CN115216342A - Preparation method of polyester-grade coal-based ethylene glycol - Google Patents
Preparation method of polyester-grade coal-based ethylene glycol Download PDFInfo
- Publication number
- CN115216342A CN115216342A CN202110399174.XA CN202110399174A CN115216342A CN 115216342 A CN115216342 A CN 115216342A CN 202110399174 A CN202110399174 A CN 202110399174A CN 115216342 A CN115216342 A CN 115216342A
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- impurities
- coal
- raw material
- activated carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 260
- 239000003245 coal Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003463 adsorbent Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 85
- 239000003054 catalyst Substances 0.000 claims description 30
- 150000001299 aldehydes Chemical class 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 19
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- -1 2-ethylhexyl Chemical group 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- OACYKCIZDVVNJL-UHFFFAOYSA-N 3-Methyl-1,2-cyclopentanedione Chemical compound CC1CCC(=O)C1=O OACYKCIZDVVNJL-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- BSABBBMNWQWLLU-UHFFFAOYSA-N hydroxypropionaldehyde Natural products CC(O)C=O BSABBBMNWQWLLU-UHFFFAOYSA-N 0.000 claims description 4
- 229940083957 1,2-butanediol Drugs 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- UIKQNMXWCYQNCS-UHFFFAOYSA-N 2-hydroxybutanal Chemical compound CCC(O)C=O UIKQNMXWCYQNCS-UHFFFAOYSA-N 0.000 claims description 3
- NEHRITNOSGFGGS-UHFFFAOYSA-N 3-ethylpentan-2-ol Chemical compound CCC(CC)C(C)O NEHRITNOSGFGGS-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 3
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 3
- 229940120503 dihydroxyacetone Drugs 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229940031723 1,2-octanediol Drugs 0.000 claims description 2
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005815 pentoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 2
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910001586 aluminite Inorganic materials 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 23
- 238000004821 distillation Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 37
- 239000000463 material Substances 0.000 description 23
- 238000011049 filling Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000011068 loading method Methods 0.000 description 16
- 238000001514 detection method Methods 0.000 description 13
- 239000012467 final product Substances 0.000 description 13
- 238000007670 refining Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000005086 pumping Methods 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 229910003023 Mg-Al Inorganic materials 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- WXONGBQFFCVVCX-UHFFFAOYSA-N butoxy(propan-2-yl)silane Chemical compound CCCCO[SiH2]C(C)C WXONGBQFFCVVCX-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/18—Solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of polyester-grade coal-based ethylene glycol, which comprises the following steps: (1) Enabling the high-purity poor-quality coal-based ethylene glycol raw material to pass through an adsorption bed, fully contacting with an adsorbent in the bed layer to perform adsorption reaction, and marking an effluent obtained by the adsorption reaction as AD-EG; (2) Feeding the AD-EG obtained in the step (1) into a fixed bed reactor for hydrofining reaction, and marking the effluent obtained after the reaction as HY-EG; (3) And (3) carrying out reduced pressure distillation on the HY-EG obtained in the step (2) to obtain a polyester-grade ethylene glycol product. According to the method, different types of micro/trace impurities in the high-purity inferior raw material are accurately and efficiently removed, so that the light transmittance of the obtained polyester-grade ethylene glycol product meets the GB/T4694-2018 specification, and the light transmittance is greatly improved at positions of 220nm, 275nm and 350nm compared with that of the raw material.
Description
Technical Field
The invention belongs to the technical field of coal-based ethylene glycol, and particularly relates to a preparation method of polyester-grade ethylene glycol by using inferior high-purity coal-based ethylene glycol as a raw material.
Background
Ethylene glycol is an organic chemical raw material with wide application, and is mainly used for producing polyester fibers, antifreeze, nonionic surfactants and other products. China is one of the countries with the largest import quantity of ethylene glycol and has higher degree of dependence on the outside. At present, two technical routes of glycol industry exist, one is that crude oil and natural gas are used as raw materials to prepare glycol by an ethylene method, the energy consumption of the production process of the method is high, and the cost is greatly influenced by the price of the raw materials. The other method for preparing the ethylene glycol by using the oxalate method with coal as the raw material can effectively save petroleum resources, accords with the energy status quo of 'more coal and less oil and gas' in China, and is developed rapidly in recent years. However, a certain amount of impurities are easily introduced in the process of preparing the ethylene glycol by the coal-based method, wherein a small amount of impurities can cause the ultraviolet transmittance of the ethylene glycol product to be seriously reduced, and the requirement of the polyester-grade product is difficult to achieve. GB/T4694-2018 states that the light transmittance of polyester-grade ethylene glycol is not less than 75%, 92% and 99% at wavelengths of 220nm, 275nm and 350 nm. The ethylene glycol product with unqualified ultraviolet transmittance is used for producing polymers, and the properties of the polymers, such as chromaticity, glossiness, strength, coloring performance and the like, are seriously influenced. Impurities affecting ultraviolet transmittance are generally considered to be aldehyde, ketone and ester impurities containing carbonyl structures. In addition, research shows that certain olefine acids and olefine acid ester substances have obvious influence on the ultraviolet transmittance at 220nm, and the olefine acid and olefine acid ester substances are often low in content in coal-based glycol and difficult to remove. Therefore, the method for preparing the polyester-grade coal-based ethylene glycol product by removing impurities in the coal-based ethylene glycol has important significance and wide economic prospect for improving the competitiveness of the coal-based ethylene glycol and reducing the import of the polyester-grade ethylene glycol in China.
Based on the background, a series of research works around coal-based ethylene glycol impurity removal and preparation of polyester-grade ethylene glycol are carried out by a plurality of researchers. For example, CN 105085175A discloses a method for adsorbing impurities in coal-based ethylene glycol by using acid leaching pretreated modified activated carbon, which is designed for a coal-based ethylene glycol process route, and can effectively adsorb impurities in coal-based ethylene glycol, so that the UV value at 220nm is increased from 50% to 84%, and finally the product reaches the polyester grade. CN 102911013A discloses a bifunctional solid acid catalyst and a solid base catalyst, which can simultaneously remove aldehyde impurities in a petroleum route and impurities such as esters, cyclic diketones and conjugated aldehydes in a coal chemical route through the reduction and catalysis of the catalysts, so that the UV values of coal-based glycol and petroleum-based glycol at 220nm are respectively increased from 50.6% and 70% to 83% and 89%. CN107973699A discloses a method for refining ethylene glycol, in which the adsorption property of coconut shell carbon and the hydrogenation reduction capability of a composite hydrogenation catalyst are used to increase the ultraviolet transmittance of ethylene glycol, and the transmittance at 220nm is increased from 3.2% to 76%. US6242655B1 describes a process for removing aldehyde impurities from high purity ethylene glycol using a cation exchange resin. According to the method, petroleum glycol is selected as a raw material, and through removing aldehyde, UV values at 220nm and 275nm are respectively increased from 93% and 96% to 96% and 97%. The research removes impurities in the ethylene glycol through different methods, obviously improves the light transmittance of the ethylene glycol, finally meets the requirements of polyester-grade products, and provides a good basis for the deep development of related work.
However, the researches all use ethylene glycol with relatively high light transmittance, relatively few impurity types and relatively low content as a raw material, and for ethylene glycol with very high raw material purity (more than or equal to 99.0%), many impurity types and extremely low light transmittance of various wave bands as a raw material, the researches for preparing polyester-grade ethylene glycol are few, and related researches need to be further deepened.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of polyester-grade coal-based ethylene glycol. According to the method, through accurate and efficient removal of different types of micro/trace impurities in the high-purity poor-quality raw material, the light transmittance of the obtained polyester-grade ethylene glycol product meets the GB/T4694-2018 specification, and is increased in a large range compared with the light transmittance of the raw material at 220nm, 275nm and 350 nm.
The preparation method of the polyester-grade coal-based ethylene glycol comprises the following steps:
(1) Enabling a high-purity inferior coal-based ethylene glycol raw material to pass through an adsorption bed, fully contacting with an adsorbent in the bed layer for adsorption reaction, and marking an effluent obtained by the adsorption reaction as AD-EG;
(2) Feeding the AD-EG obtained in the step (1) into a fixed bed reactor for hydrofining reaction, and marking the effluent obtained after the reaction as HY-EG;
(3) And (3) carrying out reduced pressure rectification on the HY-EG obtained in the step (2), and collecting the middle-rear fraction/bottom fraction of the tower top to obtain a polyester-grade ethylene glycol product recorded as VC-EG.
In the method, the high-purity inferior coal-based ethylene glycol raw material in the step (1) has the following properties: the purity of the ethylene glycol is more than or equal to 99.0 percent, the total impurity content is less than 400ppm, wherein the content of aldehyde impurities is more than 200mg/kg, and the content of UV is more than or equal to 0 percent 220nm ≤10%，0%≤UV 275nm ≤10%，30%≤UV 350nm Less than or equal to 90 percent and the chroma (platinum-cobalt) is 0 to 30.
Wherein the impurities mainly comprise aldehyde impurities, ether impurities, ketone impurities, alcohol impurities, acid and ester impurities; wherein the aldehyde impurities are one or more of formaldehyde, acetaldehyde, glycolaldehyde, hydroxypropionaldehyde, 2-hydroxybutyraldehyde and the like; the ether impurities are one or more of dimethyl ether, methyl ethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol ethyl ether, 1, 4-dioxane, etc.; the ketone impurity is one or more of 2, 3-butanedione, dihydroxyacetone, 3-methyl-1, 2-cyclopentanedione, etc.; the alcoholic impurities are one or more of 1, 2-propylene glycol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-octanediol, diethylene glycol, 3-ethyl-2-pentanol, etc.; the acid and ester impurities are one or more of methyl carbonate, ethylene carbonate, ethyl glycolate, dimethyl oxalate, diethyl oxalate and the like.
In the method, the adsorbent in the step (1) is polysilane modified activated carbon, and the polysilane structure is as follows:
wherein R is 1 Is one of alkyl, alkoxy or alkoxyalkyl, preferably alkyl, and has 1 to 8 carbon atoms; r is 2 Is one of alkyl, alkoxy or alkoxyalkyl, preferably alkyl, and has 1 to 8 carbon atoms; wherein the alkyl is one of methyl, ethyl, propyl, butyl, n-pentyl, isopropyl, isobutyl, cyclohexyl, 2-ethylhexyl, neopentyl and isopentyl; the alkoxy is methoxyOne of a group, an ethoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a n-pentyloxy group, and a 2-ethylhexyloxy group; the alkoxyalkyl is one of methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl and pentoxymethyl. m is any integer between 5 and 25, preferably any integer between 10 and 20.
In the method of the present invention, the preparation method of the polysilane-modified activated carbon in the step (1) comprises the following steps: spraying activated carbon by using a mixture of polysilane and a diluent, and then carrying out temperature programming roasting treatment in an inert atmosphere to obtain a roasted product, namely polysilane modified activated carbon; wherein the diluent is one of toluene, ethylbenzene, n-hexane, cyclohexane, n-octane, isooctane and n-heptane; the volume ratio of the polysilane modifier to the diluent is 1 to 1. The active carbon raw material is one of coal-based active carbon, wood-based active carbon and shell-based active carbon, and the specific surface area of the active carbon raw material is 500-2000 m 2 Per g, preferably 1000 to 1800m 2 (iv) g. The mass ratio of the mixture of the polysilane and the diluent to the raw material of the activated carbon is 1 to 1. The temperature programming roasting conditions are as follows: baking for 0.5 to 4 hours at the temperature of 100 to 150 ℃, and then baking for 0.5 to 4 hours at the temperature of 200 to 300 ℃. The inert atmosphere is one or more of nitrogen, helium, neon and argon. In the method of the invention, the adsorption reaction conditions in the step (1) are as follows: the temperature is 20 to 60 ℃, and preferably 30 to 50 ℃; the liquid hourly space velocity is 0.25 to 25h -1 Preferably 2.5 to 12.5 hours -1 (ii) a The reaction pressure is 0.05 to 0.6MPa, preferably 0.1 to 0.4MPa.
In the method of the present invention, the hydrorefining catalyst in the step (2) is a transition metal supported catalyst. The active metal component of the transition metal supported catalyst is any one or two of Cu, ni, pd, pt, ru and Rh, and is preferably Ni and/or Pd; the carrier of the transition metal supported catalyst is any one of alumina, chromium oxide, titanium dioxide, zirconium dioxide, silicon dioxide, activated carbon and bauxite, and preferably alumina and/or titanium dioxide.
In the method of the invention, the transition metal supported catalyst in the step (2) can also comprise a cocatalyst metal component besides the active metal component, and the cocatalyst metal component plays a role in reducing the acting force between the active metal and the carrier and improving the dispersion degree and the catalytic activity of the active component. The promoter metal component is any one or two of W, mo, mg, fe, ce, V, ca, mn and Ba.
In the method, the loading amount of the active metal component of the transition metal supported catalyst in the step (2) is 0.01-55 wt%, preferably 0.1-40 wt%; the supported amount of the cocatalyst metal component of the transition metal supported catalyst is 0.01wt% to 30wt%, preferably 0.1wt% to 15wt%.
In the method of the present invention, the hydrorefining reaction conditions in step (2) are as follows: the reaction temperature is 40 to 160 ℃, preferably 80 to 120 ℃, the reaction pressure is 0.1 to 5MPa, preferably 0.2 to 2.5MPa, the volume ratio of hydrogen to raw materials (abbreviated as hydrogen-feed ratio) is 50 to 1 to 2500, and the volume airspeed is preferably 500 to 1 to 2000 -1 Preferably 0.5 to 5h -1 。
In the method, the vacuum distillation in the step (3) is intermittent common vacuum distillation, an entrainer and a catalyst are not used in the distillation process, and the specific process conditions are as follows: the theoretical plate number is 10 to 20, the overhead pressure is 2 to 20KPa, the reflux ratio R is 3 to 12, and the reboiler temperature at the tower kettle is 100 to 160 ℃. Generally, an overhead distillate with the mass of 20wt% of the mass of the raw material, namely, an overhead front-stage fraction enriched in impurities is collected and treated separately, and the remaining overhead middle-stage and rear-stage fractions and a bottom fraction are target products.
The polyester grade glycol product obtained by the method meets the GB/T4694-2018 regulations, and has the following specific properties: the purity of the ethylene glycol is more than or equal to 99.6 percent, the aldehyde content is 0 to 8mg/kg, and the UV is more than or equal to 75 percent 220nm ≤100%，92%≤UV 275nm ≤100%，99%≤UV 350nm Less than or equal to 100 percent, and chroma (platinum-cobalt) from No. 0 to No. 5.
Compared with the prior art, the invention has the following advantages:
(1) In the prior art, the coal-based ethylene glycol raw material generally has low aldehyde content, simple impurity types and high light transmittance. The coal-based ethylene glycol raw material has the characteristics of high purity, high aldehyde content, complex impurity types and low light transmittance, and greatly increases the treatment difficulty.
(2) The invention adopts a technical route of firstly adsorbing, then hydrogenating and then rectifying aiming at the composition characteristics of complex micro/trace impurities of raw materials. The adsorption process is matched with a specific adsorbent (active hydrogen on polysilane is utilized to react with oxygen-containing groups of activated carbon at high temperature to remove oxygen-containing functional groups and generate water, and polysilane is uniformly distributed on the shallow surface of the activated carbon, so that the adsorption capacity of the activated carbon on nonpolar or weak polar impurities is remarkably improved), ether impurities with different polarities from other impurities are effectively adsorbed and removed, the adsorption process has the advantages that although the ether impurities hardly affect the light transmittance, the ether impurities and aldehyde and ketone impurities can be subjected to competitive adsorption in the hydrogenation process, the conversion efficiency of the catalyst on the aldehyde and ketone impurities is reduced, and the adsorption selectivity of the conventional adsorbent on the ether impurities is limited. After ether impurities are removed, aldehyde impurities are removed through mild hydrofining, and then acid and ester impurities which are difficult to convert in mild hydrogenation are removed through vacuum rectification.
Drawings
FIG. 1 is a GC-MC spectrum of a low-grade coal-based ethylene glycol feedstock.
FIG. 2 GC-MS spectrum of polyester grade ethylene glycol obtained in example 5.
Detailed Description
The following examples further illustrate the preparation of coal-based polyester grade ethylene glycol of the present invention, but are not intended to limit the scope of the invention.
In the examples of the invention and the comparative examples, the raw materials are high-purity low-grade coal-based ethylene glycol, and the main properties of the low-grade coal-based ethylene glycol are shown in table 1. It should be noted that the description of the properties of the raw materials in table 1 is only for the purpose of indicating the degree of the inferior quality of the high purity coal-based ethylene glycol raw material and does not constitute a limitation on the raw material selected for the present invention.
TABLE 1 Main Properties of the poor coal-based ethylene glycol feedstock
As shown in the table, the purity of the poor coal-based ethylene glycol raw material is as high as 99.2%, however, the light transmittance at 220nm and 275nm is less than 10, and the aldehyde content in the poor raw material is as high as 262mg/kg. The aldehyde impurities mainly comprise glycolaldehyde and 2-hydroxybutyraldehyde; the inferior raw material contains other impurities, wherein the ketone impurities mainly comprise 2, 3-butanedione and dihydroxyacetone; the ether impurities mainly comprise methyl ethyl ether and 1, 4-dioxane; the alcohol impurities mainly comprise 1, 2-propylene glycol, 1, 2-butanediol, 1, 2-pentanediol, 3-ethyl-2-pentanol, diethylene glycol (belonging to the same ethers); the acid and ester impurities mainly comprise ethyl glycolate, ethylene carbonate and dimethyl oxalate.
The light transmittance of the polyester grade ethylene glycol in the embodiment and the comparative example of the invention is measured by a Nigeri Japanese Kogyo U-3900 ultraviolet spectrophotometer, and the specific measurement steps and the method refer to the standard GB/T14571.4-2008.
UV in all the following examples and comparative examples 220nm 、UV 275nm 、UV 350nm The indicated values are the light transmission of ethylene glycol at 220nm, 275nm, 350 nm.
Example 1
Preparing a coating solution by using polymethylethylsilane (m = 25) as a modifier and toluene as a diluent according to a volume ratio of 1 2 Uniformly mixing coal-based activated carbon per gram according to the mass ratio of 1. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 20 ℃ for 0.25h -1 And passing the poor-quality coal-based ethylene glycol through an adsorption bed under 0.05MPa, and primarily adsorbing and refining to obtain the product AD-EG-1. Pumping AD-EG-1 into a fixed bed reactor, and feeding the AD-EG-1 into the fixed bed reactor at 40 ℃, 0.1MPa and a hydrogen-material ratio of 50 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 0.01% by weight of Pt and 0.1% by weight of Mg, and the hydrorefined product was recorded as HY-EG-1; HY-EG-1 is filled into the bottom of the batch type rectification tower as rectification materialAnd performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 10, the pressure of the tower top is 2KPa, the reflux ratio R =3 and the temperature of a reboiler of the tower bottom is 160 ℃, collecting middle and rear section fractions at the tower top, recording the middle and rear section fractions as VC-EG-1, and detecting a UV value. After detection, the final product is UV 220nm =76.8，UV 275nm =96.5，UV 350nm =99.2。
Example 2
Preparing a coating solution by using polypropylmethoxysilane (m = 5) as a modifier and n-hexane as a diluent according to a volume ratio of 1 2 Uniformly mixing the shell-based activated carbon fibers according to the mass ratio of 1/g, then heating and roasting at 150 ℃, 4h,200 ℃ and 0.5h in a helium atmosphere, and naturally cooling to obtain the polypropylmethoxysilane modified activated carbon adsorbent. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 60 ℃ for 25h -1 And passing the poor-quality coal-based ethylene glycol through an adsorption bed under the pressure of 0.6MPa, and primarily adsorbing and refining to obtain the product AD-EG-2. Pumping AD-EG-2 into a fixed bed reactor, and pumping the AD-EG-2 into the fixed bed reactor at 160 ℃, 5MPa and a hydrogen-material ratio of 2500 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Cu/Mn-TiO 2 Wherein the Cu loading was 55% wt, the Mn loading was 15% wt, and the hydrorefining product was scored as HY-EG-2; and (3) filling HY-EG-2 serving as a rectification material to the bottom of a batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 20, the pressure of the tower top is 20KPa, the reflux ratio R =12 and the temperature of a reboiler at a tower kettle is 100 ℃, collecting fractions at the middle and rear sections of the tower top, recording the fractions as VC-EG-2, and detecting the UV value. After detection, the final product is UV 220nm =77.2，UV 275nm =97.4，UV 350nm =99.5。
Example 3
Preparing a coating solution by using polyethoxy-methoxymethylsilane (m = 7) as a modifier and cyclohexane as a diluent according to a volume ratio of 1 2 Uniformly mixing coal-based activated carbon/g according to the mass ratio of 1. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 30 ℃ for 2.5h -1 0.1MPa to cause inferiorAnd (3) passing the coal-based ethylene glycol through an adsorption bed, and primarily adsorbing and refining to obtain a product which is marked as AD-EG-3. Pumping AD-EG-3 into a fixed bed reactor, and feeding the AD-EG-3 into the fixed bed reactor at 80 ℃, 0.2MPa and a hydrogen-material ratio of 500 for 1 hour and 0.5 hour -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Ni-Pt/Fe-ZrO 2 Wherein the Ni-Pt loading is 0.1% wt (Ni: pt = 1); and (3) filling HY-EG-3 serving as a rectification material into the bottom of the batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 18, the pressure of the tower top is 12KPa, the reflux ratio R =5 and the temperature of a reboiler at the tower bottom is 155 ℃, collecting middle and rear fractions at the tower top, recording the middle and rear fractions as VC-EG-3, and detecting the UV value. After detection, the final product is UV 220nm =79.4，UV 275nm =98.5，UV 350nm =99.8。
Example 4
The method comprises the steps of preparing a coating solution by using poly isopropyl-butoxysilane (m = 13) as a modifier and n-octane as a diluent according to a volume ratio of 1 2 Uniformly mixing the shell-based activated carbon fibers according to the mass ratio of 1/g to 7, then heating and roasting at 145 ℃, 2h,275 ℃ and 3.5h in a nitrogen atmosphere, and naturally cooling to obtain the polyisopropyl-butoxysilane modified activated carbon adsorbent. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 50 ℃ for 12.5h -1 And passing the inferior coal-based ethylene glycol through an adsorption bed under the pressure of 0.4MPa, and primarily adsorbing and refining to obtain the product which is marked as AD-EG-4. Pumping AD-EG-4 into a fixed bed reactor, and carrying out hydrogenation at 120 ℃, 2.5MPa and a hydrogen-material ratio of 2000 -1 Hydrofining is carried out under the condition, a hydrofining catalyst is Ni/Mo-calcium aluminum ore, wherein the Ni load is 40wt%, the Mo load is 30wt%, and a product obtained by hydrofining is marked as HY-EG-4; and (3) filling HY-EG-4 serving as a rectification material to the bottom of the batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 12, the pressure of the tower top is 18KPa, the reflux ratio R =7 and the temperature of a reboiler at the tower bottom is 125 ℃, collecting middle and rear fractions at the tower top, recording the middle and rear fractions as VC-EG-4, and detecting the UV value. After detection, the final product is UV 220nm =80.2，UV 275nm =98.9，UV 350nm =99.8。
Example 5
Using polydimethylsilane (m = 22) asModifying agent and isooctane as diluent, preparing coating liquid according to the volume ratio of 1 2 Uniformly mixing wood-based activated carbon per gram according to a mass ratio of 1. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 45 ℃ for 10h -1 And passing the inferior coal-based ethylene glycol through an adsorption bed under the pressure of 0.3MPa, and primarily adsorbing and refining to obtain the product which is marked as AD-EG-5. Pumping AD-EG-5 into a fixed bed reactor, and performing heat treatment at 115 ℃, 2MPa and a hydrogen-material ratio of 800 -1 Hydrofining is carried out under the conditions that the hydrofining catalyst is Ni/W-Ce, wherein the Ni loading is 30 percent by weight, the W loading is 10 percent by weight, and the product obtained by hydrofining is recorded as HY-EG-5; and (3) filling HY-EG-5 serving as a rectification material into the bottom of the batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 16, the pressure of the tower top is 5KPa, the reflux ratio R =10 and the temperature of a reboiler at the tower bottom is 144 ℃, collecting middle and rear fractions at the tower top, recording the middle and rear fractions as VC-EG-5, and detecting the UV value. After detection, the final product is UV 220nm =83.8，UV 275nm =99.5，UV 350nm =100。
Example 6
Preparing a coating solution by using polybutyl-isobutyl silane (m = 17) as a modifier and n-heptane as a diluent according to a volume ratio of 1 2 Uniformly mixing wood-based activated carbon per gram according to the mass ratio of 1. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 40 ℃ for 8h -1 And passing the inferior coal-based ethylene glycol through an adsorption bed under the pressure of 0.35MPa, and primarily adsorbing and refining to obtain the product which is marked as AD-EG-6. AD-EG-6 is pumped into a fixed bed reactor, and the reaction temperature is 100 ℃, the pressure is 1.5MPa, the hydrogen-material ratio is 600 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Pd/V-Cr 2 O 3 Wherein the Pd loading was 0.5% by weight, the V loading was 3% by weight, and the product obtained by hydrorefining was designated HY-EG-6; HY-EG-6 is filled to the bottom of the batch type rectifying tower as the rectifying material, the number of theoretical plates is 13, and the pressure of the tower top is 6.5KPa, reflux ratio R =6, common reduced pressure rectification is carried out at the temperature of a reboiler at the tower bottom under the condition of 100 ℃, middle and rear section fractions at the tower top are collected and recorded as VC-EG-6, and a UV value is detected. After detection, the final product is UV 220nm =82.2，UV 275nm =99.2，UV 350nm =100。
Example 7
Preparing a coating solution by using polydiethylsilane (m = 11) as a modifier and ethylbenzene as a diluent according to a volume ratio of 1 2 Uniformly mixing wood-based activated carbon per gram according to a mass ratio of 1. Filling activated carbon adsorbent into bed layer, at 52 deg.C for 15 hr -1 And passing the poor-quality coal-based ethylene glycol through an adsorption bed under the pressure of 0.5MPa, and primarily adsorbing and refining to obtain the product which is marked as AD-EG-7. Pumping AD-EG-7 into a fixed bed reactor, and reacting at 88 ℃ and 4MPa for 1 hour and 5.5 hours according to a hydrogen-material ratio of 1250 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Rh/Ba-SiO 2 Where Rh loading was 7% wt, ba loading was 4.5% wt, and the hydrorefined product was noted HY-EG-7; and (3) filling HY-EG-7 serving as a rectification material to the bottom of the batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 19, the pressure of the tower top is 11.5KPa, the reflux ratio R =8 and the temperature of a reboiler at the tower bottom is 152 ℃, collecting middle and rear fraction at the tower top, recording the middle and rear fraction as VC-EG-7, and detecting the UV value. After detection, the final product is UV 220nm =81.7，UV 275nm =99.0%，UV 350nm =99.7。
Comparative example 1
Preparing a coating solution by using polymethylethylsilane (m = 25) as a modifier and toluene as a diluent according to a volume ratio of 1 2 Uniformly mixing coal-based activated carbon per gram according to the mass ratio of 1. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 20 ℃ for 0.25h -1 And passing the poor-quality coal-based ethylene glycol through an adsorption bed under 0.05MPa, and primarily adsorbing and refining to obtain the product AD-EG-a. A is to beD-EG-a is filled to the bottom of the batch type rectification tower as a rectification material, ordinary reduced pressure rectification is carried out under the conditions that the number of theoretical plates is 10, the pressure of the tower top is 2KPa, the reflux ratio R =3 and the temperature of a reboiler at the tower bottom is 160 ℃, middle and rear-section fractions at the tower top are collected and are recorded as VC-EG-a, and the UV value is detected. After detection, the final product is UV 220nm =36.4，UV 275nm =81.2，UV 350nm =94.2。
Comparative example 2
Preparing a coating solution by using polymethylethylsilane (m = 25) as a modifier and toluene as a diluent according to a volume ratio of 1 2 Uniformly mixing coal-based activated carbon per gram according to the mass ratio of 1. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 20 ℃ for 0.25h -1 And passing the poor-quality coal-based ethylene glycol through an adsorption bed under 0.05MPa, and primarily adsorbing and refining to obtain the product AD-EG-b. Pumping AD-EG-b into a fixed bed reactor, and performing heat treatment at 40 ℃, 0.1MPa and a hydrogen-material ratio of 50 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 Wherein the Pt loading was 0.01% wt, the Mg loading was 0.1% wt, the product obtained by hydrofinishing was designated HY-EG-b, and the UV value was examined. After detection, the final product is UV 220nm =33.8，UV 275nm =86.7，UV 350nm =96.6。
Comparative example 3
Pumping the poor-quality coal-based ethylene glycol raw material into a fixed bed reactor, and performing hydrogenation treatment at 40 ℃, 0.1MPa and a hydrogen-to-material ratio of 50 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 Wherein the Pt loading is 0.01% wt, the Mg loading is 0.1% wt, the hydrorefining resultant product is noted HY-EG-c; and (3) filling HY-EG-c as a rectification material to the bottom of the batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 10, the pressure of the tower top is 2KPa, the reflux ratio R =3 and the temperature of a reboiler at the tower bottom is 160 ℃, collecting middle and rear fractions at the tower top, recording the middle and rear fractions as VC-EG-c, and detecting the UV value. After detection, the final product is UV 220nm =35.5，UV 275nm =85.4，UV 350nm =96.2。
Comparative example 4
Pumping the poor-quality coal-based ethylene glycol raw material into a fixed bed reactor, and performing hydrogenation treatment at 40 ℃, 0.1MPa and a hydrogen-to-material ratio of 50 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 0.01% by weight of Pt and 0.1% by weight of Mg, and the hydrorefined product was recorded as HY-EG-d; preparing a coating solution by using polymethylethylsilane (m = 25) as a modifier and toluene as a diluent according to a volume ratio of 1 2 Uniformly mixing coal-based activated carbon per gram according to the mass ratio of 1. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 20 ℃ for 0.25h -1 And under 0.05MPa, HY-EG-d passes through an adsorption bed, and the product obtained by preliminary adsorption and refining is marked as AD-EG-d. And (3) filling AD-EG-d serving as a rectification material to the bottom of the batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 10, the pressure of the tower top is 2KPa, the reflux ratio R =3 and the temperature of a reboiler at the tower bottom is 160 ℃, collecting middle and rear section fractions at the tower top, recording the middle and rear section fractions as VC-EG-d, and detecting the UV value. UV of the final product after detection 220nm =37.2，UV 275nm =87.0，UV 350nm =97.1。
Comparative example 5
Preparing a coating solution by using polymethylethylsilane (m = 25) as a modifier and toluene as a diluent according to a volume ratio of 1 2 Uniformly mixing coal-based activated carbon per gram according to the mass ratio of 1. Filling the activated carbon adsorbent into the bed layer, and keeping the temperature at 20 ℃ for 0.25h -1 And passing the inferior coal-based ethylene glycol through an adsorption bed under 0.05MPa, and primarily adsorbing and refining to obtain the product which is marked as AD-EG-e. Filling AD-EG-e serving as a rectification material to the bottom of a batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 10, the pressure of the tower top is 2KPa, the reflux ratio R =3 and the temperature of a reboiler at the tower bottom is 160 ℃, and collecting middle and rear fraction at the tower top, which is marked as VC-EG-e; will be provided withThe VC-EG-e raw material is pumped into a fixed bed reactor, and the reaction temperature is 40 ℃, the pressure is 0.1MPa, the hydrogen-material ratio is 50 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 The UV value was determined as HY-EG-e, where Pt loading was 0.01wt%, mg loading was 0.1 wt%. UV of the final product after detection 220nm =34.0，UV 275nm =89.2，UV 350nm =97.3。
Comparative example 6
The specific surface area is 500 m 2 The coal-based activated carbon is used as adsorbent and is filled into a bed layer at the temperature of 20 ℃ for 0.25h -1 And passing the poor-quality coal-based ethylene glycol through an adsorption bed under 0.05MPa, and primarily adsorbing and refining to obtain the product AD-EG-f. Pumping AD-EG-f into a fixed bed reactor, and feeding the AD-EG-f into the fixed bed reactor at 40 ℃, 0.1MPa and a hydrogen-material ratio of 50 -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 0.01% by weight of Pt and 0.1% by weight of Mg, and the hydrorefined product was recorded as HY-EG-f; and (3) filling HY-EG-f as a rectification material to the bottom of a batch type rectification tower, performing ordinary reduced pressure rectification under the conditions that the number of theoretical plates is 10, the pressure of the tower top is 2KPa, the reflux ratio R =3 and the temperature of a reboiler at a tower kettle is 160 ℃, collecting fractions at the middle and rear sections of the tower top, recording the fractions as VC-EG-f, and detecting the UV value. After detection, the final product is UV 220nm =48.5，UV 275nm =90.6，UV 350nm =98.4。
Example 8
The properties of the ethylene glycol products obtained in the examples and comparative examples were analyzed and evaluated according to the methods and criteria listed in table 1, and the specific results are shown in table 2:
TABLE 2 Properties of ethylene glycol products obtained in examples and comparative examples
From the above results, it can be seen that the samples UV of examples 1 to 7 220nm All greater than 75%, UV 270nm All greater than 92%, UV 350nm All over 99 percent, the aldehyde content is less than 8mg/kg, and the platinum-cobalt color is less than 5, which indicates thatHigh-purity inferior coal-based ethylene glycol is used as a raw material, and a high-quality ethylene glycol product with the performance meeting the polyester-grade ethylene glycol standard can be obtained by adopting the methods of the embodiments 1 to 7. The light transmittance of the samples of comparative examples 1-3 at 220nm, 275nm and 350nm is relatively low, especially the light transmittance at 220nm does not reach 40%, which shows that the method of examples 1-3 is difficult to deeply remove aldehydes and complex impurities, and the ethylene glycol contains many unsaturated components and cannot reach the polyester-grade ethylene glycol standard. Comparative examples 4 and 5 were prepared in the same manner as in examples 1 to 7, but the preparation steps were changed, and the results of the evaluation showed that the transmittance of the samples of comparative examples 4 and 5 at 220nm, 275nm and 350nm was only slightly higher than that of the samples of comparative examples 1 to 3 at the above wavelengths, and that there was a large difference from the standard requirements for polyester-grade ethylene glycol. Comparative example 6 in the same manner as in examples 1 to 7, but the adsorbent used in the adsorption treatment was ordinary activated carbon which was not modified with polysilane, the evaluation results showed that comparative example 6 had a relatively highest transmittance at each wavelength, but still failed to meet the polyester-grade ethylene glycol standard, as compared with comparative examples 1 to 5.
Claims (14)
1. A preparation method of polyester-grade coal-based ethylene glycol comprises the following steps: (1) Enabling the high-purity poor-quality coal-based ethylene glycol raw material to pass through an adsorption bed, fully contacting with an adsorbent in the bed layer to perform adsorption reaction, and marking an effluent obtained by the adsorption reaction as AD-EG; (2) Feeding the AD-EG obtained in the step (1) into a fixed bed reactor for hydrofining reaction, and marking the effluent obtained after the reaction as HY-EG; (3) And (3) carrying out reduced pressure rectification on the HY-EG obtained in the step (2) to obtain a polyester grade ethylene glycol product recorded as VC-EG.
2. The method of claim 1, wherein: the high-purity inferior coal-based ethylene glycol raw material in the step (1) has the following properties: the purity of the ethylene glycol is more than or equal to 99.0wt%, the total impurity content is not more than 400ppm, wherein the aldehyde impurity content is more than 200mg/kg, and the UV content is more than or equal to 0% 220nm ≤10%，0%≤UV 275nm ≤10%，30%≤UV 350nm Less than or equal to 90 percent and the chroma (platinum-cobalt) is 0 to 30.
3. The method of claim 2, wherein: the impurities comprise one or more of aldehyde impurities, ether impurities, ketone impurities, alcohol impurities, acid or ester impurities; wherein the aldehyde impurities are one or more of formaldehyde, acetaldehyde, glycolaldehyde, hydroxypropionaldehyde and 2-hydroxybutyraldehyde; the ether impurities are one or more of dimethyl ether, methyl ethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol ethyl ether and 1, 4-dioxane; the ketone impurity is one or more of 2, 3-butanedione, dihydroxyacetone, and 3-methyl-1, 2-cyclopentanedione; the alcoholic impurities are one or more of 1, 2-propylene glycol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-octanediol, diethylene glycol and 3-ethyl-2-pentanol; the acid and ester impurities are one or more of methyl carbonate, ethylene carbonate, ethyl glycolate, dimethyl oxalate and diethyl oxalate.
4. The method of claim 1, wherein: the adsorbent in the step (1) is polysilane modified activated carbon, and the polysilane structure is as follows:
wherein R is 1 Is one of alkyl, alkoxy or alkoxyalkyl, preferably alkyl, and has 1 to 8 carbon atoms; r 2 Is one of alkyl, alkoxy or alkoxyalkyl, preferably alkyl, the number of carbon atoms is 1 to 8, m is any integer between 5 and 25, preferably any integer between 10 and 20.
5. The method of claim 4, wherein: the alkyl is one of methyl, ethyl, propyl, butyl, n-pentyl, isopropyl, isobutyl, cyclohexyl, 2-ethylhexyl, neopentyl and isoamyl; the alkoxy is one of methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, n-pentoxy and 2-ethylhexoxy; the alkoxyalkyl is one of methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl and pentoxymethyl.
6. The method of claim 1, wherein: the preparation method of the polysilane modified activated carbon in the step (1) comprises the following steps: spraying activated carbon by using a mixture of polysilane and a diluent, and then carrying out temperature programming roasting treatment in an inert atmosphere to obtain a roasted product, namely polysilane modified activated carbon; wherein the diluent is one of toluene, ethylbenzene, n-hexane, cyclohexane, n-octane, isooctane and n-heptane; the volume ratio of the polysilane modifier to the diluent is 1 to 1.
7. The method of claim 6, wherein: the active carbon raw material is one of coal-based active carbon, wood-based active carbon or shell-based active carbon, and the specific surface area of the active carbon raw material is 500-2000 m 2 /g。
8. The method of claim 6, wherein: the mass ratio of the mixture of the polysilane and the diluent to the raw material of the activated carbon is 1 to 1.
9. The method of claim 6, wherein: the temperature programming roasting conditions are as follows: baking for 0.5 to 4 hours at the temperature of 100 to 150 ℃, and then baking for 0.5 to 4 hours at the temperature of 200 to 300 ℃; the inert atmosphere is one or more of nitrogen, helium, neon and argon.
10. The method of claim 1, wherein: the adsorption reaction conditions in the step (1) are as follows: the temperature is 20 to 60 ℃, and preferably 30 to 50 ℃; the liquid hourly space velocity is 0.25 to 25h -1 Preferably 2.5 to 12.5h -1 (ii) a The reaction pressure is 0.05 to 0.6MPa, preferably 0.1 to 0.4MPa.
11. The method of claim 1, wherein: the hydrofining catalyst in the step (2) is a transition metal supported catalyst; the active metal component of the transition metal supported catalyst is any one or two of Cu, ni, pd, pt, ru and Rh; the carrier of the transition metal supported catalyst is one or more of alumina, chromic oxide, titanium dioxide, zirconium dioxide, silicon dioxide, activated carbon and calcium aluminite.
12. The method of claim 1, wherein: the hydrofining reaction conditions in the step (2) are as follows: the reaction temperature is 40 to 160 ℃, preferably 80 to 120 ℃, the reaction pressure is 0.1 to 5MPa, preferably 0.2 to 2.5MPa, the volume ratio of hydrogen to the raw materials is 50 -1 Preferably 0.5 to 5h -1 。
13. The method of claim 1, wherein: the vacuum rectification in the step (3) is intermittent vacuum rectification, an entrainer and a catalyst are not used in the rectification process, and the specific process conditions are as follows: the theoretical plate number is 10 to 20, the overhead pressure is 2 to 20KPa, the reflux ratio is 3 to 12, and the reboiler temperature at the tower kettle is 100 to 160 ℃.
14. Polyester grade ethylene glycol obtainable by the process according to any one of claims 1 to 12, characterized by the following properties: the purity of the ethylene glycol is 99.9 to 100 percent, the aldehyde content is 0 to 8mg/kg, and the UV is more than or equal to 75 percent 220nm ≤100%，92%≤UV 275nm ≤100%，99%≤UV 350nm Less than or equal to 100 percent, and chroma (platinum-cobalt) from No. 0 to No. 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110399174.XA CN115216342B (en) | 2021-04-14 | 2021-04-14 | Preparation method of polyester-grade coal-based ethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110399174.XA CN115216342B (en) | 2021-04-14 | 2021-04-14 | Preparation method of polyester-grade coal-based ethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115216342A true CN115216342A (en) | 2022-10-21 |
| CN115216342B CN115216342B (en) | 2023-09-01 |
Family
ID=83604588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110399174.XA Active CN115216342B (en) | 2021-04-14 | 2021-04-14 | Preparation method of polyester-grade coal-based ethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115216342B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770778A (en) * | 1995-07-28 | 1998-06-23 | Eastman Kodak Company | Purification of ethylene glycol recovered from polyester resins |
| CN104275157A (en) * | 2014-09-10 | 2015-01-14 | 江苏金聚合金材料有限公司 | Adsorbent for purifying coal ethylene glycol and preparation method of adsorbent for purifying coal ethylene glycol |
| CN105085175A (en) * | 2015-09-15 | 2015-11-25 | 华烁科技股份有限公司 | Refining agent and refining method of coal polymer grade glycol |
| CN107311389A (en) * | 2016-04-26 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of coal ethyl glycol produces the processing method of waste water |
| CN109096049A (en) * | 2018-07-03 | 2018-12-28 | 沈阳化工大学 | A kind of method that esterification eliminates dimethyl ester mesoxalic acid and obtains polyester grade ethylene glycol |
| US20190112248A1 (en) * | 2016-03-30 | 2019-04-18 | Changchun Meihe Science and Technology Development Co., LTD. | Method for Increasing UV Transmittance of Ethylene Glycol |
-
2021
- 2021-04-14 CN CN202110399174.XA patent/CN115216342B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770778A (en) * | 1995-07-28 | 1998-06-23 | Eastman Kodak Company | Purification of ethylene glycol recovered from polyester resins |
| CN104275157A (en) * | 2014-09-10 | 2015-01-14 | 江苏金聚合金材料有限公司 | Adsorbent for purifying coal ethylene glycol and preparation method of adsorbent for purifying coal ethylene glycol |
| CN105085175A (en) * | 2015-09-15 | 2015-11-25 | 华烁科技股份有限公司 | Refining agent and refining method of coal polymer grade glycol |
| US20190112248A1 (en) * | 2016-03-30 | 2019-04-18 | Changchun Meihe Science and Technology Development Co., LTD. | Method for Increasing UV Transmittance of Ethylene Glycol |
| CN107311389A (en) * | 2016-04-26 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of coal ethyl glycol produces the processing method of waste water |
| CN109096049A (en) * | 2018-07-03 | 2018-12-28 | 沈阳化工大学 | A kind of method that esterification eliminates dimethyl ester mesoxalic acid and obtains polyester grade ethylene glycol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115216342B (en) | 2023-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107971026B (en) | Combined catalyst for preparing low-carbon olefin | |
| CN102688768A (en) | Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof | |
| CN102388009A (en) | Method for producing 1,6-hexanediol | |
| CN108855089B (en) | Ethylene glycol hydrofining catalyst and preparation method thereof | |
| CN111375415A (en) | Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method thereof | |
| CN112322349B (en) | Full conversion method and device for producing light aromatic hydrocarbon from catalytic diesel oil | |
| CN102226104B (en) | Method for producing gasoline and diesel by utilizing waste lubricating oil | |
| CN111303930B (en) | Method for hydrosilylation reaction of carbonyl compound in biological oil | |
| CN102786985B (en) | Resource utilization method for waste lubricating oil | |
| CN104045516B (en) | The method improving quality of ethylene glycol product | |
| CN111574645B (en) | Hydrogenation method for high-sulfur petroleum resin | |
| CN115216342A (en) | Preparation method of polyester-grade coal-based ethylene glycol | |
| CN101797509B (en) | Used lubricating oil complete hydrogenation type regenerated catalyst and preparation method and application thereof | |
| CN102041073A (en) | Hydrocracking method for anthracene oil | |
| CN113698273A (en) | Preparation method of 4-tert-butylcyclohexanone | |
| CN102676219A (en) | Method for utilizing coal tar to produce gasoline and diesel | |
| CN106608814B (en) | Method for improving quality of product of preparing ethylene glycol from synthesis gas | |
| CN103420791B (en) | The method of synthetic gas preparation of ethanol by hydrogenating | |
| CN102649746A (en) | Method for producing glycolic acid ester through adding hydrogen in oxalic ester | |
| CN115215729A (en) | Preparation method of polyester-grade coal-based ethylene glycol | |
| CN103842322A (en) | Method for preparing a mixture of alcohols | |
| CN112125993B (en) | Method for liquid-phase hydrofining of polyvinyl ether | |
| CN110668920A (en) | Method for preparing ethanol and co-producing cyclohexanol by using reactive distillation method | |
| CN105709808B (en) | A kind of hydrocracking catalyst and preparation method thereof | |
| CN103215069A (en) | Method for producing clean diesel by hydro-upgrading inferior distillate oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231214 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |