Hydrogenation Method

Abstract

(b) subjecting the synthesis gas to one or more water-gas shift stages in a water-gas shift unit to increase the hydrogen content of the synthesis gas and reduce the carbon monoxide content thereof to provide a hydrogen-rich gas; (c) cooling the hydrogen-rich gas and separating condensed water therefrom; and (d) passing the resulting dehydrated hydrogen-rich gas through a carbon dioxide separation unit to provide a carbon dioxide gas stream and a hydrogen gas stream. The synthesis gas from step (a) is fed to a water-gas shift reactor operated adiabatically or with cooling without adjustment of the carbon monoxide content, at an inlet temperature in the range of 200-280°C and an outlet temperature less than 360°C, containing a catalyst comprising 30-70 wt. % copper, expressed as CuO, in combination with zinc oxide, alumina, and silica, the catalyst having a silica content, expressed as SiO2, in the range of 0.1-5.0 wt. %.

Description

[Technical Field]

[0001] The present invention relates to a method for producing hydrogen, and in particular to a method for producing hydrogen that includes a water-gas shift step carried out using a copper catalyst.

[0002] Processes for producing hydrogen are known and typically involve catalytic steam reforming of natural gas to produce a synthesis gas containing hydrogen, carbon dioxide, carbon monoxide, and steam, followed by a catalytic water-gas shift to increase the hydrogen content of the synthesis gas and convert the carbon monoxide to carbon dioxide, followed by removal of carbon dioxide by absorption. The water-gas shift reaction is exothermic, and to achieve suitably low carbon monoxide outlet concentrations, it is conventionally carried out in two stages: first, using an iron-catalyzed high-temperature shift catalyst to reduce the carbon monoxide content, and, after cooling, a subsequent low-temperature shift stage using a copper catalyst.

[0003] There is a drive for higher process efficiency, and attempts have been made to perform the water-gas shift step using copper catalysts at higher inlet temperatures, either adiabatically under medium temperature shift conditions or with cooling. However, copper catalysts are susceptible to thermal degradation, and the lifetime of copper catalysts used with higher inlet temperatures and higher carbon monoxide content feedstocks is relatively short, necessitating more frequent shutdown of the hydrogenation process. Applicants have discovered that by modifying the copper catalyst with silica, the lifetime of the copper catalyst can be improved under more severe conditions, resulting in increased efficiency of the hydrogenation process.

[0004] JP 2000126597 A discloses a catalyst suitable for low-temperature shift containing 20-65% copper oxide, 10-70% zinc oxide by weight, and 0.5-5% silicon oxide by weight, which is claimed to have long-term stability. However, it does not disclose a hydrogenation process in which the water-gas shift stage is operated under adiabatic or cooled medium-temperature shift conditions without prior adjustment of the carbon monoxide content of the synthesis gas.

[0005] Accordingly, the present invention provides a method for producing hydrogen, the method comprising the steps of: (a) producing a synthesis gas comprising hydrogen, carbon monoxide, carbon dioxide, and steam in a synthesis gas generation unit; (b) subjecting the synthesis gas to one or more water-gas shift stages in a water-gas shift unit to increase the hydrogen content of the synthesis gas and reduce the carbon monoxide content thereof to provide a hydrogen-rich gas; (c) cooling the hydrogen-rich gas and separating condensed water therefrom; and (d) passing the resulting dehydrated hydrogen-rich gas through a carbon dioxide separation unit to provide a carbon dioxide gas stream and a hydrogen gas stream, wherein the synthesis gas from step (a) is fed to a water-gas shift reactor operated adiabatically or with cooling without adjustment of the carbon monoxide content, at an inlet temperature in the range of 200 to 280°C and an outlet temperature less than 360°C, and containing a catalyst comprising 30 to 70 wt. % copper, expressed as CuO, in combination with zinc oxide, alumina, and silica, the catalyst having a silica content, expressed as SiO2, in the range of 0.1 to 5.0 wt. %.

[0006] The synthesis gas comprising hydrogen, carbon monoxide, carbon dioxide, and steam provided in step (a) can be produced by any suitable means. Synthesis gas production can include one or more processes selected from adiabatic pre-reforming, catalytic steam reforming in a combustion or gas-heated reformer, autothermal reforming, and catalytic partial oxidation, which processes are applied to gaseous or vaporized hydrocarbons such as natural gas, naphtha, or refinery off-gas. Alternatively, synthesis gas production can include non-catalytic partial oxidation or gasification of a carbonaceous feedstock such as coal, biomass, or municipal waste, optionally followed by one or more stages of catalytic steam reforming or autothermal reforming.

[0007] In some embodiments, the syngas production unit includes an autothermal reformer that is fed with reformed syngas obtained from an upstream adiabatic pre-reformer or a fired steam reformer or a gas-heated reformer.

[0008] In adiabatic pre-reforming, a mixture of hydrocarbon and steam is passed through a fixed bed of pelletized Ni-containing pre-reforming catalyst at inlet temperatures ranging from 300 to 620°C and pressures ranging from 10 to 80 bar abs, with a steam-to-carbon ratio typically ranging from 1 to 4. Such catalysts typically contain 40 wt. % or more Ni (expressed as NiO) along with alumina and promoter compounds such as silica and magnesia.

[0009] In combustion steam reformers and gas-heated reformers, a mixture of hydrocarbons and steam is fed to multiple tubes packed with externally heated catalyst. The reforming catalyst used in combustion or gas-heated reformers typically contains nickel at levels ranging from 5 to 30% by weight supported on a shaped refractory oxide such as alpha alumina, magnesium aluminate, or calcium aluminate. Alternatively, structured catalysts may be used, in which nickel or a precious metal catalyst is provided as a coating layer on a formed metal or ceramic structure, or the catalyst may be provided in multiple vessels arranged within the tube. The steam reforming reaction occurs in the tubes over the steam reforming catalyst at temperatures exceeding 350°C, and the process fluid exiting the tubes typically has a temperature in the range of 650 to 950°C. The tubes are heated by a heat exchange medium flowing outside the tubes, which may have a temperature in the range of 900 to 1300°C. In combustion reformers, this heat is provided by the combustion of fuel gas and air. In gas-heated reformers, heat may be provided by flue gas, but is preferably autothermal reforming syngas. The pressure inside the tube may be in the range of 10 to 80 bar abs.

[0010] In an autothermal reformer, the feed gas is typically partially combusted in a burner device mounted near the top of the reformer. The partially combusted gas is then adiabatically passed through a bed of steam reforming catalyst located below the burner device to bring the gas composition toward equilibrium. The heat for the endothermic steam reforming reaction is provided by the hot, partially combusted reformed gas. Upon contact with the steam reforming catalyst, the endothermic steam reforming reaction cools the partially combusted reformed gas to a temperature in the range of 900–1100 °C. The steam reforming catalyst bed in the secondary reformer typically contains nickel at levels in the range of 5–30 wt.% supported on a molded refractory oxide, although layered beds can also be used in which the top catalyst layer contains a noble metal such as Pt or Rh on a zirconia support. Such steam reformer systems and catalysts are commercially available.

[0011] In a preferred method, the synthesis gas production step comprises reforming a hydrocarbon, in particular natural gas, in a gas-heated reformer to produce a gas stream comprising hydrogen, carbon monoxide, carbon dioxide and steam, and an autothermal reforming step in which the reformed gas is further reformed with oxygen in an autothermal reformer to provide a synthesis gas stream comprising hydrogen, carbon monoxide, carbon dioxide and steam.

[0012] The synthesis gas contains hydrogen, carbon monoxide, carbon dioxide, steam, and may contain small amounts of unreacted methane and small amounts of inert gases such as nitrogen and argon. The hydrogen content of the synthesis gas may be in the range of 30 to 50% by volume on a wet gas basis, i.e., taking steam into account. The carbon monoxide content of the synthesis gas may be in the range of 6 to 20% by volume on a wet gas basis. The composition of the synthesis gas may be expressed on a dry gas basis. The hydrogen content of the synthesis gas may be in the range of 60 to 80% by volume on a dry gas basis, i.e., not taking steam into account. The carbon monoxide content of the synthesis gas may be in the range of 10 to 30% by volume on a dry gas basis.

[0013] In this method, the hydrogen content of the synthesis gas mixture is increased by subjecting the synthesis gas mixture to one or more water-gas shift stages, thereby producing a hydrogen-enriched gas and simultaneously converting carbon monoxide in the reformed gas to carbon dioxide. The reaction can be illustrated as follows: CO+H2O⇔CO2+H2

[0014] The molar ratio of steam to dry gas in the feed to the water-gas shift unit may range from 0.7 to 2.0:1, preferably 0.7 to 1.2:1, and more preferably 0.7 to 1.0:1. If synthesis gas production is carried out with excess steam, it is not necessary to add steam to the synthesis gas mixture to ensure sufficient steam is available for the water-gas shift reaction. However, additional steam may be added if necessary.

[0015] The synthesis gas may be subjected to one or more water-gas shift stages in a water-gas shift unit to form a hydrogen-enriched or "shifted" gas stream.

[0016] In the present invention, the water-gas shift unit comprises at least one adiabatically operated medium-temperature shift (MTS) stage or one with cooling (so-called isothermal shift, ITS) stage. Thus, in the present invention, the water-gas shift unit comprises at least one reactor operated adiabatically or with cooling, with an inlet temperature in the range of 200-280°C and an outlet temperature below 360°C. In contrast to conventional processes, this water-gas shift stage is not operated downstream of a conventional high-temperature shift stage. Thus, in the present invention, a synthesis gas containing hydrogen and carbon monoxide is cooled to an inlet temperature in the range of 200-280°C and passed through a catalyst bed adiabatically or with cooling, without prior adjustment of the carbon monoxide content.

[0017] The use of heat exchange in an isothermal shift stage, i.e., a shift converter, so that an exothermic reaction occurs on a catalyst bed in contact with a heat-removing heat exchange surface, offers the possibility of using the synthesis gas stream in a highly efficient manner. While the term "isothermal" is used to describe a cooled shift converter, the temperature of the hydrogen-rich gas stream at the outlet of the isothermal shift converter can be 1 to 25 degrees Celsius higher than the inlet temperature, due to the possibility of a relatively small increase in gas temperature between the inlet and outlet. The inlet temperature of the isothermal shift reactor can be higher than that of an adiabatic reactor; for example, the inlet temperature of an isothermal shift reactor can be in the range of 230 to 250°C. The coolant can conveniently be water under pressure to cause partial or complete boiling. The water can be in tubes surrounded by the catalyst, or vice versa. The resulting steam can be used, for example, to drive a turbine for power generation or to provide process steam for the process. In a preferred embodiment, the steam generated by the isothermal shift stage is used to supplement the steam used in steam reforming, thereby improving the efficiency of the process.

[0018] If desired, an adiabatic low temperature shift stage can be included downstream of the isothermal shift stage to maximize hydrogen enrichment upstream of the carbon dioxide removal stage, however, the inventors have found that a single isothermal shift converter can provide excellent efficiency.

[0019] The catalyst used in the reactor operated under MTS or ITS conditions comprises 30-70 wt. % copper, expressed as CuO, in combination with zinc oxide, alumina and silica, the catalyst having a silica content, expressed as SiO2, in the range of 0.1-5.0 wt. %.

[0020] The copper content, expressed as CuO, is preferably 45 to 65 wt. The Cu:Zn weight ratio (expressed as CuO:ZnO) may be in the range of 1.4:1 to 3.0:1. The zinc content, expressed as ZnO, may be in the range of 20 to 50 wt. %, preferably 20 to 40 wt. The aluminum content, expressed as Al2O3, may be in the range of 5 to 40 wt. %, preferably 8 to 25 wt. One or more promoter metal oxides selected from oxides of Mg, Co, Mn, V, Ti, Zr, or rare earths may optionally be present in an amount ranging from 0 to 5 wt. The promoter may stabilize copper or enhance the properties of the support phase. Magnesium and zirconium compounds are preferably present in an amount ranging from 0.1 to 5 wt. %.

[0021] The catalyst contains silica, and the Si:Al atomic ratio can range from 0.004 to 0.2:1. The amount of silica in the catalyst is believed to be optimal when the Si:Al atomic ratio ranges from 0.03 to 0.09:1. Thus, the amount of silica in the catalyst is relatively low, and may be present in the calcined catalyst in an amount ranging from 0.1 to 5.0 wt %, preferably from 0.1 to 2.0 wt %, and more preferably from 0.2 to 1.0 wt %.

[0022] The catalyst produced by this method is 40 m 2 / g catalyst, preferably more than 50m 2 / g catalyst or more, preferably 55m 2 / g catalyst or more, most preferably 60m 2 / g of catalyst, with a copper surface area of ​​up to about 70 m 2 Copper surface areas of 1000 to 10 ...

[0023] The BET surface area of ​​the catalyst, determined by nitrogen physisorption (per ASTM method D3663-03), is 75 m 2 / g or more, preferably 100m 2 / g or more. The maximum is about 140m 2 / g of BET surface area can be achieved. The BET surface area is suitably determined for crushed pellets.

[0024] The catalyst may comprise CuO and ZnO, and may have a maximum intensity ratio of the ZnO peak to the CuO peak as measured by XRD of at least 0.26:1, preferably at least 0.30:1. These crystallographic characteristics result from a combination of the composition and the catalyst preparation method.

[0025] In the catalyst, zinc oxide, alumina, and silica are not substantially reduced to metals under water-gas shift process conditions and generally exist as oxides in the catalyst. In contrast, copper is more easily reduced to its active elemental form. Copper can be reduced either ex-situ or in-situ prior to use to form catalytically active copper metal crystals.

[0026] The catalysts can be prepared by single or double precipitation methods using various silica precursors, which can be added at one or more points during the preparation of the catalyst.

[0027] In one embodiment, the catalyst may be prepared by a process comprising the steps of: (i) forming, in an aqueous medium, a homogeneous mixture comprising a coprecipitate of copper and zinc compounds with alumina and silica, wherein the alumina is provided by an alumina sol; (ii) recovering, washing, and drying the homogeneous mixture to form a dry composition; and (iii) calcining and shaping the dry composition to form the catalyst.

[0028] The coprecipitate can be prepared by mixing an acidic aqueous solution containing copper and zinc compounds in appropriate ratios and combining this acidic aqueous solution with an alkaline precipitant solution. The copper and zinc compounds are preferably nitrates. The alkaline precipitant may be an alkali metal carbonate, an alkali metal hydroxide, or a mixture thereof. The alkaline precipitant preferably comprises an alkali metal carbonate. Potassium or sodium precipitants can be used, but potassium precipitants are preferred because they have been found to be more easily removed from the precipitated composition by washing than sodium. Reaction of the copper and zinc compounds with the alkaline precipitant in the acidic solution results in the precipitation of a copper-zinc mixed coprecipitate. Precipitation can be carried out at temperatures ranging from 10 to 80°C, but is preferably carried out at elevated temperatures, i.e., 40 to 80°C, more preferably 50 to 80°C, and especially 60 to 80°C, because this has been found to produce smaller crystallites, which impart a higher copper surface area after calcination.

[0029] The acidic and alkaline solutions may be added one to the other in the precipitation vessel, but are preferably added simultaneously to the precipitation vessel so that the pH in the precipitation vessel is maintained at 6 to 9, preferably 6 to 7. The resulting coprecipitate slurry is then aged, preferably in a separate aging vessel, at a temperature in the range of 10 to 80°C, preferably 40 to 80°C, more preferably 50 to 80°C, and particularly 60 to 80°C, to form crystalline copper and zinc compounds, preferably crystalline hydroxycarbonate compounds. The coprecipitation and aging preferably result in the formation of malachite [Cu(CO)(OH)], which can be determined by XRD. 2 ], smithsonite [ZnCO3] and / or zinc malachite [(Cu / Zn)2(CO3)(OH)2] phases.

[0030] The catalyst can be prepared using alumina sol. Alumina sol is an aqueous colloidal dispersion of aluminum hydroxide containing boehmite and pseudoboehmite. The pH of the dispersion is suitably less than 7, preferably in the range of 3 to 4. Preferably, the alumina sol is added to the precipitation vessel separately from the acidic metal solution or the aqueous alkaline precipitant solution, as this has been shown to improve catalyst properties. Alumina sols are commercially available or may be prepared by known methods. The alumina concentration in the sol can be 30 to 200 g / L. Particularly suitable alumina sols include dispersions of colloidally dispersed boehmite having a D50 average particle size, when dispersed, in the range of 5 to 200 nm, preferably 5 to 100 nm, and more preferably 5 to 50 nm. Such sols are commercially available.

[0031] The catalyst contains silica. When a silica sol is used as the silica source, it may be added to the acidic metal solution and / or the precipitation vessel and / or the aging vessel and / or the alumina sol. Particularly suitable silica sols include aqueous dispersions of colloidally dispersed silica having particle sizes in the range of 10-20 nm. The pH of the dispersion may be <7, preferably in the range of 2-4. The silica concentration in the sol may be 100-400 g / liter. Such sols are commercially available, for example, as Snowtex-O from Nissan Chemical and Ludox HSA from Grace.

[0032] When a water-soluble silicate, such as an alkali metal silicate, is used as the silica source, it may be added to the aqueous alkali precipitant solution, and / or the alumina sol, and / or the precipitation vessel and / or aging vessel. Suitable alkali metal silicates are soluble sodium silicate and soluble potassium silicate. Such alkali silicates are commercially available, for example, as Kasil 1 from PQ Corporation, Kasolv 16 from PQ Corporation, or Zacsil 18 from Zaclon LLC. When an alkali metal silicate is used as the silica source in the catalyst, the alkali metal in the alkali metal silicate is preferably the same as the alkali metal in the precipitant solution, since this improves catalyst washing, recovery, and bulk reprocessing of waste solutions. The amount of silicon, expressed as SiO2, in the alkali metal silicate solution can range from 15 to 30 wt.%.

[0033] When an organosilicate such as an alkyl silicate of formula Si(OR)4, where R is C1-C4 alkyl, is used as the silica source, it is preferably added to the alumina sol or precipitation and / or aging vessel since it will hydrolyze when in contact with water.

[0034] After co-precipitation and aging, the homogeneous mixture is separated and recovered using known methods, such as, for example, filtration, decanting, or centrifugation, and the mother liquor is washed to remove any remaining soluble salts.

[0035] Washing of the homogeneous mixture can be accomplished using conventional equipment such as a plate and frame filter press, for example by reslurrying the mixture one or more times with salt-free water, or by dynamic cross-flow filtration using Artisan or Shriver thickeners prior to recovery.

[0036] The recovered homogeneous mixture is dried to form a dry composition. Drying can involve heating the wet mixture in stages until a maximum temperature is reached, or continuously for an extended period of time. The drying step can be carried out using conventional drying equipment such as an oven, rotary dryer, spray dryer, or similar equipment under air or an inert gas at a temperature ranging from 90 to 150°C, preferably 90 to 130°C.

[0037] The dry composition is generally in the form of a powder. The dry composition may include one or more hydroxycarbonates of copper and zinc, as well as alumina and silica.

[0038] The dried composition is calcined and shaped to form the catalyst. The dried composition may be calcined, e.g., heated, to convert the copper and zinc compounds, and any promoter compounds, to their respective oxides before shaping, or, less preferably, the dried composition may be formed into shaped units before calcining. This latter method is less preferred because calcining the shaped units generally reduces their strength and makes pellet density more difficult to control. Preferably, calcination is carried out at a temperature in the range of 250 to 500°C, preferably 280 to 450°C.

[0039] The forming unit is preferably a pellet. Therefore, the dried or calcined powder is pelletized, optionally after pre-compression of the powder, which can improve the pelletization process. The pellets may suitably be cylindrical. Cylindrical pellets for carbon oxide conversion processes suitably have a diameter in the range of 2.5 to 10 mm, preferably 3 to 10 mm, and an aspect ratio (i.e., length / diameter) in the range of 0.5 to 2.0. Alternatively, the forming unit may be in the form of a ring. In a particularly preferred embodiment, the forming unit is in the form of a cylinder with two or more, preferably 3 to 7, grooves running along its length. Suitable dome-shaped cylinders with one or more longitudinal grooves are described in WO 2010 / 029325, which is incorporated herein by reference.

[0040] The pellets, especially cylindrical pellets with flat or domed ends as described above, preferably have a pellet density of 1.8 to 2.5 g / cm. 3 , preferably 1.9 to 2.4 g / cm 3 The density of the pellets can be easily determined by calculating the volume from the dimensions of the pellets and measuring their weight. As the density increases, the interstitial volume within the molding unit decreases, which reduces the permeability of the reaction gas. Therefore, a density of >2.5 g / cm 3 In this case, despite the high volumetric copper content, the catalyst reactivity is less than optimal. Density <1.8 g / cm 3 However, the compressive strength may be insufficient for long-term use in modern carbon oxide conversion processes.

[0041] In another embodiment, the catalyst may be prepared by a method comprising the steps of: (a) combining an acidic copper-containing solution with an alkali metal carbonate solution to form a first precipitate in a first precipitation step; (b) combining an acidic aluminum-containing solution with a basic precipitant solution, further comprising one or more metal compounds selected from copper compounds, zinc compounds, and promoter compounds, to form a second precipitate in a second precipitation step; (c) contacting the first and second precipitates together in a further mixing step to form a catalyst precursor; and (d) washing, drying, and calcining the catalyst precursor to form the copper-containing catalyst, wherein the silica precursor is included in the first precipitation step, the second precipitation step, or the precipitate mixing step. The washing, drying, calcining, and shaping can be carried out as described above.

[0042] In yet another embodiment, a catalyst may be prepared by a method comprising the steps of: (a) combining an acidic copper-containing solution with a basic precipitant solution in a first precipitation step to form a first precipitate; (b) combining an alkali metal aluminate solution with an acidic solution in a second precipitation step to form a second precipitate; (c) contacting the first and second precipitates together in a further precipitate-mixing step to form a catalyst precursor; and (d) washing, drying, and calcining the catalyst precursor to form a copper-containing catalyst, wherein at least 70 wt. % of the copper in the catalyst is present in the first precipitate, and a silica precursor is included in the first precipitation step, the second precipitation step, or the precipitate-mixing step. The washing, drying, calcining, and shaping can be carried out as described above.

[0043] Following one or more shift stages, the hydrogen-rich gas is cooled, for example, in a heat recovery unit, to a temperature below the dew point so that the vapor condenses. The liquid condensate can then be separated using one or more gas-liquid separators, which may have one or more additional cooling stages between them. Any cooling agent may be used. Preferably, the hydrogen-rich gas stream is first cooled by heat exchange with the process condensate. This results in the formation of a heated water stream that can be used to provide some or all of the steam required for steam reforming. Thus, in one embodiment, the condensate recovered from the hydrogen-rich gas is used to provide at least a portion of the steam for steam reforming. Because the condensate may contain ammonia, methanol, hydrogen cyanide, and CO2, returning the condensate to steam provides a useful way to return hydrogen and carbon to the process.

[0044] One or more further cooling stages are desirable. Cooling may be accomplished in one or more stages of heat exchange using demineralized water, air, or a combination thereof. In a preferred embodiment, cooling is achieved by heat exchange with one or more liquids in a CO2 separation unit. In a particularly preferred configuration, the hydrogen-rich gas stream is cooled by heat exchange with the condensate, followed by cooling with CO2 reboiler liquid. The cooled shifted gas may then be fed to a first gas-liquid separator, and the separated gas may be further cooled with water and / or air and fed to a second separator, and then further cooled with water and / or air and fed to a third separator. A second or third stage condensate separation is preferred. Some or all of the condensate may be used to generate steam for steam reforming. Any condensate not used to generate steam may be sent to water treatment as effluent.

[0045] Typically, the hydrogen-rich gas stream contains 10-30% by volume (on a dry basis) of carbon dioxide. In the present process, after separating the condensed water, the carbon dioxide is separated from the resulting dehydrated hydrogen-rich gas stream.

[0046] The carbon dioxide separation step may be carried out using a physical or reactive scrubbing system, preferably a reactive scrubbing system, particularly an amine scrubbing system. Carbon dioxide may also be separated by an acid gas recovery (AGR) process. In the AGR process, the dehydrated hydrogen-rich gas stream (i.e., the dehydrated shifted gas) is contacted with a suitable sorbent, such as an amine, particularly a methyldiethanolamine (MDEA) solution, to adsorb the carbon dioxide by the liquid, resulting in a loaded sorbent and a gas stream with a reduced carbon dioxide content. The loaded absorbing solution is then regenerated by heating to desorb the carbon dioxide and obtain a regenerated absorbing solution, which is then recycled to the carbon dioxide adsorption step. Alternatively, methanol or glycol may be used to capture carbon dioxide in a manner similar to that of amines. In a preferred configuration, at least a portion of this heating is heat exchanged with the hydrogen-rich gas stream. If the carbon dioxide separation process is operated as a single-pressure process, i.e., essentially the same pressure is used in the adsorption and regeneration steps, only minor recompression of the recycled carbon dioxide is required.

[0047] For example, carbon dioxide captured from AGR may be compressed and used to produce chemicals, or sent to storage or sequestration, or used in enhanced oil recovery (EOR) processes.

[0048] Upon separating the carbon dioxide, the method provides a crude hydrogen gas stream. The crude hydrogen stream may contain 90-99% by volume hydrogen, preferably 95-99% by volume hydrogen, with the remainder comprising methane, carbon monoxide, carbon dioxide, and inert gases. The methane content may be in the range of 0.25-1.5% by volume, preferably 0.25-0.5% by volume. The carbon monoxide content may be in the range of 0.5-2.5% by volume, preferably 0.5-1.0% by volume. The carbon dioxide content may be in the range of 0.01-0.5% by volume, preferably 0.01-0.1% by volume.

[0049] While this hydrogen gas stream may be sufficiently pure for many operating duties, it may be desirable to route the hydrogen to a purification unit to provide purified hydrogen gas and a fuel gas so that the fuel gas can be used in the process as an alternative to an external fuel source in order to minimize CO2 emissions from the process.

[0050] The purification unit may suitably comprise a membrane system, a temperature swing adsorption system, or a pressure swing adsorption system. Such systems are commercially available. The purification unit is preferably a pressure swing adsorption unit. Such a unit includes a regenerable porous adsorbent material that selectively captures and thereby purifies gases other than hydrogen. The purification unit produces a pure hydrogen stream, preferably greater than 99.5% by volume, more preferably greater than 99.9% by volume, which may be compressed and used in downstream power or heating processes, for example, by use as fuel in a gas turbine (GT) or by injection into a domestic or industrial network gas piping system. The pure hydrogen may also be used in downstream chemical synthesis processes. Thus, the pure hydrogen stream may be used to produce ammonia by reaction with nitrogen in an ammonia synthesis unit. Alternatively, pure hydrogen may be used with a carbon dioxide-containing gas to produce methanol in a methanol production unit. Alternatively, pure hydrogen may be used with a carbon monoxide-containing gas to synthesize hydrocarbons in a Fischer-Tropsch production unit. Any known ammonia, methanol, or Fischer-Tropsch production technology may be used. Alternatively, the hydrogen may be used to upgrade hydrocarbons, for example by hydrotreating or hydrocracking hydrocarbons in a hydrocarbon refinery, or in any other process where pure hydrogen can be used. [Brief explanation of the drawings]

[0051] The present invention will now be described with reference to the accompanying drawings, in which: [Figure 1] 1 is a schematic flow sheet of one embodiment of the present invention.

[0052] The drawings are schematic and those skilled in the art will understand that in a commercial plant additional items of equipment may be required, such as reflux drums, pumps, vacuum pumps, temperature sensors, pressure sensors, pressure relief valves, control valves, flow controllers, level controllers, holding tanks, storage tanks, etc. Providing such equipment accessories does not form part of the present invention and is in accordance with conventional chemical engineering practice.

[0053] In Figure 1, methane-containing stream 10, steam 12, and oxygen stream 14 are fed to a synthesis gas production unit 16, which includes a gas-heated reformer and an autothermal reformer. Natural gas is steam reformed with steam in externally heated catalyst-packed tubes, and the reformed gas is autothermally reformed with oxygen in the autothermal reformer to produce a synthesis gas mixture containing hydrogen, carbon dioxide, carbon monoxide, and steam. The synthesis gas mixture is cooled to a desired inlet temperature by heat exchange with water to produce steam (not shown) and fed via line 18 to a water-gas shift unit 20, which consists of an isothermal shift reactor containing a bed of water-gas shift catalyst as described herein, to produce a hydrogen-rich gas mixture with increased hydrogen and carbon dioxide content and reduced steam and carbon monoxide content. Optionally, the hydrogen-rich gas may be fed to a low-temperature shift reactor included in the water-gas shift unit downstream of the isothermal shift reactor. The hydrogen-rich gas mixture is supplied from the water-gas shift unit 20 via line 22 to a heat recovery unit 24, which cools the hydrogen-rich gas and condenses the vapor. The condensate is separated in one or more gas-liquid separators and recovered from the unit 24 via line 26. The condensate is recycled to the synthesis gas production unit 16 via line 26 to generate steam for the gas-heated reformer and / or autothermal reformer. The dehydrated hydrogen-rich gas is supplied from the heat recovery unit 24 via line 28 to a carbon dioxide removal unit 30, which operates by reactive absorption. A carbon dioxide stream is recovered from the separation unit 30 via line 32. A hydrogen stream is recovered from the carbon dioxide removal unit 30 via line 34 and sent to an optional hydrogen purification unit 36, including a membrane system, a temperature swing adsorption system, or a pressure swing adsorption system, where impurities in the hydrogen are removed to provide a high-purity hydrogen stream 38 containing greater than 99.5% H by volume.

[0054] The present invention will now be further described with reference to the following examples.

[0055] Example 1 CuO / ZnO / Al2O3 / MgO / SiO2 formulations were prepared by simultaneously precipitating a mixed metal nitrate solution containing Cu, Zn, and Mg nitrates into potassium carbonate solution at pH 6.3-6.8 and temperatures of 65-70°C, while adding a mixed colloidal dispersion (Snowtex ST-O) containing both boehmite and silica at the flow rate and concentration required to achieve the final composition shown in Table 1 below. After precipitation, the resulting slurry was aged at 65-70°C for up to 2 hours, filtered, washed, dried, and calcined at 350°C. Finally, the calcined powder was pelletized to a final pellet density of 2.32 g / ml.

[0056] X-ray diffraction (XRD) patterns were obtained for the powder catalyst using a Bruker D8 diffractometer equipped with a Goebel mirror, a LynxEye detector, and a copper X-ray tube. Phase identification was completed using Bruker EVA v5.1.0.5 software. The resulting diffraction pattern is shown in Figure 2. The intensity ratio of the ZnO peak at approximately 32.5° to the CuO peak at 35° is 0.47:1.

[0057] Comparative Example 1 The method of Example 1 was repeated except that the colloidal dispersion did not contain Snowtex ST-O.

[0058] [Table 1]

[0059] Catalytic testing was performed using an adiabatically operated Micro-Berty reactor. The synthesis gas stream was fed to the reactor via a mass flow controller. Dry gas was mixed with the water feed in a packed vaporizer vessel, and the wet gas was transferred to the heated, stirred reactor via a heated line. A condenser system downstream of the reactor removed excess water from the gas stream. The dry gas bleed was fed to a calibrated IR analyzer that measured CO, CO2, and H2 concentrations.

[0060] Catalyst Reduction. For each test, 0.8 g of catalyst was loaded into the reactor basket. Tests were carried out at 31 barg. For catalyst reduction, 2% hydrogen in nitrogen was introduced at 100 l / h and 120°C, then the reactor was heated to 280°C over 14 hours and held for 6 hours.

[0061] Testing. After reduction, the dry gas composition was set to 71% H2, 17% CO, 12% CO2 and maintained at a flow rate of 100 l / h. Simultaneously, water addition was started to achieve a steam:dry gas molar ratio of 0.8:1 and the catalyst was tested at 280 °C for 120 h while monitoring the CO conversion. The results are shown in Figure 3 and are shown in Figure 4. i The ratio of X to X is plotted for each catalyst, where X is the i is defined as the initial CO conversion measured in each case, and X is the corresponding conversion after a certain period of time online. E1 is Example 1, and CE1 is Comparative Example 1. This plot clearly shows the improved stability of the catalyst containing a small amount of silica.

[0062] In further testing, the above procedure was repeated with an initial aging period of 5 days at 280°C, followed by an additional aging period of 5 days at 300°C to accelerate aging. In this case, flow scans were performed at 220°C on both catalysts at the end of both the first and second aging periods to generate conversion versus flow rate curves. These curves were then used to estimate relative activity by taking the ratio of the flow rates required over each catalyst to achieve a particular conversion. The results are summarized in Table 2.

[0063] [Table 2]

[0064] This test also clearly demonstrates the improved performance of the silica-containing catalyst.

Claims

1. 1. A method for producing hydrogen, comprising: (a) producing a synthesis gas comprising hydrogen, carbon monoxide, carbon dioxide, and steam in a synthesis gas generation unit; (b) subjecting the synthesis gas to one or more water-gas shift stages in a water-gas shift unit to increase the hydrogen content of the synthesis gas and reduce the carbon monoxide content thereof to provide a hydrogen-rich gas; (c) cooling the hydrogen-rich gas and separating condensed water therefrom; and (d) passing the resulting dehydrated hydrogen-rich gas through a carbon dioxide separation unit to provide a carbon dioxide gas stream and a hydrogen gas stream; wherein the synthesis gas from step (a) is fed to a water-gas shift reactor operated adiabatically or with cooling without adjustment of carbon monoxide content, at an inlet temperature in the range of 200 to 280°C and an outlet temperature less than 360°C, and containing a catalyst comprising 30 to 70 wt. % copper, expressed as CuO, in combination with zinc oxide, alumina, and silica, the catalyst being SiO ２ % to 5.0 wt. %, and the water gas shift unit comprises a medium temperature shift or an isothermal shift stage.

2. The method described in claim 1, wherein generating the synthesis gas in the synthesis gas generation unit includes one or more processes selected from adiabatic pre-reforming, catalytic steam reforming in a combustion or gas-heated reformer, autothermal reforming, and catalytic partial oxidation, and these processes are applied to gaseous or vaporized hydrocarbons.

3. The method of claim 1, wherein generating the synthesis gas in the synthesis gas generation unit comprises non-catalytic partial oxidation or gasification of a carbonaceous feedstock.

4. 3. The method of claim 1 or 2, wherein generating the synthesis gas in the synthesis gas generation unit comprises supplying reformed synthesis gas obtained from an upstream adiabatic pre-reformer or a combustion steam reformer or a gas-heated reformer to an autothermal reformer.

5. 5. The method of claim 1, wherein the hydrogen content of the synthesis gas fed to the water-gas shift reactor is in the range of 30 to 50% by volume on a wet gas basis, and the carbon monoxide content of the synthesis gas fed to the water-gas shift reactor is in the range of 6 to 20% by volume on a wet gas basis.

6. The method of any one of claims 1 to 5, wherein the water gas shift unit comprises an isothermal shift stage.

7. 7. The process according to any one of claims 1 to 6, wherein the catalyst has a copper content, expressed as CuO, in the range of 45 to 65 wt.%.

8. 8. The process according to any one of claims 1 to 7, wherein the catalyst has a zinc content, expressed as ZnO, in the range of 20 to 50 wt.%.

9. The catalyst is Al ２ O ３ 9. The method according to claim 1, wherein the aluminum content, expressed as a percentage by weight, is in the range of 5 to 40% by weight.

10. 10. The method of any one of claims 1 to 9, wherein the catalyst has one or more promoter metal oxides selected from oxides of Mg, Co, Mn, V, Ti, Zr or rare earths present in an amount in the range of 0.1 to 5 wt%.

11. The catalyst is SiO ２ 11. The method according to any one of claims 1 to 10, wherein the silica content, expressed as:

12. A method according to any one of claims 1 to 11, wherein carbon dioxide removal in the carbon dioxide separation unit is carried out using a physical scrubbing system or a reactive scrubbing system.

13. A method according to any one of claims 1 to 12, wherein one or more streams in the carbon dioxide separation unit are heated by heat exchange with the hydrogen-rich gas.

14. The method of any one of claims 1 to 13, wherein the method further comprises passing the hydrogen gas stream through a purification unit to provide purified hydrogen gas.

15. 15. The method of claim 14, wherein the purification unit is a pressure swing adsorption unit or a temperature swing adsorption unit.

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