WO2022149994A1 - Catalyseur pour produire de l'hydrogène et du soufre gazeux di-atomique lors du processus de décomposition de sulfure d'hydrogène - Google Patents

Catalyseur pour produire de l'hydrogène et du soufre gazeux di-atomique lors du processus de décomposition de sulfure d'hydrogène Download PDF

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Publication number
WO2022149994A1
WO2022149994A1 PCT/RU2021/000484 RU2021000484W WO2022149994A1 WO 2022149994 A1 WO2022149994 A1 WO 2022149994A1 RU 2021000484 W RU2021000484 W RU 2021000484W WO 2022149994 A1 WO2022149994 A1 WO 2022149994A1
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Prior art keywords
hydrogen
hydrogen sulfide
sulfur
catalyst
reaction
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PCT/RU2021/000484
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English (en)
Russian (ru)
Inventor
Анатолий Николаевич СТАРЦЕВ
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Анатолий Николаевич СТАРЦЕВ
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Priority claimed from RU2021100218A external-priority patent/RU2777440C2/ru
Application filed by Анатолий Николаевич СТАРЦЕВ filed Critical Анатолий Николаевич СТАРЦЕВ
Publication of WO2022149994A1 publication Critical patent/WO2022149994A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • 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
    • 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
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • 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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • 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

Definitions

  • the invention relates to the field of chemistry, namely to methods of decomposition (utilization) of hydrogen sulfide in order to obtain hydrogen and elemental sulfur.
  • reaction product (1) is gaseous sulfur in the metastable singlet state S2 (a 1 A g ) ⁇ [2] - Startsev AN Diatomic sulfur: a mysterious molecule. // Journal of Sulfur Chemistry, - 2019, v. 40, No 4, P. 435-450, DOI: 10.1080/17415993.2019.1588273 ⁇ , which becomes solid upon cooling.
  • This endothermic process (1) starts at 500°C, but even at 1000°C the equilibrium conversion of hydrogen sulfide does not exceed 15%. To increase the conversion it is necessary to increase the temperature.
  • the reversibility of reaction (1) means that the process proceeds in both directions always near equilibrium.
  • the catalyst does not shift the equilibrium of the reaction, does not change the enthalpy and free energy of the process, but it lowers the energy barrier and increases the reaction rate in both directions equally.
  • various methods are used to separate the reaction products, and alternative energy sources are used to reduce the temperature [1].
  • an irreversible reaction occurs on the surface of sulfide catalysts at low temperatures [A.N. Startsev et al. Patent of Russia N° 2216506; A.N. Startsev et al. Patent of Russia N° 2239593; A.N. Startsev et al. Patent of Russia N° 2239594]:
  • Reaction (2) is carried out in a periodic chemisorption-catalytic mode at low temperature (mainly room temperature), so the reaction product, solid sulfur, accumulates on the catalyst surface, thereby blocking active centers, which leads to its deactivation.
  • a solid catalyst in a liquid layer that dissolves solid sulfur well [A.N. Startsev et al. Patent of Russia N° 2261838; A.N. Startsev et al. Patent of Ukraine N° 81088. A.N. Startsev et al. Patent of Ukraine N° 57481 (provisional); A.N. Startsev et al. US Patent No: 7,611,685 B2. Date: Nov. 3, 2009].
  • Reaction (4) is carried out at a low temperature, preferably room temperature, and platinum or stainless steel shavings are used as catalysts [3, 4]. Since reactions (2) and (4) are carried out at a low temperature without thermal energy supply from outside, a reasonable question arises: where does the energy come from to carry out these reactions? We proved by special experiments that reactions (2) and (4) proceed with the same efficiency in the "dark" mode, which excluded the possibility of photo-catalysis.
  • thermodynamics of irreversible reactions (2) and (4) on the surface of solid catalysts in the framework of nonequilibrium thermodynamics irreversible process in an open system [3]. It turned out [3] that the energy required to carry out reactions (2) and (4) enters the system in the form of the internal energy of hydrogen sulfide molecules. Moreover, in [3], based on the literature data on the interaction of H2S with the surface of single crystals, the possibility of carrying out reaction (4) on the surface of many solid catalysts was predicted.
  • the proposed technical solution is characterized by the following advantages and disadvantages.
  • the target product of reaction (4) is hydrogen, a generally recognized energy carrier of the future and a valuable chemical reagent.
  • the resulting hydrogen belongs to the category of "green hydrogen", since its production is based on processes that are not associated with carbon-containing raw materials.
  • the second product of reaction (4) is diatomic gaseous sulfur, obtained by us for the first time.
  • the properties of this sulfur have been studied very little, but even now it is possible to predict a very wide range of its practical use in various fields of human activity [2].
  • gaseous sulfur does not require additional activation.
  • Reaction (4) proceeds at a low temperature without the expenditure of thermal energy from the outside, in contrast to the high-temperature energy- and material-intensive Claus process used throughout the world for the utilization of hydrogen sulfide, where the products are water and solid sulfur [1]. Therefore, the proposed technical solution is an alternative to the Claus process, which can be easily adapted to existing industrial Claus plants for the utilization of hydrogen sulfide, while instead of water, the reaction product is an extremely valuable substance - hydrogen.
  • reaction products are in the gaseous state, there is no need to regenerate the catalyst due to its deactivation with solid sulfur obtained in the low-temperature process according to reaction (2). This makes it possible to carry out the gas-phase process in a continuous flow mode without the use of sulfur solvents, which greatly simplifies the technology for separating the reaction products.
  • reaction (4) is irreversible and is carried out within the framework of the thermodynamics of nonequilibrium processes for an open system only on the surface of solid catalysts (in the gas phase this process is impossible) [3], it has regularities that cannot be realized in an isolated system in within the framework of "classical" equilibrium thermodynamics.
  • a. The conversion of hydrogen sulfide is determined by the concentration of active sites on the surface of the catalyst, so 100% conversion of hydrogen sulfide is achieved by selecting the required amount of catalyst.
  • the efficiency of the catalyst depends on the degree of coverage of the surface with adsorbed hydrogen sulfide, since the reaction is bimolecular, therefore, with an increase in the degree of coverage of the surface with hydrogen sulfide, the probability of interaction between adsorbed molecules increases. This is achieved by lowering the temperature catalyst surface, so the temperature dependence is anomalous: the lower the temperature, the higher the efficiency of the catalytic system. In particular, it was shown in [3] that on the surface of some metals, the decomposition of hydrogen sulfide with the formation of hydrogen occurs already at a very low temperature of 110 - 185 K (- 163 - - 88 ° C), with the formation of atomic zero-valent sulfur.
  • the driving force of the process is the formation of reaction products in the ground electronic state (molecular singlet hydrogen, solid sulfur or diatomic gaseous sulfur in the triplet state), i.e. having the least free energy.
  • the driving force of the process is the concentration gradient at the inlet and outlet of the system, in the absence of free energy, the process stops.
  • the prototype of the proposed technical solution is 0.5% Pt/SiO 2 catalysts or stainless steel shavings [4].
  • the disadvantage of these catalytic systems is the high cost of platinum and the low mechanical strength of the chips, which leads to its destruction during operation.
  • the essence of the invention lies in the use of transition metals and / or their alloys in various combinations, massive and deposited on various carriers in order to disperse the active component, sulfide systems of transition metals and their chemical mixtures in various combinations, massive and deposited on various carriers for the purpose of dispersion active component, as catalysts for the process of low-temperature decomposition of hydrogen sulfide to produce hydrogen and gaseous diatomic sulfur.
  • dopants of non-catalytic metals and/or non-metals are introduced into the catalyst;
  • the process of decomposition of hydrogen sulfide is carried out at a temperature below 100 °C.
  • the invention is characterized by the following examples.
  • the decomposition reaction of hydrogen sulfide is carried out in a flow-through gas-phase plant at room temperature on a supported metal catalyst (Fe,Ni,Cr,Ti)/Si0 2 , prepared by a known method and simulating stainless steel chips, titanium is an alloying additive.
  • Catalyst weight 7.5 g.
  • an absorber with an aqueous solution of zinc acetate was placed as a catalyst to trap unreacted hydrogen sulfide, and then an absorber with a 5% solution of monoethanolamine (MEA) to trap gaseous sulfur.
  • Hydrogen sulfide supply 3 ml/min for 460 min.
  • the decomposition reaction of hydrogen sulfide is carried out in a flow gas-phase plant at room temperature on a bimetallic catalyst, (Cu,Mo)/Sibunit, prepared in a known manner.
  • the mass of the catalyst is 10 g.
  • an absorber with calcined aluminum oxide AI2O3 to capture gaseous sulfur and then an absorber with zinc acetate.
  • Hydrogen sulfide supplied 63.7 mmol, decomposed 62.3 mmol, conversion 98%.
  • Hydrogen liberated 59.0 mmol (hydrogen analyzer "Zircon")
  • Colorless aluminum oxide turned intense yellow, sulfur content (weight gain) 1.95 g (data of X-ray fluorescence analysis, RFLA).
  • PC diffuse reflectance spectra an intense band at 809 cm 1 is observed, which is absent in PC spectra of solid sulfur [2–4]. This band is attributed to the stretching vibrations of the sulfur bond
  • the decomposition reaction of hydrogen sulfide is carried out in a flow gas-phase plant at room temperature on a trimetallic catalyst, (Fe,Ni,Cr,P)/Al203, prepared in a known manner with the addition of phosphoric acid to stabilize the impregnating solution.
  • the mass of the catalyst is 10 g.
  • a carrier, aluminum oxide, serves as a trap for gaseous sulfur.
  • Hydrogen sulfide supplied 90.3 mmol, decomposed 87.2 mmol, conversion 96.6%. Hydrogen was released 79.0 mmol ("Zircon"). 1.56 g of sulfur (XPLA) was found on the carrier.
  • the reaction is carried out in a gas-phase mode in a flow-through installation on an aqueous suspension of bimetallic sulfide ⁇ CuZnS x ⁇ .
  • an absorber with an aqueous solution of zinc acetate is placed to capture unreacted hydrogen sulfide, and then an absorber with a 5% solution of monoethanolamine (MEA) to capture gaseous sulfur.
  • MEA monoethanolamine
  • the decomposition reaction of hydrogen sulfide is carried out in a flow gas-phase plant from example 1 in a methane stream at a temperature of (-78 ° C) on a metal catalyst, (Fe, Ni, Zn, B) / Cn6yHHT, prepared by a known method.
  • H2S supplied 32.14 mmol, reacted 32.02 mmol, conversion 99.6%. 30.6 mmol of hydrogen was obtained (hydrogen analyzer "Test-1"), 15.8 mmol of sulfur S2 (RFlA) was captured in the MEA solution (95% of the reacted H2S).
  • the decomposition reaction of hydrogen sulfide is carried out in a flow gas-phase plant from example 1 in a methane stream at a temperature of (-78 ° C) on a sulfide catalyst, (Co, Mo, 8, C) / Sibunit, prepared by a known method.
  • H2S applied 16.07 mmol, reacted 15.78 mmol, conversion 98%.
  • Received hydrogen 15.6 mmol, sulfur S2 - 7.5 mmol.
  • the appearance of sulfur in the absorber with MEA unambiguously proves its transfer through the gas phase as a result of reaction (4).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

L'invention se rapporte au domaine de la chimie, et concerne notamment des procédés de décomposition (recyclage) de sulfure d'hydrogène afin de produire de l'hydrogène et du soufre élémentaire. L'invention concerne l'utilisation de métaux de transition et/ou de leurs alliages dans différentes combinaisons, en massifs et appliqués sur divers supports en vue de la dispersion du composant actif, des systèmes de sulfure des métaux de transition et de leurs mélanges chimiques dans différentes combinaisons, en massifs et appliqués sur divers supports en vue de la dispersion du composant actif, lesquels sont utilisés comme catalyseurs du processus de décomposition à basse température de sulfure d'hydrogène pour obtenir de l'hydrogène et du soufre gazeux di-atomique. Afin de stabiliser le composant actif, on introduit dans le catalyseur des additifs de dopage de métaux non catalytiques et/ou de non-métaux; le processus de décomposition de sulfure d'hydrogène se fait à une température de moins de 100°C.
PCT/RU2021/000484 2021-01-11 2021-11-03 Catalyseur pour produire de l'hydrogène et du soufre gazeux di-atomique lors du processus de décomposition de sulfure d'hydrogène WO2022149994A1 (fr)

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RU2021100218A RU2777440C2 (ru) 2021-01-11 Катализатор для получения водорода и двухатомной газообразной серы в процессе разложения сероводорода
RU2021100218 2021-01-11

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2600375C1 (ru) * 2015-08-13 2016-10-20 Публичное акционерное общество "Газпром" Способ низкотемпературного разложения сероводорода с получением водорода и серы
CN110127602A (zh) * 2018-02-09 2019-08-16 中国石油化工股份有限公司 应用催化剂分解硫化氢的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2600375C1 (ru) * 2015-08-13 2016-10-20 Публичное акционерное общество "Газпром" Способ низкотемпературного разложения сероводорода с получением водорода и серы
CN110127602A (zh) * 2018-02-09 2019-08-16 中国石油化工股份有限公司 应用催化剂分解硫化氢的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
STARTSEV A. N., KRUGLYAKOVA O.V., RUZANKIN S.F. ET AL.: "Osobennosti nizkotemperatumogo kataliticheskogo razlozheniya serovodoroda", ZHURNAL FIZICHESKOI KHIMII, vol. 88, no. 6, 2014, pages 943 - 956 *
STARTSEV A.N.: "Nizkotemperaturnoe kataliticheskoe razlozhenie serovodoroda.", KINETIKA I KATALIZ, vol. 57, no. 4, pages 516 - 528 *

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