Classifications

• • 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
  • B01D53/02—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 adsorption, e.g. preparative gas chromatography
  • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
  • B01D53/047—Pressure swing adsorption
• • 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
  • B01D53/22—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 diffusion
  • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, 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
  • B01D53/32—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 electrical effects other than those provided for in group B01D61/00
  • B01D53/323—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 electrical effects other than those provided for in group B01D61/00 by electrostatic effects or by high-voltage electric fields
• • 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
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/86—Catalytic processes
  • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
• • 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
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/86—Catalytic processes
  • B01D53/869—Multiple step processes
• • 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
  • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
• • 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
  • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
  • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
• • 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
  • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
  • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
  • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/10—Noble metals or compounds thereof
  • B01D2255/102—Platinum group metals
  • B01D2255/1021—Platinum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/10—Noble metals or compounds thereof
  • B01D2255/102—Platinum group metals
  • B01D2255/1023—Palladium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/207—Transition metals
  • B01D2255/20715—Zirconium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/207—Transition metals
  • B01D2255/20761—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/207—Transition metals
  • B01D2255/20792—Zinc
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/209—Other metals
  • B01D2255/2092—Aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2256/00—Main component in the product gas stream after treatment
  • B01D2256/16—Hydrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/104—Oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2259/00—Type of treatment
  • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
  • B01D2259/818—Employing electrical discharges or the generation of a plasma
• • 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
  • C01B2203/0435—Catalytic purification
• • 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
  • C01B2203/0465—Composition of the impurity

Definitions

• the invention relates to a method and a plant for the production of hydrogen from raw gas, which is produced in a coke oven, according to the preambles of the independent claims.
• coke ovens from, for example, hard coal.
• coke ovens can be provided in particular in the form of a so-called coke oven battery, that is, a plurality of coke ovens juxtaposed.
• coke oven gas or crude gas may, for example, about 60 to 65% hydrogen, about 20 to 25% methane and lower levels of, inter alia, nitrogen, carbon monoxide, carbon dioxide, oxygen and heavy hydrocarbons.
• the exact composition usually varies depending on the operation of the coke oven and the coal used.
• the hydrogen can now be obtained in a very pure form.
• the raw gas can first be compressed and then one
• Pressure swing adsorption be supplied. By means of pressure swing adsorption, it is possible to remove or separate impurities from the raw gas and to provide a high-purity stream of hydrogen. If here and in the following of hydrogen, which is obtained from raw gas, is mentioned, it should be understood in particular also a gas mixture with a high proportion of hydrogen, in particular at least 90, 95 or 99 mol%.
• Pressure swing adsorption is known per se and, for example, in Yang and Lee: Adsorption dynamics of a layered bed PSA for H2 recovery from coke oven gas, AIChE Journal, Volume 44, Issue 6, June 1998, pages 1325-1334 or Takeuchi et. al .:
• catalysts for example by reacting oxygen with hydrogen to form water or steam, so that the purity of the hydrogen is further increased.
• catalysts are known, for example, by the term "deoxo.”
• the ignitable mixture can not be avoided or reduced, and in particular additionally receives a moist product gas, which usually has to be post-dried.
• This task is accomplished by a method and a plant for the extraction of
• the present invention is based on a known per se or plant for the recovery of hydrogen from raw gas, which is produced in a coke oven, as described in more detail below.
• the raw gas that is produced in the coke oven is first compressed and then impurities are separated by pressure swing adsorption.
• oxygen is depleted from the raw gas.
• non-thermal plasma is meant a plasma which is not in thermal equilibrium, i. that the electrons in the plasma have a much higher energy or temperature than the other components, which often only at
• Temperature of the electrons may be, for example, about 10 5 K or higher.
• thermal plasma ie plasma
• Ingredients have approximately the same energy or temperature, which is usually very high, for example, between some 1000 K and 10 6 K or higher.
• the non-thermal plasma can be generated in particular by means of dielectric barrier discharge (Dielectric Barrier Discharge or DBD, also known as silent electrical discharge) or by means of microwaves.
• DBD Dielectric Barrier Discharge
• microwaves can be generated, for example, in a Magetron and passed into a reaction space.
• the oxygen in the raw gas can react with other proportions in the raw gas and thus be removed from the raw gas or depleted. This can be an emergence of an ignitable mixture of oxygen and hydrogen and / or other combustible gases in
• Oxygen content (based on the amount of substance, i.e. 0.02 mol%) may be possible, while a feed gas mixture usually from a proportion of 0.6 mol% to ignitable mixtures in the pressure swing adsorption (at least in
• Coke ovens can have a maximum service life of 30 to 70 years, which usually means that leaks and thus the proportion of oxygen in the raw gas increase.
• oxygen is depleted from the raw gas by activating catalytic oxygen removal using the thermal plasma.
• catalytic oxygen removal using the thermal plasma.
• catalysts with platinum and / or palladium and / or copper and / or zinc, in particular aluminum or aluminum oxide, can be used for such a catalytic oxygen removal.
• the catalyst can be in a
• the catalyst may also be designed such that, in particular, higher hydrocarbons are separated or reacted from the crude gas.
• nickel-containing materials are suitable for this purpose. Also conceivable is a combination of several,
• Catalyst is possible, resulting in a cost savings.
• the crude gas before the pressure swing adsorption and after the raw gas is compressed, pretreated.
• This can be carried out in particular adsorptively or catalytically and / or regenerated or non-regenerated and / or using a pressure swing adsorption membrane hybrid process.
• a suitable membrane may be provided in front of the pressure swing adsorber, to enable a certain separation of the impurities before adsorption.
• the oxygen can be depleted using the non-thermal plasma from the raw gas before or after the raw gas is pretreated before pressure swing adsorption. The separation of impurities is improved by such pretreatment prior to pressure swing adsorption.
• Oxygen can be depleted of the raw gas using the non-thermal plasma after the raw gas is compressed. If no
• the generation of non-thermal plasma can thus between the compression (or a corresponding compressor) and the
• Pressure swing adsorption (or a corresponding pressure swing adsorber) take place. If a pretreatment takes place, then the generation of the nonthermal plasma can take place between the compression and the pretreatment or between the pretreatment and the pressure swing adsorption. Depending on the situation, one or the other variant can be more efficient.
• a plant according to the invention for the production of hydrogen from crude gas comprises a coke oven, in which the raw gas can be generated, a compressor, the raw gas can be supplied from the coke oven and which is adapted to compress the raw gas, and a pressure swing adsorber to which the raw gas can be supplied after exiting the compressor and which is adapted to separate impurities from the raw gas and provide hydrogen.
• Plasma generator provided which is arranged in front of the pressure swing adsorber and adapted to generate non-thermal plasma in the raw gas.
• FIG. 1 shows a plant not according to the invention for the production of hydrogen in the form of a schematic process flow diagram.
• FIG. 2 shows a preferred embodiment of a plant according to the invention in the form of a schematic process flow diagram.
• FIG. 3 shows a further preferred embodiment of a system according to the invention in the form of a schematic process flow diagram.
• FIG. 4 shows a further preferred embodiment of a system according to the invention in the form of a schematic process flow diagram.
• FIG. 5 shows a further preferred embodiment of a system according to the invention in the form of a schematic process flow diagram.
• FIG. 1 shows a plant 100 for the recovery of hydrogen (H 2 ) from crude gas is shown schematically, based on which first the underlying method for the production of hydrogen to be explained, on which the invention is based.
• a coke oven 110 which may also be a so-called coke oven battery
• coke oven gas or raw gas is also generated, which via a pipeline 115 as stream a a compressor 120, which may be, for example, a compressor , is supplied.
• This crude gas may, for example, about 60 to 65% hydrogen, about 20 to 25% methane and lower levels of, inter alia, nitrogen, carbon monoxide, carbon dioxide, oxygen and heavy hydrocarbons.
• the exact composition may vary depending on the operation of the coke oven and the coal used.
• the pressure swing adsorber requires a pressure of, for example, between 5 and 10 bar, possibly even higher, which is generated by the compressor.
• the raw gas is supplied to the pressure swing adsorber 140.
• impurities are now separated by pressure swing adsorption of the raw gas.
• impurities are meant in particular those components in the raw gas (which is a gas mixture) which are undesirable, i. present all shares except hydrogen. It is understood that not all of the pressure swing adsorption
• Impurities can be completely removed or separated.
• Typical values for the purity of the hydrogen that can be provided by the pressure swing adsorber 140 as stream b are, for example, at least 98 mol% and higher.
• the separated gas in the pressure swing adsorber 140 or the separated portions (residual gas) are supplied as stream d of the pipeline 1 15, so that it can then be used downstream, for example, as a heating gas.
• the pressure swing adsorption is at this point in specialist literature, as it was initially mentioned, for example, referenced.
• an oxygen content of 0.6 mol% or higher may be present, which may in particular also come about through leaks in the coke oven 110 and the ambient air sucked thereby.
• FIGS. 2 to 5 various preferred embodiments of a system according to the invention are now shown schematically, by means of which the present invention will be explained in more detail.
• the systems shown in FIGS. 2 to 5 correspond to the system 100 according to FIG. 1.
• FIG. 2 shows a plant 200 in which a plasma generator 150 and a catalytic converter 151 between the pipeline 1 15 and the compressor 120 are provided in comparison to the plant 100 according to FIG.
• the plasma generator 150 can be, for example, a device with two electrodes to which an alternating voltage can be applied, between which a dielectric material is introduced. In this way, a non-thermal plasma can be generated in the raw gas (stream a).
• the catalyst 151 may be, for example, a palladium, platinum, copper or zinc catalyst on an aluminum surface. Also conceivable are a combination of several of these materials or a plurality of catalysts each having one of these materials.
• the catalytic converter 151 may be arranged in a plasma field that arises during the production of the non-thermal plasma.
• the catalyst 151 may be disposed, for example, between the dielectric material and a corresponding electrode.
• the catalytic converter 151 is arranged downstream of the plasma generator 150 with respect to the current a and its current direction.
• the kataiytician oxygen removal or the removal of oxygen from the raw gas can then be carried out particularly efficiently and in particular at relatively low temperatures.
• the subsequent compression and in the pressure swing adsorber 140 so that the raw gas is already depleted of oxygen, so that no more ignitable mixture is present and a safe separation of other impurities is possible.
• Pressure swing adsorber 140 can be provided as stream b lie
• FIG. 3 shows a plant 300 in which a pretreatment device 130 is provided between the compressor 120 and the pressure swing adsorber 140 in comparison to the plant 200 according to FIG.
• the pretreatment device 130 can have, for example, a membrane in which a separation of impurities is possible even before the pressure swing adsorption. Together with the pressure swing adsorber 140 thus with the membrane a two-stage pressure swing adsorption membrane hybrid process for
• FIG. 4 shows a plant 400 in which, compared to the plant 300 according to FIG. 3, the plasma generator 150 and the catalyst 151 are now provided between the compressor 120 and the pretreatment device 130 instead of between the pipeline 115 and the compressor 120.
• FIG. 5 shows a plant 500 in which, compared to the plant 400 according to FIG. 4, the plasma generator 150 and the catalytic converter 151 instead of between the compressor 120 and the pretreatment device 130 now between the plasma generator 150
• Pre-treatment device 130 and the pressure swing adsorber 140 are provided.
• Pre-treatment device as shown for example in Figure 2, be provided between the compressor and the pressure swing adsorber.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Analytical Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
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• Environmental & Geological Engineering (AREA)
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• Inorganic Chemistry (AREA)
• Biomedical Technology (AREA)
• Health & Medical Sciences (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Separation Of Gases By Adsorption (AREA)

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• 2016
  • 2016-10-18 DE DE102016012391.5A patent/DE102016012391A1/de not_active Withdrawn
• 2017
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  • 2017-10-04 RU RU2019110119A patent/RU2739072C2/ru active
  • 2017-10-04 KR KR1020197013986A patent/KR102438581B1/ko active IP Right Grant
  • 2017-10-04 BR BR112019006827A patent/BR112019006827A2/pt active Search and Examination
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  • 2017-10-04 US US16/343,201 patent/US11298648B2/en active Active
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