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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/745—Iron
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/082—Decomposition and pyrolysis
  • B01J37/088—Decomposition of a metal salt
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
  • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
  • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present disclosure relates generally to a method for making a chromium-free water-gas shift catalyst.
• the Water Gas Shift (WGS) reaction is an important step in the production of hydrogen from hydrocarbons and/or synthesis gas (syngas) streams.
• Conventional high temperature water-gas-shift catalysts are based on iron-chromium compositions. Chromium is used to slow the sintering of the iron-based active sites during operation.
• the disclosed invention relates to formulations of non- chromium catalysts. Specifically, we disclose several methods and non-chromium compositions for producing catalysts that exhibit stable water-gas shift performance. The catalyst described below would find use in a number of applications that require a water-gas- shift reactor. The details of the catalyst application and methods for producing these catalysts are described below.
• the Water Gas Shift (WGS) reaction is an important step in the production of hydrogen from hydrocarbons.
• the forward WGS reaction shown below, is
• thermodynamically favored at lower temperatures with temperatures below 350°C required for >99% conversion in typical stream compositions:
• Water-gas shift catalytic reactors can be found in numerous processes, such as steam methane reforming to hydrogen for ammonia synthesis, fuel reforming for fuel cells, and processes for conversion of coal, natural gas, or biomass to liquid fuels or hydrogen. Because of the lower reaction temperatures required by thermodynamics, catalysts are important to increase the rate of the WGS reaction. Since hydrogen is typically the desired product from the reaction, running the reaction at lower temperatures has a direct effect on improving process efficiencies.
• a chromium-free water-gas catalyst including iron and boron are disclosed, some of which include copper, or aluminum and copper.
• the boron may reside substantially at the surface of the catalyst.
• a chromium-free water-gas catalyst may include boron and copper, and these embodiments may further include aluminum or iron.
• a process for producing a catalyst having improved thermal stability may include the steps of mixing a catalyst precursor and a source of boron to form a first mixture and then calcining the first mixture at a temperature equal to or greater that 300°C, or in other embodiments, at a temperature equal to or greater than 450°C to form the catalyst.
• the boron precursor may include a source of boron including boric acid, boron oxide, alkali borate salts, boron nitride, alkali borohydrides, ammonia borane, organoboron compounds, iron boride, aluminum boride, copper boride, iron borate, aluminum borate, copper borate, and mixtures thereof.
• the catalyst precursor may include a source of boron having a boron weight relative to the catalyst equal to or greater than 0.01% and equal to or less than 0.5%.
• the catalyst precursors may include a hydroxide of iron, a hydroxide of copper, a hydroxide of aluminum, mixtures thereof, a carbonate of iron, a carbonate of copper, a carbonate of aluminum, mixtures thereof, and mixtures of a hydroxide of iron, a hydroxide of copper, a hydroxide of aluminum, mixtures thereof, a carbonate of iron, a carbonate of copper, and a carbonate of aluminum, with a source of boron.
• FIG. 1 shows the performance of commercial Fe/Cr catalyst undergoing thermal cycling at 400 psi, showing the typical industry standard for stability during this accelerated degradation test;
• FIG. 2 shows the performance of non-chromium boron-doped catalyst sample Fe 2 0 3 - Alo .4 oCuo . ioBo . ioO x (calcined at 700°C) undergoing thermal cycling at 400 psi, showing excellent catalytic durability;
• FIG. 3 shows the performance of non-chromium catalyst sample Fe 2 0 3 -Al 0.4 oCuo . ioO x (calcined at 700°C) undergoing thermal cycling at 400 psi, showing poor durability;
• FIG. 4 shows post-testing XRD analysis showing a predominantly magnetite phase for Fe 2 0 3 -Alo .4 oCuo . ioBo . ioO x (calcined at 700°C).
• compositions were prepared and examined for WGS performance, as listed in Table 2 for testing at 100 psi and Table 3 for testing at 400 psi.
• promoters such as copper and surface area stabilizers such as boron and/or alumina were discovered to boost the surface area and/or activity, with initial WGS performance greater than commercial iron-chromium high temperature WGS catalysts.
• a co-precipitation method was used.
• Metal nitrate salts were dissolved in distilled water, for example Fe (III) nitrate nonahydrate (80-90%), Al (III) nitrate nonahydrate (8- 15%), Cu(II) nitrate hydrate-2.5-H 2 0 (2-5%), with a proportion of boron in the optimal range of 0.5 to 2 wt%, from preferably either a boric acid or sodium borate precursor.
• This acidic salt solution was subsequently added to a pre-heated (70°C) base solution of preferably NaOH, KOH and/or NH 4 OH with a molar range of 0.1 to 1 molar examined (excess base is used).
• the precipitate is aged for a given time period in the mother liquor, preferably 2 to 72 hours, then the solid precipitate is washed multiple times in distilled water to remove most of the dissolved ions, dried at 70°C, and subsequently calcined to form the catalyst.
• the compositions listed in Tables 2 and 3 are the target compositions (based on the precursor ratios used), not the measured compositions.
• the actual boron concentration in the catalyst is thought to be lower than the target for the co-precipitation procedure because not all of the boron precipitates.
• IW incipient wetness
• FIGS. 1 and 2 show the thermal degradation that occurs for the same Fe:Cu:Al ratio as FIG. 2 in the absence of boron.
• a borate phase may form, and consequently suppresses grain boundary growth and copper and/or iron sintering of the catalyst.
• the low toxicity and low cost of boron compounds could enable wide scale adoption by catalyst end users and manufacturers.
• commercial catalysts with copper suffer from pyrophoricity.
• the addition of boron and formation of metal borates may also retard flammability/reactivity in ambient oxygen/humidity containing environments.
• the surface area of samples calcined between 600 and 700°C are on the order of commercial HTS catalysts.
• the Fe 2 O 3 -Alo.40Cuo.10Bo.10Ox catalyst was further characterized by X-ray
• XPS Photoelectron Spectroscopy
• ICP-AES Inductively Coupled Plasma Atomic Emission spectroscopy
• Three variations of the catalyst were examined by XPS: calcination at 500°C, calcination at 700°C, and post-WGS testing (400 psi) of the sample calcined at 700°C.
• XPS is a surface-sensitive technique, so the analysis determines the relative ratio of elements on the surface (typically the first few nanometers). As seen in Table 4, the samples all contained Cu, Fe, B, and Al on the surface. The surface ratios do not match the target composition; therefore, it is likely that the surface of the catalyst is enriched with some species, such as Cu, B, and Al.
• ICP-AES analysis was performed on the sample calcined at 700°C to determine the bulk composition of the catalyst.
• the ratios of Fe:Cu and Fe:Al in the catalyst were similar to the target composition used in the precipitation process.
• the boron composition was lower than the target composition, and much lower than the surface composition. Based on this result, only a small fraction of boron is precipitating out with the catalyst, and the boron that is in the catalyst is concentrated at the surface. It is possible that the boron concentrates at grain boundaries of Fe, Al, or Cu. Again, without any limitation as to theoretical basis, if so, such a Fe-B, Al-B, or Cu-B phase could prevent the catalyst from sintering and deactivating. One would also expect such a phase to allow the catalyst to maintain a high surface area after calcination.
• FIG. 4 shows the XRD pattern for the Fe 2 O 3 -Alo.40Cuo.10Bo.10Ox catalyst after calcination at 700°C and durability testing at 400°C.
• the XRD pattern shows that the catalyst predominantly has a magnetite crystal structure. After calcination, one would expect the material to have a hematite structure, so this magnetite phase likely forms once the catalyst is reduced. Since the WGS reaction is believed to proceed through a redox mechanism, it is likely that multiple oxidation states and crystal structures could be present on the surface during operation.
• the significance of the XRD pattern is that separate crystal structures for aluminum, copper, or boron phases are not observed. This suggests that the heteroatoms are, for the most part, intimately mixed and contained within the same crystal structure as iron. One could also say that the heteroatoms form a solid solution with the iron oxide.
• iron-aluminum-copper-boron catalyst Fe 2 O 3 -Alo.40Cuo.10Bo.10Ox
• Metal nitrate salts and boric acid were dissolved in 250 mL of distilled water, specifically Fe (III) nitrate nonahydrate (16.165 grams), Al (III) nitrate nonahydrate (3.010 grams), Cu(II) nitrate hydrate-2.5-H 2 0 (0.470 grams), along with 0.130 grams of boric acid.
• 600 mL of 0.5 M NaOH was prepared and heated to 70°C.
• the acidic salt solution was rapidly mixed with the heated base, resulting in the formation of a solid precipitate.
• the mixture is stirred for 2 hours, and the precipitate is aged for 70 hours in the mother liquor.
• an additional 0.5 M NaOH is added dropwise until the pH of the mixture is 10, and the mixture is aged another 2 hours.
• the solid precipitate is washed multiple times, using filtration or centrifuge methods, in distilled water to remove most of the dissolved ions, and dried at 70°C, and subsequently calcined in air for 1 hour at 500°C to form the catalyst.
• iron-aluminum-copper-boron catalyst Fe 2 O 3 -Alo.40Cuo.10Bo.01Ox - IW
• Metal nitrate salts were dissolved in 250 mL of distilled water, specifically Fe (III) nitrate nonahydrate (16.165 grams), Al (III) nitrate nonahydrate (3.010 grams), and Cu(II) nitrate hydrate-2.5-H 2 0 (0.470 grams).
• 600 mL of 0.5 M NaOH was prepared and heated to 70°C.
• the acidic salt solution was rapidly mixed with the heated base, resulting in the formation of a solid precipitate.
• the mixture is stirred for 2 hours. Next, while stirring the mixture, an additional 0.5 M NaOH is added dropwise until the pH of the mixture is 10, and the mixture is aged another 2 hours. Finally, the solid precipitate is washed multiple times, using filtration or centrifuge methods, in distilled water to remove most of the dissolved ions, and dried at 70°C. Next, 0.003 to 0.120 g, preferably 0.014 g, of boric acid (or other soluble boron precursor) is dissolved in 5 mL of distilled water. The boric acid solution is then added dropwise to the dried precipitate while mixing. The wetted precipitate is then dried again at 70°C. Finally, the sample is calcined at 300 to 700°C to form the catalyst.
• boric acid or other soluble boron precursor
• a chromium-free water-gas catalyst including iron and boron
• the iron may include a plurality of iron oxides.
• the catalyst may include aluminum, while in others in may include copper, or aluminum and copper.
• the catalyst may be prepared, by way of example only and not limitation, to have a surface area of at least 30 m g, at least 60 m g, a surface area of at least 90 m g, and a surface area of at least 120 m g in various embodiments.
• the catalyst may be present in differing amounts on the surface of the catalyst.
• the catalyst may a particle surface composition by mole that is greater than 0.5% boron and less than 3.0% boron, while in other embodiments, the catalyst may have a particle surface composition by mole that is greater than 0.5% boron and less than 2% boron.
• the boron may be present in different total compositions within the catalyst.
• the catalyst may have a total composition by mass of greater than .001% boron and less than or equal to 2% boron, while in another, the catalyst may have a total composition of greater than 0.01% boron and less than or equal to 0.5% boron.
• a chromium-free water-gas catalyst may include boron and copper, and these embodiments may further include aluminum or iron.
• the catalyst includes all four; iron, boron, aluminum, and copper.
• the boron source may include a source of boron consisting of boric acid, alkali borate salts, boron nitride, alkali
• the catalyst precursor may include a source of boron having a weight relative to the catalyst equal to or greater than 0.01% and equal to or less than 0.5%.
• the catalyst precursors may include a hydroxide of iron, a hydroxide of copper, a hydroxide of aluminum, mixtures thereof, a carbonate of iron, a carbonate of copper, a carbonate of aluminum, mixtures thereof, and mixtures of a hydroxide of iron, a hydroxide of copper, a hydroxide of aluminum, mixtures thereof, a carbonate of iron, a carbonate of copper, and a carbonate of aluminum, with a source of boron.
• a hydroxide of iron, a hydroxide of copper, a hydroxide of aluminum, mixtures thereof, a carbonate of iron, a carbonate of copper, and a carbonate of aluminum with a source of boron.
• the step of calcining the first mixture may actually include the step of calcining the first mixture at a temperature equal to or greater than 450°C.

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• 2016
  • 2016-03-09 CN CN201680010633.8A patent/CN107406252A/zh active Pending
  • 2016-03-09 EP EP16762388.3A patent/EP3268307A4/de not_active Withdrawn

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