JPWO2015152159A1 - Process for producing unsaturated hydrocarbons - Google Patents
Process for producing unsaturated hydrocarbons Download PDFInfo
- Publication number
- JPWO2015152159A1 JPWO2015152159A1 JP2016511885A JP2016511885A JPWO2015152159A1 JP WO2015152159 A1 JPWO2015152159 A1 JP WO2015152159A1 JP 2016511885 A JP2016511885 A JP 2016511885A JP 2016511885 A JP2016511885 A JP 2016511885A JP WO2015152159 A1 JPWO2015152159 A1 JP WO2015152159A1
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- unsaturated hydrocarbon
- ethylene
- producing
- region
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000005977 Ethylene Substances 0.000 claims abstract description 79
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 57
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 53
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 48
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 22
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims description 73
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 28
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 28
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 239000001294 propane Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- 239000001282 iso-butane Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 150000001336 alkenes Chemical class 0.000 description 12
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001993 dienes Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- -1 zinc aluminate Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910000423 chromium oxide 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
-
- 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
- C07C5/50—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with an organic compound as an acceptor
- C07C5/52—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with an organic compound as an acceptor with a hydrocarbon as an acceptor, e.g. hydrocarbon disproportionation, i.e. 2CnHp -> CnHp+q + CnHp-q
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/86—Borosilicates; Aluminoborosilicates
-
- 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
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/60—Platinum group metals with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/86—Borosilicates; Aluminoborosilicates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
[課題]炭化水素の脱水素反応を行い、生成する水素の受容体としてのエチレンを供給しながら不飽和炭化水素を製造する方法において、エチレンのロスを最小限に留め、かつ長期に亘って収率良く不飽和炭化水素を製造する方法を提供すること。[解決手段]反応器内で炭化水素の脱水素反応を行って不飽和炭化水素を製造する方法であって、前記反応器が、第1反応領域、その下流側に設けられた第2反応領域、および前記第1反応領域と前記第2反応領域とを連結する連結領域を有し、前記方法が、炭化水素を含む原料含有ガスを前記第1反応領域に供給し、前記炭化水素の脱水素反応を行って一次生成ガスを得る工程、および前記連結領域において、前記一次生成ガスにエチレンを混合し、得られた混合ガスを前記第2反応領域に供給し、前記炭化水素の脱水素反応および前記エチレンに前記水素を付加してエタンを生成させる反応を行う工程を含む不飽和炭化水素の製造方法。[Problem] In a method for producing unsaturated hydrocarbons while carrying out dehydrogenation of hydrocarbons and supplying ethylene as an acceptor of the hydrogen to be produced, ethylene loss is kept to a minimum and is maintained over a long period of time. To provide a method for producing unsaturated hydrocarbons efficiently. [Solution] A method for producing an unsaturated hydrocarbon by dehydrogenating a hydrocarbon in a reactor, wherein the reactor comprises a first reaction zone and a second reaction zone provided downstream thereof. And a connection region connecting the first reaction region and the second reaction region, wherein the method supplies a raw material-containing gas containing hydrocarbons to the first reaction region, and dehydrogenates the hydrocarbons. Performing a reaction to obtain a primary product gas, and in the connecting region, mixing the primary product gas with ethylene, supplying the obtained mixed gas to the second reaction region, and dehydrogenating the hydrocarbon; A method for producing an unsaturated hydrocarbon, comprising a step of performing a reaction of adding the hydrogen to the ethylene to produce ethane.
Description
本発明は、炭化水素の脱水素反応を行うことによって不飽和炭化水素を製造する方法に関する。 The present invention relates to a method for producing an unsaturated hydrocarbon by performing a hydrocarbon dehydrogenation reaction.
不飽和炭化水素、特にオレフィンおよびジエンは、石油化学工業における種々の誘導体の基礎原料として大変有用である。代表的な低級オレフィンおよびジエンとして、プロピレン、1−ブテン、2−ブテン、イソブテン、1,3−ブタジエンなどが挙げられる。これらの低級オレフィンおよびジエンは、対応するパラフィンおよびまたはオレフィンを脱水素することによっても製造されることが知られており、例えばアルミナ担体上に酸化クロムを担持した触媒、アルミナ担体もしくはアルミン酸亜鉛のようなスピネル担体上に白金を担持した触媒などが、その製造に好適であることが知られている(非特許文献1)。また、特許文献1〜7には、ゼオライト担体上に白金と亜鉛を担持した触媒は、他の触媒系に比べて長期に亘って高い活性を示すことも開示されている。 Unsaturated hydrocarbons, especially olefins and dienes, are very useful as basic raw materials for various derivatives in the petrochemical industry. Representative lower olefins and dienes include propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene, and the like. These lower olefins and dienes are also known to be produced by dehydrogenating the corresponding paraffins and / or olefins. For example, a catalyst having chromium oxide supported on an alumina support, an alumina support or zinc aluminate. It is known that such a catalyst having platinum supported on a spinel carrier is suitable for its production (Non-patent Document 1). Patent Documents 1 to 7 also disclose that a catalyst in which platinum and zinc are supported on a zeolite carrier exhibits high activity over a long period of time compared to other catalyst systems.
一方、炭化水素の脱水素反応は平衡による制約を受ける。高温および/または低圧条件であるほど、生成物にとって有利となるが、高温では主にコーキングによる触媒の活性劣化が著しくなること、そして低圧にするもしくは減圧するためには特別な設備が必要となることが難点となる。 On the other hand, hydrocarbon dehydrogenation reactions are limited by equilibrium. Higher temperature and / or lower pressure conditions are advantageous for the product, but at higher temperatures, the catalytic activity is largely degraded due to coking, and special equipment is required to lower or reduce the pressure. It becomes a difficult point.
平衡を生成物側にシフトさせる別の方法としては、脱水素反応によって生成する水素を除去することが挙げられる。例えば、特許文献8は、酸素の導入による水素の除去方法を開示している。しかし安全確保の観点から、可燃物である炭化水素流に対して、高い濃度で酸素を混合することは現実的では無い。低濃度の酸素を供給する場合には、水素除去効果も限定的なものとなるため、好適な方法とは言えない。
これに対して、特許文献9は、エチレンを水素受容体として用いる炭化水素の変換方法を開示している。エチレン等のオレフィンの混合は、前記酸素の場合とは異なり、安全確保の観点から混合量を制限されない点で好適である。そして実際に水素受容体を用いると、用いない場合の平衡制限値を超えた収率が得られることも既に報告されている(特許文献10)。しかしながら、オレフィンを水素受容体として用いると、特許文献11に記述されているように、反応阻害が生じることも既に知られている。Another method for shifting the equilibrium to the product side is to remove the hydrogen produced by the dehydrogenation reaction. For example, Patent Document 8 discloses a method for removing hydrogen by introducing oxygen. However, from the viewpoint of ensuring safety, it is not realistic to mix oxygen at a high concentration with a hydrocarbon stream that is a combustible material. When supplying a low concentration of oxygen, the effect of removing hydrogen is limited, which is not a preferable method.
On the other hand, Patent Document 9 discloses a hydrocarbon conversion method using ethylene as a hydrogen acceptor. Unlike the case of oxygen, mixing of olefins such as ethylene is preferable in that the amount of mixing is not limited from the viewpoint of ensuring safety. It has already been reported that when a hydrogen acceptor is actually used, a yield exceeding the equilibrium limit value when not used is obtained (Patent Document 10). However, it is already known that reaction inhibition occurs when an olefin is used as a hydrogen acceptor, as described in Patent Document 11.
上述のように、上記の平衡を生成物側にシフトさせる効果を最大にするエチレン等のオレフィンの供給方法を見出すことは、必ずしも容易ではない。例えば低濃度のエチレンを原料炭化水素と共に供給する場合、エチレンの水素化に伴う平衡のシフトにより、生成物である不飽和炭化水素の収率は多少増加するが、エチレンが低濃度ゆえにその効果は決して大きくない。高濃度のエチレンを原料と共に供給する場合には、触媒表面上へのエチレンの強吸着により触媒活性の著しい低下を招く。同一反応器内でエチレンを分割供給する方法も考えられるが、この場合は局所的に触媒と高濃度のエチレンが接触することになり、その結果として局所的な触媒活性の著しい低下を招くことから、やはり効果的であるとは言い難い。こうした背景の下、効果的に平衡を生成物側にシフトし、生成物収率の大幅な増加を可能にするとともに、高価なエチレンのロスを最小限に止める新たなエチレン供給方法の確立が望まれる。 As described above, it is not always easy to find a method for supplying an olefin such as ethylene that maximizes the effect of shifting the equilibrium to the product side. For example, when a low concentration of ethylene is supplied together with the raw material hydrocarbon, the yield of the unsaturated hydrocarbon product is slightly increased due to the shift of the equilibrium due to the hydrogenation of ethylene. Never big. When a high concentration of ethylene is supplied together with the raw material, the catalyst activity is significantly reduced due to the strong adsorption of ethylene on the catalyst surface. A method of supplying ethylene in the same reactor in a divided manner is also conceivable, but in this case, the catalyst and high-concentration ethylene are locally in contact with each other, and as a result, the local catalytic activity is significantly reduced. After all, it is hard to say that it is effective. Against this background, it is desirable to establish a new ethylene supply method that effectively shifts the equilibrium to the product side, enables a significant increase in product yield, and minimizes the loss of expensive ethylene. It is.
したがって本発明は、炭化水素を脱水素して不飽和炭化水素を製造する方法であって、脱水素反応によって生成する水素の受容体としてのエチレンを供給しながら不飽和炭化水素を製造する方法において、エチレンのロスを最小限に留め、かつ長期に亘って収率良く不飽和炭化水素、すなわちオレフィンおよびジエンを製造する方法を提供することを課題とする。 Accordingly, the present invention relates to a method for producing an unsaturated hydrocarbon by dehydrogenating a hydrocarbon, wherein the unsaturated hydrocarbon is produced while supplying ethylene as an acceptor of hydrogen produced by the dehydrogenation reaction. An object of the present invention is to provide a method for producing unsaturated hydrocarbons, that is, olefins and dienes, with a minimum loss of ethylene and with good yield over a long period of time.
本発明者らは上記課題を解決すべく検討を開始し、水素を含む炭化水素ガスとエチレンを混合してから触媒と接触させると、触媒の性能低下が抑えられる場合があることを見い出した。そして、特定の反応器を用いてエチレンを脱水素生成ガスと混合して、水素の受容によるエチレンのエタンへの転化の割合を制御することにより、効果的に炭化水素の脱水素反応における平衡を生成物側にシフトさせるとともにエチレンのロスを最小限に止め、結果として目的生成物である不飽和炭化水素、すなわちオレフィンまたはジエンを従来よりも高効率で製造できることを見い出した。 The present inventors have started investigations to solve the above-mentioned problems, and have found that when a hydrocarbon gas containing hydrogen and ethylene are mixed and then brought into contact with the catalyst, deterioration in the catalyst performance may be suppressed. Then, by mixing ethylene with the dehydrogenation product gas using a specific reactor and controlling the rate of conversion of ethylene to ethane by the acceptance of hydrogen, the equilibrium in the hydrocarbon dehydrogenation reaction is effectively increased. It has been found that the product can be shifted to the product side and the loss of ethylene is minimized, and as a result, the target product, an unsaturated hydrocarbon, that is, olefin or diene, can be produced with higher efficiency than before.
すなわち本発明は、
反応器内で炭化水素の脱水素反応を行って不飽和炭化水素を製造する方法であって、
前記反応器が、第1反応領域、その下流側に設けられた第2反応領域、および前記第1反応領域と前記第2反応領域とを連結する連結領域を有し、
前記方法が、炭化水素(ただし、エチレンを除く。)を含む原料含有ガスを前記第1反応領域に供給し、前記炭化水素の脱水素反応を行って炭化水素、不飽和炭化水素および水素を含む一次生成ガスを得る工程、および
前記連結領域において、前記第1反応領域から供給される前記一次生成ガスにエチレンを混合し、得られた混合ガスを前記第2反応領域に供給し、前記炭化水素の脱水素反応および前記エチレンに前記水素を付加してエタンを生成させる反応を行う工程を含む
ことを特徴とする不飽和炭化水素の製造方法である。That is, the present invention
A method for producing an unsaturated hydrocarbon by dehydrogenating a hydrocarbon in a reactor,
The reactor has a first reaction region, a second reaction region provided on the downstream side thereof, and a connection region that connects the first reaction region and the second reaction region,
The method supplies a raw material-containing gas containing hydrocarbons (excluding ethylene) to the first reaction region, and performs hydrocarbon dehydrogenation to contain hydrocarbons, unsaturated hydrocarbons, and hydrogen. A step of obtaining a primary product gas; and in the connecting region, ethylene is mixed with the primary product gas supplied from the first reaction region, and the resulting mixed gas is supplied to the second reaction region, and the hydrocarbon A process for producing an unsaturated hydrocarbon, comprising a step of performing a dehydrogenation reaction of the above and a reaction of adding the hydrogen to the ethylene to produce ethane.
前記製造方法においては、エチレンのエタンへの転化率は50%以上であることが好ましく、70%以上であることがさらに好ましく、90%以上であることが特に好ましく、95%以上であることが最も好ましい。 In the production method, the conversion rate of ethylene to ethane is preferably 50% or more, more preferably 70% or more, particularly preferably 90% or more, and preferably 95% or more. Most preferred.
前記第2反応領域の下流側で前記反応器から回収されるガスの中にエチレンが含まれる場合には、該エチレンの少なくとも一部は、エタンと分離することなくオフガスとして扱ってもよく、前記連結領域に供給するエチレンの少なくとも一部として用いてもよい。 When ethylene is contained in the gas recovered from the reactor on the downstream side of the second reaction zone, at least a part of the ethylene may be treated as off-gas without being separated from ethane, You may use as at least one part of ethylene supplied to a connection area | region.
前記連結領域には、好ましくは脱水素触媒は存在しない。
前記脱水素反応の際の反応温度は、好ましくは300〜700℃の範囲にあり、さらに好ましくは400〜650℃の範囲にあり、特に好ましくは450〜600℃の範囲にある。また、前記脱水素反応の際の反応圧力は、好ましくは0.01〜3MPaの範囲にある。There is preferably no dehydrogenation catalyst in the connecting region.
The reaction temperature in the dehydrogenation reaction is preferably in the range of 300 to 700 ° C, more preferably in the range of 400 to 650 ° C, and particularly preferably in the range of 450 to 600 ° C. The reaction pressure during the dehydrogenation reaction is preferably in the range of 0.01 to 3 MPa.
原料である前記炭化水素は、好ましくはプロパン、n−ブタンおよびイソブタンから選ばれる少なくとも1種であるか、またはn−ブテンである。
前記原料含有ガスは、好ましくは水蒸気をさらに含有する。The hydrocarbon as the raw material is preferably at least one selected from propane, n-butane and isobutane, or n-butene.
The raw material-containing gas preferably further contains water vapor.
また、脱水素触媒として好ましい形態は、ゼオライトを担体とし、活性成分として亜鉛および第VIIIA族金属が担持された触媒である。このような触媒に含まれる亜鉛の量は、該触媒全体の重量を100重量%とすると、好ましくは0.01〜15重量%であり、第VIIIA族金属の量は、該触媒全体の重量を100重量%とすると、好ましくは0.01〜5重量%である。また前記第VIIIA族金属としては白金が好ましい。 A preferred form of the dehydrogenation catalyst is a catalyst in which zeolite is used as a carrier and zinc and a Group VIIIA metal are supported as active components. The amount of zinc contained in such a catalyst is preferably 0.01 to 15% by weight when the weight of the whole catalyst is 100% by weight, and the amount of the Group VIIIA metal is the weight of the whole catalyst. When it is 100% by weight, it is preferably 0.01 to 5% by weight. The Group VIIIA metal is preferably platinum.
前記ゼオライトとしてはシリカライトまたはボロシリケートが好ましく、MFI構造を有するものがより好ましい。さらに好ましいゼオライト担体は、MFI型ボロシリケートからホウ素原子の少なくとも一部を除去して得られるシリケートであり、シリケート中のホウ素原子残存率が、MFI型ボロシリケート中のホウ素原子全量の80%以下であるものが特に好ましい。 As the zeolite, silicalite or borosilicate is preferable, and one having an MFI structure is more preferable. A more preferable zeolite carrier is a silicate obtained by removing at least a part of boron atoms from MFI-type borosilicate, and the boron atom remaining rate in the silicate is 80% or less of the total amount of boron atoms in MFI-type borosilicate. Some are particularly preferred.
本発明によれば、炭化水素の脱水素反応における平衡を生成物側に大幅にシフトできるとともに、脱水素反応で生じる水素を受容するための高価なエチレンのロスを最小限に止めることができるため、経済上著しく優位に不飽和炭化水素、すなわちオレフィンまたはジエンを製造することが可能となる。 According to the present invention, the equilibrium in hydrocarbon dehydrogenation can be greatly shifted to the product side, and the loss of expensive ethylene for accepting hydrogen generated in the dehydrogenation can be minimized. This makes it possible to produce unsaturated hydrocarbons, that is, olefins or dienes, with a significant economic advantage.
以下、本発明の詳細を説明する。
本発明に係る不飽和炭化水素の製造方法は、反応器内で炭化水素の脱水素反応を行って不飽和炭化水素を製造する方法であって、前記反応器が、第1反応領域、その下流側に設けられた第2反応領域、および前記第1反応領域と前記第2反応領域とを連結する連結領域を有し、前記方法が、炭化水素(ただし、エチレンを除く。)を含む原料含有ガスを前記第1反応領域に供給し、前記炭化水素の脱水素反応を行って炭化水素、不飽和炭化水素および水素を含む一次生成ガスを得る工程、および前記連結領域において、前記第1反応領域から供給される前記一次生成ガスにエチレンを混合し、得られた混合ガスを前記第2反応領域に供給し、前記炭化水素の脱水素反応および前記エチレンに前記水素を付加してエタンを生成させる反応を行う工程を含んでいる。Details of the present invention will be described below.
The method for producing an unsaturated hydrocarbon according to the present invention is a method for producing an unsaturated hydrocarbon by carrying out a hydrocarbon dehydrogenation reaction in a reactor, wherein the reactor comprises a first reaction region, downstream thereof. A second reaction region provided on the side, and a connection region that connects the first reaction region and the second reaction region, and the method contains a raw material containing a hydrocarbon (excluding ethylene). Supplying a gas to the first reaction region and performing a dehydrogenation reaction of the hydrocarbons to obtain a primary product gas containing hydrocarbons, unsaturated hydrocarbons and hydrogen, and in the connection region, the first reaction region Ethylene is mixed with the primary product gas supplied from, the obtained mixed gas is supplied to the second reaction zone, and the hydrocarbon is dehydrogenated and the hydrogen is added to the ethylene to produce ethane. Perform the reaction It contains a degree.
本発明において、前記「反応器」は、前記第1反応領域、前記連結領域および前記第2反応領域(以下、これらをまとめて「直列に連結した反応領域」ともいう。)を含む反応システムの全体を意味する。前記「第1反応領域」は、炭化水素の脱水素反応が行われる領域を意味し、前記「第2反応領域」は、炭化水素の脱水素反応およびエチレンへの水素の付加反応が行われる領域を意味する。 In the present invention, the “reactor” is a reaction system including the first reaction region, the connection region, and the second reaction region (hereinafter collectively referred to as “reaction region connected in series”). Means the whole. The “first reaction region” means a region where a hydrocarbon dehydrogenation reaction is performed, and the “second reaction region” is a region where a hydrocarbon dehydrogenation reaction and a hydrogen addition reaction to ethylene are performed. Means.
前記「直列に連結した反応領域」の系列数は、単一でも良く、複数でも良い。また、各反応領域をそれぞれ別の容器内に設けて、複数の容器を連結して一つの反応器を構成しても良いし、一つの容器内に複数の反応領域を設けて反応器を構成しても良い。あるいはこれらの構成を組み合せてもよい。 The number of series of “reaction regions connected in series” may be single or plural. Also, each reaction region may be provided in a separate container, and a plurality of containers may be connected to constitute one reactor, or a plurality of reaction regions may be provided in one container to constitute a reactor. You may do it. Alternatively, these configurations may be combined.
前記第1反応領域および前記第2反応領域には、通常、脱水素触媒が充填されている。触媒床方式としては公知の触媒床方式のいずれを適用しても良く、触媒床としては固定床、移動床、流動床などが例示できる。一方、前記連結領域には、脱水素触媒が存在しないことが好ましい。脱水素触媒が前記連結領域に存在すると、局所的に触媒と高濃度のエチレンが接触することになり、その結果として局所的な触媒活性の著しい低下を招くことがある。 The first reaction zone and the second reaction zone are usually filled with a dehydrogenation catalyst. Any known catalyst bed system may be applied as the catalyst bed system, and examples of the catalyst bed include a fixed bed, a moving bed, and a fluidized bed. On the other hand, it is preferable that no dehydrogenation catalyst exists in the connection region. When the dehydrogenation catalyst is present in the connection region, the catalyst and high-concentration ethylene are locally in contact with each other, and as a result, the local catalyst activity may be significantly reduced.
本発明では、脱水素反応によって不飽和炭化水素へと変換される炭化水素が反応器に供給される。前記炭化水素としては、炭素数3〜6の脂肪族炭化水素が好ましい。前記炭化水素として特に好ましい化合物は、プロパン、ノルマルブタン、イソブタン、1−ブテン、2−ブテンおよびこれらの混合物である。 In the present invention, hydrocarbons that are converted to unsaturated hydrocarbons by dehydrogenation are fed to the reactor. As said hydrocarbon, a C3-C6 aliphatic hydrocarbon is preferable. Particularly preferred compounds as the hydrocarbon are propane, normal butane, isobutane, 1-butene, 2-butene and mixtures thereof.
本発明で製造される不飽和炭化水素は、原料である前記炭化水素と同一の炭素数を有し且つ炭素炭素不飽和結合の数が前記原料炭化水素よりも少なくとも一つ多い炭化水素であり、工業的な有用性の観点から好ましくはオレフィン(二重結合が1分子内に1つ存在する不飽和炭化水素)およびジエン(二重結合が1分子内に2つ存在する不飽和炭化水素)である。すなわち本発明の不飽和炭化水素の製造方法は、好ましくはオレフィンまたはジエンの製造方法である。上記不飽和炭化水素として特に好ましい化合物は、プロピレン、1−ブテン、2−ブテン、イソブテン、1,3−ブタジエンおよびこれらのと混合物である。1−ブテンと2−ブテンの混合物は通常、n−ブテンと呼ばれる。 The unsaturated hydrocarbon produced in the present invention is a hydrocarbon having the same carbon number as the raw material hydrocarbon and having at least one more carbon-carbon unsaturated bond than the raw material hydrocarbon, From the viewpoint of industrial utility, olefins (unsaturated hydrocarbons having one double bond in one molecule) and dienes (unsaturated hydrocarbons having two double bonds in one molecule) are preferable. is there. That is, the method for producing unsaturated hydrocarbons of the present invention is preferably a method for producing olefins or dienes. Particularly preferred compounds as the unsaturated hydrocarbon are propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene, and mixtures thereof. A mixture of 1-butene and 2-butene is usually referred to as n-butene.
原料である炭化水素のガスは、本発明の効果を阻害しない他のガス(不活性ガス)とともに反応器に供給されても良く、不活性ガスの例として水蒸気、窒素ガス、二酸化炭素ガス、水素ガス、メタンガスなどを挙げることができる。このうち特に、水蒸気が好ましい。炭化水素ガスとこれらの不活性ガスとの混合方法および混合比率については特に制限されない。さらに前記原料含有ガスは、本発明の効果を阻害しない程度の微量のエチレンを含んでいても良いが、好ましくはエチレンを含まない。 The hydrocarbon gas as the raw material may be supplied to the reactor together with other gas (inert gas) that does not impair the effects of the present invention. Examples of the inert gas include water vapor, nitrogen gas, carbon dioxide gas, hydrogen Examples thereof include gas and methane gas. Among these, water vapor is particularly preferable. The mixing method and mixing ratio of hydrocarbon gas and these inert gases are not particularly limited. Further, the raw material-containing gas may contain a trace amount of ethylene that does not hinder the effects of the present invention, but preferably does not contain ethylene.
また本発明では、前記連結領域において、上流側の第1反応領域から供給される一次生成ガス(このガスには、脱水素反応で生じた不飽和炭化水素および水素、ならびに原料である炭化水素が含まれている。)にエチレンを混合し、得られた混合ガスを下流側の第2反応領域に供給する。前記「第2反応領域」の下流側には、前記「第2反応領域」で生成したガスと系外から供給されるエチレンとを混合する連結領域を介して、さらに前記「第2反応領域」が設けられてもよい。 In the present invention, the primary product gas supplied from the upstream first reaction region (in this gas, unsaturated hydrocarbons and hydrogen generated in the dehydrogenation reaction, and hydrocarbons as raw materials) And ethylene is mixed, and the obtained mixed gas is supplied to the second reaction zone on the downstream side. On the downstream side of the “second reaction zone”, the “second reaction zone” is further connected via a connection zone for mixing the gas generated in the “second reaction zone” and ethylene supplied from outside the system. May be provided.
エチレンは、前記第2反応領域で水素の付加反応によりエタンへ転化される。エチレンのエタンへの転化率は、エチレンのロスを最小限に止めるという観点から50%以上であることが好ましく、70%以上であることがさらに好ましく、90%以上であることが特に好ましく、95%以上であることが最も好ましい。エチレンのエタンへの転化率は、供給したエチレンの総量と反応器より得られる生成ガス中に含まれるエタンの量比から計算される。エチレンのエタンへの転化率は、エチレン供給速度によって調節され、第一反応領域からの水素供給速度(A)に対してエチレン供給速度(B)を低くするほど、転化率を高くすることができる。各連結部におけるエチレン供給速度は統一されていても、異なっていても良く、上流側の反応領域からの生成ガス中のエチレン濃度を測定しながら連結部へのエチレン供給速度を調節しても良い。 Ethylene is converted to ethane by hydrogen addition reaction in the second reaction zone. The conversion of ethylene to ethane is preferably 50% or more from the viewpoint of minimizing ethylene loss, more preferably 70% or more, particularly preferably 90% or more, and 95 % Or more is most preferable. The conversion ratio of ethylene to ethane is calculated from the total amount of ethylene supplied and the ratio of ethane contained in the product gas obtained from the reactor. The conversion rate of ethylene to ethane is adjusted by the ethylene supply rate, and the lower the ethylene supply rate (B) relative to the hydrogen supply rate (A) from the first reaction zone, the higher the conversion rate can be. . The ethylene supply rate in each connecting portion may be unified or different, and the ethylene supplying rate to the connecting portion may be adjusted while measuring the ethylene concentration in the product gas from the upstream reaction region. .
第2反応領域の下流側で反応器より得られる生成ガス中にエチレンが含まれる場合、このエチレンの少なくとも一部は、エタンと共にオフガスとして処理してもよく、または、連続式で、もしくはバッチ式で複数回、本発明の製造方法を実施する場合にエタンと共に反応器にリサイクルしてもよい。またオフガスは、燃料ガスとして用いても良いし、熱分解炉に供給してエチレン製造原料として用いてもよい。 When ethylene is contained in the product gas obtained from the reactor on the downstream side of the second reaction zone, at least a part of this ethylene may be treated as off-gas together with ethane, or continuously or batchwise. When the production method of the present invention is carried out a plurality of times, it may be recycled to the reactor together with ethane. The off gas may be used as a fuel gas or may be supplied to a pyrolysis furnace and used as an ethylene production raw material.
前記脱水素反応の際の反応温度の範囲は、好ましくは300〜700℃であり、さらに好ましくは400〜650℃であり、特に好ましくは450〜600℃である。反応温度が前記の下限値以上であると、原料である炭化水素が高い平衡転化率で不飽和炭化水素に転化するため、ワンパスで高い収率で不飽和炭化水素が製造される。また、反応温度が前記の上限値以下であると、コーキング速度が大きくならず、触媒の活性劣化が抑えられるとともに、エタンとエチレンとの間の平衡がエタン側に有利となる。 The range of the reaction temperature in the dehydrogenation reaction is preferably 300 to 700 ° C, more preferably 400 to 650 ° C, and particularly preferably 450 to 600 ° C. When the reaction temperature is equal to or higher than the lower limit, the hydrocarbon as a raw material is converted to an unsaturated hydrocarbon at a high equilibrium conversion rate, so that the unsaturated hydrocarbon is produced in a high yield with a single pass. Further, when the reaction temperature is not more than the above upper limit value, the coking rate is not increased, the catalyst activity deterioration is suppressed, and the equilibrium between ethane and ethylene is advantageous to the ethane side.
反応器に供給される原料炭化水素の分圧の範囲は、好ましくは0.001〜1MPaであり、さらに好ましくは0.005〜0.5MPaである。分圧が低いほど原料である炭化水素の平衡転化率は高くなり、ワンパスでの不飽和炭化水素の収率は大きくなる。希釈ガスを炭化水素と共に反応器に供給することで、炭化水素の分圧を低くすることが可能である。 The range of the partial pressure of the raw material hydrocarbon supplied to the reactor is preferably 0.001 to 1 MPa, and more preferably 0.005 to 0.5 MPa. The lower the partial pressure, the higher the equilibrium conversion rate of the hydrocarbon as a raw material, and the higher the yield of unsaturated hydrocarbons in one pass. By supplying the dilution gas to the reactor together with the hydrocarbon, the partial pressure of the hydrocarbon can be lowered.
反応圧力の範囲は、好ましくは0.01〜3MPaであり、さらに好ましくは0.1〜1.5MPaである。反応圧力が低いほど原料である炭化水素の平衡転化率は高くなり、一度の操作での不飽和炭化水素の収率は大きくなる。0.1MPaよりも低い圧力で実施する場合には、圧力を低く保つための特別な設計および設備を用いても構わない。 The range of reaction pressure becomes like this. Preferably it is 0.01-3 MPa, More preferably, it is 0.1-1.5 MPa. The lower the reaction pressure, the higher the equilibrium conversion rate of the hydrocarbon as a raw material, and the higher the yield of unsaturated hydrocarbons in a single operation. When carrying out at a pressure lower than 0.1 MPa, a special design and equipment for keeping the pressure low may be used.
本発明の製造方法は気相で実施されるため、連続式の反応装置にて反応を実施することが好ましい。このとき、触媒の使用量は重量空間速度WHSV(単位重量の触媒および単位時間当たりの、原料である炭化水素の供給重量)で表すのが簡便であり、また適切である。なお、原料である炭化水素の供給重量にはエチレン供給重量は含まれない。本発明においてWHSVの範囲は、特に限定されないが、好ましくは0.01〜50h-1であり、さらに好ましくは0.1〜20h-1である。Since the production method of the present invention is carried out in the gas phase, the reaction is preferably carried out in a continuous reaction apparatus. At this time, the amount of catalyst used is simply and appropriately expressed by the weight hourly space velocity WHSV (the weight of the feedstock hydrocarbon per unit weight of catalyst and unit time). The feed weight of the hydrocarbon as a raw material does not include the feed weight of ethylene. In the present invention, the range of WHSV is not particularly limited, but is preferably 0.01 to 50 h −1 , more preferably 0.1 to 20 h −1 .
本発明では、好ましくは、活性成分として第VIIIA族金属を担持した触媒が脱水素触媒として用いられる。触媒担体としては、アルミナ担体、アルミン酸亜鉛やアルミン酸マグネシウムのようなスピネル担体、ハイドロタルサイト焼成体、シリカ担体、ゼオライト担体などが利用できる。ゼオライト担体としては、酸性質を抑えたものあるいは持たないものが好ましい。 In the present invention, a catalyst carrying a Group VIIIA metal as an active component is preferably used as the dehydrogenation catalyst. As the catalyst carrier, an alumina carrier, a spinel carrier such as zinc aluminate or magnesium aluminate, a calcined hydrotalcite, a silica carrier, a zeolite carrier and the like can be used. As the zeolite carrier, those with or without acid properties are preferred.
前記第VIIIA族金属とは、旧IUPAC方式の表記であり、IUPAC方式で言えば、第8〜10族の金属である。第VIIIA族の金属として、例えば白金、パラジウム、ルテニウム、イリジウム、ロジウム、ニッケルなどが挙げられる。これらの中でも、触媒活性の観点から白金が好ましい。 The Group VIIIA metal is an old IUPAC system notation, which is a Group 8-10 metal in the IUPAC system. Examples of the Group VIIIA metal include platinum, palladium, ruthenium, iridium, rhodium, and nickel. Among these, platinum is preferable from the viewpoint of catalytic activity.
前記脱水素触媒に含まれる第VIIIA族金属の量の範囲は、触媒全体の重量(100重量%)に対する第VIIIA族金属原子の重量の割合として、好ましくは0.01〜5重量%、さらに好ましくは0.05〜3重量%、特に好ましくは0.1〜1.5重量%である。 The range of the amount of the Group VIIIA metal contained in the dehydrogenation catalyst is preferably 0.01 to 5% by weight, more preferably as the ratio of the weight of the Group VIIIA metal atom to the total weight of the catalyst (100% by weight). Is 0.05 to 3% by weight, particularly preferably 0.1 to 1.5% by weight.
本発明では、活性成分の1つとして、第VIIIA族金属に加えて亜鉛も含む脱水素触媒が好ましく用いられる。前記脱水素触媒に含まれる亜鉛の量は、触媒全体の重量(100重量%)に対する亜鉛金属原子の重量の割合として、好ましくは0.01〜15重量%の範囲が好ましく、さらに好ましくは0.05〜5重量%、特に好ましくは0.1〜3重量%である。 In the present invention, as one of the active components, a dehydrogenation catalyst containing zinc in addition to the Group VIIIA metal is preferably used. The amount of zinc contained in the dehydrogenation catalyst is preferably in the range of 0.01 to 15% by weight, and more preferably in the range of 0.01 to 15% by weight as the ratio of the weight of zinc metal atoms to the weight of the whole catalyst (100% by weight). It is 05 to 5% by weight, particularly preferably 0.1 to 3% by weight.
亜鉛と第VIIIA族金属との割合は、モル比(Znのモル数/第VIIIA族金属のモル数)として通常0.5以上、好ましくは0.5〜50、より好ましくは1〜30、さらに好ましくは1〜20である。 The ratio of zinc to the Group VIIIA metal is usually 0.5 or more, preferably 0.5 to 50, more preferably 1 to 30, as the molar ratio (number of moles of Zn / number of moles of Group VIIIA metal). Preferably it is 1-20.
前記ゼオライトとは、結晶性の多孔質アルミノケイ酸塩の総称として用いられる名前であり、トポロジーに従った構造コードにより分類される。各構造コードに対しては構造、組成、結晶学的データに関する情報が知られている(例えばAtlas of Zeolite Structure Types、4th Ed.、Elsevier 1996、他にCollection of Simulated XRD Powder Patterns for Zeolites、Elsevier 1996)。また、同様の結晶構造を有するアルミノケイ酸塩以外の化合物として、アルミニウムを含まないシリカライトや、アルミニウムの代わりに鉄、ガリウム、チタンなどを含むメタロケイ酸塩などもゼオライトに含まれる(例えば「ゼオライトの科学と工学」、講談社サイエンティフィク)。 The zeolite is a name used as a general term for crystalline porous aluminosilicates, and is classified by a structure code according to the topology. For each structure code, information about the structure, composition, crystallographic data is known (eg Atlas of Zeolite Structure Types, 4th Ed., Elsevier 1996, and others of Collection of Simulated XRD Powder Patterns 96). ). Further, as a compound other than an aluminosilicate having a similar crystal structure, silicalite not containing aluminum, metallosilicate containing iron, gallium, titanium and the like instead of aluminum are also included in zeolite (for example, “zeolite of Science and Engineering ", Kodansha Scientific).
本発明においては、アルミニウムを含まないシリカライトもしくはアルミニウムの代わりにホウ素を含むメタロケイ酸塩であるボロシリケートを、触媒担体として用いることが好ましい。 In the present invention, silicalite containing no aluminum or borosilicate which is a metallosilicate containing boron instead of aluminum is preferably used as a catalyst carrier.
本発明で用いられるシリカライトもしくはボロシリケート中のアルミニウム含有量は特に限定されないが、これらゼオライト中のシリカ/アルミナモル比(SiO2のモル数/Al2O3のモル数)は100以上であることが好ましく、500以上であることがより好ましく、1000以上であることが特に好ましく、2000以上であることが最も好ましい。シリカ/アルミナモル比が100以上であると、製造された不飽和炭化水素がアルミニウムに起因する酸点上でオリゴマー化するなどの副反応が抑制される。シリカ/アルミナモル比が2000以上であれば、こうした副反応をさらに効果的に抑制できる。The aluminum content in the silicalite or borosilicate used in the present invention is not particularly limited, but the silica / alumina molar ratio (number of moles of SiO 2 / number of moles of Al 2 O 3 ) in these zeolites is 100 or more. Is more preferably 500 or more, particularly preferably 1000 or more, and most preferably 2000 or more. When the silica / alumina molar ratio is 100 or more, side reactions such as oligomerization of the produced unsaturated hydrocarbon on the acid sites caused by aluminum are suppressed. If the silica / alumina molar ratio is 2000 or more, such side reactions can be more effectively suppressed.
ボロシリケート中のホウ素含有量は特に限定されないが、100〜30000ppmが好ましく、500〜10000ppmがより好ましく、1000〜80000ppmが特に好ましい。 The boron content in the borosilicate is not particularly limited, but is preferably 100 to 30000 ppm, more preferably 500 to 10000 ppm, and particularly preferably 1000 to 80000 ppm.
シリカライトもしくはボロシリケート中のアルカリ金属およびアルカリ土類金属の含有量は、特に限定されないが、これらの金属が実質的に存在しないことが好ましい。「実質的に存在しない」とは、シリカライトもしくはボロシリケート中のアルカリ金属およびアルカリ土類金属の含有量が各々300ppm以下であることを指す。 The content of alkali metal and alkaline earth metal in silicalite or borosilicate is not particularly limited, but it is preferable that these metals are not substantially present. “Substantially absent” means that the content of alkali metal and alkaline earth metal in silicalite or borosilicate is 300 ppm or less, respectively.
さらには、前記シリカライトおよび前記ボロシリケートがMFI構造を有していることが好ましい。
MFI構造を有するボロシリケート(以下「MFI型ボロシリケート」ともいう。)をそのまま担体として用いてもよいが、前記MFI型ボロシリケートからホウ素原子の少なくとも一部を除去して得られるシリケートを担体として用いることがさらに好ましい。Furthermore, it is preferable that the silicalite and the borosilicate have an MFI structure.
A borosilicate having an MFI structure (hereinafter also referred to as “MFI-type borosilicate”) may be used as a carrier as it is, but a silicate obtained by removing at least a part of boron atoms from the MFI-type borosilicate is used as a carrier. More preferably, it is used.
前記MFI型ボロシリケートからホウ素原子の少なくとも一部を除去した後のシリケート中のホウ素原子残存率は、前記ボロシリケート中のホウ素原子全量の80%以下であることが好ましく、50%以下であることがより好ましく、30%以下であることが特に好ましく、20%以下であることが最も好ましい。 The boron atom remaining rate in the silicate after removing at least a part of boron atoms from the MFI-type borosilicate is preferably 80% or less of the total amount of boron atoms in the borosilicate, and is 50% or less. Is more preferably 30% or less, and most preferably 20% or less.
ホウ素原子残存率は、ホウ素原子を除去する前のボロシリケートにおけるホウ素原子の含有量と、ホウ素原子を除去した後のシリケートにおけるホウ素原子の含有量との比較により算出される。前記ボロシリケートからホウ素原子の少なくとも一部を除去する方法に制限はなく、公知の方法、例えば無機酸もしくは有機酸の水溶液で処理する方法などが採用される。 The boron atom residual rate is calculated by comparing the boron atom content in the borosilicate before removing the boron atom and the boron atom content in the silicate after removing the boron atom. The method for removing at least a part of boron atoms from the borosilicate is not limited, and a known method such as a method of treating with an aqueous solution of an inorganic acid or an organic acid is employed.
本発明に好適の脱水素触媒は、第VIIIA族金属化合物や亜鉛化合物を触媒担体に担持した後、乾燥および焼成を行うことで製造できる。乾燥条件は特に制限されないが、乾燥は、通常は80〜150℃で所定の時間実施される。焼成条件も特に制限されないが、焼成は、通常は400〜600℃で所定の時間実施される。焼成時の雰囲気についても特に制限されないが、焼成は、通常は空気流通下で実施される。 A dehydrogenation catalyst suitable for the present invention can be produced by supporting a Group VIIIA metal compound or zinc compound on a catalyst carrier, followed by drying and calcination. The drying conditions are not particularly limited, but drying is usually performed at 80 to 150 ° C. for a predetermined time. Although the firing conditions are not particularly limited, the firing is usually performed at 400 to 600 ° C. for a predetermined time. The atmosphere during firing is not particularly limited, but firing is usually performed under air circulation.
第VIIIA族金属および亜鉛は、例えば対応する金属硝酸塩、金属塩化物または金属錯体などの金属化合物を使用して、触媒担持することが可能である。触媒担体への担持は、イオン交換法あるいは含浸法など公知の方法により実施することができ、担持の序列についても特に制限されない。前記の第VIIIA族金属化合物としては、例えば塩化白金酸、塩化テトラアンミン白金、水酸化テトラアンミン白金、硝酸テトラアンミン白金などが挙げられる。前記の亜鉛化合物としては、例えば硝酸亜鉛、塩化亜鉛、酢酸亜鉛などが挙げられる。 The Group VIIIA metal and zinc can be supported on a catalyst using, for example, a metal compound such as the corresponding metal nitrate, metal chloride or metal complex. Support on the catalyst carrier can be carried out by a known method such as an ion exchange method or an impregnation method, and the order of support is not particularly limited. Examples of the Group VIIIA metal compound include chloroplatinic acid, tetraammineplatinum chloride, tetraammineplatinum hydroxide, and tetraammineplatinum nitrate. Examples of the zinc compound include zinc nitrate, zinc chloride, and zinc acetate.
脱水素触媒は、反応領域に充填するにあたり、採用する前記触媒床方式に適した任意の形態で用いることができ、粉末、顆粒でも良いし、ペレット、球状、円柱状など、成型したものでも良い。成型方法について制限はなく、押し出し成型、打錠成型、コーティング成型など公知の方法が採用される。 The dehydrogenation catalyst can be used in any form suitable for the catalyst bed system employed when filling the reaction region, and may be a powder, a granule, or a molded one such as a pellet, a sphere, or a cylinder. . There is no restriction | limiting about a shaping | molding method, Well-known methods, such as extrusion molding, tableting shaping | molding, and coating shaping | molding, are employ | adopted.
触媒を反応器中で不飽和炭化水素製造に用いる際には、事前に触媒を活性化するための前処理を実施しても良く、前処理には、通常は、前記触媒に水素あるいは一酸化炭素などの還元性ガスを接触させる。これらの還元性ガスは希釈せずに用いても良いし、上述の不活性ガスで適宜希釈して用いても良い。 When the catalyst is used for the production of unsaturated hydrocarbons in the reactor, a pretreatment for activating the catalyst may be performed in advance, and the pretreatment usually involves adding hydrogen or monoxide to the catalyst. Contact a reducing gas such as carbon. These reducing gases may be used without being diluted, or may be appropriately diluted with the above-described inert gas.
不飽和炭化水素の製造に供して一定時間が経過し、触媒活性が低下した場合には、不飽和炭化水素の製造に供するのを中止し、再生処理と呼ばれる方法によって触媒を再活性化してもよい。その方法は特に制限されないが、通常は所定の温度で酸素を含むガスを触媒と接触させることにより、触媒表面上に付着したコークとよばれる炭化水素の重質物を燃焼除去する方法が採用される。 When a certain amount of time has passed since the production of unsaturated hydrocarbons and the catalytic activity has decreased, the production of unsaturated hydrocarbons is stopped and the catalyst can be reactivated by a method called regeneration treatment. Good. The method is not particularly limited, but usually a method of burning and removing heavy hydrocarbons called coke deposited on the catalyst surface by contacting a gas containing oxygen at a predetermined temperature with the catalyst is adopted. .
脱水素触媒の再生は、反応領域の触媒床方式に適した公知の方法であれば、特に限定されない。例えば、固定床であれば、触媒を系列から切り離して、容器内に充填したままで触媒を再生した後、触媒を系列に再び連結する方法を用いて良い。移動床や流動床であれば、充填されている触媒の一部を抜き出して、再生処理を施した後に反応領域へ戻すことで、触媒を循環させつつ、連続的に再生処理を施しても良い。 The regeneration of the dehydrogenation catalyst is not particularly limited as long as it is a known method suitable for the catalyst bed system in the reaction zone. For example, in the case of a fixed bed, a method may be used in which the catalyst is separated from the series, the catalyst is regenerated while being filled in the container, and then the catalyst is reconnected to the series. In the case of a moving bed or a fluidized bed, a part of the packed catalyst may be extracted and returned to the reaction region after being subjected to a regeneration process, whereby the regeneration process may be continuously performed while circulating the catalyst.
以下に実施例を示して本発明をより詳細に説明するが、本発明はこれら実施例に限定されるものではない。
(触媒調製1)
MFI型ボロシリケート10gを、1N硝酸水溶液200ml中で80℃、2時間攪拌した後、ろ過してケーキとろ液に分別した。さらに、ろ別されたケーキを、1N硝酸水溶液200ml中で80℃、2時間攪拌した後、ろ過してケーキとろ液に分別する、という操作を2回繰り返し、次いでろ別されたケーキを、使用された洗浄液が中性になるまで蒸留水で洗浄した。洗浄されたケーキを、空気を流通させ120℃に保持した静置式電気炉内で3時間かけて乾燥させた後、引き続いて500℃で4時間焼成して、MFI型ボロシリケートからホウ素原子の少なくとも一部を除去したシリケートを得た。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(Catalyst preparation 1)
10 g of MFI-type borosilicate was stirred in 200 ml of 1N nitric acid aqueous solution at 80 ° C. for 2 hours, and then filtered to separate into a cake and a filtrate. Furthermore, the operation of stirring the filtered cake in 200 ml of 1N nitric acid aqueous solution at 80 ° C. for 2 hours and then filtering to separate the cake and the filtrate was repeated twice, and then the filtered cake was used. Washed with distilled water until the washed solution was neutral. The washed cake was dried for 3 hours in a static electric furnace in which air was circulated and maintained at 120 ° C., and then calcined at 500 ° C. for 4 hours. From the MFI-type borosilicate, at least boron atoms were baked. A silicate with a part removed was obtained.
(触媒調製2)
触媒調製1で得たシリケート2gに、硝酸亜鉛六水和物0.058gを含む水溶液0.66gを添加して、incipient−wetness法にて亜鉛イオンを含浸させた。亜鉛イオンが含浸されたシリケートを、空気を流通させ120℃に保持した静置式電気炉内で3時間かけて乾燥させた後、引き続いて500℃、4時間焼成して、亜鉛が担持されたシリケートを調製した。(Catalyst preparation 2)
To 2 g of the silicate obtained in Catalyst Preparation 1, 0.66 g of an aqueous solution containing 0.058 g of zinc nitrate hexahydrate was added and impregnated with zinc ions by an incipient-wetness method. The silicate impregnated with zinc ions is dried for 3 hours in a static electric furnace maintained at 120 ° C. through which air is circulated, and then baked at 500 ° C. for 4 hours to silicate on which zinc is supported Was prepared.
(触媒調製3)
触媒調製2で得た亜鉛が担持されたシリケート1.5gに、塩化白金酸六水和物0.0127gを含有する水溶液0.375gを添加して、incipient−wetness法にて白金イオンを含浸させた。白金イオンが含浸されたシリケートを、空気を流通させ120℃に保持した静置式電気炉内で3時間かけて乾燥させた後、引き続いて500℃、4時間焼成して、白金および亜鉛が担持されたシリケートの粉末を得た。このシリケートの白金担持量は0.32重量%、亜鉛担持量は0.64重量%であった。
次に、得られた粉末を円板状に圧縮成型した後に破砕し、篩で250〜500マイクロメートルに粒度を整えて、触媒Aを得た。(Catalyst preparation 3)
Add 0.375 g of an aqueous solution containing 0.0127 g of chloroplatinic acid hexahydrate to 1.5 g of the zinc-supported silicate obtained in Catalyst Preparation 2, and impregnate it with platinum ions by the incipient-wetness method. It was. The silicate impregnated with platinum ions is dried for 3 hours in a static electric furnace maintained at 120 ° C. through which air is circulated, and then baked at 500 ° C. for 4 hours to support platinum and zinc. Silicate powder was obtained. This silicate had a platinum loading of 0.32 wt% and a zinc loading of 0.64 wt%.
Next, the obtained powder was compression-molded into a disk shape and then crushed, and the particle size was adjusted to 250 to 500 micrometers with a sieve to obtain Catalyst A.
[実施例1]
2本の小型固定床反応管(反応管1、反応管2)に、触媒Aを0.1gずつ充填した後、各触媒Aに前処理(600℃で2時間加熱)を施した。続いて2本の反応管を、反応管内のガスの流れの上流側から下流側に向かって反応管1、2の順に直列に連結し、反応管1に、炭化水素としてプロパンを毎時3.2g、窒素を毎時3.0gの速度で供給を始めると共に、反応管1と反応管2を繋ぐ配管(連結部)に、エチレンを毎時0.97gの速度で供給し始めた。連結部には、触媒Aを充填しなかった。そしてプロパン供給開始直後に、各反応管の温度設定を500℃に変更した。実際に2つの反応管の温度が500℃になるまでには、約40分かかった。プロパンの供給開始時刻を反応開始時刻として、反応管2から排出される生成ガスの各経過時間における各炭化水素成分と水素の濃度をGCで分析し、その分析結果に基づいて、プロパンとエチレンの転化率やプロピレンの収率を算定した。結果を表1に示す。なおこの条件でのWHSVは16hr-1であった。[Example 1]
Two small fixed bed reaction tubes (reaction tube 1, reaction tube 2) were filled with 0.1 g of catalyst A, and each catalyst A was pretreated (heated at 600 ° C. for 2 hours). Subsequently, the two reaction tubes were connected in series in the order of reaction tubes 1 and 2 from the upstream side to the downstream side of the gas flow in the reaction tube, and 3.2 g / hour of propane was added to the reaction tube 1 as a hydrocarbon. Nitrogen was started to be supplied at a rate of 3.0 g / h, and ethylene was started to be supplied to a pipe (connecting portion) connecting the reaction tube 1 and the reaction tube 2 at a rate of 0.97 g / h. The connecting portion was not filled with catalyst A. Immediately after the start of propane supply, the temperature setting of each reaction tube was changed to 500 ° C. It took about 40 minutes for the temperature of the two reaction tubes to reach 500 ° C. Using the propane supply start time as the reaction start time, the hydrocarbon components and hydrogen concentrations at each elapsed time of the product gas discharged from the reaction tube 2 are analyzed by GC. Based on the analysis results, the propane and ethylene concentrations are analyzed. Conversion and propylene yield were calculated. The results are shown in Table 1. Note that the WHSV under these conditions was 16 hr −1 .
[比較例1]
エチレンを供給しなかったことと、反応管1に、プロパンを毎時3.2g、窒素を毎時4.0gの速度で供給したこと以外は実施例1と同様にしてプロパン脱水素反応を行った。結果を表2に示す。エチレンを用いないと、プロピレン収率は反応平衡値近傍に制限されていることが分かる。[Comparative Example 1]
The propane dehydrogenation reaction was performed in the same manner as in Example 1 except that ethylene was not supplied and that the reaction tube 1 was supplied with 3.2 g of propane and nitrogen at a rate of 4.0 g per hour. The results are shown in Table 2. It can be seen that without ethylene, the propylene yield is limited to around the reaction equilibrium value.
[比較例2]
エチレンを各連結部からではなく反応管1に、毎時0.97gの速度で、プロパンや窒素と共に供給した以外は、実施例1と同様にしてプロパン脱水素反応を行った。結果を表3に示す。また、実施例1、比較例1、および比較例2の転化率の推移を図1に示した。実施例1との比較から、一括でエチレンを供給した場合、エチレン転化率やプロパン転化率が時間経過に従って低下しやすいことが分かる。[Comparative Example 2]
A propane dehydrogenation reaction was carried out in the same manner as in Example 1 except that ethylene was supplied to the reaction tube 1 instead of from each connecting portion at a rate of 0.97 g per hour together with propane and nitrogen. The results are shown in Table 3. Moreover, transition of the conversion rate of Example 1, Comparative Example 1, and Comparative Example 2 is shown in FIG. From the comparison with Example 1, it can be seen that when ethylene is supplied all at once, the ethylene conversion rate and the propane conversion rate tend to decrease with time.
[実施例2]
実施例1と同様にして、2本の小型固定床反応管(反応管1、反応管2)に、触媒Aを充填した後、各触媒Aを前処理(600℃で2時間加熱)した。続いて2本の反応管を、反応管内のガスの流れの上流側から下流側に向かって反応管1、2の順に直列に連結し、反応管1に、炭化水素として1−ブテンを毎時0.64g、窒素を毎時1.68g、水蒸気を毎時0.51gの速度で供給を始めると共に、各反応管の温度設定を500℃に変更した。実際に2つの反応管の温度が500℃になるまでには、約40分かかった。反応管の温度が500℃になった時から50時間、そのままのガス供給速度条件で流通処理を継続して、触媒に予備反応処理を施した。その後、反応管1と反応管2を繋ぐ配管(連結部)に、エチレンを毎時0.08gの速度で供給し始めると共に、窒素の流量を毎時1.60gに変更した。連結部には、実施例1と同様に、触媒Aを充填しなかった。そしてエチレンの供給開始時刻を反応開始時刻として、反応管2から排出される生成ガスの各経過時間における各炭化水素成分と水素の濃度をGCで分析し、その分析結果に基づいて、ノルマルブテンとエチレンの転化率やブタジエンの収率を算定した。結果を表4に示す。この条件でのWHSVは3.2hr-1であった。なおノルマルブテンの転化率は、次の式に従って算定した。
X=(Y−Z)/Y×100
ここでXはノルマルブテン転化率、Yは単位時間あたりの1−ブテン供給モル量、Zは生成ガス中の未反応1−ブテン、トランス−2−ブテン、およびシス−2−ブテンの総モル量)を意味する。[Example 2]
In the same manner as in Example 1, two small fixed bed reaction tubes (reaction tube 1 and reaction tube 2) were filled with catalyst A, and then each catalyst A was pretreated (heated at 600 ° C. for 2 hours). Subsequently, the two reaction tubes are connected in series in the order of reaction tubes 1 and 2 from the upstream side to the downstream side of the gas flow in the reaction tube, and 1-butene is added to the reaction tube 1 as a hydrocarbon at 0 hour per hour. .64 g, nitrogen was supplied at a rate of 1.68 g / h, and water vapor was supplied at a rate of 0.51 g / h, and the temperature setting of each reaction tube was changed to 500 ° C. It took about 40 minutes for the temperature of the two reaction tubes to reach 500 ° C. The flow treatment was continued under the same gas supply rate conditions for 50 hours after the temperature of the reaction tube reached 500 ° C., and the catalyst was subjected to preliminary reaction treatment. Thereafter, ethylene was started to be supplied at a rate of 0.08 g / hr to the pipe (connecting portion) connecting the reaction tube 1 and the reaction tube 2 and the nitrogen flow rate was changed to 1.60 g / hr. As in Example 1, the connecting portion was not filled with the catalyst A. Then, using the ethylene supply start time as the reaction start time, the concentration of each hydrocarbon component and hydrogen in each elapsed time of the product gas discharged from the reaction tube 2 is analyzed by GC. Based on the analysis result, normal butene and The ethylene conversion rate and butadiene yield were calculated. The results are shown in Table 4. The WHSV under these conditions was 3.2 hr −1 . The normal butene conversion was calculated according to the following formula.
X = (Y−Z) / Y × 100
Where X is the normal butene conversion, Y is the molar amount of 1-butene fed per unit time, and Z is the total molar amount of unreacted 1-butene, trans-2-butene and cis-2-butene in the product gas. ).
[比較例3]
エチレンを供給しなかったことと、50時間の予備反応処理の後、予備反応処理条件と同一の供給速度で1−ブテン、窒素および水蒸気を含む原料含有ガスを反応管1に供給したこと以外は、実施例2と同様にして1−ブテン脱水素反応を行った。結果を表5に示す。[Comparative Example 3]
Except that ethylene was not supplied, and after 50 hours of pre-reaction treatment, the raw material-containing gas containing 1-butene, nitrogen and water vapor was supplied to the reaction tube 1 at the same supply rate as the pre-reaction treatment conditions. The 1-butene dehydrogenation reaction was carried out in the same manner as in Example 2. The results are shown in Table 5.
[比較例4]
エチレンを、各連結部からではなく反応管1に、毎時0.08gの速度で、1−ブテン、窒素ならびに水蒸気と共に供給した以外は、実施例2と同様にして1−ブテン脱水素反応を行った。結果を表6に示す。[Comparative Example 4]
The 1-butene dehydrogenation reaction was carried out in the same manner as in Example 2 except that ethylene was supplied to the reaction tube 1 instead of from each connecting portion at a rate of 0.08 g per hour together with 1-butene, nitrogen and water vapor. It was. The results are shown in Table 6.
Claims (23)
前記反応器が、第1反応領域、その下流側に設けられた第2反応領域、および前記第1反応領域と前記第2反応領域とを連結する連結領域を有し、
前記方法が、炭化水素(ただし、エチレンを除く。)を含む原料含有ガスを前記第1反応領域に供給し、前記炭化水素の脱水素反応を行って炭化水素、不飽和炭化水素および水素を含む一次生成ガスを得る工程、および
前記連結領域において、前記第1反応領域から供給される前記一次生成ガスにエチレンを混合し、得られた混合ガスを前記第2反応領域に供給し、前記炭化水素の脱水素反応および前記エチレンに前記水素を付加してエタンを生成させる反応を行う工程を含む
不飽和炭化水素の製造方法。A method for producing an unsaturated hydrocarbon by dehydrogenating a hydrocarbon in a reactor,
The reactor has a first reaction region, a second reaction region provided on the downstream side thereof, and a connection region that connects the first reaction region and the second reaction region,
The method supplies a raw material-containing gas containing hydrocarbons (excluding ethylene) to the first reaction region, and performs hydrocarbon dehydrogenation to contain hydrocarbons, unsaturated hydrocarbons, and hydrogen. A step of obtaining a primary product gas; and in the connecting region, ethylene is mixed with the primary product gas supplied from the first reaction region, and the resulting mixed gas is supplied to the second reaction region, and the hydrocarbon A process for producing an unsaturated hydrocarbon, comprising a step of performing a dehydrogenation reaction of the above and a reaction of adding the hydrogen to the ethylene to produce ethane.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014073070 | 2014-03-31 | ||
JP2014073070 | 2014-03-31 | ||
PCT/JP2015/059946 WO2015152159A1 (en) | 2014-03-31 | 2015-03-30 | Method for producing unsaturated hydrocarbon |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2015152159A1 true JPWO2015152159A1 (en) | 2017-04-13 |
JP6446033B2 JP6446033B2 (en) | 2018-12-26 |
Family
ID=54240482
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016511885A Expired - Fee Related JP6446033B2 (en) | 2014-03-31 | 2015-03-30 | Process for producing unsaturated hydrocarbons |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP6446033B2 (en) |
TW (1) | TW201542513A (en) |
WO (1) | WO2015152159A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3000800A1 (en) * | 2014-09-23 | 2016-03-30 | Borealis AG | An endothermic gas phase catalytic dehydrogenation process |
JP6633440B2 (en) * | 2016-03-31 | 2020-01-22 | 三菱ケミカル株式会社 | Alkane dehydrogenation catalyst and method for producing alkene using the same |
US10221110B2 (en) * | 2016-12-08 | 2019-03-05 | Evonik Degussa Gmbh | Dehydrogenation of olefin-rich hydrocarbon mixtures |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008523013A (en) * | 2004-12-09 | 2008-07-03 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing propene from propane |
JP2009531368A (en) * | 2006-03-29 | 2009-09-03 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing propene from propane |
JP2009544746A (en) * | 2006-07-28 | 2009-12-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Long-term method for continuous degenerative hydrocarbon partial dehydrogenation of hydrocarbons to be dehydrogenated |
JP2012512015A (en) * | 2008-12-18 | 2012-05-31 | ティッセンクルップ ウーデ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Variations in tin impregnation of alkane dehydrogenation catalysts. |
JP2012519685A (en) * | 2009-03-05 | 2012-08-30 | ユーオーピー エルエルシー | Hydrocarbon dehydrogenation method |
-
2015
- 2015-03-30 WO PCT/JP2015/059946 patent/WO2015152159A1/en active Application Filing
- 2015-03-30 JP JP2016511885A patent/JP6446033B2/en not_active Expired - Fee Related
- 2015-03-31 TW TW104110418A patent/TW201542513A/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008523013A (en) * | 2004-12-09 | 2008-07-03 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing propene from propane |
JP2009531368A (en) * | 2006-03-29 | 2009-09-03 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing propene from propane |
JP2009544746A (en) * | 2006-07-28 | 2009-12-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Long-term method for continuous degenerative hydrocarbon partial dehydrogenation of hydrocarbons to be dehydrogenated |
JP2012512015A (en) * | 2008-12-18 | 2012-05-31 | ティッセンクルップ ウーデ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Variations in tin impregnation of alkane dehydrogenation catalysts. |
JP2012519685A (en) * | 2009-03-05 | 2012-08-30 | ユーオーピー エルエルシー | Hydrocarbon dehydrogenation method |
Also Published As
Publication number | Publication date |
---|---|
WO2015152159A1 (en) | 2015-10-08 |
JP6446033B2 (en) | 2018-12-26 |
TW201542513A (en) | 2015-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5828975B2 (en) | Catalyst regeneration | |
JP6595606B2 (en) | Catalyst and process for producing olefins | |
US9713804B2 (en) | Catalyst composition for the dehydrogenation of alkanes | |
TWI729287B (en) | Processes for regenerating catalysts | |
WO2011133262A1 (en) | Regenerable composite catalysts for hydrocarbon aromatization | |
TW201821159A (en) | Hydrocarbon conversion process | |
US20200078776A1 (en) | Modified Crystalline Aluminosilicate for Dehydration of Alcohols | |
JP4335144B2 (en) | Method for producing lower olefin | |
JP5061852B2 (en) | Alkene production method | |
JP6446033B2 (en) | Process for producing unsaturated hydrocarbons | |
JP6698110B2 (en) | Catalyst and hydrocarbon conversion process using the catalyst | |
JP6426711B2 (en) | Method for producing unsaturated hydrocarbon | |
KR102464447B1 (en) | Catalyst system and process for conversion of hydrocarbon feed using the catalyst system | |
TW201822879A (en) | Hydrocarbon conversion catalyst system | |
JP6527364B2 (en) | Process for producing a product containing butadiene | |
JPH1033987A (en) | Catalyst for producing aromatic hydrocarbon | |
JP6782718B2 (en) | How to convert hydrocarbon feedstock | |
JP2023001522A (en) | Method for producing cyclopentadiene | |
JP2022127708A (en) | Method of producing benzene | |
TW201707788A (en) | A hydrocarbon conversion catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171006 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180626 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20180823 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181024 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20181120 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181130 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6446033 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |