UA61556U - DEVICE FOR JOINT UTILIZATION hydrogen sulfide and carbon monoxide - Google Patents

Abstract

A device for joint utilization of hydrogen sulfide and carbon monoxide with electrolytic method. It has a case filled with electrolyte mixture with homogeneous catalyst (cathode and anode) or without it. Inside the case there are placed positive oxidizing and negative fuel gas-diffusion electrodes with current taps, and in which cathode and anode chamber is separated with the proton-wire membrane, and an aqueous solution of salts is used as the electrolyte, and carbon in various allotropic modifications with catalyst or without it is used as the electrodes. Metal from d- and p-groups, oxides, carbides, sulfides and carbonates of metals on the electrode are used as a catalyst. A catalyst based on metal complex or 2 or more metals from d- or p-groups is used as a homogeneous catalyst in the electrolyte mixture, and homogeneous anode and cathode catalyst may be identical or different in structure. An electric current, useful products of the structure of HASBOC reducing agent, useful products of the structure of CDHEOFNG of oxidazing agent (where A, C, E, F, G ≥ 0; B, D ≥ 1) are produced at the same time.

Claims (1)

UKRAINE (19) OA (11) 61 556 (13) in ( (51) IPC (2011.01) Sy p25B 3/00 IN NOM 8/22 (2006.01) MINISTRY OF EDUCATION issued under the SCIENCES OF UKRAINE (F) P I S responsibility to it власника пеРЖАвний ДЕллелдМеНт ДО ПАТЕНТУ тету ВЛАСНОСТІ НА КОРИСНУ МОДЕЛЬ нЛляМШЛМНЛООВООНВЦ ТТ ЮІЕИКККІІИІІІІІОООТІТЬЬОООЬЬИЕІШШШШШШОЛІО.О ООЛІООИООВВОВООЛОВЛЛІЕИТОКОЛИЛОЬИХОХВОИСТЛООХХЬТТЬТЬИТНЬТЬТЬОСХХІХОТЛТИТТООХЗООТОВОООООВВЛОЛОВТИИОТОТИОТОИТНЯ» (54) ПРИСТРІЙ ДЛЯ СУМІСНОЇ УТИЛІЗАЦІЇ СІРКОВОДНЮ І ОКСИДІВ ВУГЛЕЦЮ 1 2 (21) иго1015048 електроди з струмовідводами, і в якому катодну та (22) 14.12.2010 анодну the chamber is separated by a proton-conducting membrane (24) 07/25/2011, as an electrolyte, an aqueous solution is used (46) 07/25/2011, Byul.Mo 14, 2011, salts, as electrodes use carbon in (72) POLUNKIN, YEVHEN VASYLOVYCH, ZUBENKO various allotropic modifications with or without catalysts STEPAN OLEKSANDROVYCH, KRYVOSHEEVA LU-, as a catalyst using metal DMYLA IVANIVNA, STARZHYNSKA LYUDMYLA from ad- and p-groups, oxides, carbides, sulfides, and carbo- IVANIVNA nates of metals on the electrode as a homogeneous cataly- (73) INSTITUTE OF BIO-ORGANIC CHEMISTRY AND PETROLEUM in the electrolyte mixture use catalysts based on a complex of metal or 2 or (57) Device for of the combined utilization of hydrogen sulfide and more metals from the a- or p-group, and a homogeneous carbon cathodic electrolytic method, which anodic and cathodic lyzer can be the same, differs in that it has a body, filled or different in structure, and also differs in an electrolyte mixture with with a homogeneous catalyst that simultaneously receives an electric current, rum (cathodic and anodic) or without it, all-environmentally useful products of the NaAZvOs composition from the reducing agent, a positive oxidizing product of the SoNeOeMe composition from the oxidizing agent is placed in the core of the body (where A, vyy and negative fuel gas diffusion C, E, B, 020; 8.0 2 1). - o The useful model belongs to electrochemistry, and the boiling point is 445 "C) and temperatures are similar to the conversion of chemical energy into electricity. Sulfur is obtained in the following ways with the production of useful products, and it can be in aggregate states: gaseous IZ, 4), at a temperature of 650-1050 "C (IZ), 700-1200 "C (Id; liquid 5-7) |Ce) used in electrical devices of various purposes, for example, in electric generators - at temperatures of 120-370 "C I51, »120 7С |bЙ, 120- about current, fuel cells. Device for 180 C (71; sulfur in the colloidal state (7-12) at temperature IR F) combined utilization of carbon oxides and hydrogen sulfide temperatures: 20-120 7C G71, 60 "C I8I, 25 "C (9), room- t- can be used to purify gases from tn (10, 11), »4 "C (12). (Ce) hydrogen sulfide, to purify gases of the petrochemical industry. According to the temperature of the process. Utilization of carbon oxides with the use of various designs and systems. by the production of substances that have a transitional degree. The membrane that deoxidation (different from 4) will give a new source divides the cathode and anode chambers and the electrolyte into starting substances for petrochemicals. which dissolves the fuel. At the moment, among those submitted to the general public, there is a structure that produces gaseous sulfur at the gas utilization plant, which includes a solid oxide ion-conducting hydrogen sulfide with the production of an electric membrane |Z, 4), liquid - zeolite membrane (5), there are a number of achievements of pro-oric energy. tone-conducting polymer membrane (6,7), colloidal - etc. Among them are works on the utilization of gases that mis- proton-conducting polymer membrane (7-12. ty hydrogen sulfide as impurities that can poison catalyst when working on the main fuel of the oxidation of hydrogen sulphide acids is the accumulation of (hydrogen) 1, 2), at temperatures of 600 "С (11 and colloidal sulfur on the active part of the catalyst - 10002С (21, with the receipt of electrical energy. electrode system (7-9, 12), and/or its removal with the main sulfur-containing product of oxidation of the electrolyte. hydrogen sulfide was sulfur (3-12). According to the aggregate states of sulfur (melting point 113 "С, As an oxidizer in sulfur-oxidizing systems, it is fed into the cathode chamber for an hour. Potematic compounds present oxygen in its pure form nciostatic electrosynthesis is then connected, and/or air. controlled by a potentiostat/galvanostat, fuel oxidation can occur not only within 3 hours. The liquid electrolyte was at temp- with the help of oxygen, and also with the help of other oxidization of the surrounding environment, primarily oxygen-containing compounds, such as 192227C, and CO" is supplied to the cathode with a pressure of 1 bar. nitrogen oxides, sulfur oxides, phosphorus oxides, The electrosynthesis experiment was carried out with hydrogen peroxide, and non-oxygen-containing compounds: chlorine, with a cell potential ranging from 250 to bromine (131). 800 mV. The electrosynthetic products were contained in the device for obtaining useful products from the liquid electrolyte in the cathode chamber and were CO" was shown (|14| (prototype), where CO" was re-analyzed by gas chromatography. is formed by protons in the electrolysis cell, where the disadvantage of the device, chosen as a prototype is protons produced by electrolysis of water from the extract, which he uses to restore CO" by the release of oxygen and passed through protons from water produced by applying a conductive membrane. In the CO2 reduction chamber, an electric current that pushes additional protons from the first chamber and electrons from the outside is a requirement for water quality, as well as the fact that electric current sources reduce CO2 into carbon, energy must be supplied from the outside, leading to - hydrogen and methanol. tax costs of electric energy. The main examples of reactions of reduction of CO" on the basis of a useful model, the problem of the cathode is as follows: improvement of the device with the aim of simultaneous reduction of CO5,8Н and СН2НоО; lysis of carbon oxides and hydrogen sulfide from the obtained 2С05.14Н' i 14e - СоНе,4Ноо; of useful products for industry and with 2С05.12Н' and 12e - SON. YAN; for the purpose of replacing energy costs for the extraction of electricity - 2С05.12Н' i 12e - С»ННОН «from ZNO; energy СО2Н'-2е - СО - HO. The task is solved using the method and the device are illustrated by the following device for the combined disposal of hydrogen sulfide by storage. and carbon oxides by the electrolytic method, Example 1. which differs in that it has a body filled with an experimental sample of a well-known cell, which is selected by an electrolyte mixture with a homogeneous catalyze- the prototype is shown in fig. 1 rum (cathode and anode) or without it, inside The cell contains a proton-conducting membrane 3, inside the body there is a positive oxide-platinum crushed anode 1 and a copper small and negative fuel gas-diffusion cathode 5. In the cell, a proton-conducting membrane - electrodes with current drains, and in which the cathode and anode of the chamber, made of hydrophilic ionic material, are separated by a proton-conducting membrane - which is described in (15), divides the structure into two chambers. on, as an electrolyte, an aqueous solution is used. In the anode chamber, the platinum mass 1 is held by salts, as the electrodes use carbon in a wire mesh, which serves as a current drain for various allotropic modifications with anode catalysts. In the role of electrocatalyst 2 in the anode with or without them, the metal of water oxidation is used as a catalyst, platinum black is used, it is placed from ad- and p-groups, oxides, carbides, sulfides and carbon in the carbon fabric, in the amount of 2 mg/cm7 . Electnates of metals on the electrode, as a homogeneous catalyst-catalyst 4, which is used as a cathode in the electrolyte mixture, is used as a catalyst- consists of a mixture of oxides of Si, 2p, and AI with a catalyst based on a metal complex or 2 or the number of 45 956 wt. Sy, 27.5 905 wt. 27pO, more metals from the a- or p-group, and homogeneous cata- 27.5 9o wt. A2Oz placed in the carbon fabric, anodic and cathodic lyzers can be the same in the amount of 1 mg/cm Sys, and placed in a cell in or different in structure. internal contact with the proton-conducting membrane. The task is solved by the fact that, as the selected 3. Current conductor for the cathode is copper, hydrogen sulfide, which has a lower enema 5, is connected to the external electrical wiring. rgy ionization than hydrogen and water. This makes it possible- The cell is designed in such a way that the assembly does not apply electrical energy, but the current conductors 1 and 5, electrocatalysts 2 receive it additionally and 4, the proton-conducting membrane Z are compressed together in These problems are solved as follows: the structure of the cell for ensuring a good 1) creation of a gas-liquid device that transports ions, electrons and molecules in reactions- has a positive gas-diffusion carbon, plan zone on the electrocatalyst. tin or skeletal silver electrode, negative - Cathode chamber 6 is filled with an aqueous solution of external carbon metallized or oxide ele- 01M КНСО", which acts as an alleviator of ktrod with a catalyst and fuel-electrolyte transportation of CO" and retention for the following mixture, which contains contains hydrogen sulfide. as a catalyst for the analysis of methanol production in the cell, elements of the COg group are used, the composition is passed through this solution, during which platinum, palladium, iridium, osmium, ruthe-chemical synthesis is included to ensure saturation with it, rhodium, gold, magnesium, aluminum, titanium, silicon, the product, CO" supplied to the cathode chamber 6, germanium, oxides, carbides, sulfides, and carbonates were first passed through the trap of moisture, metals; or creating a gas-liquid device, a hydrocarbon trap and an oxygen trap. which has a gas-diffusion carbon anode, fuel- Before electrosynthesis, a pre-electrolyte-catalytic mixture that contains water in the anode chamber. After that, in the amount of 0.5 dm'/min. CO" itself hydrogen sulfide and a homogeneous catalyst on the basis of new metal complexes of the group, which include Water (including sea) 1.0-99.9 d elements and p-group metals; sodium chloride 0.1-45.0 2) creation of a gas-liquid device, which sodium sulfate 0.1-45.0 has a gas-diffusion carbon cathode, oxidizing-potassium chloride 0.1-40.0 electrolyte-catalytic mixture, which contains potassium sulfate 0.1-30.0 carbon oxide or oxides, reaction products and magnesium homochloride 0.1-45.0 gene catalyst based on metal complexes magnesium sulfate 0.1-45.0 of the group that includes d -elements and sodium meta-carbonate 0.01-45.0 li p-group; potassium carbonate 0.0-45.0 3) as a fuel-electrolyte mixture, potassium hydroxide 0.0-45.0 is used, a solution of hydrogen sulfide and salts that dissolve sodium hydroxide 0.0-45.0. are in water, including sea water, or gas. New, in the application, there are: use as oxidizing hydrogen sulfide, which is passed through the hydrogen sulfide of carbon oxides (CO, CO), near-catalytic layer, which is in the environment of the and the way, in contrast to the previous ones, the ability of the electrolyte in the following composition ratio to simultaneously produce electrical energy and currents, 9 by mass: sleep products. Hydrogen sulfide 0.3 - 90.0 Comparative analysis with prototypes showed, water (including sea) 1.0 - 99.9 that this useful model has the presence of new components: sodium chloride 0.1-45.0: oxidizer - carbon oxides; of products - sodium sulfate 0.1 - 45.0, organic, oxygen-containing compounds, urea; potassium chloride 0.1-40.0 electrodes with a catalyst selected for this purpose potassium sulfate 0.1-30.0 type of fuel; homogeneous catalysts for magnesium oxide-chloride 0.1 - 45.0% hydrogen sulfide; homogeneous catalysts for magnesium sulfate 0.1-45.0 reduction of carbon oxides. sodium carbonate 0.01-10.0 Thus, the proposed useful model 4) as an oxidizer-electrolyte mixture is used - meets the "novelty" criterion. solution of carbon oxides and salts, which dissolve in Fig. 2 schematically depicts the proposed device in water, including seawater, which has the following form: body 1 gaseous carbon oxides that are passed through porous membranes; 2 is filled with an electrocatalytic layer, which is in a sulfur mixture. The positive electrode 3 is placed inside the case with the electrolyte in the following ratio; and negative fuel components, 9Uo mass: electrode 4 with current leads 5 (-) and 6 (tk). Со» 0.1-90.0 During the operation of the device, reduction of СО» and СО occurs at the cathode (Ф6) 0.0-90.0 according to the reactions: (1) СНзОН (ад, - 20ОН - НСНоО aa) and 2Н2О i 2e Es - 0.95 V (2) So 6H' i ve - SNug) i NO Eso - 0.497 V (3) CYANON i 2H" i 2e - SoN i NO Eso - 0.46 V (4) SNzZON (aa) CO) 2Nya i 2e - SNSOON (zd) i- NgO Eso - 0.35 V (5) SNav) i- 20H - CHzOH aa) i- NgO i 2e Eo - 0.25 V (6) SNSO i 2" i 2e - SoNOH Eo - 0.1928 (7) СОd(vu - Ma) - 6Н i be - СО(МН»)» и H2гО Eo - 0.18 (8) HсHO ad) - NgO - HСООН (zd), i 2H ee Es - -0.056 V (99 СНЗСООН (zd i 2NI i 2e - SNUSNO ad) and NgO Es - -0.1188 (10) SOdu i 2H' i 2e - CO NO Eo - -0.128 A in the electrolyte the following reactions: (11720057 KAN' de c0, i 2NoO Eo - 0.441 V (12) cO57 - ZN' i 2e - NSOO i NO Es - 0.227 V (13) NSOO I 5N/ i 4e - SNZON z NO Eso - 0.199 V (14) СО5 Ж 6Н' i 4e - HCNO i 2NoO Eso - 0.197 V (15 НСОО»- ЗН" i 2e - HCNO i ЗОН Eso - 0.167 V As can be seen from the above reactions, the products of the reaction, which at (20) also have the ability to oxidize Nobad - 5 2H' i 2e Eo - -0.142 In the continuation of recovery, they will act as semi-products. Electromotive force (EMF) of the system At the anode, hydrogen sulfide is oxidized from the formed E - E - Oxidizer - E - Reducer, which can vary from different anions according to the reaction: E: - 0.95 - (- 0.311) - 1.261 V to E2 - 0 ,1 - (- 0.003) - -0.097 V, but at the same time some (16) Neb(g) t 4HgO - Be- 5047. Eb --0311 8 reactions (8-10) will not take place, but in each case Es res" 0, which sub-1on' 077 affirms the electrochemical validity of the work of this or: element. (17) 5Н5-7е-55 и 5Н' Eсо - -0.003 V The minimum content of hydrogen sulfide in the fuel- (18) 4Н5-6е - з 4н' ES - -0.033 V in the electrolyte mixture is determined by the solubility of Нг5 (19) ЗН5 -4е- - With IZN Eso - -0.097 V in water-salt solutions. as a positive elect- various modifications of carbon gas purification from hydrogen sulfide are used, for example, electrode gases with a hydrophobized barrier layer, gas and gas condensate deposits, preventing which still need perfection due to poisoning or loss of hydrocarbons, purification of petroleum gases with their recovery products, which allow safe industry (primarily, emissions from the baking process, stability of reactor characteristics and hydrotreating), purification of hydrogen from inert hydrogen sulfide in seawater. (oxidation of hydrogen sulphide takes place gently without losses. Negative and positive electrodes perform hydrogen). Utilization of carbon oxides produced from carbon in various allotropic forms (depending on the substances that have a transition degree of oxidation depending on the purpose of the device) with a catalyst (different from 4) will provide a new source of substances selected from the groups: 1 - RI, Ra, VY, If, O5, Vy; 2 - A!, low substances for petrochemistry, bypassing Ad, Sy processes; Z - Ma, A, Sa; 4 -51, Ti, Se; 5 - Mo, MU, M; their work with synthesis gas, which takes place at high oxides, carbides, sulfides and carbonates or without temperatures and pressures. him Catalysts are selected according to the criteria of sufficient activity and stability under real operating conditions. in the form of metal 13.08.1964, 4.03.1969. or its compounds and applied to the electrode by chemical 2. 2007/112435Mu/0, НО1ТМ8/12, "Boiia ochide iei or electrochemical deposition, sputtering or sei rgosez5 apa arragatse5", PShei 28.03.2006, in a mixture with a conductive binder. Applied on 10/4/2007. on graphite, alloys of metals with aluminum are treated 3. Patent 492001505, nOtnV/o6, with alkali to obtain a porous structure of catalysis- "Eiesitospetisai No sopmegviop" Shea tora. 09/29/1988, 04/24/1990. Electrodes prepared by this method have a high specific surface area and sufficient activity in hydrogen sulfide oxidation reactions. 05/13/2003, 11/20/2003. As a positive electrode, an electrode is used. .1985. The electrolytic mixture may contain homogeneous b. Patent 2328355СА, НО1М8/22, НО1ТМ8/06, new catalyst on the basis of metal complexes of ГрунНОоТМ8/12, С2581/00, СО ИВ 17/04, "Eiiesitospetisai pi, which includes d-elements and metals of ochidayop oi Pudgodep zside ", Pay 04/16/1999, p-groups. 28.10.1999. The proposed useful model is illustrated in 7. Patent 324952205, I5 SI. 204-922, a scheme for implementing the proposed device. "Eiesiospetisai! ohidayop oi pudgodep ziide", yeh Fig. 2. 23.02.1965, 3.05.1966. As electrodes (3, 4) electrop- 8. Patent 5 3874930, НО1ТМ27/30, "Ршве! sei rovidin graphite, activated zuvziet ipsiiaipud zotsgse oi ishe! sopiaipipd pudgtodep coal with a catalyst applied to it is poured into the cell: for ziyide apa teschShoi ой изипд", yey 01.29.1970, hydrogen sulfide - from Sy; for O» and СО» - with Re from hydro- and 01.04.1975. electrically insulated copper current drain (6). as 9. Patent 0127595ER, С25811/4, НО1ТМА/90, the fuel-electrolyte mixture uses water-notMv8/22, СстТОоКк1/10, "Nuagodep ziyae ny solution of the composition: hydrogen sulfide 0.378 9o wt., Masi desotroziop sei! saga|uis taiepaiv5 Shtegeiog", Pea 18 g/l. The process takes place under dynamic conditions from 03/26/1984 to 12/05/1984. by passing a fuel-electrolyte mixture with 10. Patent 432018005, НО1ТМ8/18, "Рше! sei", at a speed of 100 ml/h. Between the cells is tPEA 14.10.1980, 16.03.1982. proton-conducting membrane MF-4-SK (2). Volt- 11. Patent 2004/114430М/0, НО1М, "Chemical ampere characteristics are recorded when a current source is applied - a fuel cell, working resistance data from 10 to 10,000 Ohms, measurement is simple for hydrogen sulfide", application 22.06. 2004, conducted at a temperature of 20 "C. 29.12.2004. The results are shown in Fig. C as a comparison 12. Patent 2006/025758UUO, НО1М8/08, works of the device for utilization of hydrogen sulfide from oxide- НО1ТМ8/20, "Rgosezz apa tset! seiY ivipd H25 seh! by ignition with air and oxidation of hydrogen sulphide according to the depegaypo eyesiis romzheg, on 30.08.2005, with the help of CO". At the current density values of 09.03.2006. more than "0" reaction of hydrogen sulfide oxidation pro- 13. Filshtyh V. Toplyvnye zlement!. - M.: walks with the formation of an electric current, on both Myr, 1968.-419 p. curves, it is greater than "0", which indicates the oxidation of 14. Patent 2008/017838UUO, С2583/04, "Erivation of hydrogen sulfide by air oxygen and CO". oxidant (air or COg) and supply 15. Patent 03/023890U0, nOtM8/10, hydrogen sulfide current value is 0.0 μA/cm". НО1Тв1/12, Со8Е26/00, 2261/00, С2589/02, Device for compatible utilization of carbon oxides - "Nuagorpiiis roiuteiz apa INeig ize ip eiesiisai! seiYv", this and hydrogen sulfide can be used for 9.09.2002, 20.03.2003.