WO2018216555A1 - ガスの脱硫剤および脱硫方法 - Google Patents
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- WO2018216555A1 WO2018216555A1 PCT/JP2018/018772 JP2018018772W WO2018216555A1 WO 2018216555 A1 WO2018216555 A1 WO 2018216555A1 JP 2018018772 W JP2018018772 W JP 2018018772W WO 2018216555 A1 WO2018216555 A1 WO 2018216555A1
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Definitions
- the present invention relates to a gas desulfurization agent and a desulfurization method.
- the steam reforming process is a process for obtaining hydrocarbon main component gas by reacting hydrocarbon with steam, and is used for industrial hydrogen production and fuel reforming of fuel cells.
- Raw materials mainly composed of light hydrocarbons such as natural gas, liquefied petroleum gas (LPG) and city gas made from these as raw materials for the steam reforming process are made of heavy hydrocarbons that tend to cause carbon deposition. It is particularly suitable because it contains little and has a low sulfur content.
- natural gas and liquefied petroleum gas (LPG) usually contain a trace amount of sulfur compounds. Even in the case of city gas produced using liquefied natural gas (LNG) that does not substantially contain sulfur as a main raw material, a trace amount of odorant is added to ensure safety during transportation.
- LNG liquefied natural gas
- odorants are organic sulfur compounds such as tertiary butyl mercaptan (TBM), tetrahydrothiophene (THT), and dimethyl sulfide (DMS).
- TBM tertiary butyl mercaptan
- THT tetrahydrothiophene
- DMS dimethyl sulfide
- hydrodesulfurization As typical desulfurization methods performed prior to steam reforming of hydrocarbons, a hydrodesulfurization (hydrodesulfurization) method, an adsorptive desulfurization method, an ultrahigh-order desulfurization method, and the like are known.
- hydrodesulfurization organic sulfur compounds in hydrocarbon raw materials are reacted with hydrogen using a Co-Mo or Ni-Mo catalyst and hydrocracked, and then the generated hydrogen sulfide is adsorbed on zinc oxide and removed.
- Non-Patent Documents 1 and 2 Hydrodesulfurization is widely used in practice, for example, as a desulfurization process for fuel oil in petroleum refining.
- Non-patent Document 2 adsorption of hydrogen sulfide to zinc oxide may cause an equilibrium reaction, and a small amount of sulfur remains. Further, it is said that several tens of ppb of sulfur leaks to the steam reforming catalyst (Non-patent Document 2).
- the adsorptive desulfurization method is a method in which a sulfur compound is adsorbed and removed at room temperature using a zeolite containing a transition metal such as Ag or Cu (Patent Document 1, Non-Patent Document 3).
- the adsorptive desulfurization method is advantageous in that desulfurization can be performed at room temperature. Another advantage is that no addition of hydrogen is required.
- the desulfurization capacity per volume is small.
- the adsorption performance is further deteriorated when moisture is contained in the gas.
- Ag which is relatively resistant to moisture is particularly expensive.
- the ultra-high-order desulfurization method removes sulfur in the raw material by bringing the hydrocarbon raw material into contact with a copper-zinc-based desulfurizing agent in the temperature range of about 100 ° C. to 400 ° C. in the presence of hydrogen.
- Patent Documents 2 and 3 since the concentration of the sulfur content after the treatment can be reduced to 1 ppb or less, poisoning of the steam reforming catalyst can be prevented over a long period of time.
- Patent Document 4 a mixed aqueous solution containing a copper compound and a zinc compound and an alkaline substance aqueous solution are mixed to cause precipitation, and the resulting precipitate is fired.
- a desulfurization agent obtained by using a copper oxide-zinc oxide mixture molded body, impregnating the molded body with an element of iron or nickel, further firing, and then firing the resulting oxide fired body with hydrogen.
- this desulfurization agent shows high desulfurization performance even at low temperatures, there is still a high need for a higher-performance desulfurization agent in cases such as a fuel cell where installation capacity is restricted and replacement is restricted. .
- Non-Patent Document 4 reports the results of comparing the activity of various elements for hydrodesulfurization reaction of dibenzothiophene (DBT), which is relatively difficult to desulfurize, at 400 ° C.
- the activity of transition metals in the fourth period (Ti to Ni), the fifth period (Zr to Pd), and the sixth period (Ta to Au) are shown, Ru (379.5), Ir (171.8),
- the activity of Rh (106.1) is high, and other than the platinum group, Mo (8.0), Cr (4.8), W (3.2), Nb (1.7), Ni (1.5 ), Ti (1.4), Co (1.4), etc. are said to show activity (in parentheses, the number of molecules of DBT reacted per mole of metal per second is divided by 10 16) Numbers indicate relative activity per atom).
- Patent Document 5 discloses that one or more of group VIII metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) of the periodic table are used for removing trace sulfur compounds in a gas.
- a method for removing trace sulfur compounds characterized in that a desulfurizing agent supported on an inorganic carrier containing 50% by weight or more of zinc oxide is brought into contact with the gas, has been proposed.
- a desulfurization agent supporting ruthenium (0.1 or 0.5 wt%), platinum (0.1 wt%) or nickel (0.5 wt%) on a zinc oxide support is used, and pentyl mercaptan is included.
- An example of desulfurization of n-heptane is shown.
- a desulfurization agent combining Ru and Ni has also been proposed.
- nickel is converted into an oxide (NiO) in an amount of 50 to 95% by mass
- molybdenum is converted into an oxide (MoO 3 ) in an amount of 0.5 to 25% by mass
- ruthenium is converted into an oxide (
- a hydrocarbon desulfurization agent characterized by containing 0.1% to 12% by mass in terms of RuO 2 ) and an inorganic oxide is disclosed.
- This desulfurizing agent is said to be able to remove sulfur content in hydrocarbons such as kerosene, jet fuel, naphtha, gasoline, LPG, and natural gas very efficiently, and to significantly increase the 50 mass ppb breakthrough time.
- Ni has a high activity of decomposing hydrocarbons, if the raw fuel gas contains hydrocarbons and olefins of C5 or higher, it causes carbon deposition in a relatively short period of time depending on the operating conditions, and serves as a desulfurizing agent. May lose functionality.
- JP 2001-286753 A JP-A-1-123627 JP-A-1-123628 JP-A-11-61154 JP-A 61-263634 JP 2007-254728 A
- a high-performance gas that has high desulfurization capability even at low temperatures and maintains long-term desulfurization performance, which can be used even when the installed capacity is restricted and replacement is restricted, such as fuel cells. It is desirable to provide a desulfurization agent and a desulfurization method.
- the present invention has been made in view of such a situation, and the object thereof is to have a high desulfurization performance even at a low temperature, and to keep the sulfur compound concentration slipping to the subsequent stage at a very low level for a long time, Another object of the present invention is to provide a high-performance gas desulfurization agent having a high desulfurization capacity and capable of treating gas over a long period of time with a small amount of desulfurization agent, and a desulfurization method using the desulfurization agent.
- the characteristic configuration of the gas desulfurization agent according to the present invention is: It contains zinc oxide, aluminum oxide and copper, and further comprises 1.0% by mass to 10% by mass of nickel and 0.1% by mass to 1.0% by mass of ruthenium.
- the desulfurizing agent comprises nickel and ruthenium as components in a mixture of zinc oxide, aluminum oxide and copper.
- the mixture includes not only a state in which components are mixed but also a state like a composite oxide.
- a desulfurization agent has the high desulfurization performance with respect to gas (gases, such as raw fuel gas), even at comparatively low temperature. Therefore, when used as a desulfurization agent for a desulfurizer or the like, the concentration of sulfur compounds that slip (leak) to the downstream (downstream side) of the desulfurizer can be kept at a very low level for a long time.
- the desulfurizing agent having the above configuration has a high desulfurization capacity. Therefore, the amount of desulfurizing agent used can be reduced.
- sulfur compounds contained in the gas can be decomposed and removed over a long period of time.
- the desulfurization agent of the said structure contains copper or copper oxide of a metal state as copper, Preferably metal copper is included as main copper.
- the desulfurizing agent having the above-described configuration includes nickel in the metal state or an oxide thereof as nickel, and preferably includes nickel in the metal state (metal nickel) as the main nickel.
- the desulfurizing agent having the above structure includes ruthenium in a metal state or an oxide thereof as ruthenium, and preferably includes ruthenium in a metal state (metal ruthenium) as main ruthenium.
- the characteristic configuration of the gas desulfurization method according to the present invention is: A desulfurizing agent containing zinc oxide, aluminum oxide and copper, and further containing 1.0% by mass to 10% by mass of nickel and 0.1% by mass to 1.0% by mass of ruthenium is produced in the presence of hydrogen. The sulfur compound in the gas is decomposed and removed.
- the desulfurization agent exhibits high desulfurization performance for gas (gas such as raw fuel gas) even at a relatively low temperature. Therefore, it is possible to keep the sulfur compound concentration slipping downstream in a very low level for a long time. Moreover, according to the said structure, the sulfur compound contained in gas can be decomposed
- the desulfurization agent is preferably reduced in advance in the presence of hydrogen, its copper component, ruthenium component and nickel component. It is preferable to bring the gas into contact with the gas after the reduction because it exhibits a high ability to decompose and remove sulfur compounds.
- the desulfurizing agent of the present invention contains zinc oxide, aluminum oxide and copper, and further contains 1 to 10% by mass of nickel and 0.1 to 1.0% by mass of ruthenium. .
- the desulfurizing agent of the present invention is usually produced by firing in air. And it is used after carrying out a reduction process before using for a desulfurization reaction.
- Zinc and aluminum are presumed to be in an oxidized state (ZnO, Al 2 O 3 ) both at the stage of production and after the reduction treatment.
- Copper, nickel and ruthenium are presumed to be mainly oxides (Cu 2 O, NiO, RuO 2 ) at the stage of firing in the air (manufactured stage) and mainly in the metallic state after the reduction treatment. Is done.
- the desulfurization agent of the present invention contains zinc oxide, aluminum oxide and copper oxide at the time of production. Moreover, the desulfurization agent of this invention contains a zinc oxide, an aluminum oxide, and copper (metallic copper) at the time of use, and may contain a copper oxide further.
- the desulfurization agent of this invention contains 1.0 mass%-10 mass% nickel among the mass of the whole desulfurization agent, when it sees with the mass at the time of converting nickel into a metal state. Moreover, when it sees by the mass at the time of converting ruthenium into a metal state, 0.1 mass%-1.0 mass% ruthenium is included among the mass of the whole desulfurization agent.
- the desulfurizing agent of the present invention contains nickel oxide as a nickel component and ruthenium oxide as a ruthenium component at the time of manufacture. Moreover, the desulfurization agent of this invention contains metallic nickel as a nickel component, and metallic ruthenium as a ruthenium component at the time of use. Similarly to the case of copper, nickel oxide and ruthenium oxide may be included in some cases.
- the desulfurizing agent of the present invention is used after being reduced in the presence of hydrogen and then in contact with gas in the presence of hydrogen. Then, sulfur compounds in the gas can be decomposed and removed.
- FIG. 1 In the method for producing a desulfurizing agent of the present invention, first, a water-soluble copper compound such as copper nitrate (Cu (NO 3 ) 2 ) and a water-soluble zinc compound such as zinc nitrate (Zn (NO 3 ) 2 ) are mixed with aluminum. It is mixed with an aqueous alkaline substance in the presence of the compound. At this time, the aluminum compound may be dissolved or gelled. And the precipitation is produced by the said mixing. Furthermore, the obtained precipitate is baked to obtain a mixture of copper oxide, zinc oxide and aluminum oxide. Hereinafter, this mixture is referred to as a copper oxide-zinc oxide-aluminum oxide mixture.
- the mixture is molded into a copper oxide-zinc oxide-aluminum oxide mixture molded body.
- the copper oxide-zinc oxide-aluminum oxide mixture molded body is impregnated with an aqueous solution containing nickel and ruthenium and fired.
- nickel and ruthenium are supported on the carrier to obtain the desulfurization agent of the present invention.
- molding by compression molding by compression
- a compression molding method for example, a tableting method can be used.
- a commercially available product may be used as the molded product of the copper oxide-zinc oxide-aluminum oxide mixture.
- a copper oxide-zinc oxide-aluminum oxide mixture molded product that is commercially available as a desulfurizing agent, methanol synthesis catalyst, or carbon monoxide conversion catalyst may be diverted.
- a commercially available molded product of copper oxide-zinc oxide-aluminum oxide is used as a carrier, it can be impregnated with an aqueous solution containing nickel and ruthenium and calcined to obtain the desulfurizing agent of the present invention.
- a molding aid such as graphite may be added to a commercially available copper oxide-zinc oxide-aluminum oxide mixture molded body.
- the function as a desulfurization agent is not impaired unless these molding aids are extremely excessive.
- a water-soluble nickel compound can be used as a nickel raw material for preparing an aqueous solution containing nickel and ruthenium.
- nickel nitrate, nickel acetate, nickel chloride or the like can be used as the water-soluble nickel compound.
- nickel nitrate and nickel acetate are particularly suitable. These are preferable because of high solubility. Moreover, these are because chlorine ions do not remain in the prepared desulfurizing agent, and the desulfurization performance is not impaired by the residual chlorine ions.
- ruthenium raw material for preparing an aqueous solution containing nickel and ruthenium ruthenium nitrate (Ru (NO 3 ) 3 ), ruthenium nitrosyl nitrate (Ru (NO) (NO 3 ) 3 ), ruthenium chloride and the like can be used. .
- ruthenium nitrate and nitrosyl ruthenium nitrate are particularly suitable. This is because chlorine ions do not remain in the prepared desulfurization agent, and desulfurization performance is not impaired by the residual chlorine ions.
- the content of copper, zinc and aluminum in the desulfurizing agent is 10% by mass to 50% by mass as CuO and 30% by mass as ZnO in terms of mass ratio (content in the desulfurizing agent) to the desulfurizing agent after production and before use.
- ZnO is an essential component for fixing sulfur as ZnS. If the prescription amount of ZnO is too small, the desulfurization capacity decreases.
- Copper has a catalytic action on the decomposition of organic sulfur compounds. In addition to this catalytic action, it contributes to the fixation of sulfur as Cu 2 S, CuS or the like. Therefore, desulfurization performance cannot be obtained if the amount of copper is too small.
- Al 2 O 3 contributes to the specific surface area and strength. Therefore, if the prescription amount of Al 2 O 3 is too small, the desulfurization performance is lowered. Moreover, there is a concern that practical strength cannot be obtained if the prescription amount of Al 2 O 3 is too small.
- the contents of nickel and ruthenium in the desulfurizing agent are 1.0% by mass to 10% by mass as Ni and 0.1% by mass to 1.0% by mass as Ru in a mass ratio with respect to the desulfurizing agent.
- the mass ratio with respect to the desulfurizing agent is 3.0 mass% to 10 mass% as Ni, and 0.1 mass% to 1.0 mass% as Ru. More preferably, the mass ratio with respect to the desulfurizing agent is 3.0 mass% to 6.0 mass% as Ni and 0.1 mass% to 1.0 mass% as Ru.
- the content of nickel and ruthenium in the desulfurizing agent was 1.0% by mass to 6.0% by mass as Ni, and 0.1% by mass to 1.0% by mass as Ru in terms of mass ratio to the desulfurizing agent.
- the mass ratio with respect to the desulfurizing agent may be 1.0 mass% to 3.0 mass% as Ni and 0.1 mass% to 1.0 mass% as Ru.
- the content of nickel and ruthenium in the desulfurizing agent is 0.01 to 1 in terms of the Ru / Ni mass ratio.
- the mass ratio of Ru / Ni is 0.02 to 0.4.
- the desulfurization agent of the present invention can be obtained by impregnating a carrier made of a copper oxide-zinc oxide-aluminum oxide mixture with an aqueous solution in which predetermined nickel and ruthenium are dissolved, evaporating to dryness, and firing. It is.
- the baking after the evaporation to dryness may be performed in air at about 250 ° C. to 350 ° C. for about 1 hour to 10 hours. If the firing temperature is too low, the nickel or ruthenium compound used for loading is not sufficiently decomposed and the desired performance cannot be obtained. If the calcination temperature is too high, the specific surface area of the desulfurizing agent becomes small and the desired performance cannot be obtained.
- Nickel and ruthenium may be supported on the carrier in a plurality of times. Alternatively, nickel and ruthenium may be sequentially supported by first supporting nickel on a carrier and then further supporting ruthenium on the carrier.
- the desulfurization agent obtained above is reduced in the presence of hydrogen and then brought into contact with the raw fuel gas G1 (gas) in the presence of hydrogen.
- the sulfur compound in the raw fuel gas G1 is decomposed and removed.
- the desulfurization agent (manufactured desulfurization agent) obtained above is reduced in the presence of hydrogen and then brought into contact with the raw fuel gas G1 (gas) in the presence of hydrogen. The case where the sulfur compound of the raw fuel gas G1 is decomposed and removed will be described.
- the raw fuel gas G1 as a gas is mainly composed of light hydrocarbons (about C1 to C4) such as natural gas, liquefied petroleum gas, and city gas using these as raw materials. When used as a gas, it exhibits particularly excellent performance.
- the desulfurization method of the present invention includes mercaptans (thiols) such as tertiary butyl mercaptan (TBM), tetrahydrothiophene (THT), and dimethyl sulfide (DMS), which are generally used as odorants, and sulfide (thioether).
- mercaptans such as tertiary butyl mercaptan (TBM), tetrahydrothiophene (THT), and dimethyl sulfide (DMS), which are generally used as odorants, and sulfide (thioether). Exhibits excellent desulfurization performance for organic sulfur compounds contained in the raw fuel gas G1.
- the raw fuel gas G1 exemplified above may contain hydrogen sulfide, carbonyl sulfide, and disulfides in addition to the above, but the desulfurizing agent of the present invention has a removing ability for these, so if it is a small amount, There is no problem even if it is mixed.
- the raw fuel gas G1 exemplified above may contain a trace amount of hydrogen, carbon monoxide, oxygen, nitrogen, carbon dioxide and moisture depending on the production method.
- hydrogen, carbon monoxide, oxygen, nitrogen, and carbon dioxide are 4%, 0.05%, and 0.01% at maximum, respectively.
- %, 1.0%, and 0.5% both based on volume may be included.
- the methane activity of the desulfurizing agent of the present invention has a relatively small influence as compared with a desulfurizing agent containing Ni as a main component. It is better not to include oxygen because the desulfurization agent may be oxidized and the desulfurization performance may be reduced. However, if it is about 0.1%, oxygen is quickly removed by reacting with hydrogen on the desulfurization agent. The temperature rise due to is small, so it is not a problem.
- the desulfurizing agent (manufactured desulfurizing agent) is reduced by reduction treatment in the presence of hydrogen before being brought into contact with the raw fuel gas G1.
- the temperature for performing the reduction treatment is about 150 to 350 ° C.
- hydrogen (hydrogen gas) of about 1 to 10% by volume is added to an inert gas such as nitrogen.
- the reduction time is calculated from the flow rate of the gas used for the reduction treatment and the hydrogen content, and the time required to achieve the reduction stoichiometrically is about 1.5 to 3 times that time. good. If the reduction temperature is too low, the reduction is not completed, and if it is too high, the performance is reduced due to sintering of the desulfurizing agent. If the hydrogen concentration (volume concentration of hydrogen gas) of the gas used for the reduction treatment is too low, it is necessary to flow a large amount of gas before the reduction is completed, which is economically disadvantageous. On the other hand, if the hydrogen concentration of the gas used for the reduction treatment is too high, it is not preferable because a rapid temperature rise occurs due to the reaction heat generated by the reaction between hydrogen and the oxidized desulfurizing agent. For example, a rapid reduction in temperature may make it impossible to maintain a predetermined reduction temperature.
- the desulfurization method of the present invention is performed by filling a desulfurization agent in a desulfurization agent container, keeping the desulfurization agent at a predetermined temperature by external heating or the like, and passing the raw fuel gas G1 to which hydrogen is added.
- the desulfurization reaction does not generate a large exotherm or endotherm unless the concentration of the sulfur compound is extremely high. Therefore, the raw fuel gas G1 or the raw fuel gas G1 to which hydrogen gas has been added can be preheated to a temperature suitable for desulfurization in advance, and the desulfurization agent container itself can be reacted in an adiabatic state without being heated or cooled.
- the raw fuel gas G1 or the raw fuel gas G1 to which hydrogen gas has been added can be preheated to about 150 ° C. to 350 ° C., which is the temperature for performing the reduction treatment.
- the amount of hydrogen to be added may be determined depending on the type and amount of sulfur compound contained in the raw material, but since the sulfur content is usually in the ppm level, it is 0 in molar ratio to the raw fuel gas G1. 0.001 or more, preferably about 0.01 to 0.5, more preferably about 0.01 to 0.2.
- the hydrogen produced by the steam reforming reaction may contain carbon monoxide, carbon dioxide, and steam, but there is no major problem unless the molar ratio with respect to the raw fuel gas G1 exceeds about 0.01.
- FIG. 1 shows a schematic flow diagram (one example) of a desulfurization system when desulfurization is performed as a pretreatment for the steam reforming process.
- a desulfurization system 100 shown in FIG. 1 includes a desulfurizer 1 enclosing a desulfurizing agent and a reformer 2 enclosing a reforming catalyst.
- the desulfurization system 100 is a reaction system that desulfurizes the supplied raw fuel gas G1 and further steam reforms to obtain a reformed fuel gas G3 containing hydrogen.
- the desulfurization system 100 will be specifically described.
- the raw fuel gas G1 is supplied from the supply path 11 to the desulfurizer 1 and becomes a desulfurizing agent outlet gas G2.
- the desulfurizing agent outlet gas G2 is supplied from the desulfurizer 1 to the reformer 2 connected downstream via the reformer flow path 12.
- a steam supply path 21 is connected to the reformer channel 12, and steam S as water is supplied to the reformer channel 12. Therefore, the desulfurizing agent outlet gas G2 and the water vapor S are supplied to the reformer 2.
- the desulfurization agent outlet gas G2 reformed by the reformer 2 becomes the reformed fuel gas G3.
- the reformed fuel gas G3 is supplied to the next process such as a fuel cell (not shown) through the reformed gas passage 13 connected to the downstream side of the reformer 2.
- a part of the reformed fuel gas G3 is returned to the desulfurizer 1 as a recycle gas G4 through a return path 31 branched from the reformed gas path 13 and connected to the supply path 11.
- Example 1 Commercially available copper oxide-zinc oxide-aluminum oxide mixture molding as a support (manufactured by Zude Chemie Catalysts, MDC-7, 3 mm tablet, CuO: 45 mass%, ZnO: 45 mass%, Al 2 O 3 : 6 mass%) To 30.02 g, 23 g of an aqueous solution in which ruthenium nitrate (containing 0.062 g as Ru) and nickel nitrate (containing 0.927 g as Ni) was added dropwise and impregnated for 3 hours.
- ruthenium nitrate containing 0.062 g as Ru
- Ni nickel nitrate
- a heat-resistant glass reaction tube (inner diameter 14 mm) was filled with 10 g of desulfurizing agent A to form a desulfurizing agent layer.
- This desulfurizing agent layer corresponds to the desulfurizer 1.
- reducing gas mixed with 2% hydrogen gas (volume basis) in nitrogen gas is 60 liters per hour (0 ° C., 1 ° C.
- the volume was reduced at a standard pressure of atmospheric pressure), and reduction treatment was performed for 1 hour. That is, the desulfurizing agent A was reduced in the presence of hydrogen.
- nitrogen gas containing 150 ppm of DMS and 2% hydrogen (both based on volume) is supplied at 20 liters per hour (standard condition at 0 ° C. and 1 atm) while maintaining the lower end of the desulfurizing agent layer at 250 ° C. In volume). That is, the desulfurizing agent A was brought into contact with the raw fuel gas G1 in the presence of hydrogen.
- nitrogen is used as a component of the raw fuel gas G1 instead of hydrocarbons such as methane. That is, as the raw fuel gas G1, a model gas in a reducing atmosphere in which a predetermined amount of DMS as a sulfur compound (odorant) is added to nitrogen (a hydrocarbon substitute gas) is used.
- the concentrations of DMS, hydrogen sulfide, and methane in the desulfurization agent outlet gas G2 were analyzed with a gas chromatograph (GC-14B manufactured by Shimadzu Corporation, with FPD and FID detector).
- the DMS concentration of the desulfurization agent outlet gas G2 was not initially detected, and became 3.8 ppb after 22 hours, 5.0 ppb after 23 hours, 5.3 ppb after 24 hours, and 6.6 ppb after 25 hours.
- Example 2 A desulfurizing agent B containing 0.2% by mass of Ru and 1% by mass of Ni was obtained in the same manner as in Example 1 except that the amount of Ni and the amount of Ru were changed. When the desulfurization performance was evaluated in the same manner as in Example 1, the 5 ppb breakthrough time was 9.4 hours.
- Example 1 The copper oxide-zinc oxide-aluminum oxide mixture molded body used in Example 1 was used as it was as a desulfurization agent (desulfurization agent C).
- desulfurization agent C a desulfurization agent
- the DMS concentration of the desulfurization agent outlet gas G2 was not detected at first, 3.4 ppb after 6 hours, 18.9 ppb after 7 hours, and 64.2 ppb after 8 hours. It became.
- the 5 ppb breakthrough time is 6.2 hours.
- Example 2 A desulfurization agent D containing 0.2% by mass of Ru was obtained in the same manner as in Example 1 except that Ni was not used. When the desulfurization performance was evaluated in the same manner as in Example 1, the 5 ppb breakthrough time was 8.2 hours.
- Example 4 A desulfurization agent F containing 3% by mass of Ni was obtained in the same manner as in Example 1 except that Ru was not used. When desulfurization performance was evaluated in the same manner as in Example 1, the 5 ppb breakthrough time was 20.6 hours.
- Example 5 A desulfurization agent G containing 1% by mass of Ni was obtained in the same manner as in Example 2 except that Ru was not used. When the desulfurization performance was evaluated in the same manner as in Example 1, the 5 ppb breakthrough time was 7.0 hours.
- Example 1 The results of Example 1, Example 2 and Comparative Examples 1 to 5 are summarized in Table 1.
- the desulfurization agent A supporting 0.2% by mass of Ru and 3% by mass of Ni has a breakthrough time of 5 ppb of 23.0 hours, and is a copper oxide-zinc oxide-aluminum oxide disclosed in Patent Documents 2 and 3.
- the breakthrough time was about four times that of 6.2 hours for a certain desulfurizing agent C.
- the breakthrough time of the desulfurizing agent F supporting Ni was 20.6 hours.
- the desulfurizing agent B supporting 1% by mass of Ni and 0.2% by mass of Ru has a breakthrough time of 5 ppb of 9.4 hours, and the desulfurizing agent G supporting 1% by mass of Ni is 7.0 hours. It became. Based on the breakthrough time of the desulfurizing agent C as a carrier, the extension of the 5 ppb breakthrough time is 0.8 hours by loading 1% by mass of Ni, and 2.0 hours by loading 0.2% by mass of Ru. The total value is 2.8 hours.
- the desulfurization agents A and B have high desulfurization performance with respect to sulfur compounds such as DMS and hydrogen sulfide even at a low temperature of about 250 ° C., and slip (leak) to the subsequent stage (downstream side of the desulfurizer 1).
- the sulfur compound concentration could be kept at a very low level for a long time, had a high desulfurization capacity, and treated (desulfurized) the raw fuel gas G1 over a long period of time with a small amount of desulfurizing agent used.
- Example 3 Commercially available copper oxide-zinc oxide-aluminum oxide mixture molding as a carrier (manufactured by Zude Chemie Catalysts, MDC-7, 3 mm tablet, CuO: 41 mass%, ZnO: 46 mass%, Al 2 O 3 : 9 mass%) To 50.02 g, 37 g of an aqueous solution in which ruthenium nitrate (containing 0.050 g as Ru) and nickel nitrate (containing 3.201 g as Ni) were dropped was impregnated over 3 hours.
- ruthenium nitrate containing 0.050 g as Ru
- Ni nickel nitrate
- Example 4 A desulfurization agent I containing 0.2% by mass of Ru and 6% by mass of Ni was obtained in the same manner as in Example 3 except that the amount of Ru was changed. When the desulfurization performance was evaluated in the same manner as in Example 1, the 5 ppb breakthrough time was 37.8 hours.
- Example 7 The copper oxide-zinc oxide-aluminum oxide mixture molded body used in Example 3 was used as it was as a desulfurization agent (desulfurization agent K). When the desulfurization performance was evaluated in the same manner as in Example 1, the 5 ppb breakthrough time was 5.3 hours.
- Example 3 The results of Example 3, Example 4, Comparative Example 6 and Comparative Example 7 are summarized in Table 2.
- the desulfurization agent H carrying 0.1% by weight of Ru and 6% by weight of Ni has a 5ppb breakthrough time of 33.4 hours, and the desulfurization agent I carrying 0.2% by weight of Ru and 6% by weight of Ni is The 5 ppb breakthrough time was 37.8 hours, which was clearly longer than the 5.3 hours of the desulfurizing agent K, which is copper oxide-zinc oxide-aluminum oxide disclosed in Patent Documents 2 and 3.
- the 5 ppb breakthrough time of the desulfurizing agent J supporting only 6% by mass of Ni is 30.8 hours, as described above.
- Example 5 [Desulfurization test of city gas] 24 g of an aqueous solution in which ruthenium nitrate (containing 0.070 g as Ru) and nickel nitrate (containing 2.099 g as Ni) was dropped was added dropwise to 35 g of the same molded body used as the carrier in Example 3, and was taken for 3 hours. And impregnated. Then, after evaporating to dryness on a hot plate as a heater and drying for 1 hour in a dryer set at 110 ° C., using a muffle furnace as a firing furnace, at a temperature rising rate of 3 ° C. per minute in the air. The temperature was raised to 300 ° C. and held at 300 ° C. for 1 hour as firing. And the desulfurization agent L containing 0.2 mass% Ru and 6 mass% Ni was obtained.
- the desulfurization agent L was filled in a stainless steel reaction tube (inner diameter 15.7 mm) with 10 cc (12.5 g).
- a stainless steel reaction tube filled with the desulfurizing agent L corresponds to the desulfurizer 1. Then, the whole reaction tube is put in a thermostat kept at 250 ° C., and a reducing gas obtained by mixing 2% hydrogen (volume basis) with nitrogen gas is 150 liters per hour (volume at a standard state of 0 ° C. and 1 atm). Distributed for 3 hours.
- the temperature of the incubator is maintained at 250 ° C., and 13 liters of city gas mixed with 2% hydrogen (volume basis) is used as the raw fuel gas G1, 60 liters per hour (0 ° C., 1 atm. ).
- the 13A city gas as the raw fuel gas G1 contains about 3.1 ppm of DMS and about 2.4 ppm of TBM as an odorant (sulfur compound).
- the concentrations of DMS, TBM and hydrogen sulfide in the desulfurizing agent outlet gas G2 were analyzed with a gas chromatograph (GC-14B, equipped with FPD detector).
- the DMS concentration of the desulfurization agent outlet gas G2 was not initially detected, and became 17 ppb after 158 hours, 19 ppb after 160 hours, and 28 ppb after 162 hours.
- the time until the DMS concentration of the desulfurizing agent outlet gas G2 exceeds 20 ppb (20 ppb breakthrough time) is 160.3 hours under this condition. It should be noted that TBM and hydrogen sulfide were not detected in the desulfurization agent outlet gas G2 until 200 hours. It is considered that TBM was decomposed by the desulfurizing agent and hydrogen sulfide was absorbed by the desulfurizing agent.
- Example 5 The results of Example 5 and Comparative Example 8 are summarized in Table 3.
- the desulfurization agent J supporting only 6% by mass of Ni has a 20 ppb breakthrough time of 90.3 hours, whereas the desulfurization agent L supporting 0.2% by mass of Ru and 6% by mass of Ni has 160 3 hours. From this result, it became clear that the desulfurization agent containing both Ru and Ni exhibits high performance even in the desulfurization of a gas containing hydrocarbon as a main component.
- the desulfurization agent L has a high desulfurization performance with respect to sulfur compounds such as DMS, TBM, and hydrogen sulfide even at a low temperature of about 250 ° C., and keeps the concentration of the sulfur compound slipping downstream in a very low level for a long time.
- the raw fuel gas G1 was treated (desulfurized) over a long period of time with a high desulfurization capacity and a small amount of desulfurizing agent.
- the desulfurization system 100 has exemplified the case where the desulfurizer 1 is provided on the upstream side of the reformer 2 (that is, the case where the reformer 2 is located on the downstream side of the desulfurizer 1).
- the desulfurization system 100 is not necessarily used in combination with the reformer 2, but can be used in combination with other process equipment such as a reactor.
- the desulfurization agent and the desulfurization method of the present invention exhibit its desulfurization performance even when the gas contains other components as long as the gas contains hydrogen and the gas can be brought into contact with the desulfurization agent in a reducing atmosphere. .
- copper of the manufactured desulfurization agent was copper oxide, and before using the manufactured desulfurization agent for a desulfurization reaction, the desulfurization method used for desulfurization after performing a reduction process was illustrated.
- the copper of the manufactured desulfurizing agent is metallic copper, the reduction treatment may not be included.
- the nickel component of the manufactured desulfurizing agent is an oxide, and the desulfurization method in which the manufactured desulfurizing agent is used for desulfurization after being reduced before being subjected to the desulfurization reaction is exemplified. .
- the nickel component of the produced desulfurizing agent is metallic nickel, the reduction treatment may not be included.
- the ruthenium component of the produced desulfurizing agent is an oxide
- the desulfurization method in which the produced desulfurizing agent is used for desulfurization after being reduced before being subjected to the desulfurization reaction is exemplified.
- the ruthenium component of the produced desulfurizing agent is metal ruthenium
- the reduction treatment may not be included.
- the present invention can be applied to a raw fuel gas desulfurization agent and a desulfurization method used for, for example, a fuel gas reformer of a fuel cell.
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Abstract
Description
水蒸気改質プロセスの原料として、天然ガス、液化石油ガス(LPG)やこれらを原料とする都市ガスのような軽質炭化水素を主成分とする原燃料は、炭素析出を引き起こしやすい重質炭化水素をほとんど含まず、硫黄分も少ないので、特に好適である。しかし、天然ガス、液化石油ガス(LPG)にも、通常は微量の硫黄化合物が含まれる。また、実質的に硫黄分を含まない液化天然ガス(LNG)を主原料として製造される都市ガスであっても、輸送時の安全性確保のため、微量の付臭剤が添加されている。
水素化脱硫は、Co-Mo系あるいはNi-Mo系触媒を用いて炭化水素原料中の有機硫黄化合物を水素と反応させて水素化分解した後、生成した硫化水素を酸化亜鉛に吸着させて除去する方法である(非特許文献1、2)。水素化脱硫は、石油精製における燃料油の脱硫プロセスとしても用いられるなど、幅広く実用に供されている。しかし、硫化水素の酸化亜鉛への吸着が平衡反応となることもあり、微量の硫黄分の残存が避けられない。
また、数十ppbの硫黄分が水蒸気改質触媒にリークするとされている(非特許文献2)。
吸着脱硫法は、常温で脱硫が行えることが利点である。また、水素の添加が不要である点が利点である。しかし、体積当たりの脱硫能力が小さいという課題がある。また、ガス中に水分が含まれると吸着性能がさらに低下するという課題がある。さらに、比較的水分に強いAgは特に高価である、などの課題がある。
この方法では、処理後の硫黄分の濃度は1ppb以下に低減できるため、水蒸気改質触媒の被毒を長期にわたって防ぐことができる。しかし、水素化脱硫と同様に300℃以下で十分な脱硫性能を得るには、多量の脱硫剤を要する点は課題といえる。
この方法では、脱硫処理する際に水素は添加されていないことから、反応機構の詳細は不明であるものの、水素化脱硫反応は生じていないものと推測され、炭素析出を引き起こすことなく長期にわたって脱硫性能が維持できるか、また、メルカプタンよりも難脱硫性の有機硫黄化合物、例えばDMSなどについてどの程度安定して除去できるかは不明である。
一方、NiやCoは単独での脱硫性能はそれほど高いものではない。Ruも上記文献では高活性とされるものの、高価であることもあり、実際の適用例は少ない。
例えば、特許文献6には、ニッケルを酸化物(NiO)換算で50質量%から95質量%、モリブデンを酸化物(MoO3)換算で0.5質量%から25質量%、ルテニウムを酸化物(RuO2)換算で0.1質量%から12質量%、および無機酸化物を含有することを特徴とする炭化水素用脱硫剤が開示されている。この脱硫剤は、灯油、ジェット燃料、ナフサ、ガソリン、LPG、天然ガスなど炭化水素中の硫黄分を極めて効率よく除去でき、50質量ppb破過時間を著しく増加させることができるとされている。
酸化亜鉛、酸化アルミニウムおよび銅を含み、さらに1.0質量%から10質量%のニッケルおよび0.1質量%から1.0質量%のルテニウムを含んでなる点にある。
また、上記構成の脱硫剤は、高い脱硫容量を有する。そのため、脱硫剤の使用量を少なくすることができる。また、長期にわたってガスに含まれる硫黄化合物を分解除去しうる。
また、上記構成の脱硫剤は、ニッケルとして、金属状態のニッケルないしその酸化物を含み、好ましくは主たるニッケルとして金属状態のニッケル(金属ニッケル)を含む。
また、上記構成の脱硫剤は、ルテニウムとして、金属状態のルテニウムないしその酸化物を含み、好ましくは主たるルテニウムとして金属状態のルテニウム(金属ルテニウム)を含む。
酸化亜鉛、酸化アルミニウムおよび銅を含み、さらに1.0質量%から10質量%のニッケルおよび0.1質量%から1.0質量%のルテニウムを含んでなる脱硫剤を、水素の共存下でガスに接触させて、前記ガス中の硫黄化合物を分解除去する点にある。
また、上記構成によれば、脱硫剤の高い脱硫容量を活かして、少ない脱硫剤の使用量で長期にわたってガスに含まれる硫黄化合物を分解除去しうる。
以下に本発明の実施形態にかかるガスの脱硫剤および脱硫方法を説明する。
本発明の脱硫剤は、酸化亜鉛、酸化アルミニウムおよび銅を含み、さらに1質量%から10質量%のニッケルおよび0.1質量%から1.0質量%のルテニウムを含んでなることを特徴とする。
そして、脱硫反応に供する前に還元処理してから使用される。
亜鉛およびアルミニウムは、製造された段階でも還元処理後の段階でも酸化状態(ZnO、Al2O3)にあると推測される。
銅、ニッケルおよびルテニウムは、空気中で焼成した段階(製造された段階)では、主に酸化物(Cu2O,NiO,RuO2)であり、還元処理後は主に金属状態にあると推測される。
また、本発明の脱硫剤は、使用時は、酸化亜鉛、酸化アルミニウムおよび銅(金属銅)を含み、さらに酸化銅を含む場合がある。
また、本発明の脱硫剤は、使用時は、ニッケル成分として金属ニッケル、およびルテニウム成分として金属ルテニウムを含む。上記銅の場合と同様に、それぞれニッケルの酸化物、ルテニウムの酸化物を含む場合がある。
本発明の脱硫剤の製造方法に制約はないが、好ましくは、特許文献4と同様の方法で製造される。
本発明の脱硫剤の製造方法は、まず、硝酸銅(Cu(NO3)2)などの水溶性銅化合物と、硝酸亜鉛(Zn(NO3)2)などの水溶性亜鉛化合物とを、アルミニウム化合物の共存下にアルカリ物質水溶液と混合させる。この際、アルミニウム化合物は、溶解していてもゲル状であってもよい。
そして、当該混合により、沈澱を生じさせる。
さらに、得られた沈澱を焼成し、酸化銅と、酸化亜鉛と、酸化アルミニウムとの混合物を得る。以下、この混合物を、酸化銅-酸化亜鉛-酸化アルミニウム混合物と称する。
市販の酸化銅-酸化亜鉛-酸化アルミニウム混合物成型体を担体として用いる場合も、これにニッケルおよびルテニウムを含有する水溶液を含浸させ、焼成して、本発明の脱硫剤を得ることができる。
なお、市販の酸化銅-酸化亜鉛-酸化アルミニウム混合物成型体には、グラファイトなどの成型助剤が添加されている場合がある。しかし、これら成型助剤は極端に多すぎない限り、脱硫剤としての機能を損なうことはない。
上記ニッケルの原料のうち、硝酸ニッケル、酢酸ニッケルが特に好適である。これらは、溶解度が高く、好ましいためである。また、これらは、調製された脱硫剤に塩素イオンを残留させることが無く、塩素イオンの残留により脱硫性能を損なうことが無いためである。
上記ルテニウムの原料のうち、硝酸ルテニウム、ニトロシル硝酸ルテニウムが特に好適である。これらは、調製された脱硫剤に塩素イオンを残留させることが無く、塩素イオンの残留により脱硫性能を損なうことが無いためである。
好ましくは、脱硫剤に対する質量比で、Niとして3.0質量%から10質量%、Ruとして0.1質量%から1.0質量%である。より好ましくは、脱硫剤に対する質量比で、Niとして3.0質量%から6.0質量%、Ruとして0.1質量%から1.0質量%である。
また、脱硫剤中のニッケルおよびルテニウムの含有量は、脱硫剤に対する質量比で、Niとして1.0質量%から6.0質量%、Ruとして0.1質量%から1.0質量%であってもよく、脱硫剤に対する質量比で、Niとして1.0質量%から3.0質量%、Ruとして0.1質量%から1.0質量%であってもよい。
焼成温度が低すぎると、担持に用いたニッケルあるいはルテニウム化合物の分解が不十分となって所望の性能が得られない。
焼成温度が高すぎると、脱硫剤の比表面積が小さくなって、やはり所望の性能が得られない。
あるいは、ニッケルおよびルテニウムは、まずニッケルを担体に担持した後に、さらにルテニウムを担体に担持する逐次担持の方法によってもよい。
本発明の原燃料ガスG1(ガス)の脱硫方法は、上記で得られた脱硫剤を水素の共存下で還元処理した後、水素の共存下で原燃料ガスG1(ガス)に接触させて、原燃料ガスG1の硫黄化合物を分解除去するものである。
本実施形態においては、脱硫方法として、上記で得られた脱硫剤(製造された脱硫剤)を水素存在下で還元処理した後、水素の共存下で原燃料ガスG1(ガス)に接触させて、原燃料ガスG1の硫黄化合物を分解除去する場合を説明する。
例えば、天然ガス系都市ガスであっても、バイオガスを混合している場合は、水素、一酸化炭素、酸素、窒素、二酸化炭素が、それぞれ最大で4%、0.05%、0.01%、1.0%、0.5%(いずれも体積基準)程度含まれる可能性がある。
酸素は、脱硫剤が酸化されて脱硫性能が低下する恐れがあるため、含まれない方が良いが、0.1%程度であれば脱硫剤上で水素と反応して速やかに除去され、反応による温度上昇も小さいので問題にはならない。
上記還元処理を行う場合の温度は、150℃から350℃程度である。
還元処理に用いるガスは、たとえば窒素などの不活性ガス中に1体積%から10体積%程度の水素(水素ガス)を添加したものとする。
還元温度は、低すぎると還元が完結せず、高すぎると脱硫剤の焼結による性能低下を引き起こす。
還元処理に用いるガスの水素濃度(水素ガスの体積濃度)が低すぎると、還元を完結するまでに多量のガスを流す必要があり、経済的に不利となる。逆に、還元処理に用いるガスの水素濃度が高すぎると、水素と酸化状態の脱硫剤との反応による反応熱で、急激な温度上昇が起こるため好ましくない。たとえば、急激な温度上昇により、所定の還元温度を保つことが不可能になることもある。
脱硫反応は、硫黄化合物の濃度が極端に高くない限り、大きな発熱も吸熱も生じない。
そのため、原燃料ガスG1、あるいは水素ガスを添加した原燃料ガスG1をあらかじめ脱硫に好ましい温度に予熱しておき、脱硫剤容器自体は加熱も冷却もしない断熱状態で反応させることもできる。たとえば、原燃料ガスG1、あるいは水素ガスを添加した原燃料ガスG1を、上記還元処理を行う場合の温度である、150℃から350℃程度に予熱しておくこともできる。
水蒸気改質プロセスの前処理として脱硫を行う際の脱硫システムのフロー概略図(一例)を図1に示す。
図1に示す脱硫システム100は、脱硫剤を封入した脱硫器1と、改質触媒を封入した改質器2とを有する。脱硫システム100は、供給された原燃料ガスG1を脱硫し、およびさらに水蒸気改質して、水素を含有する改質燃料ガスG3を得る反応システムである。
原燃料ガスG1が、供給路11から脱硫器1に供給されて、脱硫剤出口ガスG2になる。
脱硫剤出口ガスG2は、脱硫器1から改質器流路12を介して下流側に接続される改質器2に供給される。改質器流路12には、水蒸気供給路21が接続されて、水としての水蒸気Sが改質器流路12に供給される。したがって、改質器2には、脱硫剤出口ガスG2と、水蒸気Sとが供給される。
改質器2で改質された脱硫剤出口ガスG2は改質燃料ガスG3となる。改質燃料ガスG3は、改質器2の下流側に接続された改質ガス流路13を介して、例えば燃料電池(図示せず)などの次工程へ供される。
改質燃料ガスG3の一部は、リサイクルガスG4として、改質ガス流路13から分岐して供給路11へ接続される返送路31を介して脱硫器1へ返送される。
以下、実施例を示し、本発明をより詳細に説明する。
なお、本発明はこれらの実施例に限定されるものではない。
担体としての市販の酸化銅-酸化亜鉛-酸化アルミニウム混合物成型体(ズードケミー触媒社製、MDC-7、3mmタブレット、CuO:45質量%、ZnO:45質量%、Al2O3:6質量%)30.02gに、硝酸ルテニウム(Ruとして0.062g含有)、硝酸ニッケル(Niとして0.927g含有)を溶解した23gの水溶液を滴下し、3時間かけて含浸させた。
その後、加熱器としてのホットプレート上で蒸発乾固し、110℃に設定した乾燥器で1時間乾燥した後、焼成炉としてのマッフル炉を用いて、空気中毎分10℃の昇温速度で300℃まで昇温し、焼成として、300℃に1時間保持した。そして、0.2質量%のRuと3質量%のNiを含む脱硫剤Aを得た。
そして、この脱硫剤層の下端部(出口側)を250℃に保持するよう加熱しながら、窒素ガスに2%の水素ガス(体積基準)を混合した還元ガスを毎時60リットル(0℃、1気圧の標準状態における体積)で流通し、1時間還元処理を行った。つまり、脱硫剤Aを水素存在下で還元した。
脱硫剤出口ガスG2のDMS濃度は、当初は検出されず、22時間後に3.8ppb、23時間後に5.0ppb、24時間後に5.3ppb、25時間後に6.6ppbとなった。
なお、25時間まで脱硫剤出口ガスG2中に硫化水素は検出されず、メタン濃度は約300ppmでほぼ一定であった。DMSは硫化水素とメタンに分解され、硫化水素は脱硫剤に吸収されたと考えられる。
Ni量、及びRu量を変えた他は実施例1と同様にして0.2質量%のRuと1質量%のNiを含む脱硫剤Bを得た。実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は9.4時間となった。
実施例1で用いた酸化銅-酸化亜鉛-酸化アルミニウム混合物成型体をそのまま脱硫剤として用いた(脱硫剤C)。
実施例1と同様にして脱硫性能を評価したところ、脱硫剤出口ガスG2のDMS濃度は、当初は検出されず、6時間後に3.4ppb、7時間後に18.9ppb、8時間後に64.2ppbとなった。5ppb破過時間は6.2時間となる。
Niを用いなかった他は実施例1と同様にして0.2質量%のRuを含む脱硫剤Dを得た。
実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は8.2時間となった。
Ru量を変えた他は比較例2と同様にして1.0質量%のRuを含む脱硫剤Eを得た。
実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は8.6時間となった。
Ruを用いなかった他は実施例1と同様にして3質量%のNiを含む脱硫剤Fを得た。
実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は20.6時間となった。
Ruを用いなかった他は実施例2と同様にして1質量%のNiを含む脱硫剤Gを得た。実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は7.0時間となった。
0.2質量%のRuと3質量%のNiを担持した脱硫剤Aは、5ppb破過時間が23.0時間となり、特許文献2,3に開示される酸化銅-酸化亜鉛-酸化アルミニウムである脱硫剤Cの6.2時間と比較して約4倍の破過時間となった。
0.2質量%のRuを担持した脱硫剤D、1.0質量%のRuを担持した脱硫剤Eは、それぞれ8.2時間および8.6時間の破過時間であり、3質量%のNiを担持した脱硫剤Fの破過時間は20.6時間であった。Ruのみの担持では、破過時間の延長効果は小さく、0.2質量%のRu担持では2.0時間延ばすに過ぎない。0.2質量%のRuと3質量%のNiの担持では、16.8時間破過時間が伸びており、3質量%Niのみの14.5時間、0.2質量%Ruのみの2.0時間の合計よりも長いことから、本発明のNiとRuの組み合わせが、脱硫性能を発揮させる上で相乗効果を発揮していることは明らかである。
担体としての市販の酸化銅-酸化亜鉛-酸化アルミニウム混合物成型体(ズードケミー触媒社製、MDC-7、3mmタブレット、CuO:41質量%、ZnO:46質量%、Al2O3:9質量%)50.02gに、硝酸ルテニウム(Ruとして0.050g含有)、硝酸ニッケル(Niとして3.201g含有)を溶解した37gの水溶液を滴下し、3時間かけて含浸させた。
その後、加熱器としてのホットプレート上で蒸発乾固し、110℃に設定した乾燥器で一晩乾燥した後、焼成炉としてのマッフル炉を用いて、空気中毎分2℃の昇温速度で300℃まで昇温し、焼成として、300℃に1時間保持した。そして、0.1質量%のRuと6質量%のNiを含む脱硫剤Hを得た。実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は33.4時間となった。
Ru量を変えた他は実施例3と同様にして0.2質量%のRuと6質量%のNiを含む脱硫剤Iを得た。実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は37.8時間となった。
Ruを用いなかった他は実施例3と同様にして6質量%のNiを含む脱硫剤Jを得た。実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は30.8時間となった。
実施例3で用いた酸化銅-酸化亜鉛-酸化アルミニウム混合物成型体をそのまま脱硫剤として用いた(脱硫剤K)。実施例1と同様にして脱硫性能を評価したところ、5ppb破過時間は5.3時間となった。
0.1質量%のRuと6質量%のNiを担持した脱硫剤Hは5ppb破過時間が33.4時間、0.2質量%のRuと6質量%のNiを担持した脱硫剤Iは5ppb破過時間が37.8時間となり、特許文献2,3に開示される酸化銅-酸化亜鉛-酸化アルミニウムである脱硫剤Kの5.3時間と比較して明らかに長い結果となった。
また、比較例6、実施例3および実施例4を比較すると、6質量%のNiのみを担持した脱硫剤Jの5ppb破過時間が30.8時間であるのに対して、上述のように0.1質量%のRuと6質量%のNiを担持した脱硫剤Hでは33.4時間、0.2質量%のRuと6質量%のNiを担持した脱硫剤Iでは37.8時間となり、Ruの担持量を増加するにつれて破過時間が長くなっている。この結果から、NiおよびRuの両方を含む脱硫剤が顕著に高い脱硫性能を示すことが明らかである。
〔都市ガスの脱硫試験〕
実施例3で担体として用いたものと同じ成型体35gに、硝酸ルテニウム(Ruとして0.070g含有)、硝酸ニッケル(Niとして2.099g含有)を溶解した24gの水溶液を滴下し、3時間かけて含浸させた。
その後、加熱器としてのホットプレート上で蒸発乾固し、110℃に設定した乾燥器で1時間乾燥した後、焼成炉としてのマッフル炉を用いて、空気中毎分3℃の昇温速度で300℃まで昇温し、焼成として、300℃に1時間保持した。そして、0.2質量%のRuと6質量%のNiを含む脱硫剤Lを得た。
脱硫剤出口ガスG2のDMS濃度は当初は検出されず、158時間後に17ppb、160時間後に19ppb、162時間後に28ppbとなった。
比較例6で用いたものと同じ脱硫剤Jをステンレス製反応管(内径15.7mm)に10cc(12.4g)充填した。脱硫剤Jが充填されたステンレス製反応管が、脱硫器1に相当する。実施例5と同様にして脱硫性能を評価したところ20ppb破過時間は90.3時間となった。
6質量%のNiのみを担持した脱硫剤Jの20ppb破過時間が90.3時間であるのに対して、0.2質量%のRuと6質量%のNiを担持した脱硫剤Lでは160.3時間となっている。この結果から、RuおよびNiの両方を含む脱硫剤は炭化水素を主成分とするガスの脱硫においても高い性能を発揮することが明らかとなった。
(1)上記実施形態では、脱硫システム100は、改質器2の上流側に脱硫器1を設ける場合(つまり、脱硫器1の下流側に改質器2がある場合)を例示した。
しかしながら、脱硫システム100は、改質器2と必ず組み合わせて用いるものでは無く、その他の反応器などのプロセス装置と組み合わせて利用することができる。
同様に、上記実施形態では、製造された脱硫剤のニッケル成分が酸化物であり、当該製造された脱硫剤を脱硫反応に供する前に、還元処理してから脱硫に使用する脱硫方法を例示した。しかし、当該製造された脱硫剤のニッケル成分が金属ニッケルである場合、還元処理を含まなくてもよい。
また、上記実施形態では、製造された脱硫剤のルテニウム成分が酸化物であり、当該製造された脱硫剤を脱硫反応に供する前に、還元処理してから脱硫に使用する脱硫方法を例示した。しかし、当該製造された脱硫剤のルテニウム成分が金属ルテニウムである場合、還元処理を含まなくてもよい。
2 改質器
11 供給路
12 改質器流路
13 改質ガス流路
21 水蒸気供給路
31 返送路
G1 原燃料ガス
G2 脱硫剤出口ガス
G3 改質燃料ガス
G4 リサイクルガス
S 水蒸気
100 脱硫システム
Claims (2)
- 酸化亜鉛、酸化アルミニウムおよび銅を含み、さらに1.0質量%から10質量%のニッケルおよび0.1質量%から1.0質量%のルテニウムを含んでなる、ガスの脱硫剤。
- 酸化亜鉛、酸化アルミニウムおよび銅を含み、さらに1.0質量%から10質量%のニッケルおよび0.1質量%から1.0質量%のルテニウムを含んでなる脱硫剤を、水素の共存下でガスに接触させて、前記ガス中の硫黄化合物を分解除去することを特徴とする、ガスの脱硫方法。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020153225A1 (ja) * | 2019-01-23 | 2020-07-30 | 大阪瓦斯株式会社 | ガスの脱硫剤および脱硫方法 |
WO2020170491A1 (ja) * | 2019-02-22 | 2020-08-27 | パナソニックIpマネジメント株式会社 | 脱硫器の前処理方法、水素生成装置の起動準備方法および燃料電池システムの起動準備方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3058711B1 (fr) * | 2016-11-14 | 2021-04-30 | Air Liquide | Procede de production de gaz de synthese pour la mise en œuvre d'une liquefaction de gaz naturel |
CN113546644B (zh) * | 2021-06-27 | 2022-05-27 | 昆明理工大学 | 焦炉煤气有机硫深度脱除催化剂的制备方法和应用 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61263634A (ja) | 1985-05-16 | 1986-11-21 | Toa Nenryo Kogyo Kk | 微量硫黄化合物の除去法 |
JPH01123627A (ja) | 1987-11-05 | 1989-05-16 | Osaka Gas Co Ltd | 脱硫剤の製造方法 |
JPH01123628A (ja) | 1987-11-05 | 1989-05-16 | Osaka Gas Co Ltd | 耐高温高次脱硫剤の製造方法 |
JPH06212173A (ja) * | 1992-11-28 | 1994-08-02 | Osaka Gas Co Ltd | 炭化水素の脱硫方法 |
JPH1161154A (ja) | 1997-08-21 | 1999-03-05 | Osaka Gas Co Ltd | 脱硫剤の製造方法および炭化水素の脱硫方法 |
JPH11335101A (ja) * | 1998-03-27 | 1999-12-07 | Osaka Gas Co Ltd | 水素製造装置 |
JP2001286753A (ja) | 2000-02-01 | 2001-10-16 | Tokyo Gas Co Ltd | 燃料ガス中の硫黄化合物吸着剤及びその除去方法 |
JP2007254728A (ja) | 2006-02-24 | 2007-10-04 | Cosmo Oil Co Ltd | 炭化水素用脱硫剤 |
CN102211029A (zh) * | 2010-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | 一种柴油加氢脱硫硫化物催化剂的制备方法 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58161918A (ja) | 1982-03-17 | 1983-09-26 | Natl Inst For Res In Inorg Mater | 高純度マグネシア粉末の製造法 |
JPS59152205A (ja) * | 1983-02-14 | 1984-08-30 | Mitsubishi Gas Chem Co Inc | メタノ−ルの水蒸気改質法 |
CA1267914A (en) * | 1985-10-03 | 1990-04-17 | Hajime Nagahara | Process for producing cycloolefins |
JPH01161154A (ja) | 1987-12-17 | 1989-06-23 | Toshiba Corp | 自動化学分析装置の恒温槽 |
US5302470A (en) * | 1989-05-16 | 1994-04-12 | Osaka Gas Co., Ltd. | Fuel cell power generation system |
WO2001072417A1 (fr) * | 2000-03-31 | 2001-10-04 | Idemitsu Kosan Co., Ltd. | Agent desulfurant pour hydrocarbures derives de petrole, procede de fabrication d'hydrogene pour pile a combustible et procede de fabrication d'agent desulfurant a base de nickel |
US20030183803A1 (en) * | 2002-03-28 | 2003-10-02 | Price Ashley G. | Desulfurization and novel compositions for same |
US6930074B2 (en) * | 2002-04-26 | 2005-08-16 | Conocophillips Company - I. P. Legal | Desulfurization and sorbent for the same |
KR20070019428A (ko) * | 2005-08-12 | 2007-02-15 | 에스케이 주식회사 | 유기황화합물 제거용 탈황제, 이의 제조방법 및 이를이용한 유기황화합물의 제거방법 |
KR100696622B1 (ko) * | 2005-10-19 | 2007-03-19 | 삼성에스디아이 주식회사 | 연료전지용 마이크로 개질 반응기 및 그 제조방법 |
JP4706857B2 (ja) * | 2006-05-30 | 2011-06-22 | 戸田工業株式会社 | 金属カルボニルを除去する触媒、水素を含む混合改質ガスを製造する方法、金属カルボニルを除去する方法、燃料電池システム |
JP5666777B2 (ja) * | 2006-10-13 | 2015-02-12 | 出光興産株式会社 | 一酸化炭素転換用触媒およびそれを用いた一酸化炭素変成方法 |
WO2008126743A1 (ja) * | 2007-04-10 | 2008-10-23 | Idemitsu Kosan Co., Ltd. | 触媒前駆体物質及びそれを用いた触媒 |
ES2431791T3 (es) * | 2007-08-13 | 2013-11-28 | Asahi Kasei Chemicals Corporation | Catalizador para la producción de éster del ácido carboxílico, procedimiento de producción del mismo y procedimiento para la producción de éster del ácido carboxílico |
WO2010113506A1 (ja) * | 2009-03-31 | 2010-10-07 | 新日本石油株式会社 | 炭化水素用脱硫剤前駆体及びその製造方法、炭化水素用脱硫剤焼成前駆体及びその製造方法、炭化水素用脱硫剤及びその製造方法、炭化水素の脱硫方法並びに燃料電池システム |
GB0916161D0 (en) * | 2009-09-15 | 2009-10-28 | Johnson Matthey Plc | Desulphurisation process |
KR101988065B1 (ko) * | 2011-07-27 | 2019-06-11 | 사우디 아라비안 오일 컴퍼니 | 가스성 탄화수소로부터 황 화합물의 제거에 유용한 촉매 조성물, 이의 제조공정 및 이의 용도 |
US8906227B2 (en) * | 2012-02-02 | 2014-12-09 | Suadi Arabian Oil Company | Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds |
EP2876100A4 (en) * | 2012-07-23 | 2016-08-17 | Sekisui Chemical Co Ltd | SYSTEM FOR THE PRODUCTION OF AN OXIGENT PRODUCT AND METHOD FOR THE PRODUCTION OF AN OXIGINATED PRODUCT |
US8920635B2 (en) * | 2013-01-14 | 2014-12-30 | Saudi Arabian Oil Company | Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds |
JP6607387B2 (ja) * | 2015-02-02 | 2019-11-20 | パナソニックIpマネジメント株式会社 | 脱硫方法及び脱硫器 |
JP6212173B2 (ja) | 2016-06-24 | 2017-10-11 | テイ・エス テック株式会社 | 車両用シートのシートフレーム |
-
2018
- 2018-05-15 WO PCT/JP2018/018772 patent/WO2018216555A1/ja active Application Filing
- 2018-05-15 JP JP2019519594A patent/JP7012712B2/ja active Active
- 2018-05-15 US US16/614,892 patent/US10814312B2/en active Active
- 2018-05-15 EP EP18805196.5A patent/EP3632538B1/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61263634A (ja) | 1985-05-16 | 1986-11-21 | Toa Nenryo Kogyo Kk | 微量硫黄化合物の除去法 |
JPH01123627A (ja) | 1987-11-05 | 1989-05-16 | Osaka Gas Co Ltd | 脱硫剤の製造方法 |
JPH01123628A (ja) | 1987-11-05 | 1989-05-16 | Osaka Gas Co Ltd | 耐高温高次脱硫剤の製造方法 |
JPH06212173A (ja) * | 1992-11-28 | 1994-08-02 | Osaka Gas Co Ltd | 炭化水素の脱硫方法 |
JPH1161154A (ja) | 1997-08-21 | 1999-03-05 | Osaka Gas Co Ltd | 脱硫剤の製造方法および炭化水素の脱硫方法 |
JPH11335101A (ja) * | 1998-03-27 | 1999-12-07 | Osaka Gas Co Ltd | 水素製造装置 |
JP2001286753A (ja) | 2000-02-01 | 2001-10-16 | Tokyo Gas Co Ltd | 燃料ガス中の硫黄化合物吸着剤及びその除去方法 |
JP2007254728A (ja) | 2006-02-24 | 2007-10-04 | Cosmo Oil Co Ltd | 炭化水素用脱硫剤 |
CN102211029A (zh) * | 2010-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | 一种柴油加氢脱硫硫化物催化剂的制备方法 |
Non-Patent Citations (6)
Title |
---|
JOSE ANTONIO DE LOS REYES H. ET AL.: "Kinetic approach in the comparison of supported and unsupported ternary nickel-ruthenium-sulphur compounds in hydrotreating reactions", APPLIED CATALYSIS A: GENERAL, vol. 103, 1993, pages 79 - 85, XP055553682 * |
MATSUHISA, CATALYST, vol. 48, no. 5, 2006, pages 326 |
S. SATOKAWAY. KOBAYASHIH. FUJIKI, APPLIED CATALYSIS B: ENVIRONMENTAL., vol. 56, 2005, pages 51 |
See also references of EP3632538A4 |
SHIBA, CATALYST, vol. 1, no. 1, 1959, pages 49 |
T.A. PECORAROR. R. CHIANELLI, JOURNAL OF CATALYSIS, vol. 67, 1981, pages 430 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020153225A1 (ja) * | 2019-01-23 | 2020-07-30 | 大阪瓦斯株式会社 | ガスの脱硫剤および脱硫方法 |
JP7446244B2 (ja) | 2019-01-23 | 2024-03-08 | 大阪瓦斯株式会社 | ガスの脱硫剤および脱硫方法 |
WO2020170491A1 (ja) * | 2019-02-22 | 2020-08-27 | パナソニックIpマネジメント株式会社 | 脱硫器の前処理方法、水素生成装置の起動準備方法および燃料電池システムの起動準備方法 |
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EP3632538A4 (en) | 2020-12-23 |
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US20200108371A1 (en) | 2020-04-09 |
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