CN103204467A - Device and method for continuously and steadily decomposing and making up hydrogen with hydrogen sulfide - Google Patents
Device and method for continuously and steadily decomposing and making up hydrogen with hydrogen sulfide Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 30
- 239000011810 insulating material Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000075 oxide glass Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 208000028659 discharge Diseases 0.000 claims 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 239000000155 melt Substances 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 claims 1
- 239000000919 ceramic Substances 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000010453 quartz Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 description 15
- 238000005265 energy consumption Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000004645 scanning capacitance microscopy Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000013068 supply chain management Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910015711 MoOx Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- 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
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- Physical Or Chemical Processes And Apparatus (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明提供了一种硫化氢持续稳定分解制取氢气的装置和方法，属于制氢和气体纯化技术领域；在本发明中硫化氢气体或含硫化氢的气体以螺旋模式，沿轴向逆向旋流通过介质阻挡放电区域，放电区的高能电子将硫化氢分解，分解产生的硫被及时离心分离出来，通过控制放电区温度，使硫离开放电区；本发明的优点是，在常压和非催化条件下，只用介质阻挡放电实现硫化氢的高能效分解，分解产生的氢气和硫能及时离开放电区域，反应可持续稳定进行，硫化氢分解率和能量利用率高；本发明的方法适用于天然气、石油和煤化学工业中的含硫化氢气体分解制氢气；本方法对气体的来源和组成没有特殊要求或者限制，因而对于硫化氢分解制取氢气和单质硫有普遍适用性。
The invention provides a device and method for continuously and stably decomposing hydrogen sulfide to produce hydrogen, belonging to the technical field of hydrogen production and gas purification; The high-energy electrons in the discharge area decompose the hydrogen sulfide, and the sulfur produced by the decomposition is centrifugally separated in time. By controlling the temperature of the discharge area, the sulfur leaves the discharge area; Under catalytic conditions, only the dielectric barrier discharge is used to realize the high-energy-efficiency decomposition of hydrogen sulfide, the hydrogen and sulfur generated by the decomposition can leave the discharge area in time, the reaction can be carried out continuously and stably, and the hydrogen sulfide decomposition rate and energy utilization rate are high; the method of the present invention is suitable for It is used in natural gas, petroleum and coal chemical industries to decompose hydrogen sulfide-containing gas to produce hydrogen; this method has no special requirements or restrictions on the source and composition of the gas, so it has universal applicability for hydrogen sulfide decomposition to produce hydrogen and elemental sulfur.
Description
Technical field
The invention belongs to hydrogen manufacturing and gas purification technology field, relate to a kind of hydrogen sulfide that can make and under normal pressure and on-catalytic condition, be decomposed into hydrogen and elemental sulfur apparatus and method continually and steadily.
Technical background
H
2S extensively exists in the waste gas of industries such as oil and natural gas exploitation, petrochemical complex, Coal Chemical Industry, is the sour gas of a kind of severe toxicity, stench, need be with H from the requirement of environmental protection and corrosion aspect
2S carries out nuisanceless processing.Main employing Crouse (Claus) method is elemental sulfur and water with its partial oxidation at present, but Crouse (Claus) method has only reclaimed H
2Sulphur among the S, hydrogen have then generated water in oxidising process, cause the waste of hydrogen resource.
In common nonmetal hydride (water, methyl alcohol and hydrogen sulfide), the ionic dissociation energy of hydrogen sulfide is minimum, and therefore theoretically, it is the easiest that hydrogen is produced in the hydrogen sulfide thermolysis.But the hydrogen sulfide decomposition reaction is strong endothermic reaction, is subjected to the restriction of thermodynamic(al)equilibrium, and considerable transformation efficiency is only at high temperature just arranged.Such as, the transformation efficiency the when rate of decomposition of hydrogen sulfide only is 20%, 1200 ℃ in the time of 1000 ℃ is 38%(Slimane R.B., GasTIPS, and 2004,30-34).Electrochemistry and photocatalysis method also can be realized H
2Hydrogen and sulphur are produced in the S decomposition, but have the many or low shortcoming of reaction efficiency of operation steps.In order to break the chemical reaction equilibrium restriction, the investigator has adopted film reaction technology and nonequilibrium plasma technology etc., but the development and application of the mould material of high temperature resistant and anti-sulphur becomes the key that realizes utilizing the technological breakthrough of film reaction decomposing hydrogen sulfide.Utilize non-equilibrium plasma technology decomposing H
2S can and shrink in normal glow discharge, microwave discharge, corona discharge pulse and the dielectric barrier discharge etc. and realize in arc discharge, rotation glow discharge.H
2Energy consumption (the 3.7eV/H that required energy loss-rate methane steam reforming generates hydrogen is decomposed in the S arc discharge
2) high (J Appl Phys, 1998,84:1215 – 1221).H
2Required energy consumption also generates hydrogen than methane steam reforming energy consumption height (Plasma Chem Plasma Process, 1993,13:77 – 91) is decomposed in S rotation glow discharge.
Open source literature International journal of hydrogen energy, 2012,37:1335-1347. has reported a kind of H
2S shrinks the method that normal glow discharge is decomposed.Its technical characterictic is: when system pressure is 0.197 normal atmosphere, experimental temperature is between 2000-4000K the time, under optimal conditions, and H
2The energy consumption that S shrinks normal glow discharge is 2.35eV/H
2S, this system temperature height, pressure is low, severe reaction conditions.
Open source literature International journal o f hydrogen energy, 2012,37:10010-10019. has reported a kind of H
2The method that S decomposes.Its technical characterictic is: utilize the microwave plasma body technique at 2400K, and under the atmospheric pressure, H
2S almost can decompose fully, but the hydrogen after decomposing and sulphur at high temperature can be rapidly compound and generation H
2S, and still do not have corresponding quenching device so far.
Open source literature Chem Eng Sci, 2007,62:2216 – 2227. have reported a kind of corona discharge pulse decomposing H of utilizing
2The method of S.Its technical characterictic is: H
2The mixed gas of S and argon gas is 1.322 normal atmosphere at pressure, and under the room temperature, flow velocity is 1.18 * 10
-4SCMs
-1, H
2The S percentage composition is 16% o'clock, H under the corona discharge pulse
2The rate of decomposition of S is about 28%, and minimum decomposition energy consumption is 17eV/H
2S.
Open source literature Chem Eng Sci, 2009,64:4826 – 4834. have reported and have utilized the corona discharge pulse decomposing H
2The method of S.Its technical characterictic is: be 1.322 normal atmosphere at pressure, under the room temperature, flow velocity is 1.18 * 10
-4SCMs
-1, work as H
2The S percentage composition is 8%, and the mixed gas of argon gas and nitrogen is as filling under the gas H
2The transformation efficiency of S is about 33%, and energy consumption has dropped to 4.9eV/H
2S.But so low gas velocity, lower concentration and low-conversion are meaningless in industrial production.
Dielectric barrier discharge have can under atmospheric pressure work, large space discharge, can prevent from forming characteristics such as local spark or arc discharge in the discharge space, thereby have good industrial applications prospect.
Patent documentation CN102408095A(2012) reported a kind of dielectric barrier discharge H that utilizes
2The method that S decomposes.Its technical characterictic is: add photocatalyst in stainless steel wire and kaolin are respectively the line cartridge type dielectric impedance reactor of high voltage electrode and ground-electrode, realize H
2S decomposes preparation hydrogen and elemental sulfur, decomposes the sulphur deposition of generation in the beds downstream.
Open source literature International journal of hydrogen energy, 2012,37:1335-1347. has reported and has utilized the dielectric barrier discharge decomposing H
2The method of S.Its technical characterictic is: under 0.246 normal atmosphere and room temperature, and H
2When the S gas flow rate is 0.09l/min, realized H
2The rate of decomposition of S is 18.5%, and energy consumption is 12eV/H
2S decomposes the sulphur deposition of generation at inside reactor.
Open source literature Plasma Chemistry and Plasma Processing, 1992,12:275-285. has reported and has utilized the dielectric barrier discharge decomposing H
2The method of S.Its technical characterictic is: under atmospheric pressure, utilize dielectric barrier discharge in ozonizer with H
2S decomposes generation hydrogen and sulphur, and experimental temperature is from 443.16-833.16K, and total gas flow rate is 50-100cm
3/ min, H
2The S percentage composition is 20-100%, studies show that Ar can cut down the consumption of energy and voltage breakdown, but its energy consumption is still very high after adding Ar, decomposes energy consumption between 37-106eV/H
2S.
Open source literature International journal of hydrogen energy, 2012,37:2204-2209. has reported and has utilized the dielectric barrier discharge decomposing H
2The method of S.Its technical characterictic is: H
2The rate of decomposition of S gas and energy expenditure depend on service temperature, the residence time, discharge frequency and H
2The initial content of S gas studies show that H
2The rate of decomposition of S under low temperature is higher.
Open source literature Applied Energy, 2012,95:87 – 92. have reported and have utilized the dielectric barrier discharge decomposing H
2The method of S.Its technical characterictic is: at normal temperatures and pressures, utilize dielectric barrier discharge, and under The optimum reaction conditions, H in the unstripped gas
2The content of S be 25%(all the other be argon gas), when flow is 150mL/min, can realize H
2The rate of decomposition of S is 16%, and energy consumption is 1.6eV/H
2S studies show that H under low concentration
2S can obtain higher conversion, and transformation efficiency improves with concentration and reduces, and the sulphur deposition that reaction generates can not in time be removed at inside reactor.
Open source literature Int.J.Energy Res, 2012:2924-2930. have reported and have utilized the dielectric barrier discharge decomposing H
2The method of S.Its technical characterictic is: be filled with MoOx/Al
2O
3In the dielectric barrier discharge reactor of catalyzer, unstripped gas is H
2The mixed gas of S and Ar, H
2The volume content of S is 5%, and total gas flow rate is 150mL/min, discharges H 10 minutes
2The S transformation efficiency is 48%, and energy consumption is 0.92kJ/l H
2S.Decompose the sulphur of producing and be attached to catalyzer and inside reactor, cause catalyst deactivation and system electric capacity to change, it is very unstable to discharge, with the prolongation of discharge time, H
2The rate of decomposition of S reduces gradually.
Master's thesis " plasma body cooperative ZnS decomposing H
2S hydrogen manufacturing ", 2012. have reported plasma body cooperative ZnS decomposing H
2The situation of rate of decomposition, not mentioned H have been reported in S hydrogen manufacturing
2Efficiency and stability problem that S decomposes.
Summary of the invention
The purpose of this invention is to provide the continual and steady apparatus and method of producing hydrogen of decomposing of a kind of hydrogen sulfide, hydrogen sulfide or hydrogen sulfide containing gas are with helicon mode in the present invention, reverse eddy flow passes through electrical discharge zone vertically, form reverse vortex, utilize the high-energy electron of region of discharge that hydrogen sulfide is decomposed, decomposing the sulphur that produces is come out by centrifugation in time, promote the decomposition reaction forward to carry out, an elemental sulfur part that generates is discharged with the hydrogen of unreacted unstripped gas and generation, a part is attached on middle tube inwall and the inner tank theca, by control region of discharge temperature, make the elemental sulfur fusing, along leaving region of discharge under the wall flow, improve hydrogen sulfide rate of decomposition and capacity usage ratio.
The present invention is achieved through the following technical solutions.
The present invention relates to the continual and steady device of producing hydrogen that decomposes of a kind of hydrogen sulfide, this device comprises central electrode, electrical discharge zone, circulating liquid ground-electrode for the coaxial sleeve tube reactor; Central electrode is the metal of inner core parcel, zone between inner core and the middle tube is electrical discharge zone, urceolus and middle tube form chuck, the outer tube side wall lower end is provided with the circulating liquid import, the outer tube side wall upper end is provided with the circulating liquid outlet, feed circulating liquid as ground-electrode in the chuck that middle tube and urceolus form, and electrical discharge zone and barrel are carried out temperature control; Fix a metal electric current in the bottom of urceolus and middle tube annular space and derive line, the one end gos deep into chuck and contacts with the liquid ground-electrode, and the other end stretches out urceolus and is connected with grounding wire; The sidewall that stretches out urceolus in middle tube lower end is provided with raw material gas inlet, lower end at middle tube is provided with relief outlet, the intake method of unstripped gas is circumferential air inlet, guarantee that air inlet is with helicon mode, reverse eddy flow passes through electrical discharge zone vertically, increase gas in the residence time of electrical discharge zone, and the sulphur of generation is come out by centrifugation in time, promote the decomposition reaction forward to carry out; The sulphur that decompose to produce partly is attached on the barrel, and the temperature by control circulating liquid ground-electrode makes the elemental sulfur fusing between 119 ℃-444 ℃, flow down along tube wall, leaves region of discharge.
Dielectric barrier discharge decomposing hydrogen sulfide provided by the invention produces hydrogen and elemental sulfur has the following advantages:
(1) these apparatus and method have improved the homogeneity of hydrogen sulfide discharge;
(2) these apparatus and method have reduced energy waste, have improved capacity usage ratio, have improved hydrogen sulfide and have decomposed the efficiency of producing hydrogen;
(3) intake method of unstripped gas is circumferential air inlet in these apparatus and method, and air inlet is with helicon mode, and reverse eddy flow passes through electrical discharge zone vertically, gas increased in the residence time of electrical discharge zone, the sulphur that produces is come out by centrifugation in time, promotes the decomposition reaction forward to carry out, and rate of decomposition improves;
(4) these apparatus and method can make the elemental sulfur that decomposes generation in time leave electrical discharge zone, discharge sustain is stablized carried out, and are beneficial to industrialization promotion.
Description of drawings
Fig. 1 is the structural representation of coaxial sleeve tube reactor of the present invention;
Fig. 2 is the vertical view of coaxial sleeve tube reactor of the present invention.
Wherein tube, 5-inner core, 6-chuck, the import of 7-circulating liquid, 8-raw material gas inlet, 9-grounding wire, 10-relief outlet among 1-central electrode, the outlet of 2-circulating liquid, 3-urceolus, the 4-.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
The continual and steady device of producing hydrogen that decomposes of a kind of hydrogen sulfide, as shown in Figure 1, reactor shell is the coaxial sleeve structure made from insulating material, urceolus 3 all seals with the above and below of middle tube 4, form chuck 6, it is the circulating liquid as temperature control and ground-electrode in the chuck 6, middle tube 4 seals and is fixed on the insulating material with inner core 5, the top open-ended of inner core 5, its top barrel is fixed on the insulating material, be provided with central electrode 1 in the inner core 5, its part of stretching out insulating material is connected with the high voltage end of ac step-up transformer, fix a metal electric current at urceolus 3 with the bottom of middle tube 4 annular spaces and derive line, the one end gos deep into chuck 6 and contacts with the circulating liquid ground-electrode, the other end stretches out urceolus 3 and is connected with grounding wire 9, and the material of central electrode 1 and grounding wire 9 is platinum, rhodium, palladium, gold, copper, tungsten, iron and nickeliferous and stainless steel titanium; Urceolus 3 side wall lower ends are provided with circulating liquid import 7, urceolus 3 sidewall upper are provided with circulating liquid outlet 2, the sidewall that stretches out urceolus 3 in middle tube 4 lower ends is provided with raw material gas inlet 8, lower end at middle tube 4 is provided with relief outlet 10, reactant carries out exoelectrical reaction in the tubular annular space space that middle tube 4 and inner core 5 constitute, in tube 4 be reactor shell with the barrel of inner core 5, be again the block media of discharge, urceolus 3, middle tube 4 and inner core 5 are made by insulating material; Insulating material comprises oxide glass, corundum, pottery and quartzy.
The continual and steady method of producing hydrogen of decomposing of a kind of hydrogen sulfide, its concrete steps are:
(1) feed nitrogen in the device of plasma decomposes hydrogen sulfide, remove the air in the electrical discharge zone, export its discharge as the liquid of ground-electrode and from circulating liquid from the feeding of circulating liquid entrance simultaneously, fluid temperature is room temperature;
(2) in raw material gas inlet hydrogen sulfide or hydrogen sulfide containing gas are circumferentially fed, air inlet is with helicon mode, and reverse eddy flow forms reverse vortex by electrical discharge zone vertically; Connect ac high voltage source, then by voltage regulator and frequency regulator, ac high-voltage progressively is loaded on the electrode of plasma producing apparatus, make and form the plasma discharge field between central electrode and the liquid ground-electrode, and reaching even discharge condition, the interior hydrogen sulfide of electrical discharge zone this moment is subjected to effect of electric field generation ionization;
(3) hydrogen sulfide is decomposed into hydrogen and elemental sulfur in electrical discharge zone generation ionization, and the elemental sulfur part of generation is discharged with the hydrogen of unreacted unstripped gas and generation, and a part is attached on middle tube inwall and the inner tank theca;
(4) when the sulphur that adheres on the wall has a strong impact on discharge, in discharge, make the fluid temperature in the chuck reach 120 ℃, make on the tube inwall and the fusing of the elemental sulfur on the inner tank theca, flow out electrical discharge zone with liquid form, treat again the circulating liquid temperature to be returned to room temperature after sulphur fusing on the wall is left, carry out so repeatedly; After reacted gas process aqueous sodium hydroxide solution and two sections absorptions of copper sulfate solution, hydrogen content chromatographic instrument on-line analysis in the tail gas.
The continual and steady method of producing hydrogen of decomposing of a kind of hydrogen sulfide, its concrete steps are:
(1) feed nitrogen in the device of plasma decomposes hydrogen sulfide, remove the air in the electrical discharge zone, export its discharge as the liquid of ground-electrode and from circulating liquid from the feeding of circulating liquid entrance simultaneously, fluid temperature remains on 120 ℃;
(2) at the unstripped gas inlet mouth hydrogen sulfide or hydrogen sulfide containing gas are circumferentially fed, air inlet is with helicon mode, and reverse eddy flow forms reverse vortex by electrical discharge zone vertically; Connect ac high voltage source, then by voltage regulator and frequency regulator, ac high-voltage progressively is loaded on the electrode of plasma producing apparatus, make and form the plasma discharge field between central electrode and the liquid ground-electrode, and reaching even discharge condition, the interior hydrogen sulfide of electrical discharge zone this moment is subjected to effect of electric field generation ionization;
(3) hydrogen sulfide is decomposed into hydrogen and elemental sulfur in electrical discharge zone generation ionization, and the elemental sulfur part of generation is discharged with the hydrogen of unreacted unstripped gas and generation, and a part is attached on middle tube inwall and the inner tank theca;
(4) after reacted gas process aqueous sodium hydroxide solution and two sections absorptions of copper sulfate solution, hydrogen content chromatographic instrument on-line analysis in the tail gas.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are had been described in detail; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included among the protection of the present invention.
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| WO2019154245A1 (en) * | 2018-02-09 | 2019-08-15 | 中国石油化工股份有限公司 | Low temperature plasma reaction device and hydrogen sulphide decomposition method |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546367A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Device and method for directly synthesizing hydrogen peroxide at room temperature |
| CN1900042A (en) * | 2006-07-18 | 2007-01-24 | 大连海事大学 | Device for preparing propionic aldehyde by directly oxidizing propylene with molecular oxygen |
| CN102408095A (en) * | 2011-08-20 | 2012-04-11 | 大连理工大学 | A method for decomposing hydrogen sulfide to prepare hydrogen and elemental sulfur |
| CN102721083A (en) * | 2012-06-26 | 2012-10-10 | 哈尔滨工程大学 | Plasma-catalysis gaseous swirl nozzle |
| CN203307046U (en) * | 2013-04-24 | 2013-11-27 | 滨州学院 | Device for preparing hydrogen by continuously and stably decomposing hydrogen sulfide |
-
2013
- 2013-04-24 CN CN2013101441384A patent/CN103204467A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546367A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Device and method for directly synthesizing hydrogen peroxide at room temperature |
| CN1900042A (en) * | 2006-07-18 | 2007-01-24 | 大连海事大学 | Device for preparing propionic aldehyde by directly oxidizing propylene with molecular oxygen |
| CN102408095A (en) * | 2011-08-20 | 2012-04-11 | 大连理工大学 | A method for decomposing hydrogen sulfide to prepare hydrogen and elemental sulfur |
| CN102721083A (en) * | 2012-06-26 | 2012-10-10 | 哈尔滨工程大学 | Plasma-catalysis gaseous swirl nozzle |
| CN203307046U (en) * | 2013-04-24 | 2013-11-27 | 滨州学院 | Device for preparing hydrogen by continuously and stably decomposing hydrogen sulfide |
Non-Patent Citations (2)
| Title |
|---|
| E. LINGA REDDY ET AL.: "Production of hydrogen from hydrogen sulfide assisted by dielectric barrier discharge", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》, vol. 37, 30 November 2011 (2011-11-30), pages 2204 - 2209, XP028441432, DOI: doi:10.1016/j.ijhydene.2011.10.118 * |
| K. GUTSOL ET AL: "Plasma assisted dissociation of hydrogen sulfide", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》, vol. 37, 17 November 2011 (2011-11-17), pages 1335 - 1347, XP028437595, DOI: doi:10.1016/j.ijhydene.2011.10.048 * |
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