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Definitions

• the present invention belongs to the field of water vapor reforming catalytic processes and the catalysts used in these processes.
• the production of hydrogen from biomass, in particular ethanol, is of great interest to new industrial units and fuel cells and the object of the present invention.
• steam reforming The most commonly used process for industrial scale hydrogen production is steam reforming. It is a multi-step process with different operating conditions and catalysts. In the so-called “steam reforming" stage, which uses nickel-type catalysts on refractory supports such as alumina, calcium aluminate or magnesium aluminate, the main reactions that occur are:
• the steam reforming process uses natural gas, refinery gas, propane, butane, liquefied petroleum gas or naphtha as raw materials.
• the deactivation of catalysts used in the steam reforming process by coke formation is the main difficulty to be solved for the industrial viability of hydrogen production from ethanol.
• Ethene formed from ethanol dehydration is one of the main compounds that favor coke formation in steam reforming of ethanol.
• the maximum permissible ethylene content in the feed is considered to be around 1% v / v. Above this value the loss of catalyst activity makes the process economically unfeasible.
• oxides and mixed oxides such as MgO, Al 2 0 3 , V 2 0 5 , ZnO, Ti0 2 , La 2 0 3 , Ce0 2 , Sm 2 0 3 , La 2 0 3 -Al 2 O 3 , CeO 2 -Al 2 O 3 , MgO-Al 2 O 3 ; Co supported as Co / Al 2 0 3 , Co / La 2 0 3 , Co / Si0 2 , Co / MgO, Co / Zr0 2 , Co / ZnO, Co / Ti0 2 , Co / V 2 0 5 , Co / Ce0 2 , Co / Sm 2 0 3> Co / C0 2 -Zr0 2 , Co / C; Ni supported as Ni / La 2 0 3, Ni (La 2 0 3 -AI 2 , Ni supported as Ni / La 2 0 3, Ni (La 2 0 3 -AI 2 , Ni supported as Ni
• a second technical solution, and scope of the present invention would be the prior conversion of ethanol into industrially used raw materials, which converts ethanol into a methane-free, gas free olefins and other organic contaminants such as acetaldehydes, ketones, acetates and others by combining suitable process conditions and catalysts which exhibit low coke formation.
• gas may then be used as a filler of a conventional hydrogen production unit using natural gas, LPG, refinery gas, naphtha or combinations thereof as raw materials.
• Noble metal containing catalysts tend to have higher coke resistance than equivalent catalysts using nickel as the active phase. However, producing them requires higher costs, which tends to make their industrial use unfeasible. Thus, although known for a long time, such noble metal-based catalysts have not found industrial application in large-scale hydrogen production.
• catalysts used for the production of hydrogen from natural gas, propane, butane, LPG, refinery gas or naphtha, in large capacity units (defined herein as having a production capacity above 10,000 Nm 3 / day), comprise nickel supported on refractory materials such as alumina, calcium aluminate or magnesium aluminate and may be promoted by others. elements such as alkali metals (especially potassium) and rare earths (especially lanthanum).
• Nickel-based catalysts can undergo serious coke deactivation when used for ethanol steam reforming, the rate of coke formation being influenced by the type of catalyst and operating conditions.
• Ni / AI 2 O 3 catalyst exhibits good activity and selectivity for hydrogen production at temperatures above 550 ° C. At lower temperatures there is the appearance of ethylene in the products accompanied by rapid loss of activity associated with coke deposition.
• WO 2009/004462 A1 teaches how to produce hydrogen and carbon nanotubes (a special type of coke) from the decomposition of ethanol on catalysts based on nickel supported on lanthanum.
• Publication WO 2009/009844 A2 teaches the addition of oxygen to the ethanol and water vapor feed associated with the use of specific cerium oxide-based catalysts with promoters selected from the alkali and lanthanide group for production. of H 2 from ethanol.
• a possible technique that can be applied to the production of hydrogen from ethanol would be its prior conversion to raw materials, which are already used industrially for the production of large scale hydrogen such as naphtha, natural gas or light hydrocarbons such as methane, ethane, propane and butane.
• the hydrocarbon stream After a first step of prior conversion of ethanol, the hydrocarbon stream would feed into the conventionally existing industrial hydrogen production process, where hydrocarbons would be converted to the mixture of H 2 , CO, CO 2 and residual methane.
• H 2 (or if desired the H 2 / CO mixture) would be purified by conventional amine absorption techniques or via pressure swing adsorption (PSA).
• PSA pressure swing adsorption
• US 2006/0057058 A1 teaches a method for producing a hydrogen rich gas from ethanol characterized by:
• the catalyst comprises Pt, Pd or Cu on a support.
• the catalyst comprises Pt, Pd or Cu on a support. selected from the group alumina, silica alumina, zirconia and zeolites, particularly zeolite HZSM5);
• the invention does not report data on catalyst stability. Hydrogen produced in accordance with this invention supplies a fuel cell and is therefore suitable for small scale use.
• Patent document WO / 2009/130197 discloses a method for converting ethanol to methane in a preformer. According to the method, ethanol and water vapor are put to react on a a catalyst comprising platinum on a support of Zr0 2 and Ce0 2 in the temperature range 300 ° C to 550 ° C.
• the present invention relates to a process for producing hydrogen from ethanol and to a specific catalytic system for use in said process.
• An essential feature of the present invention is the conversion of ethanol as a first step in the process to a methane-rich, olefin-free gas ( ⁇ 1%) with low carbon monoxide ( ⁇ 2%) and other organic contaminants. , such as acetaldehyde.
• the present invention may be implemented in large scale industrial hydrogen production units, with replacement of the pretreatment section catalysts (usually ZnO and CoMo are used) and use of the process conditions described therein.
• the present invention relates to a process for producing hydrogen from ethanol and to the use in that process of specific nickel-based catalysts.
• the process of producing hydrogen from ethanol is characterized by two steps, which actually result from the combination of two processes carried out in series.
• a pre-reforming process comprises reactions that produce a high methane gas and in the second stage, a typical configuration of the industrially used steam reforming process is suitable for receiving the product generated in the first stage. Therefore, the present invention can be implemented in existing industrial hydrogen production units by replacing the pretreatment section or pretreading section catalysts with suitable catalysts and appropriate process conditions for carrying out the first step. in accordance with the present invention.
• the operating pressure may be that used in the industrial practice of the steam reforming process, ie by the state of the art between 1 kgf / cm 2 and 40 kgf / cm 2 , preferably between 10 kgf / cm 2 and 25 kgf / cm 2 , the maximum value being defined by the limitations of the building materials of the industrial unit.
• high methane gas is used as charge of a hydrogen production unit by the steam reforming process.
• a typical configuration of the industrially suitable steam reforming process for receiving the high methane gas generated in the first step comprises the following additional steps:
• steam reforming process configurations known in industrial practice can be used to process the high methane gas generated in the first process step, such as process configurations containing pre-reforming, secondary reforming, "shift” reactors. "Medium” (MTS), “low shift” (LTS) and methanation and purification of hydrogen rich gas through the use of aqueous amine solutions.
• Steam reforming process configurations for synthesis gas production may also be used, such as streams containing in addition to hydrogen, significant CO contents for use in petrochemical processes such as methanol production or Fischer Tropsch processes.
• the catalysts of the present invention comprise nickel on a low acid inorganic support, selected from zinc oxide, calcium titanate and calcium or magnesium aluminate, or a mixture thereof, which support may be modified by alkali metals, particularly by the addition of potassium to achieve a content between 0,1% w / w and 10% w / w, preferably from 1% to 5% potassium.
• the process of preparing the inorganic oxide-supported nickel-based catalyst for use in the process claimed by the present invention comprises the following steps:
• an inorganic nickel salt preferably nitrate, acetate or carbonate, which may contain one or more elements of the lanthanide (or rare earth) group, preferably lanthanum or cerium;
• steps 2 to 4 may be repeated more than once until the desired NiO content in the support is achieved. Desired contents are between 10% w / w and 40% w / w NiO, preferably between 12% and 20%.
• additives may be included in the impregnation, compounds for controlling pH, increasing solubility or preventing phase precipitation. Non-limiting examples of these compounds are nitric acid, sulfuric acid, phosphoric acid, ammonium hydroxide, ammonium carbonate, hydrogen peroxide (H 2 O 2 ), sugars or combinations of these compounds.
• an alumina content of between 5% and 50% is added to obtain a mechanical strength of the catalysts suitable for industrial use.
• the carrier particles may be in various forms suitable for industrial use in the steam reforming process, such as spheres, cylinders, cylinders with one central hole (rashing rings) and cylinders with several holes.
• Nickel oxide catalysts on the support need transformation to the active phase of nickel metal on the support. The so-called reduction may be effected prior to feeding ethanol and water vapor by passing a hydrogen flow or reducing agent such as ammonia, methanol or acetaldehyde at temperatures between 300 ° C and 550 ° C.
• the catalyst may be reduced externally as a final step in the process of its production by passing a hydrogen stream or a reducing agent such as ammonia, methanol or acetaldehyde under temperature conditions between 300 ° C to 550 ° C, for 1 to 5 hours, then cooled and subjected to airflow at temperatures between 20 ° C and 60 ° C for 1 to 5 hours.
• the catalysts may contain low levels of noble metals, particularly Pd and Pt in contents of less than 0.5% w / w, or preferably less than 0.1% w / w, to accelerate the reduction step.
• the catalysts thus prepared may be used to produce a gas with a high methane content, an olefin content of less than 1% w / w and a low CO content, at pressures between 1 kgf / cm and 50 kgf / cm and temperatures. 300 ° C to 550 ° C from the mixture of ethanol, hydrogen and water vapor with molar ratios H 2 / ethanol between 0,2 mol / mol and 0,6 mol / mol and molar ratios H 2 O / ethanol between 1 mol / mol and 10 mol / mol, which allow to operate for long periods without loss of performance by coke formation.
• High methane gas may be used for hydrogen production through the steam reforming process.
• the present invention also optionally provides for the use of commercial "methane” classified catalysts or “pre-reformed” catalysts, both nickel based, provided that they are used under the taught process conditions.
• Results were obtained in a microactivity unit operating at atmospheric pressure.
• the catalysts were milled to the range 100 mesh to 150 mesh. Ethanol was fed through the carrier gas (hydrogen or nitrogen) through a saturator maintained at 10 ° C.
• the analyzes of the charge and the formed product were performed by gas chromatography.
• This comparative example teaches that commercial zinc oxide-based adsorbents and cobalt- and molybdenum-containing hydrotreating catalysts are used in the pre-treatment step.
• Industrial steam reforming process loads are not suitable for processing a feed of ethanol, hydrogen and water vapor under industrially used temperature conditions in pretreatment reactors as they lead to a high rate of ethylene formation. and other by-products, particularly acetaldehyde and light olefins.
• This example further illustrates the beneficial effect of the presence of water vapor (comparison between Examples 2.1 and 2.2) and the reduction of space velocity (comparison between Examples 2.4 and 2.5) in reducing the formation of ethylene and other light olefins.
• the present invention claims the replacement of the ZnO-based catalysts and hydrotreatment of the filler pretreatment section by nickel-based catalysts prepared in accordance with the present invention as a solution for ethanol production in waste reforming units. existing steam.
• This comparative example according to the present invention teaches the use of a zinc oxide type support for the preparation of a nickel oxide based catalyst and its use in the production of hydrogen from ethanol.
• the following samples were prepared:
• Sample 3A 95 grams of commercial zinc oxide-based adsorbent (ZINOX390) was impregnated by the incipient impregnation method with 38 ml of aqueous solution containing 19,5 grams of Ni (N0 3 ) 2 6H 2 0. The sample was then dried at 110 ° C overnight and calcined at 450 ° C in air for 4 hours to give 5% w / w zinc oxide supported NiO;
• Sample 3B 94 grams of the catalyst from Example 5 was soaked through the Incipient impregnation method with 40 ml of aqueous solution containing 21,4 grams of Ni (NO 3 ) 2 6H 2 0. The sample was then dried at 110 ° C overnight and calcined at 450 ° C. C for 4 hours to give 10% w / w zinc oxide supported NiO;
• Sample 3C 95 grams of the catalyst of Example 6 were soaked by the incipient impregnation method with 40 ml of aqueous solution containing 21,7 grams of nickel nitrate Ni (NO 3 ) 2 6H 2 0. Then dried. sample at 110 ° C overnight and calcined at 450 ° C in air for 4 hours to give
• This comparative example according to the present invention teaches the use of an alkali-promoted zinc oxide support for the preparation of a nickel oxide catalyst and its use in the production of hydrogen from ethanol. .
• a potassium-promoted zinc oxide support was prepared as follows: 150 grams of commercial zinc oxide-based adsorbent (ZINOX390) was impregnated with 60 ml of aqueous solution containing 3.1 grams of zinc oxide. potassium; The sample was then dried at 110 ° C overnight and calcined at 450 ° C for 4 hours to give 2% K 2 O on zinc oxide.
• ZINOX390 commercial zinc oxide-based adsorbent
• Sample 4A 95 grams of the material prepared in Example were impregnated.
• Sample 4C 79 grams of the catalyst of Example 8 was soaked by the incipient impregnation method with 26 ml of aqueous solution containing 20,2 grams of nickel nitrate Ni (NO 3 ) 2 6H 2 0. Then dried. The sample was taken at 110 ° C overnight and calcined at 450 ° C in air for 4 hours to give 15% w / w of potassium-promoted zinc oxide supported NiO.
• Example 3 The catalysts prepared in Examples 3 and 4 were previously reduced in hydrogen flux and water vapor at 450 ° C for 2 hours and then tested similarly to that described in Example 1.
• This comparative example demonstrates that commercial natural gas and naphtha steam reforming catalysts exhibit high deactivation, shown by the sharp drop in conversion in Table 4 when used for the steam reforming of ethanol in the presence of hydrogen and under existing temperature conditions in the pretreatment section of existing hydrogen generating units.
• the catalysts were previously reduced in hydrogen flux and water vapor at 450 ° C for 2 hours and then tested similarly to that reported in Example 1.
• This example shows that commercial catalysts known in industrial practice as methanation catalysts originally used in the conversion of carbon monoxide and carbon dioxide to hydrogen for methane production can be surprisingly used in accordance with the present invention for conversion of ethanol to a methane-rich, olefin-free gas in the presence of hydrogen and water vapor and the temperature conditions used in the pretreatment section of existing hydrogen generating units by the steam reforming process.
• the catalysts were previously reduced in hydrogen flux and water vapor at 450 ° C for 2 hours and then tested similarly to that described in Example 1.
• the activity and deactivation properties were influenced by the type of commercial catalyst used, indicating that the preparation of specific catalysts for the conversion of ethanol to hydrogen would be desirable as proposed in the present invention.
• This example teaches the preparation of a catalyst, according to the present invention, based on nickel-based alumina support and promoted by alkali metals.
• 300 grams of commercial aluminum hydroxide (PURAL SB, marketed by SASOL) was impregnated with 180 ml of aqueous solution containing 7.1 grams of potassium hydroxide. The sample was then dried at 110 ° C for 12 hours and air calcined at 1200 ° C for 4 hours to obtain a potassium-promoted alumina-type support. The sample was then impregnated by the incipient impregnation method with aqueous solution containing nickel nitrate, dried at 10 ° C and calcined at 450 ° C. The procedure was repeated twice more to obtain a catalyst containing 15% NiO (15% NiO / 2% K / alumina).
• This example teaches the preparation of a catalyst according to the present invention based on nickel based on magnesium aluminate support and promoted by alkali metals. Initially, a magnesium aluminate support was prepared from the following steps:
• the calcination temperature used was 1,100 ° C.
• the prepared support was then impregnated to the pore volume with aqueous KOH solution and then calcined at 1200 ° C for 4 hours to give a support with 1.5% w / w KOH.
• 12 grams of the support thus obtained was impregnated with 39 ml of an aqueous solution containing 23 grams of Ni (NO 3 ) 2 6H 2 O.
• the material was dried and calcined at 450 ° C for 4 hours. hours to obtain 5% potassium-promoted magnesium aluminate-supported NiO.
• the procedure was repeated until 15% of potassium-promoted magnesium aluminate supported NiO was obtained.
• This example teaches the preparation of a catalyst, according to the present invention, based on nickel-based calcium aluminate support and promoted by alkali metals.
• 300 grams of commercial calcium aluminate (SECAR 80) was soaked to the pore volume with an aqueous KOH solution and then calcined at 1200 ° C for 4 hours to obtain a promoted calcium aluminate support. by 1.5% w / w KOH.
• 114 grams of the support thus obtained was impregnated with 31 ml of an aqueous solution containing 23 grams of Ni (NO 3 ) 2 6H 2 O. The material was dried and calcined at 450 ° C for 4 hours to give 5% NiO supported on potassium promoted calcium aluminate. The procedure was repeated until 15% of potassium-promoted calcium aluminate supported NiO was obtained.
• This example teaches the preparation of a catalyst according to the present invention in its preferred embodiment, nickel based on alkali metal titanate type supports.
• 190 grams of commercial calcium titanate (Certronic) is impregnated with 68 ml of an aqueous solution containing 39 grams of Ni (NO 3 ) 2 6H 2 O.
• the sample was then dried at 110 ° C for one night and then dried. calcined at 450 ° C in air for 4 hours to give 5% w / w of calcium titanate supported NiO.
• the procedure was repeated two more times to obtain the catalyst containing 15% w / w calcium titanate supported NiO.
• Example 12 This example teaches the preparation of a nickel-based catalyst on the alumina-calcium type support. 235 grams of CATAPAL alumina was impregnated with 141 ml of aqueous solution containing 63 grams of Ca (NO 3 ) 2 4H 2 O. The sample was then dried at 110 ° C for 1 night and calcined at 600 ° C. C for 4 hours air. 230 grams of the above support was soaked to the pore volume with 160 ml of aqueous solution containing 99.4 grams of Ni (NO 3 ) 2 6H 2 0. The sample was then dried at 110 ° C overnight. and calcined at 450 ° C in air for 4 hours to give 10% w / w alumina supported NiO. The impregnation and calcination procedure was repeated to obtain the final catalyst containing 20% NiO supported on calcium modified alumina.
• This comparative example (Table 6) demonstrates that preferred catalysts of the present invention consisting of nickel on low acid supports have high stability and selectivity for producing a high methane, olefin-free gas under existing temperature conditions. in the pretreatment section of existing hydrogen generating units. The catalysts were previously reduced in hydrogen and water vapor flow at 450 ° C for 2 hours and then tested similarly to that described in Example 1.
• the catalyst according to the present invention consists of Ni on alumina-type supports, calcium aluminates, magnesium aluminates and calcium titanates and may be promoted by alkali metals such as potassium.
• This example shows that, according to the present invention, the use of hydrogen, with molar ratios between 0.1 mol / mol and 1.0 mol / mol in the ethanol and water vapor mixture, is essential to avoid coke formation. .
• a typical molar ratio of between 0.01 mol / mol and 0.05 mol / mol is used industrially for natural gas steam reforming and between 0.1 mol / mol to 0.3 mol / mol for reforming. naphtha steam.
• Tables 7 and 8 present the results obtained with commercial pre-reforming and methanation catalysts, respectively, which are typically used in hydrogen production by the steam reforming process.
• Pre-reforming and methanation catalysts are used in the production steps of a high H 2 gas from natural gas, LPG or naphtha.
• This example shows the use of catalysts according to the present invention, in their preferred embodiment, Ni-type on low acid supports.
• the reaction conditions were described in Example 14. The results show excellent stability without increased pressure drop, indicative of coke formation on the catalysts (Table 9).

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