WO2022255180A1 - 硫化水素製造装置および硫化水素の製造方法 - Google Patents
硫化水素製造装置および硫化水素の製造方法 Download PDFInfo
- Publication number
- WO2022255180A1 WO2022255180A1 PCT/JP2022/021348 JP2022021348W WO2022255180A1 WO 2022255180 A1 WO2022255180 A1 WO 2022255180A1 JP 2022021348 W JP2022021348 W JP 2022021348W WO 2022255180 A1 WO2022255180 A1 WO 2022255180A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen sulfide
- sulfur
- production apparatus
- catalyst
- sulfide production
- Prior art date
Links
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 364
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 364
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 405
- 239000003054 catalyst Substances 0.000 claims abstract description 346
- 239000011593 sulfur Substances 0.000 claims abstract description 301
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 301
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 216
- 239000007788 liquid Substances 0.000 claims abstract description 209
- 239000001257 hydrogen Substances 0.000 claims abstract description 115
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 115
- 238000010438 heat treatment Methods 0.000 claims abstract description 103
- 230000019086 sulfide ion homeostasis Effects 0.000 claims description 215
- 238000004891 communication Methods 0.000 claims description 73
- 238000012546 transfer Methods 0.000 claims description 70
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 9
- 230000002265 prevention Effects 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000000463 material Substances 0.000 description 51
- 238000011084 recovery Methods 0.000 description 45
- 229910052782 aluminium Inorganic materials 0.000 description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000010935 stainless steel Substances 0.000 description 21
- 229910001220 stainless steel Inorganic materials 0.000 description 21
- 238000004080 punching Methods 0.000 description 19
- 238000007747 plating Methods 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 150000002739 metals Chemical class 0.000 description 13
- 238000005987 sulfurization reaction Methods 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000009413 insulation Methods 0.000 description 7
- 230000001737 promoting effect Effects 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C01B17/16—Hydrogen sulfides
- C01B17/161—Preparation from elemental sulfur
- C01B17/162—Preparation from elemental sulfur from elemental sulfur and hydrogen
-
- 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
- C01B17/16—Hydrogen sulfides
Definitions
- the present invention relates to a hydrogen sulfide production apparatus and a method for producing hydrogen sulfide.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2016-150860.
- Patent Document 1 discloses a lithium sulfide production method for synthesizing lithium sulfide by the reaction of lithium hydroxide and hydrogen sulfide, wherein hydrogen is applied to a heated porous material placed inside a reaction tank.
- Patent document 1 describes that such a production method can reduce the production cost of lithium sulfide, has excellent workability, and can obtain lithium sulfide with high purity.
- Patent Document 1 With the hydrogen sulfide production technology of Patent Document 1, etc., it was difficult to achieve a sufficiently high production efficiency. There is also room for improvement in the stability of production efficiency.
- the present invention has been made in view of the above circumstances, and provides a hydrogen sulfide production apparatus capable of stably producing hydrogen sulfide with high efficiency.
- a hydrogen sulfide production apparatus for producing hydrogen sulfide by reacting sulfur vapor and hydrogen gas, a reactor having a liquid sulfur charge therein; a first heating means for heating liquid sulfur to produce sulfur vapor; a hydrogen supply member connected to the reactor; A hydrogen sulfide production device.
- the hydrogen sulfide production apparatus according to [1] above, The interior of the reactor comprises a catalyst support member provided above the liquid sulfur filling section and a heat insulating member provided above the catalyst support member, further comprising a second heating means for heating a space formed by the catalyst supporting member, the heat insulating member, and the inner wall of the reactor; A hydrogen sulfide production apparatus, wherein an upper space and a lower space of the heat insulating member communicate with each other at a part of the heat insulating member or around the heat insulating member.
- FIG. 1 is a vertical cross-sectional view of a hydrogen sulfide production apparatus according to Embodiment 1-1.
- FIG. 2 is a top view of a heat insulating member of the hydrogen sulfide production apparatus according to Embodiment 1-1.
- FIG. 2 is a top view of a catalyst support member of the hydrogen sulfide production apparatus according to Embodiment 1-1.
- FIG. 1 is a longitudinal sectional view of a hydrogen sulfide production apparatus according to Embodiment 1-2.
- FIG. 1 is a longitudinal sectional view of a hydrogen sulfide production apparatus of Reference Example 1.
- FIG. 1 is a graph showing temperatures in reactors of hydrogen sulfide production apparatuses of Example 1 and Reference Example 1.
- FIG. 2 is a longitudinal sectional view of a hydrogen sulfide production apparatus according to Embodiment 2-1.
- FIG. FIG. 10 is a top view of a heat insulating member of the hydrogen sulfide production apparatus according to Embodiment 2-1;
- FIG. 10 is a top view of a catalyst support member of the hydrogen sulfide production apparatus according to Embodiment 2-1.
- 2 is a longitudinal sectional view of a hydrogen sulfide production apparatus according to Embodiment 2-2.
- FIG. FIG. 3 is a vertical cross-sectional view of a hydrogen sulfide production apparatus according to Embodiment 3-1;
- FIG. 10 is a top view of a catalyst support member of the hydrogen sulfide production apparatus according to Embodiment 3-1;
- FIG. 10 is a vertical cross-sectional view of a hydrogen sulfide production apparatus according to Embodiment 3-2;
- a hydrogen sulfide production apparatus of the present invention is a hydrogen sulfide production apparatus for producing hydrogen sulfide by reacting sulfur vapor and hydrogen gas, and is a reactor having a liquid sulfur filling section therein and heating liquid sulfur.
- FIG. 1-1 An example of the hydrogen sulfide production apparatus of this embodiment (Embodiment 1-1) is shown in FIG. 1-1.
- FIG. 1-1 is a longitudinal sectional view of a hydrogen sulfide production apparatus 1-1 according to Embodiment 1-1.
- FIG. 1-2 is a top view of a heat insulating member 1-7 provided in the hydrogen sulfide production apparatus 1-1.
- FIG. 1-3 is a top view of a catalyst support member 1-6 provided in the hydrogen sulfide production apparatus 1-1.
- the hydrogen sulfide production apparatus 1-1 in this embodiment is an apparatus for producing hydrogen sulfide by reacting sulfur vapor and hydrogen gas.
- a hydrogen sulfide production apparatus 1-1 includes a reactor 1-3 having a liquid sulfur filling section 1-2 therein, and a mantle heater 1-4 as a first heating means for heating liquid sulfur to generate sulfur vapor. , and a hydrogen supply pipe 1-5 as a hydrogen supply member connected to the reactor 1-3.
- the hydrogen sulfide production apparatus 1-1 includes a catalyst support member 1-6 provided above the liquid sulfur filling section 1-2 inside the reactor 1-3, and a catalyst support member 1-6 provided above the catalyst support member 1-6. and a heat insulating member 1-7.
- a hydrogen sulfide production apparatus 1-1 includes a catalyst filling section 1-8 formed by a catalyst supporting member 1-6, a heat insulating member 1-7 and an inner wall of a reactor 1-3. is provided with a jacket heater 1-9 which is a second heating means for heating the .
- the upper space and the lower space of the heat insulating member 1-7 communicate with each other at a part of the heat insulating member 1-7 or around the heat insulating member 1-7.
- Sulfur vapor generated in the liquid sulfur filling section 1-2 by the heating of the mantle heater 1-4 is supplied to the catalyst filling section 1-8 through the communication hole 1-161 provided in the catalyst support member 1-6. .
- the catalyst support member 1-6 is provided with a hydrogen supply pipe through hole 1-162, and the hydrogen supply pipe 1-5 passes through the hydrogen supply pipe through hole 1-162 and is connected to the liquid sulfur filling part 1-2. is doing. Further, the catalyst support member 1-6 is provided with a temperature sensor through-hole 1-163, and the temperature sensor 1-15 passes through the temperature sensor through-hole 1-163 to the liquid sulfur filling portion 1-2. Connected.
- the hydrogen gas supplied to the liquid sulfur filling section 1-2 through the hydrogen supply pipe 1-5 is also supplied to the catalyst filling section 1-8 through the communication hole 1-161 provided in the catalyst support member 1-6. be done.
- the supply amount of hydrogen gas can be adjusted by a hydrogen supply control valve 1-13 provided in the hydrogen supply pipe 1-5.
- the generated hydrogen sulfide gas is supplied to the upper space of the heat insulating member 1-7 through the portion where the upper space and the lower space of the heat insulating member 1-7 are in communication, and is supplied to the upper space of the heat insulating member 1-7.
- the amount of hydrogen sulfide gas recovered can be adjusted by a hydrogen sulfide recovery control valve 1-14 provided in the hydrogen sulfide recovery pipe 1-10.
- a pressure regulating valve 1-11 is provided in the hydrogen sulfide recovery pipe 1-10, and the pressure inside the reactor 1-3 can be adjusted by opening and closing the pressure regulating valve 1-11.
- the hydrogen sulfide recovery pipe 1-10 is also provided with a hydrogen sulfide detector 1-12, which can detect the flow rate of hydrogen sulfide.
- the inventor conducted various studies on the reasons why the efficiency of producing hydrogen sulfide and the stability of the output of hydrogen sulfide were not sufficient in conventional hydrogen sulfide production equipment. As a result, it was found that hydrogen sulfide can be stably produced with high efficiency by highly controlling the temperature distribution inside the catalyst filling section 1-8, which is the site of the hydrogen sulfide producing reaction.
- the present invention has been made based on such findings.
- the hydrogen sulfide production apparatus 1-1 of the present embodiment is provided with a heat insulating member 1-7 in the upper part of the apparatus, the release of heat from the upper part of the hydrogen sulfide production apparatus 1-1 is prevented, and the hydrogen sulfide production reaction proceeds.
- the temperature of the entire interior of the catalyst filling section 1-8, which is a field, is kept high, and as a result, the temperature distribution in the catalyst filling section 1-8 can be highly controlled. Therefore, according to the hydrogen sulfide production apparatus 1-1 of the present embodiment, hydrogen sulfide can be stably produced with high efficiency.
- reactor 1-3 hydrogen sulfide is produced by the reaction between hydrogen gas and sulfur vapor.
- the reactor 1-3 comprises a catalyst support member 1-6 provided above the liquid sulfur filling section 1-2, and a heat insulating member 1-7 provided above the catalyst support member 1-6.
- the sulfur vapor generated in the liquid sulfur filling section 1-2 is supplied to the space (catalyst filling section 1-8) surrounded by the catalyst supporting member 1-6, the heat insulating member 1-7 and the inner wall of the reactor 1-3. Then, the sulfur vapor and the hydrogen gas react in the catalyst filling section 1-8 to produce hydrogen sulfide.
- a hydrogen supply pipe 1-5 is connected to the reactor 1-3, and hydrogen gas is supplied from the hydrogen supply pipe 1-5.
- the hydrogen supply pipe 1-5 is preferably arranged so that the hydrogen supply port 1-500, which is the outlet of hydrogen gas, is positioned below the catalyst support member 1-6. Since hydrogen gas has a lower specific gravity than air, it is supplied from below to the catalyst support member 1-6, and is passed upward through the reactor 1-3 to fill the catalyst filling section 1-8. This is because it can efficiently contact with the catalyst. In addition, fresh hydrogen gas is continuously supplied by continuously ventilating the hydrogen gas upwardly of the reactor 1-3.
- the heat insulating member 1-7 is preferably provided with a plurality of communication holes 1-171 as shown in FIG. 1-2. By doing so, the sulfur vapor generated in the liquid sulfur filling section 1-2 and the hydrogen gas supplied from the hydrogen supply pipe 1-5 are delivered to the catalyst filling section 1-8 through the communication hole 1-171. This is because it is efficiently supplied.
- the catalyst support member 1-6 is preferably provided with a plurality of communication holes 1-161 as shown in FIG. 1-3. By doing so, the sulfur vapor generated in the liquid sulfur filling section 1-2 and the hydrogen gas supplied from the hydrogen supply pipe 5 are efficiently transferred to the catalyst filling section 1-8 through the communication hole 1-161. because it is supplied.
- the catalyst is preferably packed in layers so as to be in contact with the inner wall surface of the reactor 1-3. By doing so, the catalyst can be heated by heat transfer from the inner wall surface of the reactor 1-3, and the heating efficiency can be increased.
- the temperature of the catalyst-filled portion 1-8 is preferably 300° C. or higher, more preferably 330° C. or higher, and still more preferably 360° C. or higher in all regions. When the temperature of the catalyst-filled portion is equal to or higher than the above lower limit in all regions, hydrogen sulfide can be stably produced with high efficiency.
- the temperature of the catalyst-filled portion 1-8 is preferably 500° C. or less, more preferably 480° C. or less, and even more preferably 450° C. or less in all regions. By keeping the temperature of the catalyst-filled portion below the above upper limit in all regions, it becomes possible to prevent deactivation of the catalyst due to excessive heating and to maintain the sulfur resistance of the device.
- the temperature of the catalyst-filled portion 1-8 is usually measured at the horizontal central portion of the catalyst-filled portion 1-8.
- the catalyst filled in the catalyst filling section 1-8 is a catalyst for promoting the hydrogen sulfide generation reaction, and is preferably made of a material having both resistance to sulfurization and resistance to hydrogenation, such as activated carbon, It is composed of one or more materials selected from zeolite and activated alumina. From the viewpoint of reducing impurities, the catalyst is preferably composed of one or more materials selected from zeolite and activated alumina, and is composed of activated alumina that is inexpensive and highly stable at high temperatures. It is particularly preferred to have In addition, from the viewpoint of promoting the reaction between hydrogen gas and sulfur vapor more effectively, metals such as silver, platinum, molybdenum, cobalt, nickel, iron and vanadium may be supported in the pores of the catalyst.
- the reactor 1-3 is made of one or more sulfur-resistant materials selected from quartz, boron nitride, silicon nitride, aluminum, stainless steel, etc., from the viewpoint of preventing corrosion by sulfur. is preferred.
- the reactor 1-3 has an inner surface treated to resist sulfur.
- sulfur-resistant treatment include plating with metals or alloys having high sulfuration resistance, such as tin plating, chrome plating, gold plating, hot-dip aluminum plating, or alloy plating containing these metals.
- a metal diffusion permeation treatment may be used as a means of anti-sulfur treatment.
- a calorizing treatment is a treatment for diffusing and permeating a metal such as aluminum into an object to be treated. It is known that when a metal diffusion permeation layer is formed on the surface of an object to be treated by subjecting the object to calorizing treatment, the anti-sulfuration performance is improved.
- an object to be treated is embedded in a steel case together with a mixture of Fe—Al alloy powder and NH 4 Cl powder, the case is hermetically sealed, and the case is heated in a furnace to form aluminum on the surface of the object to be treated. It is possible to form an aluminum diffusion permeation layer in which is diffusely permeated.
- Mantle heater 1-4 In the hydrogen sulfide production apparatus 1-1 of the present embodiment, the mantle heater 1-4 is used as the first heating means for heating the liquid sulfur charging section 1-2 to generate sulfur vapor.
- the temperature of the liquid sulfur filled portion 1-2 is, for example, 180°C or higher and 445°C or lower, preferably 250°C or higher and 400°C or lower, more preferably 300°C or higher and 350°C or lower.
- the temperature of the mantle heater 1-4 is configured so that the temperature of the liquid sulfur filling section 1-2 can be adjusted to the temperature range described above. Since the necessary heating temperature changes according to the diameter of the liquid sulfur filling portion 1-2 and the filling amount of the catalyst, the temperature range of the mantle heater 1-4 is not particularly limited, but is preferably 250 ° C. or higher and 400 ° C. or lower. , more preferably 300° C. or higher and 350° C. or lower.
- the mantle heater 1-4 is used as the first heating means, but the present invention is not limited to this, and any device may be used as long as it can heat the liquid sulfur filling section 1-2.
- the hydrogen supply pipe 1-5 is a member for supplying hydrogen gas to the reactor 1-3.
- the hydrogen supply pipe 1-5 is preferably arranged so that the hydrogen supply port 1-500, which is the outlet of hydrogen gas, is positioned below the catalyst support member 1-6. Since hydrogen gas has a lower specific gravity than air, it is supplied from below to the catalyst support member 1-6, and is passed upward through the reactor 1-3 to fill the catalyst filling section 1-8. This is because it can efficiently contact with the catalyst. In addition, fresh hydrogen gas is continuously supplied by continuously ventilating the hydrogen gas upwardly of the reactor 1-3.
- the hydrogen supply pipe 1-5 may have a hydrogen supply control valve 1-13 for adjusting the supply amount of hydrogen gas. It is possible to control the amount of hydrogen gas supplied by adjusting the opening and closing of the hydrogen supply control valve 1-13. preferred.
- the material for the hydrogen supply pipe 1-5 it is possible to use the material described above as the material for the reactor 1-3.
- the hydrogen supply pipe 1-5 is used as the hydrogen supply member. There may be.
- the catalyst support member 1-6 is a member for placing a catalyst for promoting the hydrogen sulfide generation reaction, and is provided above the liquid sulfur filling section 1-2.
- the catalyst is preferably packed in layers so as to be in contact with the inner wall surface of the reactor 1-3. Therefore, the catalyst support member 1-6 is preferably arranged so as to be in contact with the inner wall surface of the reactor 1-3 so that the catalyst can be placed in this manner.
- the catalyst support member 1-6 is preferably provided with a plurality of communication holes 1-161 as shown in FIG. 1-3.
- a plurality of communication holes 1-161 in the catalyst support member 1-6 the sulfur vapor generated in the liquid sulfur filling section 1-2 and the hydrogen supplied from the hydrogen supply pipe 5 can be communicated through a plurality of communication holes. This is because the catalyst can be efficiently supplied to the catalyst filling section 1-8 through the hole 1-161.
- the catalyst support member 1-6 may be of any material and shape as long as the catalyst can be placed thereon.
- metals, ceramics, and the like can be used as the material of the catalyst support member.
- the shape of the catalyst support member 1-6 it is preferable to have communication holes such as punching metal.
- communication holes such as punching metal.
- porous plates described above may be stacked and used as the catalyst support member 1-6.
- the area ratio of the communication holes 1-161 provided in the catalyst support member 1-6 is usually 10% or more and 50% or less, preferably 20% or more, from the viewpoint of improving the contact efficiency between the sulfur vapor and the catalyst. 40% or less.
- the diameter of the communication hole provided in the catalyst supporting member 1-6 depends on the diameter of the catalyst to be placed, but is usually 26 ⁇ m or more and 1000 ⁇ m or less, preferably 45 ⁇ m or more and 800 ⁇ m or less.
- the catalyst support member 1-6 may be provided with a hydrogen supply pipe through-hole 1-162, in which case the hydrogen supply pipe 1-5 passes through the hydrogen supply pipe through-hole 1-162 to reach the liquid sulfur filling portion. Connect to 1-2. Further, the catalyst support member 1-6 may be provided with a temperature sensor through-hole 1-163. Connect to part 1-2.
- the material for the catalyst support member 1-6 it is possible to use the material described above as the material for the reactor 1-3.
- the heat insulating member 1-7 is a member for insulating the inside of the reactor 1-3, and is provided above the catalyst supporting member 1-6.
- the heat insulating member 1-7 By providing the heat insulating member 1-7, heat release from the upper portion of the hydrogen sulfide production apparatus 1-1 is prevented, and the entire temperature inside the catalyst filling section 1-8, which is the site of the hydrogen sulfide production reaction, is high. As a result, the temperature distribution in the catalyst filling section 1-8 can be highly controlled. Therefore, according to the hydrogen sulfide production apparatus 1-1 of the present embodiment, hydrogen sulfide can be stably produced with high efficiency. In the hydrogen sulfide production apparatus 1-1 of the present embodiment, the temperature tends to drop more easily in the upper part of the apparatus than in the lower part of the apparatus where the liquid sulfur filling section 1-2, which is the place where sulfur vapor is generated, exists. be. Therefore, the use of the heat insulating member 1-7 to prevent heat release from the upper portion of the hydrogen sulfide production apparatus 1-1 is an effective means for highly controlling the temperature distribution in the catalyst filling section 1-8.
- the heat insulating member 1-7 is preferably arranged above the catalyst filling section 1-8 so as to cover the entire catalyst filling section 1-8. By doing so, the release of heat to the outside of the reactor 1-3 is further prevented. Also, the side surface of the heat insulating member 1-7 is preferably provided so as to be in contact with the inner wall of the reactor 1-3, as shown in FIG. 1-1. By doing so, the heat insulating member 1-7 is also heated, and the heat insulating member 1-7 itself has a certain heat capacity, so that the heat insulating effect of the heat insulating member 1-7 is further enhanced.
- the upper space and the lower space of the heat insulating member 1-7 are communicated in a part of the heat insulating member 1-7 or around the heat insulating member 1-7.
- the heat insulating member is preferably a metal substrate or a ceramic substrate provided with communication holes.
- the heat insulating member 1-7 is preferably provided with a communicating hole 1-171 as shown in FIG. 1-2.
- the generated hydrogen sulfide moves to the upper part of the heat insulating member 1-7 through the plurality of communicating holes 1-171, and the sulfide connected to the upper space of the heat insulating member 1-7. It can be recovered by the hydrogen recovery pipe 1-10.
- heat insulating member 1-7 for example, one or more selected from metal mesh such as stainless steel mesh and aluminum mesh; punching metal such as stainless steel punching and aluminum punching; expanded metal such as stainless steel expanded and aluminum expanded.
- metal mesh such as stainless steel mesh and aluminum mesh
- punching metal such as stainless steel punching and aluminum punching
- expanded metal such as stainless steel expanded and aluminum expanded.
- a porous plate or the like can be used.
- the area ratio of the communication holes provided in the heat insulating member 1-7 is usually 0.2% or more and 50% or less, preferably 0.5%, from the viewpoint of the balance between the improvement of heat insulation efficiency and the improvement of hydrogen sulfide recovery. 40% or less.
- the diameter of the communication hole provided in the heat insulating member 1-7 is usually 26 ⁇ m or more and 10000 ⁇ m or less, preferably 45 ⁇ m or more and 5000 ⁇ m or less.
- a hydrogen supply pipe through-hole 1-172 may be provided in the heat insulating member 1-7, and in that case, the hydrogen supply pipe 1-5 penetrates the hydrogen supply pipe through-hole 1-172 to reach the liquid sulfur filling part 1. -2. Further, the heat insulating member 1-7 may be provided with a temperature sensor through-hole 1-173, in which case the temperature sensor 1-15 penetrates the temperature sensor through-hole 1-173 and enters the liquid sulfur filling portion. Connect to 1-2.
- a jacket heater 1-9 is used as the second heating means.
- the jacket heater 1-9 heats the space (catalyst filling section 1-8) formed by the catalyst supporting member, the heat insulating member and the inner wall of the reactor. That is, the catalyst support member and the space above the catalyst support member are heated. Thereby, the catalyst can be heated to promote the hydrogen sulfide generation reaction.
- the temperature of the jacket heater 1-9 is configured so that the temperature of the catalyst filling portion 1-8 can be adjusted within the above temperature range.
- the temperature range of the jacket heater 1-9 is not particularly limited, but the temperature range is preferably 300° C. or higher. , more preferably 330° C. or higher, and even more preferably 360° C. or higher.
- the temperature of the jacket heater 1-9 By adjusting the temperature of the jacket heater 1-9 to be equal to or higher than the above lower limit, hydrogen sulfide can be stably produced with high efficiency.
- the temperature range is preferably 500° C. or lower, more preferably 480° C. or lower, and even more preferably 450° C. or lower.
- the jacket heater 1-9 is used as the second heating means, but is not limited to this, as long as the space formed by the catalyst supporting member, the heat insulating member and the inner wall of the reactor can be heated. Such heating means may be used.
- a hydrogen sulfide recovery pipe 1-10 is used as a hydrogen sulfide recovery member for recovering hydrogen sulfide gas from the reactor 1-3.
- the hydrogen sulfide recovery pipe 1-10 may have a hydrogen sulfide recovery adjustment valve 1-14 that adjusts the recovery amount of hydrogen sulfide gas.
- a hydrogen sulfide recovery adjustment valve 1-14 that adjusts the recovery amount of hydrogen sulfide gas.
- the hydrogen sulfide recovery pipe 1-10 may be provided with a pressure regulating valve 1-11.
- the internal pressure of the reactor 1-3 can be adjusted by opening and closing the pressure regulating valve 1-11.
- the hydrogen sulfide recovery pipe 1-10 may be provided with a hydrogen sulfide detector 1-12 for detecting the flow rate of hydrogen sulfide.
- a temperature sensor 1-15 is a member for measuring the temperature of each region of the reactor 1-3.
- the temperature sensor 1-15 is arranged at the horizontal center of the reactor 1-3. is preferred.
- FIG. 1-4 An example of the hydrogen sulfide production apparatus of this embodiment (Embodiment 1-2) is shown in FIG. 1-4.
- FIG. 1-4 is a longitudinal sectional view of a hydrogen sulfide production apparatus 1-21 according to Embodiment 1-2.
- the hydrogen sulfide production apparatus 1-21 further includes a heat transfer member arranged in contact with or in close proximity to the lower surface of the catalyst support member.
- the heat transfer member 1-22 under the catalyst support member 1-6, the heat from the jacket heater 1-9 covering the outside of the reactor 1-3 can be easily transmitted toward the center of the catalyst packed portion. , the heat uniformity in the horizontal direction of the catalyst packing is improved.
- the heat transfer member 1-22 is preferably arranged so as to be in contact with the inner wall of the catalyst filling section 1-8. This is for more efficient transmission of heat from the jacket heater 1-9.
- the heat transfer member 1-22 is preferably provided with a plurality of communication holes. By providing a plurality of communication holes in the heat transfer member, the sulfur vapor generated in the liquid sulfur filling section 1-2 and the hydrogen gas supplied from the hydrogen supply pipe 1-5 pass through the plurality of communication holes. This is because the catalyst can be efficiently supplied to the catalyst filling section 1-8.
- the material of the heat transfer member 1-22 is not particularly limited, and the materials described above as the material of the reactor 1-3 can be used.
- the shape of the heat transfer member 1-22 is preferably a plate having an appropriate thickness and provided with communication holes.
- one or more porous plates selected from stainless steel plates or aluminum plates having a thickness of 20 mm or more with communicating holes can be used.
- the area ratio of the communication holes provided in the heat transfer member 1-22 is usually 0.2% or more and 50% or less from the viewpoint of improving heat transfer and improving the contact efficiency between the sulfur vapor and the catalyst, and is preferably is 0.5% or more and 40% or less.
- the diameter of the communication hole provided in the heat transfer member 1-22 is usually 26 ⁇ m or more and 10000 ⁇ m or less, preferably 45 ⁇ m or more and 5000 ⁇ m or less.
- the heat transfer member 1-22 may be provided with a hydrogen supply pipe through-hole, and in that case, the hydrogen supply pipe 1-5 penetrates the hydrogen supply pipe through-hole and connects to the liquid sulfur filling section 1-2. . Further, the heat transfer member 1-22 may be provided with a temperature sensor through hole, in which case the temperature sensor 1-15 passes through the temperature sensor through hole and is connected to the liquid sulfur filling section 1-2. do.
- the liquid sulfur filled in the liquid sulfur filling section 1-2 is heated by the mantle heater 1-4 to generate sulfur vapor.
- the temperature of the liquid sulfur filling portion 1-2 is not particularly limited as long as it is a temperature at which sulfur vapor is generated, and is, for example, 180° C. or higher and 445° C. or lower, preferably 250° C. or higher and 400° C. or lower, and more preferably. is 300° C. or more and 350° C. or less.
- the temperature of the liquid sulfur filled part 1-2 is equal to or higher than the above lower limit, the sulfur vapor pressure becomes more moderate, and the concentration of the obtained hydrogen sulfide gas becomes higher, so that hydrogen sulfide can be generated more efficiently. can be done.
- the sulfur vapor pressure can be reduced to 1 atm or lower, and the amount of sulfur passing through the reactor without reacting with hydrogen gas can be suppressed. .
- sulfur vapor and hydrogen gas are supplied to the catalyst heated by the jacket heater 1-9, so that hydrogen gas and hydrogen gas are produced on the surface of the catalyst. Sulfur vapor reacts to generate hydrogen sulfide gas.
- the concentration of hydrogen sulfide gas during recovery is preferably 1% by volume or more, more preferably 3% by volume or more. Further, the concentration of hydrogen sulfide gas during recovery is preferably 50% by volume or less, more preferably 30% by volume or less.
- the heat insulating member 1-7 is provided in the upper part of the hydrogen sulfide production apparatus 1-1, liquid sulfur provided in the lower part of the apparatus A temperature drop in a region far from the filling section 1-2 (the source of hydrogen sulfide gas) is prevented, and the temperature of the entire catalyst filling section 1-8 is kept high.
- the temperature of the catalyst which is the site of the hydrogen sulfide production reaction, can be highly controlled, and hydrogen sulfide can be stably produced with high efficiency.
- the temperature in the catalyst-filled portion 1-8 is preferably 300° C. or higher, more preferably 330° C. or higher, and even more preferably 360° C. or higher in all regions. Since the temperature in the catalyst filling section 1-8 is equal to or higher than the above lower limit in all regions, hydrogen sulfide can be stably produced with high efficiency.
- the temperature in the catalyst-filled portion 1-8 is preferably 500° C. or less, more preferably 480° C. or less, and even more preferably 450° C. or less in all regions.
- FIG. 2-1 An example of the hydrogen sulfide production apparatus of this embodiment (Embodiment 2-1) is shown in FIG. 2-1.
- FIG. 2-1 is a longitudinal sectional view of a hydrogen sulfide production apparatus 2-1 according to Embodiment 2-1.
- FIG. 2-2 is a top view of a heat insulating member 2-7 provided in the hydrogen sulfide production apparatus 2-1.
- FIG. 2-3 is a top view of the catalyst support member 2-6 provided in the hydrogen sulfide production apparatus 2-1.
- the hydrogen sulfide production device 2-1 of this embodiment is a device that produces hydrogen sulfide by reacting sulfur vapor and hydrogen gas.
- a hydrogen sulfide production apparatus 2-1 includes a reactor 2-3 having a liquid sulfur filling section 2-2 therein, and a mantle heater 2-4 as a first heating means for heating liquid sulfur to generate sulfur vapor. , and a hydrogen supply pipe 2-5 as a hydrogen supply member connected to the reactor 2-3.
- a catalyst support member 2-6 provided above the liquid sulfur filling section 2-2, and a catalyst supporting member 2-6 and a liquid sulfur filling section 2-2 A heat insulating member 2-7 is provided.
- the hydrogen sulfide production apparatus 2-1 includes a catalyst support member 2-6 and a jacket heater 2-9 as second heating means for heating the space above the catalyst support member 2-6.
- the upper space and the lower space of the heat insulating member 2-7 communicate with each other around the portion or the heat insulating member 2-7.
- the temperature of the liquid sulfur filling section 2-2 is usually adjusted to 250-400°C, preferably 300-350°C, in order to generate sulfur vapor.
- the temperature of the liquid sulfur filling section 2-2 is usually measured at the horizontal central portion of the liquid sulfur filling section 2-2.
- the problem here is that the vapor pressure of sulfur fluctuates exponentially in this temperature range, so even a deviation of several degrees Centigrade greatly fluctuates the amount of sulfur vapor generated. Therefore, in order to control the amount of sulfur vapor generated to a desired level and stably produce hydrogen sulfide with high production efficiency, it is necessary to avoid heat transfer from the reactor 2-3 as much as possible. Regarding this point, in the hydrogen sulfide production apparatus 2-1 of the present embodiment, since the heat insulating member 2-7 is provided between the catalyst support member 2-6 and the liquid sulfur filling section 2-2, the reactor Heat transfer from 2-3 to the liquid sulfur filling section 2-2 is prevented, and the temperature of the liquid sulfur filling section 2-2 is prevented from rising excessively. Therefore, the amount of sulfide vapor generated can be controlled to a desired level, and hydrogen sulfide can be stably produced with high production efficiency.
- the reactor 2-3 In the reactor 2-3, hydrogen sulfide is produced by the reaction between hydrogen gas and sulfur vapor.
- the reactor 2-3 includes a catalyst support member 2-6 provided above the liquid sulfur filling section 2-2, the catalyst support member 2-6 and the liquid sulfur filling section 2-2. and a heat insulating member 2-7 provided between.
- the sulfur vapor generated in the liquid sulfur filling section 2-2 is supplied to the space above the catalyst supporting member 2-6.
- the space above the catalyst supporting member 2-6 is filled with a catalyst.
- the space filled with the catalyst above the catalyst support member 2-6 is called a catalyst filling section 2-8, and sulfur vapor and hydrogen gas react in the catalyst filling section 2-8 to produce hydrogen sulfide. be done.
- a hydrogen supply pipe 2-5 is connected to the reactor 2-3, and hydrogen gas is supplied from the hydrogen supply pipe 2-5.
- the hydrogen supply pipe 2-5 is preferably arranged so that the hydrogen supply port 2-500, which is the outlet of hydrogen gas, is positioned below the catalyst support member 2-6. Since the hydrogen gas is supplied from below to the catalyst supporting member 2-6, it can be ventilated upwardly of the reactor 2-3 and efficiently come into contact with the catalyst filled in the catalyst filling section 2-8. is. In addition, fresh hydrogen gas is continuously supplied by continuously ventilating the hydrogen gas upwardly of the reactor 2-3.
- the heat insulating member 2-7 is preferably provided with a plurality of communication holes 2-171 as shown in FIG. 2-2. By doing so, the sulfur vapor generated in the liquid sulfur filling section 2-2 and the hydrogen gas supplied from the hydrogen supply pipe 2-5 are delivered to the catalyst filling section 2-8 through the communication hole 2-171. This is because it is efficiently supplied.
- the catalyst support member 2-6 is preferably provided with a plurality of communication holes 2-161 as shown in FIG. 2-3. By doing so, the sulfur vapor generated in the liquid sulfur filling section 2-2 and the hydrogen gas supplied from the hydrogen supply pipe 2-5 are delivered to the catalyst filling section 2-8 through the communication hole 2-161. This is because it is efficiently supplied.
- a catalyst (not shown) is placed on the catalyst support member 2-6 to promote the reaction of hydrogen sulfide generation from hydrogen gas and sulfur vapor.
- the catalyst is preferably packed in layers so as to be in contact with the inner wall surface of the reactor 2-3. This is because the catalyst can be heated by heat transfer from the inner wall surface of the reactor 2-3, and the heating efficiency can be increased.
- the temperature of the catalyst filling section 2-8 is usually adjusted to 300-500°C, preferably 360-450°C, in order to promote the hydrogen sulfide generation reaction.
- the temperature of the catalyst-filled portion 2-8 is usually measured at the horizontal central portion of the catalyst-filled portion 2-8.
- the catalyst filled in the catalyst filling section 2-8 is a catalyst for promoting the hydrogen sulfide generation reaction, and is preferably made of a material having both resistance to sulfurization and resistance to hydrogenation, such as activated carbon, It is composed of one or more materials selected from zeolite and activated alumina. From the viewpoint of reducing the amount of impurities, the catalyst is preferably composed of one or more materials selected from zeolite and activated alumina, and is composed of activated alumina that is inexpensive and highly stable at high temperatures. It is particularly preferred that In addition, from the viewpoint of promoting the reaction between hydrogen gas and sulfur vapor more effectively, metals such as silver, platinum, molybdenum, cobalt, nickel, iron and vanadium may be supported in the pores of the catalyst.
- Materials for the reactor 2-3 include metals, ceramics, etc., but sulfur-resistant materials are preferred.
- sulfur-resistant materials include sulfur-resistant metallic materials such as stainless steel and aluminum, and sulfur-resistant ceramic materials such as quartz, boron nitride, and silicon nitride.
- the inner surface of the reactor 2-3 is preferably anti-sulfurized.
- anti-sulfur treatment examples include plating with metals or alloys with high anti-sulfurization performance, such as tin plating, chrome plating, gold plating, hot dip aluminum plating, or alloy plating containing these metals.
- a metal diffusion permeation treatment may be used as a means of anti-sulfur treatment. It is known that when a metal diffusion and permeation layer is formed on the surface of the article to be treated by subjecting the article to metal diffusion and permeation treatment, the anti-sulfurization performance is improved.
- a calorizing treatment that diffuses and permeates aluminum can be used. In the calorizing treatment, an object to be treated is embedded in a steel case together with a compounding agent consisting of Fe—Al alloy powder and NH 4 Cl powder, the case is sealed, and the case is heated in a furnace to remove the surface of the object to be treated. It is possible to improve the anti-sulfuration performance of the object to be treated by forming an aluminum diffused and permeated layer in which aluminum is diffused and permeated.
- Mantle heater 2-4 In this embodiment, a mantle heater 2-4 is used as the first heating means.
- the mantle heater 2-4 is means for heating the liquid sulfur filling section 2-2 in order to generate sulfur vapor.
- the temperature of the mantle heater 2-4 is configured so that the temperature of the liquid sulfur filling section 2-2 can be adjusted to the temperature range described above. Since the necessary heating temperature changes with the diameter of the liquid sulfur filling portion 2-2 and the filling amount of the catalyst, the temperature range of the mantle heater 2-4 is not particularly limited, but is preferably 250 to 400 ° C. It is preferably 300-350°C.
- the mantle heater 2-4 is used as the first heating means, but the present invention is not limited to this, as long as it is possible to heat liquid sulfur. There may be.
- a high frequency induction heating device or the like can be used.
- the hydrogen supply pipe 2-5 is a member for supplying hydrogen gas to the reactor 2-3.
- the hydrogen supply pipe 2-5 is preferably arranged so that the hydrogen supply port 2-500, which is the outlet of hydrogen gas, is positioned below the catalyst support member 2-6. Since the hydrogen gas is supplied from below to the catalyst supporting member 2-6, it can be ventilated upwardly of the reactor 2-3 and efficiently come into contact with the catalyst filled in the catalyst filling section 2-8. is. In addition, fresh hydrogen gas is continuously supplied by continuously ventilating the hydrogen gas upwardly of the reactor 2-3.
- the hydrogen supply pipe 2-5 may have a hydrogen supply control valve 2-13 for adjusting the supply amount of hydrogen gas, as shown in FIG. 2-1. It is possible to control the amount of hydrogen gas supplied by adjusting the opening/closing of the hydrogen supply control valve 2-13. preferred.
- the material for the hydrogen supply pipe 2-5 it is possible to use the material described above as the material for the reactor 2-3.
- the hydrogen supply pipe 2-5 is used as the hydrogen supply member, but the present invention is not limited to this, as long as it is possible to supply hydrogen gas to the reactor 2-3. There may be.
- the catalyst support member 2-6 is a member for mounting a catalyst that accelerates the reaction of hydrogen sulfide generation from hydrogen gas and sulfur vapor.
- the catalyst is preferably packed in layers so as to be in contact with the inner wall surface of the reactor 2-3. Therefore, the catalyst support member 2-6 is preferably arranged so as to be in contact with the inner wall surface of the reactor 2-3 so that the catalyst can be placed in this way.
- the catalyst support member 2-6 is preferably provided with a plurality of communication holes 2-161 as shown in FIG. 2-3.
- a plurality of communication holes 2-161 in the catalyst support member 6 the sulfur vapor generated in the liquid sulfur filling section 2-2 and the hydrogen supplied from the hydrogen supply pipe 2-5 are transmitted through a plurality of communication holes. This is because the catalyst can be efficiently supplied to the catalyst filling section 2-8 through the hole 2-161.
- the catalyst support member 2-6 may be provided with a hydrogen supply pipe through hole 2-162. -162 to connect to reactor 2-3.
- the catalyst support member 2-6 may be provided with a temperature sensor through hole 2-163. 163 to connect to the reactor 2-3.
- the temperature sensor through-hole 2-163 is located at the horizontal central portion of the catalyst support member 2-6. is preferably provided in
- the material for the catalyst support member 2-6 it is possible to use the material described above as the material for the reactor 2-3.
- the shape of the catalyst supporting member 2-6 is not particularly limited as long as the catalyst can be placed thereon, but it is preferable that the member has a plurality of communication holes 2-161 as described above.
- one or more kinds of porous plates selected from metal mesh such as aluminum mesh and stainless steel mesh; punching metal such as aluminum punching and stainless steel punching; expanded metal such as aluminum expanded and stainless steel expanded, etc. can be used. can.
- porous plates described above may be stacked and used as the catalyst support member 2-6.
- the diameter of the communication hole 2-161 provided in the catalyst supporting member 2-6 depends on the diameter of the catalyst to be placed, but is usually 26 ⁇ m or more and 1000 ⁇ m or less, preferably 45 ⁇ m or more and 800 ⁇ m or less.
- the heat insulating member 2-7 is a member for preventing heat transfer from the reactor 2-3 to the liquid sulfur filling section 2-2, and is provided between the catalyst supporting member 2-6 and the liquid sulfur filling section 2-2. placed in between.
- the heat insulating member 2-7 is preferably a disk-shaped member as shown in FIG. 2-2. Further, as shown in FIG. 2-1, the disk-shaped heat insulating member 2-7 is located between the catalyst support member 2-6 and the liquid sulfur filling section 2-2, and covers the entire liquid sulfur filling section 2-2. It is preferably configured to cover. By doing so, the heat transfer from the reactor 2-3 to the liquid sulfur filling section 2-2 is further prevented, and the temperature of the liquid sulfur filling section 2-2 is prevented from rising excessively. become. Therefore, it becomes possible to control the concentration of sulfur vapor to a desired concentration and stably produce hydrogen sulfide with high production efficiency.
- the heat insulating member 2-7 is preferably provided with a plurality of communication holes 2-171 as shown in FIG. 2-2.
- the heat insulating member 2-7 is preferably provided with a plurality of communication holes 2-171 as shown in FIG. 2-2.
- the heat insulating member 2-7 may be provided with a hydrogen supply pipe through hole 2-172. 172 to connect to reactor 2-3.
- the heat insulating member 2-7 may be provided with a temperature sensor through hole 2-173. through and connected to the reactor 2-3. Further, since the temperature of the reactor 2-3 is usually measured at the horizontal center of the reactor 2-3, the temperature sensor through-hole 2-173 is located at the horizontal center of the heat insulating member 2-7. is preferably provided.
- the material for the heat insulating member 2-7 it is possible to use the material described above as the material for the reactor 2-3.
- the shape of the heat insulating member 2-7 is not particularly limited, it is preferably provided with a plurality of communication holes 2-171 as described above.
- one or more kinds of porous plates selected from metal mesh such as aluminum mesh and stainless steel mesh; punching metal such as aluminum punching and stainless steel punching; expanded metal such as aluminum expanded and stainless steel expanded, etc. can be used. can.
- porous plates described above may be stacked and used as the heat insulating member 2-7.
- the area ratio of the communication hole 2-171 provided in the heat insulating member 2-7 is usually 0.2% or more and 50% or less from the viewpoint of the balance between the improvement of the heat insulation efficiency and the improvement of the supply efficiency of sulfur vapor and hydrogen gas. and preferably 0.5% or more and 40% or less.
- the diameter of the communication hole 2-171 provided in the heat insulating member 2-7 is usually 26 ⁇ m or more and 10000 ⁇ m or less, preferably 26 ⁇ m or more and 10000 ⁇ m or less, from the viewpoint of improving the heat insulation efficiency and improving the supply efficiency of sulfur vapor and hydrogen gas. It is 45 ⁇ m or more and 5000 ⁇ m or less.
- the thickness of the heat insulating member 2-7 is preferably 0.5 mm or more, more preferably 1.5 mm or more, from the viewpoint of improving heat insulation efficiency. There is no particular upper limit to the thickness of the heat insulating member 7, but it is usually 20 mm or less.
- a jacket heater 2-9 is used as the second heating means.
- the jacket heater 2-9 heats the catalyst support member 2-6 and the space above the catalyst support member 2-6. As a result, the catalyst filled in the catalyst filling section 2-8 is heated, and the hydrogen sulfide generation reaction can be accelerated.
- the temperature of the jacket heater 2-9 is configured so that the temperature of the catalyst filling section 2-8 can be adjusted within the above temperature range. Since the necessary heating temperature changes with the diameter of the catalyst filling portion 2-8 and the amount of catalyst filled, the temperature range of the jacket heater 2-9 is not particularly limited, but is preferably 300 to 500° C., and is more preferable. is 360-450°C.
- the jacket heater 2-9 is used as the second heating means, but the present invention is not limited to this, as long as it is possible to heat the catalyst as long as it is possible.
- a high frequency induction heating device or the like can be used.
- the hydrogen sulfide recovery pipe 2-10 is a member for recovering hydrogen sulfide generated by reaction between sulfur vapor and hydrogen gas.
- a pressure regulating valve 2-11 may be provided in the hydrogen sulfide recovery pipe 2-10, and the pressure inside the reactor 2-3 can be adjusted by opening and closing the pressure regulating valve 2-11.
- the hydrogen sulfide recovery pipe 2-10 may be provided with a hydrogen sulfide detector 2-12, which is a member for detecting the flow rate of hydrogen sulfide.
- the hydrogen sulfide recovery pipe 2-10 may be provided with a hydrogen sulfide recovery adjustment valve 2-14, which is a member for adjusting the recovery amount of the hydrogen sulfide gas.
- a temperature sensor 2-15 is a member for measuring the temperature of each region of the reactor 2-3.
- the temperature sensor 2-15 is arranged at the horizontal center of the reactor 2-3. is preferred.
- the heat insulating member 2-7 is provided between the catalyst support member 2-6 and the liquid sulfur filling section 2-2, the heat from the reactor 2-3 Heat transfer to the liquid sulfur filling section 2-2 is prevented, and the temperature of the liquid sulfur filling section 2-2 is prevented from rising excessively. Therefore, the concentration of sulfur vapor can be controlled to a desired concentration, and hydrogen sulfide can be stably produced with high production efficiency.
- FIG. 2-4 An example of the hydrogen sulfide production apparatus of this embodiment (Embodiment 2-2) is shown in FIG. 2-4.
- FIG. 2-4 is a longitudinal sectional view of a hydrogen sulfide production apparatus 2-21 according to Embodiment 2-2.
- the hydrogen sulfide production device 2-21 further includes a heat transfer member 2-22 arranged in contact with or close to the lower surface of the catalyst support member 2-6.
- the heat transfer member 2-22 under the catalyst support member 2-6, the heat from the jacket heater 2-9 covering the outside of the catalyst filling section 2-8 is transferred horizontally to the catalyst filling section 2-8.
- the heat is easily transmitted in the direction, and the uniformity of heat in the horizontal direction of the catalyst filling portion 2-8 is improved.
- the heat transfer member 2-22 is preferably arranged so as to be in contact with the inner wall of the catalyst filling section 2-8. This is for more efficient transmission of heat from the jacket heater 2-9.
- the heat transfer member 2-22 is preferably provided with a plurality of communication holes. By providing a plurality of communication holes in the heat transfer member, the sulfur vapor generated in the liquid sulfur filling section 2-2 and the hydrogen gas supplied from the hydrogen supply pipe 2-5 pass through the plurality of communication holes. This is for efficient supply to the catalyst filling section 2-8.
- the material of the heat transfer member 2-22 is not particularly limited, and the materials described above as the material of the reactor 2-3 can be used. It is preferable to use an aluminum alloy, aluminum nitride, or the like.
- the shape of the heat transfer member 2-22 is not particularly limited, it is preferable that the heat transfer member 2-22 is provided with a plurality of communication holes.
- the heat transfer member 2-22 is provided with a plurality of communication holes.
- one or more porous plates selected from stainless steel plates or aluminum plates having a thickness of 20 mm or more with communicating holes can be used.
- porous plates described above may be stacked and used as the heat transfer member 2-22.
- the area ratio of the communication holes provided in the heat transfer member 2-22 is usually 0.2% or more and 50% or less from the viewpoint of the balance between the improvement of the heat transfer efficiency and the improvement of the sulfur vapor and hydrogen gas supply efficiency. , preferably 0.5% or more and 40% or less.
- the diameter of the communication hole provided in the heat transfer member 2-22 is usually 26 ⁇ m or more and 10000 ⁇ m or less, preferably 45 ⁇ m or more and 5000 ⁇ m or less.
- a jacket heater 2-9 covering the outside of the catalyst filling section 2-8 is provided by providing the heat transfer member 2-22 under the catalyst support member 2-6.
- the heat from the catalyst is more easily transmitted in the horizontal direction of the catalyst-filled portion 2-8, and the heat uniformity in the horizontal direction of the catalyst-filled portion 2-8 is improved. Therefore, hydrogen sulfide can be produced more stably with higher production efficiency.
- liquid sulfur is heated by the mantle heater 2-4 to generate sulfur vapor.
- the temperature of the liquid sulfur filling section 2-2 is usually adjusted to 250-400°C, preferably 300-350°C, in order to generate sulfur vapor.
- the temperature of the liquid sulfur filling section 2-2 is usually measured at the horizontal central portion of the liquid sulfur filling section 2-2.
- the problem here is that the vapor pressure of sulfur fluctuates exponentially in this temperature range, so even a deviation of several degrees Centigrade greatly fluctuates the amount of sulfur vapor generated. Therefore, in order to control the amount of sulfur vapor generated to a desired level and stably produce hydrogen sulfide with high production efficiency, it is necessary to avoid heat transfer from the reactor 2-3 as much as possible. Regarding this point, in the hydrogen sulfide production apparatus 2-1 of the present embodiment, since the heat insulating member 2-7 is provided between the catalyst support member 6 and the liquid sulfur filling section 2-2, the reactor 2- 3 to the liquid sulfur filling section 2-2, preventing the temperature of the liquid sulfur filling section 2-2 from rising excessively. Therefore, the amount of sulfur vapor generated can be controlled to a desired level, and hydrogen sulfide can be stably produced with high production efficiency.
- the hydrogen sulfide production process using the hydrogen sulfide production device 2-1 sulfur vapor and hydrogen gas are supplied to the catalyst heated by the jacket heater 2-9, so that hydrogen gas and sulfur are produced on the surface of the catalyst. Reacts steam to generate hydrogen sulfide gas. At this time, by supplying an excessive amount of hydrogen gas, it is possible to recover hydrogen sulfide gas in a state diluted with hydrogen gas. This makes it possible to reduce the concentration of hydrogen sulfide gas contained in the exhaust gas that is generated during pressure adjustment, reaction completion, or the like, so that exhaust gas treatment can be made simpler.
- the concentration of hydrogen sulfide gas during recovery is preferably 1% by volume or more, more preferably 3% by volume or more. Further, the concentration of hydrogen sulfide gas during recovery is preferably 50% by volume or less, more preferably 30% by volume or less.
- the temperature of the catalyst filling section 2-8 is usually adjusted to 300-500°C, preferably 360-450°C, in order to promote the hydrogen sulfide generation reaction.
- the temperature of the catalyst-filled portion 2-8 is usually measured at the horizontal central portion of the catalyst-filled portion 2-8.
- FIG. 3-1 An example of the hydrogen sulfide production apparatus of this embodiment (Embodiment 3-1) is shown in FIG. 3-1.
- FIG. 3-1 is a longitudinal sectional view of a hydrogen sulfide production apparatus 3-1 according to Embodiment 3-1.
- the hydrogen sulfide production device 3-1 in this embodiment is a device for producing hydrogen sulfide by reacting sulfur vapor and hydrogen gas.
- FIG. 3-2 is a top view of an example of the catalyst support member of the hydrogen sulfide production apparatus of this embodiment.
- a hydrogen sulfide production apparatus 3-1 includes a reactor 3-3 having a liquid sulfur filling section 3-2 therein, and a mantle heater 3-4 as a first heating means for heating liquid sulfur to generate sulfur vapor. , a hydrogen supply pipe 3-5, which is a hydrogen supply member connected to the reactor 3-3, and a liquid sulfur supply pipe 3-7, which is a liquid sulfur supply member connected to the liquid sulfur filling section 3-2. Prepare.
- a catalyst support member 3-6 is provided above the liquid sulfur filling section 3-2. Inside the reactor 3-3, the catalyst supporting member 3-6 and the inner wall of the reactor 3-3 form a catalyst filling portion 3-8. In addition, the reactor 3-3 is equipped with a jacket heater 3-9 as second heating means for heating the catalyst filling section 3-8.
- the liquid sulfur supply pipe 3-7 is configured to be able to constantly supply liquid sulfur to the liquid sulfur filling section 3-2. Then, sulfur vapor is generated by heating the liquid sulfur supplied to the liquid sulfur filling section 3-2 through the liquid sulfur supply pipe 3-7. Since liquid sulfur can be constantly supplied, the amount of sulfur vapor generated can be controlled to a desired amount. Therefore, it is possible to control the concentration of sulfur vapor in the catalyst filling section 3-8, which is the site of the hydrogen sulfide producing reaction, to a desired concentration, and to stably produce hydrogen sulfide with high production efficiency.
- reactor 3-3 In the reactor 3-3, hydrogen sulfide is produced by the reaction between hydrogen gas and sulfur vapor.
- the reactor 3-3 comprises a catalyst support member 3-6 provided above the liquid sulfur filling 3-2.
- the sulfur vapor generated in the liquid sulfur filling section 3-2 is supplied to the space (catalyst filling section 3-8) surrounded by the catalyst supporting member 3-6 and the inner wall of the reactor 3-3, and the catalyst filling section 3 At -8, sulfur vapor and hydrogen gas react to produce hydrogen sulfide.
- a hydrogen supply pipe 5 is connected to the reactor 3-3, and hydrogen gas is supplied from the hydrogen supply pipe 3-5.
- the hydrogen supply pipe 3-5 is preferably arranged so that the hydrogen supply port 3-500, which is the outlet of hydrogen gas, is positioned below the catalyst support member 3-6. Since hydrogen gas has a lower specific gravity than air, it is supplied from below to the catalyst supporting member 3-6, and thus is ventilated upwardly of the reactor 3-3 and filled in the catalyst filling section 3-8. This is because it can efficiently contact with the catalyst. In addition, fresh hydrogen gas is continuously supplied by continuously ventilating the hydrogen gas upwardly of the reactor 3-3.
- the catalyst support member 3-6 is preferably provided with a plurality of communication holes 3-161 as shown in FIG. 3-2. By doing so, the sulfur vapor generated in the liquid sulfur filling section 3-2 and the hydrogen gas supplied from the hydrogen supply pipe 3-5 are delivered to the catalyst filling section 3-8 through the communication hole 3-161. This is because it is efficiently supplied.
- a catalyst (not shown) is placed on the catalyst support member 3-6 to promote the reaction of hydrogen sulfide from hydrogen gas and sulfur vapor.
- the catalyst is preferably packed in layers so as to be in contact with the inner wall surface of the reactor 3-3. By doing so, the catalyst can be heated by heat transfer from the inner wall surface of the reactor 3-3, and the heating efficiency can be increased.
- the temperature in the catalyst-filled portion 3-8 is preferably 300° C. or higher, more preferably 330° C. or higher, and even more preferably 360° C. or higher. Since the temperature of the catalyst filling section 3-8 is equal to or higher than the above lower limit in all regions, hydrogen sulfide can be stably produced with high efficiency.
- the temperature in the catalyst filling section 3-8 is preferably 500° C. or less, more preferably 480° C. or less, and even more preferably 450° C. or less. By keeping the temperature of the catalyst filling section 3-8 below the above upper limit in all regions, it becomes possible to prevent deactivation of the catalyst due to excessive heating and to maintain the sulfur resistance of the apparatus. Incidentally, the temperature in the catalyst filling section 3-8 is usually measured at the horizontal central portion of the catalyst filling section 8. As shown in FIG.
- the catalyst filled in the catalyst filling section 3-8 is a catalyst for promoting the hydrogen sulfide generation reaction, and is preferably made of a material having both resistance to sulfurization and resistance to hydrogenation, such as activated carbon, It is composed of one or more materials selected from zeolite and activated alumina. From the viewpoint of reducing impurities, the catalyst is preferably composed of one or more materials selected from zeolite and activated alumina, and is composed of activated alumina that is inexpensive and highly stable at high temperatures. It is particularly preferred to have In addition, from the viewpoint of promoting the reaction between hydrogen gas and sulfur vapor more effectively, metals such as silver, platinum, molybdenum, cobalt, nickel, iron and vanadium may be supported in the pores of the catalyst.
- the reactor 3-3 is made of one or more sulfur-resistant materials selected from quartz, boron nitride, silicon nitride, aluminum, stainless steel, etc., from the viewpoint of preventing corrosion by sulfur. is preferred.
- the inner surface of the reactor 3-3 is anti-sulfurized.
- anti-sulfur treatment examples include plating with metals or alloys with high anti-sulfurization performance, such as tin plating, chrome plating, gold plating, hot dip aluminum plating, or alloy plating containing these metals.
- a metal diffusion permeation treatment may be used as a means of anti-sulfur treatment. It is known that when a metal diffusion and permeation layer is formed on the surface of the article to be treated by subjecting the article to metal diffusion and permeation treatment, the anti-sulfurization performance is improved.
- a calorizing treatment that diffuses and permeates aluminum can be used. In the calorizing treatment, an object to be treated is embedded in a steel case together with a compounding agent consisting of Fe—Al alloy powder and NH 4 Cl powder, the case is sealed, and the case is heated in a furnace to remove the surface of the object to be treated. It is possible to improve the anti-sulfuration performance of the object to be treated by forming an aluminum diffused and permeated layer in which aluminum is diffused and permeated.
- Mantle heater 3-4 In this embodiment, a mantle heater 3-4 is used as the first heating means for heating the liquid sulfur charging section 3-2 to generate sulfur vapor.
- the mantle heater 3-4 is means for heating the liquid sulfur filling section 3-2 in order to generate sulfur vapor.
- the temperature in the liquid sulfur filling section 3-2 is usually 180°C or higher and 445°C or lower, preferably 250°C or higher and 400°C or lower, and more preferably 300°C or higher and 350°C or lower. By keeping the temperature of the liquid sulfur filling section 3-2 within the above range, it is possible to stably generate sulfur vapor.
- the temperature in the liquid sulfur filling section 3-2 is usually measured at the horizontal central portion of the liquid sulfur filling section 3-2.
- the temperature of the mantle heater 3-4 is configured so that the temperature of the liquid sulfur filling section 3-2 can be adjusted within the above temperature range. Since the necessary heating temperature changes according to the diameter of the liquid sulfur filling portion 3-2 and the filling amount of the catalyst, the temperature range of the mantle heater 3-4 is not particularly limited, but is preferably 250° C. or higher and 400° C. or lower. , more preferably 300° C. or higher and 350° C. or lower.
- the mantle heater 3-4 is used as the first heating means, but the present invention is not limited to this, and any heating means can be used as long as it can heat liquid sulfur.
- any heating means can be used as long as it can heat liquid sulfur.
- the hydrogen supply pipe 3-5 is a member for supplying hydrogen gas to the reactor 3-3.
- the hydrogen supply pipe 3-5 is preferably arranged so that the hydrogen supply port 3-500, which is the outlet of hydrogen gas, is positioned below the catalyst support member 3-6. Since hydrogen gas has a lower specific gravity than air, it is supplied from below to the catalyst supporting member 3-6, and thus is ventilated upwardly of the reactor 3-3 and filled in the catalyst filling section 3-8. This is because it can efficiently contact with the catalyst. In addition, fresh hydrogen gas is continuously supplied by continuously ventilating the hydrogen gas upwardly of the reactor 3-3.
- the hydrogen supply pipe 3-5 may have a hydrogen supply control valve 3-13 for adjusting the supply amount of hydrogen gas, as shown in FIG. 3-1. It is possible to control the amount of hydrogen gas supplied by adjusting the opening/closing of the hydrogen supply control valve 3-13. preferred.
- the material for the hydrogen supply pipe 3-5 it is possible to use the material described above as the material for the reactor 3-3.
- the hydrogen supply pipe 3-5 is used as the hydrogen supply member, but the present invention is not limited to this, and any member can be used as long as it is possible to supply hydrogen gas to the reactor 3-3. There may be.
- the catalyst support member 3-6 is a member for mounting a catalyst that accelerates the reaction of hydrogen sulfide generation from hydrogen gas and sulfur vapor.
- the catalyst is preferably packed in layers so as to be in contact with the inner wall surface of the reactor 3-3. Therefore, the catalyst support member 3-6 is preferably arranged so as to be in contact with the inner wall surface of the reactor 3-3 so that the catalyst can be placed in this manner.
- the catalyst support member 3-6 is preferably provided with a plurality of communication holes 3-161 as shown in FIG. 3-2.
- a plurality of communication holes 3-161 in the catalyst support member 3-6 the sulfur vapor generated in the liquid sulfur filling section 3-2 and the hydrogen supplied from the hydrogen supply pipe 3-5 can This is because the catalyst is efficiently supplied to the catalyst filling section 3-8 through the communication hole 3-161.
- the catalyst support member 3-6 may be provided with a hydrogen supply pipe through hole 3-162 as shown in FIG. -162 to connect to reactor 3-3.
- the catalyst support member 3-6 may be provided with a temperature sensor through hole 3-163. 163 to connect to the reactor 3-3.
- the temperature sensor through-hole 3-163 is located at the horizontal center of the catalyst support member 3-6. It is preferably provided in the part.
- the material for the catalyst support member 3-6 it is possible to use the material described above as the material for the reactor 3-3.
- the shape of the catalyst support member 3-6 is not particularly limited as long as the catalyst can be placed thereon, but as described above, it is preferable that a plurality of communication holes 3-161 are provided.
- one or more kinds of porous plates selected from metal mesh such as aluminum mesh and stainless steel mesh; punching metal such as aluminum punching and stainless steel punching; expanded metal such as aluminum expanded and stainless steel expanded, etc. can be used. can.
- porous plates described above may be stacked and used as the catalyst support member 3-6.
- the area ratio of the communication holes 3-161 provided in the catalyst support member 3-6 is usually 10% or more and 50% or less, preferably 20% or more, from the viewpoint of improving the contact efficiency between the sulfur vapor and the catalyst. 40% or less.
- the diameter of the communication hole provided in the catalyst support member 3-6 depends on the diameter of the catalyst to be placed, but is usually 26 ⁇ m or more and 1000 ⁇ m or less, preferably 45 ⁇ m or more and 800 ⁇ m or less.
- the liquid sulfur supply pipe 3-7 is a member for supplying liquid sulfur to the liquid sulfur filling section 3-2 and is connected to the liquid sulfur filling section 3-2.
- the liquid sulfur supply pipe 3-7 is configured to constantly supply liquid sulfur to the liquid sulfur filling section 3-2.
- the liquid sulfur supply pipe 3-7 may be provided with a liquid sulfur supply adjustment valve 3-19 for adjusting the supply amount of liquid sulfur.
- liquid sulfur supply pipe 3-7 may be provided with a backflow prevention gas supply member 3-18 that prevents backflow of hydrogen sulfide gas, and the backflow prevention gas such as hydrogen is supplied from the backflow prevention gas supply member 3-18.
- a backflow prevention gas supply member 3-18 that prevents backflow of hydrogen sulfide gas
- the backflow prevention gas such as hydrogen is supplied from the backflow prevention gas supply member 3-18.
- the temperature inside the liquid sulfur supply pipe 3-7 is preferably 120°C or higher and 160°C or lower, more preferably 130°C or higher and 150°C or lower. Since the temperature in the liquid sulfur supply pipe 3-7 is equal to or higher than the lower limit value, the sulfur in the liquid sulfur supply pipe 3-7 can be moved in a liquid state. In addition, since the temperature in the liquid sulfur supply pipe 3-7 is equal to or lower than the above upper limit value, it is possible to prevent the sulfur in the liquid sulfur supply pipe 3-7 from becoming rubbery sulfur, and the sulfur is smoothed. can be supplied to
- the material of the liquid sulfur supply pipe 3-7 it is possible to use the material described above as the material of the reactor 3-3.
- liquid sulfur supply pipe 3-7 is used as the liquid sulfur supply member, but the present invention is not limited to this. Such a member may be used.
- the hydrogen sulfide production apparatus 3-1 of the present embodiment includes a sulfur storage container 3-17, which is a member for storing sulfur to be supplied to the liquid sulfur filling section 3-2, and heats the sulfur storage container 3-17. It is preferable that the sulfur container 3-17 and the liquid sulfur filling unit 3-2 are connected by a liquid sulfur supply pipe 3-7. .
- the sulfur container 3-17 may further include a sulfur introduction pipe for introducing sulfur into the sulfur container 3-17 from the outside, or liquid sulfur may be supplied from the sulfur container 3-17.
- a carrier gas inlet tube may also be provided for introducing a carrier gas for pushing the sulfur out to tube 3-7.
- the sulfur containing container 3-17 may further include a pipe serving as both a sulfur introduction pipe and a carrier gas introduction pipe.
- the sulfur in the sulfur container 3-17 is liquefied by heating by the sulfur container heating means 3-16, and the liquefied sulfur flows through the liquid sulfur supply pipe 3-7 to the liquid sulfur filling section. 3-2.
- the temperature in the sulfur container 3-17 is preferably 120°C or higher and 160°C or lower, more preferably 130°C or higher and 150°C or lower.
- the sulfur contained in the sulfur container 3-17 can be sufficiently liquefied.
- the temperature in the sulfur container 3-17 is equal to or lower than the above upper limit, it is possible to prevent the sulfur contained in the sulfur container 3-17 from becoming rubbery sulfur, and liquid sulfur It becomes possible to smoothly supply sulfur through the supply pipe 3-7.
- the temperature of the sulfur storage container heating means 3-16 is configured so that the temperature of the liquid sulfur filling portion 3-2 can be adjusted to the temperature range described above. Since the necessary heating temperature changes with the diameter of the liquid sulfur filling part 3-2 and the filling amount of the catalyst, the temperature range of the sulfur container heating means 3-16 is not particularly limited, but is preferably 120 ° C. or more and 160 ° C. or less, more preferably 130° C. or higher and 150° C. or lower.
- a jacket heater 3-9 is used as the second heating means.
- the jacket heater 3-9 heats the space (catalyst filling section 3-8) formed by the catalyst supporting member, the heat insulating member and the inner wall of the reactor. That is, the catalyst support member and the space above the catalyst support member are heated. Thereby, the catalyst can be heated to promote the hydrogen sulfide production reaction.
- the temperature of the jacket heater 3-9 is configured so that the temperature of the catalyst filling section 3-8 can be adjusted within the above temperature range.
- the temperature range of the jacket heater 3-9 is not particularly limited, but the temperature range is preferably 300° C. or higher. , more preferably 330° C. or higher, and even more preferably 360° C. or higher.
- the temperature of the jacket heater 3-9 By adjusting the temperature of the jacket heater 3-9 to be equal to or higher than the above lower limit, hydrogen sulfide can be stably produced with high efficiency.
- the temperature range is preferably 500° C. or lower, more preferably 480° C. or lower, and even more preferably 450° C. or lower.
- the jacket heater 3-9 is used as the second heating means.
- the jacket heater 3-9 may be used.
- a high frequency induction heating device or the like can be used.
- the hydrogen sulfide recovery pipe 3-10 is a member for recovering hydrogen sulfide generated by reaction between sulfur vapor and hydrogen gas.
- a pressure regulating valve 3-11 may be provided in the hydrogen sulfide recovery pipe 3-10, and the pressure inside the reactor 3-3 can be adjusted by opening and closing the pressure regulating valve 3-11. Further, the hydrogen sulfide recovery pipe 3-10 may be provided with a hydrogen sulfide detector 3-12, which is a member for detecting the flow rate of hydrogen sulfide. Furthermore, the hydrogen sulfide recovery pipe 3-10 may be provided with a hydrogen sulfide recovery control valve 3-14, which is a member for adjusting the recovery of the recovery amount of hydrogen sulfide gas.
- a temperature sensor 3-15 is a member for measuring the temperature of each region of the reactor 3-3.
- the temperature sensor 3-15 is arranged at the horizontal center of the reactor 3-3. is preferred.
- FIG. 3-3 An example of the hydrogen sulfide production apparatus of this embodiment (Embodiment 3-2) is shown in FIG. 3-3.
- FIG. 3-3 is a longitudinal sectional view of a hydrogen sulfide production apparatus 3-21 according to Embodiment 3-2.
- the hydrogen sulfide production device 3-21 further includes a heat transfer member 3-22 arranged in contact with or in close proximity to the lower surface of the catalyst support member 3-6.
- the heat transfer member 3-22 under the catalyst support member 3-6, the heat from the jacket heater 3-9 covering the outside of the catalyst filling section 3-8 is transferred horizontally to the catalyst filling section 3-8. This is because the heat is easily transmitted in the direction, and the uniformity of heat in the horizontal direction of the catalyst filling portion 3-8 is improved.
- the heat transfer member 3-22 is preferably arranged so as to be in contact with the inner wall of the catalyst filling section 3-8. This is for more efficient transmission of heat from the jacket heater 3-9.
- the heat transfer member 3-22 is preferably provided with a plurality of communication holes. By providing a plurality of communication holes in the heat transfer member, the sulfur vapor generated in the liquid sulfur filling section 3-2 and the hydrogen gas supplied from the hydrogen supply pipe 3-5 pass through the plurality of communication holes. This is for efficient supply to the catalyst filling section 3-8.
- the material of the heat transfer member 3-22 is not particularly limited, and the materials described above as the material of the reactor 3-3 can be used.
- the shape of the heat transfer member 3-22 is not particularly limited, it is preferable that the heat transfer member 3-22 is provided with a plurality of communication holes.
- the heat transfer member 3-22 is provided with a plurality of communication holes.
- one or more porous plates selected from stainless steel plates or aluminum plates having a thickness of 20 mm or more with communicating holes can be used.
- porous plates described above may be stacked and used as the heat transfer member 3-22.
- the area ratio of the communication holes provided in the heat transfer member 3-22 is usually 0.2% or more and 50% or less from the viewpoint of improving heat transfer and improving the contact efficiency between sulfur vapor and the catalyst, and is preferably is 0.5% or more and 40% or less.
- the diameter of the communication hole provided in the heat transfer member 3-22 is normally 26 ⁇ m or more and 10000 ⁇ m or less, preferably 45 ⁇ m or more and 5000 ⁇ m or less.
- a jacket heater 3-9 covering the outside of the catalyst filling section 3-8 is provided by providing the heat transfer member 3-22 under the catalyst support member 3-6.
- the heat from the catalyst can be easily transmitted in the horizontal direction of the catalyst-filled portion 3-8, and the heat uniformity in the horizontal direction of the catalyst-filled portion 3-8 is improved. Therefore, hydrogen sulfide can be produced more stably with higher production efficiency.
- the liquid sulfur supply pipe 3-7 is configured to be able to constantly supply liquid sulfur to the liquid sulfur filling section 3-2.
- Liquid sulfur supplied to the liquid sulfur filling section 3-2 through the liquid sulfur supply pipe 3-7 is heated by the mantle heater 3-4 to generate sulfur vapor. Since liquid sulfur can be constantly supplied, the amount of sulfur vapor generated can be controlled to a desired amount. Therefore, it is possible to control the concentration of sulfur vapor in the catalyst filling section 3-8, which is the site of the hydrogen sulfide producing reaction, to a desired concentration, and to stably produce hydrogen sulfide with high production efficiency.
- the hydrogen sulfide production apparatus of Embodiment 3-1 or 3-2 includes a sulfur storage container 3-17, which is a member for storing sulfur to be supplied to the liquid sulfur filling section 3-2, and a sulfur storage container 3- 17, and the sulfur container 3-17 and the liquid sulfur filling section 3-2 are connected by a liquid sulfur supply pipe 3-7.
- the sulfur in the sulfur container 3-17 is liquefied by heating the sulfur container heating means 3-16, and the liquefied sulfur is supplied through the liquid sulfur supply pipe 3-7. It is supplied to the liquid sulfur filling section 3-2.
- the temperature in the sulfur container 3-17 is preferably 120°C or higher and 160°C or lower, more preferably 130°C or higher and 150°C or lower.
- the temperature in the liquid sulfur filling section 3-2 is usually 180°C or higher and 445°C or lower, preferably 250°C or higher and 400°C or lower, and more preferably 300°C or higher and 350°C or lower. By keeping the temperature of the liquid sulfur filling section 3-2 within the above range, it is possible to stably generate sulfur vapor.
- the temperature in the liquid sulfur filling section 3-2 is usually measured at the horizontal central portion of the liquid sulfur filling section 3-2.
- the catalyst Hydrogen gas and sulfur vapor react on the surface to generate hydrogen sulfide gas.
- the concentration of hydrogen sulfide gas during recovery is preferably 1% by volume or more, more preferably 3% by volume or more. Further, the concentration of hydrogen sulfide gas during recovery is preferably 50% by volume or less, more preferably 30% by volume or less.
- the temperature in the catalyst-filled portion 3-8 is preferably 300° C. or higher, more preferably 330° C. or higher, and even more preferably 360° C. or higher. Since the temperature of the catalyst filling section 3-8 is equal to or higher than the above lower limit in all regions, hydrogen sulfide can be stably produced with high efficiency.
- the temperature in the catalyst filling section 3-8 is preferably 500° C. or less, more preferably 480° C. or less, and even more preferably 450° C. or less. By keeping the temperature of the catalyst filling section 3-8 below the above upper limit in all regions, it becomes possible to prevent deactivation of the catalyst due to excessive heating and to maintain the sulfur resistance of the device. Incidentally, the temperature in the catalyst filling portion 3-8 is usually measured at the horizontal central portion of the catalyst filling portion 3-8.
- the hydrogen sulfide production apparatus of this embodiment may include members other than the members described above.
- each part of the hydrogen sulfide production apparatus of the present embodiment may be integrally formed.
- Another reaction device may be connected downstream of the hydrogen sulfide production device of the present embodiment.
- a reactor for producing sulfides of metals such as lithium may be connected downstream of the hydrogen sulfide production apparatus of the present embodiment, and the hydrogen sulfide produced by the hydrogen sulfide production apparatus of the present embodiment may be supplied.
- Hydrogen sulfide obtained by the production process using the hydrogen sulfide production apparatus of the present embodiment can be used, for example, in reactions for sulfurizing metals such as lithium.
- the sulfide obtained by sulfidation using hydrogen sulfide obtained by the production process using the hydrogen sulfide production apparatus of the present embodiment is, for example, a positive electrode active material for batteries, a negative electrode active material, a solid electrolyte material, It can be suitably used as an intermediate raw material for chemicals.
- Example 1 is an example of Embodiment 1-2 above.
- a hydrogen sulfide production apparatus 21 shown in FIG. 1-4 corresponding to Embodiment 1-2 was produced.
- Each member used for making the hydrogen sulfide production apparatus is as follows.
- ⁇ Reactor 1-3 SUS316L reaction tube (inner diameter 133.8 mm, height 672 mm) with inner wall calorized with aluminum
- ⁇ Hydrogen supply pipe 1-5 SUS316L pipe (diameter 15 mm, length 750 mm) with inner wall calorized with aluminum
- ⁇ Catalyst support member 1-6 Aluminum punching metal (diameter 133 mm, thickness 0.5 mm, hole diameter 0.5 mm, hole diameter area ratio 27.9%)
- ⁇ Insulation member 1-7 One piece of aluminum punching metal (diameter 133 mm, thickness 1.5 mm, hole diameter 5 mm, hole diameter area ratio 32.1%) and aluminum punching metal (diameter 133 mm, thickness 0.5 mm, hole diameter 0) .5 mm, hole diameter area ratio 27.9%) stacked at 8 mm intervals
- Heat transfer member 1-22 Aluminum plate material (diameter
- Reactor 1-3 was filled with 520 g of sulfur (not shown), and heat transfer member 1-22 was placed above the sulfur-filled top.
- the area filled with sulfur in the lower part of the reactor 1-3 is the liquid sulfur filling section 1-2.
- a catalyst support member 1-6 was placed above the heat transfer member 1-22, and 1.1 kg (not shown) of activated alumina (diameter 1 to 2 mm, specific surface area 270 m 2 /g) was placed on the catalyst support member 1-6. was filled.
- a region filled with activated alumina is a catalyst-filled portion 1-8.
- a heat insulating member 1-7 was placed on the upper portion filled with activated alumina.
- a temperature sensor 1-15 was penetrated from above the reactor 1-3 so that the tip of the temperature sensor 1-15 reached the bottom of the reactor 1-3.
- a temperature sensor 1-15 penetrated through the center of the reactor 1-3 in the horizontal direction. Further, the hydrogen supply pipe 1-5 was passed through the reactor 1-3 from above, and the hydrogen supply port 1-500 of the hydrogen supply pipe 1-5 reached the liquid sulfur filling section 1-2.
- hydrogen gas was introduced from the hydrogen supply pipe 1-5 into the liquid sulfur filling section 1-2 at a flow rate of 1.0 L/min.
- the temperature of the mantle heater 1-4 was set to 200° C.
- the temperature of the jacket heater 1-9 was set to 400° C. to heat the liquid sulfur filling section 1-2 and the catalyst filling section 1-8, respectively.
- the sulfur filled in the liquid sulfur filling section 1-2 became liquid, and sulfur vapor was generated from the liquid sulfur.
- the activated alumina filled in the catalyst filling portion 1-8 was thereby heated. Hydrogen sulfide gas was generated from the hydrogen gas supplied from the hydrogen supply pipe 1-5 and the generated sulfur vapor.
- a hydrogen sulfide production apparatus 1-31 was produced in the same manner as in Example 1 except that the heat insulating member 1-7 and the heat transfer member 1-22 were omitted, and hydrogen sulfide gas was generated.
- the configuration of the hydrogen sulfide production device 1-31 is shown in FIG. 1-5.
- FIG. 1-6 shows the temperature of each region of the reactor 1-3 measured by the temperature sensor 1-15 after 150 minutes from the start of heating in the hydrogen sulfide production apparatus of Example 1 and Reference Example 1.
- the temperature of the catalyst filling portion exceeded 400°C.
- the temperature of the catalyst filling portion was lower than that of Example 1, and was below 400°C. From this, it is understood that the hydrogen sulfide production apparatus of Embodiment 1-2 can stably produce hydrogen sulfide with higher efficiency because the inside of the catalyst filling portion is maintained at a high temperature.
- Hydrogen sulfide production device 1-2 Liquid sulfur filling section 1-3 Reactor 1-4 Mantle heater 1-5 Hydrogen supply pipe 1-6 Catalyst supporting member 1-7 Heat insulating member 1-8 Catalyst filling section 1-9 Jacket heater 1-10 Hydrogen sulfide recovery pipe 1-11 Pressure control valve 1-12 Hydrogen sulfide detector 1-13 Hydrogen supply control valve 1-14 Hydrogen sulfide recovery control valve 1-15 Temperature sensor 1-21 Hydrogen sulfide production device 1 -22 Heat transfer member 1-31 Hydrogen sulfide production device 1-51 Communication hole 1-161 Communication hole 1-162 Hydrogen supply pipe through hole 1-163 Temperature sensor through hole 1-171 Communication hole 1-172 Hydrogen supply pipe penetration Hole 1-173 Temperature sensor through hole 1-500 Hydrogen supply port 2-1 Hydrogen sulfide production device 2-2 Liquid sulfur filling unit 2-3 Reactor 2-4 Mantle heater 2-5 Hydrogen supply pipe 2-6 Catalyst support Member 2-7 Heat insulating member 2-8 Cata
- a hydrogen sulfide production apparatus for producing hydrogen sulfide by reacting sulfur vapor and hydrogen gas, a reactor having a liquid sulfur charge therein; a first heating means for heating liquid sulfur to produce sulfur vapor; a hydrogen supply member connected to the reactor; with The interior of the reactor comprises a catalyst support member provided above the liquid sulfur filling section and a heat insulating member provided above the catalyst support member, further comprising a second heating means for heating a space formed by the catalyst supporting member, the heat insulating member, and the inner wall of the reactor; A hydrogen sulfide production apparatus, wherein an upper space and a lower space of the heat insulating member communicate with each other at a part of the heat insulating member or around the heat insulating member.
- [A2] The hydrogen sulfide production apparatus according to [A1] above, The hydrogen sulfide production apparatus, wherein the heat insulating member is a metal substrate or a ceramic substrate provided with communication holes.
- [A3] The hydrogen sulfide production apparatus according to [A1] or [A2] above, A hydrogen sulfide production apparatus, further comprising a heat transfer member disposed in contact with or in close proximity to the lower surface of the catalyst support member.
- [A4] The hydrogen sulfide production apparatus according to any one of [A1] to [A3] above, A hydrogen sulfide production device, wherein the inner surface of the device is anti-sulfurized.
- [A5] A method for producing hydrogen sulfide, comprising reacting sulfur vapor and hydrogen gas using the hydrogen sulfide production apparatus according to any one of [A1] to [A4] above.
- a hydrogen sulfide production apparatus for producing hydrogen sulfide by reacting sulfur vapor and hydrogen gas, a reactor having a liquid sulfur charge therein; a first heating means for heating liquid sulfur to produce sulfur vapor; a hydrogen supply member connected to the reactor; with Inside the reactor, a catalyst support member provided above the liquid sulfur filling section, and a heat insulating member provided between the catalyst support member and the liquid sulfur filling section, further comprising a second heating means for heating the catalyst support member and the space above the catalyst support member; An upper space and a lower space of the heat insulating member are in communication at a portion of the heat insulating member or around the heat insulating member, Hydrogen sulfide production equipment.
- [B2] The hydrogen sulfide production apparatus according to [B1] above, The hydrogen sulfide production apparatus, wherein the heat insulating member is a metal substrate or a ceramic substrate provided with communication holes.
- [B3] The hydrogen sulfide production apparatus according to [B1] or [B2] above, A hydrogen sulfide production apparatus, further comprising a heat transfer member disposed in contact with or in close proximity to the lower surface of the catalyst support member.
- [B4] The hydrogen sulfide production apparatus according to any one of [B1] to [B3] above, A hydrogen sulfide production device, wherein the inner surface of the device is anti-sulfurized.
- [B5] A method for producing hydrogen sulfide, wherein sulfur vapor and hydrogen gas are reacted in the hydrogen sulfide production apparatus according to any one of [B1] to [B4] above.
- a hydrogen sulfide production apparatus for producing hydrogen sulfide by reacting sulfur vapor and hydrogen gas, a reactor having a liquid sulfur charge therein; a first heating means for heating liquid sulfur to produce sulfur vapor; a hydrogen supply member connected to the reactor; a liquid sulfur supply member connected to the liquid sulfur filling section; with The interior of the reactor comprises a catalyst support member provided above the liquid sulfur filling section, Further comprising a second heating means for heating a space formed by the catalyst support member and the inner wall of the reactor, Hydrogen sulfide production equipment.
- [C2] The hydrogen sulfide production apparatus according to [C1] above, A sulfur container and a sulfur container heating means for heating the sulfur container, The hydrogen sulfide production apparatus, wherein the sulfur storage container and the liquid sulfur filling section are connected by the liquid sulfur supply member.
- [C3] The hydrogen sulfide production apparatus according to [C2] above, The hydrogen sulfide production apparatus, wherein the liquid sulfur supply member includes a backflow prevention gas supply member that prevents backflow of hydrogen sulfide gas.
- [C4] The hydrogen sulfide production apparatus according to any one of [C1] to [C3] above, A hydrogen sulfide production apparatus, further comprising a heat transfer member disposed in contact with or in close proximity to the lower surface of the catalyst support member.
- [C5] The hydrogen sulfide production apparatus according to any one of [C1] to [C4] above, A hydrogen sulfide production device, wherein the inner surface of the device is anti-sulfurized.
- [C6] A method for producing hydrogen sulfide, comprising reacting sulfur vapor and hydrogen gas using the hydrogen sulfide production apparatus according to any one of [C1] to [C5] above.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
特許文献1には、水酸化リチウムと硫化水素との反応によって硫化リチウムを合成する硫化リチウムの製造方法であって、反応槽の内部に配置され、かつ、加熱された多孔質材に対し、水素ガスと硫黄蒸気を供給して前記水素ガスと前記硫黄蒸気を反応させることにより、硫化水素ガスと前記水素ガスを含む反応ガスを生成する工程(A)と、生成した前記反応ガスを粒子状の水酸化リチウムに接触させて前記硫化水素ガスと前記水酸化リチウムを反応させることにより、粒子状の硫化リチウムを生成する工程(B)と、を含む硫化リチウムの製造方法が記載されている。そして、特許文献1には、このような製造方法は、硫化リチウムの製造原価を抑えることができるとともに、作業性に優れ、さらに純度が高い硫化リチウムを得ることができると記載されている。
[1]
硫黄蒸気と水素ガスとを反応させて硫化水素を製造する硫化水素製造装置であって、
内部に液体硫黄充填部を有する反応器と、
液体硫黄を加熱して硫黄蒸気を生成させる第1加熱手段と、
上記反応器に接続された水素供給部材と、
を備える、硫化水素製造装置。
[2]
上記[1]に記載の硫化水素製造装置であって、
上記反応器の内部には、上記液体硫黄充填部の上方に設けられた触媒支持部材と、上記触媒支持部材の上方に設けられた断熱部材と、を備え、
上記触媒支持部材、上記断熱部材および上記反応器の内壁とで形成される空間を加熱する第2加熱手段をさらに備え、
上記断熱部材の一部または上記断熱部材の周囲において、上記断熱部材の上部空間と下部空間とが連通している、硫化水素製造装置。
[3]
上記[2]に記載の硫化水素製造装置であって、
上記断熱部材は、連通孔の設けられた、金属基板ないしセラミックス基板である、硫化水素製造装置。
[4]
上記[2]または[3]に記載の硫化水素製造装置であって、
上記触媒支持部材の下面に接してまたは近接して配置された伝熱部材をさらに備える、硫化水素製造装置。
[5]
上記[2]~[4]のいずれか一つに記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。
[6]
上記[1]に記載の硫化水素製造装置であって、
上記反応器の内部には、上記液体硫黄充填部の上方に設けられた、触媒支持部材と、上記触媒支持部材と上記液体硫黄充填部との間に設けられた、断熱部材と、を備え、
上記触媒支持部材および上記触媒支持部材の上部の空間を加熱する第2加熱手段をさらに備え、
上記断熱部材の一部または上記断熱部材の周囲において、上記断熱部材の上部空間と下部空間とが連通している、
硫化水素製造装置。
[7]
上記[6]に記載の硫化水素製造装置であって、
上記断熱部材は、連通孔の設けられた、金属基板ないしセラミックス基板である、硫化水素製造装置。
[8]
上記[6]または[7]に記載の硫化水素製造装置であって、
上記触媒支持部材の下面に接してまたは近接して配置された、伝熱部材をさらに備える、硫化水素製造装置。
[9]
上記[6]~[8]のいずれか一つに記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。
[10]
上記[1]に記載の硫化水素製造装置であって、
上記液体硫黄充填部に接続された液体硫黄供給部材をさらに備え、
上記反応器の内部には、上記液体硫黄充填部の上方に設けられた、触媒支持部材を備え、
上記触媒支持部材および上記反応器の内壁とで形成される空間を加熱する第2加熱手段をさらに備える、
硫化水素製造装置。
[11]
上記[10]に記載の硫化水素製造装置であって、
硫黄収容容器と、当該硫黄収容容器を加熱する硫黄収容容器加熱手段と、を備え、
上記硫黄収容容器と上記液体硫黄充填部とは、上記液体硫黄供給部材により接続されている、硫化水素製造装置。
[12]
上記[10]または[11]に記載の硫化水素製造装置であって、
上記液体硫黄供給部材は、硫化水素ガスの逆流を防止する逆流防止ガス供給部材を備える、硫化水素製造装置。
[13]
上記[10]~[12]のいずれか一つに記載の硫化水素製造装置であって、
上記触媒支持部材の下面に接してまたは近接して配置された、伝熱部材をさらに備える、硫化水素製造装置。
[14]
上記[10]~[13]のいずれか一つに記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。
[15]
上記[1]~[14]のいずれか一つに記載の硫化水素製造装置を用いて硫黄蒸気と水素ガスとを反応させることを特徴とする硫化水素の製造方法。
本発明の硫化水素製造装置は、内部に液体硫黄充填部を有する反応器を備えるため、本発明の硫化水素製造装置によると、液体硫黄充填部に充填された液体状の硫黄から、硫黄蒸気を発生させることになる。
これにより、硫黄蒸気の発生量を精密に制御することが可能となり、より高い製造効率を達成することが可能となる。また、硫黄蒸気の発生量を精密に制御することが可能となることにより、高い製造効率を安定性良く維持することも可能となる。
本実施形態の硫化水素製造装置の一例(実施形態1-1)を図1-1に示す。
硫化水素製造装置1-1は、内部に液体硫黄充填部1-2を有する反応器1-3と、液体硫黄を加熱して硫黄蒸気を生成させる第1加熱手段であるマントルヒーター1-4と、反応器1-3に接続された水素供給部材である水素供給管1-5と、を備える。
反応器1-3では、水素ガスと硫黄蒸気との反応により硫化水素が生成されている。
液体硫黄充填部1-2で発生した硫黄蒸気は、触媒支持部材1-6、断熱部材1-7および反応器1-3の内壁によって囲まれた空間(触媒充填部1-8)へと供給され、触媒充填部1-8において硫黄蒸気と水素ガスとが反応し、硫化水素が生成される。
反応器1-3には水素供給管1-5が接続されており、水素供給管1-5から水素ガスが供給される。
触媒充填部1-8の温度は、全ての領域において、好適には500℃以下であり、より好適には480℃以下であり、さらに好適には450℃以下である。触媒充填部の温度が全ての領域において上記上限値以下であることにより、過度な加熱による触媒の失活を防止すること、装置の耐硫性を維持することが可能になる。
尚、触媒充填部1-8の温度は、通常、触媒充填部1-8の水平方向中心部において測定される。
また、水素ガスと硫黄蒸気との反応をより効果的に促進する観点から、触媒の細孔には銀、プラチナ、モリブデン、コバルト、ニッケル、鉄、バナジウム等の金属が担持されていてもよい。
耐硫処理の手段としては、スズめっき、クロムめっき、金めっき、溶融アルミニウムめっき、またはこれらの金属を含有する合金めっき等、耐硫化性能の高い金属または合金によるめっき処理を挙げることができる。
たとえば、被処理物をFe-Al合金粉及びNH4Cl粉よりなる調合剤と共に鋼製ケース内に埋め込み、ケースを密閉し、それを炉内にて加熱することにより、被処理物表面にアルミニウムが拡散滲透されたアルミニウム拡散滲透層を形成することが可能である。
本実施形態の硫化水素製造装置1-1では、液体硫黄充填部1-2を加熱して硫黄蒸気を発生させる第1加熱手段として、マントルヒーター1-4を用いている。
必要な加熱温度は液体硫黄充填部1-2の径や触媒の充填量に伴い変化するため、マントルヒーター1-4の温度域は特に限定されないが、好適には250℃以上400℃以下であり、より好適には300℃以上350℃以下である。
水素供給管1-5は、反応器1-3に水素ガスを供給するための部材である。
触媒支持部材1-6は、硫化水素生成反応を促進するための触媒を載置するための部材であり、液体硫黄充填部1-2の上方に設けられている。
また、触媒支持部材1-6には温度センサ用貫通孔1-163が設けられていてもよく、その場合、温度センサ1-15が温度センサ用貫通孔1-163を貫通して液体硫黄充填部1-2に接続する。
断熱部材1-7は、反応器1-3内部を断熱するための部材であり、触媒支持部材1-6の上方に設けられている。
本実施形態の硫化水素製造装置1-1においては、硫黄蒸気発生の場である液体硫黄充填部1-2が存在する装置下部に比較して、装置上部のほうがより温度が低下しやすい傾向にある。したがって、断熱部材1-7により硫化水素製造装置1-1上部からの熱の放出を防止することは、触媒充填部1-8内の温度分布を高度に制御するにあたり有効な手段である。
また、断熱部材1-7の側面は、図1-1に示されるように、反応器1-3の内壁に接するように設けられていることが好ましい。このようにすることで、断熱部材1-7も加熱され、断熱部材1-7自体も一定の熱容量を有するため、断熱部材1-7による保温効果がより一層高まる。
本実施形態の硫化水素製造装置1-1では、第2加熱手段として、ジャケットヒーター1-9を用いている。ジャケットヒーター1-9は、触媒支持部材、断熱部材および反応器の内壁とで形成される空間(触媒充填部1-8)を加熱する。すなわち、触媒支持部材および触媒支持部材の上部の空間を加熱する。これにより、触媒を加熱して硫化水素生成反応を促進させることができる。
ジャケットヒーター1-9の温度が上記下限値以上に調整されていることにより、硫化水素を高い効率で安定的に生産できるようになる。
ジャケットヒーター1-9の温度が上記上限値以下に調整されていることにより、過度な加熱による触媒の失活を防止すること、装置の耐硫性を維持することが可能になる。
本実施形態の硫化水素製造装置1-1では、反応器1-3から硫化水素ガスを回収する硫化水素回収部材として、硫化水素回収管1-10を用いている。
温度センサ1-15は、反応器1-3の各領域の温度を測定するための部材である。
本実施形態の硫化水素製造装置の一例(実施形態1-2)を図1-4に示す。
硫化水素製造装置1-21は、触媒支持部材の下面に接してまたは近接して配置された、伝熱部材をさらに備える。
実施形態1-1または1-2の硫化水素製造装置を用いた硫化水素の製造方法について説明する。
液体硫黄充填部1-2の温度が上記下限値以上であることにより、硫黄蒸気圧がより適度となり、得られる硫化水素ガスの濃度が高くなるので、硫化水素の生成をより効率的におこなうことができる。また、液体硫黄の温度が上記上限値以下であることにより、硫黄蒸気圧を1気圧以下にすることができ、水素ガスと反応せずに反応器を通過する硫黄の量を抑制することができる。
触媒充填部1-8内の温度が全ての領域において上記下限値以上であることにより、硫化水素を高い効率で安定的に生産できるようになる。
触媒充填部1-8内の温度が全ての領域において上記上限値以下であることにより、過度な加熱による触媒の失活を防止すること、装置の耐硫性を維持することが可能になる。
本実施形態の硫化水素製造装置の一例(実施形態2-1)を図2-1に示す。
この点に関して、本実施形態の硫化水素製造装置2-1においては、触媒支持部材2-6と液体硫黄充填部2-2との間に断熱部材2-7が設けられているため、反応器2-3から液体硫黄充填部2-2への熱の伝搬が防止され、液体硫黄充填部2-2の温度が過度に上昇することが防止されている。したがって、硫化蒸気を所望の発生量に制御し、硫化水素を高い生産効率で安定的に生産することができる。
反応器2-3では、水素ガスと硫黄蒸気との反応により硫化水素が生成されている。具体的に言うと、反応器2-3は、液体硫黄充填部2-2の上方に設けられた、触媒支持部材2-6と、触媒支持部材2-6と液体硫黄充填部2-2との間に設けられた、断熱部材2-7と、を備える。
本実施形態では触媒支持部材2-6の上部の触媒が充填される空間を触媒充填部2-8と呼び、触媒充填部2-8において硫黄蒸気と水素ガスとが反応し、硫化水素が生成される。
また、水素ガスと硫黄蒸気との反応をより効果的に促進する観点から、触媒の細孔には銀、プラチナ、モリブデン、コバルト、ニッケル、鉄、バナジウム等の金属が担持されていてもよい。
たとえば、アルミニウムを拡散滲透処理するカロライジング処理を用いることができる。カロライジング処理では被処理物をFe-Al合金粉及びNH4Cl粉よりなる調合剤と共に鋼製ケース内に埋め込み、ケースを密閉し、それを炉内にて加熱することにより、被処理物表面にアルミニウムが拡散滲透されたアルミニウム拡散滲透層を形成して被処理物の耐硫化性能を向上することが可能である。
本実施形態では、第1加熱手段としてマントルヒーター2-4を用いている。
必要な加熱温度は液体硫黄充填部2-2の径や触媒の充填量に伴い変化するため、マントルヒーター2-4の温度域は特に限定されないが、好適には250~400℃であり、より好適には300~350℃である。
水素供給管2-5は、反応器2-3に水素ガスを供給するための部材である。
触媒支持部材2-6は、水素ガスと硫黄蒸気とから硫化水素が生成される反応を促進する触媒を載置するための部材である。
たとえば、アルミニウムメッシュやステンレスメッシュなどの金属メッシュ;アルミニウムパンチングやステンレスパンチングなどのパンチングメタル;アルミニウムエキスパンドやステンレスエキスパンドなどのエキスパンドメタル等から選択される一種または二種以上の多孔性板等を用いることができる。
断熱部材2-7は、反応器2-3から液体硫黄充填部2-2への熱の伝搬を防止するための部材であり、触媒支持部材2-6と液体硫黄充填部2-2との間に設けられている。
本実施形態では、第2加熱手段としてジャケットヒーター2-9を用いている。
必要な加熱温度は触媒充填部2-8の径や触媒の充填量に伴い変化するため、ジャケットヒーター2-9の温度域は特に限定されないが、好適には300~500℃であり、より好適には360~450℃である。
硫化水素回収管2-10は、硫黄蒸気と水素ガスの反応により発生した硫化水素を回収するための部材である。
温度センサ2-15は、反応器2-3の各領域の温度を測定するための部材である。
本実施形態の硫化水素製造装置の一例(実施形態2-2)を図2-4に示す。
硫化水素製造装置2-21は、触媒支持部材2-6の下面に接してまたは近接して配置された、伝熱部材2-22をさらに備える。
実施形態2-1または2-2の硫化水素製造装置を用いた硫化水素の製造方法について説明する。
この点に関して、本実施形態の硫化水素製造装置2-1においては、触媒支持部材6と液体硫黄充填部2-2との間に断熱部材2-7が設けられているため、反応器2-3から液体硫黄充填部2-2への熱の伝搬が防止され、液体硫黄充填部2-2の温度が過度に上昇することが防止されている。したがって、硫黄蒸気を所望の発生量に制御し、硫化水素を高い生産効率で安定的に生産することができる。
この際、水素ガスの供給量を過剰にすることで、硫化水素ガスを水素ガスで希釈された状態で回収することが可能である。これにより、圧力調整時や反応終了時等に発生する排ガス中に含まれる硫化水素ガスの濃度を低減できるため、排ガス処理をより単純なものにすることができる。
回収時における硫化水素ガスの濃度は、好ましくは1体積%以上であり、より好ましくは3体積%以上である。また、回収時における硫化水素ガスの濃度は、好ましくは50体積%以下であり、より好ましくは30体積%以下である。
本実施形態の硫化水素製造装置の一例(実施形態3-1)を図3-1に示す。
また、反応器3-3は、触媒充填部3-8を加熱する第2加熱手段であるジャケットヒーター3-9を備える。
液体硫黄を常時供給可能であることにより、硫黄蒸気の発生量を所望の発生量に制御可能である。したがって、硫化水素生成反応の場である触媒充填部3-8における硫黄蒸気の濃度を所望の濃度に制御し、硫化水素を高い生産効率で安定的に生産することが可能である。
反応器3-3では、水素ガスと硫黄蒸気との反応により硫化水素が生成されている。反応器3-3は、液体硫黄充填部3-2の上方に設けられた、触媒支持部材3-6を備える。
触媒充填部3-8内の温度は、好適には500℃以下であり、より好適には480℃以下であり、さらに好適には450℃以下である。触媒充填部3-8の温度が全ての領域において上記上限値以下であることにより、過度な加熱による触媒の失活を防止すること、装置の耐硫性を維持することが可能になる。
尚、触媒充填部3-8内の温度は、通常、触媒充填部8の水平方向中心部において測定される。
また、水素ガスと硫黄蒸気との反応をより効果的に促進する観点から、触媒の細孔には銀、プラチナ、モリブデン、コバルト、ニッケル、鉄、バナジウム等の金属が担持されていてもよい。
たとえば、アルミニウムを拡散滲透処理するカロライジング処理を用いることができる。カロライジング処理では被処理物をFe-Al合金粉及びNH4Cl粉よりなる調合剤と共に鋼製ケース内に埋め込み、ケースを密閉し、それを炉内にて加熱することにより、被処理物表面にアルミニウムが拡散滲透されたアルミニウム拡散滲透層を形成して被処理物の耐硫化性能を向上することが可能である。
本実施形態では、液体硫黄充填部3-2を加熱して硫黄蒸気を発生させるための第1加熱手段としてマントルヒーター3-4を用いている。
尚、液体硫黄充填部3-2内の温度は、通常、液体硫黄充填部3-2の水平方向中心部において測定される。
必要な加熱温度は液体硫黄充填部3-2の径や触媒の充填量に伴い変化するため、マントルヒーター3-4の温度域は特に限定されないが、好適には250℃以上400℃以下であり、より好適には300℃以上350℃以下である。
水素供給管3-5は、反応器3-3に水素ガスを供給するための部材である。
触媒支持部材3-6は、水素ガスと硫黄蒸気とから硫化水素が生成される反応を促進する触媒を載置するための部材である。
たとえば、アルミニウムメッシュやステンレスメッシュなどの金属メッシュ;アルミニウムパンチングやステンレスパンチングなどのパンチングメタル;アルミニウムエキスパンドやステンレスエキスパンドなどのエキスパンドメタル等から選択される一種または二種以上の多孔性板等を用いることができる。
液体硫黄供給管3-7は液体硫黄充填部3-2に液体硫黄を供給するための部材であり、液体硫黄充填部3-2に接続されている。
本実施形態の硫化水素製造装置3-1は、液体硫黄充填部3-2に供給する硫黄を収容しておくための部材である硫黄収容容器3-17と、硫黄収容容器3-17を加熱するための部材である硫黄収容容器加熱手段3-16とを備え、硫黄収容容器3-17と液体硫黄充填部3-2とは、液体硫黄供給管3-7で接続されていることが好ましい。
必要な加熱温度は液体硫黄充填部3-2の径や触媒の充填量に伴い変化するため、硫黄収容容器加熱手段3-16の温度域は特に限定されないが、好適には120℃以上160℃以下であり、より好適には130℃以上150℃以下である。
本実施形態の硫化水素製造装置3-1では、第2加熱手段として、ジャケットヒーター3-9を用いている。
ジャケットヒーター3-9の温度が上記下限値以上に調整されていることにより、硫化水素を高い効率で安定的に生産できるようになる。
ジャケットヒーター3-9の温度が上記上限値以下に調整されていることにより、過度な加熱による触媒の失活を防止すること、装置の耐硫性を維持することが可能になる。
硫化水素回収管3-10は、硫黄蒸気と水素ガスの反応により発生した硫化水素を回収するための部材である。
温度センサ3-15は、反応器3-3の各領域の温度を測定するための部材である。
本実施形態の硫化水素製造装置の一例(実施形態3-2)を図3-3に示す。
硫化水素製造装置3-21は、触媒支持部材3-6の下面に接してまたは近接して配置された、伝熱部材3-22をさらに備える。
実施形態3-1または3-2の硫化水素製造装置を用いた硫化水素の製造方法について説明する。
液体硫黄を常時供給可能であることにより、硫黄蒸気の発生量を所望の発生量に制御可能である。したがって、硫化水素生成反応の場である触媒充填部3-8における硫黄蒸気の濃度を所望の濃度に制御し、硫化水素を高い生産効率で安定的に生産することが可能である。
尚、液体硫黄充填部3-2内の温度は、通常、液体硫黄充填部3-2の水平方向中心部において測定される。
この際、水素ガスの供給量を過剰にすることで、硫化水素ガスを水素ガスで希釈された状態で回収することが可能である。これにより、圧力調整時や反応終了時等に発生する排ガス中に含まれる硫化水素ガスの濃度を低減できるため、排ガス処理をより単純なものにすることができる。
回収時における硫化水素ガスの濃度は、好ましくは1体積%以上であり、より好ましくは3体積%以上である。また、回収時における硫化水素ガスの濃度は、好ましくは50体積%以下であり、より好ましくは30体積%以下である。
触媒充填部3-8内の温度は、好適には500℃以下であり、より好適には480℃以下であり、さらに好適には450℃以下である。触媒充填部3-8の温度が全ての領域において上記上限値以下であることにより、過度な加熱による触媒の失活を防止すること、装置の耐硫性を維持することが可能になる。
尚、触媒充填部3-8内の温度は、通常、触媒充填部3-8の水平方向中心部において測定される。
本実施形態の硫化水素製造装置は、上記で説明した部材以外の部材を備えていてもよい。
たとえば、本実施形態の硫化水素製造装置の下流にリチウム等の金属の硫化物を生成させる反応装置を接続し、本実施形態の硫化水素製造装置で製造された硫化水素を供給してもよい。
本実施形態の硫化水素製造装置を用いた製造プロセスにより得られる硫化水素は、たとえば、リチウム等の金属を硫化させる反応に用いることができる。
本実施形態の硫化水素製造装置を用いた製造プロセスにより得られる硫化水素を用いて硫化されることにより得られた硫化物は、例えば、電池用の正極活物質、負極活物質、固体電解質材料、化学薬品の中間原料として好適に用いることができる。
実施例1は、上記の実施形態1-2の実施例である。
・反応器1-3 アルミニウムで内壁がカロライジング処理されたSUS316L製反応管(内径133.8mm高さ672mm)
・水素供給管1-5 アルミニウムで内壁がカロライジング処理されたSUS316L製パイプ(直径15mm長さ750mm)
・触媒支持部材1-6 アルミニウム製パンチングメタル(直径133mm、厚み0.5mm、孔径0.5mm、孔径の面積比27.9%)
・断熱部材1-7 アルミニウム製パンチングメタル(直径133mm、厚み1.5mm、孔径5mm、孔径の面積比32.1%)1枚と、アルミニウム製パンチングメタル(直径133mm、厚み0.5mm、孔径0.5mm、孔径の面積比27.9%)1枚とを8mm間隔で重ねたもの
・伝熱部材1-22 アルミニウム製板材(直径133mm、厚み20mm、孔径5mm、孔径の面積比8.3%)
伝熱部材1-22の上部に触媒支持部材1-6を配置し、触媒支持部材1-6上に活性アルミナ(直径1~2mm、比表面積270m2/g)1.1kg(図示せず)を充填した。活性アルミナが充填された領域が触媒充填部1-8である。
活性アルミナを充填した上部に断熱部材1-7を配置した。
反応器1-3上方から温度センサ1-15を貫通させ、温度センサ1-15の先端は反応器1-3底面に到達するようにした。温度センサ1-15は反応器1-3の水平方向中心部を貫通するようにした。また、反応器1-3上方から水素供給管1-5を貫通させ、水素供給管1-5の水素供給口1-500は液体硫黄充填部1-2に到達するようにした。
次いで、マントルヒーター1-4の温度を200℃、ジャケットヒーター1-9の温度を400℃にし、液体硫黄充填部1-2と触媒充填部1-8をそれぞれ加熱した。
これにより、液体硫黄充填部1-2に充填された硫黄が液体状態になり、液体状態になった硫黄から硫黄蒸気が発生した。また、これにより、触媒充填部1-8に充填された活性アルミナが加熱された。水素供給管1-5から供給された水素ガスと、発生した硫黄蒸気から、硫化水素ガスが発生した。
断熱部材1-7と伝熱部材1-22とを除いた以外は実施例1と同様にして硫化水素製造装置1-31を作製し、硫化水素ガスを発生させた。硫化水素製造装置1-31の構成を図1-5に示す。
1-2 液体硫黄充填部
1-3 反応器
1-4 マントルヒーター
1-5 水素供給管
1-6 触媒支持部材
1-7 断熱部材
1-8 触媒充填部
1-9 ジャケットヒーター
1-10 硫化水素回収管
1-11 圧力調整弁
1-12 硫化水素検出器
1-13 水素供給調節弁
1-14 硫化水素回収調節弁
1-15 温度センサ
1-21 硫化水素製造装置
1-22 伝熱部材
1-31 硫化水素製造装置
1-51 連通孔
1-161 連通孔
1-162 水素供給管用貫通孔
1-163 温度センサ用貫通孔
1-171 連通孔
1-172 水素供給管用貫通孔
1-173 温度センサ用貫通孔
1-500 水素供給口
2-1 硫化水素製造装置
2-2 液体硫黄充填部
2-3 反応器
2-4 マントルヒーター
2-5 水素供給管
2-6 触媒支持部材
2-7 断熱部材
2-8 触媒充填部
2-9 ジャケットヒーター
2-10 硫化水素回収管
2-11 圧力調整弁
2-12 硫化水素検出器
2-13 水素供給調節弁
2-14 硫化水素回収調節弁
2-15 温度センサ
2-21 硫化水素製造装置
2-22 伝熱部材
2-161 連通孔
2-162 水素供給管用貫通孔
2-163 温度センサ用貫通孔
2-171 連通孔
2-172 水素供給管用貫通孔
2-173 温度センサ用貫通孔
2-500 水素供給口
3-1 硫化水素製造装置
3-2 液体硫黄充填部
3-3 反応器
3-4 マントルヒーター
3-5 水素供給管
3-6 触媒支持部材
3-7 液体硫黄供給管
3-8 触媒充填部
3-9 ジャケットヒーター
3-10 硫化水素回収管
3-11 圧力調整弁
3-12 硫化水素検出器
3-13 水素供給調節弁
3-14 硫化水素回収調節弁
3-15 温度センサ
3-16 硫黄収容容器加熱手段
3-17 硫黄収容容器
3-18 逆流防止ガス供給部材
3-19 液体硫黄供給調整弁
3-21 硫化水素製造装置
3-22 伝熱部材
3-161 連通孔
3-162 水素供給管用貫通孔
3-163 温度センサ用貫通孔
3-500 水素供給口
[A1]
硫黄蒸気と水素ガスとを反応させて硫化水素を製造する硫化水素製造装置であって、
内部に液体硫黄充填部を有する反応器と、
液体硫黄を加熱して硫黄蒸気を生成させる第1加熱手段と、
上記反応器に接続された水素供給部材と、
を備え、
上記反応器の内部には、上記液体硫黄充填部の上方に設けられた触媒支持部材と、上記触媒支持部材の上方に設けられた断熱部材と、を備え、
上記触媒支持部材、上記断熱部材および上記反応器の内壁とで形成される空間を加熱する第2加熱手段をさらに備え、
上記断熱部材の一部または上記断熱部材の周囲において、上記断熱部材の上部空間と下部空間とが連通している、硫化水素製造装置。
[A2]
上記[A1]に記載の硫化水素製造装置であって、
上記断熱部材は、連通孔の設けられた、金属基板ないしセラミックス基板である、硫化水素製造装置。
[A3]
上記[A1]または[A2]に記載の硫化水素製造装置であって、
上記触媒支持部材の下面に接してまたは近接して配置された伝熱部材をさらに備える、硫化水素製造装置。
[A4]
上記[A1]~[A3]のいずれか一つに記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。
[A5]
上記[A1]~[A4]のいずれか一つに記載の硫化水素製造装置を用いて硫黄蒸気と水素ガスとを反応させることを特徴とする硫化水素の製造方法。
硫黄蒸気と水素ガスとを反応させて硫化水素を製造する硫化水素製造装置であって、
内部に液体硫黄充填部を有する反応器と、
液体硫黄を加熱して硫黄蒸気を生成させる第1加熱手段と、
上記反応器に接続された水素供給部材と、
を備え、
上記反応器の内部には、上記液体硫黄充填部の上方に設けられた、触媒支持部材と、上記触媒支持部材と上記液体硫黄充填部との間に設けられた、断熱部材と、を備え、
上記触媒支持部材および上記触媒支持部材の上部の空間を加熱する第2加熱手段をさらに備え、
上記断熱部材の一部または上記断熱部材の周囲において、上記断熱部材の上部空間と下部空間とが連通している、
硫化水素製造装置。
[B2]
上記[B1]に記載の硫化水素製造装置であって、
上記断熱部材は、連通孔の設けられた、金属基板ないしセラミックス基板である、硫化水素製造装置。
[B3]
上記[B1]または[B2]に記載の硫化水素製造装置であって、
上記触媒支持部材の下面に接してまたは近接して配置された、伝熱部材をさらに備える、硫化水素製造装置。
[B4]
上記[B1]~[B3]のいずれか一つに記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。
[B5]
上記[B1]~[B4]のいずれか一つに記載の硫化水素製造装置において、硫黄蒸気と水素ガスとを反応させることを特徴とする硫化水素の製造方法。
硫黄蒸気と水素ガスとを反応させて硫化水素を製造する硫化水素製造装置であって、
内部に液体硫黄充填部を有する反応器と、
液体硫黄を加熱して硫黄蒸気を生成させる第1加熱手段と、
上記反応器に接続された水素供給部材と、
上記液体硫黄充填部に接続された液体硫黄供給部材と、
を備え、
上記反応器の内部には、上記液体硫黄充填部の上方に設けられた、触媒支持部材を備え、
上記触媒支持部材および上記反応器の内壁とで形成される空間を加熱する第2加熱手段をさらに備える、
硫化水素製造装置。
[C2]
上記[C1]に記載の硫化水素製造装置であって、
硫黄収容容器と、当該硫黄収容容器を加熱する硫黄収容容器加熱手段と、を備え、
上記硫黄収容容器と上記液体硫黄充填部とは、上記液体硫黄供給部材により接続されている、硫化水素製造装置。
[C3]
上記[C2]に記載の硫化水素製造装置であって、
上記液体硫黄供給部材は、硫化水素ガスの逆流を防止する逆流防止ガス供給部材を備える、硫化水素製造装置。
[C4]
上記[C1]~[C3]のいずれか一つに記載の硫化水素製造装置であって、
上記触媒支持部材の下面に接してまたは近接して配置された、伝熱部材をさらに備える、硫化水素製造装置。
[C5]
上記[C1]~[C4]のいずれか一つに記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。
[C6]
上記[C1]~[C5]のいずれか一つに記載の硫化水素製造装置を用いて硫黄蒸気と水素ガスとを反応させることを特徴とする硫化水素の製造方法。
Claims (15)
- 硫黄蒸気と水素ガスとを反応させて硫化水素を製造する硫化水素製造装置であって、
内部に液体硫黄充填部を有する反応器と、
液体硫黄を加熱して硫黄蒸気を生成させる第1加熱手段と、
前記反応器に接続された水素供給部材と、
を備える、硫化水素製造装置。 - 請求項1に記載の硫化水素製造装置であって、
前記反応器の内部には、前記液体硫黄充填部の上方に設けられた触媒支持部材と、前記触媒支持部材の上方に設けられた断熱部材と、を備え、
前記触媒支持部材、前記断熱部材および前記反応器の内壁とで形成される空間を加熱する第2加熱手段をさらに備え、
前記断熱部材の一部または前記断熱部材の周囲において、前記断熱部材の上部空間と下部空間とが連通している、硫化水素製造装置。 - 請求項2に記載の硫化水素製造装置であって、
前記断熱部材は、連通孔の設けられた、金属基板ないしセラミックス基板である、硫化水素製造装置。 - 請求項2または3に記載の硫化水素製造装置であって、
前記触媒支持部材の下面に接してまたは近接して配置された伝熱部材をさらに備える、硫化水素製造装置。 - 請求項2~4のいずれか一項に記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。 - 請求項1に記載の硫化水素製造装置であって、
前記反応器の内部には、前記液体硫黄充填部の上方に設けられた、触媒支持部材と、前記触媒支持部材と前記液体硫黄充填部との間に設けられた、断熱部材と、を備え、
前記触媒支持部材および前記触媒支持部材の上部の空間を加熱する第2加熱手段をさらに備え、
前記断熱部材の一部または前記断熱部材の周囲において、前記断熱部材の上部空間と下部空間とが連通している、
硫化水素製造装置。 - 請求項6に記載の硫化水素製造装置であって、
前記断熱部材は、連通孔の設けられた、金属基板ないしセラミックス基板である、硫化水素製造装置。 - 請求項6または7に記載の硫化水素製造装置であって、
前記触媒支持部材の下面に接してまたは近接して配置された、伝熱部材をさらに備える、硫化水素製造装置。 - 請求項6~8のいずれか一項に記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。 - 請求項1に記載の硫化水素製造装置であって、
前記液体硫黄充填部に接続された液体硫黄供給部材をさらに備え、
前記反応器の内部には、前記液体硫黄充填部の上方に設けられた、触媒支持部材を備え、
前記触媒支持部材および前記反応器の内壁とで形成される空間を加熱する第2加熱手段をさらに備える、
硫化水素製造装置。 - 請求項10に記載の硫化水素製造装置であって、
硫黄収容容器と、当該硫黄収容容器を加熱する硫黄収容容器加熱手段と、を備え、
前記硫黄収容容器と前記液体硫黄充填部とは、前記液体硫黄供給部材により接続されている、硫化水素製造装置。 - 請求項10または11に記載の硫化水素製造装置であって、
前記液体硫黄供給部材は、硫化水素ガスの逆流を防止する逆流防止ガス供給部材を備える、硫化水素製造装置。 - 請求項10~12のいずれか一項に記載の硫化水素製造装置であって、
前記触媒支持部材の下面に接してまたは近接して配置された、伝熱部材をさらに備える、硫化水素製造装置。 - 請求項10~13のいずれか一項に記載の硫化水素製造装置であって、
当該装置内表面が耐硫処理されている、硫化水素製造装置。 - 請求項1~14のいずれか一項に記載の硫化水素製造装置を用いて硫黄蒸気と水素ガスとを反応させることを特徴とする硫化水素の製造方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020237042278A KR20240005076A (ko) | 2021-05-31 | 2022-05-25 | 황화수소 제조장치 및 황화수소의 제조방법 |
CN202280039236.9A CN117412919A (zh) | 2021-05-31 | 2022-05-25 | 硫化氢制造装置以及硫化氢的制造方法 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-091944 | 2021-05-31 | ||
JP2021-091943 | 2021-05-31 | ||
JP2021091944A JP2022184227A (ja) | 2021-05-31 | 2021-05-31 | 硫化水素製造装置および硫化水素の製造方法 |
JP2021-091945 | 2021-05-31 | ||
JP2021091943A JP2022184226A (ja) | 2021-05-31 | 2021-05-31 | 硫化水素製造装置および硫化水素の製造方法 |
JP2021091945A JP2022184228A (ja) | 2021-05-31 | 2021-05-31 | 硫化水素製造装置および硫化水素の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022255180A1 true WO2022255180A1 (ja) | 2022-12-08 |
Family
ID=84323102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/021348 WO2022255180A1 (ja) | 2021-05-31 | 2022-05-25 | 硫化水素製造装置および硫化水素の製造方法 |
Country Status (2)
Country | Link |
---|---|
KR (1) | KR20240005076A (ja) |
WO (1) | WO2022255180A1 (ja) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01257109A (ja) * | 1988-04-07 | 1989-10-13 | Jgc Corp | 硫化水素の製造方法 |
JPH0255210A (ja) * | 1988-08-17 | 1990-02-23 | Jgc Corp | 硫化水素の製造方法 |
JPH03103311A (ja) * | 1989-09-14 | 1991-04-30 | Jgc Corp | 硫化水素の製造方法およびその製造装置 |
WO2013027431A1 (ja) * | 2011-08-23 | 2013-02-28 | 日揮株式会社 | 硫化水素合成反応器、硫化水素製造装置、硫化水素ナトリウム製造装置、及びそれらの方法 |
US20170166447A1 (en) * | 2015-12-10 | 2017-06-15 | Chevron Phillips Chemical Company Lp | Hydrogen Sulfide Production Process and Related Reactor Vessels |
JP2020142963A (ja) * | 2019-03-07 | 2020-09-10 | 住友金属鉱山株式会社 | 硫化水素ガス生成プラント及び硫化水素ガス生成方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6508673B2 (ja) | 2015-02-16 | 2019-05-08 | 古河機械金属株式会社 | 硫化リチウムの製造方法 |
-
2022
- 2022-05-25 WO PCT/JP2022/021348 patent/WO2022255180A1/ja active Application Filing
- 2022-05-25 KR KR1020237042278A patent/KR20240005076A/ko unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01257109A (ja) * | 1988-04-07 | 1989-10-13 | Jgc Corp | 硫化水素の製造方法 |
JPH0255210A (ja) * | 1988-08-17 | 1990-02-23 | Jgc Corp | 硫化水素の製造方法 |
JPH03103311A (ja) * | 1989-09-14 | 1991-04-30 | Jgc Corp | 硫化水素の製造方法およびその製造装置 |
WO2013027431A1 (ja) * | 2011-08-23 | 2013-02-28 | 日揮株式会社 | 硫化水素合成反応器、硫化水素製造装置、硫化水素ナトリウム製造装置、及びそれらの方法 |
US20170166447A1 (en) * | 2015-12-10 | 2017-06-15 | Chevron Phillips Chemical Company Lp | Hydrogen Sulfide Production Process and Related Reactor Vessels |
JP2020142963A (ja) * | 2019-03-07 | 2020-09-10 | 住友金属鉱山株式会社 | 硫化水素ガス生成プラント及び硫化水素ガス生成方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20240005076A (ko) | 2024-01-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2085354B1 (en) | Hydrogen generating apparatus and fuel cell system | |
KR20090114408A (ko) | 마이크로파 보조 촉매 상 메탄 분해를 이용한 수소 농후 연료 제조 방법 및 시스템 | |
JP2004171989A (ja) | 燃料電池用水素発生装置 | |
JP5389525B2 (ja) | アンモニア分解筒 | |
JP2019087616A (ja) | 窒化物半導体製造装置および製造方法 | |
WO2022255180A1 (ja) | 硫化水素製造装置および硫化水素の製造方法 | |
JP4862449B2 (ja) | 脱硫器 | |
EP2777088B1 (en) | Hydrogen generator | |
TW200934585A (en) | Novel reactor for carrying out very high temperature and high pressure reactions | |
JP2007112644A (ja) | Co除去装置,燃料改質装置及び燃料電池システム | |
JP2022184226A (ja) | 硫化水素製造装置および硫化水素の製造方法 | |
CN117412919A (zh) | 硫化氢制造装置以及硫化氢的制造方法 | |
JP2022184227A (ja) | 硫化水素製造装置および硫化水素の製造方法 | |
WO2010134544A1 (ja) | シリコン製造装置及びシリコン製造方法 | |
JP2007042653A (ja) | 燃料電池用のシフト反応器、燃料電池用の燃料処理装置、燃料電池システム及び燃料電池用のシフト反応器の運転方法 | |
KR100651269B1 (ko) | 금속 산화물의 수소환원 장치 및 이를 이용한 몰리브덴산화물의 수소환원 방법 | |
JP2022184229A (ja) | 硫化リチウム製造装置および硫化リチウムの製造方法 | |
WO2022255181A1 (ja) | 硫化リチウム製造装置および硫化リチウムの製造方法 | |
CN108311708B (zh) | 一种制备电子级纳米钼粉的方法 | |
CN117396427A (zh) | 硫化锂制造装置以及硫化锂的制造方法 | |
KR101978999B1 (ko) | 니켈 알루미늄 합금체, 이를 이용한 장치 및 그 제조 방법 | |
JP4413040B2 (ja) | シフト反応装置 | |
JP2008239390A (ja) | 改質反応装置、燃料電池発電装置および水素製造装置 | |
JP6106212B2 (ja) | 複合体大量合成装置、複合体合成装置用反応器及びこれを用いた複合体合成方法 | |
JP2008303117A (ja) | カーボンナノチューブ製造装置及びカーボンナノチューブの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22815930 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280039236.9 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 20237042278 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020237042278 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22815930 Country of ref document: EP Kind code of ref document: A1 |