WO2015015463A1 - Procédé et usine associée pour la production d'hydrogène - Google Patents

Procédé et usine associée pour la production d'hydrogène Download PDF

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Publication number
WO2015015463A1
WO2015015463A1 PCT/IB2014/063615 IB2014063615W WO2015015463A1 WO 2015015463 A1 WO2015015463 A1 WO 2015015463A1 IB 2014063615 W IB2014063615 W IB 2014063615W WO 2015015463 A1 WO2015015463 A1 WO 2015015463A1
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reactor
sulfur
reaction
process according
section
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PCT/IB2014/063615
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English (en)
Inventor
Flavio MANENTI
Sauro PIERUCCI
Lucio Molinari
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Politecnico Di Milano
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/54—Preparation of sulfur dioxide by burning elemental sulfur
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention concerns a process for producing hydrogen from sulfur with steam in the presence of oxygen or air.
  • the former are economically disadvantageous since the production cost of hydrogen is higher than the market price, whereas the latter are inevitably linked to the cost and availability of fossil fuels.
  • WO2012154041 and WO2012154043 describe a process for producing hydrogen, that substantially exploits the aforementioned H 2 S splitting cycle in the sulfur production process according to Claus method, where by operating in conditions of low air or oxygen content, the pyrolysis reaction of H 2 S is promoted to give S and H 2 .
  • the purpose of the present invention is to obtain a process for producing hydrogen that is cost-effective and that is energy-sustainable.
  • a purpose of the present invention is to have a process that has affinity with different industrial processes of inorganic chemistry, refinery and treatment of gas and oil, substantially reducing the investment, plant revamping and operating costs for producing hydrogen, but also substantially reducing operating costs for compressing hydrogen, thanks to pressure boosts of the same conventional plants.
  • this process for producing hydrogen comprises the endothermal reaction of sulfur with steam, wherein energy supply is provided by the exothermal oxidation of a portion of said sulfur to S0 2 according to the following scheme: R2: S + 0 2 ⁇ S0 2
  • volume amount of fed oxygen to carry out the aforementioned exothermal reaction R2 is comprised between 5 and 25% on the total volume of the reactants gaseous mixture .
  • This process can be carried out in a plant or production unit that can be independent or can be integrated with production units of the conventional type such as a Claus production unit for producing sulfur, production units for producing sulfuric acid with all variants thereof, production units for purifying natural gas, for dehydrosulfurization reaction of petroleum deposits and for coal or hydrocarbons gasification.
  • a Claus production unit for producing sulfur production units for producing sulfuric acid with all variants thereof
  • production units for purifying natural gas for dehydrosulfurization reaction of petroleum deposits and for coal or hydrocarbons gasification.
  • Figure 1 represents a block diagram of the thermal reactor wherein the hydrogenation process object of the present invention is carried out.
  • Figure 2 represents a block diagram of the regenerative thermal reactor wherein the process according to the present invention is carried out.
  • Figure 3 represents a block diagram of a production unit for carrying out the process according to the present invention in the presence of oxygen.
  • Figure 4 represents a block diagram of a production unit for carrying out the process according to the present invention in the presence of air.
  • Figure 5 represents a block diagram of a conventional Claus sulfur recovery unit.
  • Figure 6 represents a block diagram of a production unit for carrying out the process in the presence of air according to the present invention integrated with a Claus recovery unit.
  • Figure 7 represents a block diagram of a production unit for carrying out the process according to the present invention in the presence of oxygen, only integrated with the catalytic section of the Claus process.
  • Figure 8 represents a block diagram of a unit for producing sulfuric acid of the conventional type.
  • Figure 9 represents a block diagram of a production unit for carrying out the process according to the present invention with oxygen integrated with the plant for producing sulfuric acid.
  • Figure 10 represents a block diagram of a production unit for carrying out the process of the invention with oxygen applied to the plant for producing sulfuric acid, only associated with the catalytic section of Claus process.
  • Figure 1 1 represents a block diagram of a production unit for carrying out the process according to the present invention with oxygen only associated with a catalytic section of Claus process applied to the production of sulfuric acid according to Uhde technology.
  • Figure 12 represents a block diagram of a production unit for carrying out the process according to the present invention with pure oxygen only applied to the catalytic section of the Claus process, integrated with a dehydrosulfurization unit of petroleum deposits.
  • Figure 13 represents a block diagram of a production unit for carrying out the process in the presence of air according to the present invention integrated with a production unit for ammonia synthesis.
  • oxygen we mean pure oxygen, oxygen-enriched air, combustion air.
  • gaseous mixture of reactants we mean the mixture of reactants involved in the reactions Rl and R2, possibly in the presence of inert gases, preferably nitrogen.
  • Claus catalytic train we mean the series of catalytic converters and condensers for sulfur recovery, located downstream the thermal section of a Claus unit.
  • operative unit we mean a plant for carrying out the process of the invention comprising a reactor and at least one separation section capable of separating hydrogen from the other gases leaving the reactor and at least one recycling section of the unconverted reactants.
  • independent operative unit we mean an operative unit for carrying out the process of the invention wherein "the at least one separation section” and/or “the at least one recycling section” are different from those belonging to operative units intended for other industrial processes.
  • integrated operative unit we mean those operative units in which "the at least one separation section” and/or “the at least one recycling section” belong to an operative unit intended for other industrial processes.
  • portions of S we mean the volume % of S that reacts directly with the amount of oxygen being fed according to the reaction scheme R2, said percentage volume being calculated on the total volume of the gaseous mixture of the reactants.
  • This reaction and the related reactor for producing hydrogen according to the present invention represent the pivotal element of the innovative process.
  • This reaction is endothermal.
  • the reactor is also fed with air, oxygen-enriched air or pure oxygen, since the reaction of a portion of the sulfur with the aforementioned gases that takes place according to the following scheme R2:
  • R2 S + 0 2 - S0 2 is highly exothermal.
  • the amount of oxygen is generally comprised between 5 and 25 vol % on the total volume of the gaseous mixture fed at the thermal reactor, more preferably between 5 and 15 vol % when the regeneration is very effective so as to obtain temperatures of the reaction Rl, that allow high conversions to hydrogen, while ensuring optimal partial combustion conditions to prevent the excessive oxidation of the system (S0 2 to S0 3 and H 2 to H 2 0.)
  • the process according to the present invention is preferably carried out in a regenerative thermal reactor or in a thermal reactor.
  • the latter is a refractory PFR, wherein gaseous streams pass in a turbulent flow, and it is connected to a waste heat boiler.
  • gases leaving the thermal reactor cool down, while entering the boiler on the tubes side, whereas medium-high pressure steam is generated on the shell side.
  • this steam can be sent to the thermal reactor as reactant.
  • the thermal reactor can assume different configurations with reactants fed at one or more areas. For example, feed can occur in a burner where sulfur, oxygen and steam flow together or where sulfur and oxygen flow together, and steam is fed elsewhere.
  • the operating temperature of the reactor is preferably comprised between 1000-1550 °C, more preferably at temperatures higher than 1300°C, compatibly with the activation of the reaction of sulfur with steam and with the technological limits of construction and operation of the furnace and for residence times of between 0.1 and 3 seconds.
  • the operating pressure can vary from conditions slightly above ambient pressure up to medium-high pressures, like for example 30-100 bar.
  • Low pressures preferably 1.3-1.8 absolute bar
  • high pressures have better affinity with high pressure processes using hydrogen (like methanol or hydrodesulfurization).
  • Residence times are preferably comprised between 0.5 and 1.5 seconds.
  • the thermal reactor is simulated by using complex kinetic schemes (Manenti et al. Multi-scale modelling of Claus thermal furnace and waste heat boiler using detailed kinetics. Computers and Chemical Engineering, 59, 219-225, 2013), that comprise 2426 chemical reactions and 142 species.
  • the detailed kinetic scheme was validated on more than 20 sulfur recovery plants in good agreement with the predictions of the model and the industrial data.
  • the simulation of the invention cannot be carried out through commercial software, since the main process simulators are not equipped with complex kinetic schemes. Therefore, this simulation is carried out with the aforementioned tools, previously validated in field.
  • the thermal reactor is schematized in Figure 1.
  • the data of the simulations are given in the following tables 1 and 2.
  • the reactor is a (energy-integrated) regenerative thermal reactor.
  • the regenerative thermal reactor preferably comprises:
  • a regenerative section consisting of a tubular PFR reactor in which the gases pass in a turbulent flow
  • said regenerative thermal reactor possibly being connected to a waste heat boiler.
  • FIG. 2 An embodiment of this type of reactor is shown in figure 2.
  • the reactor receives the stream of sulfur and steam at relatively low temperature (for example 250°C).
  • the stream is preheated up to 700 °C and beyond in the regenerative section by exchanging heat in counter-current with the effluents of the furnace (for example at 1300°C).
  • oxygen is supplied to further increase the temperature up to the desired value (1300-1550°C).
  • the effluents finally exchange heat with inlet gas .
  • the simulation data for the integrated reactor are given in the following tables 3 and 4.
  • Table 3 Data for the regenerative thermal reactor simulation: case at 1300°C.
  • the plant for conducting the process of the present invention also comprises a conversion/ condensation/ compression section that allows the separation of the various components of the gaseous mixture leaving the reactor, said separation being able to be particularly differentiated, according to the uses of the various streams, besides hydrogen, that can be obtained, and also according to the production site wherein the process of the invention is conducted.
  • the separation can be realized by succeeding operations, even in a different order, or by integrated operations.
  • the joint separation of H 2 S and S0 2 can take place by catalytic converters of Claus type. It is possible to take advantage of existing technologies for the separation (e.g., condensers, phase separators, membranes, absorption/stripper columns). Hereafter some possible variants are given.
  • Figure 3 shows a particular preferred embodiment of the independent production unit intended only for producing hydrogen obtained with the process according to the present invention carried out by feeding the thermal reactor (indicated with “NEW” in the figures), in addition to elemental sulfur (S x ) and steam, pure oxygen.
  • NGW elemental sulfur
  • H 2 S Unlike H 2 S, hydrogen does not have acid behavior, therefore it is not absorbed by water-amine solution and is released at the top of the absorption tower. Absorbed H 2 S at the absorption column is stripped at the top of these processes stripper column, associated with the absorption column.
  • the operating conditions of the absorption column can be reformulated based on hydrogen compression requirements. Absorption can be promoted at higher pressures.
  • S0 2 and H 2 S are not recycled to the reactor, but can be supplied to different chemical plants: S0 2 can be stored as liquid or sent to the sulfuric acid production cycle; alternatively H 2 S and S0 2 can be fed to a Claus line for the production of elemental sulfur.
  • the production unit for carrying out the process according to the present invention is therefore able to produce hydrogen, and is energy-sustainable and with the possibility of zero emissions, for example if the production unit according to the present invention is associated with a hydrodesulfurization process. Moreover, recycling unconverted S 2 and H 2 0 is accomplished by pumping liquids with low operating costs. The separations for hydrogen purification can take place without any additional compression cost, if compared with classical separation processes technologies (amine washing).
  • the production unit does not differ from that of Figure 3 with the sole difference that the product is a H 2 /N 2 mixture, that can be used directly for some chemical productions (ammonia) or it needs a further separation of H 2 from N 2 .
  • a further aspect of the present invention as shown above are the fields of application of the process of the invention in industrial processes known in inorganic chemistry and in refinery.
  • a conventional Claus recovery unit is shown in Figure 5.
  • the acid gas (H 2 S) to be treated is fed with combustion air to a Claus furnace, indicated in the figures with CTF where partial combustion of H 2 S takes place to give S0 2 according to the reaction:
  • the residue is usually a small percentage of unreacted H 2 S (e.g. due to H 2 S/S0 2 molar ratios slightly above 2) leaving the furnace.
  • the stream is then sent to amine washing to reduce the residual H 2 S, after flowing in a hydrogenation and quenching section for the transformation of the sulfur compounds into H 2 S and, then, for separation of the process water.
  • the washing process is carried out in an absorption column indicated in the figures with ABSORBER and in a stripper column indicated in the figures with STRIPPER.
  • a heat exchanger is associated with the absorber for energy recovery, not represented in the figures.
  • the stream to be purified is fed at the bottom of the ABSORBER and, rising up the column, meets an amine solution in counter-current that reduces the content of H 2 S and of other acidic compounds (e.g. C0 2 ).
  • the purified stream leaves the top of the ABSORBER.
  • the amine solution rich in H 2 S is sent, after heat exchange, to a stripper indicated in the figures with STRIPPER.
  • the STRIPPER operates at low pressures to promote the outflow of gases absorbed in the ABSORBER.
  • H 2 S is recycled from the head of the STRIPPER and is recycled upstream, as Claus furnace feed, in addition to other acid gas sent to Claus process.
  • Amine washing is also used for other processes in refinery or for natural gas, to separate for example methane or light hydrocarbons from H 2 S.
  • the composition leaving the reactor is shown in tables 1-2 for the thermal reactor, whereas for the regenerative thermal reactor, reference is made to tables 3-4.
  • the effluents of the CTF Claus furnace and the reactor NEW of the process according to the invention are both conveyed to the first condenser indicated with Cond for sulfur separation.
  • it is possible to exert optimally both the process of the invention and the Claus process to reach an optimal H 2 S/S0 2 ratio equal to 2 entering the catalytic converters, indicated with CC1 and CC2 also in this figure. This is possible by suitably dosing the combustion air to the two thermal reactors.
  • the invention not only makes it possible to have a closed cycle as far the use of the sulfur and hydrogen production are concerned, but it also makes it possible to manage at the best Claus catalytic conversion train, by adding a degree of freedom to the control system of the entire plant, since a specific amount of S0 2 and H 2 S is provided, permitting the ratio of 2 to be reached for H 2 S/S0 2 fed to the catalytic train.
  • the mixture of H 2 S, S0 2 , H 2 0 and H 2 (also including N 2 of the combustion air) is fed to the CC1 and CC2, where the Claus reaction (R5) takes place.
  • H 2 is inert on the catalytic bed, in the condensation and intermediate removal operations.
  • the effluents leaving the third condenser will contain H 2 S in a very small fraction thanks to the better control of Claus process, by the introduction of the process according to the invention, together with H 2 and N 2 .
  • the water formed both with the process of the invention and with Claus process is previously separated.
  • H 2 and N 2 are then recovered at the top of the ABSORBER; the H 2 S is recovered at the STRIPPER and recycled upstream.
  • the invention also takes advantage that the catalytic converters, indicated in the figures with CC1 and CC2, actually replace the separation process of S0 2 from the stream that contains hydrogen.
  • a second revamp (Revamp-2) of the sulfur recovery units is shown in Figure 7. It ⁇ makes it possible to produce pure hydrogen instead of N 2 /H 2 mixture.
  • the thermal section of Claus (Claus furnace and waste heat boiler) is removed.
  • the invention can receive 0 2 as feed (no longer air), as well as steam and elemental sulfur coming from the pit.
  • the thermal reactor of the invention generates the aforementioned hydrogen-rich stream. This stream, as in Revamp-1, is sent to the first condenser indicated in the figures with Cond for S 2 separation. It is then sent to sulfur pit indicated in the Figures with SULFUR PIT and fed back to the reactor NEW.
  • the condenser Cond At G st either before or after) the condenser Cond the stream leaving the reactor meets the acid gas (H 2 S) and is dosed in order to reach the optimal H 2 S/S0 2 ratio for Claus reaction (R5).
  • S 2 , H 2 0 and 0 2 streams fed to the reactor NEW can be suitably controlled, also in this case providing a further degree of freedom to manage the catalytic train of Claus process.
  • sulfuric acid encompasses the direct oxidation of sulfur compounds, like acid gas (H 2 S) according to the global reaction R4 or elemental sulfur (S 2 ) according to the global reaction R3, proposed hereafter:
  • the invention enters the production process of sulfuric acid generating hydrogen and forming in part or entirely the amount of S0 2 required to avoid the oxidation furnace for the reaction R3.
  • the conventional process for producing sulfuric acid is shown in Figure 8; the entry of the invention in a possible revamp (Revamp- 1) is shown in Figure 9. Since the thermal furnace for direct oxidation of S 2 to S0 2 (R3) is replaced by the process of the invention, wherein S0 2 is still obtained, the net return is the entire production of hydrogen obtained with the process according to the invention.
  • the production unit for carrying out the process according to the invention offers the possibility of unbalancing the formation of S0 2 at expense of H 2 S.
  • H 2 S has, indeed, a shorter ignition time than sulfur and hydrogen itself, so that it would be the first compound that, upon coming in contact with 0 2 /air, is oxidized to S0 2 and H 2 0 and, by partial pyrolysis, promotes the formation of further hydrogen.
  • R8 S0 2 + 3 H 2 -» H 2 S + 2 H 2 0 and subsequent use of H 2 S in a furnace for primary oxidation of 3 ⁇ 4S to S0 2 .
  • the corresponding reactor wherein said possible primary oxidation takes place is not represented. If the primary oxidation is not foreseen in the sulfuric acid production technology, H 2 S generated by hydrogenation is conveyed to the start of the catalytic section of Claus process.
  • Hydrogen produced by the invention allows the production of sulfuric acid with zero emissions to be made sustainable, providing H 2 necessary for the reaction R8.
  • Natural gas is a mixture of so-called light or volatile hydrocarbon compounds, often associated with a certain percentage of H 2 S varying according to the deposit.
  • Kashagan Kazakhstan
  • H 2 S high content of H 2 S (about 20%).
  • the need is felt to purify the natural gas from H 2 S and the most common technology is amine washing, already mentioned in the previous cases. Since the removal of large amounts of H 2 S has the problem that this gas needs to be stored and treated, usually Claus technologies are exploited for partial combustion and production of sulfur. In this context of co-presence of washing plants and of sulfur lines, the process of the invention entry allows significant amounts of hydrogen to be produced.
  • Hydrodesulfurization processes are particularly important for removing sulfur from petroleum deposits for the production of fuels with low sulfur content, but also for removing sulfur from the increasingly common biofuels of second or third generation.
  • Hydrocarbon deposits containing sulfur are treated in a strongly reducing environment usually at high pressure operative conditions to promote the reaction:
  • R9 Ri-S- R 2 + 2 H 2 -» RjH + R 2 H + H 2 S wherein R] and R 2 are alkyl residues of hydrocarbon chains.
  • the hydrogen necessary for the hydrodesulfurization reaction is provided by the process of the invention ( Figure 12). In this figure, a preferred embodiment of the production unit to carry out this process is represented. The hydrogen is supplied in excess to the hydrodesulfurization reactor indicated with HYDRODESULF and the residual hydrogen, together with H 2 S therein formed, are sent to a washing station.
  • R10 N 2 + 3 H 2 ⁇ 2 NH 3 particularly high pressures and large amounts of H 2 are necessary.
  • the invention makes it possible to partially or entirely sustain the supply of N 2 and H 2 for the production of ammonia through the use of all of the aforementioned variants encompassing the use of air (or enriched air) for the energy sustainment of the thermal reactor of the invention.
  • Figure 13 shows a preferred embodiment and in particular one that considers the use of the plant shown in Figure 4, so that the effluents from Sep 4 are fed to the ammonia production plant. Also in this case the production of H 2 can be associated with the Claus process.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé destiné à produire de l'hydrogène comprenant une réaction endothermique entre du soufre et de la vapeur d'eau, l'alimentation en énergie étant réalisée par une oxydation exothermique d'une partie dudit soufre en SO2 selon le schéma suivant : R2 : S + O2 -> SO2 et ladite réaction endothermique étant mise en œuvre selon la réaction théorique globale R1, qui ne prend pas en compte la réaction R2 précitée, R1 : S + 2 H2O-> SO2 + 2 H2. La quantité en volume d'oxygène, introduit pour mettre en œuvre la réaction exothermique R2 précitée, est comprise entre 5 et 25 % par rapport au volume total du mélange réactionnel gazeux. Ce procédé peut être mis en œuvre à la fois dans une unité de traitement indépendante ou dans une unité complémentaire d'unités de récupération de soufre installées dans des usines pétrochimiques, des raffineries et des usines de production de gaz naturel, ou dans la production d'acide sulfurique ou d'ammoniac.
PCT/IB2014/063615 2013-08-02 2014-08-01 Procédé et usine associée pour la production d'hydrogène WO2015015463A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114901589A (zh) * 2019-12-13 2022-08-12 凯密迪公司 氨和硫酸一体化生产设备和方法
WO2022171359A1 (fr) * 2021-02-15 2022-08-18 Linde Gmbh Production d'hydrogène à partir d'un gaz acide de raffinerie et d'un extracteur d'eau acide

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WO2012154041A1 (fr) 2011-05-06 2012-11-15 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé de récupération de soufre à zéro émission avec production d'hydrogène simultanée

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EP0039745A1 (fr) * 1980-05-14 1981-11-18 Europäische Atomgemeinschaft (Euratom) Procédé pour la fabrication simultanée d'hydrogène et d'acide sulfurique ou de sulfates à partir du soufre et de l'eau
WO2012154043A1 (fr) 2011-05-06 2012-11-15 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé de récupération de soufre à zéro émission avec production simultanée d'hydrogène
WO2012154041A1 (fr) 2011-05-06 2012-11-15 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé de récupération de soufre à zéro émission avec production d'hydrogène simultanée

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* Cited by examiner, † Cited by third party
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CN114901589A (zh) * 2019-12-13 2022-08-12 凯密迪公司 氨和硫酸一体化生产设备和方法
WO2022171359A1 (fr) * 2021-02-15 2022-08-18 Linde Gmbh Production d'hydrogène à partir d'un gaz acide de raffinerie et d'un extracteur d'eau acide

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