WO2010035710A1 - Desulfurizing agent, method for producing same, and method for desulfurizing hydrocarbon oil - Google Patents
Desulfurizing agent, method for producing same, and method for desulfurizing hydrocarbon oil Download PDFInfo
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- WO2010035710A1 WO2010035710A1 PCT/JP2009/066374 JP2009066374W WO2010035710A1 WO 2010035710 A1 WO2010035710 A1 WO 2010035710A1 JP 2009066374 W JP2009066374 W JP 2009066374W WO 2010035710 A1 WO2010035710 A1 WO 2010035710A1
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- WIPO (PCT)
- Prior art keywords
- nickel
- zinc
- desulfurization
- desulfurizing agent
- mass
- Prior art date
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 99
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 68
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 47
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 43
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011701 zinc Substances 0.000 claims abstract description 50
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003929 acidic solution Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 239000011787 zinc oxide Substances 0.000 claims abstract description 19
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 17
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 76
- 230000023556 desulfurization Effects 0.000 claims description 76
- 229910052717 sulfur Inorganic materials 0.000 claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- 239000011593 sulfur Substances 0.000 claims description 29
- 239000012670 alkaline solution Substances 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 16
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 57
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000003502 gasoline Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 150000003464 sulfur compounds Chemical class 0.000 description 7
- 229940053662 nickel sulfate Drugs 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000003915 liquefied petroleum gas Substances 0.000 description 5
- 150000002898 organic sulfur compounds Chemical class 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/393—
-
- B01J35/612—
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Definitions
- the present invention relates to a desulfurizing agent used when desulfurizing sulfur compounds in hydrocarbon oil, a method for producing the desulfurizing agent, and a desulfurizing method for hydrocarbon oil using the desulfurizing agent.
- the sulfur content of the fuel Reduction is increasingly required.
- the sulfur content of gasoline and light oil is regulated to sulfur-free (sulfur content of 10 ppm by mass or less), and further low sulfur content, that is, zero sulfur (sulfur content of 1 ppm by mass or less) fuel oil is also sought. It has been.
- hydrodesulfurization which is a desulfurization technique that has been used mainly in the past (for example, desulfurization in a high-temperature, high-pressure hydrogen atmosphere using an alumina catalyst supporting cobalt, nickel, and molybdenum), gasoline and diesel oil
- hydrodesulfurization reaction which is a high temperature / high pressure reaction, has a higher Since operation at high pressure is required, energy consumption increases and hydrogen consumption also becomes enormous. Further, in the above hydrodesulfurization, if an attempt is made to react under mild conditions by reducing the space velocity, a huge amount of catalyst is required.
- nickel is supported on a mixture of zinc oxide, alumina and nacre as a desulfurization agent for desulfurizing catalytic cracking gasoline (gasoline fraction obtained from fluid catalytic cracking unit) while suppressing octane loss.
- a desulfurizing agent has been proposed (Patent Document 1). However, since this desulfurizing agent has a small specific surface area, a sufficient desulfurization level cannot be obtained, and a high reaction temperature of 300 ° C. or higher is required.
- catalytic cracking gasoline can be highly desulfurized by desulfurization under specific conditions using a desulfurization agent containing nickel and zinc (Patent Document 3, 4).
- this method requires a relatively high reaction temperature of 300 ° C., which is not sufficient from the viewpoint of economical desulfurization.
- the life of the desulfurizing agent to be used is not sufficient, there is a problem that the period until the activity recovery treatment with hydrogen or the replacement with a new desulfurizing agent is relatively short.
- this invention makes it a subject to provide the desulfurization agent which can desulfurize hydrocarbon oil stably over a long term under specific conditions, and its manufacturing method.
- the present inventors can stably reduce the sulfur content for a long period of time by treating hydrocarbon oil with a specific desulfurizing agent under specific conditions, The inventors have found that such a desulfurizing agent can be produced with good productivity by a specific method, and have arrived at the present invention.
- the present invention (1) A method for producing a desulfurization agent, wherein an alkaline solution and an acidic solution containing nickel and zinc are simultaneously dropped into water to form a precipitate. (2) The method for producing a desulfurization agent according to (1), wherein nickel sulfate is used as a nickel raw material and zinc sulfate is used as a zinc raw material.
- desulfurization of hydrocarbon oil can be carried out stably and economically over a long period of time.
- Such a desulfurizing agent can be produced with good productivity by the method for producing a desulfurizing agent of the present invention.
- the desulfurization agent of the present invention contains nickel and zinc, and can be obtained by, for example, precipitating metal components such as zinc and nickel by a coprecipitation method, filtering, washing, molding, and firing. it can.
- the nickel content relative to the total mass of the desulfurizing agent is preferably 1 to 30% by mass, more preferably 3 to 24% by mass, and particularly preferably 5 to 20% by mass.
- the zinc content with respect to the total mass of the desulfurizing agent is preferably 30 to 80% by mass, more preferably 40 to 75% by mass, and particularly preferably 45 to 70% by mass.
- the life of the desulfurizing agent is long, and when the nickel content is 20% by mass or less and the zinc content is 45% by mass or more. In particular, the life of the desulfurizing agent is prolonged.
- the total content of nickel and zinc is preferably in the range of 35 to 85% by mass, particularly 50 to 85% by mass with respect to the total mass of the desulfurizing agent.
- the desulfurization agent of the present invention contains nickel and zinc as oxides and may further contain elements other than nickel, zinc and oxygen, but from the viewpoint of the life of the desulfurization agent, the inclusion of elements other than nickel, zinc and oxygen A smaller amount is preferred. Therefore, in the desulfurization agent of the present invention, the total content of nickel oxide (NiO) and zinc oxide (ZnO) is preferably 90% by mass or more, more preferably 94% by mass or more, further preferably based on the total mass of the desulfurization agent. Preferably it is 96 mass% or more, Most preferably, it is 99 mass% or more.
- the mass ratio of zinc atoms to nickel atoms (Zn / Ni) in the desulfurizing agent is preferably in the range of 1 to 15, more preferably in the range of 3 to 12, and particularly preferably in the range of 3 to 8.
- the mass ratio of zinc atom to nickel atom (Zn / Ni) is less than 1, the life of the desulfurizing agent is remarkably shortened, and when it exceeds 15, the life of the desulfurizing agent is shortened.
- the crystallite diameter (X) of nickel oxide is 5.0 nm or less, preferably 4.5 nm or less, more preferably 3.0 nm or less
- the crystallite diameter of zinc oxide ( Y) is 15 nm or less, preferably 12 nm or less, more preferably 10 nm or less, and particularly preferably 8 nm or less.
- the crystallite diameter of nickel oxide exceeds 5.0 nm, the contact efficiency between nickel and hydrocarbon oil is reduced, and the ability to take in sulfur is reduced.
- the crystallite diameter of zinc oxide is 15 nm. If it exceeds 1, zinc oxide is not preferable because the efficiency of fixing sulfur decreases.
- the ratio (Y / X) of the crystallite diameter (Y) of the zinc oxide and the crystallite diameter (X) of the nickel oxide is preferably 2 or more, and more preferably 2.5 or more.
- the ratio of the crystallite diameter of zinc oxide to the crystallite diameter of nickel oxide is less than 2, the contact efficiency between nickel and hydrocarbon oil decreases, and the sulfur compound in the hydrocarbon oil is taken into the desulfurization agent. At the same time as the ability is reduced, the efficiency with which zinc fixes sulfur is reduced.
- the desulfurization agent of the present invention has a total pore volume (V1) of 0.35 to 1.00 mL / g, preferably 0.45 to 1.00 mL / g, more preferably 0.50 to 1.00 mL / g, Particularly preferred is 0.60 to 1.00 mL / g. If the total pore volume of the desulfurizing agent is less than 0.35 mL / g, the space in which the desulfurization reaction occurs mainly decreases, which is not preferable. On the other hand, if it exceeds 1.00 mL / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged into a reactor having a constant capacity is reduced, which is not preferable.
- the desulfurization agent of the present invention preferably has a pore volume (V2) having a pore diameter of 2 to 30 nm of 0.08 to 0.50 mL / g, more preferably 0.15 to 0.40 mL / g, and particularly preferably. Is 0.20 to 0.30 mL / g. If the volume of the pores having a pore diameter of 2 to 30 nm is less than 0.08 mL / g, the space in which the desulfurization reaction occurs mainly decreases, which is not preferable.
- the volume of the pores having a pore diameter of 2 to 30 nm exceeds 0.50 mL / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged in a reactor with a constant volume is reduced, resulting in a shorter life. Absent.
- the ratio (V2 / V1) of the pore volume (V2) having a pore diameter of 2 to 30 nm with respect to the total pore volume (V1) is preferably 0.15 to 1.00. It is preferably 0.30 to 0.60.
- the ratio (V2 / V1) is less than 0.15, the contact efficiency between the hydrocarbon oil and nickel in the pores deteriorates, or sufficient strength is obtained when the desulfurizing agent is used industrially. It is not preferable because it disappears.
- the ratio (V2 / V1) is 0.60 or less, preferable contact efficiency can be obtained by an appropriate combination of pores having a large diameter and small pores.
- the desulfurizing agent of the present invention has a specific surface area of 70 m 2 / g or more, preferably 75 m 2 / g or more, more preferably 90 m 2 / g or more.
- a specific surface area is 200 m ⁇ 2 > / g or less, Preferably it is 170 m ⁇ 2 > / g or less, More preferably, it is 150 m ⁇ 2 > / g or less.
- the specific surface area of the desulfurizing agent exceeds 200 m 2 / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged in a reactor having a certain capacity is reduced, which is not preferable.
- the desulfurizing agent of the present invention is preferably used after being treated at 200 to 350 ° C., particularly 250 to 300 ° C. in a hydrogen atmosphere.
- a treatment temperature under a hydrogen atmosphere of less than 200 ° C. is not preferable because nickel is not reduced.
- the treatment temperature exceeds 350 ° C., nickel is sintered and the activity is lowered, which is not preferable.
- the desulfurizing agent of the present invention is preferably prepared by a coprecipitation method.
- the preparation method by coprecipitation method contains more nickel and zinc effective for desulfurization in the desulfurization agent than the production method in which a porous carrier such as alumina is impregnated with metal components such as zinc and nickel, and is fired. Therefore, the life of the desulfurizing agent can be extended.
- the method of impregnating the zinc oxide support with nickel is not preferable because the specific surface area and the pore volume are reduced due to the blockage of the pores of the zinc oxide support and the desulfurization activity is lowered.
- the desulfurization agent of the present invention is particularly preferably prepared by simultaneously dropping an acidic solution and an alkaline solution containing nickel and zinc into water to produce a precipitate containing nickel and zinc.
- the water used preferably has a pH of 6.0 to 8.0.
- the simultaneous dropping of the acidic solution and the alkaline solution means that the acidic solution is dropped while the acidic solution is dropped for a period of 80% by volume or more, preferably 90% by volume or more. It means that the acidic solution is being dropped while the alkaline solution is being dropped while the solution is being dropped and the amount of 80% by volume or more, preferably 90% by volume or more of the alkaline solution is being dropped.
- the acidic solution containing nickel and zinc is obtained by dissolving zinc, nickel sulfate, nitrate, acetate, etc. with water, and the pH is preferably 5.0 or less, more preferably 4.5 or less. Yes, particularly preferably 4.0 or less, preferably 0.5 or more, more preferably 2.0 or more. If the pH of the acidic solution exceeds 5.0, it is not preferable because the nucleation rate in the solution becomes slow and the crystal grows easily, and the degree of dispersion of nickel and zinc becomes low.
- the pH of the acidic solution is too low, particularly less than 0.5, the amount of the coprecipitation solution is small, the viscosity is high and stirring is difficult, and it is difficult to obtain a uniform physical property, which is not preferable.
- the total concentration of nickel and zinc in the acidic solution is preferably in the range of 0.3 to 3.0 mol / L, and more preferably in the range of 0.3 to 1.0 mol / L.
- the dropping amount of the acidic solution is preferably in the range of 0.3 to 4.0 L with respect to 1 L of water, and more preferably in the range of 1.0 to 3.5 L.
- the acid solution is preferably prepared using nickel sulfate as the nickel raw material and zinc sulfate as the zinc raw material.
- the specific surface area of the desulfurizing agent is increased by preparing the desulfurizing agent using nickel sulfate as the nickel raw material and zinc sulfate as the zinc raw material.
- the crystallite diameter of the nickel oxide and the crystallite diameter of the zinc oxide Can be reduced.
- the nickel sulfate and zinc sulfate used as raw materials may be hydrates or anhydrides.
- sodium carbonate, ammonium carbonate, or the like can be used for the alkaline solution, and sodium carbonate is preferably used.
- the pH of the alkaline solution is preferably 11-13.
- the cation concentration in the alkaline solution is preferably in the range of 0.3 to 4.0 mol / L, and more preferably in the range of 0.3 to 1.5 mol / L.
- examples of the cation in the alkaline solution include sodium ion and ammonium ion.
- the crystallite diameter of nickel oxide and the crystallite diameter of zinc oxide can be made sufficiently small by setting the cation concentration in the alkaline solution to 4.0 mol / L or less.
- the productivity of the desulfurizing agent is lowered.
- the dropping amount of the alkaline solution is preferably in the range of 0.3 to 4.0 L with respect to 1 L of water, and more preferably in the range of 1.0 to 3.5 L.
- the pH during coprecipitation is preferably 7.0 to 9.0. If the pH during coprecipitation is less than 7.0, a part of nickel does not precipitate, which is not preferable. On the other hand, if the pH during coprecipitation exceeds 9.0, an alkaline component tends to remain in the precipitation, which is not preferable. Moreover, after dropping the acidic solution and the alkaline solution into water, it is desirable to continuously stir for 1 hour or more. Further, the liquid temperature at the time of coprecipitation is preferably in the range of 50 to 70 ° C. from the viewpoint of the solubility of the alkali component.
- the precipitate generated in the above step needs to be dried after filtration, but the drying temperature is preferably 100 to 200 ° C. Further, the temperature in the subsequent firing is preferably 300 to 400 ° C., more preferably 300 to 350 ° C. A calcination temperature of less than 300 ° C. is not preferable because the salt is not completely decomposed when the nickel and zinc components are precipitated. On the other hand, if the firing temperature exceeds 400 ° C., crystallization of nickel and zinc oxide formed by decomposition of the salt proceeds, and the degree of dispersion of nickel with respect to zinc is lowered, which is not preferable.
- the desulfurizing agent refers to a desulfurizing agent having a sulfur sorption function.
- the desulfurization agent having a sulfur sorption function here is to fix the sulfur atom in the organic sulfur compound to the desulfurization agent, and for hydrocarbon residues other than the sulfur atom in the organic sulfur compound in the organic sulfur compound.
- the hydrocarbon compound from which the sulfur atom is removed may be further subjected to a reaction such as hydrogenation, isomerization, or decomposition to become another compound.
- a reaction such as hydrogenation, isomerization, or decomposition to become another compound.
- sulfur since sulfur is fixed to the desulfurizing agent, unlike a hydrorefining treatment, sulfur compounds such as hydrogen sulfide are not generated as a product. This eliminates the need for equipment for removing hydrogen sulfide, which is economically advantageous.
- the raw material hydrocarbon oil to be subjected to the desulfurization method according to the present invention is not particularly limited as long as it is a hydrocarbon oil containing a sulfur content, but preferably contains 2 ppm by mass or more of sulfur content, more preferably 2 to 1, 000 ppm by mass, more preferably 2 to 100 ppm by mass, particularly preferably 2 to 40 ppm by mass.
- sulfur content exceeds 1,000 ppm by mass, the life of the desulfurizing agent is shortened, which is not preferable.
- the hydrocarbon oil as a raw material include base materials corresponding to LPG fraction, gasoline fraction, naphtha fraction, kerosene fraction, light oil fraction, etc. that are generally produced in refineries and the like.
- the LPG fraction is a fuel gas mainly composed of propane, propylene, butane, butylene, and industrial raw material gas.
- the LPG fraction is usually stored in a liquid phase in a spherical tank under pressure as called LPG (liquefied petroleum gas) or at a low temperature near atmospheric pressure. Stored in state.
- LPG liquefied petroleum gas
- the gasoline fraction is generally composed mainly of hydrocarbons having 4 to 11 carbon atoms, the density (15 ° C.) is 0.783 g / cm 3 or less, the 10% distillation temperature is 24 ° C.
- the naphtha fraction is composed of gasoline fraction components (hole naphtha, light naphtha, heavy naphtha, or hydrodesulfurized naphtha thereof) or a raw material for catalytic reforming (desulfurized heavy naphtha) for producing a gasoline base.
- the boiling point range is almost the same as that of the gasoline fraction or it is included in the boiling range of the gasoline fraction. Therefore, it is often used in the same meaning as the gasoline fraction.
- the kerosene fraction is generally a hydrocarbon mixture having a boiling range of 150 to 280 ° C.
- the gas oil fraction is generally a hydrocarbon mixture having a boiling range of 190 to 350 ° C.
- the hydrocarbon oil as a raw material is not limited to those produced at refineries and the like, but contains 2 to 1,000 mass ppm of sulfur, petroleum (hydrocarbon) gas produced from petrochemical, A fraction having a similar boiling range may be used.
- hydrocarbon oils that can be preferably used include those obtained by further fractionating hydrocarbons obtained by pyrolysis or catalytic cracking of heavy oils.
- hydrocarbon oil as the raw material to be subjected to the desulfurization method according to the present invention is catalytic cracked gasoline and light oil fraction. Since catalytically cracked gasoline contains a large amount of olefins, hydrorefining with a hydrodesulfurization catalyst that is generally performed hydrogenates the olefin content and greatly reduces the octane number. However, in the desulfurization method of the present invention, almost no olefin content is present. Not hydrogenated. In addition, since the gas oil fraction contains a large amount of aromatics, the amount of hydrogen consumed is large because the aromatics are hydrogenated in the hydrorefining using a hydrodesulfurization catalyst that is generally performed.
- the aromatic content is hardly hydrogenated.
- the sulfur content is usually about 10,000 mass ppm
- the sulfur content was reduced to some extent by hydrorefining with a hydrodesulfurization catalyst, specifically about 5 to 50 mass ppm. Thereafter, it is preferable to apply the desulfurization method of the present invention. When there is much sulfur content, the lifetime of a desulfurization agent will fall large.
- the reaction temperature is 50 to 300 ° C., preferably 100 to 300 ° C.
- the reaction temperature is less than 50 ° C.
- the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed.
- the reaction temperature exceeds 300 ° C.
- the desulfurizing agent is sintered, and both the desulfurization rate and the desulfurization capacity are lowered, which is not preferable. If the reaction temperature is 100 ° C. or higher, the desulfurization rate is sufficiently high and desulfurization can be performed efficiently.
- the reaction pressure is 0.2 to 5.0 MPa in gauge pressure, preferably 0.2 to 3.0 MPa, particularly preferably 0.2 to 2.0 MPa.
- the reaction pressure is less than 0.2 MPa, the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed.
- the reaction pressure exceeds 5.0 MPa, side reactions such as hydrogenation of olefins and aromatics contained in the hydrocarbon oil proceed, which is not preferable. If the reaction pressure is 3.0 MPa or less, side reactions such as hydrogenation of olefins and aromatics can be sufficiently suppressed, and if it is 2.0 MPa or less, these side reactions can be reliably prevented.
- the liquid hourly space velocity exceeds 2.0 h ⁇ 1 , preferably 2.1 h ⁇ 1 or more.
- the LHSV is preferably 50.0 h ⁇ 1 or less, more preferably 20.0 h ⁇ 1 or less, and even more preferably 10.0 h ⁇ 1 or less. If the LHSV is 2.0 h ⁇ 1 or less, the amount of oil passing is limited or the desulfurization reactor becomes too large, so it is not preferable because it cannot economically desulfurize. On the other hand, if LHSV exceeds 50.0 h ⁇ 1 , a contact time sufficient for desulfurization cannot be obtained, and the desulfurization rate decreases, which is not preferable.
- LHSV is 2.1 h ⁇ 1 or more
- desulfurization can be performed sufficiently economically, and if LHSV is 20.0 h ⁇ 1 or less, the contact time is sufficiently long, so that the desulfurization rate is improved. If it is 10.0 h ⁇ 1 or less, the desulfurization rate is particularly high.
- the hydrogen / oil ratio is not particularly limited, but is preferably 0.01 to 200 NL / L, more preferably 0.01 to 100 NL / L, and more preferably 0.1 to 100 NL for a fraction containing a large amount of olefins such as catalytic cracked gasoline. / L is particularly preferred. If the hydrogen / oil ratio is less than 0.01 NL / L, desulfurization does not proceed sufficiently, which is not preferable. On the other hand, when the hydrogen / oil ratio exceeds 200 NL / L, the ratio of side reactions such as hydrogenation of olefins increases, which is not preferable.
- the hydrogen / oil ratio is preferably 1 to 1000 NL / L, more preferably 10 to 500 NL / L, and particularly preferably 50 to 400 NL / L.
- the hydrogen / oil ratio is less than 1 NL / L, desulfurization does not proceed sufficiently, which is not preferable.
- the hydrogen / oil ratio exceeds 1000 NL / L, the hydrogen flow rate becomes too high, and the hydrogen compressor becomes undesirably large.
- the hydrogen used may contain impurities such as methane, but the hydrogen purity is preferably 50% by volume or more, more preferably 80% by volume or more, and particularly 95% by volume or more so that the hydrogen compressor does not become too large. preferable. If the sulfur compound such as hydrogen sulfide is contained in the hydrogen, the life of the desulfurizing agent is shortened. Therefore, the sulfur content in the hydrogen is preferably 1,000 ppm by volume or less, more preferably 100 ppm by volume or less, especially 10 ppm. A capacity of ppm or less is preferred.
- the resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 350 degreeC for 3 hours, and obtained the desulfurization agent (I).
- the desulfurizing agent (I) has a nickel content of 17.3% by mass, a zinc content of 59.5% by mass and a sodium content of 0.01% by mass, and the ratio of the nickel content to the zinc content (mass ) Was 0.29.
- the ratio of the crystallite diameter of zinc oxide to that of nickel oxide was 2.4.
- the metal content was measured by the alkali melting ICP method, the crystallite diameter of the oxide was measured by XRD, and the pore volume was measured by the BJH method by nitrogen adsorption / desorption method.
- the reactor was filled with the desulfurizing agent (I), subjected to reduction treatment at 300 ° C. for 16 hours in a hydrogen stream, and then an oil passage test for hydrocarbon oil was performed.
- hydrocarbon oil heavy catalytic cracked gasoline having a sulfur content of 13 mass ppm was used.
- hydrocarbon oil was started to flow from the reactor inlet.
- the time (cycle length) for maintaining the desulfurization rate of 50% or more was 400 hours.
- the sulfur content was measured based on ASTM D 5453 (ultraviolet fluorescence method).
- Example 1 An acidic solution A having a pH of 2.6 (total concentration of nickel and zinc: 2.7 mol / L) in which 178.5 g of zinc nitrate hexahydrate and 58.2 g of nickel nitrate hexahydrate were dissolved in 300 mL of water was prepared. Further, an alkaline solution B (sodium ion concentration: 3.3 mol / L) having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
- the acidic solution A and alkaline solution B prepared above were added dropwise while stirring 600 mL of distilled water having a pH of 7.0 at a temperature of 60 ° C.
- the acidic solution A and the alkaline solution B started dripping almost simultaneously, and the dripping was completed in 60 minutes. Thereafter, stirring was continued for 1 hour.
- the pH after dropping all was 8.2 at a temperature of 28 ° C.
- the resulting precipitate was filtered and washed with water. Then, after drying at 120 ° C. for 16 hours, calcination was performed at 350 ° C. for 3 hours to obtain a desulfurization agent (II).
- Example 2 The amount of water when preparing the acidic solution A is 1,000 mL (pH 3.2, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water when preparing the alkaline solution B is 1,000 mL.
- a desulfurizing agent (III) was obtained in the same manner as in Example 1 except that the pH was adjusted to 11.4 and the sodium ion concentration was 1.0 mol / L. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
- Example 3 The amount of water when preparing the acidic solution A is 2,000 mL (pH 3.6, total concentration of nickel and zinc: 0.4 mol / L), and the amount of water when preparing the alkaline solution B is 2,000 mL.
- a desulfurizing agent (IV) was obtained in the same manner as in Example 1 except that the pH was adjusted to 11.3 and the sodium ion concentration was 0.5 mol / L. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
- Example 4 An acidic solution A was prepared by changing the nitrate of Example 1 to a sulfate. Specifically, 172.5 g of zinc sulfate heptahydrate and 52.6 g of nickel sulfate hexahydrate were dissolved in 300 mL of water, and sulfuric acid was added dropwise to add acid solution A having a pH of 1.6 (total concentration of nickel and zinc). : 2.7 mol / L). Further, an alkaline solution B (sodium ion concentration: 3.3 mol / L) having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
- an alkaline solution B sodium ion concentration: 3.3 mol / L having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
- the acidic solution A and alkaline solution B prepared above were added dropwise while stirring 600 mL of distilled water having a pH of 7.0 at a temperature of 60 ° C.
- the acidic solution A and the alkaline solution B started dripping almost simultaneously, and the dripping was completed in 60 minutes. Thereafter, stirring was continued for 1 hour.
- the pH after dropping all was 8.2 at a temperature of 28 ° C.
- the resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 350 degreeC for 3 hours, and obtained the desulfurization agent (V).
- Example 5 The amount of water in the acidic solution A is 1,000 mL (pH 2.3, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water in the alkaline solution B is 1,000 mL (pH 11.4, sodium ion concentration).
- the desulfurizing agent (VI) was obtained in the same manner as in Example 4 except that the amount was 1.0 mol / L). Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
- Example 6 The amount of water in the acidic solution A is 2,000 mL (pH 4.3, total concentration of nickel and zinc: 0.4 mol / L), and the amount of water in the alkaline solution B is 2,000 mL (pH 11.3, sodium ion concentration). : 0.5 mol / L), a desulfurization agent (VII) was obtained in the same manner as in Example 4. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
- Example 7 The amount of water in the acidic solution A is 1,000 mL (pH 4.8, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water in the alkaline solution B is 1,000 mL (pH 11.4, sodium ion concentration).
- the desulfurization agent (VIII) was obtained in the same manner as in Example 4 except that the calcination was performed at 280 ° C. for 2 hours. Further, an oil passage test for hydrocarbon oil was conducted in the same manner as in Comparative Example 1 except that the reduction temperature was 250 ° C. The results are shown in Table 1.
- the desulfurization agents of the examples according to the present invention can exhibit a sufficient desulfurization effect over a long period of time even at a reaction temperature of 140 ° C.
- the desulfurization agent of Comparative Example 1 was prepared by adding an acidic solution to an alkaline solution to prepare a desulfurization agent, so that the crystallite diameters of nickel oxide and zinc oxide were too large, and as a result, the specific surface area was too small. The period during which the desulfurization rate can be maintained at 50% or more was short.
- Example 1 and Example 4 and Example 2 and Example 5 the desulfurization agent prepared using nickel sulfate and zinc sulfate as raw materials was obtained by using the crystallite diameters of nickel oxide and zinc oxide. Is small, the specific surface area is large, and it can be seen that the period during which the desulfurization rate is maintained at 50% or more is long.
Abstract
Disclosed is a desulfurizing agent which can stably and economically desulfurize a hydrocarbon oil for a long time under specific conditions. Also disclosed is a method for producing the desulfurizing agent. The desulfurizing agent is characterized in that nickel and zinc are contained therein in the form of oxides, that the specific surface area thereof is 70-200 m2/g, that the nickel oxide has a crystallite size of not more than 5 nm, that the zinc oxide has a crystallite size of not more than 15 nm, and that the total pore volume thereof is 0.35-1.00 mL/g. The method for producing the desulfurizing agent is characterized in that a precipitate is formed by dropping an alkali solution and an acidic solution containing nickel and zinc into water at the same time.
Description
本発明は、炭化水素油中の硫黄化合物を脱硫する際に用いる脱硫剤、該脱硫剤の製造方法、及び該脱硫剤を用いた炭化水素油の脱硫方法に関する。
The present invention relates to a desulfurizing agent used when desulfurizing sulfur compounds in hydrocarbon oil, a method for producing the desulfurizing agent, and a desulfurizing method for hydrocarbon oil using the desulfurizing agent.
２１世紀の自動車及びその燃料においては環境問題への対応が大きな課題であり、地球温暖化ガスであるＣＯ2排出削減とＮＯｘ等のいわゆる自動車排出ガス削減との両方の観点から、燃料の硫黄分低減が益々求められている。具体的には、ガソリンや軽油の硫黄分は、サルファー・フリー（硫黄分１０質量ｐｐｍ以下）に規制され、さらに低硫黄分、すなわちゼロ・サルファー（硫黄分１質量ｐｐｍ以下）の燃料油も求められている。
In the 21st century automobiles and their fuels, dealing with environmental issues is a major issue. From the viewpoint of reducing CO 2 emissions, which are global warming gases, and so-called automobile exhaust emissions such as NOx, the sulfur content of the fuel Reduction is increasingly required. Specifically, the sulfur content of gasoline and light oil is regulated to sulfur-free (sulfur content of 10 ppm by mass or less), and further low sulfur content, that is, zero sulfur (sulfur content of 1 ppm by mass or less) fuel oil is also sought. It has been.
従来、主に用いられてきた脱硫技術である水素化脱硫法（例えば、コバルト、ニッケル、モリブデンを担持したアルミナ触媒を用いて、高温高圧水素雰囲気下で脱硫する方法）を適用してガソリンや軽油などの燃料油に残存する硫黄化合物を除去し、硫黄分を１０質量ｐｐｍ以下、さらには１質量ｐｐｍ以下にするには、高温・高圧の反応である水素化脱硫反応において従来よりもさらに高温・高圧での操作が求められるため、エネルギー消費が大きくなり、また、水素消費量なども膨大になる。また、上記水素化脱硫において、空間速度を下げてマイルドな条件で反応させようとすると、膨大な触媒量を要する。そのため、水素化脱硫反応法を適用する場合には、いずれにせよ多大なコストアップとなることは避けられない。さらに、上記水素化脱硫を適用した場合、ガソリン基材については、オレフィン分まで水素化されてしまうため、オクタン価のロスが大きい。
Applying hydrodesulfurization, which is a desulfurization technique that has been used mainly in the past (for example, desulfurization in a high-temperature, high-pressure hydrogen atmosphere using an alumina catalyst supporting cobalt, nickel, and molybdenum), gasoline and diesel oil In order to remove the sulfur compounds remaining in the fuel oil and reduce the sulfur content to 10 ppm by mass or less, and further to 1 ppm by mass or less, the hydrodesulfurization reaction, which is a high temperature / high pressure reaction, has a higher Since operation at high pressure is required, energy consumption increases and hydrogen consumption also becomes enormous. Further, in the above hydrodesulfurization, if an attempt is made to react under mild conditions by reducing the space velocity, a huge amount of catalyst is required. Therefore, when the hydrodesulfurization reaction method is applied, any increase in cost is inevitable in any case. Furthermore, when the above hydrodesulfurization is applied, the gasoline base material is hydrogenated to the olefin content, resulting in a large octane loss.
この問題に対して、オクタン価のロスを抑制しながら接触分解ガソリン（流動接触分解装置から得られるガソリン留分）を脱硫するための脱硫剤として、酸化亜鉛、アルミナ及び真珠岩の混合物にニッケルを担持した脱硫剤が提案されている（特許文献１）。しかしながら、この脱硫剤では、比表面積が小さいため、十分な脱硫レベルが得られないと共に、３００℃以上の高い反応温度が必要となる。
In response to this problem, nickel is supported on a mixture of zinc oxide, alumina and nacre as a desulfurization agent for desulfurizing catalytic cracking gasoline (gasoline fraction obtained from fluid catalytic cracking unit) while suppressing octane loss. A desulfurizing agent has been proposed (Patent Document 1). However, since this desulfurizing agent has a small specific surface area, a sufficient desulfurization level cannot be obtained, and a high reaction temperature of 300 ° C. or higher is required.
一方、炭化水素油を特定の条件下で吸着剤と接触させて硫黄化合物を吸着させる工程と、吸着剤に水素を通気させることにより吸着剤から硫黄化合物を脱離させる工程とを繰り返すことにより、オレフィンの水素化反応など不要な反応を抑制しつつガソリンの基材となる炭化水素油に含まれる硫黄分を連続的に低減する方法が提案されている（特許文献２参照）。しかしながら、このような吸着剤を用いる方法も、水素非存在下であることや室温での脱硫であることによって頻繁に再生処理を行う必要があり、経済的な脱硫という観点からは必ずしも満足できる方法ではない。
On the other hand, by repeating the step of adsorbing the sulfur compound by contacting the hydrocarbon oil with the adsorbent under specific conditions and the step of desorbing the sulfur compound from the adsorbent by passing hydrogen through the adsorbent, There has been proposed a method for continuously reducing the sulfur content contained in hydrocarbon oil serving as a gasoline base material while suppressing unnecessary reactions such as olefin hydrogenation (see Patent Document 2). However, the method using such an adsorbent also needs to be frequently regenerated by being in the absence of hydrogen or by desulfurization at room temperature, and is always a satisfactory method from the viewpoint of economical desulfurization. is not.
これに対して、本発明者らは、ニッケルと亜鉛を含む脱硫剤を用いて特定の条件のもとで脱硫することで、接触分解ガソリンを高度に脱硫できることを見いだしている（特許文献３、４）。しかしながら、この方法では、３００℃と比較的高い反応温度が必要であり、経済的な脱硫という観点では十分とは言えなかった。また、使用する脱硫剤の寿命が十分ではないため、水素による活性回復処理又は新しい脱硫剤との交換までの期間が比較的短いという問題もあった。
In contrast, the present inventors have found that catalytic cracking gasoline can be highly desulfurized by desulfurization under specific conditions using a desulfurization agent containing nickel and zinc (Patent Document 3, 4). However, this method requires a relatively high reaction temperature of 300 ° C., which is not sufficient from the viewpoint of economical desulfurization. In addition, since the life of the desulfurizing agent to be used is not sufficient, there is a problem that the period until the activity recovery treatment with hydrogen or the replacement with a new desulfurizing agent is relatively short.
上述したように、炭化水素油の硫黄分を１０質量ｐｐｍ、さらには１質量ｐｐｍ以下まで比較的マイルドな条件において長期間にわたって安定にかつ経済的に脱硫する方法は、未だ確立されていない。そこで、本発明は、特定の条件下で炭化水素油を長期間にわたって安定にかつ経済的に脱硫できる脱硫剤及びその製造方法を提供することを課題とする。
As described above, a method for desulfurizing stably and economically over a long period of time under a relatively mild condition where the sulfur content of the hydrocarbon oil is 10 ppm by mass or even 1 ppm by mass or less has not been established yet. Then, this invention makes it a subject to provide the desulfurization agent which can desulfurize hydrocarbon oil stably over a long term under specific conditions, and its manufacturing method.
本発明者らは、上記課題を解決するために鋭意研究した結果、炭化水素油を特定の条件のもと特定の脱硫剤によって処理することで長期間安定的に硫黄分を低減でき、また、特定の方法によってかかる脱硫剤を良好な生産性で製造できることを見出し、この発明に至った。
As a result of earnest research to solve the above problems, the present inventors can stably reduce the sulfur content for a long period of time by treating hydrocarbon oil with a specific desulfurizing agent under specific conditions, The inventors have found that such a desulfurizing agent can be produced with good productivity by a specific method, and have arrived at the present invention.
すなわち、本発明は、
（１）水に、アルカリ溶液とニッケル及び亜鉛を含有する酸性溶液とを同時に滴下して、沈殿を生成させることを特徴とする脱硫剤の製造方法である。
（２）ニッケル原料として硫酸ニッケルを用い、亜鉛原料として硫酸亜鉛を用いる前記（１）に記載の脱硫剤の製造方法である。
（３）ニッケル及び亜鉛を酸化物として含有し、比表面積が７０～２００ｍ2／ｇであり、ニッケル酸化物の結晶子径（Ｘ）が５ｎｍ以下、亜鉛酸化物の結晶子径（Ｙ）が１５ｎｍ以下であり、全細孔容積（Ｖ１）が０.３５～１.００ｍＬ／ｇであることを特徴とする脱硫剤である。
（４）ニッケルの含有量が１～３０質量％、亜鉛の含有量が３０～８０質量％であり、ニッケル原子に対する亜鉛原子の質量比（Ｚｎ／Ｎｉ）が１～１５である前記（３）に記載の脱硫剤である。
（５）硫黄分を２質量ｐｐｍ以上含有する炭化水素油を前記（３）又は（４）に記載の脱硫剤と水素存在下で、温度５０～３００℃、圧力０.２～５.０ＭＰａ、液空間速度が２.０ｈ-1を超える条件で接触させる炭化水素油の脱硫方法である。 That is, the present invention
(1) A method for producing a desulfurization agent, wherein an alkaline solution and an acidic solution containing nickel and zinc are simultaneously dropped into water to form a precipitate.
(2) The method for producing a desulfurization agent according to (1), wherein nickel sulfate is used as a nickel raw material and zinc sulfate is used as a zinc raw material.
(3) It contains nickel and zinc as oxides, the specific surface area is 70 to 200 m 2 / g, the crystallite diameter (X) of nickel oxide is 5 nm or less, and the crystallite diameter (Y) of zinc oxide is It is a desulfurization agent characterized by having a total pore volume (V1) of 0.35 to 1.00 mL / g and 15 nm or less.
(4) The above (3), wherein the nickel content is 1 to 30% by mass, the zinc content is 30 to 80% by mass, and the mass ratio of zinc atoms to nickel atoms (Zn / Ni) is 1 to 15 Is a desulfurizing agent.
(5) A hydrocarbon oil containing 2 mass ppm or more of sulfur content in the presence of the desulfurization agent and hydrogen described in (3) or (4) above at a temperature of 50 to 300 ° C., a pressure of 0.2 to 5.0 MPa, This is a hydrocarbon oil desulfurization method in which the liquid space velocity is contacted under a condition exceeding 2.0 h −1 .
（１）水に、アルカリ溶液とニッケル及び亜鉛を含有する酸性溶液とを同時に滴下して、沈殿を生成させることを特徴とする脱硫剤の製造方法である。
（２）ニッケル原料として硫酸ニッケルを用い、亜鉛原料として硫酸亜鉛を用いる前記（１）に記載の脱硫剤の製造方法である。
（３）ニッケル及び亜鉛を酸化物として含有し、比表面積が７０～２００ｍ2／ｇであり、ニッケル酸化物の結晶子径（Ｘ）が５ｎｍ以下、亜鉛酸化物の結晶子径（Ｙ）が１５ｎｍ以下であり、全細孔容積（Ｖ１）が０.３５～１.００ｍＬ／ｇであることを特徴とする脱硫剤である。
（４）ニッケルの含有量が１～３０質量％、亜鉛の含有量が３０～８０質量％であり、ニッケル原子に対する亜鉛原子の質量比（Ｚｎ／Ｎｉ）が１～１５である前記（３）に記載の脱硫剤である。
（５）硫黄分を２質量ｐｐｍ以上含有する炭化水素油を前記（３）又は（４）に記載の脱硫剤と水素存在下で、温度５０～３００℃、圧力０.２～５.０ＭＰａ、液空間速度が２.０ｈ-1を超える条件で接触させる炭化水素油の脱硫方法である。 That is, the present invention
(1) A method for producing a desulfurization agent, wherein an alkaline solution and an acidic solution containing nickel and zinc are simultaneously dropped into water to form a precipitate.
(2) The method for producing a desulfurization agent according to (1), wherein nickel sulfate is used as a nickel raw material and zinc sulfate is used as a zinc raw material.
(3) It contains nickel and zinc as oxides, the specific surface area is 70 to 200 m 2 / g, the crystallite diameter (X) of nickel oxide is 5 nm or less, and the crystallite diameter (Y) of zinc oxide is It is a desulfurization agent characterized by having a total pore volume (V1) of 0.35 to 1.00 mL / g and 15 nm or less.
(4) The above (3), wherein the nickel content is 1 to 30% by mass, the zinc content is 30 to 80% by mass, and the mass ratio of zinc atoms to nickel atoms (Zn / Ni) is 1 to 15 Is a desulfurizing agent.
(5) A hydrocarbon oil containing 2 mass ppm or more of sulfur content in the presence of the desulfurization agent and hydrogen described in (3) or (4) above at a temperature of 50 to 300 ° C., a pressure of 0.2 to 5.0 MPa, This is a hydrocarbon oil desulfurization method in which the liquid space velocity is contacted under a condition exceeding 2.0 h −1 .
本発明の脱硫剤を特定の条件下で適用する事により、炭化水素油の脱硫を長期間にわたって安定かつ経済的に実施する事ができる。また、かかる脱硫剤は、本発明の脱硫剤の製造方法により、良好な生産性で製造できる。
By applying the desulfurizing agent of the present invention under specific conditions, desulfurization of hydrocarbon oil can be carried out stably and economically over a long period of time. Such a desulfurizing agent can be produced with good productivity by the method for producing a desulfurizing agent of the present invention.
［脱硫剤］
本発明の脱硫剤はニッケルと亜鉛を含むものであり、例えば、共沈法によって亜鉛やニッケルなどの金属成分を沈殿させてろ過、洗浄し、成形、焼成等の工程を経ることによって得ることができる。 [Desulfurizing agent]
The desulfurization agent of the present invention contains nickel and zinc, and can be obtained by, for example, precipitating metal components such as zinc and nickel by a coprecipitation method, filtering, washing, molding, and firing. it can.
本発明の脱硫剤はニッケルと亜鉛を含むものであり、例えば、共沈法によって亜鉛やニッケルなどの金属成分を沈殿させてろ過、洗浄し、成形、焼成等の工程を経ることによって得ることができる。 [Desulfurizing agent]
The desulfurization agent of the present invention contains nickel and zinc, and can be obtained by, for example, precipitating metal components such as zinc and nickel by a coprecipitation method, filtering, washing, molding, and firing. it can.
脱硫剤総質量に対するニッケル含有量は、好ましくは１～３０質量％、より好ましくは３～２４質量％、特に好ましくは５～２０質量％である。また、脱硫剤総質量に対する亜鉛含有量は、好ましくは３０～８０質量％であり、より好ましくは４０～７５質量％、特に好ましくは４５～７０質量％である。ニッケル含有量が３０質量％を超えたり、亜鉛含有量が３０質量％未満の場合、脱硫剤の寿命が短くなるため好ましくない。一方、ニッケル含有量が２４質量％以下、亜鉛含有量が４０質量％以上の場合、脱硫剤の寿命が長く、また、ニッケル含有量が２０質量％以下、亜鉛含有量が４５質量％以上の場合、脱硫剤の寿命が特に長くなる。なお、ニッケル及び亜鉛の総含有量は、脱硫剤の総質量に対して３５～８５質量％、特には５０～８５質量％の範囲が好ましい。
The nickel content relative to the total mass of the desulfurizing agent is preferably 1 to 30% by mass, more preferably 3 to 24% by mass, and particularly preferably 5 to 20% by mass. Further, the zinc content with respect to the total mass of the desulfurizing agent is preferably 30 to 80% by mass, more preferably 40 to 75% by mass, and particularly preferably 45 to 70% by mass. When nickel content exceeds 30 mass% or zinc content is less than 30 mass%, since the lifetime of a desulfurization agent becomes short, it is unpreferable. On the other hand, when the nickel content is 24% by mass or less and the zinc content is 40% by mass or more, the life of the desulfurizing agent is long, and when the nickel content is 20% by mass or less and the zinc content is 45% by mass or more. In particular, the life of the desulfurizing agent is prolonged. The total content of nickel and zinc is preferably in the range of 35 to 85% by mass, particularly 50 to 85% by mass with respect to the total mass of the desulfurizing agent.
本発明の脱硫剤はニッケル及び亜鉛を酸化物として含有し、ニッケル、亜鉛及び酸素以外の元素を更に含んでもよいが、脱硫剤の寿命の観点からは、ニッケル、亜鉛及び酸素以外の元素の含有量は少ない方が好ましい。そのため、本発明の脱硫剤において、酸化ニッケル（ＮｉＯ）および酸化亜鉛（ＺｎＯ）の総含有量は、脱硫剤の総質量に対して好ましくは９０質量％以上、より好ましくは９４質量％以上、さらに好ましくは９６質量％以上、特に好ましくは９９質量％以上である。
The desulfurization agent of the present invention contains nickel and zinc as oxides and may further contain elements other than nickel, zinc and oxygen, but from the viewpoint of the life of the desulfurization agent, the inclusion of elements other than nickel, zinc and oxygen A smaller amount is preferred. Therefore, in the desulfurization agent of the present invention, the total content of nickel oxide (NiO) and zinc oxide (ZnO) is preferably 90% by mass or more, more preferably 94% by mass or more, further preferably based on the total mass of the desulfurization agent. Preferably it is 96 mass% or more, Most preferably, it is 99 mass% or more.
また、脱硫剤中のニッケル原子に対する亜鉛原子の質量比（Ｚｎ／Ｎｉ）は１～１５の範囲が好ましく、３～１２の範囲が更に好ましく、３～８の範囲が特に好ましい。ニッケル原子に対する亜鉛原子の質量比（Ｚｎ／Ｎｉ）が１未満では、脱硫剤の寿命が著しく短くなり好ましくなく、１５を超えても脱硫剤の寿命が短くなり好ましくない。
The mass ratio of zinc atoms to nickel atoms (Zn / Ni) in the desulfurizing agent is preferably in the range of 1 to 15, more preferably in the range of 3 to 12, and particularly preferably in the range of 3 to 8. When the mass ratio of zinc atom to nickel atom (Zn / Ni) is less than 1, the life of the desulfurizing agent is remarkably shortened, and when it exceeds 15, the life of the desulfurizing agent is shortened.
本発明の脱硫剤は、ニッケル酸化物の結晶子径（Ｘ）が５.０ｎｍ以下、好ましくは４.５ｎｍ以下、より好ましくは３.０ｎｍ以下であり、また、亜鉛酸化物の結晶子径（Ｙ）が１５ｎｍ以下、好ましくは１２ｎｍ以下、より好ましくは１０ｎｍ以下、特に好ましくは８ｎｍ以下である。ニッケル酸化物の結晶子径が５.０ｎｍを超えると、ニッケルと炭化水素油との接触効率が低下して硫黄を取り込む能力が低下するため好ましくなく、一方、亜鉛酸化物の結晶子径が１５ｎｍを超えると、酸化亜鉛が硫黄を固定化する効率が低下するため好ましくない。
In the desulfurizing agent of the present invention, the crystallite diameter (X) of nickel oxide is 5.0 nm or less, preferably 4.5 nm or less, more preferably 3.0 nm or less, and the crystallite diameter of zinc oxide ( Y) is 15 nm or less, preferably 12 nm or less, more preferably 10 nm or less, and particularly preferably 8 nm or less. When the crystallite diameter of nickel oxide exceeds 5.0 nm, the contact efficiency between nickel and hydrocarbon oil is reduced, and the ability to take in sulfur is reduced. On the other hand, the crystallite diameter of zinc oxide is 15 nm. If it exceeds 1, zinc oxide is not preferable because the efficiency of fixing sulfur decreases.
また、亜鉛酸化物の結晶子径（Ｙ）とニッケル酸化物の結晶子径（Ｘ）の比（Ｙ／Ｘ）は２以上であることが好ましく、２.５以上であることがより好ましい。亜鉛酸化物の結晶子径とニッケル酸化物の結晶子径の比が２未満であると、ニッケルと炭化水素油との接触効率が低下して炭化水素油中の硫黄化合物を脱硫剤中に取り込む能力が低下すると同時に、亜鉛が硫黄を固定化する効率が低下するため好ましくない。
The ratio (Y / X) of the crystallite diameter (Y) of the zinc oxide and the crystallite diameter (X) of the nickel oxide is preferably 2 or more, and more preferably 2.5 or more. When the ratio of the crystallite diameter of zinc oxide to the crystallite diameter of nickel oxide is less than 2, the contact efficiency between nickel and hydrocarbon oil decreases, and the sulfur compound in the hydrocarbon oil is taken into the desulfurization agent. At the same time as the ability is reduced, the efficiency with which zinc fixes sulfur is reduced.
本発明の脱硫剤は、全細孔容積（Ｖ１）が０.３５～１.００ｍＬ／ｇ、好ましくは０.４５～１.００ｍＬ／ｇ、より好ましくは０.５０～１.００ｍＬ／ｇ、特に好ましくは０.６０～１.００ｍＬ／ｇである。脱硫剤の全細孔容積が０.３５ｍＬ／ｇ未満では、主として脱硫反応が起こる空間が少なくなるため好ましくない。一方、１.００ｍＬ／ｇを超えると、脱硫剤の嵩密度が小さくなって一定容量の反応器に充填できる質量が少なくなり寿命が短くなるため好ましくない。
The desulfurization agent of the present invention has a total pore volume (V1) of 0.35 to 1.00 mL / g, preferably 0.45 to 1.00 mL / g, more preferably 0.50 to 1.00 mL / g, Particularly preferred is 0.60 to 1.00 mL / g. If the total pore volume of the desulfurizing agent is less than 0.35 mL / g, the space in which the desulfurization reaction occurs mainly decreases, which is not preferable. On the other hand, if it exceeds 1.00 mL / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged into a reactor having a constant capacity is reduced, which is not preferable.
本発明の脱硫剤は、細孔径が２～３０ｎｍである細孔の容積（Ｖ２）が好ましくは０.０８～０.５０ｍＬ／ｇ、より好ましくは０.１５～０.４０ｍＬ／ｇ、特に好ましくは０.２０～０.３０ｍＬ／ｇである。細孔径が２～３０ｎｍの細孔の容積が０.０８ｍＬ／ｇ未満であると、主として脱硫反応が起こる空間が少なくなるため好ましくない。また、細孔径が２～３０ｎｍの細孔の容積が０.５０ｍＬ／ｇを超えると、脱硫剤の嵩密度が小さくなって一定容量の反応器に充填できる質量が少なくなり寿命が短くなるため好ましくない。
The desulfurization agent of the present invention preferably has a pore volume (V2) having a pore diameter of 2 to 30 nm of 0.08 to 0.50 mL / g, more preferably 0.15 to 0.40 mL / g, and particularly preferably. Is 0.20 to 0.30 mL / g. If the volume of the pores having a pore diameter of 2 to 30 nm is less than 0.08 mL / g, the space in which the desulfurization reaction occurs mainly decreases, which is not preferable. In addition, if the volume of the pores having a pore diameter of 2 to 30 nm exceeds 0.50 mL / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged in a reactor with a constant volume is reduced, resulting in a shorter life. Absent.
本発明の脱硫剤において、全細孔容積（Ｖ１）に対する細孔径が２～３０ｎｍである細孔の容積（Ｖ２）の比（Ｖ２／Ｖ１）は、好ましくは０.１５～１.００、より好ましくは０.３０～０.６０である。該比（Ｖ２／Ｖ１）が０.１５未満であると、炭化水素油と細孔中のニッケルとの接触効率が悪くなったり、脱硫剤を工業的に使用する際に十分な強度が得られなくなるため好ましくない。該比（Ｖ２／Ｖ１）が０.６０以下であれば、径の大きな細孔と小さな細孔との適度な組み合わせにより、好ましい接触効率が得られる。
In the desulfurization agent of the present invention, the ratio (V2 / V1) of the pore volume (V2) having a pore diameter of 2 to 30 nm with respect to the total pore volume (V1) is preferably 0.15 to 1.00. It is preferably 0.30 to 0.60. When the ratio (V2 / V1) is less than 0.15, the contact efficiency between the hydrocarbon oil and nickel in the pores deteriorates, or sufficient strength is obtained when the desulfurizing agent is used industrially. It is not preferable because it disappears. When the ratio (V2 / V1) is 0.60 or less, preferable contact efficiency can be obtained by an appropriate combination of pores having a large diameter and small pores.
本発明の脱硫剤は、比表面積が７０ｍ2／ｇ以上であり、好ましくは７５ｍ2／ｇ以上、より好ましくは９０ｍ2／ｇ以上である。脱硫剤の比表面積が７０ｍ2／ｇ未満では、脱硫剤の寿命が短くなり好ましくない。また、比表面積は２００ｍ2／ｇ以下であり、好ましくは１７０ｍ2／ｇ以下であり、より好ましくは１５０ｍ2／ｇ以下である。脱硫剤の比表面積が２００ｍ2／ｇを超えると、脱硫剤の嵩密度が小さくなって一定容量の反応器に充填できる質量が少なくなり寿命が短くなるため好ましくない。
The desulfurizing agent of the present invention has a specific surface area of 70 m 2 / g or more, preferably 75 m 2 / g or more, more preferably 90 m 2 / g or more. When the specific surface area of the desulfurizing agent is less than 70 m 2 / g, the life of the desulfurizing agent is shortened, which is not preferable. Moreover, a specific surface area is 200 m < 2 > / g or less, Preferably it is 170 m < 2 > / g or less, More preferably, it is 150 m < 2 > / g or less. When the specific surface area of the desulfurizing agent exceeds 200 m 2 / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged in a reactor having a certain capacity is reduced, which is not preferable.
本発明の脱硫剤は、水素雰囲気下２００～３５０℃、特には２５０～３００℃で処理して用いられることが好ましい。水素雰囲気下での処理温度が２００℃未満では、ニッケルが還元されないため好ましくない。また、該処理温度が３５０℃を超えると、ニッケルがシンタリングしてしまって活性が低くなるため好ましくない。
The desulfurizing agent of the present invention is preferably used after being treated at 200 to 350 ° C., particularly 250 to 300 ° C. in a hydrogen atmosphere. A treatment temperature under a hydrogen atmosphere of less than 200 ° C. is not preferable because nickel is not reduced. On the other hand, when the treatment temperature exceeds 350 ° C., nickel is sintered and the activity is lowered, which is not preferable.
本発明の脱硫剤は、共沈法により調製されることが好ましい。共沈法による調製方法は、アルミナのような多孔質担体に亜鉛やニッケルなどの金属成分を含浸、担持して焼成する製造方法に比べて脱硫に有効なニッケルと亜鉛を脱硫剤中に多く含ませることができるため脱硫剤の長寿命化を達成できる。また、酸化亜鉛担体にニッケルを含浸する方法は、酸化亜鉛担体の細孔の閉塞により比表面積及び細孔容積が減少し、脱硫活性が低くなるため好ましくない。
The desulfurizing agent of the present invention is preferably prepared by a coprecipitation method. The preparation method by coprecipitation method contains more nickel and zinc effective for desulfurization in the desulfurization agent than the production method in which a porous carrier such as alumina is impregnated with metal components such as zinc and nickel, and is fired. Therefore, the life of the desulfurizing agent can be extended. In addition, the method of impregnating the zinc oxide support with nickel is not preferable because the specific surface area and the pore volume are reduced due to the blockage of the pores of the zinc oxide support and the desulfurization activity is lowered.
本発明の脱硫剤は、水に、ニッケル及び亜鉛を含有する酸性溶液とアルカリ溶液とを同時に滴下して、ニッケルと亜鉛を含有する沈殿を生成させることにより調製されることが特に好ましい。ここで、使用する水は、ｐＨが６.０～８.０であることが好ましい。なお、本発明において、酸性溶液とアルカリ溶液との同時滴下とは、酸性溶液の８０容量％以上の量、好ましくは９０容量％以上の量を滴下している期間、酸性溶液を滴下しつつアルカリ溶液が滴下されており、且つ、アルカリ溶液の８０容量％以上の量、好ましくは９０容量％以上の量を滴下している期間、アルカリ溶液を滴下しつつ酸性溶液が滴下されていることを指し、酸性溶液及びアルカリ溶液の滴下の開始と終了が完全に一致していることを要さない。
The desulfurization agent of the present invention is particularly preferably prepared by simultaneously dropping an acidic solution and an alkaline solution containing nickel and zinc into water to produce a precipitate containing nickel and zinc. Here, the water used preferably has a pH of 6.0 to 8.0. In the present invention, the simultaneous dropping of the acidic solution and the alkaline solution means that the acidic solution is dropped while the acidic solution is dropped for a period of 80% by volume or more, preferably 90% by volume or more. It means that the acidic solution is being dropped while the alkaline solution is being dropped while the solution is being dropped and the amount of 80% by volume or more, preferably 90% by volume or more of the alkaline solution is being dropped. In addition, it is not necessary that the start and end of the dropping of the acidic solution and the alkaline solution completely coincide with each other.
上記ニッケルと亜鉛を含む酸性溶液は、亜鉛やニッケルの硫酸塩、硝酸塩、酢酸塩等を水で溶解することにより得られ、そのｐＨは好ましくは５.０以下、より好ましくは４.５以下であり、特に好ましくは４.０以下であり、好ましくは０.５以上、より好ましくは２.０以上である。酸性溶液のｐＨが５.０を超えると、溶液中での核の生成速度が遅くなって結晶が成長し易くなり、ニッケルと亜鉛の分散度が低くなるため好ましくない。一方、酸性溶液のｐＨが低すぎると、特に０.５未満であると、共沈溶液の液量が少なくなって粘度が高く撹拌しにくくなり均一な物性のものが得られにくいため好ましくない。
The acidic solution containing nickel and zinc is obtained by dissolving zinc, nickel sulfate, nitrate, acetate, etc. with water, and the pH is preferably 5.0 or less, more preferably 4.5 or less. Yes, particularly preferably 4.0 or less, preferably 0.5 or more, more preferably 2.0 or more. If the pH of the acidic solution exceeds 5.0, it is not preferable because the nucleation rate in the solution becomes slow and the crystal grows easily, and the degree of dispersion of nickel and zinc becomes low. On the other hand, if the pH of the acidic solution is too low, particularly less than 0.5, the amount of the coprecipitation solution is small, the viscosity is high and stirring is difficult, and it is difficult to obtain a uniform physical property, which is not preferable.
上記酸性溶液中のニッケル及び亜鉛の総濃度は、０.３～３.０ｍｏｌ／Ｌの範囲が好ましく、０.３～１.０ｍｏｌ／Ｌの範囲が更に好ましい。酸性溶液中のニッケル及び亜鉛の総濃度を３.０ｍｏｌ／Ｌ以下とすることで、ニッケル酸化物の結晶子径及び亜鉛酸化物の結晶子径を十分に小さくすることができる。一方、酸性溶液中のニッケル及び亜鉛の総濃度が０.３ｍｏｌ／Ｌ未満では、脱硫剤の生産性が低下する。なお、酸性溶液の滴下量は、水１Ｌに対して０.３～４.０Ｌの範囲が好ましく、１.０～３.５Ｌの範囲が更に好ましい。
The total concentration of nickel and zinc in the acidic solution is preferably in the range of 0.3 to 3.0 mol / L, and more preferably in the range of 0.3 to 1.0 mol / L. By setting the total concentration of nickel and zinc in the acidic solution to 3.0 mol / L or less, the crystallite diameter of nickel oxide and the crystallite diameter of zinc oxide can be sufficiently reduced. On the other hand, when the total concentration of nickel and zinc in the acidic solution is less than 0.3 mol / L, the productivity of the desulfurizing agent is lowered. The dropping amount of the acidic solution is preferably in the range of 0.3 to 4.0 L with respect to 1 L of water, and more preferably in the range of 1.0 to 3.5 L.
上記酸性溶液は、ニッケル原料として硫酸ニッケルを用い、亜鉛原料として硫酸亜鉛を用いて調製されることが好ましい。ニッケル原料として硫酸ニッケルを用い、亜鉛原料として硫酸亜鉛を用いて脱硫剤を調製することで、脱硫剤の比表面積を増大させ、更に、ニッケル酸化物の結晶子径及び亜鉛酸化物の結晶子径を小さくすることができる。なお、原料として使用する硫酸ニッケル及び硫酸亜鉛は、水和物でも無水物でもよい。
The acid solution is preferably prepared using nickel sulfate as the nickel raw material and zinc sulfate as the zinc raw material. The specific surface area of the desulfurizing agent is increased by preparing the desulfurizing agent using nickel sulfate as the nickel raw material and zinc sulfate as the zinc raw material. Furthermore, the crystallite diameter of the nickel oxide and the crystallite diameter of the zinc oxide Can be reduced. The nickel sulfate and zinc sulfate used as raw materials may be hydrates or anhydrides.
また、上記アルカリ溶液には、炭酸ナトリウム、炭酸アンモニウム等を用いることができるが、なかでも炭酸ナトリウムを用いることが好ましい。該アルカリ溶液のｐＨは、１１～１３が好ましい。
Further, sodium carbonate, ammonium carbonate, or the like can be used for the alkaline solution, and sodium carbonate is preferably used. The pH of the alkaline solution is preferably 11-13.
上記アルカリ溶液中の陽イオン濃度は、０.３～４.０ｍｏｌ／Ｌの範囲が好ましく、０.３～１.５ｍｏｌ／Ｌの範囲が更に好ましい。ここで、アルカリ溶液中の陽イオンとしては、ナトリウムイオン、アンモニウムイオン等が挙げられる。なお、アルカリ溶液中の陽イオン濃度を４.０ｍｏｌ／Ｌ以下とすることで、ニッケル酸化物の結晶子径及び亜鉛酸化物の結晶子径を十分に小さくすることができる。一方、アルカリ溶液中の陽イオン濃度が０.３ｍｏｌ／Ｌ未満では、脱硫剤の生産性が低下する。なお、アルカリ溶液の滴下量は、水１Ｌに対して０.３～４.０Ｌの範囲が好ましく、１.０～３.５Ｌの範囲が更に好ましい。
The cation concentration in the alkaline solution is preferably in the range of 0.3 to 4.0 mol / L, and more preferably in the range of 0.3 to 1.5 mol / L. Here, examples of the cation in the alkaline solution include sodium ion and ammonium ion. In addition, the crystallite diameter of nickel oxide and the crystallite diameter of zinc oxide can be made sufficiently small by setting the cation concentration in the alkaline solution to 4.0 mol / L or less. On the other hand, when the cation concentration in the alkaline solution is less than 0.3 mol / L, the productivity of the desulfurizing agent is lowered. The dropping amount of the alkaline solution is preferably in the range of 0.3 to 4.0 L with respect to 1 L of water, and more preferably in the range of 1.0 to 3.5 L.
共沈させる際のｐＨは、７.０～９.０が好ましい。共沈させる際のｐＨが７.０未満では、ニッケルの一部が沈殿しないため好ましくない。一方、共沈させる際のｐＨが９.０を超えると、沈殿中にアルカリ成分が残存しやすいため好ましくない。また、水に酸性溶液及びアルカリ溶液を滴下した後は、１時間以上継続して撹拌することが望ましい。更に、共沈させる際の液温は、アルカリ成分の溶解度の点から５０～７０℃の範囲が好ましい。
The pH during coprecipitation is preferably 7.0 to 9.0. If the pH during coprecipitation is less than 7.0, a part of nickel does not precipitate, which is not preferable. On the other hand, if the pH during coprecipitation exceeds 9.0, an alkaline component tends to remain in the precipitation, which is not preferable. Moreover, after dropping the acidic solution and the alkaline solution into water, it is desirable to continuously stir for 1 hour or more. Further, the liquid temperature at the time of coprecipitation is preferably in the range of 50 to 70 ° C. from the viewpoint of the solubility of the alkali component.
上記の工程で生成した沈殿物は、ろ過後に乾燥する必要があるが、乾燥温度は１００～２００℃が好ましい。また、その後の焼成における温度は３００～４００℃が好ましく、３００～３５０℃が更に好ましい。焼成温度が３００℃未満では、ニッケルおよび亜鉛成分が沈殿した際の塩が完全に分解しないため好ましくない。一方、焼成温度が４００℃を超えると、塩が分解してできるニッケルと亜鉛の酸化物の結晶化が進み、ニッケルの亜鉛に対する分散度が低くなるため好ましくない。
The precipitate generated in the above step needs to be dried after filtration, but the drying temperature is preferably 100 to 200 ° C. Further, the temperature in the subsequent firing is preferably 300 to 400 ° C., more preferably 300 to 350 ° C. A calcination temperature of less than 300 ° C. is not preferable because the salt is not completely decomposed when the nickel and zinc components are precipitated. On the other hand, if the firing temperature exceeds 400 ° C., crystallization of nickel and zinc oxide formed by decomposition of the salt proceeds, and the degree of dispersion of nickel with respect to zinc is lowered, which is not preferable.
なお、本発明において、脱硫剤とは、硫黄収着機能を持った脱硫剤をいう。ここでいう硫黄収着機能を持った脱硫剤とは、有機硫黄化合物中の硫黄原子を脱硫剤に固定化するとともに、有機硫黄化合物中の硫黄原子以外の炭化水素残基については有機硫黄化合物中の炭素－硫黄結合が開裂することによって脱硫剤から脱離させる機能をもった脱硫剤をいう。この有機硫黄化合物中の炭化水素残基が脱離する際には、硫黄との結合が開裂した炭素に、系内に存在する水素が付加する。したがって、有機硫黄化合物から硫黄原子が除かれた炭化水素化合物が生成物として得られることになる。ただし、硫黄原子が除かれた炭化水素化合物が、さらに水素化、異性化、分解等の反応を受け、別の化合物になっても構わない。一方、硫黄は脱硫剤に固定化されるため、水素化精製処理とは異なり、生成物として硫化水素などの硫黄化合物を発生しない。そのため、硫化水素を除去する設備が不要となり、経済的に有利である。
In the present invention, the desulfurizing agent refers to a desulfurizing agent having a sulfur sorption function. The desulfurization agent having a sulfur sorption function here is to fix the sulfur atom in the organic sulfur compound to the desulfurization agent, and for hydrocarbon residues other than the sulfur atom in the organic sulfur compound in the organic sulfur compound. A desulfurization agent having a function of desorbing from a desulfurization agent by cleavage of the carbon-sulfur bond. When the hydrocarbon residue in the organic sulfur compound is eliminated, hydrogen present in the system is added to the carbon whose bond with sulfur is cleaved. Therefore, a hydrocarbon compound obtained by removing sulfur atoms from the organic sulfur compound is obtained as a product. However, the hydrocarbon compound from which the sulfur atom is removed may be further subjected to a reaction such as hydrogenation, isomerization, or decomposition to become another compound. On the other hand, since sulfur is fixed to the desulfurizing agent, unlike a hydrorefining treatment, sulfur compounds such as hydrogen sulfide are not generated as a product. This eliminates the need for equipment for removing hydrogen sulfide, which is economically advantageous.
［炭化水素油］
本発明による脱硫方法の対象となる原料の炭化水素油は、硫黄分を含む炭化水素油であれば特に限定されないが、硫黄分を２質量ｐｐｍ以上含むものが好ましく、より好ましくは２～１,０００質量ｐｐｍ、より一層好ましくは２～１００質量ｐｐｍ、特に好ましくは２～４０質量ｐｐｍ含むものである。硫黄分が１,０００質量ｐｐｍを超えると、脱硫剤の寿命が短くなり好ましくない。 [Hydrocarbon oil]
The raw material hydrocarbon oil to be subjected to the desulfurization method according to the present invention is not particularly limited as long as it is a hydrocarbon oil containing a sulfur content, but preferably contains 2 ppm by mass or more of sulfur content, more preferably 2 to 1, 000 ppm by mass, more preferably 2 to 100 ppm by mass, particularly preferably 2 to 40 ppm by mass. When the sulfur content exceeds 1,000 ppm by mass, the life of the desulfurizing agent is shortened, which is not preferable.
本発明による脱硫方法の対象となる原料の炭化水素油は、硫黄分を含む炭化水素油であれば特に限定されないが、硫黄分を２質量ｐｐｍ以上含むものが好ましく、より好ましくは２～１,０００質量ｐｐｍ、より一層好ましくは２～１００質量ｐｐｍ、特に好ましくは２～４０質量ｐｐｍ含むものである。硫黄分が１,０００質量ｐｐｍを超えると、脱硫剤の寿命が短くなり好ましくない。 [Hydrocarbon oil]
The raw material hydrocarbon oil to be subjected to the desulfurization method according to the present invention is not particularly limited as long as it is a hydrocarbon oil containing a sulfur content, but preferably contains 2 ppm by mass or more of sulfur content, more preferably 2 to 1, 000 ppm by mass, more preferably 2 to 100 ppm by mass, particularly preferably 2 to 40 ppm by mass. When the sulfur content exceeds 1,000 ppm by mass, the life of the desulfurizing agent is shortened, which is not preferable.
原料の炭化水素油として、具体的には、製油所などで一般的に生産されるＬＰＧ留分、ガソリン留分、ナフサ留分、灯油留分、軽油留分などに相当する基材が挙げられる。ＬＰＧ留分は、プロパン、プロピレン、ブタン、ブチレンなどを主成分とする燃料ガスおよび工業用原料ガスである。該ＬＰＧ留分は、通常は、ＬＰＧ（液化石油ガス）と称されるように、加圧下の球状タンクに液相の状態で貯蔵されるか、大気圧近傍の低温下にて、液相の状態で貯蔵される。上記ガソリン留分は、一般に炭素数４～１１の炭化水素を主体とし、密度（１５℃）が０.７８３ｇ／ｃｍ3以下、１０％留出温度が２４℃以上、９０％留出温度が１８０℃以下である。上記ナフサ留分は、ガソリン留分の構成成分（ホールナフサ、軽質ナフサ、重質ナフサ、又はそれらの水素化脱硫ナフサ）あるいはガソリン基材を製造する接触改質の原料（脱硫重質ナフサ）となる成分などの総称であり、沸点範囲がガソリン留分と殆ど同じ範囲か、ガソリン留分の沸点範囲に包含されるものである。したがって、ガソリン留分と同じ意味で用いられることも多い。上記灯油留分は、一般に沸点範囲１５０～２８０℃の炭化水素混合物である。上記軽油留分は、一般に沸点範囲１９０～３５０℃の炭化水素混合物である。
Specific examples of the hydrocarbon oil as a raw material include base materials corresponding to LPG fraction, gasoline fraction, naphtha fraction, kerosene fraction, light oil fraction, etc. that are generally produced in refineries and the like. . The LPG fraction is a fuel gas mainly composed of propane, propylene, butane, butylene, and industrial raw material gas. The LPG fraction is usually stored in a liquid phase in a spherical tank under pressure as called LPG (liquefied petroleum gas) or at a low temperature near atmospheric pressure. Stored in state. The gasoline fraction is generally composed mainly of hydrocarbons having 4 to 11 carbon atoms, the density (15 ° C.) is 0.783 g / cm 3 or less, the 10% distillation temperature is 24 ° C. or more, and the 90% distillation temperature is 180 °. It is below ℃. The naphtha fraction is composed of gasoline fraction components (hole naphtha, light naphtha, heavy naphtha, or hydrodesulfurized naphtha thereof) or a raw material for catalytic reforming (desulfurized heavy naphtha) for producing a gasoline base. The boiling point range is almost the same as that of the gasoline fraction or it is included in the boiling range of the gasoline fraction. Therefore, it is often used in the same meaning as the gasoline fraction. The kerosene fraction is generally a hydrocarbon mixture having a boiling range of 150 to 280 ° C. The gas oil fraction is generally a hydrocarbon mixture having a boiling range of 190 to 350 ° C.
また、原料の炭化水素油は、製油所などで生産されるものには限らず、硫黄分を２～１,０００質量ｐｐｍ含有し、石油化学から生産される石油（炭化水素）ガスや前記と同様な沸点範囲を有する留分でも構わない。好ましく使用できる炭化水素油としては、重質油を熱分解又は接触分解して得られた炭化水素をさらに分留したものが挙げられる。
The hydrocarbon oil as a raw material is not limited to those produced at refineries and the like, but contains 2 to 1,000 mass ppm of sulfur, petroleum (hydrocarbon) gas produced from petrochemical, A fraction having a similar boiling range may be used. Examples of hydrocarbon oils that can be preferably used include those obtained by further fractionating hydrocarbons obtained by pyrolysis or catalytic cracking of heavy oils.
なお、本発明による脱硫方法の対象となる原料の炭化水素油として特に好ましいのは、接触分解ガソリンや軽油留分である。接触分解ガソリンはオレフィンを多く含むため、一般的に行われる水素化脱硫触媒による水素化精製ではオレフィン分が水素化されてオクタン価が大きく低下してしまうが、本発明の脱硫方法ではオレフィン分はほとんど水素化されない。また、軽油留分には芳香族分が多く含まれるため、一般的に行われる水素化脱硫触媒による水素化精製では芳香族分が水素化されるため水素の消費量が多いが、本発明の脱硫方法では芳香族分はほとんど水素化されない。ただし、軽油留分の場合、通常硫黄分が１０,０００質量ｐｐｍ程度含まれるため、水素化脱硫触媒による水素化精製で硫黄分をある程度低減、具体的には５～５０質量ｐｐｍ程度まで低減したのち、本発明の脱硫方法を適用することが好ましい。硫黄分が多いと、脱硫剤の寿命が大きく低下してしまう。
Particularly preferred as the hydrocarbon oil as the raw material to be subjected to the desulfurization method according to the present invention is catalytic cracked gasoline and light oil fraction. Since catalytically cracked gasoline contains a large amount of olefins, hydrorefining with a hydrodesulfurization catalyst that is generally performed hydrogenates the olefin content and greatly reduces the octane number. However, in the desulfurization method of the present invention, almost no olefin content is present. Not hydrogenated. In addition, since the gas oil fraction contains a large amount of aromatics, the amount of hydrogen consumed is large because the aromatics are hydrogenated in the hydrorefining using a hydrodesulfurization catalyst that is generally performed. In the desulfurization method, the aromatic content is hardly hydrogenated. However, in the case of diesel oil fraction, since the sulfur content is usually about 10,000 mass ppm, the sulfur content was reduced to some extent by hydrorefining with a hydrodesulfurization catalyst, specifically about 5 to 50 mass ppm. Thereafter, it is preferable to apply the desulfurization method of the present invention. When there is much sulfur content, the lifetime of a desulfurization agent will fall large.
［脱硫反応条件］
炭化水素油を脱硫剤と接触させる条件としては、反応温度が５０～３００℃であり、好ましくは１００～３００℃である。反応温度が５０℃未満であると、脱硫速度が低下し、効率的に脱硫ができず好ましくない。また、反応温度が３００℃を超えると、脱硫剤がシンタリングし、脱硫速度、脱硫容量とも低下し好ましくない。なお、反応温度が１００℃以上であれば、脱硫速度が十分に高く、効率的に脱硫を行うことができる。 [Desulfurization reaction conditions]
As conditions for bringing the hydrocarbon oil into contact with the desulfurizing agent, the reaction temperature is 50 to 300 ° C., preferably 100 to 300 ° C. When the reaction temperature is less than 50 ° C., the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed. On the other hand, when the reaction temperature exceeds 300 ° C., the desulfurizing agent is sintered, and both the desulfurization rate and the desulfurization capacity are lowered, which is not preferable. If the reaction temperature is 100 ° C. or higher, the desulfurization rate is sufficiently high and desulfurization can be performed efficiently.
炭化水素油を脱硫剤と接触させる条件としては、反応温度が５０～３００℃であり、好ましくは１００～３００℃である。反応温度が５０℃未満であると、脱硫速度が低下し、効率的に脱硫ができず好ましくない。また、反応温度が３００℃を超えると、脱硫剤がシンタリングし、脱硫速度、脱硫容量とも低下し好ましくない。なお、反応温度が１００℃以上であれば、脱硫速度が十分に高く、効率的に脱硫を行うことができる。 [Desulfurization reaction conditions]
As conditions for bringing the hydrocarbon oil into contact with the desulfurizing agent, the reaction temperature is 50 to 300 ° C., preferably 100 to 300 ° C. When the reaction temperature is less than 50 ° C., the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed. On the other hand, when the reaction temperature exceeds 300 ° C., the desulfurizing agent is sintered, and both the desulfurization rate and the desulfurization capacity are lowered, which is not preferable. If the reaction temperature is 100 ° C. or higher, the desulfurization rate is sufficiently high and desulfurization can be performed efficiently.
また、反応圧力は、ゲージ圧で０.２～５.０ＭＰａ、好ましくは０.２～３.０ＭＰａ、特に好ましくは０.２～２.０ＭＰａである。反応圧力が０.２ＭＰａ未満だと、脱硫速度が低下し、効率的に脱硫ができず好ましくない。また、反応圧力が５.０ＭＰａを超えると、炭化水素油中に含まれるオレフィン分や芳香族分の水素化等の副反応が進行し好ましくない。なお、反応圧力が３.０ＭＰａ以下であれば、オレフィン分や芳香族分の水素化等の副反応を十分に抑制でき、２.０ＭＰａ以下であれば、これら副反応を確実に防止できる。
The reaction pressure is 0.2 to 5.0 MPa in gauge pressure, preferably 0.2 to 3.0 MPa, particularly preferably 0.2 to 2.0 MPa. When the reaction pressure is less than 0.2 MPa, the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed. On the other hand, when the reaction pressure exceeds 5.0 MPa, side reactions such as hydrogenation of olefins and aromatics contained in the hydrocarbon oil proceed, which is not preferable. If the reaction pressure is 3.0 MPa or less, side reactions such as hydrogenation of olefins and aromatics can be sufficiently suppressed, and if it is 2.0 MPa or less, these side reactions can be reliably prevented.
更に、液空間速度（ＬＨＳＶ）は、２.０ｈ-1を超え、好ましくは２.１ｈ-1以上である。また、ＬＨＳＶは、好ましくは５０.０ｈ-1以下、より好ましくは２０.０ｈ-1以下、より一層好ましくは１０.０ｈ-1以下である。ＬＨＳＶが２.０ｈ-1以下だと、通油量が制限されたり、脱硫リアクターが大きくなり過ぎたりするため、経済的に脱硫できず好ましくない。また、ＬＨＳＶが５０.０ｈ-1を超えると、脱硫するのに十分な接触時間が得られず、脱硫率が低下するため好ましくない。なお、ＬＨＳＶが２.１ｈ-1以上であれば、十分経済的に脱硫を行うことができ、ＬＨＳＶが２０.０ｈ-1以下であれば、接触時間が十分に長いため、脱硫率が向上し、１０.０ｈ-1以下であれば、脱硫率が特に高くなる。
Furthermore, the liquid hourly space velocity (LHSV) exceeds 2.0 h −1 , preferably 2.1 h −1 or more. The LHSV is preferably 50.0 h −1 or less, more preferably 20.0 h −1 or less, and even more preferably 10.0 h −1 or less. If the LHSV is 2.0 h −1 or less, the amount of oil passing is limited or the desulfurization reactor becomes too large, so it is not preferable because it cannot economically desulfurize. On the other hand, if LHSV exceeds 50.0 h −1 , a contact time sufficient for desulfurization cannot be obtained, and the desulfurization rate decreases, which is not preferable. If LHSV is 2.1 h −1 or more, desulfurization can be performed sufficiently economically, and if LHSV is 20.0 h −1 or less, the contact time is sufficiently long, so that the desulfurization rate is improved. If it is 10.0 h −1 or less, the desulfurization rate is particularly high.
水素／油比は特に限定しないが、接触分解ガソリンのようにオレフィンを多く含む留分の場合０.０１～２００ＮＬ／Ｌが好ましく、０.０１～１００ＮＬ／Ｌが更に好ましく、０.１～１００ＮＬ／Ｌが特に好ましい。水素／油比が０.０１ＮＬ／Ｌ未満だと、十分に脱硫が進行せず好ましくない。また、水素／油比が２００ＮＬ／Ｌを超えると、オレフィンの水素化などの副反応が起こる割合が多くなり好ましくない。
The hydrogen / oil ratio is not particularly limited, but is preferably 0.01 to 200 NL / L, more preferably 0.01 to 100 NL / L, and more preferably 0.1 to 100 NL for a fraction containing a large amount of olefins such as catalytic cracked gasoline. / L is particularly preferred. If the hydrogen / oil ratio is less than 0.01 NL / L, desulfurization does not proceed sufficiently, which is not preferable. On the other hand, when the hydrogen / oil ratio exceeds 200 NL / L, the ratio of side reactions such as hydrogenation of olefins increases, which is not preferable.
また、軽油留分のように多環芳香族を含む留分の場合、水素／油比は１～１０００ＮＬ／Ｌが好ましく、１０～５００ＮＬ／Ｌが更に好ましく、５０～４００ＮＬ／Ｌが特に好ましい。水素／油比が１ＮＬ／Ｌ未満だと、十分に脱硫が進行せず好ましくない。また、水素／油比が１０００ＮＬ／Ｌを超えると、水素流量が多くなりすぎて、水素コンプレッサーが大きくなり好ましくない。
In the case of a fraction containing polycyclic aromatics such as a light oil fraction, the hydrogen / oil ratio is preferably 1 to 1000 NL / L, more preferably 10 to 500 NL / L, and particularly preferably 50 to 400 NL / L. When the hydrogen / oil ratio is less than 1 NL / L, desulfurization does not proceed sufficiently, which is not preferable. On the other hand, if the hydrogen / oil ratio exceeds 1000 NL / L, the hydrogen flow rate becomes too high, and the hydrogen compressor becomes undesirably large.
使用する水素は、メタン等の不純物を含んでいてもよいが、水素コンプレッサーが大きくなり過ぎないよう、水素純度は５０容量％以上が好ましく、さらには８０容量％以上、特には９５容量％以上が好ましい。なお、水素中に硫化水素などの硫黄化合物が含まれると脱硫剤の寿命が短くなるので、水素中の硫黄分は、１,０００容量ｐｐｍ以下が好ましく、さらには１００容量ｐｐｍ以下、特には１０容量ｐｐｍ以下が好ましい。
The hydrogen used may contain impurities such as methane, but the hydrogen purity is preferably 50% by volume or more, more preferably 80% by volume or more, and particularly 95% by volume or more so that the hydrogen compressor does not become too large. preferable. If the sulfur compound such as hydrogen sulfide is contained in the hydrogen, the life of the desulfurizing agent is shortened. Therefore, the sulfur content in the hydrogen is preferably 1,000 ppm by volume or less, more preferably 100 ppm by volume or less, especially 10 ppm. A capacity of ppm or less is preferred.
以下に、実施例により具体的に説明するが、本発明はこれらの例により何ら制限されるものではない。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
（比較例１）
硝酸亜鉛六水和物１７８.５ｇ及び硝酸ニッケル六水和物５８.２ｇを水に溶解したｐＨ２.６の溶液（ニッケル及び亜鉛の総濃度：２.７ｍｏｌ／Ｌ）３００ｍＬを調製した。また、炭酸ナトリウム１０４ｇを水に溶解したｐＨ１２.２の溶液（ナトリウムイオン濃度：４.０ｍｏｌ／Ｌ）２５０ｍＬを６０℃に加温し、これに前記調製した亜鉛及びニッケル含有の酸性溶液を全量滴下し、その後１時間継続して撹拌した。全量滴下後のｐＨは、温度２６℃下において８.１であった。得られた沈殿物をろ過した後、水で洗浄した。その後、１２０℃で１６時間乾燥後、３５０℃で３時間焼成して脱硫剤（Ｉ）を得た。脱硫剤（Ｉ）は、ニッケル含有量が１７.３質量％、亜鉛含有量が５９.５質量％、ナトリウム含有量が０.０１質量％であり、亜鉛含有量に対するニッケル含有量の比（質量）は０.２９であった。また、亜鉛酸化物の結晶子径とニッケル酸化物の結晶子径の比は２.４であった。尚、金属分の含有量はアルカリ融解ＩＣＰ法で測定し、酸化物の結晶子径はＸＲＤで測定し、細孔容積は窒素吸脱着法によるＢＪＨ法で測定した。 (Comparative Example 1)
300 mL of a solution of pH 2.6 (total concentration of nickel and zinc: 2.7 mol / L) in which 178.5 g of zinc nitrate hexahydrate and 58.2 g of nickel nitrate hexahydrate were dissolved in water was prepared. In addition, 250 mL of a solution having a pH of 12.2 (sodium ion concentration: 4.0 mol / L) in which 104 g of sodium carbonate was dissolved in water was heated to 60 ° C., and the zinc- and nickel-containing acidic solution prepared above was added dropwise thereto. And then stirred continuously for 1 hour. The pH after dropping all was 8.1 at a temperature of 26 ° C. The resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 350 degreeC for 3 hours, and obtained the desulfurization agent (I). The desulfurizing agent (I) has a nickel content of 17.3% by mass, a zinc content of 59.5% by mass and a sodium content of 0.01% by mass, and the ratio of the nickel content to the zinc content (mass ) Was 0.29. The ratio of the crystallite diameter of zinc oxide to that of nickel oxide was 2.4. The metal content was measured by the alkali melting ICP method, the crystallite diameter of the oxide was measured by XRD, and the pore volume was measured by the BJH method by nitrogen adsorption / desorption method.
硝酸亜鉛六水和物１７８.５ｇ及び硝酸ニッケル六水和物５８.２ｇを水に溶解したｐＨ２.６の溶液（ニッケル及び亜鉛の総濃度：２.７ｍｏｌ／Ｌ）３００ｍＬを調製した。また、炭酸ナトリウム１０４ｇを水に溶解したｐＨ１２.２の溶液（ナトリウムイオン濃度：４.０ｍｏｌ／Ｌ）２５０ｍＬを６０℃に加温し、これに前記調製した亜鉛及びニッケル含有の酸性溶液を全量滴下し、その後１時間継続して撹拌した。全量滴下後のｐＨは、温度２６℃下において８.１であった。得られた沈殿物をろ過した後、水で洗浄した。その後、１２０℃で１６時間乾燥後、３５０℃で３時間焼成して脱硫剤（Ｉ）を得た。脱硫剤（Ｉ）は、ニッケル含有量が１７.３質量％、亜鉛含有量が５９.５質量％、ナトリウム含有量が０.０１質量％であり、亜鉛含有量に対するニッケル含有量の比（質量）は０.２９であった。また、亜鉛酸化物の結晶子径とニッケル酸化物の結晶子径の比は２.４であった。尚、金属分の含有量はアルカリ融解ＩＣＰ法で測定し、酸化物の結晶子径はＸＲＤで測定し、細孔容積は窒素吸脱着法によるＢＪＨ法で測定した。 (Comparative Example 1)
300 mL of a solution of pH 2.6 (total concentration of nickel and zinc: 2.7 mol / L) in which 178.5 g of zinc nitrate hexahydrate and 58.2 g of nickel nitrate hexahydrate were dissolved in water was prepared. In addition, 250 mL of a solution having a pH of 12.2 (sodium ion concentration: 4.0 mol / L) in which 104 g of sodium carbonate was dissolved in water was heated to 60 ° C., and the zinc- and nickel-containing acidic solution prepared above was added dropwise thereto. And then stirred continuously for 1 hour. The pH after dropping all was 8.1 at a temperature of 26 ° C. The resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 350 degreeC for 3 hours, and obtained the desulfurization agent (I). The desulfurizing agent (I) has a nickel content of 17.3% by mass, a zinc content of 59.5% by mass and a sodium content of 0.01% by mass, and the ratio of the nickel content to the zinc content (mass ) Was 0.29. The ratio of the crystallite diameter of zinc oxide to that of nickel oxide was 2.4. The metal content was measured by the alkali melting ICP method, the crystallite diameter of the oxide was measured by XRD, and the pore volume was measured by the BJH method by nitrogen adsorption / desorption method.
リアクターに脱硫剤（Ｉ）を充填し、水素気流中３００℃で１６時間還元処理を行った後、炭化水素油の通油試験を実施した。炭化水素油としては、硫黄分が１３質量ｐｐｍの重質接触分解ガソリンを用いた。反応温度１４０℃、反応圧力０.３ＭＰａ、水素／油比＝１００ＮＬ／Ｌ、ＬＨＳＶ＝５.０ｈ-1の条件下、リアクターの入口から炭化水素油の通油を開始した。その結果、脱硫率５０％以上を維持する時間（サイクルレングス）は４００時間であった。尚、硫黄分は、ＡＳＴＭ Ｄ ５４５３（紫外蛍光法）に準拠して測定した。
The reactor was filled with the desulfurizing agent (I), subjected to reduction treatment at 300 ° C. for 16 hours in a hydrogen stream, and then an oil passage test for hydrocarbon oil was performed. As the hydrocarbon oil, heavy catalytic cracked gasoline having a sulfur content of 13 mass ppm was used. Under the conditions of a reaction temperature of 140 ° C., a reaction pressure of 0.3 MPa, a hydrogen / oil ratio = 100 NL / L, and LHSV = 5.0 h −1 , hydrocarbon oil was started to flow from the reactor inlet. As a result, the time (cycle length) for maintaining the desulfurization rate of 50% or more was 400 hours. In addition, the sulfur content was measured based on ASTM D 5453 (ultraviolet fluorescence method).
（実施例１）
硝酸亜鉛六水和物１７８.５ｇ及び硝酸ニッケル六水和物５８.２ｇを水３００ｍＬに溶解したｐＨ２.６の酸性溶液Ａ（ニッケル及び亜鉛の総濃度：２.７ｍｏｌ／Ｌ）を調製した。また、炭酸ナトリウム１０４ｇを水３００ｍＬに溶解したｐＨ１２.０のアルカリ溶液Ｂ（ナトリウムイオン濃度：３.３ｍｏｌ／Ｌ）を調製した。 Example 1
An acidic solution A having a pH of 2.6 (total concentration of nickel and zinc: 2.7 mol / L) in which 178.5 g of zinc nitrate hexahydrate and 58.2 g of nickel nitrate hexahydrate were dissolved in 300 mL of water was prepared. Further, an alkaline solution B (sodium ion concentration: 3.3 mol / L) having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
硝酸亜鉛六水和物１７８.５ｇ及び硝酸ニッケル六水和物５８.２ｇを水３００ｍＬに溶解したｐＨ２.６の酸性溶液Ａ（ニッケル及び亜鉛の総濃度：２.７ｍｏｌ／Ｌ）を調製した。また、炭酸ナトリウム１０４ｇを水３００ｍＬに溶解したｐＨ１２.０のアルカリ溶液Ｂ（ナトリウムイオン濃度：３.３ｍｏｌ／Ｌ）を調製した。 Example 1
An acidic solution A having a pH of 2.6 (total concentration of nickel and zinc: 2.7 mol / L) in which 178.5 g of zinc nitrate hexahydrate and 58.2 g of nickel nitrate hexahydrate were dissolved in 300 mL of water was prepared. Further, an alkaline solution B (sodium ion concentration: 3.3 mol / L) having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
ｐＨ７.０の蒸留水６００ｍＬを温度６０℃に加温撹拌しながら、前記調製した酸性溶液Ａとアルカリ溶液Ｂを滴下した。酸性溶液Ａとアルカリ溶液Ｂは、ほぼ同時に滴下を開始し、６０分で滴下を終了した。その後、１時間継続して撹拌した。全量滴下後のｐＨは、温度２８℃下において８.２であった。得られた沈殿物をろ過した後、水で洗浄した。その後、１２０℃で１６時間乾燥後、３５０℃で３時間焼成して脱硫剤（ＩＩ）を得た。
The acidic solution A and alkaline solution B prepared above were added dropwise while stirring 600 mL of distilled water having a pH of 7.0 at a temperature of 60 ° C. The acidic solution A and the alkaline solution B started dripping almost simultaneously, and the dripping was completed in 60 minutes. Thereafter, stirring was continued for 1 hour. The pH after dropping all was 8.2 at a temperature of 28 ° C. The resulting precipitate was filtered and washed with water. Then, after drying at 120 ° C. for 16 hours, calcination was performed at 350 ° C. for 3 hours to obtain a desulfurization agent (II).
次に、得られた脱硫剤（ＩＩ）を用いて、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。
Next, using the obtained desulfurizing agent (II), an oil passage test of hydrocarbon oil was carried out in the same manner as in Comparative Example 1. The results are shown in Table 1.
（実施例２）
酸性溶液Ａを調製する際の水の量を１,０００ｍＬ（ｐＨ３.２、ニッケル及び亜鉛の総濃度：０.８ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂを調製する際の水の量を１,０００ｍＬ（ｐＨ１１.４、ナトリウムイオン濃度：１.０ｍｏｌ／Ｌ）にした以外、実施例１と同様の方法により脱硫剤（ＩＩＩ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 2)
The amount of water when preparing the acidic solution A is 1,000 mL (pH 3.2, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water when preparing the alkaline solution B is 1,000 mL. A desulfurizing agent (III) was obtained in the same manner as in Example 1 except that the pH was adjusted to 11.4 and the sodium ion concentration was 1.0 mol / L. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
酸性溶液Ａを調製する際の水の量を１,０００ｍＬ（ｐＨ３.２、ニッケル及び亜鉛の総濃度：０.８ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂを調製する際の水の量を１,０００ｍＬ（ｐＨ１１.４、ナトリウムイオン濃度：１.０ｍｏｌ／Ｌ）にした以外、実施例１と同様の方法により脱硫剤（ＩＩＩ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 2)
The amount of water when preparing the acidic solution A is 1,000 mL (pH 3.2, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water when preparing the alkaline solution B is 1,000 mL. A desulfurizing agent (III) was obtained in the same manner as in Example 1 except that the pH was adjusted to 11.4 and the sodium ion concentration was 1.0 mol / L. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
（実施例３）
酸性溶液Ａを調製する際の水の量を２,０００ｍＬ（ｐＨ３.６、ニッケル及び亜鉛の総濃度：０.４ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂを調製する際の水の量を２,０００ｍＬ（ｐＨ１１.３、ナトリウムイオン濃度：０.５ｍｏｌ／Ｌ）にした以外、実施例１と同様の方法により脱硫剤（ＩＶ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 3)
The amount of water when preparing the acidic solution A is 2,000 mL (pH 3.6, total concentration of nickel and zinc: 0.4 mol / L), and the amount of water when preparing the alkaline solution B is 2,000 mL. A desulfurizing agent (IV) was obtained in the same manner as in Example 1 except that the pH was adjusted to 11.3 and the sodium ion concentration was 0.5 mol / L. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
酸性溶液Ａを調製する際の水の量を２,０００ｍＬ（ｐＨ３.６、ニッケル及び亜鉛の総濃度：０.４ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂを調製する際の水の量を２,０００ｍＬ（ｐＨ１１.３、ナトリウムイオン濃度：０.５ｍｏｌ／Ｌ）にした以外、実施例１と同様の方法により脱硫剤（ＩＶ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 3)
The amount of water when preparing the acidic solution A is 2,000 mL (pH 3.6, total concentration of nickel and zinc: 0.4 mol / L), and the amount of water when preparing the alkaline solution B is 2,000 mL. A desulfurizing agent (IV) was obtained in the same manner as in Example 1 except that the pH was adjusted to 11.3 and the sodium ion concentration was 0.5 mol / L. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
（実施例４）
実施例１の硝酸塩を硫酸塩に変更して、酸性溶液Ａを調製した。具体的には、硫酸亜鉛七水和物１７２.５ｇ及び硫酸ニッケル六水和物５２.６ｇを水３００ｍＬに溶解し、硫酸を滴下してｐＨ１．６の酸性溶液Ａ（ニッケル及び亜鉛の総濃度：２.７ｍｏｌ／Ｌ）を調製した。また、炭酸ナトリウム１０４ｇを水３００ｍＬに溶解したｐＨ１２.０のアルカリ溶液Ｂ（ナトリウムイオン濃度：３.３ｍｏｌ／Ｌ）を調製した。 Example 4
An acidic solution A was prepared by changing the nitrate of Example 1 to a sulfate. Specifically, 172.5 g of zinc sulfate heptahydrate and 52.6 g of nickel sulfate hexahydrate were dissolved in 300 mL of water, and sulfuric acid was added dropwise to add acid solution A having a pH of 1.6 (total concentration of nickel and zinc). : 2.7 mol / L). Further, an alkaline solution B (sodium ion concentration: 3.3 mol / L) having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
実施例１の硝酸塩を硫酸塩に変更して、酸性溶液Ａを調製した。具体的には、硫酸亜鉛七水和物１７２.５ｇ及び硫酸ニッケル六水和物５２.６ｇを水３００ｍＬに溶解し、硫酸を滴下してｐＨ１．６の酸性溶液Ａ（ニッケル及び亜鉛の総濃度：２.７ｍｏｌ／Ｌ）を調製した。また、炭酸ナトリウム１０４ｇを水３００ｍＬに溶解したｐＨ１２.０のアルカリ溶液Ｂ（ナトリウムイオン濃度：３.３ｍｏｌ／Ｌ）を調製した。 Example 4
An acidic solution A was prepared by changing the nitrate of Example 1 to a sulfate. Specifically, 172.5 g of zinc sulfate heptahydrate and 52.6 g of nickel sulfate hexahydrate were dissolved in 300 mL of water, and sulfuric acid was added dropwise to add acid solution A having a pH of 1.6 (total concentration of nickel and zinc). : 2.7 mol / L). Further, an alkaline solution B (sodium ion concentration: 3.3 mol / L) having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
ｐＨ７.０の蒸留水６００ｍＬを温度６０℃に加温撹拌しながら、前記調製した酸性溶液Ａとアルカリ溶液Ｂを滴下した。酸性溶液Ａとアルカリ溶液Ｂは、ほぼ同時に滴下を開始し、６０分で滴下を終了した。その後、１時間継続して撹拌した。全量滴下後のｐＨは、温度２８℃下において８.２であった。得られた沈殿物をろ過した後、水で洗浄した。その後、１２０℃で１６時間乾燥後、３５０℃で３時間焼成して脱硫剤（Ｖ）を得た。
The acidic solution A and alkaline solution B prepared above were added dropwise while stirring 600 mL of distilled water having a pH of 7.0 at a temperature of 60 ° C. The acidic solution A and the alkaline solution B started dripping almost simultaneously, and the dripping was completed in 60 minutes. Thereafter, stirring was continued for 1 hour. The pH after dropping all was 8.2 at a temperature of 28 ° C. The resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 350 degreeC for 3 hours, and obtained the desulfurization agent (V).
次に、得られた脱硫剤（Ｖ）を用いて、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。
Next, using the obtained desulfurizing agent (V), an oil passage test of hydrocarbon oil was carried out in the same manner as in Comparative Example 1. The results are shown in Table 1.
（実施例５）
酸性溶液Ａの水の量を１,０００ｍＬ（ｐＨ２．３、ニッケル及び亜鉛の総濃度：０.８ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂの水の量を１,０００ｍＬ（ｐＨ１１.４、ナトリウムイオン濃度：１.０ｍｏｌ／Ｌ）にした以外、実施例４と同様の方法により脱硫剤（ＶＩ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 5)
The amount of water in the acidic solution A is 1,000 mL (pH 2.3, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water in the alkaline solution B is 1,000 mL (pH 11.4, sodium ion concentration). The desulfurizing agent (VI) was obtained in the same manner as in Example 4 except that the amount was 1.0 mol / L). Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
酸性溶液Ａの水の量を１,０００ｍＬ（ｐＨ２．３、ニッケル及び亜鉛の総濃度：０.８ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂの水の量を１,０００ｍＬ（ｐＨ１１.４、ナトリウムイオン濃度：１.０ｍｏｌ／Ｌ）にした以外、実施例４と同様の方法により脱硫剤（ＶＩ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 5)
The amount of water in the acidic solution A is 1,000 mL (pH 2.3, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water in the alkaline solution B is 1,000 mL (pH 11.4, sodium ion concentration). The desulfurizing agent (VI) was obtained in the same manner as in Example 4 except that the amount was 1.0 mol / L). Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
（実施例６）
酸性溶液Ａの水の量を２,０００ｍＬ（ｐＨ４．３、ニッケル及び亜鉛の総濃度：０.４ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂの水の量を２,０００ｍＬ（ｐＨ１１.３、ナトリウムイオン濃度：０.５ｍｏｌ／Ｌ）にした以外、実施例４と同様の方法により脱硫剤（ＶＩＩ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 6)
The amount of water in the acidic solution A is 2,000 mL (pH 4.3, total concentration of nickel and zinc: 0.4 mol / L), and the amount of water in the alkaline solution B is 2,000 mL (pH 11.3, sodium ion concentration). : 0.5 mol / L), a desulfurization agent (VII) was obtained in the same manner as in Example 4. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
酸性溶液Ａの水の量を２,０００ｍＬ（ｐＨ４．３、ニッケル及び亜鉛の総濃度：０.４ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂの水の量を２,０００ｍＬ（ｐＨ１１.３、ナトリウムイオン濃度：０.５ｍｏｌ／Ｌ）にした以外、実施例４と同様の方法により脱硫剤（ＶＩＩ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 6)
The amount of water in the acidic solution A is 2,000 mL (pH 4.3, total concentration of nickel and zinc: 0.4 mol / L), and the amount of water in the alkaline solution B is 2,000 mL (pH 11.3, sodium ion concentration). : 0.5 mol / L), a desulfurization agent (VII) was obtained in the same manner as in Example 4. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
（実施例７）
酸性溶液Ａの水の量を１,０００ｍＬ（ｐＨ４．８、ニッケル及び亜鉛の総濃度：０.８ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂの水の量を１,０００ｍＬ（ｐＨ１１.４、ナトリウムイオン濃度：１.０ｍｏｌ／Ｌ）にし、焼成を２８０℃にて２時間行った以外は、実施例４と同様の方法により脱硫剤（ＶＩＩＩ）を得た。また、還元温度を２５０℃とした以外は比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 7)
The amount of water in the acidic solution A is 1,000 mL (pH 4.8, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water in the alkaline solution B is 1,000 mL (pH 11.4, sodium ion concentration). The desulfurization agent (VIII) was obtained in the same manner as in Example 4 except that the calcination was performed at 280 ° C. for 2 hours. Further, an oil passage test for hydrocarbon oil was conducted in the same manner as in Comparative Example 1 except that the reduction temperature was 250 ° C. The results are shown in Table 1.
酸性溶液Ａの水の量を１,０００ｍＬ（ｐＨ４．８、ニッケル及び亜鉛の総濃度：０.８ｍｏｌ／Ｌ）にし、アルカリ溶液Ｂの水の量を１,０００ｍＬ（ｐＨ１１.４、ナトリウムイオン濃度：１.０ｍｏｌ／Ｌ）にし、焼成を２８０℃にて２時間行った以外は、実施例４と同様の方法により脱硫剤（ＶＩＩＩ）を得た。また、還元温度を２５０℃とした以外は比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Example 7)
The amount of water in the acidic solution A is 1,000 mL (pH 4.8, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water in the alkaline solution B is 1,000 mL (pH 11.4, sodium ion concentration). The desulfurization agent (VIII) was obtained in the same manner as in Example 4 except that the calcination was performed at 280 ° C. for 2 hours. Further, an oil passage test for hydrocarbon oil was conducted in the same manner as in Comparative Example 1 except that the reduction temperature was 250 ° C. The results are shown in Table 1.
（比較例２）
実施例１で得た脱硫剤（ＩＩ）９ｇに、ベーマイト（Ｃａｔａｐａｌ－Ｃ１、Ｓａｓｏｌ社製）を１ｇ添加し、水を適宜加えてメノー乳鉢により混合した後、１２０℃で１６時間乾燥した後、３５０℃にて３時間焼成し脱硫剤（ＩＸ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Comparative Example 2)
After 1 g of boehmite (Catapal-C1, manufactured by Sasol) was added to 9 g of the desulfurizing agent (II) obtained in Example 1, water was appropriately added and mixed in a menor mortar, and then dried at 120 ° C. for 16 hours. Calcination was performed at 350 ° C. for 3 hours to obtain a desulfurization agent (IX). Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
実施例１で得た脱硫剤（ＩＩ）９ｇに、ベーマイト（Ｃａｔａｐａｌ－Ｃ１、Ｓａｓｏｌ社製）を１ｇ添加し、水を適宜加えてメノー乳鉢により混合した後、１２０℃で１６時間乾燥した後、３５０℃にて３時間焼成し脱硫剤（ＩＸ）を得た。また、比較例１と同様にして炭化水素油の通油試験を実施した。結果を表１に示す。 (Comparative Example 2)
After 1 g of boehmite (Catapal-C1, manufactured by Sasol) was added to 9 g of the desulfurizing agent (II) obtained in Example 1, water was appropriately added and mixed in a menor mortar, and then dried at 120 ° C. for 16 hours. Calcination was performed at 350 ° C. for 3 hours to obtain a desulfurization agent (IX). Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
表１に示す通り、本発明に従う実施例の脱硫剤は、反応温度１４０℃でも十分な脱硫効果を長期間にわたって発揮できることが分かる。一方、比較例１の脱硫剤は、アルカリ溶液に酸性溶液を滴下して脱硫剤を調製したため、ニッケル酸化物及び亜鉛酸化物の結晶子径が大きくなり過ぎ、結果として、比表面積が小さ過ぎるため、脱硫率５０％以上を維持できる期間が短かった。
As shown in Table 1, it can be seen that the desulfurization agents of the examples according to the present invention can exhibit a sufficient desulfurization effect over a long period of time even at a reaction temperature of 140 ° C. On the other hand, the desulfurization agent of Comparative Example 1 was prepared by adding an acidic solution to an alkaline solution to prepare a desulfurization agent, so that the crystallite diameters of nickel oxide and zinc oxide were too large, and as a result, the specific surface area was too small. The period during which the desulfurization rate can be maintained at 50% or more was short.
また、実施例１～３の結果から、脱硫剤の調製に用いる酸性溶液及びアルカリ溶液の濃度を低くするに従って、ニッケル酸化物及び亜鉛酸化物の結晶子径が小さくなり、比表面積が大きくなって、サイクルレングスが長くなることが分かる。
Further, from the results of Examples 1 to 3, as the concentration of the acidic solution and the alkaline solution used for the preparation of the desulfurizing agent is decreased, the crystallite diameters of nickel oxide and zinc oxide are decreased, and the specific surface area is increased. It can be seen that the cycle length becomes longer.
更に、実施例１と実施例４、並びに実施例２と実施例５の比較から、原料として硫酸ニッケル及び硫酸亜鉛を使用して調製した脱硫剤は、ニッケル酸化物及び亜鉛酸化物の結晶子径が小さく、比表面積が大きく、脱硫率５０％以上を維持できる期間が長いことが分かる。
Furthermore, from the comparison between Example 1 and Example 4 and Example 2 and Example 5, the desulfurization agent prepared using nickel sulfate and zinc sulfate as raw materials was obtained by using the crystallite diameters of nickel oxide and zinc oxide. Is small, the specific surface area is large, and it can be seen that the period during which the desulfurization rate is maintained at 50% or more is long.
Claims (5)
- 水に、アルカリ溶液とニッケル及び亜鉛を含有する酸性溶液とを同時に滴下して、沈殿を生成させることを特徴とする脱硫剤の製造方法。 A method for producing a desulfurization agent, wherein an alkaline solution and an acidic solution containing nickel and zinc are simultaneously dropped into water to form a precipitate.
- ニッケル原料として硫酸ニッケルを用い、亜鉛原料として硫酸亜鉛を用いる請求項１に記載の脱硫剤の製造方法。 The method for producing a desulfurizing agent according to claim 1, wherein nickel sulfate is used as the nickel raw material and zinc sulfate is used as the zinc raw material.
- ニッケル及び亜鉛を酸化物として含有し、比表面積が７０～２００ｍ2／ｇであり、ニッケル酸化物の結晶子径が５ｎｍ以下、亜鉛酸化物の結晶子径が１５ｎｍ以下であり、全細孔容積が０.３５～１.００ｍＬ／ｇであることを特徴とする脱硫剤。 It contains nickel and zinc as oxides, has a specific surface area of 70 to 200 m 2 / g, nickel oxide crystallite diameter of 5 nm or less, zinc oxide crystallite diameter of 15 nm or less, total pore volume Is a desulfurization agent, characterized in that the ratio is 0.35 to 1.00 mL / g.
- ニッケルの含有量が１～３０質量％、亜鉛の含有量が３０～８０質量％であり、ニッケル原子に対する亜鉛原子の質量比（Ｚｎ／Ｎｉ）が１～１５である請求項３に記載の脱硫剤。 The desulfurization according to claim 3, wherein the content of nickel is 1 to 30% by mass, the content of zinc is 30 to 80% by mass, and the mass ratio of zinc atoms to nickel atoms (Zn / Ni) is 1 to 15. Agent.
- 硫黄分を２質量ｐｐｍ以上含有する炭化水素油を請求項３又は４に記載の脱硫剤と水素存在下で、温度５０～３００℃、圧力０.２～５.０ＭＰａ、液空間速度が２.０ｈ-1を超える条件で接触させる炭化水素油の脱硫方法。 A hydrocarbon oil containing 2 mass ppm or more of a sulfur content in the presence of the desulfurizing agent and hydrogen according to claim 3 or 4, a temperature of 50 to 300 ° C., a pressure of 0.2 to 5.0 MPa, and a liquid space velocity of 2. A method for desulfurizing a hydrocarbon oil to be contacted under a condition exceeding 0 h- 1 .
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| JP2012030211A (en) * | 2010-08-03 | 2012-02-16 | Japan Petroleum Energy Center | Method of manufacturing desulfurizing agent for hydrocarbon |
| EP2548935A4 (en) * | 2010-03-19 | 2015-07-22 | Japan Petroleum Energy Ct | Desulfurizing agent and manufacturing method therefor |
| WO2024013756A1 (en) * | 2022-07-11 | 2024-01-18 | Hindustan Petroleum Corporation Limited | Method for preparation of mesoporous adsorbent for desulfurization of hydrocarbons |
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| JP2004230317A (en) * | 2003-01-31 | 2004-08-19 | Nippon Oil Corp | Desulfurization catalyst and desulfurization method for hydrocarbon, and fuel cell system |
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| EP2548935A4 (en) * | 2010-03-19 | 2015-07-22 | Japan Petroleum Energy Ct | Desulfurizing agent and manufacturing method therefor |
| JP2012030211A (en) * | 2010-08-03 | 2012-02-16 | Japan Petroleum Energy Center | Method of manufacturing desulfurizing agent for hydrocarbon |
| WO2024013756A1 (en) * | 2022-07-11 | 2024-01-18 | Hindustan Petroleum Corporation Limited | Method for preparation of mesoporous adsorbent for desulfurization of hydrocarbons |
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