CN101115700B - Method for producing aromatic compound and method for producing hydrogenated aromatic compound - Google Patents
Method for producing aromatic compound and method for producing hydrogenated aromatic compound Download PDFInfo
- Publication number
- CN101115700B CN101115700B CN2006800040248A CN200680004024A CN101115700B CN 101115700 B CN101115700 B CN 101115700B CN 2006800040248 A CN2006800040248 A CN 2006800040248A CN 200680004024 A CN200680004024 A CN 200680004024A CN 101115700 B CN101115700 B CN 101115700B
- Authority
- CN
- China
- Prior art keywords
- gas
- aromatics
- hydrogen
- circuit
- aromatic compound
- 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.)
- Active
Links
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 40
- 239000007789 gas Substances 0.000 claims abstract description 279
- 238000000034 method Methods 0.000 claims abstract description 140
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 114
- 239000001257 hydrogen Substances 0.000 claims abstract description 114
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 113
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 103
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 98
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 78
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 78
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 73
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 70
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 67
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims description 59
- 238000005984 hydrogenation reaction Methods 0.000 claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 69
- 238000006243 chemical reaction Methods 0.000 abstract description 65
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 230000002211 methanization Effects 0.000 abstract 2
- 235000011089 carbon dioxide Nutrition 0.000 description 85
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 57
- 150000001875 compounds Chemical class 0.000 description 48
- 239000000203 mixture Substances 0.000 description 46
- -1 methane.In addition Chemical class 0.000 description 22
- 239000000571 coke Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 17
- 239000000446 fuel Substances 0.000 description 16
- 229910052914 metal silicate Inorganic materials 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000002309 gasification Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000012545 processing Methods 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
- 238000011084 recovery Methods 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000112 cooling gas Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001344 alkene derivatives Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- ZIZHEHXAMPQGEK-UHFFFAOYSA-N dirhenium decacarbonyl Chemical group [Re].[Re].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] ZIZHEHXAMPQGEK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229940063583 high-density polyethylene Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 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
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- CBSVJWYOTGMOBT-UHFFFAOYSA-N nitric acid rhenium Chemical compound [Re].[N+](=O)(O)[O-] CBSVJWYOTGMOBT-UHFFFAOYSA-N 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 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
- 238000001149 thermolysis Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/04—Benzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
-
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed is an industrially advantageous process for producing an aromatic compound by means of a catalytic reaction of a lower hydrocarbon. The process comprises: a methanization step where a hydrogen-containing gas is allowed to contact with carbon monoxide and/or carbon dioxide in the presence of a catalyst to cause the reaction of the hydrogen in the gas with carbon monoxide and/or carbon dioxide, thereby converting these components into methane and water; and an aromatic compound synthesis step where a lower hydrocarbon is reacted with methane produced in the methanization step in the presence of a catalyst to generate a gaseous product containing an aromatic compound and hydrogen.
Description
Technical field
The present invention relates to the manufacture method of aromatics, at length, include the manufacture method of the aromatics that is beneficial to the industrial catalyzed reaction of utilizing lower hydrocarbon such as methane.In addition, the manufacture method that also relates to a kind of aromatics hydrogenant hydroaromatic compound that the present invention is obtained.
Background technology
For the manufacturing of the aromatics of the catalyzed reaction of utilizing lower hydrocarbon such as methane, the scheme (patent documentation 1～7) of the improvement of many relevant catalyzer has been proposed.
Patent documentation 1: the spy opens flat 10-272366 communique
Patent documentation 2: the spy opens flat 11-60514 communique
Patent documentation 3: the spy opens the 2001-334151 communique
Patent documentation 4: the spy opens the 2001-334152 communique
Patent documentation 5: the spy opens the 2002-336704 communique
Patent documentation 6: the spy opens the 2004-97891 communique
Patent documentation 7: the spy opens the 2004-269398 communique
But, for the improvement of operation self, as if fully do not mention, according to inventor's etc. research, found following problem.
Promptly, in the industry of the aromatics of the catalyzed reaction of utilizing lower hydrocarbon is made, the reacted gas that contains the unreacted lower hydrocarbon should be recycled, but in the aromatic series reaction of lower hydrocarbon, produce by product hydrogen, contain hydrogen in the generation gas that in the aromatics synthesis procedure, obtains.Therefore, separated the gas that contains the unreacted lower hydrocarbon behind the aromatics,, thereby can not obtain industrial sufficient reaction effect then because hydrogen dilutes lower hydrocarbon if directly use.
Summary of the invention
The problem that invention will solve
The present invention finishes in view of above-mentioned practical situation, and its purpose is, a kind of industrial manufacture method of utilizing the catalyzed reaction aromatics of lower hydrocarbon such as methane that helps is provided.
Solve the method for problem
In order to solve above-mentioned problem, what the inventor etc. concentrated one's attention on to study found that, can solve above-mentioned problem by combination methanation operation and aromatics synthesis procedure, so that finished the present invention.That is, the present invention relates to following (1)～(12).
(1) a kind of manufacture method of aromatics comprises following operation:
Methanation operation: in the presence of catalyzer, the gas that contains hydrogen is contacted with carbon monoxide and/or carbonic acid gas, make hydrogen and carbon monoxide and/or carbon dioxide reaction in the gas, change methane and water into;
The aromatics synthesis procedure: in the presence of catalyzer, the methane reaction that makes lower hydrocarbon and obtain in the methanation operation obtains containing the resultant gas of aromatics and hydrogen.
(2) manufacture method of above-mentioned (1) described aromatics, wherein, separation of aromatic compounds from the resultant gas that the aromatics synthesis procedure obtains, and the gas that contains hydrogen of remnants is supplied to the methanation operation.
(3) manufacture method of above-mentioned (1) described aromatics, wherein, separation of aromatic compounds from the resultant gas that the aromatics synthesis procedure obtains, then, from the gas that contains hydrogen of remnants, isolate hydrogen, separated hydrogen is supplied to the methanation operation, the residual gas of isolating hydrogen and obtaining is supplied to the aromatics synthesis procedure.
(4) a kind of manufacture method of aromatics, it comprises the operation of following (i)～(iii):
(i) aromatics synthesis procedure: in the presence of catalyzer, make the lower hydrocarbon reaction, obtain containing the resultant gas of aromatics, lower hydrocarbon and hydrogen;
(ii) aromatics separation circuit: Separation and Recovery aromatics and lower hydrocarbon and contain the gas of hydrogen from the resultant gas that above-mentioned aromatics synthesis procedure, obtains;
(iii) methanation operation: in the presence of catalyzer, carbon monoxide and/or carbonic acid gas are contacted with the gas that contains hydrogen with the lower hydrocarbon of isolating aromatics in above-mentioned aromatics separation circuit, make hydrogen and carbon monoxide and/or carbon dioxide reaction in the gas, be transformed into methane and water
And described method comprises that the gas circulation that will obtain in the methanation operation is supplied to the device of aromatics synthesis procedure.
(5) manufacture method of above-mentioned (4) described aromatics, wherein, from the gas that contains hydrogen that the aromatics separation circuit obtains, isolate hydrogen, separated hydrogen is supplied to the methanation operation, the residual gas of isolating hydrogen and obtaining is supplied to the aromatics synthesis procedure.
(6) each described manufacture method in above-mentioned (1)～(5), wherein, the lower hydrocarbon that will contain carbon monoxide and/or carbonic acid gas is supplied to above-mentioned methanation operation.
(7) each described manufacture method in above-mentioned (1)～(5) is supplied to above-mentioned aromatics synthesis procedure with the lower hydrocarbon that does not contain carbon monoxide and/or carbonic acid gas in fact.
(8) each described manufacture method in above-mentioned (1)～(7), wherein, the carbon monoxide and/or the carbonic acid gas that supply in the above-mentioned methanation operation are carbon monoxide and/or the carbonic acid gas that reclaims outside reaction system.
(9) each described manufacture method in above-mentioned (1)～(8), wherein, the supply of the carbonic acid gas in the above-mentioned methanation operation is following to be carried out: the gas that will isolate aromatics in above-mentioned separation circuit is divided into first fraction and second fraction, second fraction of burning, the carbonic acid gas that will reclaim from this burning and gas-exhausting supplies in the methanation operation with first fraction.
(10) a kind of manufacture method of hydroaromatic compound wherein, in the presence of catalyzer, will adopt the aromatics hydrogenation that each method obtains in above-mentioned (1)～(9), obtain hydroaromatic compound.
(11) manufacture method of above-mentioned (10) described hydroaromatic compound wherein, is isolated hydroaromatic compound, and the gas circulation of remnants is used in the methanation operation from the resultant gas that hydrogenation process obtains.
(12) manufacture method of above-mentioned (10) or (11) described hydroaromatic compound, wherein, the resultant gas that contains aromatics and hydrogen that the aromatics synthesis procedure is obtained supplies to hydrogenation process.
The invention effect
The manufacture method of aromatics of the present invention is owing to can reduce the hydrogen that is supplied to the aromatics synthesis procedure, and can consume the raw material of the arch-criminal's who is regarded as greenhouse effects of the earth carbonic acid gas, thereby can be at the industrial aromatics of advantageously making as lower hydrocarbon (methane).
Description of drawings
Fig. 1 is the schema of an example that the manufacture method of aromatics of the present invention is shown.
Fig. 2 is another routine schema that the manufacture method of aromatics of the present invention is shown.
Nomenclature
A: aromatics synthesis procedure
B: aromatics separation circuit
C: methanation operation
D: carbonic acid gas is removed operation
E: transformationreation operation
F: hydrogenation process
G: hydroaromatic compound separation circuit
Embodiment
Below, explain the present invention, but the explanation of the structure condition of the following stated being the typical example of embodiments of the present invention, the present invention is not limited to these contents.
The manufacture method of aromatics of the present invention comprises methanation operation and the necessary operation of aromatics synthesis procedure conduct, this methanation operation is: in the presence of catalyzer, the gas that contains hydrogen is contacted with carbon monoxide and/or carbonic acid gas, make hydrogen and carbon monoxide and/or carbon dioxide reaction in the gas, change methane and water into; Described aromatics synthesis procedure is: in the presence of catalyzer, the methane reaction that makes lower hydrocarbon and obtain in the methanation operation obtains containing the resultant gas of aromatics and hydrogen.
As the preferred embodiment of the present invention, enumerate method as described below, comprise these three operations of aromatics synthesis procedure, aromatics separation circuit and methanation operation as necessary operation, and have the device that the gas circulation that will obtain in the methanation operation is supplied to the aromatics synthesis procedure.
In the present invention, except the gas that contains lower hydrocarbon that does not contain carbon monoxide and/or carbonic acid gas in fact, can also use the various gases that contain lower hydrocarbon that contain carbon monoxide and/or carbonic acid gas to make aromatics.In addition, these gases are supplied to suitable operation, and above-mentioned what is called " does not contain carbon monoxide and/or carbonic acid gas in fact " and is meant and can contain the amount that can not cause the carbon monoxide and/or the carbonic acid gas of dysgenic scope to the catalyzed reaction in the aromatics synthesis procedure.In addition, following reaction formula is an example of the reaction formula that takes place in operation described later, and formula (1) and (1 ') are the reaction formula of aromatics synthesis procedure, and formula (2) and (3) are the reaction formula of methanation operation.
[Chemical formula 1]
CH
4→1/6C
6H
6+3/2H
2……(1)
C
2H
4→1/3C
6H
6+H
2……(1’)
CO+3H
2→CH
4+H
2O……(2)
CO
2+4H
2→CH
4+2H
2O……(3)
＜unstripped gas 〉
What is called among the present invention " lower hydrocarbon " is meant the hydrocarbon compound of carbonatoms 1～4, particularly, can enumerate methane, ethane, propane, normal butane, Trimethylmethane and their unsaturates, the unsaturated hydrocarbon compound of optimization methane and carbonatoms 2～4, more preferably methane.
As the gas that contains lower hydrocarbon that does not contain carbon monoxide and/or carbonic acid gas in fact, can enumerate the waste gas of Sweet natural gas (LNG, NG), LPG, methane gas hydrate (methane hydrate), petroleum chemistry or refining of petroleum etc. typically.As the lower hydrocarbon gas that contains carbon monoxide and/or carbonic acid gas, can enumerate coke(oven)gas, gasification gas, lhv gas oxidizing gases, heavy oil residue aerification gas, petroleum coke aerification gas, modification furnace gases, oxo-synthesis gas, biogas, biomass gas oxidizing gases (biomass-gasified gas), effluent gas oxidizing gases etc.Coke(oven)gas also contains lower hydrocarbon, but contains carbon monoxide and/or carbonic acid gas, can be used as the methane generation and uses with unstripped gas.Contain the hydrogen of the amount that depends on its kind in the above-mentioned gas that contains lower hydrocarbon, the hydrogen that can also use manufacturing, by-product is as hydrogen source.
And above-mentioned lower hydrocarbon supplies to following aromatics synthesis procedure with the gas that contains lower hydrocarbon, but the generation of above-mentioned methane preferably is supplied to methanation operation described later with unstripped gas.Do not contain in fact under the situation of the gas that contains lower hydrocarbon of carbon monoxide and/or carbonic acid gas, this gas is supplied to the aromatics synthesis procedure, perhaps can be supplied to the methanation operation yet with carbon monoxide and/or carbonic acid gas.In addition, under the situation of the various gases that contain lower hydrocarbon that contain carbon monoxide and/or carbonic acid gas, also can be supplied to the methanation operation.Under the situation of the various gases that contain lower hydrocarbon that contain carbon monoxide and/or carbonic acid gas, carbon monoxide in this gas and/or carbonic acid gas are converted to methane shown in above-mentioned formula (2) and (3), then, be supplied to the aromatics synthesis procedure.Therefore, under the situation of the various gases that contain lower hydrocarbon that contain carbon monoxide and/or carbonic acid gas, by this gas is supplied to the methanation operation, carbon monoxide that has caused when having avoided directly being supplied to the aromatics synthesis procedure and/or carbonic acid gas are to the dilution problem of lower hydrocarbon.
＜(i) aromatics synthesis procedure 〉
In the aromatics synthesis procedure, in the presence of catalyzer, make the lower hydrocarbon reaction, obtain containing the resultant gas of aromatics, lower hydrocarbon and hydrogen.
As catalyzer, preference such as spy open the catalyzer of 2001-334151 communique record, promptly, the catalyzer of making by catalystic material and metal silicate, this catalystic material must have more than one of Re or its compound, according to hope also comprise Zn, Ga, Co, Fe or their compound more than one, Cr, W, Mo or their compound more than one, rare earth metal or its compound more than one.
As metal silicate, preferably has the porous insert of a plurality of pores as carrier.For example under the situation of aluminosilicate, can enumerate molecular sieve 5A (UTA), faujusite (NaY) and NaX, ZSM-5 as the various porous supports of forming that constitute by silicon-dioxide and aluminum oxide, ZSM-11, ZSM-22, ZSM-48, β-Si zeolite, MCM-22 etc.In addition, be under the situation of carrier of main component with phosphoric acid, can be set forth in the porous support with representatives such as SAPO-5, SAPO-34, VPI-5 and have 4～8
Miniature pore or the carrier of passage.
Can further enumerate the CVD method by having used organosilane oxide compound (silicone alkoxide) etc. and the middle fine pore of the middle pore porous support of FSM-16 or MCM-41 etc. is adjusted into 4～8
Modification in pore material etc., the middle pore porous support of described FSM-16 or MCM-41 etc. is main component with silicon-dioxide and contains partial oxidation aluminium as composition, and with middle pore (10～100
) tubular pore (passage) be feature.
As metal silicate, except the aluminosilicate that comprises silicon-dioxide or aluminum oxide, can also preferably use and contain Fe, Ti, Mn, Cr, In, Ga, Mo, W, Co, V, Zn etc. and fine pore is 4～8
The porous supports such as titanosilicate that comprise silicon-dioxide and titanium dioxide.
In addition, preferred little or middle pore is 4～8
Carrier, more preferably 5.5 ± 1
The metal silicate of scope, and further preferred surface is long-pending is 200～1000m
2The metal silicate of/g.In addition, for example under the situation of aluminosilicate, the ratio that contains as silicon-dioxide and aluminum oxide, can use the aluminosilicate of ratio=1～8000 of the silica/alumina of the porous support that can obtain usually, but in order to obtain practical transformation efficiency and selection rate, the ratio of preferred silica/alumina is 10～100.
When catalystic materials such as Re load on the metal silicate, can prepare precursor.As the example of precursor, can enumerate halogenide such as muriate, bromide; Inorganic acid salts such as nitrate, vitriol, phosphoric acid salt; Carboxylate salt or organic metal salts such as metal carbonylcomplex or cyclopentadiene base complex such as carbonate, acetate, oxalate.Particularly, as the example of the precursor of rhenium, remove rhenium carbonyl compound (Re
2(CO)
10, Re
6(CO), (C
5H
5)
2Re (CO)
2, CH
3ReO
3) in addition, also can enumerate halogenide such as muriate, bromide; Inorganic acid salts such as nitrate, vitriol, phosphoric acid salt; Carboxylate salts such as carbonate, acetate, oxalate.As precursor, can also use compound complex salt or composite oxides.
Charge capacity when making above-mentioned catalystic material load on the above-mentioned metal silicate is not particularly limited, and as the value based on total catalyst weight, each catalystic material group is generally 0.001～50 weight %, preferred 0.01～40 weight %.In addition, during from a plurality of group selection catalystic material, as the value based on total catalyst weight, the total amount of the charge capacity of catalystic material is generally 0.002～50 weight %, preferred 0.02～40 weight %.In addition, above-mentioned charge capacity scope is illustrated in the catalystic material when using precursor the charge capacity as precursor.
As making catalystic material load on method on the metal silicate, have (i) to make the solution of organic solvents such as the aqueous solution of precursor of above-mentioned metal or alcohol and make it the method for osmotic load in metal silicate, (ii) utilize the ion transform method to make the catalystic material load after, in non-active gas or oxygen, carry out methods of heating treatment.When being described more specifically an example of this method, at first, for example can make nitric acid rhenium aqueous solution osmotic load in metal silicate, carry out drying again, after removing the solvent of appropriate amount, in containing the Oxygen Flow of nitrogen or in the pure oxygen gas flow, usually 250～800 ℃, preferably 350～600 ℃ of following heat treated, the metal silicate catalysts of rhenium of having made load.In addition, when using composite oxides or compound complex salt to obtain catalyzer, also can obtain the catalyzer made by composite oxides salt or compound complex salt by same carrying method or heating treatment method.
By rhenium and/or its compound (hereinafter referred to as " first composition "), be selected from least a (hereinafter referred to as " second composition ") in zinc, gallium, iron, cobalt and their compound according to expectation; Be selected from least a (hereinafter referred to as " the 3rd composition ") in chromium, tungsten, molybdenum or their compound according to expectation; Be selected from least a in rare earth metal or its compound according to expectation; The catalyzer made from carrier can be by following method manufacturing: after being carried on first composition on the metal silicate, the later composition of the method for the later composition of second composition selected according to expectation of load, second composition selected with first composition and according to expectation loads on method on the metal silicate, makes each composition be carried on method on the metal silicate simultaneously with suitable order successively.Wherein, preferably at first make first composition be carried on method on the metal silicate.Then, both each composition of load successively, the also multiple composition of load simultaneously.
Catalyzer can be the arbitrary shape in Powdered, particulate state, other shape.In addition, owing to shortened the inductive phase that generates aromatics, catalyzer can be implemented to comprise by hydrogen or hydrazine, metal hydride BH for example
3, NaH, AlH
3Catalyst activation process Deng the pre-treatment of carrying out.
The employed lower hydrocarbon of reaction raw materials can be used all gases that contains lower hydrocarbon with the advantage amount.Particularly, can illustrate usually and contain 50 weight %, preferably contain the LNG etc. of 70% above methane.
Reaction is usually carried out with the reaction formation of intermittent type or flow type, but preferably carries out with the flow type reaction formation of fixed bed, moving-bed, fluidized-bed etc.Temperature of reaction is generally 300～800 ℃, preferred 450～775 ℃; Reaction pressure is generally 0.1～10kg/cm
2(gauge pressure, down together), preferred 1～7kg/cm
2Weight time and space speed (WHSV) is generally 0.1～10, preferred 0.5～5.0.
By above-mentioned reaction, obtaining with aromatic hydrocarbon such as benzene, toluene is the aromatics of main component.In addition, be accompanied by this reaction, by-product hydrogen.
＜(ii) aromatics separation circuit 〉
In the aromatics separation circuit, Separation and Recovery " aromatics " and " lower hydrocarbon of unreacted lower hydrocarbon, generation and contain the gas of hydrogen " in the generation gas that from above-mentioned aromatics synthesis procedure, obtains." lower hydrocarbon (lower hydrocarbon of unreacted lower hydrocarbon and generation) and contain the gas of hydrogen " of isolating aromatics is sent to following methanation operation.In addition, the composition of aromatics of the present invention is benzene,toluene,xylene, naphthalene, Three methyl Benzene, naphthalene, methylnaphthalene, dimethylnaphthalene etc., preferred benzene, toluene, naphthalene.In addition, the so-called lower hydrocarbon that generates is at the ethane that generates by-product the aromatic process from lower hydrocarbon, ethene etc.
The tripping device of aromatics is not particularly limited, but preferably uses heat exchanger cooling gas, makes the higher-boiling compound condensation, with the separator method of carrying out gas-liquid separation of band air purifier.At this moment, in order to increase the condensed fluid composition, can reduce cooling temperature with refrigerator.When aromatics is benzene, for example boost to the pressure of subsequent processing (methanation operation), be cooled to 6 ℃ and separate.The preferred high pressure of pressure, but when boosting to the above high pressure of needed pressure, produce kinetic equation loss.In addition, the preferred low temperature of temperature, when making temperature be reduced to less than 6 ℃, aromatics (benzene) solidifies, and separates to be difficult to carry out.When making temperature be reduced to less than 1 ℃, need to separate and remove moisture, moreover it is big that cooling apparatus becomes, equipment cost improves.As other separation method, can enumerate the separation method that uses absorption liquid.
Aromatics is separated as liquid component, on the other hand, the composition of gas of having isolated the unreacted lower hydrocarbon of aromatics and having contained hydrogen is according to unstripped gas composition etc. and different, thereby can not stipulate without exception, as gaseous constituent, except that ethane and hydrogen, be hydrocarbon of carbon monoxide, carbonic acid gas, carbonatoms 2～5 etc.
In addition, the gas that contains hydrogen that obtains in the aromatics separation circuit also can directly be supplied to the methanation operation, but it is preferred: as from the gas that contains hydrogen, to isolate hydrogen, isolating hydrogen is supplied to the methanation operation, the residual gas (is the gas of main component with unreacted lower hydrocarbon) of isolating hydrogen is supplied to the aromatics synthesis procedure, and this is effective to industry.
As the method for separating hydrogen gas from the gas that contains hydrogen, can enumerate the method for using the Hydrogen Separation film or pressure vibration absorption method (PSA method) etc.
＜(iii) methanation operation 〉
In the methanation operation, make hydrogen and carbon monoxide and/or carbon dioxide reaction in the gas, change into methane and water.
As hydrogen source, can enumerate usually in the hydrogen that produces in the hydrogen of industrial use, the aromatics synthesis procedure, aromatics synthesis procedure as what unstripped gas was used and contain H at above-mentioned (i) at above-mentioned (i)
2Gas in hydrogen etc., for example can use coke(oven)gas, gasification gas, lhv gas oxidizing gases, heavy oil residue aerification gas, petroleum coke aerification gas, modification furnace gases, oxo-synthesis gas, biogas, biomass gas oxidizing gases, effluent gas oxidizing gases etc.
In addition, make, the hydrogen of by-product also can be used as hydrogen source, for example (a) is by from above-mentioned unstripped gas, petroleum chemistry, the waste gas separated hydrogen of discharging in the refining of petroleum technology, (b) with petroleum naphtha, LNG, hydrocarbon such as LPG are raw material and have used water vapour, oxygen, the hydrogen of the modification of carbonic acid gas etc., (c) used the methane direct pyrolysated hydrogen of plasma body etc., (d) make the hydrogen of the by-product at alkali workshop by oneself, (e) utilize hydrogen that the electrolysis used electric water makes etc., this electricity is by having used waterpower, firepower, wind-force, atomic generating produces.
Use buck electrolysis, High Temperature High Pressure water electrolysis method, solid macromolecule electrolyte water electrolysis method, high-temperature vapor electrolytic process etc. in the electrolysis of water.The hydrogen that can also use solar cell power generation to make.In addition, also can use the photodecomposition catalyst water of decomposition that utilizes titanium oxide etc. and the hydrogen of making.
Except that electrolysis, can also use the hydrogen that utilizes thermochemistry hydrogen manufacturing process to make, this thermochemistry hydrogen manufacturing process is: the thermolysis of water being divided into several chemical reactions, only using the heat of decomposing the low temperature of needed temperature than direct heat, is hydrogen and oxygen with water decomposition.At this moment, also can use the exit gas of nuclear fuel as the high-temperature gas stove of thermal source.In addition, in the decomposition of water, can also use gamma-rays, near-ultraviolet ray isoradial as energy source.Moreover, established when being energy source social with hydrogen, can utilize hydrogen as energy source.
In addition, owing to consumed carbon monoxide and/or carbonic acid gas in this methanation operation, thereby the present invention also can be used as the industrial carbon dioxide treatment technology and occupies a tiny space.
The methanation operation particularly, is for example carried out in the mode of following (A)～(E) shown in above-mentioned formula (2) and (3).
(A) by in the presence of catalyzer, " lower hydrocarbon (lower hydrocarbon of unreacted lower hydrocarbon and the generation) " reaction that makes carbon monoxide and/or carbonic acid gas and in above-mentioned aromatics separation circuit, isolate aromatics, make hydrogen and carbon monoxide and/or carbon dioxide reaction in the gas, change into methane and water.In addition, the feed rate of carbon monoxide and/or carbonic acid gas is many, during the hydrogen deficient in the gas, also can append the gas that contains hydrogen from the outside.
When (B) gas that is supplied to the methanation operation is " the various gases that contain lower hydrocarbon that contain carbon monoxide and/or carbonic acid gas ", in the presence of catalyzer, " containing the hydrogen in the gas of lower hydrocarbon (lower hydrocarbon of unreacted lower hydrocarbon and generation) and hydrogen " of making the hydrogen in carbon monoxide in this gas and/or carbonic acid gas and this gas or isolate aromatics in above-mentioned aromatics separation circuit reacts, and changes into methane.In addition, the amount that contains carbon monoxide in the gas of lower hydrocarbon and/or carbonic acid gas is less than the amount of hydrogen and when not enough, also can appends carbon monoxide and/or carbonic acid gas from the outside.The gas that can also contain hydrogen from outside additional services.
When (C) gas that is supplied to the methanation operation is for " gas that contains lower hydrocarbon that does not contain carbon monoxide and/or carbonic acid gas in fact ", supply with carbon monoxide and/or carbonic acid gas, in the presence of catalyzer, " containing the hydrogen in the gas of lower hydrocarbon (lower hydrocarbon of unreacted lower hydrocarbon and generation) and the hydrogen " reaction that makes the hydrogen in this carbon monoxide and/or carbonic acid gas and this gas or isolate aromatics in above-mentioned aromatics separation circuit changes into methane.In addition, the feed rate of carbon monoxide and/or carbonic acid gas is many, when the hydrogen in the gas is not enough, can contain the gas of hydrogen from outside additional services.
(D) in above-mentioned (A)～(C) described method, use the gas that contains hydrogen from the outside as unstripped gas, in the presence of catalyzer, make it reaction, change into methane.
(E) in the presence of catalyzer, by making carbon monoxide and/or carbonic acid gas and containing the gas reaction of hydrogen, make hydrogen and carbon monoxide and/or carbon dioxide reaction in the gas, change into methane and water.
The gas that obtains in above-mentioned methanation operation is circulated in the aromatics synthesis procedure, but owing in the reaction (above-mentioned formula (1)) of aromatics synthesis procedure, there is the balance of reaction, thereby the hydrogen content of the unstripped gas in the aromatics synthesis procedure is low more, reactivity is high more, is favourable.Therefore, at above-mentioned (A) with (B), carbon monoxide that the content ratio of the hydrogen in the gas is corresponding and/or carbonic acid gas preferably are supplied to the methanation operation with carbon monoxide and/or carbonic acid gas, and the hydrogen content in the gas are adjusted into the expected value that converts methane and water to for a long time.
As carbon monoxide and/or the carbonic acid gas of supplying with the methanation operation, can use the carbon monoxide and/or the carbonic acid gas that outside the system of manufacturing process of the present invention, reclaim.Particularly, under the situation of carbonic acid gas, can use the carbonic acid gas that from various burning and gas-exhaustings, reclaims.For example can enumerate from generating turbine or the carbonic acid gas of the exhaust gas recovery of the combustion gases of boiler, the various process furnace of chemical plant, various incinerators etc.
In addition, the present invention is because can be by methanation reaction with carbon monoxide and/or carbon dioxide fixationization, so from the viewpoint of the discharge that reduces carbonic acid gas, be effective.
Catalyzer can use without limits as the known well-known catalysts of methanation reaction catalyzer.Typical catalyzer is a nickel catalyzator.Temperature of reaction is generally 200～500 ℃.Methanation reaction is owing to be strong exothermic reaction, so the carbon monoxide in the inlet gas and/or concentration of carbon dioxide be when high, reactor design need be become 2～3 sections multistage and at centre design water cooler, or utilizes reactant gases and control reaction temperature again.Carbon monoxide and/or carbonic acid gas are transformed into methane up to almost reaching Compositional balance.In addition, when the hydrocarbon compound that carbonatoms is big is sneaked into to unstripped gas, water vapour can be added in the methanation operation with can be this hydrocarbon modification.Be added into 0.8～4.5 times of carbon weight that water vapour in the methanation operation preferably is supplied to the methanation operation.
In the present invention, recommend following mode: the gas that will isolate aromatics in above-mentioned separation circuit is divided into first fraction and second fraction, second fraction of burning will be supplied to the methanation operation with first fraction from the carbonic acid gas that these combustion gases reclaim.In such a manner, above-mentioned incendiary thermal source can be used on the temperature of reaction of keeping the aromatics synthesis procedure, and, reclaim the outer carbonic acid gas of the system that is discharged to, from saving the viewpoint of environment from damage, be preferred.Moreover, accumulate in intrasystem viewpoint from preventing non-condensing gas such as nitrogen or impurity, also be preferred.In addition, consider the temperature of reaction of aromatics synthesis procedure, determine the first above-mentioned fraction and the partition ratio of second fraction.
As the method that from burning and gas-exhausting, reclaims carbonic acid gas, for example preferred spy opens the method for flat 5-184865 communique record, that is, burning and gas-exhausting is contacted with monoethanolamine (MEA) aqueous solution, remove the carbonic acid gas that contains in the burning and gas-exhausting and the method for recovery.As the MEA aqueous solution, the aqueous solution that preferred concentration 35 weight % are above.
The summary of the method for above-mentioned open communique record is as described below.That is, use the equipment that mainly comprises burning and gas-exhausting water cooler, decarbonation tower, MEA aqueous solution regenerator column.
The burning and gas-exhausting water cooler is the structure of turriform formula, and the top in the tower is provided with spray nozzle, and middle portion forms filling part, and the additional humidification cooling water circulating pump that is provided with.And, common 100～150 ℃ burning and gas-exhausting is supplied with from the top of burning and gas-exhausting water cooler and after the derivation of bottom, is supplied to the bottom of decarbonation tower, during this period, contact with humidification water coolant, obtain being generally 50～150 ℃ burning and gas-exhausting from spray nozzle.
The top of decarbonation tower in tower is provided with the nozzle that is used to spray the MEA aqueous solution, forms filling part at middle portion, and the additional MEA aqueous solution overboard pump that is provided with absorbing carbon dioxide.And the burning and gas-exhausting of bottom that is supplied to the decarbonation tower exchanges with the MEA aqueous solution and to contact in the decarbonation tower, and the carbonic acid gas in the burning and gas-exhausting is absorbed by the MEA aqueous solution and removes.The burning and gas-exhausting of having removed carbonic acid gas is discharged from outside the system from the top of decarbonation tower.
The top of MEA aqueous solution regenerator column in tower is provided with the nozzle that is used to spray MEA draining solution, forms filling part at middle portion, and the additional regenerative heater (reboiler) that is provided with.And, the MEA aqueous solution that has absorbed carbonic acid gas with heat exchanger cooling after, be supplied in the MEA aqueous solution regenerator column, regenerate by regenerative heater (reboiler).By the carbonic acid gas of MEA aqueous solution desorb outside the top discharge system of MEA aqueous solution regenerator column.
In the present invention, utilize the hydrogen that contains in the unstripped gas,, can easily convert the aromatics of above-mentioned manufacturing to hydroaromatic compound by the following operation that goes on to say as above-mentioned methane source.
＜(iv) hydroaromatic compound synthesis procedure 〉
In the hydroaromatic compound synthesis procedure, can be in the presence of catalyzer, the aromatics hydrogenation with reclaiming in the above-mentioned aromatics separation circuit obtains hydroaromatic compound.
The hydrogenation of aromatics is known from ancient times technology, in the present invention, can use known in the past arbitrary technology.For example, as catalyzer, can enumerate and contain the rhodium that is selected from as reactive metal, iridium, platinum, ruthenium, rhenium, palladium, molybdenum, nickel, tungsten, vanadium, osmium, cobalt, chromium, iron, their oxide compound, at least a metal load catalyzer in their sulfide etc.Temperature of reaction is generally 150～300 ℃, preferred 180～270 ℃; Reaction pressure is generally 4～80kg/cm
2, preferred 9～70kg/cm
2
In the present invention, as hydrogen source, for example preferred the use will above-mentioned coke(oven)gas etc. be carried out conversion (Shift) and reacted the gas that contains hydrogen that reduces the carbon monoxide in the gas and obtain.Transformationreation CO+H
2O → CO
2+ H
2Formula represent, be to well known to a person skilled in the art reaction.Catalyzer uses iron-chromium-based catalysts, copper-zinc system catalyst, and temperature of reaction is generally 180～480 ℃, and reaction pressure is generally 1～34kg/cm
2In addition, as the method that reduces the carbon monoxide in the gas, also can utilize above-mentioned methanation reaction.In addition, as hydrogen source, for example also can utilize the gas that contains hydrogen that from above-mentioned coke(oven)gas etc., has reduced carbon monoxide by pressure vibration absorption (PSA) method or the method for using the Hydrogen Separation film.
＜(the v) separation circuit of hydroaromatic compound 〉
In the hydroaromatic compound separation circuit, from the resultant gas delivery that above-mentioned hydroaromatic compound synthesis procedure, obtains and reclaim hydroaromatic compound and contain the gas of hydrogen.As the composition of hydroaromatic compound, above-mentioned hydride (C such as benzene are arranged
6H
12Deng).As gaseous constituent, except that lower hydrocarbon and carbonic acid gas, hydrogen etc. is arranged.
The separation method of hydroaromatic compound is not particularly limited, but the method that preferably makes the higher-boiling compound condensation and carry out gas-liquid separation with the separator that has air purifier with heat exchanger cooling gas.And, keep the pressure of hydrogenation and be cooled to 6 ℃, separate hydroaromatic compound.
Fig. 1 is the schema of an example that the manufacture method of aromatics of the present invention is shown.Manufacture method shown in this figure is to use gasification gas (H
2, CO, CO
2, N
2) and coke(oven)gas (H
2, CH
4, CO, CO
2, N
2) mixed gas as unstripped gas, except that aromatics synthesis procedure (A), aromatics separation circuit (B), methanation operation (C),, comprise that also carbonic acid gas removes operation (D) according to the preferred mode of the present invention.In addition,, produce hydroaromatic compound simultaneously, have transformationreation operation (E), hydrogenation process (F) and hydroaromatic compound separation circuit (G) for the modification of part coke(oven)gas.Gas is as described below to the circulation of each operation.
Gasification gas is supplied to methanation operation (C) from circuit (1).Coke(oven)gas is imported by circuit (2), is divided into two flow directions, and a flow direction is to collaborate to be supplied to methanation operation (C) to circuit (1) as the mixed gas with gasification gas from circuit (3); Another flow direction is to be supplied to transformationreation operation (E) from circuit (4).
The gas that obtains in methanation operation (C) (gas that contains methane) is supplied to aromatics synthesis procedure (A) from circuit (5), and the resultant gas that obtains in this operation is supplied to aromatics separation circuit (B) from circuit (6).
Isolating the gas that contains unreacted methane and hydrogen of aromatics in aromatics separation circuit (B) derives from circuit (7), be divided into two flow directions, a flow direction is to be supplied to methanation operation (C) as recycle gas from circuit (8), and another flow direction is as be used for the fuel use that reaction heat is supplied with aromatics synthesis procedure (A) from circuit (9).
That is, the gas of circuit (9) side with from the air mixed of circuit (10), by circuit (11) use that in aromatics synthesis procedure (A), acts as a fuel.And burning and gas-exhausting is supplied to carbonic acid gas from circuit (12) and removes operation (D), and the carbonic acid gas that reclaims in this operation is supplied to methanation operation (C) from circuit (13) with the gas that utilizes again of circuit (8) side.
Isolating aromatics can also be isolated benzene cut (C as required in aromatics separation circuit (B)
6H
6) and composition in addition (is the high boiling point composition of representative with the composition of carbonatoms more than 7).Such separation for example can easily be carried out by suitable distillation tower.
In addition, in illustrated embodiment, omitted the record of distillation tower, as typical performance, above-mentioned 2 compositions are removed from circuit (14) and (15) of aromatics separation circuit (B) respectively.
The benzene that takes out from circuit (14) is supplied to hydrogenation process (F) and carries out hydrogen treatment.The needed hydrogen of hydrogen treatment is supplied with by circuit (16) from transformationreation operation (E).The gas that obtains in hydrogenation process (F) is supplied to hydroaromatic compound separation circuit (G) by circuit (17), and the gas that has separated hydroaromatic compound utilizes gas to be supplied to methanation operation (C) by circuit (18) conduct again.And, take out hydroaromatic compound from circuit (19).
Fig. 2 is another routine schema that the manufacture method of aromatics of the present invention is shown.Manufacture method shown in this figure is to use coke(oven)gas (H
2, CH
4, CO, CO
2, N
2) and the burning and gas-exhausting that reclaims from the outside as unstripped gas, except that aromatics synthesis procedure (A), aromatics separation circuit (B), methanation operation (C),, comprise that also carbonic acid gas removes operation (D) according to the preferred mode of the present invention.Gas is as described below to the circulation of each operation.
Coke(oven)gas is supplied to methanation operation (C) from circuit (1).And the burning and gas-exhausting that reclaims from the outside is supplied to carbonic acid gas from circuit (20) and removes operation (D).
The gas that obtains in methanation operation (C) (gas that contains methane) is supplied to aromatics synthesis procedure (A) from circuit (5), and the resultant gas that obtains in this operation is supplied to aromatics separation circuit (B) from circuit (6).
Isolating the gas that contains unreacted lower hydrocarbon and hydrogen of aromatics in aromatics separation circuit (B) is derived from circuit (7), be divided into two flow directions, a flow direction is that conduct utilizes gas to be supplied to methanation operation (C) from circuit (8) again, and another flow direction is to use as the fuel that is used for reaction heat aromatics synthesis procedure (A) from circuit (9).
That is, the gas of circuit (9) side with from the air mixed of circuit (10), by circuit (11) use that in aromatics synthesis procedure (A), acts as a fuel.And burning and gas-exhausting is supplied to carbonic acid gas from circuit (12) and removes operation (D).In addition, the burning and gas-exhausting that reclaims from the outside is supplied to carbonic acid gas from circuit (20) and removes operation (D).Remove the carbonic acid gas that reclaims in the operation (D) at carbonic acid gas and be supplied to methanation operation (C) from circuit (13).
Isolating aromatics can also be isolated benzene cut (C as required in aromatics separation circuit (B)
6H
6) and composition in addition (is the high boiling point composition of representative with the composition of carbonatoms more than 7).Such separation for example can easily be carried out by suitable distillation tower.
In addition, in illustrated embodiment, omitted the record of distillation tower, as typical performance, 2 above-mentioned compositions are removed from circuit (14) and (15) of aromatics separation circuit (B) respectively.
In addition, be not limited to hydroaromatic compound with the aromatics of above-mentioned method manufacturing, also can be as all raw materials of the aromatics derivative of making usually.Under the situation of benzene, for example, can make ethylbenzene (raw material of vinylbenzene, polystyrene resin), make isopropyl benzene (raw material of phenol, dihydroxyphenyl propane, polycarbonate resin), make senior alkyl benzene (raw material of alkyl benzene sulphonate (ABS)) by alkylation by alkylation by alkylation by ethene by higher alkene by propylene.In addition, can make alkyl benzenes such as toluene, dimethylbenzene by alkylation by methyl alcohol etc.In addition, for example, can make terephthalic acid, can make polyethylene terephthalate by the reaction of terephthalic acid and ethylene glycol by the oxidizing reaction of p-Xylol.
Under the situation of the hexanaphthene of hydroaromatic compound, can make pimelinketone, hexalin, hexanolactam.Ring-opening polymerization by hexanolactam can be made 6-nylon.In addition, can make tetrahydrobenzene by the dehydrogenation of hexanaphthene, and make hexanodioic acid as raw material.Hexanodioic acid and hexamethyl diamine reactant become 6,6-nylon.
Aromatics particularly under the situation of benzene, at first, can be made maleic anhydride by the selective oxidation reaction, by it is carried out catalytic hydrogenation, makes gamma-butyrolactone, tetrahydrofuran (THF), 1,4-butyleneglycol etc. again.By making the reaction of alkylamine or ammonia and gamma-butyrolactone, can make N-alkyl-2-Pyrrolidone.In addition, by 1, the 4-butyleneglycol can optionally be made tetrahydrofuran (THF) by dehydration reaction, then, and can be by the polytetramethylene glycol ether of manufacturing oligomerization resultants such as acid catalyst.
Can be by 1, polybutylene terephthalate is made in the condensation reaction of 4-butyleneglycol and terephthalic acid.In addition, can make phthalic acid and derivative thereof by oxidation by the naphthalene class.In addition, can make light alkenes such as ethene, propylene, butylene by the catalytic decomposition of aromatics or hydroaromatic compound.And, as by their deutero-light alkene derivatives, for example ethene derivatives, can enumerate oxyethane based on oxidizing reaction, ethylene glycol, thanomin, glycol ethers etc., based on chlorating vinyl chloride monomer, 1, polyvinyl chloride (PVC) RESINS, vinylidene chloride etc.In addition, by the polymerization of ethene, can make alpha-olefin (in addition, can be raw material with the alpha-olefin, make higher alcohols), low density or highdensity polyethylene etc. by oxidizing reaction and the hydrogenation followed.In addition, can be by making vinyl acetate with the reaction of acetic acid, moreover, can make acetaldehyde and as the vinyl acetic monomer of its derivative etc. by watt gram (Wacker) reaction.As acryloyl derivative, can enumerate vinyl cyanide based on ammonia oxidation; Propenal, vinylformic acid and acrylate based on selective oxidation; Based on oxo alcohols such as the butyraldehyde-n of oxidizing reaction, 2-Ethylhexyl Alcohols; Polypropylene based on propylene polymerization; Propylene oxide and propylene glycol based on Selective Oxidation of Propylene; Based on Isopropanediol of propylene hydration etc.In addition, can make acetone by a watt gram reaction.And, can utilize acetone to make hexone or acetone cyanohydrin (acetone cyanhydrin).Can make (methyl) methyl acrylate by acetone cyanohydrin.Moreover, can make divinyl by the oxydehydrogenation of butylene.And, can make 1 through acetoxylation, hydrogenation, hydrolysis by divinyl, the 4-butyleneglycol, and can make pyrrolidinone compounds such as gamma-butyrolactone, N-Methyl pyrrolidone as raw material, by dehydration reaction, can make tetrahydrofuran (THF), polytetramethylene glycol etc.In addition, can make various synthetic rubber by divinyl.
Embodiment
Below, by embodiment, illustrate in greater detail the present invention, as long as but the present invention is no more than its purport, then and be defined in following embodiment.
Embodiment 1:
Use gasification gas (H
2, CO, CO
2, N
2) and coke(oven)gas (H
2, CH
4, CO, CO
2, N
2) mixed gas as the unstripped gas of supplying with from the outside, according to schema shown in Figure 1, make aromatics continuously.Coke(oven)gas carries out desulfurization, detar, uses after taking off the pre-treatment of dirt according to usual method.
Moreover the aromatics synthetic catalyst is opened the method preparation of the embodiment 2 of 2005-255605 according to the spy.That is, as the catalyzer raw material, use inorganic components: organic binder bond: water=65.4: 13.6: 21.0 (weight ratio), inorganic components are SiO
2/ Al
2O
3The ZSM-5 zeolite of (mol ratio)=40 (MFI type zeolite): clay: the mixture of glass fibre=82.5: 10.5: 7.0 (weight ratio).At first, mixing catalyzer raw material becomes formed body, then, and after under 100 ℃ dry 5 hours, 750 ℃ of calcinings down.Then, the sintered compact that obtains is dipped in the ammonium molybdate aqueous solution, makes molybdenum composition (charge capacity of molybdenum is 6 weight %) be penetrated into sintered compact.The molybdenum load sintered compact that calcining obtains under 550 ℃ 10 hours obtains catalyst precursor, then, and at C
4H
10+ 11H
2Under the environment of mixed gas, handled 24 hours down, obtain catalyzer at 350 ℃.
＜methanation operation (C): the use of nickel catalyzator 〉
In methanation operation (C), supply with gasification gas, supply with coke(oven)gas, supply with utilizing gas (gas that contains methane and hydrogen) again, supply with carbonic acid gas, supply with from circuit (18) and utilize gas (gas that contains methane and hydrogen) again from circuit (1) respectively from aromatics separation circuit described later (B) from hydroaromatic compound separation circuit described later (G) from circuit (13) from circuit (8) from circuit (3).The condition of methanation operation (C) is a pressure: 10kg/cm
2, temperature (inlet): 350 ℃, GHSV:300h
-1The composition (being cooled to 40 ℃ with water cooler, the composition behind the separating and condensing water) of the composition of the gas of supply methanation operation and the gas (gas that contains methane) that generates in the methanation operation is as shown in table 1.
Table 1
| Be supplied to gas (the flow 534kNm of methanation operation 3/H) | The gas that in the methanation operation, generates (flow 407kNm 3/H) | |
| CH 4(mole %) | 55 | 81 |
| H 2(mole %) | 28 | 6 |
| CO (mole %) | 3 | - |
| CO 2(mole %) | 3 | - |
| N 2(mole %) | 9 | 12 |
| Other (mole %) | 2 | 1 |
＜aromatics synthesis procedure (A): the use of Mo/ zeolite series catalysts 〉
The gas (gas that contains methane) that will obtain in methanation operation (C) is decompressed to 3kg/cm
2, be supplied to aromatics synthesis procedure (A) from circuit (5), supply with the catalyzed reaction of methane.The condition of aromatics synthesis procedure (A) is a pressure: 3kg/cm
2, temperature: 750 ℃, GHSV:100h
-1The composition of the resultant gas that obtains in aromatics synthesis procedure (A) is as shown in table 2.
Table 2
| The gas that in the aromatics synthesis procedure, generates (flow 44kNm 3/H) | |
| CH 4(mole %) | 63 |
| H 2(mole %) | 23 |
| N 2(mole %) | 11 |
| C 6H 6(mole %) | 1.5 |
| Other (mole %) | 1.5 |
The temperature of reaction of aromatics synthesis procedure (A) is by keeping from the heat that the fuel of circuit (11) produces with heat exchanger utilization burning, should be from the fuel of circuit (11) promptly from the unreacted methane of circuit (9) with contain the gas of hydrogen and Air mixing gas from circuit (10).
Table 3
| Act as a fuel by circuit (9) gas supplied (flow 18kNm 3/H) | |
| CH 4(mole %) | 64 |
| H 2(mole %) | 23 |
| N 2(mole %) | 11 |
| Other (mole %) | 2 |
The burning and gas-exhausting that generates in above-mentioned burning is supplied to titanium dioxide by circuit (12) and removes operation (D), the carbonic acid gas 11kNm that reclaims in this operation
3/ H boosts to 10kg/cm
2After, be supplied to methanation operation (C) by circuit (13).Carbonic acid gas is removed operation (D) and is opened the method for the embodiment record of flat 5-184865 communique based on the spy, and the absorption liquid of carbonic acid gas uses the MEA aqueous solution of 40 weight % concentration to carry out.
＜aromatics separation circuit (B) 〉
The resultant gas that obtains in aromatics synthesis procedure (A) is supplied to aromatics separation circuit (B) by circuit (6) and handles.That is, resultant gas is boosted to 10kg/cm by compressor
2, then, being cooled to gas temperature with refrigerator is 6 ℃.And, utilize the separator that has air purifier to be separated into phlegma and gas.
Separated gas (unreacted methane and the gas that contains hydrogen) is derived by circuit (7), be divided into two flow directions, a flow direction is that conduct utilizes gas to be supplied to methanation operation (C) by circuit (8) again, and another flow direction is to use as the fuel that is used for reaction heat aromatics synthesis procedure (A) from circuit (9).On the other hand, separated phlegma is at pressure: 10kg/cm
2, reflux ratio: distill processing under 0.5 the condition, be separated into benzene and other composition.The take-off rate of benzene is 22T/H.
＜transformationreation operation (E): the use of iron-chromium-based catalysts 〉
The coke(oven)gas that is supplied to transformationreation operation (E) by circuit (4) is processed in transformationreation operation (E).The condition of transformationreation is a pressure: 20kg/cm
2, temperature: 250 ℃, GHSV:300h
-1
＜hydrogenation process (F): the use of nickel catalyzator 〉
Above-mentioned benzene 22T/H is supplied to respectively from circuit (14), the gas that contains hydrogen that obtains above-mentioned transformationreation operation (E) from circuit (16) and keeps pressure is 20kg/cm
2, temperature is 200 ℃ hydrogenation process (F).GHSV is 500h
-1The unstripped gas before the hydrogenation of supplying with from each circuit and the composition of the resultant gas behind the hydrogenation are as shown in table 4.
Table 4
| Unstripped gas (flow 38kNm before the hydrogenation 3/H) | Resultant gas (flow 19kNm behind the hydrogenation 3/H) | |
| CH 4(mole %) | 22 | 44 |
| H 2(mole %) | 51 | 4 |
| CO 2(mole %) | 7 | 14 |
| N 2(mole %) | 2 | 4 |
| C 6H 6(mole %) | 16 | - |
| C 6H 12(mole %) | - | 32 |
| Other (mole %) | 2 | 2 |
＜hydroaromatic compound separation circuit (G) 〉
The resultant gas that obtains in hydrogenation process (F) is supplied to hydroaromatic compound separation circuit (G) by circuit (17) and handles.That is, resultant gas is cooled to after gas temperature is 1 ℃ with refrigerator, utilizes the separator that has air purifier to be separated into phlegma and gas.Phlegma (the C that is recovered
6H
12) turnout be 23T/H.In addition, the gas that is recovered is as utilizing gas to be supplied to methanation operation (C) from circuit (18) again.
Table 5
| Utilize gas (flow 25kNm again from what circuit (18) was supplied with 3/H) | |
| CH 4(mole %) | 64 |
| CO 2(mole %) | 20 |
| H 2(mole %) | 6 |
| N 2(mole %) | 6 |
| Other (mole %) | 5 |
Embodiment 2
Use coke(oven)gas (H
2, CH
4, CO, CO
2, N
2) as the unstripped gas of supplying with from the outside,, make aromatics continuously according to schema shown in Figure 2.Coke(oven)gas carries out desulfurization, detar, uses after taking off the pre-treatment of dirt according to usual method.
＜methanation operation (C): the use of nickel catalyzator 〉
In methanation operation (C), supply with coke(oven)gas, supply with utilizing gas (gas that contains methane and hydrogen) again, supply with carbonic acid gas from circuit (1) respectively from aromatics separation circuit described later (B) from circuit (13) from circuit (8).The condition of methanation operation (C) is a pressure: 10kg/cm
2, temperature (inlet): 280 ℃, GHSV:300h
-1The composition (being cooled to 40 ℃ with water cooler, the composition behind the separating and condensing water) that supplies to the composition of gas of methanation operation and the gas (gas that contains methane) that generates in the methanation operation is as shown in table 6.
Table 6
| Be supplied to gas (the flow 615kNm of methanation operation 3/H) | The gas that in the methanation operation, generates (flow 486kNm 3/H) | |
| CH 4(mole %) | 56 | 79 |
| H 2(mole %) | 28 | 8 |
| CO (mole %) | 1 | - |
| CO 2(mole %) | 4 | - |
| N 2(mole %) | 10 | 13 |
| Other (mole %) | 1 | 1 |
＜aromatics synthesis procedure (A): the use of Mo/ zeolite series catalysts 〉
The gas (gas that contains methane) that will obtain in methanation operation (C) is decompressed to 3kg/cm
2, be supplied to aromatics synthesis procedure (A) from circuit (5), supply with the catalyzed reaction of methane.The condition of aromatics synthesis procedure (A) is a pressure: 3kg/cm
2, temperature: 750 ℃, GHSV:100h
-1The composition of the resultant gas that obtains in aromatics synthesis procedure (A) is as shown in table 7.
Table 7
| The gas that in the aromatics synthesis procedure, generates (flow 615kNm 3/H) | |
| CH 4(mole %) | 62 |
| H 2(mole %) | 24 |
| N 2(mole %) | 11 |
| C 6H 6(mole %) | 2 |
| Other (mole %) | 1 |
The temperature of reaction of aromatics synthesis procedure (A) is by keeping from the heat that the fuel of circuit (11) produces with heat exchanger utilization burning, should be from the fuel of circuit (11) promptly from the unreacted lower hydrocarbon of circuit (9) with contain the gas of hydrogen and Air mixing gas from circuit (10).
Table 8
| Act as a fuel by circuit (9) gas supplied (flow 15kNm 3/H) | |
| CH 4(mole %) | ?63 |
| H 2(mole %) | ?24 |
| N 2(mole %) | ?12 |
| Other (mole %) | ?1 |
The burning and gas-exhausting that generates in above-mentioned burning is supplied to carbonic acid gas by circuit (12) and removes operation (D).In addition, the burning and gas-exhausting that reclaims from the outside is supplied to carbonic acid gas by circuit (20) and removes operation (D).And, remove the carbonic acid gas 24kNm that reclaims in the operation (D) at carbonic acid gas
3/ H boosts to 10kg/cm
2After, be supplied to methanation operation (C) by circuit (13).Carbonic acid gas is removed operation (D) and is opened the method for the embodiment record of flat 5-184865 communique based on the spy, and the absorption liquid of carbonic acid gas uses the MEA aqueous solution of 40 weight % concentration to carry out.
＜aromatics separation circuit (B) 〉
The resultant gas that obtains in aromatics synthesis procedure (A) is supplied to aromatics separation circuit (B) by circuit (6) and handles.That is, resultant gas is boosted to 10kg/cm by compressor
2, then, being cooled to gas temperature with refrigerator is 6 ℃.And, utilize the separator that has air purifier to be separated into phlegma and gas.
Separated gas (unreacted lower hydrocarbon and the gas that contains hydrogen) is derived by circuit (7), be divided into two flow directions, a flow direction is that conduct utilizes gas to be supplied to methanation operation (C) by circuit (8) again, and another flow direction is to use as the fuel that is used for reaction heat aromatics synthesis procedure (A) from circuit (9).On the other hand, separated phlegma is at pressure: 10kg/cm
2, reflux ratio: distill processing under 0.5 the condition, be separated into benzene and other composition.The take-off rate of benzene is 29T/H.
Embodiment 3
Use coke(oven)gas (H
2, CH
4, CO, CO
2, N
2) and the mixed gas of the carbonic acid gas that reclaims from burning and gas-exhausting as the unstripped gas of supplying with from the outside, according to schema shown in Figure 2, make aromatics continuously.Coke(oven)gas carries out desulfurization, detar, uses after taking off the pre-treatment of dirt according to usual method.
＜methanation operation (C): the use of nickel catalyzator 〉
In methanation operation (C), supply with coke(oven)gas, supply with utilizing gas (lower hydrocarbon and contain the gas of hydrogen) again, supply with carbonic acid gas, supply with from circuit (18) and utilize gas (lower hydrocarbon and contain the gas of hydrogen) again from circuit (3) respectively from aromatics separation circuit described later (B) from hydroaromatic compound separation circuit described later (G) from circuit (13) from circuit (8).These gases all are supplied to methanation operation (C) via circuit (1).The condition of methanation operation (C) is a pressure: 10kg/cm
2, temperature (inlet): 350 ℃, GHSV:300h
-1The composition (being cooled to 40 ℃ with water cooler, the composition behind the separating and condensing water) of the composition of the gas of supply methanation operation and the gas (gas that contains methane) that generates in the methanation operation is as shown in table 9.
Table 9
| Be supplied to gas (the flow 512kNm of methanation operation 3/H) | The gas that in the methanation operation, generates (flow 402kNm 3/H) | |
| CH 4(mole %) | 54 | 76 |
| H 2(mole %) | 24 | 3 |
| CO (mole %) | 1 | - |
| CO 2(mole %) | 8 | 5 |
| N 2(mole %) | 12 | 15 |
| Other (mole %) | 1 | 1 |
＜aromatics synthesis procedure (A): the use of Mo/ zeolite series catalysts 〉
The gas (gas that contains methane) that will obtain in methanation operation (C) is decompressed to 3kg/cm
2, be supplied to aromatics synthesis procedure (A) from circuit (5), supply with the catalyzed reaction of methane.The condition of aromatics synthesis procedure (A) is a pressure: 3kg/cm
2, temperature: 750 ℃, GHSV:100h
-1The composition of the resultant gas that obtains in aromatics synthesis procedure (A) is as shown in table 10.
Table 10
| The gas that in the aromatics synthesis procedure, generates (flow 437kNm 3/H) | |
| CH 4(mole %) | 59 |
| H 2(mole %) | 20 |
| CO 2(mole %) | 4 |
| N 2(mole %) | 14 |
| C 6H 6(mole %) | 1 |
| Other (mole %) | 2 |
The temperature of reaction of aromatics synthesis procedure (A) is by keeping from the heat that the fuel of circuit (11) produces with heat exchanger utilization burning, should be from the fuel of circuit (11) promptly from the unreacted lower hydrocarbon of circuit (9) with contain the gas of hydrogen and Air mixing gas from circuit (10).
Table 11
| Act as a fuel by circuit (9) gas supplied (flow 13kNm 3/H) | |
| CH 4(mole %) | 60 |
| H 2(mole %) | 20 |
| CO 2(mole %) | 5 |
| N 2(mole %) | 14 |
| Other (mole %) | 1 |
The burning and gas-exhausting that generates in above-mentioned burning is supplied to carbonic acid gas by circuit (12) and removes operation (D).In addition, the burning and gas-exhausting that reclaims from the outside is supplied to carbonic acid gas by circuit (20) and removes operation (D).And, remove the carbonic acid gas 21kNm that reclaims in the operation (D) at carbonic acid gas
3/ H boosts to 10kg/cm
2After, be supplied to methanation operation (C) from circuit (13) via circuit (1).Carbonic acid gas is removed operation (D) and is opened the method for the embodiment record of flat 5-184865 communique based on the spy, and the absorption liquid of carbonic acid gas uses the MEA aqueous solution of 40 weight % concentration to carry out.
＜aromatics separation circuit (B) 〉
The resultant gas that obtains in aromatics synthesis procedure (A) is supplied to aromatics separation circuit (B) by circuit (6) and handles.That is, resultant gas is boosted to 10kg/cm by compressor
2, then, being cooled to gas temperature with refrigerator is 6 ℃.Then, utilize the separator that has air purifier to be separated into phlegma and gas.
Separated gas (unreacted lower hydrocarbon and the gas that contains hydrogen) is derived by circuit (7), be divided into two flow directions, a flow direction is that conduct utilizes gas to be supplied to methanation operation (C) from circuit (8) via circuit (1) again, and another flow direction is to use as the fuel that is used for reaction heat aromatics synthesis procedure (A) from circuit (9).On the other hand, separated phlegma is at pressure: 10kg/cm
2, reflux ratio: distill processing under 0.5 the condition, be separated into benzene and other composition.The take-off rate of benzene is 20T/H.
＜transformationreation operation (E): the use of iron-chromium-based catalysts 〉
The coke(oven)gas that is supplied to transformationreation operation (E) by circuit (4) is processed in transformationreation operation (E).The condition of transformationreation is a pressure: 20kg/cm
2, temperature: 250 ℃, GHSV:300h
-1
＜hydrogenation process (F): the use of nickel catalyzator 〉
Above-mentioned benzene 20T/H is supplied to respectively from circuit (14), the gas that contains hydrogen that obtains above-mentioned transformationreation operation (E) from circuit (16) and keeps pressure is 20kg/cm
2, temperature is 200 ℃ hydrogenation process (F).GHSV is 500h
-1The unstripped gas before the hydrogenation of supplying with from each circuit and the composition of the resultant gas behind the hydrogenation are as shown in table 12.
Table 12
| Unstripped gas (flow 35kNm before the hydrogenation 3/H) | Resultant gas (flow 18kNm behind the hydrogenation 3/H) | |
| CH 4(mole %) | 22 | 43 |
| H 2(mole %) | 51 | 5 |
| CO 2(mole %) | 7 | 14 |
| N 2(mole %) | 2 | 3 |
| C 6H 6(mole %) | 16 | - |
| C 6H 12(mole %) | - | 32 |
| Other (mole %) | 2 | 3 |
＜hydroaromatic compound separation circuit (G) 〉
The resultant gas that obtains in hydrogenation process (F) is supplied to hydroaromatic compound separation circuit (G) by circuit (17) and handles.That is, after resultant gas is cooled to gas temperature and is 1 ℃ with refrigerator, utilize the separator that has air purifier to be separated into phlegma and gas.Phlegma (the C that is recovered
6H
12) turnout be 21T/H.In addition, the gas that is recovered is as utilizing gas to be supplied to methanation operation (C) from circuit (18) via circuit (1) again.
Table 13
| Utilize gas (flow 12kNm again from what circuit (18) was supplied with 3/H) | |
| CH 4(mole %) | 63 |
| CO 2(mole %) | 20 |
| H 2(mole %) | 7 |
| N 2(mole %) | 5 |
| Other (mole %) | 5 |
Claims (3)
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP042574/2005 | 2005-02-18 | ||
| JP2005042573 | 2005-02-18 | ||
| JP042573/2005 | 2005-02-18 | ||
| JP2005042574 | 2005-02-18 | ||
| JP262774/2005 | 2005-09-09 | ||
| JP2005262774 | 2005-09-09 | ||
| JP2005262765 | 2005-09-09 | ||
| JP262765/2005 | 2005-09-09 | ||
| PCT/JP2006/302339 WO2006087971A1 (en) | 2005-02-18 | 2006-02-10 | Process for production of aromatic compound and process for production of hydrogenated aromatic compound |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101449950A Division CN101823930B (en) | 2005-02-18 | 2006-02-10 | Method for producing aromatic compound and method for producing hydrogenated aromatic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101115700A CN101115700A (en) | 2008-01-30 |
| CN101115700B true CN101115700B (en) | 2011-06-01 |
Family
ID=36916379
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800040248A Active CN101115700B (en) | 2005-02-18 | 2006-02-10 | Method for producing aromatic compound and method for producing hydrogenated aromatic compound |
| CN2010101449950A Active CN101823930B (en) | 2005-02-18 | 2006-02-10 | Method for producing aromatic compound and method for producing hydrogenated aromatic compound |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101449950A Active CN101823930B (en) | 2005-02-18 | 2006-02-10 | Method for producing aromatic compound and method for producing hydrogenated aromatic compound |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN101115700B (en) |
| WO (1) | WO2006087971A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2005319530B2 (en) * | 2004-12-22 | 2009-04-23 | Exxonmobil Chemical Patents, Inc. | Production of aromatic hydrocarbons from methane |
| RU2458899C2 (en) * | 2006-06-23 | 2012-08-20 | Эксонмобил Кемикэл Пейтентс Инк. | Producing aromatic hydrocarbons and synthetic gas from methane |
| US20100004495A1 (en) * | 2006-11-02 | 2010-01-07 | Erik Fareid | Process for producing carbon dioxide and methane by catalytic gas reaction |
| WO2009020045A1 (en) | 2007-08-03 | 2009-02-12 | Mitsui Chemicals, Inc. | Process for production of aromatic hydrocarbons |
| CN101774876B (en) * | 2010-01-27 | 2013-04-24 | 清华大学 | Method for preparing aromatic hydrocarbon by aromatizing methane and special-purpose reaction system thereof |
| AR090778A1 (en) * | 2012-04-23 | 2014-12-03 | Shell Int Research | A PROCESS FOR THE AROMATIZATION OF A GAS CURRENT CONTAINING METHANE |
| US9809758B2 (en) * | 2014-07-24 | 2017-11-07 | Exxonmobil Chemical Patents Inc. | Production of xylenes from syngas |
| CN104844403B (en) * | 2015-03-25 | 2017-05-17 | 清华大学 | System and method for directly preparing aromatic hydrocarbon from methane |
| JP6933745B1 (en) * | 2020-03-27 | 2021-09-08 | 三菱パワー株式会社 | Biogas utilization metanation system |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08127544A (en) * | 1994-10-31 | 1996-05-21 | Agency Of Ind Science & Technol | Production of methane from carbon dioxide and hydrogen |
| JP2615433B2 (en) * | 1994-10-31 | 1997-05-28 | 工業技術院長 | Catalyst for producing methane from carbon dioxide and method for producing methane |
| JPH11179204A (en) * | 1997-12-19 | 1999-07-06 | Cosmo Sogo Kenkyusho Kk | Gas methanation catalyst containing carbon monoxide and carbon dioxide and method for producing the same |
| JP2001334151A (en) * | 2000-05-30 | 2001-12-04 | Masaru Ichikawa | Catalyst for converting lower hydrocarbon into aromatic compound and method for producing aromatic compound and hydrogen from lower hydrocarbon as raw material |
| JP3985038B2 (en) * | 2001-07-12 | 2007-10-03 | 独立行政法人産業技術総合研究所 | Process for producing aromatic hydrocarbons and hydrogen from lower hydrocarbons |
| JP4565277B2 (en) * | 2003-03-07 | 2010-10-20 | 勝 市川 | Lower hydrocarbon aromatization catalytic reaction method, aromatization catalytic reactor, aromatic compound and hydrogen production method |
-
2006
- 2006-02-10 WO PCT/JP2006/302339 patent/WO2006087971A1/en not_active Application Discontinuation
- 2006-02-10 CN CN2006800040248A patent/CN101115700B/en active Active
- 2006-02-10 CN CN2010101449950A patent/CN101823930B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006087971A1 (en) | 2006-08-24 |
| CN101823930B (en) | 2013-11-06 |
| CN101823930A (en) | 2010-09-08 |
| CN101115700A (en) | 2008-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101115700B (en) | Method for producing aromatic compound and method for producing hydrogenated aromatic compound | |
| CN1990435B (en) | Olefin production via oxygenate conversion | |
| CN112638849B (en) | Process for the production of methanol from synthesis gas without carbon dioxide removal | |
| CN101184714B (en) | Methanol synthesis | |
| CN101270297B (en) | Technique for synthesis of gas cobalt base Fischer-Tropsch synthetic liquid fuel and byproduct of aromatic hydrocarbons with coal base | |
| CN102015590B (en) | Styrene monomer process based on oxidative dehydrogenation of ethylbenzene using CO2 as soft oxidant | |
| CN102686540A (en) | Method for generating hydrocarbons, in particular gasoline, from synthesis gas | |
| JP2009179591A (en) | Method for producing methanol | |
| JP5082254B2 (en) | Method for producing aromatic compound and method for producing hydrogenated aromatic compound | |
| CN102585951A (en) | Novel process for co-production of liquefied synthesis gas, pure hydrogen and methanol from coke-oven gas | |
| CN1043291A (en) | Prepare ammonia by hydrocarbon-containing feedstock | |
| CN101863729A (en) | Method for preparing low-carbon olefin by hydrocarbon cracking | |
| CN110171804B (en) | Hydrogen production and purification integrated device and use method | |
| CN104098419B (en) | Coal, natural gas combination preparing light olefins from methanol system and method | |
| CN102718627B (en) | Preparation method of ethanol by adding hydrogen to ethyl acetate | |
| JP2003007321A (en) | Direct reforming combined system of hybrid fuel cell using low-grade hydrocarbon | |
| CN107285978A (en) | The preparation method of normal butane | |
| CN104892339B (en) | A kind of method that normal butane is prepared by iso-butane | |
| KR20240095299A (en) | Maleic anhydride hydrogenation method and succinic acid production method comprising the same | |
| CN101113127B (en) | Method for preparing menthol by using refinery gas as raw material | |
| CN110201609B (en) | A kind of equipment and method for co-producing olefins and aromatics by using synthesis gas hydrogenation | |
| CN1155511A (en) | Process and apparatus for converting methanol vapor into hydrogen | |
| JP2009084257A (en) | Method for producing aromatic compound | |
| CN113845939B (en) | A new process for absorbing and stabilizing unit and comprehensive utilization method of its products | |
| CN102872772B (en) | With the reaction unit that methyl alcohol and ethanol are raw material combined producing dimethyl ether and ethene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: MITSUBISHI CHEMICAL Corp. Address before: Tokyo, Japan Patentee before: MITSUBISHI RAYON Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170830 Address after: Tokyo, Japan Patentee after: MITSUBISHI RAYON Co.,Ltd. Address before: Tokyo, Japan Patentee before: MITSUBISHI CHEMICAL Corp. |
|
| TR01 | Transfer of patent right |