JP6973828B2 - 触媒の充填方法およびこれを用いたブタジエンの製造方法 - Google Patents
触媒の充填方法およびこれを用いたブタジエンの製造方法 Download PDFInfo
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- JP6973828B2 JP6973828B2 JP2020526573A JP2020526573A JP6973828B2 JP 6973828 B2 JP6973828 B2 JP 6973828B2 JP 2020526573 A JP2020526573 A JP 2020526573A JP 2020526573 A JP2020526573 A JP 2020526573A JP 6973828 B2 JP6973828 B2 JP 6973828B2
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- catalyst
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- ferrite
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- 239000003054 catalyst Substances 0.000 title claims description 183
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 29
- 238000011049 filling Methods 0.000 title claims description 25
- 239000002245 particle Substances 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 229910000859 α-Fe Inorganic materials 0.000 claims description 32
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 26
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 26
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 24
- 230000003197 catalytic effect Effects 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000007865 diluting Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000008188 pellet Substances 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical group O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000002243 precursor Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000020169 heat generation Effects 0.000 description 7
- 239000000376 reactant Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- BHXSRLKYVPSYMQ-UHFFFAOYSA-N C=CC=C.C=CC=C Chemical compound C=CC=C.C=CC=C BHXSRLKYVPSYMQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- YICCTZQUAAGDTO-UHFFFAOYSA-N but-1-ene Chemical compound CCC=C.CCC=C YICCTZQUAAGDTO-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 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
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- VITRLXDSBBVNCZ-UHFFFAOYSA-K trichloroiron;hydrate Chemical compound O.Cl[Fe](Cl)Cl VITRLXDSBBVNCZ-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/001—Controlling catalytic processes
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0207—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
- C07C11/167—1, 3-Butadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
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- B01J2208/00327—Controlling the temperature by direct heat exchange
- B01J2208/00336—Controlling the temperature by direct heat exchange adding a temperature modifying medium to the reactants
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- B01J2208/00017—Controlling the temperature
- B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
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- B01J2208/00628—Controlling the composition of the reactive mixture
- B01J2208/00637—Means for stopping or slowing down the reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J2219/00245—Avoiding undesirable reactions or side-effects
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Description
(A)フェライト系触媒成形体と希釈物質粒子とを混合するステップ;および
(B)前記フェライト系触媒成形体と前記希釈物質粒子とが混合された状態で触媒反応器に充填させるステップ
を含む触媒の充填方法を提供する。
前述した触媒の充填方法によって、触媒反応器に触媒を充填するステップ;および
前記触媒反応器でブテンを含む原料を酸化的脱水素化反応させてブタジエンを製造するステップ
を含むブタジエンの製造方法を提供する。
また、本明細書の一実施形態は、フェライト系触媒成形体と希釈物質粒子とが混合された状態で充填された触媒反応器を提供する。
収率(%)=[(生成された1,3−ブタジエンのモル数)/(供給されたブテンのモル数)]×100
切り替え率(%)=[(反応したブテンのモル数)/(供給されたブテンのモル数)]×100
選択度(%)=[(生成された1,3−ブタジエン、または、COxのモル数)/(反応したブテンのモル数)]×100
[化学式1]
AFe2O4
1)金属酸化物の製造
塩化亜鉛(ZnCl2)12.019gおよび塩化第二鉄(FeCl3)47.662gを155.59g蒸留水に溶解させ、金属前駆体溶液を用意した。このとき、前記金属前駆体溶液に含まれる金属成分等のモル比は、Zn:Fe=1:2であった。前記用意された金属前駆体水溶液にpH9になるようにアンモニア水溶液を滴下し、1時間撹拌して共沈させた。この後、共沈液を減圧ろ過して共沈物を得ており、これを90℃で16時間乾燥した後、空気雰囲気下で、80℃で1℃/minの昇温速度で650℃まで昇温させた後、6時間維持してスピネル構造を有する亜鉛−鉄酸化物(ZnFe2O4)の粉末を製造した。
前記製造された金属酸化物の粉末を0.6mm〜0.85mmに粉砕した後、液状バインダーとして水とイソプロピルアルコールとの混合物を投与した後、ニーダーを用いて均一に練って、押出成形機を用いて直径が1.5mm〜3mmであり、断面が円形であり、高さが1.5mm〜9mmである円筒形ペレットに成形した。成形ペレットを90℃で12時間乾燥および500℃で4時間熱処理した。
前記製造例1で製造したフェライト系触媒成形体20ccおよび直径2mm〜3mmのα−Al2O3ball130ccを混合し、反応器の全区間で触媒成形体の比率が10.17wt%になるように充填した。
前記製造例1で製造したフェライト系触媒成形体25ccおよび直径2mm〜3mmのα−Al2O3ball125ccを混合し、反応器の全区間で触媒成形体の比率が13.00wt%になるように充填した。
前記製造例1で製造したフェライト系触媒成形体20ccおよび直径2mm〜3mmのα−Al2O3ball130ccを、下記の表1のように、反応器の上段および下段での比率を異ならせて反応器に充填した。このとき、反応器の反応が開始する区間(上段)の触媒比率は3.65wt%であった。
前記製造例1で製造したフェライト系触媒成形体45ccおよび直径2mm〜3mmのα−Al2O3ball105ccを混合し、反応器の全区間で触媒成形体の比率が25wt%になるように充填した。
前記製造例1の2)酸化的脱水素化反応用の触媒の製造後に、常用のアルミナシリケート支持体(alumina silicate support)180gに触媒17.8gをコーティングし、フェライト系触媒成形体全体の重量に対する触媒比率が9wt%になるように成形した。
得られたフェライト系触媒成形体150ccを追加で希釈することなく、反応器に充填した。
前記製造例1で製造したフェライト系触媒成形体150ccを希釈物質と混合することなく、反応器の全区間で触媒成形体を充填した。
前記実施例1〜4および比較例1〜2の反応器のそれぞれにおいて、ブテンを含む原料を酸化的脱水素化反応させ、ホットスポットの移動速度、ブテンの切り替え率、ブタジエンの選択度、COxの選択度、ホットスポットの温度変化を測定した結果を、下記表2に示した。
Claims (9)
- (A)フェライト系触媒成形体と希釈物質粒子とを混合するステップ;および
(B)前記フェライト系触媒成形体と前記希釈物質粒子とが混合された状態で触媒反応器に充填させるステップ
を含み、
前記希釈物質粒子は、アルミニウムオキサイドであり、
前記フェライト系触媒は、亜鉛フェライト触媒であり、
前記触媒反応器内の反応が開始される区間で、前記フェライト系触媒成形体と前記希釈物質粒子との重量の合計に対し、前記フェライト系触媒成形体の重量比率が10wt%〜15wt%になるように充填させるものである、ブテンの酸化的脱水素化反応用の触媒の充填方法。 - 前記触媒反応器内の全区間で、前記フェライト系触媒成形体と前記希釈物質粒子との重量の合計に対し、前記フェライト系触媒成形体の重量比率が10wt%〜15wt%になるように充填させるものである、請求項1に記載の触媒の充填方法。
- 前記フェライト系触媒成形体は、ペレット型(pellet type)、ボール型(ball type)または中空型に成形されたものである、請求項1または2に記載の触媒の充填方法。
- 前記ペレットは円筒形ペレットであり、前記ペレットの直径が1mm〜5mmのものである、請求項3に記載の触媒の充填方法。
- 前記希釈物質粒子は、直径1mm〜5mmのボール型(ball type)のものである、請求項1から4のいずれか一項に記載の触媒の充填方法。
- 請求項1〜5のいずれか一項に記載の触媒の充填方法によって、触媒反応器に触媒を充填するステップ;および
前記触媒反応器でブテンを含む原料を酸化的脱水素化反応させてブタジエンを製造するステップ
を含む、ブタジエンの製造方法。 - 前記酸化的脱水素化反応の触媒のホットスポット(hot spot)の移動速度が0〜0.5mm/hrのものである、請求項6に記載のブタジエンの製造方法。
- フェライト系触媒成形体と希釈物質粒子とが混合された状態で充填された、触媒反応器であって、
前記触媒は、ブテンの酸化的脱水素化反応用の触媒であり、
前記希釈物質粒子は、アルミニウムオキサイドであり、
前記フェライト系触媒は、亜鉛フェライト触媒であり、
前記触媒反応器内の反応が開始される区間で、前記フェライト系触媒成形体と前記希釈物質粒子との重量の合計に対し、前記フェライト系触媒成形体の重量比率が10wt%〜15wt%のものである、触媒反応器。 - 前記触媒反応器内の全区間で、前記フェライト系触媒成形体と前記希釈物質粒子との重量の合計に対し、前記フェライト系触媒成形体の重量比率が10wt%〜15wt%のものである、請求項8に記載の触媒反応器。
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