Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/72—Other features
  • C10J3/74—Construction of shells or jackets
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2200/00—Details of gasification apparatus
  • C10J2200/06—Catalysts as integral part of gasifiers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0916—Biomass
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0973—Water
  • C10J2300/0979—Water as supercritical steam

Definitions

• the invention relates to the use of an alloy in a process for the hydrothermal gasification of saline educts, in particular in the gasification of aqueous biomass in supercritical water.
• Ni-base alloys 2.4633 and 2.4646 strongly corrode under certain conditions in supercritical water.
• the two Ni base alloys 2.4633 and 2.4646 corrode even more than the Ni base alloy 2.4856 over a comparable pressure and temperature range in an oxidizing environment (O 2 and HCl).
• alloys which are suitable in processes for the hydrothermal gasification of saline educts, in particular in the gasification of aqueous biomass in supercritical water, at least as the inner surfaces of reaction vessels without these by appreciable corrosion are damaged.
• molybdenum in processes for hydrothermal gasification in the presence of saline educts has a negative effect on the corrosion resistance, in particular potassium salts. This is crucial for biomass since potassium is present in different proportions in each biomass. This finding is surprising in that molybdenum is known to increase corrosion resistance. Obviously, this does not apply to the hydrothermal gasification with saline educts under the conditions of supercritical water.
• an alloy which comprises at least 25% by weight of iron or at least 25% by weight of nickel and only a minor proportion, ie 0.1% by weight or less, of molybdenum, preferably 0.01% by weight or less of molybdenum, proposed.
• reaction vessels are used for reaction vessels or at least for their internal surfaces, i. those surfaces which come into contact with the reaction educts, intermediates or products.
• Reaction vessels made of these alloys can be used in continuous as well as discontinuous processes (batch operation).
• These alloys are particularly useful in processes for converting biomass into gaseous products with wet biomass, i. Biomass with a water content of at least 50% by weight, in particular of at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight.
• a corrosion of up to 0.9 mm was observed in 143 hours.
• the temperature plays a role in a corrosive attack, the corrosion rate at the entrance of the reactor is much higher than in the second half of the reactor. This indicates that the first part of the reactor is amplified precipitating salts accelerate corrosion.
• the alloys used according to the invention are Ni-Cr alloys.
• the composition of some representatives of this class as maximum values in% by weight results from Table 1 , in which the molybdenum-containing alloys 2.4856, 1.4591 and 1.4401 are listed for comparison with: ⁇ b> Table 1 ⁇ / b> alloy C al Si Ti Mn Fe Cu Co Nb Not a word Y Zr Cr Ni 2.4856 * 0.03 0.40 0.40 0.40 0.40 3.0 1.0 3.8 10.0 23.0 rest 1.4591 * 0,015 ⁇ 0.5 ⁇ 2.0 rest ⁇ 1.2 ⁇ 2.0 35 33 1.4401 * ⁇ 0.07 ⁇ 1.0 ⁇ 2.0 rest 2.5 18 13 2.4646 0.05 4.5 0.20 0.50 3.0 0.01 0.10 16.0 rest 2.4633 0.25 2.40 0.50 0.20 0, 10 11.0 0.10 0, 12 0.10 26.0 rest * Comparative Examples
• Table 2 shows the corrosion-related removal in mg / cm 2 after 143 hours exposure of the mentioned materials at a pressure of 25 MPa and a temperature of 600 ° C. in an aqueous solution with 3000 ppm KHCO 3 : ⁇ b> Table 2 ⁇ / b> Material No. (trade name) Material removal (mg / cm 2 ) 2.4633 (Nicrofer 6025) -10.6 1.4591 (Alloy 33) * -15.6 Chrome* -19.3 2.4663 (Inconel 617) * -41.8 1.4401 (SS316) * -43.7 2.4856 (Inconel 625) * ** * Comparative Examples ** Very high removal that could not be determined because the sample was largely corroded.
• Table 3 shows the corrosion rate as material removal per 1000 hours at different potassium salt concentrations under comparable pressure and temperature conditions.
• the alloys 2.4646 and especially 2.4633 showed surprisingly much less corrosion under otherwise comparable conditions: ⁇ b> Table 3 ⁇ / b> attempt alloy Material removal (mm / 1000 hours) 3000 ppm K 2 CO 3 30-40 MPa, 660-700 ° C 2.4856 * - 6.92 2.4646 -0.87 2.4633 -0.07 200-256 ppm K 2 CO 3 30 MPa, 680-690 ° C 2.4856 * -2.94 2.4646 -0.87 2.4633 -0.10 * Comparative Examples
• Ni-base alloys 2.4633 and 2.4646 corrode even more than the Ni-base alloy 2.4856 under certain conditions in supercritical water in a comparable pressure and temperature range, but in an oxidizing environment (O 2 and HCl), The data presented here show that this effect does not occur in hydrothermal gasification in supercritical water.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Processing Of Solid Wastes (AREA)
• Manufacture And Refinement Of Metals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2007
  • 2007-03-08 EP EP07004732A patent/EP1845148A3/fr not_active Withdrawn

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