WO2002102943A1 - Procede de conversion d'un materiau contenant des hydrocarbures en un gaz contenant du methane - Google Patents

Procede de conversion d'un materiau contenant des hydrocarbures en un gaz contenant du methane Download PDF

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Publication number
WO2002102943A1
WO2002102943A1 PCT/NL2002/000337 NL0200337W WO02102943A1 WO 2002102943 A1 WO2002102943 A1 WO 2002102943A1 NL 0200337 W NL0200337 W NL 0200337W WO 02102943 A1 WO02102943 A1 WO 02102943A1
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WIPO (PCT)
Prior art keywords
methanization
methane
gas
hydrogen
gas flow
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PCT/NL2002/000337
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English (en)
Inventor
Renee Van Yperen
Anton Bastiaan Alderliesten
Mathieu Andre De Bas
Petrus Franciscus Maria Theresia Van Nisselrooy
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Gastec N.V.
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Application filed by Gastec N.V. filed Critical Gastec N.V.
Priority to EP02736279A priority Critical patent/EP1390456A1/fr
Publication of WO2002102943A1 publication Critical patent/WO2002102943A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas

Definitions

  • the invention relates to a method for converting hydrocarbon-containing materials such as biomass to a methane-containing gas. More in particular, the invention relates to such a method wherein the conversion takes place with high efficiency.
  • Biomass such as wood and other vegetable material and other hydrocarbon-containing materials, can be combusted directly, whether or not after admixing fossil fuels.
  • the heat released can be used to generate heat and power, for instance in the form of electricity.
  • the gasses which are released in such biological degradation can then be combusted, likewise yielding heat and/or power.
  • hydrocarbon-containing materials such as biomass. Economic analyses show that from an economic point of view, gasifying is an interesting option, certainly for the future.
  • the hydrocarbon-containing material is converted to a gas rich in CO and H2 and often containing small amounts of hydrocarbon. To subsequently make the energy contained therein useful, these gasses need to be combusted, for instance in a (natural) gas engine.
  • the engines used for converting chemical energy to work need to undergo adjustments in order to make them suitable for gasses which have been obtained in the conventional manner from biomass or other hydrocarbon- containing material. For instance, engines driven by fuel gas (a gas mixture containing substantially CO and H2) often have a considerably lower efficiency and specific load than natural gas engines.
  • GB-A-1 227 156 describes a method for converting hydrocarbons to a methane-containing gas.
  • hydrocarbons such as, for instance, propane or naphtha are gasified by means of steam reforming, followed by methanization.
  • US-A-3 854895 describes the gasification of coal in the presence of steam and oxygen for obtaining fuel gas.
  • This fuel gas is converted in three methanization steps to a methane-containing gas.
  • An essential step in this process is converting a part of the CO to CO2 and hydrogen gas, followed by washing out of the CO2. for obtaining a proper ratio of hydrogen, carbon monoxide and carbon dioxide.
  • GB-A-1 391 034 describes a process corresponding to the one of US-A-3 854 895 for forming synthetic natural gas (SNG) from coal.
  • SNG synthetic natural gas
  • US-A-3 642 460 describes a process for making methane from a paraffin flow. To this end, the hydrocarbons are subjected to a steam reforming step, followed by a methanization step. During both steps, water cooling takes place. The thus obtained steam is recirculated.
  • SNG is made from biomass and/or fossil fuel by first gasifying and then carrying out a methanization step.
  • hydrogen gas By feeding hydrogen gas to the gasification step, it is intended in this reactor to already produce a considerable amount of methane,
  • a typical fuel gas obtained by gasification of biomass contains 1 - 5 % by volume of unsaturated hydrocarbons, among which approximately 0.5 vol.% of aromatic compounds, in particular so-called BTX'cs (i.e. benzene, toluene, xylene and naphthalene compounds).
  • BTX'cs i.e. benzene, toluene, xylene and naphthalene compounds.
  • the object of the present invention is to provide for a method for making a methane-rich product from hydrocarbon-containing material, such as biomass, which at least partly eliminates the above-mentioned disadvantages. It has been found that if at least a part of the hydrogen of the methane- containing gas flow, obtained by methanization of a fuel gas, is separated and is used in the methanization, this object can be achieved. Therefore, the present invention relates to a method for producing a methane-rich gas, comprising the following steps:
  • a methane-rich product is a product which contains at least 50 vol.%, preferably more than 75 vol.% and most preferably more than 90 vol.% CH 4 .
  • This methane-rich product can, inter alia, be used in SNG. For instance, in the Netherlands, for SNG, inter alia the following requirements are set:
  • Fuel gas is understood to mean a gas which consists for an important part of CO and Ho, for instance of more than 30 vol.% CO and more than 10 vol.% H2.
  • a typical fuel gas composition comprises 40-55 vol. % CO and 20-40 vol.% H2.
  • the method according to the invention can be very well used with both economic and environmental advantage, starting from a feed flow which comprises hydrocarbon-containing waste such as plastic.
  • a practical embodiment of the invention preferably comprises the following steps: a) converting hydrocarbon-containing material to a fuel gas in a gasifier; bl) cleaning the fuel gas in a cleaner for removal of contaminants; b2) passing the cleaned fuel gas through a guard bed; c) methanizing the product of the preceding step in a methanization reactor; whereby heat is released; d) removing water and drying the methanized gas; e) separating hydrogen from the methane-rich product of the preceding step, wherein this hydrogen is used in the methanization reaction or the preceding process; £) reprocessing the product of the preceding step in a reprocessing unit into a methane-rich product.
  • a gas Due to the conversion of fuel gas to a methane-rich product according to the invention, a gas can be obtained which can be converted very effectively to useful energy via existing infrastructures, such as the gas network, in existing and new high efficiency apparatuses, such as central heating installations, combined heat and energy plants, gas engines, etc. Moreover, by preparing the fuel gas from renewable sources (such as biomass), the gas obtained is durable. Methane has a higher energy density or calorific value (indicated in J/m 3 ) than fuel gas.
  • the methane-rich product produced according to the method of the invention can be reprocessed to a product with a Wobbe-index and calorific value comparable to that of natural gas of a particular origin (the composition of natural gas varies per country and/or per location).
  • the Wobbe- index is a measure for the amount of enthalpy which can be added with a particular gas composition per unit of time to a system, for instance an engine or a stove.
  • the efficiency obtained per unit of hydrocarbon-containing material is much higher than when the fuel gas is used directly for the production of electricity, or higher than when the hydrocarbon-containing material is directly converted to electricity, not via gasification but via conventional routes.
  • the methane- rich product can be used directly for, for instance, heating, or as a fuel for WK -units with, for instance, gas engines.
  • hydrocarbon-containing material such as biomass (vegetable or animal) is gasified, i.e. converted to a gas mixture containing substantially CO and H2.
  • gasification medium air, oxygen or steam. Combinations thereof are also possible.
  • air gasifier has as a drawback that, with it, nitrogen from the air is introduced into the process. This nitrogen needs to be removed so that, generally, the costs of operation of the installation according to the invention will prove to be higher than when one of the gasifiers of the other type is used.
  • oxygen gasifiers, steam gasifiers and combinations thereof are preferred.
  • Another great advantage of oxygen gasifiers, steam gasifiers and combinations thereof is that the temperature in the gasifier and at the end of the gasifier can be considerably higher than in an air gasifier. As a result, the amount of tar present in the fuel gas decreases strongly. The gasification process with oxygen is exothermic, hence, heat is released.
  • the gasification process with steam is endothermic, hence, it requires heat.
  • the gasification process with oxygen can produce the heat for the gasification process with steam.
  • the heat can, at least partly, be added to the feed flow (biomass, waste, etc. and/or the oxygen and steam to be used) by heating this with the heat released elsewhere in the process or by using it to cool the fuel gas coming from the gasifier.
  • the combination of oxygen and steam gasification and the use of residual heat for the steam gasification process more CO and H can be produced from the same amount of biomass, waste or other organic flow, because less of the feed flow (or fossil fuel) needs to be combusted to CO2 and H2O and the steam is also an extra source of hydrogen.
  • a sufficient amount of energy from residual sources is fed into the gasification process, even with use of biomass, a part of the CO 2 formation as a result of the presence of oxygen in the biomass can be prevented.
  • the ratio of CO and H2 in the fuel gas after the gasifier can to some extent be controlled by setting the pressure and the temperature at the end of the gasifier.
  • the fuel gas After the gasifier, the fuel gas can be cooled with the oxygen and/or steam feed flows by heat exchange before the gasifier. As a result, a large part of the heat of the fuel gas after the gasifier can effectively be returned to the gasification process to improve the total efficiency of the process. Also, the fuel gas can be cooled down while forming high pressure steam, which can be converted with a steam turbine to useful work, for instance into electricity or compression work.
  • the contaminating components in the fuel gas are reduced to an acceptable level for the methanization step.
  • concentrations of sulfur compounds, halogen compounds and nitrogen compounds need to havo an acceptable level.
  • other contaminating components such as tars, ammonia, (heavy) metals and dust also have to be reduced to an acceptable level.
  • cleaning gasses such as processes based on washing, adsorption and/or particle separation.
  • mercury Hg
  • Cd cadmium
  • Se the volatile metals
  • NH3, HiS and halogens are preferably removed by washing processes (scrubbing).
  • washing processes scrubbing
  • the saturated washin liquid can be purified in a waste water treatment plant.
  • HCN and COS are converted via hydrolysis in the washing liquid to, inter alia, NHa and HgS.
  • An alternative is simultaneous catalytic hydrolysis of HCN and COS at temperatures above 200*C.
  • H 2 S it can be desirable, in particular for H 2 S, to use regenerative washing processes and to reprocess the released H 2 S in a Claus- unit (suitable for > 20 tons S/day) to sulfur.
  • a Claus- unit suitable for > 20 tons S/day
  • washing processes exist which oxidize H2S in the washing liquid to sulfur.
  • the through-put speed of the gas through the guard bed is bound to a maximum. This results in a minimal size of the adsorbent volume in the guard bed.
  • the amount of adsorbent and the through-put speed through the guard bed depend, inter alia, on the desired degree of purity, the frequency with which the beds are replaced and the degree of contamination in the preceding cleaning step.
  • One of the current materials for adsorbing H2S is, inter alia, activated alumina.
  • a very suitable chemical adsorbent for H 2 S is zinc oxide (ZnO).
  • ZnO zinc oxide
  • This adsorbent acts optimally at approximately 200-350°C. This is advantageous as such temperatures are well in line with the required temperatures for the shift reaction and the methanization reaction. As a result, it is possible to omit a cooling or heating step between the guard bed and the methanization step.
  • the guard bed based on ZnO makes it possible to reduce the content of sulfur compounds to less than 100 ppb (mol/mol).
  • Halogen compounds in the gas can react with ZnO to volatile and corrosive zinc halogenides, which are transported with the process gas to the methanization reactor, where they precipitate on the catalyst and deactivate it.
  • an adsorption bed on the basis of ZnO can be combined with a layer of an adsorbent which adsorbs the halogen compounds before the process gas reaches the ZnO adsorbent.
  • the layer can consist of, for instance, activated alumina or sodium aluminate on an alumina carrier material.
  • the guard bed has been placed before the methanization reactor, also possible precipitation of dust and metals on the methanization catalyst can be strongly reduced, since the guard bed captures these substances in an efficient manner in case they had not been removed to a sufficient extent yet.
  • the guard bed can be designed in a so-called two-bed system. Then, two beds with adsorbent are arranged next to each other and the feed can be circuited thus, that it is guided over one of the two beds. The bed which is not in operation can then be replaced or regenerated, without the processing needing to be interrupted. After replacement or regeneration, the flow can be diverted for flowing through the regenerated bed so that the other bed can be replaced or regenerated. Particularly effective is the so-called "lead/lag" configuration, which comprises at least two beds, and wherein a ("lag") bed contains the regenerated or fresh adsorption material. The lag-bed is serially connected with a partly loaded (“lead”) bed, which is the first to be flowed through.
  • the lead-bed When the lead-bed has been loaded to a particular value, it is regenerated or renewed, while, temporarily, only the lag-bed provides for the adsorption. After regeneration, the regenerated bed is deployed as lag-bed and the cycle can be repeated. This configuration can easily be obtained by switching the flows. In this manner, a maximum loading of the adsorbent is obtained.
  • a typical fuel gas composition such as it can be obtained by gasification of hydrocarbon-containing materials and after cleaning and passage through the guard bed, is represented in Table 1.
  • Air or oxygen gasifiers and gasification feeds with a relatively low moisture content give a fuel gas with a H2 CO ratio of typically 0.5 - 1. Otherwise comparable feeds with a high moisture content (30 - 40%) and/or steam gasification yield a H2/CO ratio of >1.
  • the use of O2 and steam in the gasifier under the conditions wherein the water-gas-shift reaction occurs can increase the Hs CO ratio. In this manner, a H2/CO ratio of 2 to 3 can be achieved.
  • Methanization reaction Methanization of the cleaned fuel gas takes place in a methanization reactor.
  • the methanization of fuel gas can proceed according to reaction (ID. and/or (III).
  • the methanization catalyst deactivates.rapidly through crack reactions and carbonization.
  • externally acquired hydrogen for instance obtained from green current or other CO 2 - neutral methods of preparation
  • Another possiDin ⁇ y would be to produce hydrogen via the water-gas-shift reaction (I) by means of adding steam, in situ, i.e. in the methanization reactor. The hydrogen formed with the aid of the shift reaction could then be used to convert the remaining CO to methane.
  • the methanization step upstream of the methanization step, for instance in one of the preceding purification or separation steps. It is also possible to pass the hydrogen- rich gas flow to the fuel gas production step. Also if the fuel gas production step is carried out in the presence of oxygen (for instance from air), the recycling of the hydrogen-rich gas flow can be advantageously used.
  • oxygen gasifier two zones can be distinguished. In the first zone, combustion of the hydrocarbons takes place, whereby water, CO2 and heat are produced. In the second zone, all oxygen has been used up and the hydrogen can be safely, i.e. without an explosive mixture being formed, be recycled.
  • the methanization step can be carried out with an amount of H2 which is sufficient for converting both the unsaturated hydrocarbons (if present) and the CO. If the amount of H2 (mol) with which the methanization is carried out is given by:
  • ⁇ is preferably equal to 1 to 2 (mol mol), more preferably 1.5 to 2 and b is preferably at least 0.4, more preferably greater than 0.7 and most preferably greater than 1 (mol/mol).
  • H2 in these amounts can easily bo separated from the methane-rich gas flow after the methanization reaction, for instance and preferably by using a membrane.
  • the requirements regarding the Wobbe-index and the calorific value of the produced gas can differ, for instance depending on the country where the gas will be distributed and, generally, need to fall within a certain range.
  • a methane-rich gas with a Wobbe-index and calorific value corresponding to the existing requirements often a part of the CO 2 and the water needs to be removed and, optionally, other elements need to be added.
  • the obtained methane-rich gas can be mixed with methane-rich gas, such as natural gas, so as to meet the respective requirements.
  • methane-rich gas such as natural gas
  • the available amount of H2 for the methanization step increases with the methanization temperature, it is possible to work at a higher temperature than in conventional processes without the thermodynamic CH yield decreasing distinctly. This is favorable in particular because the methanization reaction proceeds more rapidly at higher temperatures than at lower temperatures. As a result, the CH 4 yield is not limited by the catalyst kinetics. At higher temperatures, the available amount of H2 reaches a maximum and will start to decrease at still higher temperatures, so that the thermodynamic CH4 equilibrium concentration also starts to decrease.
  • the initial temperature of the methanization catalyst is preferably not higher than 600 ⁇ C. More preferably, the methanization reaction is carried out at a catalyst initial temperature of 350-500°C, most preferably of 375-425°C.
  • An important advantage of the method according to the present invention is that the temperature at which the methanization is carried out is far less critical than in conventional processes. As a result, the methanization can be carried out in a simpler reactor, without there being the necessity of complex cooling systems. The reason for this is that due to the excess of H 2 which is present, up to the temperature mentioned of 600°C, there will always be sufficient CH4 production. The unreacted H2 is separated from the CH 4 and reused for the methanization.
  • the pressure will therefore be generally chosen on economic grounds, and will preferably be between 1-100 bara, preferably 1- 50 bara, most preferably 1-15 bara.
  • the pressure of the product will have to be adjusted to the pressure in the gas network.
  • the methane-rich product will have to be brought to approximately 10 bara. In this case, it is economically advantageous to operate the methanization reactor at approximately 12 bara.
  • Suitable catalysts are catalysts based on nickel, on platinum and/or on ruthenium.
  • nickel catalysts are economically advantageous.
  • nickel catalysts are more susceptible to contaminations, in particular to contamination by sulfur and halogen compounds, than the platinum and ruthenium -based catalysts.
  • these components will still have to be removed for a large part, so that, technically and economically, the uso of nickel catalysts is of very great interest.
  • Typical nickel catalysts for methanization comprise 20 - 80 % by weight, preferably 35 - 70% by weight, for instance 60% by weight of nickel on an alumina carrier, while the weight percentages are defined as grams of metallic nickel per gram of catalyst.
  • the methanization according to the invention can be carried out without, or with limited heat dissipation.
  • the heat can be recovered from the product gas and be usefully employed elsewhere in the process. Through this process integration, the efficiency of the entire installation increases even more.
  • a steam turbine electric power can be generated.
  • This power can for instance be utilized for driving a compressor which compresses the fuel gas or the final methane-rich product to the desired pressure.
  • This compressor can be placed after the gasifier, preferably after step bl). As the gas is compressed, the temperature rises, thereby bringing it closer to the temperature required for step b2).
  • placing the compressor has as an advantage that consequently, higher pressures can be realized, as a result of which the equipment can bo of more compact design.
  • a higher pressure is favorable to the position of the equilibrium of the methanization reaction. Therefore, the compressor can also be advantageously placed after step b2).
  • By placing the compressor an important amount of electricity for heating the gas flow is saved.
  • the steam, which partially condenses in the turbine is condensed after the steam turbine in an air cooler and recycled with a pump to the storage tank for the cooling water of the reactor.
  • the heat which is recovered from the product gas after the methanization reactor can be used for operating a heat pump.
  • a heat pump known in the art, elsewhere in the process, for instance in the reprocessing, cooling can take place.
  • a cooling system For removing water, a cooling system can be used, with the gas being cooled to approximately 40°C, if the methanization is carried out at increased pressure.
  • a part of the cooling path can be done by bringing at least a part of the product gas in heat exchange with (a part of) the gas to be methanized.
  • For further cooling to approximately 40°C use can be made of cooling water, which can be recooled in air of in a cooling tower with, for instance, river water.
  • the methanized gas needs to be dried, so as to free it from the remaining residues of water, so that the required dew point (in the Netherlands, for instance, -20°C) is reached.
  • This can be accomplished in different manners.
  • the gas can be dried by passing it through a fixed bed of silica gel or molecular sieves.
  • a suitable absorbent such as glycol (for instance triethylene glycol).
  • the hydrogen-rich gas flow is recirculated and can, for instance, be fed to the fuel gas at a suitable location.
  • the hydrogen-rich gas flow can be supplied at any suitable point before the methanization step.
  • the above-mentioned considerations should be taken into account if the hydrogen-rich gas flow is guided to a fuel gas production step operated with oxygen.
  • the separation of hydrogen can be carried out with conventional means, but is preferably carried out with a membrane filter.
  • a membrane filter entails lower investment and operating costs.
  • the desired purity can be controlled in a relatively simple manner by setting the permeate pressure.
  • membrane units are relatively compact and the required ground surface is small in comparison to conventional units.
  • the membrane separation of H2 can also be combined with partial H2O- removal, whereby the permeate is formed by a mixture of H2 and H2O.
  • An advantage of this combined H2 H2O separation is that, in principle, the abovementioned cooling to 40°C in step d) can be omitted. It suffices to collect water behind the membrane, for instance by passing the mixture into a drum. After removal of a part of the water, thus, a water-saturated flow of H2 is obtained. This water-saturated flow of H2 can then, for instance, be guided to the methanization step.
  • Reprocessing the methane-rich product comprises techniques common in the gas industry for removing CO2, any residual water, nitrogen and/or other undesired components so that the desired specifications can be met. Also, in this step, an odorant (for instance totrahydrothiophene, THT) can be added.
  • THT totrahydrothiophene
  • the CO2 concentration needs to be set.
  • PSA pressure swing absorption
  • MCA membrane gas absorption
  • scrubber technologies etc.
  • a PSA system preferably a system is used with two or more absorbers filled with CMS (Carbon Molecular Sieves), so that the separation process can be carried out semi-continuously. ⁇ n addition to the removal of CO2, also (a part of) nitrogen and the water, if present, can be removed.
  • CMS Carbon Molecular Sieves
  • polyimide-membrane systems are utilized. These have a relatively high chemical resistance and, in comparison to other polymer membranes, can be used to a relatively high temperature (up to 150°C).
  • This pre-separation has as an advantage, that the volume flows can be smaller and therefore the equipment too.
  • Another advantage is that less steam needs to be added to the reactor, since the risk of carbonization has considerably decreased due to the removal of CO2, while the final SNG production remains guaranteed.
  • the separation of CO2 before the methanization step therefore not only leads to an extra reduction of the total volume flows (and a corresponding reduction of the equipment), but also increases the efficiency of the total plant.
  • the Wobbe-index of the produced methane- rich product is measured.
  • the Wobbe-index is determined to a considerable extent by the CO2 content of the SNG and is therefore strongly dependent on the efficiency of the CO2 removal.
  • the Wobbe- index decreases in time because of saturation of the CMS in the absorber.
  • the production phase is stopped at that moment when the time average Wobbe- index meets the quality requirements for natural gas.
  • the Wobbe-index is for instance determined as described in EP-A-0 665 953.
  • a mixing of the product gas in time takes place by means of a buffer vessel. This happens in two series-connected mixing vessels in which a perforated tube provides for proper mixing.
  • the odorant THT can be added with the aid of a dosing pump.
  • the methane-rich product can be analyzed before it will be added as SNG to the gas network.
  • the methane content of the product gas can be set on the basis of the desired use and contains an amount of methane such that when it is added to a gas network, the respective requirements with regard to the quality of the gas are met. For other uses, technical and economic factors play a role in determining the ideal amount of methane and CO2 in the product gas.
  • a fuel gas which has been obtained by gasifying hydrocarbons in a gasification step (not represented) and largely cleaning in the cleaning step bl (not represented) is raised in pressure with the aid of a compressor to 13 bara.
  • the temperature of the gas increases considerably. This is favorable since the successive guard beds operate at a temperature of 200 - 350"C.
  • step (b2) the sulfur compounds and halogen compounds are virtually completely removed (sulfur compounds ⁇ 150 ppb (mol/mol) and halogen compounds ⁇ 30 ppb (mol/mol).
  • the cleaned gas is passed to the methanization reactor (c), together with an amount of steam. In the methanization reactor, the conversion of CO and hydrogen to methane takes place.
  • the methanized gas from the reactor is cooled for condensing the added steam. This can be combined with the preheating of the feed of the methanization reactor.
  • last residues of water can be removed in a supplemental drying step (not represented) so that the desired requirements (for instance to a dew point of -20°C) are met.
  • the thus obtained product gas consists mainly of CO2, CH 4 , and H2.
  • the hydrogen is separated from the product gas. In Fig. 1, this i& done by means of membrane separation.
  • the hydrogen-rich gas is returned to the feed of the reactor by adding this to the fuel gas before the compression step.
  • the greater part of the COa is removed from the methane-rich product gas.
  • this also takes place in a membrane separation step, but it can also be carried out in, for instance, a PSA-installation.
  • the separation is carried out such, that a methane-rich product gas having the desired Wobbe-index is obtained.
  • Reprocessing the gas comprises, for instance, odorizing with the aid of THT. After this, the gas is suitable for distribution.
  • a preferred embodiment of the invention is represented, identical to the one of Fig. 1, but supplemented with a step wherein the greater part of the CO2 in the feed is separated in a pre-separation step.
  • the separated CO2 is transported to the last CO2 separation step.
  • the methanizing reactor and the supplementary equipment can be of smaller dimensions, without this having to lead to a decrease of the SNG- production.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention se rapporte à un procédé de conversion de matériaux contenant des hydrocarbures telles que la biomasse en un gaz contenant du méthane. Plus particulièrement, l'invention concerne un procédé permettant de réaliser cette conversion avec une grande efficacité. Selon le procédé, au moins une partie de l'hydrogène du flux de gaz contenant du méthane obtenu par méthanisation d'un gaz combustible est séparé et utilisé dans la méthanisation, une carbonisation réduite se produit et, outre cela, l'étape de méthanisation peut être effectuée avec l'équipement le plus rudimentaire.
PCT/NL2002/000337 2001-05-28 2002-05-27 Procede de conversion d'un materiau contenant des hydrocarbures en un gaz contenant du methane WO2002102943A1 (fr)

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EP02736279A EP1390456A1 (fr) 2001-05-28 2002-05-27 Procede de conversion d'un materiau contenant des hydrocarbures en un gaz contenant du methane

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NL1018159A NL1018159C2 (nl) 2001-05-28 2001-05-28 Werkwijze voor het omzetten van koolwaterstofhoudend materiaal in een methaanbevattend gas.
NL1018159 2001-05-28

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2903994A1 (fr) * 2006-07-18 2008-01-25 Inst Francais Du Petrole Procede de traitement de gaz naturel avec valorisation de l'hydrogene sulfure et du dioxyde de carbone
EP2261308A1 (fr) 2009-05-07 2010-12-15 Haldor Topsøe A/S Procédé de production de gaz naturel
WO2011060539A1 (fr) 2009-11-18 2011-05-26 G4 Insights Inc. Procédé et système d'hydrogazéification de la biomasse
EP2403926A1 (fr) * 2009-03-05 2012-01-11 G4 Insights Inc. Processus et système de transformation thermochimique de la biomasse
WO2015011503A1 (fr) * 2013-07-26 2015-01-29 Advanced Plasma Power Limited Procédé de production d'un substitut du gaz naturel
CN105316055A (zh) * 2015-11-04 2016-02-10 天津凯德实业有限公司 一种沼气膜分离提纯二氧化碳气源热泵系统
CN105829507A (zh) * 2013-10-28 2016-08-03 苏伊士环能集团 生产代用天然气的设备和方法以及包括其的网络
EP2906666B1 (fr) 2012-10-11 2018-06-20 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Procédé et système pour produire substitute du gaz naturel contenant methane
US10653995B2 (en) 2009-11-18 2020-05-19 G4 Insights Inc. Sorption enhanced methanation of biomass

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061475A (en) * 1974-07-09 1977-12-06 Metallgesellschaft Aktiengesellschaft Process for producing a gas which can be substituted for natural gas
JPH06184570A (ja) * 1992-12-18 1994-07-05 Mitsubishi Kakoki Kaisha Ltd 都市ガスの製造方法
JPH09279170A (ja) * 1996-04-15 1997-10-28 Sumitomo Seika Chem Co Ltd 都市ガス製造方法および装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061475A (en) * 1974-07-09 1977-12-06 Metallgesellschaft Aktiengesellschaft Process for producing a gas which can be substituted for natural gas
JPH06184570A (ja) * 1992-12-18 1994-07-05 Mitsubishi Kakoki Kaisha Ltd 都市ガスの製造方法
JPH09279170A (ja) * 1996-04-15 1997-10-28 Sumitomo Seika Chem Co Ltd 都市ガス製造方法および装置

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199431, Derwent World Patents Index; Class E36, AN 1994-253112, XP002191082 *
DATABASE WPI Section Ch Week 199802, Derwent World Patents Index; Class H06, AN 1998-015058, XP002191081 *

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2903994A1 (fr) * 2006-07-18 2008-01-25 Inst Francais Du Petrole Procede de traitement de gaz naturel avec valorisation de l'hydrogene sulfure et du dioxyde de carbone
US8541637B2 (en) 2009-03-05 2013-09-24 G4 Insights Inc. Process and system for thermochemical conversion of biomass
EP2403926A4 (fr) * 2009-03-05 2013-07-24 G4 Insights Inc Processus et système de transformation thermochimique de la biomasse
EP2403926A1 (fr) * 2009-03-05 2012-01-11 G4 Insights Inc. Processus et système de transformation thermochimique de la biomasse
CN102341485A (zh) * 2009-03-05 2012-02-01 G4因赛特公司 用于生物质的热化学转化的方法和系统
CN102341485B (zh) * 2009-03-05 2015-06-10 G4因赛特公司 用于生物质的热化学转化的方法和系统
US8530529B2 (en) 2009-05-07 2013-09-10 Haldor Topsoe A/S Process for the production of substitute natural gas
EP2261308A1 (fr) 2009-05-07 2010-12-15 Haldor Topsøe A/S Procédé de production de gaz naturel
EP2501787A4 (fr) * 2009-11-18 2013-05-22 G4 Insights Inc Procédé et système d'hydrogazéification de la biomasse
WO2011060539A1 (fr) 2009-11-18 2011-05-26 G4 Insights Inc. Procédé et système d'hydrogazéification de la biomasse
EP2501787A1 (fr) * 2009-11-18 2012-09-26 G4 Insights Inc. Procédé et système d'hydrogazéification de la biomasse
US10653995B2 (en) 2009-11-18 2020-05-19 G4 Insights Inc. Sorption enhanced methanation of biomass
US10190066B2 (en) 2009-11-18 2019-01-29 G4 Insights Inc. Method and system for biomass hydrogasification
US9394171B2 (en) 2009-11-18 2016-07-19 G4 Insights Inc. Method and system for biomass hydrogasification
EP2906666B1 (fr) 2012-10-11 2018-06-20 Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Procédé et système pour produire substitute du gaz naturel contenant methane
WO2015011503A1 (fr) * 2013-07-26 2015-01-29 Advanced Plasma Power Limited Procédé de production d'un substitut du gaz naturel
US20160194573A1 (en) * 2013-07-26 2016-07-07 Advanced Plasma Power Limited Process for producing a substitute natural gas
US20160257897A1 (en) * 2013-10-28 2016-09-08 Gdf Suez Device and method for producing substitute natural gas and network comprising same
CN105829507A (zh) * 2013-10-28 2016-08-03 苏伊士环能集团 生产代用天然气的设备和方法以及包括其的网络
US10023820B2 (en) * 2013-10-28 2018-07-17 Gdf Suez Device and method for producing substitute natural gas and network comprising same
CN105316055A (zh) * 2015-11-04 2016-02-10 天津凯德实业有限公司 一种沼气膜分离提纯二氧化碳气源热泵系统

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