Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
  • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
  • C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1406—Multiple stage absorption
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1425—Regeneration of liquid absorbents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/002—Removal of contaminants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/002—Removal of contaminants
  • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
  • C10K1/006—Hydrogen cyanide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/02—Dust removal
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
  • C10K1/06—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials combined with spraying with water
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
  • C10K1/26—Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/10—Inorganic absorbents
  • B01D2252/103—Water
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/40—Nitrogen compounds
  • B01D2257/406—Ammonia
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/40—Nitrogen compounds
  • B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
• • 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
  • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
  • C01B2203/0415—Purification by absorption in liquids

Definitions

• the present invention relates to process for the purification for syngas.
• the invention also relates to a clean syngas obtained by said process.
• syngas refers to synthesis gas, which is a common term to refer to gas mixtures comprising carbon monoxide and hydrogen.
• Syngas produced by such known gasification processes contains impurities, in particular soot and nitrogenous impurities, such as ammonia (NH3) and hydrogen cyanide (HCN) .
• NH3 ammonia
• HCN hydrogen cyanide
• Syngas can be used in a variety of chemical processes, in which it is converted in a desired product . Usually such conversion is a catalytic process, for example a Fischer-Tropsch process.
• Catalysts used in those conversion processes are often very sensitive to certain impurities in the syngas which would cause fouling (soot) and/or poisoning (NH3, HCN) of the catalyst used. Deactivation of the catalyst and selectivity loss, often irreversible, will occur as a result. Accordingly, it is important that impurities, such as soot, NH3 and HCN, are effectively removed from the syngas before using the syngas as feed in a catalytic conversion process.
• NH3 and HCN are removed from the syngas by hydrolysis of HCN to NH3 at elevated temperature followed by passing the hydrolysed syngas over an acidic cation exchange resin in the presence of water to remove NH3.
• WO-99/38795-A1 discloses a process for producing and cleaning a syngas.
• HCN is catalytically converted into NH3 which, along with some of the HCN, is subsequently removed from the syngas with water to form an aqueous solution of NH3 and HCN.
• the hydrocarbon gas feed to the synthesis gas generator is then used to strip NH3 and HCN from the aqueous solution of NH3 and HCN that was formed.
• the NH3 and HCN are consumed to form clean water. A portion of the resulting clean water is recycled back into the process where it is used to scrub the synthesis gas, with the remainder used for other purposes or sent to disposal.
• US-4189307 discloses a process for producing clean HCN-free syngas from raw syngas leaving a partial- oxidation gas generator by a continuous process
• HCN-containing aqueous absorbent resulting from this scrubbing step is then processed, for example, by stripping it or by reacting it in the gas generator.
• other acid gases if present, may be removed from the synthesis gas in said acid-gas- removal zone.
• US-2012/0202897-Al discloses a method for removing hydrogen sulphide and other impurities, such as NH3, COS, HCN and small alkali metal compounds from syngas obtained from gasification of a biomass feedstock.
• the method comprises contacting the syngas with an aqueous absorbent containing low levels of certain metal ions to absorb the impurities.
• US-2012/0202897-Al refers in particular to sulphur compounds as impurities to be removed: the absorbed sulphur compound reacts with the metal ions in the aqueous absorbent to form metal sulphide
• this method is carried out in a single vessel comprising three successive spray sections separated by sieve plates.
• the syngas enters the column via an inlet distributon in the bottom part and is countercurrently contacted with the aqueous absorbent containing the metal ions in the successive spray sections.
• step (b) cooling the soot-lean syngas resulting from step (a) to a temperature in the range of from 20 to 50°C;
• step (c) contacting the cooled soot-lean syngas resulting from step (b) with water to remove HCN and NH3 resulting in clean syngas and HCN/NH3-rich waste water,
• step (i) in step (a) the raw syngas is cooled below its dew point by its contact with water;
• step (ii) the HCN/NH3-rich waste water resulting from step (c) is passed through at least one stripping column resulting in a clean water stream and a waste stream;
• step(iii) at least 50% (v/v) part of the clean water stream is recycled to step(c) .
• the invention also relates to a clean syngas
• An advantage is that the purified syngas can be used in catalytic conversion processes without negatively effecting the catalyst.
• step (a) of the process according to the present invention the raw syngas is contacted with water to remove soot, resulting in a soot-rich waste water and a soot-lean syngas.
• raw syngas is contacted with water in step (a) at a temperature range of from 120 to 160°C, preferably at a range of from 130 to 160°C and at a pressure in the range of from 35 to 80 bar, preferably 45 to 60 bar.
• the amount of clean water added at the start-up of the plant in step (a) can be neglected in view of the the amount of water generated in the present process, for example the condensed water from syngas, recycled to step (a) .
• raw syngas syngas containing impurities, in particular soot and nitrogenous impurities, such as ammonia (NH3) and hydrogen cyanide (HCN) .
• the amount of soot in the raw syngas in a range between 25 and 65% (v/v) .
• the temperature of the raw syngas in step (a) is in a range of from 110 to 220°C, preferably 120 to 180 °C.
• the raw syngas is cooled below its dew point by its contact with water.
• This water may be clean water, condensed water from syngas and/or recycled water.
• the water added in step (a) originates from condensed water from syngas.
• the temperature of water in step (a) is between 10 and 60°C, preferably between 20 to 50°C.
• the heat contained in the raw syngas is effectively transferred to the water (i.e. cooling of the raw syngas) and any soot particles contained in the raw syngas can be effectively captured by water droplets condensing on such soot partices.
• the dew point of a typical raw syngas is between 140 and 150 °C.
• step (a) a soot-rich waste water and a soot-lean syngas is obtained.
• the amount of soot in the soot-rich waste water is in the range of 25 to 65 %
• step (v/v) based on the total amount of soot in the raw syngas.
• soot-lean syngas is meant that the soot content in the syngas is virtually nill .
• the raw gas obtained in step (a) is soot-free syngas.
• the temperature of the soot-rich waste water obtained in step (a) is between 120 and 160°C, preferably 120°C.
• a first part of the soot-rich waste water resulting from step (a) is preferably cooled and re-used in step (a) .
• the soot-rich waste water is cooled by a heat exchanger, such as an air and/or water cooler.
• part of the colled soot-rich waste water is recycled to step (a) .
• a second part of the soot-rich waste water is cleaned before further
• %(v/v) Preferably between 60 and 90 %(v/v), more preferably between 70 to 85 % (v/v) , even more preferably 83 % (v/v) , of the soot-rich wast water is cleaned before further treatment.
• the soot-rich waste water is preferably cleaned from absorbed contaminants in at least one waste water stripper.
• the cleaning step of the second part of the soot-rich wast water is at a pressure between 3 and 5 bar and at a temperature between 130 and 160°C.
• the temperature of the soot-lean syngas will usually be between 40 and 80 °C lower than the temperature of the raw syngas and will be in the range of from lOOto 140°C.
• step (b) of the process according to the present invention the soot-lean syngas resulting from step (a) is cooled to a temperature in the range of from 20 to 50°C.
• the soot-lean syngas in step(b) is preferably cooled by a series of heat exchangers, such as air and/or water coolers .
• step (c)of the process according to the present invention the cooled soot-lean syngas resulting from step (b) is contacted with water to remove HCN and NH3 resulting in clean syngas and HCN/NH3-rich waste water.
• the cooled soot-lean syngas from step (b) is contacted with water at a termperature range of from 20 to 50°C and a pressure between 40 to 60 bar.
• the water used in step (c) has a temperature between 10 and 60°C, preferably 20 to 50°C.
• the amount of HCN and NH3 in soot-lean syngas is between 10 and 100 ppbv based on the total amount of HCN and NH3 in raw syngas .
• the amount of HCN and NH3 in the clean syngas is virtually nihil .
• the HCN/NH3-rich waste water resulting from step (c) is passed through at least one stripping column resulting in clean water stream and a waste stream.
• the waste water stream may comprise from 10 to 100 ppbv of HCN and NH3.
• at least 50% (v/v) part of the clean water stream is recycled to step (c) .
• HCN/NH3 rich waste water stream is recycled to step (c) . Also, at most 10% (v/v) of the clean water stream obtained from the HCN/NH3 rich wast water stream is recycled to step (a)
• the present invention provides a clean syngas.
• the clean syngas preferably contains no soot (virtually nihil) and 10 to 100 ppbv of HCN and NH3 based on the total amount of soot, HCN and NH3 in the raw syngas .
• the Figure schematically shows a process scheme of a preferred embodiment of the process according to the present invention.
• the process scheme is generally referred to with reference numeral 1.
• a raw syngas 10 enters a soot scrubber 2 to obtain a soot-rich waste water stream 20 and a soot-lean syngas 30.
• the soot-rich waste water stream 20 is fed to a water stripper 3 to obtain a clean water stream 40 for further treatment. Part of stream 20 is recycled to soot scrubber
• the soot-lean syngas 30 is cooled with a heat
• HCN/NH3 scrubber 5 to obtain a purified clean syngas 60 and a HCN/NH3-rich waste water stream 70.
• the HCN/NH3 rich waste water stream 70 is fed into a HCN/NH3 stripper
• the clean water stream 80 is recycled back to the HCN/NH3 scrubber 5. Part of the clean water stream 80 is recycled back to the scrubber 2.

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Citations (8)

• 2018
  • 2018-12-19 WO PCT/EP2018/085870 patent/WO2019129578A1/en unknown
  • 2018-12-19 EP EP18819155.5A patent/EP3732128A1/en not_active Withdrawn
  • 2018-12-19 US US16/958,125 patent/US20200339897A1/en not_active Abandoned
  • 2018-12-19 RU RU2020124715A patent/RU2020124715A/ru unknown

Patent Citations (8)

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