment 118: The hydrogenation catalyst of any one of embodiments 106 to 116, wherein the porous support has a BET-determined surface area within the range of 2 m ² /g to 9 m ² /g or 2 m ² /g to 8 m ² /g or from 2 m ² /g to 7 m ² /g or from 2 m ² /g to 6 m ² /g or from 2 m ² /g to 5 m ² /g or from 3 m ² /g up to 10 m ² /g or from 4 m ² /g to 10 m ² /g or from 5 m ² /g to 10 m ² /g or from 6 m ² /g to 10 m ² /g or from 2 m ² /g to 6 m ² /g or from 3 m ² /g to 7 m ² /g or from 4 m ² /g to 8 m ² /g or from 5 m ² /g to 9 m ² /g.

Embodiment 119: The hydrogenation catalyst of any one of embodiments 106 to 118, wherein the porous support has a pore volume within the range of 0.10 ml/g to 1.0 ml/g.

Embodiment 120: The hydrogenation catalyst of any one of embodiments 106 to 118, wherein the porous support has a pore volume within the range of 0.10 ml/g to 0.80 ml/g or 0.20 ml/g to 0.80 ml/g or from 0.30 ml/g to 0.80 ml/g or from 0.20 ml/g to 0.70 ml/g or from 0.30 ml/g to 0.70 ml/g.

Embodiment 121: A hydrogenation catalyst composition comprising:

a porous carrier present in the composition in an amount within the range of 90% (wt.) to 99.9% (wt.);

palladium present in the composition in an amount within the range of at least 0.02% (wt.) based on the weight of the element; And

one or more ionic liquids present in the composition in a combined amount of up to 10% by weight,

wherein the hydrogenation catalyst has a BET surface area of not more than 10 m ² /g and a pore volume of at least 0.05 ml/g.

Embodiment 122 The hydrogenation catalyst of Embodiment 121 comprising palladium in an amount of at least 0.03% by weight or at least 0.04% by weight or at least 0.05% (wt.) or at least 0.06% (wt.) or at least 0.07% (wt.) or at least 0.08% (wt.) or at least 0.09% (wt.) or at least 0.1% (wt.) or at least 0.11% (wt.) or at least 0. 12% (wt.) or at least 0.13% (wt.) or at least 0.14% (wt.) or at least 0.15% (wt.).

Embodiment 123. The hydrogenation catalyst of Embodiment 121 or Embodiment 122 containing palladium in an amount of no more than 0.5% by weight (for example, no more than 0.4% by weight) or not more than 0.3% (wt.) or not more than 0.2% (wt.)).

Embodiment 124: The hydrogenation catalyst of Embodiment 121 containing palladium in an amount within the range of 0.02 wt% to 0.5 wt% or 0.02 wt% to 0.45 % (wt.) or from 0.03% (wt.) to 0.4% (wt.) or from 0.03% (wt.) to 0.35% (wt.) or from 0.04% ( wt.) to 0.3% (wt.) or from 0.04% (wt.) to 0.25% (wt.).

Embodiment 125: The hydrogenation catalyst of any one of embodiments 121 to 124, further comprising at least one promoter (e.g., silver, gold, zinc, tin, lead, gallium, cadmium, copper, bismuth, sodium, cesium or potassium) present in the composition in an amount within the range of 0.05% (wt.) to 0.25% (wt.), for example, from 0.08% (wt.) to 0.25% (wt.). ) or from 0.1% (wt.) to 0.25% (wt.) based on the mass of the element.

Embodiment 126: The hydrogenation catalyst of any one of embodiments 121 to 125 having a BET surface area within the range of 2 m ² /g to 10 m ² /g.

Embodiment 127: The hydrogenation catalyst of any one of Embodiments 121 to 125 having a BET surface area within the range of 2 m ² /g to 9 m 2 /g or 2 m ^{2 /} g to 8 m ² / g or from 2 m ² /g to 7 m ² /g or from 2 m ² /g to 6 m ² /g or from 2 m ² /g to 5 m ² /g or from 3 m ² /g to 10 m ² /g or from 4 m ² /g to 10 m ² /g or from 5 m ² /g to 10 m ² /g or from 6 m ² /g to 10 m ² /g or from 2 m ² /g to 6 m ² /g or from 3 m ² /g to 7 m ² /g or from 4 m ² /g to 8 m ² /g or from 5 m ² /g to 9 m ² /g.

Embodiment 128: The hydrogenation catalyst of any one of embodiments 121 to 127 having a pore volume within the range of 0.05 ml/g to 1.0 ml/g.

Embodiment 129: The hydrogenation catalyst of any one of embodiments 121 to 127 having a pore volume within the range of 0.05 ml/g to 0.4 ml/g.

Embodiment 130: The hydrogenation catalyst of any one of embodiments 121 to 129 having a pore volume within the range of 0.10 ml/g to 1.0 ml/g, for example, 0.10 ml/g to 0.80 ml /g or from 0.10 ml/g to 0.60 ml/g or from 0.10 ml/g to 0.40 ml/g or from 0.10 ml/g to 0.30 ml/g.

Embodiment 131: The hydrogenation catalyst of any of embodiments 121 to 129 having a pore volume within the range of 0.20 ml/g to 1.0 ml/g, for example, 0.20 ml/g to 0.80 ml /g or from 0.20 ml/g to 0.60 ml/g or from 0.20 ml/g to 0.40 ml/g or from 0.20 ml/g to 0.35 ml/g.

Embodiment 132: The hydrogenation catalyst of any one of embodiments 121 to 129 having a pore volume within the range of 0.40 ml/g to 1.0 ml/g, for example, 0.40 ml/g to 0.80 ml /g or from 0.40 ml/g to 0.60 ml/g.

Embodiment 133: The hydrogenation catalyst of any of embodiments 121 to 132, wherein the difference between the pore volume of the support and the pore volume of the catalyst (i.e., including palladium, any promoters, and ionic liquid) is in the range of 10 to 90% of the pore volume carrier.

Embodiment 134: The hydrogenation catalyst of any of embodiments 121 to 132, wherein the difference between the pore volume of the support and the pore volume of the catalyst (i.e., including palladium, any promoters, and ionic liquid) is in the range of 10 to 80% of the pore volume carrier, for example, 20 - 80% or 30 - 80% or 40 - 80% of the pore volume of the carrier.

Embodiment 135: The hydrogenation catalyst of any of embodiments 121 to 132, wherein the difference between the pore volume of the support and the pore volume of the catalyst (i.e., including palladium, any promoters, and ionic liquid) is in the range of 10 to 70% of the pore volume carrier, for example, 20 - 70% or 30 - 70% or 40 - 70%; or in the range of 10 – 60% of the pore volume of the carrier, for example, 20 – 60% or 30 – 60% or 40 – 60%.

Embodiment 136: The hydrogenation catalyst of any one of embodiments 106 to 135, wherein the ionic liquid is present in an amount ranging from 0.1% by weight to 10% by weight, for example, from 0.1% by weight. ) to 8% (wt.) or from 0.1% (wt.) to 6% (wt.) or from 0.1% (wt.) to 4% (wt.) or from 0.1% (wt. .) to 3% (wt.) or from 0.1% (wt.) to 2% (wt.) or from 0.1% (wt.) to 1% (wt.).

Embodiment 137: The hydrogenation catalyst of any one of embodiments 106 to 135, wherein the ionic liquid is present in an amount ranging from 0.2% by weight to 3% by weight.

Embodiment 138: The hydrogenation catalyst of any one of embodiments 106 to 135, wherein the ionic liquid is present in an amount ranging from 0.5% by weight to 4% by weight.

Embodiment 139: The hydrogenation catalyst of any of embodiments 106 through 138 containing silver as a promoter.

Embodiment 140. The hydrogenation catalyst of any one of embodiments 106 to 139, wherein the porous support is a porous alumina support, for example, an alpha-alumina porous support.

Embodiment 141: The hydrogenation catalyst of any one of embodiments 106 to 140, wherein the thickness of the ionic liquid shell on the outer surface of the catalyst is in the range of 10 to 2000 μm, such as 100 to 1000 μm or 100 to 800 μm.

Embodiment 142. The hydrogenation catalyst from any of embodiments 106 to 138, wherein at least one ionic liquid is selected from 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-butyl-1 trifluoromethanesulfonate -methylpyrrolidinium, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tricyanomethide, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium methylphosphonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium tetracyanoborate, Tris 1-butyl-1-methylpyrrolidinium (pentafluoroethyl)trifluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium tricyanomethide, 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-tetracyanoborate ethyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, 1-methyl-3-octylimidazolium trifluoromethanesulfonate, ethyldimethyl(2-methoxyethyl)ammonium tris(pentafluoroethyl)trifluorophosphate, tributylmethylammonium dicyanamide, tris(pentafluoroethyl)trifluorophosphate tricycle ohexyltetradecylphosphonium and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Embodiment 143. Any of the processes of Embodiments 1 through 59 and 67 through 105 using a catalyst that is as described in any of Embodiments 106 through 142.

Claims (41)

1. A method of starting a reactor for selective hydrogenation, wherein the reactor contains one or more catalyst layers, each of which contains a catalyst composition containing an ionic liquid and suitable for the selective hydrogenation of acetylene in a process gas containing at least 10 mol%. ethylene, at least 1 ppm. mole of acetylene and at least 5 mol%. hydrogen, the method including obtaining one or more catalyst layers at no more than a first temperature, wherein the catalyst layer is in contact with a first gas containing less than 2 mol%. hydrogen, wherein the first gas is non-reactive in the presence of a catalyst at the first temperature; heating one or more catalyst beds in the presence of a first gas to at least a second temperature, wherein the second temperature is at least 20° C. higher than the first temperature, wherein the first gas is unreactive in the presence of the catalyst at the second temperature; and after that replacing the first gas in contact with the catalyst composition by introducing a process gas stream that is to be hydrogenated in the selective hydrogenation reactor while the catalyst bed is at at least a second temperature; And allowing the process gas to flow through the catalyst bed until the acetylene concentration leaving the selective hydrogenation reactor is less than 1 ppm. mole. 2. The method of claim 1, wherein the catalyst of one or more catalyst layers in the selective hydrogenation reactor is contacted with carbon monoxide in an amount not exceeding 100 ppm. mole, and the process gas is a cracking process effluent stream, a depropanizer overhead stream, a depanter overhead stream, or a refinery off-gas stream, wherein no additional carbon monoxide is introduced into the process gas. 3. A method of starting a reactor for selective hydrogenation, wherein the selective hydrogenation reactor contains one or more catalyst beds, each of which contains a catalyst composition containing an ionic liquid and suitable for the selective hydrogenation of acetylene in a process gas containing at least 10 mol%. ethylene, at least 1 ppm. mole. acetylene and at least 5 mol%. hydrogen, the method including providing one or more catalyst layers at no more than a first temperature, the catalyst layer being in contact with a process gas; heating one or more catalyst layers in the presence of a process gas to at least a second temperature, wherein the second temperature is at least 20° C. higher than the first temperature, and the heating of one or more catalyst layers is carried out at a rate of 3-20 °C/hour; And allowing the process gas to flow through the catalyst bed until the acetylene concentration leaving the selective hydrogenation reactor is less than 1 ppm. mol, and at least 90% of the acetylene present in the process gas is hydrogenated, and no more than 1 mol%. of the total amount of acetylene and ethylene present in the process gas is converted into ethane. 4. A method of starting a reactor for selective hydrogenation, wherein the selective hydrogenation reactor contains one or more catalyst beds, each of which contains a catalyst composition containing an ionic liquid and suitable for the selective hydrogenation of acetylene in a process gas containing at least 10 mol%. ethylene, at least 1 ppm. mole of acetylene and at least 5 mol%. hydrogen, the method including: obtaining one or more catalyst layers at no more than a first temperature, wherein the one or more catalyst layers are in contact with a first gas containing less than 2 mol%. hydrogen, the first gas being unreactive in the presence of the catalyst at the first temperature where the catalyst in the selective hydrogenation reactor has not been contacted with a gas containing carbon monoxide at a concentration greater than 2000 ppm. mole; And introducing a process gas stream into one or more catalyst beds and without adding carbon monoxide to the process gas. 5. The method of claim 4, comprising increasing the temperature of one or more catalyst beds from a first temperature to at least a second temperature. 6. Method according to any one of paragraphs. 1–3 and 5, where the first temperature is no more than 40°C; And the second temperature is within the range of 40°C to 140°C. 7. A method of starting a reactor for selective hydrogenation, wherein the selective hydrogenation reactor contains one or more catalyst beds, each of which contains a catalyst composition containing an ionic liquid and suitable for the selective hydrogenation of acetylene in a process gas containing at least 10 mol%. ethylene, at least 1 ppm. mole. acetylene and at least 5 mol%. hydrogen, the method including drying one or more catalyst layers at a temperature of at least 50°C; after that cooling the one or more dried catalyst layers to a first temperature less than the drying temperature and in the range of 31-50° C., and contacting the catalyst composition of the one or more catalyst layers with the process gas at the first temperature; after that heating one or more catalyst layers in the presence of process gas to at least a second temperature, the second temperature being at least 20° C. higher than the first temperature; And allowing the process gas to flow through the catalyst bed until the acetylene concentration leaving the selective hydrogenation reactor is less than 1 ppm such that at least 90% of the acetylene present in the process gas is hydrogenated and not more than 1% mol. of the total amount of acetylene and ethylene present in the process gas is converted into ethane. 8. Method according to any one of paragraphs. 1–7, where the first temperature is in the range of 31–45°C. 9. Method according to any one of paragraphs. 1-8, where selective hydrogenation is carried out at a second temperature within the range of 40°C to 140°C. 10. Method according to any one of paragraphs. 1–8, where selective hydrogenation is carried out at an hourly gas space velocity in the range from 7500 to 40000 h ^–1 . 11. Method according to any one of paragraphs. 1-8, wherein ethylene in the process gas is present in an amount of at least 20 mol%, and acetylene in the process gas is present in an amount of at least 500 ppm. mole. 12. Method according to any one of paragraphs. 1–8, where hydrogen in the process gas is present in an amount ranging from 5 mol%. up to 35% mol. 13. Method according to any one of paragraphs. 1–8, where the process gas contains no more than 5 mol%. carbon-containing components other than C ₁ components, for example, methane, carbon monoxide and carbon dioxide, C ₂ components, for example, ethylene, ethane and acetylene, and C ₃ components, for example, propane, propylene, methyl acetylene and propadiene. 14. Method according to any one of paragraphs. 1–8, where the catalyst composition contains a porous carrier selected from aluminum oxide, silicon dioxide, titanium dioxide and mixtures thereof and present in the catalyst composition in an amount of from 90 wt%. up to 99.9% wt. 15. Method according to any one of paragraphs. 1–8, where the catalyst composition contains palladium in an amount of at least 0.02 wt%. 16. Method according to any one of paragraphs. 1–8, where the catalyst composition contains at least one ionic liquid in a total amount of up to 10 wt%. 17. Method according to any one of paragraphs. 1-8, where at least one ionic liquid is selected from 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate , 1-butyl-3-methylimidazolium tricyanomethide, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl methylphosphonate -3-methylimidazolium, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium tetracyanoborate, 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, bis 1-butyl-3-methylimidazolium (trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium tricyanomethide, 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium tetracyanoborate, 1-tris(pentafluoroethyl)trifluorophosphate ethyl 3-methylimidazolium, 1-methyl-3-octylimidazolium trifluoromethanesulfonate, ethyldimethyl(2-methoxyethyl)ammonium tris(pentafluoroethyl)trifluorophosphate, tributylmethylammonium dicyanamide, tricyclohexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate and 1-ethyl bis(trifluoromethylsulfonyl)imide -3-methylimidazolium . 18. Method according to any one of paragraphs. 1–8, where the catalyst composition contains: porous carrier present in the composition in an amount within the range of 90% of the mass. up to 99.9% wt.; palladium present in the composition in an amount ranging from 0.02 wt%. up to 0.5% wt. for example, within the range of 0.03 wt%. up to 0.4% wt. or from 0.04% wt. up to 0.3% wt. in terms of the mass of the element; And one or more ionic liquids present in the composition in a total amount of up to 10 wt%. 19. Method according to any one of paragraphs. 1–8, where the catalyst composition contains porous carrier present in the composition in an amount within the range of 90% of the mass. up to 99.9% wt.; palladium present in the composition in an amount of at least 0.02 wt%. in terms of the mass of the element; And one or more ionic liquids present in the composition in a total amount of up to 10% by weight, wherein the hydrogenation catalyst has a BET surface area of not more than 10 m ² /g and a pore volume of at least 0.05 ml/g.